DE102008005945A1 - Process for the preparation of polyolefins with syndiotactic structural elements, polyolefins and their use - Google Patents

Abstract

The present invention relates to processes for the preparation of polyolefins, polyolefins and their use, in particular as an adhesive or as a component of adhesives.

Description

The The present invention relates to processes for the preparation of polyolefins, with syndotactic structural elements polyolefins and their use, especially as an adhesive or as a component of adhesives.

The use of metallocene compounds as catalyst in olefin polymerization has long been known. Kaminsky et al. have shown that the catalyst system cyclopentadienylzirconium dichloride / methylaluminoxane (Cp ₂ ZrCl ₂ / MAO) is well suited for the polymerization of Adv. Organomet. Chem. 1980, 18, 99-149 ). The employed MAO or methylaluminoxane (a partial hydrolysis product of trimethylaluminum) acts as cocatalyst in this reaction. Since that time, the use of metallocene compounds in conjunction with MAO has been widely used in polymerization reactions. Thus, there are a variety of publications dealing with the metallocene-catalyzed olefin polymerization, such as propene, see for example US 5,476,914 . EP 351 391 . EP 351 392 . EP 426 63 . EP 433 987 . EP 422 498 . US 6,255,425 . EP 480,390 . EP 459 264 . EP 516,018 . US 5,459,117 . EP 666 267 . DE 19 707 034 . WO 99/20664 and WO 2000/037514 ,

at the polymerization of propene or its higher homologues, There may be the formation of different relative stereoisomers. The regularity with which the configurative Repeating units in the backbone of a macromolecule succession is called tacticity. For determination the tacticity one considers the monomer units of a Polymer chain and represents the relative configuration of each (pseudo) asymmetric Chain atom relative to the previous solid. Of isotacticity one speaks, if the hereby determined relative configuration all (pseudo) asymmetric chain atoms are always the same, d. H. the chain of just a single configurational repetition unit is constructed. Syndiotacticity, on the other hand, if the relative configuration is consecutive (pseudo) asymmetric Chain atoms in each case is just opposite, d. H. the chain alternating from two different configurative repeating units is constructed. Finally, in atactic polymers the different configurational repeating units along the chain randomly arranged.

The physical properties of propylene polymers are primarily dependent on the structure of the macromolecules and thus also on the crystallinity, their molecular weight and the molecular weight distribution, and can be influenced by the polymerization process used and in particular the polymerization catalyst used [ R. Vieweg, A. Schley, A. Schwarz (eds); Plastic manual; Vol. IV / "Polyolefins"; C. Hanser Verlag, Munich 1969 ].

On the basis of their tacticity, polypropylene polymers are thus subdivided into atactic, isotactic and syndiotactic polymers. Special forms also include the so-called hemi-isotactic polypropylene polymers and the so-called stereoblock polymers. The latter are usually polymers with isotactic and atactic stereo blocks, which behave like thermoplastic elastomers, since a physical crosslinking of the polymer chains takes place, which leads to a combination of different crystalline polymer regions ( AF Mason, GW Coates in: "Macromolecular Engineering"; Wiley-VCH, Weinheim; 2007 ).

Atactic polypropylene has a low softening point, low density and good solubility in organic solvents. Classic atactic polypropylene (aPP) is characterized by a very broad molecular weight distribution, which on the one hand leads to a broad melting range, and on the other hand brings high low molecular weight fractions, which tend more or less to migrate. aPP has a very low tensile strength of about 1 MPa, but on the other hand has a very high elongation at break of up to 2000% ( H.-G. Elias; Macromolecules; Vol. III; Wiley-VCH; Weinheim; 2001 ). Due to the low softening point, the heat resistance of aPP formulations is correspondingly low, which leads to a strong limitation of the range of use. Purely atactic polypropylene polymers can also be prepared by metallocene catalysis, whereby both very low molecular weight and relatively high molecular weight polymers can be obtained ( L. Resconi in: "Metallocenes Based Polyolefins"; J. Scheirs, W. Kaminsky (ed.); J. Wiley &Sons;Weinheim; 1999 ).

Syndiotactic polypropylene is highly transparent and is characterized by good heat resistance, with the melting temperature below that of isotactic polypropylene. It has high breaking strengths with moderate elongation at break ( AF Mason, GW Coates in Macromolecular Engineering, Wiley-VCH, Weinheim, 2007 ). A disadvantage is the slow crystallization observed in many cases from the melt. Due to physical entanglements, the melt viscosity of syndiotactic polypropylene at comparable molar mass is significantly higher than that of isotactic polypropylene, ie one can achieve the same melt viscosity with significantly lower molecular weights. Syndiotactic and isotactic polypropylene are immiscible above a certain molecular weight, corresponding polymer blends tend to phase separation. Show polymer blends of syndiotactic polypropylene with other polyolefins a significantly higher elongation at break than blends with isotactic polypropylene ( T. Shiomura, N. Uchikawa, T. Asanuma, R. Sugimoto, I. Fujio, S. Kimura, S. Harima, M. Akiyama, M. Kohno, N. Inoue in: "Metallocenes Based Polyolefins", J. Scheirs , W. Kaminsky (ed.); J. Wiley &Sohn;Weinheim; 1999 ) Classic heterogeneous Ziegler-Natta catalysts are unable to produce syndiotactic polypropylene.

Isotactic polypropylene is characterized by a high melting temperature and good tensile strength. For 100% isotactic polypropylene, the calculated melting temperature is 185 ° C. and the enthalpy of fusion is about 207 J / g ( J. Bicerano; JMS; Rev. Macromol. Chem. Phys .; C38 (1998); 391ff ). However, as a homopolymer, it has a relatively low cold resistance and a high brittleness and a poor heat sealability or weldability. The tensile strength (fracture) is about 30 MPa, with virtually no elongation at break occurs. Improved material properties can be adjusted by co- or terpolymerization with ethylene and 1-butene, wherein the comonomer content for copolymers with ethylene in the usual way <8 ma-% and for terpolymers with ethylene and 1-butene at <12 ma-%. ( H.-G. Elias; Macromolecules; Vol. III; Wiley-VCH; Weinheim; 2001 ). At the same MFR (melt flow rate), isotactic polypropylene prepared by classical heterogeneous Ziegler-Natta catalysis shows a significantly lower intrinsic viscosity than polypropylene prepared by metallocene catalysis. The impact strength of the metallocene-based polymer is in a wide range of molecular weights over that of the Ziegler-Natta material. The proportion of xylene-soluble constituents in isotactic poly (propylene) homopolymer which was obtained by metallocene catalysis is usually clearly <1 ma-%, in random copolymers with ethylene xylene-soluble fractions of not more than 5 ma-% are found, depending on the ethylene fraction ( W. Spaleck in: "Metallocenes Based Polyolefins"; J. Scheirs, W. Kaminsky (ed.); J. Wiley &Sohn;Weinheim; 1999 ).

Since the solubility of polypropylene depends both on the molecular weight and on its crystallinity, appropriate fractionation can be carried out by solution experiments [ A. Lehtinen; Macromol. Chem. Phys .; 195 (1994); 1539ff ].

It has long been known that by extraction with ether amorphous atactic moieties [ J. Boor; "Ziegler-Natta Catalysts and Polymerization"; Academic Press; New York; 1979 ] and low molecular weight low crystallinity constituents [ G. Natta, I. Pasquon, A. Zambelli, G. Gatti; Makromol. Chem .; 70 (1964); 191ff ] obtained from polypropylene polymers. Highly crystalline isotactic polymers, on the other hand, have a very low solubility both in aliphatics and in ethers, even at elevated temperature [ BA Krentsel, YV Kissin, VI Kleiner, LL Stotskaya; "Polymers and Copolymers of higher 1-olefins", pages 19/20, Hanser Publ .; Munich, 1997 ]. The soluble polymer components generally have no or only a very low crystallinity, and show no melting point YV Kissin; Isospecific polymerization of olefins; Springer Verlag, New York, 1985 ]. Tetrahydrofuran-soluble polypropylene oligomers have very low number-average molecular weights of significantly less than 1500 g / mol [ H. El Mansouri, N. Yagoubi, D. Scholler, A. Feigenbaum, D. Ferrier; J. Appl. Polym. Sci .; 71 (1999); 371ff ].

The different types of polymers differ significantly in theirs Material properties. The crystallinity of highly isotactic or syndiotactic polymers is due to their high order very high. Atactic polymers, however, have a higher amorphous portion and consequently a lower crystallinity on. High crystallinity polymers show many material properties especially in the field of hot melt adhesives undesirable are. For example, high crystallinity results in low molecular weight polymers to a very rapid crystallization with open times ("open time" = time span in which the parts to be bonded can be connected to each other) sometimes less than a second. This leads the application (eg in the nozzle application by Spraying), even at the slightest temperature fluctuations To block the application and thus a very poor process stability. Add to that the extreme short period of time in which after joining the joining of Adhesive bond can be made. Highly crystalline polymers are also Hard at room temperature, brittle and only show a great deal low flexibility, what with bonds as well is undesirable. On top of that, for the meltdown of highly crystalline polymers at points (at the place of entry) and over the entire line system very high amounts of energy what is needed besides economic effects especially to negative consequences for the process capability leads. The cited disclosures describe mainly the formation of highly isotactic or syndiotactic polypropylenes or copolymers with ethylene and / or higher olefins. However, the polymers mentioned are suitable for use as hot melt adhesives or adhesive raw material unsuitable.

In many cases, the use and the use of supported catalyst systems is described. The use of solid support components to which metallocenes and cocatalysts are attached or attached to have numerous disadvantages. That's the reaction tion rather than homogeneously of a heterogeneous nature, ie adsorption and mass transfer processes play an important role in the course of the reaction. In the reactive connection z. B on solid particles containing water of crystallization, it comes through the moisture to a poorly reproducible and uncontrolled partial deactivation of metallocene and cocatalyst. If, as in many cases, additional organoaluminum compounds are present, an uncontrolled change in the molecular structure of the alkylaluminoxane may also occur (for example, due to the formation of additional molecular weight). In addition, the accessibility of the polymerization-active centers is sterically restricted by the support surface, so that in most cases the catalyst productivity decreases and polymers with a higher tacticity are formed, which is undesirable in the present case as described above. In addition, such solids, both as such, as well as a slurry, very difficult to dose evenly, because the density differences between solid component and suspending medium usually very high and a stable homogeneous distribution of the solid particles in the suspending medium is therefore not reachable. Furthermore, fluctuations in the flow rate, z. As in the metered addition of such solids lurries to the polymerization space for the uncontrolled settling of solids in low-flow areas of the metering on the one hand blockages arise, on the other hand, a uniform reproducible supply of the reaction chamber with polymerization catalyst is impossible.

Next the above-mentioned disadvantages of catalyst solids slurries occur when using suspension oils as they often do to reduce the rate of descent of the solid particles described become more problems in the field of adhesive raw materials. Such oils are known in the adhesive sector as a release agent, so prevent the desired adhesion. In addition, they generally have a very high boiling point, they are no longer readily available and above all never completely separate from the polymers, which leads to inferior material properties with adhesive raw materials.

Also often described, for. In WO 2006/069205 , Cocatalyst systems based on organic boron compounds. However, such compounds have an extremely poor solubility in aliphatic solvents and are therefore not precisely metered into them (see above, metering of solids slurries) or suitable for a homogeneous reaction regime. On the other hand, because of their molecular structure (many have aromatic substituents), they have some solubility in aromatic solvents, the use of which is also disadvantageous in the present case.

WO 01/46278 describes 1-olefin copolymers of predominantly amorphous character, which are obtained by metallocene catalysis, which should be necessary for their use as hot melt adhesives no or only minimal additions of tackifier resins. The copolymers consist of A: 60 to 94% of a C ₃ -C ₆ 1-olefin, B: 6-40 mol% of one or more C ₄ -C ₁₀ 1-olefins and optionally C: 0-10 mol% another unsaturated monomer (preferably ethylene). The statistical distribution of the comonomer B particularly disturbs the crystallinity of the polymers since only a few areas still reach the minimum block length necessary for crystallization (see, for example, US Pat. S. Davison, GL Taylor; Br. Polym. J .; 4 (1972); 65ff ). This can be seen inter alia from the low melting point of the described polymers. Largely amorphous polymers also have a very unbalanced material behavior. In particular, the cohesion of such polymers in relation to the adhesion is clearly underdeveloped, which is why cohesive adhesive failure often occurs in the corresponding adhesive bonds. Such polymers with a low melting point also lead in bonds to a poor heat resistance, which precludes numerous applications. Also, the crystallinity of the described polymers is so low that a rather poor cohesion results. Comonomers with more than 4 carbon atoms are also very expensive, which makes the products in terms of their applications and the product prices to be achieved uneconomical. A freedom from aromatics is difficult to guarantee via the preparation process described, especially as is preferably polymerized in aromatic solvents, and the Cokatalystaor used does not dissolve in aliphatic solvents. The high reaction temperatures, which are (in some cases far above) the melting points of the polymers produced, lead to very high reaction pressures, which make economical operation of the polymerization process difficult. In addition, many of the monomers according to the invention are present in the supercritical state in large parts of the stated process window (T _R 40-250 ° C., p _R 10-3000 bar), which requires a great deal of technical effort to control the process, and the economic viability of the process further limits. There is therefore a need for polymers having improved properties, in particular for use in or as hot-melt adhesive formulations, in particular for those which, with good adhesive and cohesive properties, additionally have high transparency and high flexibility.

In addition to the mentioned different processes are also a number of methods for Implementation of the polymerizations with metallocene catalysts described (see above citations). These processes share the use of cocatalysts, with MAO being the most commonly used cocatalyst. MAO is soluble only in aromatic solvents, that is, the polymerization must be carried out in the presence of an aromatic solvent, or at least the co-catalyst must be introduced together with aromatic solvents in the polymerization with. In many cases, aromatic solvents are, due to their toxicological classification, a strong limitation for the polymers produced in them. This applies in particular to hygiene articles (eg baby diapers) and applications in the field of food packaging. The solvents must be completely removed by complex degassing from the polymers, which is complicated by their high boiling points, and in addition to the high thermal load of the polymers leads to high process / Herstellkosten. Even aromatic solvents, such as xylene, which have not been reported to pose a toxicological hazard yet, are under increased scrutiny and will in all likelihood be subject to further restrictions in the coming years regarding their use or permissible limit concentrations in packaging. In addition, the use of aromatic solvents in the polymerization process in almost all cases is an indication of a high crystallinity / tacticity of the polymers produced, since highly crystalline polymers with high tacticity of known dimensions are distinguished in particular by the fact that they are insoluble in aliphatic solvents , For chlorinated solvents, whether aromatic or aliphatic, the toxicological concern is the same in virtually all cases as for the non-halogenated aromatic solvents. Although they have in many cases a lower boiling point than the common aromatic solvents, but their toxicological concern is in many cases, especially with respect to carcinogenicity and reproductive toxicity even higher. Their use is therefore associated with a significant health risk for the end-users of the polymers produced or a significant financial risk for the polymer manufacturers and processors.

In EP 480,390 In the examples, isotactic and highly syndiotactic polymers are obtained, with the isotactic index of the examples between The problem is the search for a process for the production of polyolefins with high tacticity, high molecular weight and narrow molecular weight distribution, high molecular weight polyolefins with high tacticity (and therefore high crystallinity) but especially not for use as adhesive raw materials, in particular not for the hotmelt adhesives commonly used in the packaging sector.The polymerization methods mentioned are solution polymerization, slurry polymerization and gas-phase polymerisation Because of the inherent stickiness of the polymer particles produced, they can not be reasonably prepared in slurry and gas-phase processes, because after a short time the polymer particles formed become clumped. Adhesive raw materials always have a certain surface tack due to their determination in order to be able to ensure good adhesion to the materials to be bonded. This surface tack also occurs during the polymerization, provided that processes are chosen in which solid particles are formed during the polymerization. Particularly in the case of gas phase polymerization, the described phenomenon has a strongly negative effect, since the formation of a stable fluidized bed is necessary for carrying out a gas phase polymerization. Although sticky polymers such. For example, EPDM is made by gas-phase polymerization, but a high amount of release agents (such as waxes or oils) must be used to prevent clumping. These release agents are very difficult or impossible to remove and therefore lead to a product which can not be used as adhesive raw material. As in the case of gas phase polymerization, the formation of particles also takes place in slurry polymerization, which rapidly agglomerate in the case of adhesive raw materials and lead to a blockage of pipelines. In addition, such sticky particles quickly accumulate on all non-moving reactor parts (such as the reactor walls) and lead to so-called reactor fouling (ie more or less rapid growth of the reactor).

As preparation method for the aluminoxanes used, inter alia, the preparation is described directly in the suspending medium (for example monomer) used for the polymerization. In this case, water is introduced into the polymerization vessel, which adversely affects the catalyst activity of the later added metallocene. As a solvent for the aluminoxanes and for the likewise described preforming of metallocene and aluminoxane, alkanes of the formula C _m H _{2m + 2} with m ≥ 6 or so-called technical gasoline or diesel oil fractions having a boiling range of z. B. 100-120 ° C or 140-170 ° C used. Solvents with a high boiling point, however, have the disadvantage of poor separability from the polymer, so that they at least partially remain in the polymer and affect its material properties. The preformation of metallocene and aluminoxane component, which is intended to increase the polymerization activity and to improve the grain morphology of the resulting polymers, is also described. It is thus expressly made to Slurrypolymerisate, with a higher crystallinity (better morphology) is considered an improvement. Higher crystalline polymers, however, are particularly unsuitable for hot melt adhesive applications (see above).

It there is a need for alternative polymerization processes, in particular the preparation of aromatics-free polymers, in particular for hot melt adhesive applications.

Surprisingly the present invention solves the complex requirement profile.

Accordingly a first subject of the present invention is a method for Preparation of polyolefins comprising contacting a Metallocene compound, at least one first solvent, wherein the at least one first solvent is not halogenated aliphatic solvent is, at least an alkyl-modified methylaluminoxane component, optionally dissolved in a second solvent and / or suspended, wherein the second solvent may be the same or different from the first solvent, and at least one 1-olefin monomer in a reaction space and subsequent polymerization of the at least one 1-olefin monomer at a reaction temperature to form polyolefins, thereby characterized in that the reaction temperature is above the boiling point the first or the first solvent (s) and particularly preferred below the softening point (determined by the ring and ball method) of the polymer produced according to the invention.

The inventive method has the advantage that such a procedure in particular a simple direct and complete Separation of the solvent used allows the polymer. For the method described in the present invention it is an essential characteristic because of this Already in the first evaporation stage a large part of the solvent can be separated. At the same time by the temperature limitation to the top (softening point of the invention Polymers) an excessive thermal Exposure of the polymers produced avoided and a for the metallocene catalysts used according to the invention ensures optimal reaction temperature.

Essential for the process is that the reaction temperature in the stationary Reaktionszudtand above the boiling point the first solvent or solvents) and preferably simultaneously below the softening point of the invention produced Polymers lies.

The at least one first solvent is selected from non-halogenated aliphatic solvents. Preferably the solvent has a boiling point at normal pressure of not more than 101 ° C. Preferably, the aliphatic Solvent a boiling temperature at atmospheric pressure of not more than 80 ° C, preferably not more than 60 ° C, more preferably not more than 40 ° C and in particular preferably not more than 20 ° C.

Especially these are the non-halogenated aliphatic solvents to linear or cyclic aliphatic compounds with no more as 7 C-atoms, preferably with not more than 6 C-atoms and especially preferably with not more than 5 C atoms. This is particularly preferred non-halogenated aliphatic solvents selected from the group comprising propane, butane, pentane, cyclopentane, methylcyclopentane, Hexane, cyclohexane, methylcyclohexane, heptane or mixtures thereof. Most preferably, the solvent is propane and / or n-butane.

The metallocene compound which is preferably used in the present process is selected from compounds according to the formula I. XR ¹ ₂ (CpR ² R ³ R ⁴ R ⁵ ) (FluR ⁶ R ⁷ R ⁸ R ⁹ R ¹⁰ R ¹¹ R ¹² R ¹³ ) MCl ₂ I wherein M is a transition metal selected from the group comprising Zr, Hf and Ti, preferably Zr, in which Cp is cyclopentadienyl and Flu is fluorenyl, and in which XR ¹ ₂ (with X = Si or C) bridges the cyclopentadienyl and the fluorenyl Connecting ligands,
R ^{1 is} selected from linear or branched alkyl groups having 1 to 6 C atoms, alkoxylalkyl groups having 1 to 6 C atoms, aryl groups or alkoxyaryl groups
and with R ² to R ¹³ selected from the group comprising H and / or linear or branched alkyl groups having 1 to 10 C atoms.

worin R¹ bis R¹³ die vorab genannte Bedeutung haben.Preferably, R ⁴ , R ⁷ and R ^{12 are} linear or branched alkyl groups having 1 to 10 C atoms and R ² , R ³ , R ⁵ , R ⁶ , R ⁸ to R ¹¹ and R ¹³ H. The metallocene compound is preferably one of Formula II,

wherein R ¹ to R ^{13 have} the abovementioned meaning.

linear and branched alkyl groups having 1 to 10 C atoms are in particular Substituents selected from the group comprising methyl, ethyl, Propyl, iso-propyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, Nonyl, decyl.

alkoxyalkyl groups with 1 to 6 carbon atoms are in particular selected from the Group comprising methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, Ethoxyethyl and ethoxypropyl.

aryl groups are in particular selected from the group comprising benzyl, Phenyl and indenyl.

alkoxyaryl are in particular selected from the group comprising methoxyphenyl, methoxybenzyl, Dimethoxyphenyl, ethyoxyphenyl, methoxy-ethoxyphenyl and methoxyindenyl, where at least one alkoxy group in para position to the linkage of the aryl ring with the ligand bridge.

All most preferably the metallocene compound in the present inventive method Dimethyimethylen- (cyclopentadienyl) - (fluorenyl) zirconium dichloride, Dimethylmethylene (3-tert-butylcyclopentadienyl) - (fluorenyl) zirconium dichloride, Dimethylsilyl (cyclopentadienyl) - (fluorenyl) zirconium dichloride, Diphenylmethylene (cyclopentadienyl) - (fluorenyl) zirconium dichloride, Diphenylsilyl (cyclopentadienyl) - (fluorenyl) zirconium dichloride or di (paramethoxyphenyl) -methylene (2,7-di-tert-butyl-fluorenyl) - (cyclopentadienyl) -zirconium dichloride.

The The compounds mentioned are preferably present as a racemic mixture of enantiomers and most preferably do not contain the enantiomorphic, optical inactive meso form to a significant extent. The proportion of meso-form is not larger in the present invention than 5mA%, preferably not more than 3mA% and particularly preferably not greater than 1 % by mass.

Of the Catalyst is preferably added to the polymerization space together with a high excess of aliphatic hydrocarbon (s) especially preferably fed to the first solvent, it being particularly preferred in homogeneous form, i. H. Completely is supplied dissolved.

The in the polymerization used 1-olefin monomers basically from all known to the expert 1-olefins to be selected. In particular, this is at least one 1-olefin monomer selected from the group comprising ethylene and linear 1-olefins. Suitable linear 1-olefins are in particular propene and / or 1-butene.

at the reaction of the inventive Process are preferably the metallocene compound and the at least one methylaluminoxane component modified by alkyl groups Reaction space supplied in a homogeneous form. this happens in particular, by the metallocene compound in the first solvent and the at least one alkyl-modified methylaluminoxane component dissolved in the second solvent and the reaction space, with preference only immediately before entering the reaction space or first in the reaction space itself, more preferably only in the reaction space itself a mixing of the two feed streams takes place. Of the fed to the polymerization space (metallocene) Katalysatorfeed preferably contains no aluminum compounds. This has the advantage that no uncontrolled preforming and / or Side reaction of metallocene catalyst and cocatalyst takes place, the poorly reproducible catalyst activities and polymerization results.

und/oder der Formel IV für den cyclischen Typ

wobei in den Formeln III und IV R⁵ Methyl und/oder iso-Butyl bedeutet und n eine ganze Zahl von 2 bis 50 ist. Insbesondere sind 15 bis 45 mol-% der Reste R⁵ iso-Butyl, bevorzugt 17 bis 45 mol-%, besonders bevorzugt 19 bis 43 mol-% und insbesondere bevorzugt 20 bis 40 mol-%. Erst durch den Anteil an iso-Butyl-Resten wird eine Löslichkeit des Cokatalysators in nicht aromatischen Lösungsmitteln ermöglicht. Vorzugsweise liegt der Cokatalysator in einem zweiten Lösungsmittel gelöst vor, dessen Siedetemperatur insbesondere bevorzugt bei maximal 101°C liegt. Das zweite Lösungsmittel des Cokatalysators ist vorzugsweise ein nicht. halogeniertes Lösungsmittel, besonders bevorzugt ein nicht halogeniertes nicht aromatisches Lösungsmittel, insbesondere ausgewählt aus cyclischen und/oder linearen Alkanen mit 3–7 C-Atomen, bevorzugt mit 4–6 C-Atomen, wobei vorzugsweise die Siedetemperatur des zweiten Lösungsmittels deutlich unterhalb der Polymerisationstemperatur liegt, dies ist jedoch nicht zwingend. Insbesondere handelt es sich bei dem zweiten Lösungsmittel um Propan, n-Butan, n-Pentan, Cyclopentan, Methylcyclopentan, n-Hexan, Cyclohexan, Methylcyclohexan und/oder n-Heptan.The at least one alkyl-modified methylaluminoxane component serves as cocatalyst in the process according to the invention. In particular, the cocatalyst is a compound of formula III for the linear type

and / or the formula IV for the cyclic type

wherein in the formulas III and IV R ^{5 is} methyl and / or iso-butyl and n is an integer from 2 to 50. In particular, 15 to 45 mol% of the radicals R ^{5 are} isobutyl, preferably 17 to 45 mol%, particularly preferably 19 to 43 mol% and particularly preferably 20 to 40 mol%. Only by the proportion of iso-butyl radicals is a solubility of the cocatalyst in non-aromatic solvents possible. The cocatalyst is preferably dissolved in a second solvent whose boiling point is particularly preferably at a maximum of 101 ° C. The second solvent of the cocatalyst is preferably not. halogenated solvent, more preferably a non-halogenated non-aromatic solvent, in particular selected from cyclic and / or linear alkanes having 3-7 C-atoms, preferably 4-6 C-atoms, wherein preferably the boiling point of the second solvent is significantly below the polymerization temperature but this is not mandatory. In particular, the second solvent is propane, n-butane, n-pentane, cyclopentane, methylcyclopentane, n-hexane, cyclohexane, methylcyclohexane and / or n-heptane.

Of the Proportion of the second solvent in the total amount of solvent in the polymerization is very low, preferably below 5 m%, in particular below 2 ma-%. Even if the second solvent should have a higher boiling temperature than the selected one Polymerization temperature, so are still the previously described achieved advantages of the invention, since the proportion of the second solvent is very low, and thus substantially also has no influence on the course of the polymerization. All in all is in the inventive method throughout Process flow to the use of aromatic and or halogenated, especially chlorinated solvent omitted, and only unhalogenated, aliphatic solvents are used. During the entire polymerization process is preferably as solvent, suspending medium and / or monomer none Hydrocarbon compound having more than 7 carbon atoms used.

at the reaction space for carrying out the inventive Process may be a stirred tank, a stirred tank cascade with at least two stirred tanks, a flow tube and / or a flow tube with forced delivery (eg Screw machine) act. The above can Reactors either as a single solution or in any Combination can be used. For example, the use the tubular reactor with forced conveying either as a sole solution or in combination with a stirred tank or stirred tank cascade. Here are both a Series and a parallel connection of the individual reactors possible. Preferred in the individual solutions while the stirred tank, particularly preferably is the continuous Stirred tank. In the combinations, a cascade is preferred several continuous stirred tank used, especially Preferably, the continuous stirred tank is in combination with the flow tube with forced delivery. For the case where a batch or continuous stirred tank, or a continuous stirred tank cascade or a continuous one Flow tube is / will be used in the first solvent or polymerized in the initially charged monomer, preferably in the first solvent. In the case of a reactor combination of continuous Stirred tank or continuous stirred tank cascade and continuous flow tube with forced delivery (eg a screw machine) is also in the first solvent or polymerized in the initially charged monomer, preferably in the submitted Monomer. In this case, preference is given either between the continuous stirred tank or the continuous stirred tank cascade and the continuous Flow tube with forced delivery or inside the first half of the reactor length of the continuous Flow tube with forced delivery used Solvent and / or unreacted monomer components completely or partially removed. The preferred reaction spaces have the advantage of optimizing the process parameters can be done to the different target polymers. invention Polymers with very narrow molecular weight distribution can be z. B. optimal in a continuous stirred tank (with a short residence time) or in the flow tube. For wider Molmassenverteilungen is a stirred tank cascade or a combination from stirred tank / stirred tank cascade and flow tube prefers. If it is polymerized in the initially charged monomer, then one is Combination of stirred tank, flow tube and / or Flow tube with forced delivery preferred because so the increasing viscosity of the monomer due to the increasing monomer conversion Polymerization by the different reactor concepts used can be optimally countered. In the latter case is an at least partial Separation of solvent and / or residual monomer is preferred, because so the monomer concentration is increased, resulting in this Reaction stage allows rapid quantitative implementation.

In the case of a continuous reaction, the mean residence time is adjusted so that in the stationary reaction state, the average monomer conversion over all reaction spaces used at least 85%, preferably at least at least 90%, more preferably at least 92%, and most preferably at least 95%.

For the case of a stirred tank and / or a stirred tank cascade the removal of the resulting heat of reaction takes place essentially (i.e., with the exception of the inevitable heat radiation the reactor used or the reactor combination used) not over the reactor walls. An explicit cooling the reactor walls, in particular using a tempering medium, does not take place. In addition, preferably for the cited case in the stationary state of Polymerization reaction of the polymerization over the Reactor walls no thermal energy supplied. All in all is particularly preferred when the polymerization is essentially (i.e. H. during the stationary reaction state) autothermally runs. This has the advantage that it is on the reactor wall does not come to the formation of caking, the longer term lead to a growth of the reactor space, and thus make a production interruption and manual cleaning necessary. In addition, such caking for thermal cracking tend to be what the color stability of in this reaction space impaired polymers. The latter is particular for polyolefin copolymers with syndiotactic structural elements important as these are also used in transparent bonds become.

To Completion of the polymerization is preferably a part of the evaporation of inert solvent and residual monomers needed thermal energy by using the reaction heat applied.

Farther are preferred in the process according to the invention neither before nor during the polymerization and / or the Solvent / monomer separation release agents such as oils and / or Waxes used. This has the advantage that the inventive Polymer does not contain any release agents that have the adhesive properties in an undesirable manner and in the final product to a lead to poor performance. The otherwise necessary Separation of the release agent either at greatly increased Temperatures (risk of product discoloration) and / or very low pressures (expensive / expensive technology) or a purification of the polymers by reprecipitation and / or Extraction (expensive / expensive technology) can be omitted.

in the Case of polymerization in one or more solvents the polymerization temperature is above the atmospheric Boiling point of at least one solvent used.

in the Case of the polymerization in the monomer presented is the polymerization temperature above the atmospheric boiling point at least one used monomers. Is used for the polymerization in one Solvent or the polymerization in the initially charged monomer a discontinuous or continuous stirred tank and / or a continuous stirred tank cascade and / or a continuous flow tube used, so is the polymerization temperature is preferably between 50 and 120 ° C, preferably at 55-115 ° C, more preferably at 60-110 ° C, and more preferably at 65-105 ° C.

Especially the polymerization temperature is in the stationary state of reaction below the softening point (determined by the ring and ball method) the polymers prepared, preferably at least 10 K below the softening temperature, preferably at least 15 K, especially preferably at least 20K and most preferably at least 25 K. The latter is a particularly outstanding feature of the method according to the invention, because it despite this temperature control when using the inventive Method not for the formation of macroscopic polymer particles (as they are present in a slurry polymerization) in the polymerization medium comes, but is polymerized in a homogeneous phase.

Becomes the polymerization in whole or in part in a continuous Flow tube with forced delivery (for example a screw machine) carried out, the polymerization temperature in this reactor / reactor part also over 120 ° C. lie, especially if within this reactor / reactor part also a degassing takes place. The residence time of the polymerization in areas of elevated temperature, however, is in proportion to total residence time in the reaction part very low, which is why no negative influences occur.

When carrying out solution polymerizations at lower polymerization temperatures, in particular when the polymerization temperature is below the boiling point of the solvent used, it is difficult to remove the exothermic energy released by the polymerization, since these are only available via reactor wall cooling or internal cooling coils, but can not be done via boiling cooling. When dissipating the heat via wall cooling and internal cooling coils but it very quickly leads to the formation of caking, which hinder the heat dissipation and eventually make impossible. This would have process disturbances and a poor temperature stability of the polymerization reaction and thus a poor Reproducible speed of the properties of the polymers produced. In contrast, polymerizations at higher temperatures than the invention are also disadvantageous because the metallocenes of the invention generally lose their polymerization activity at temperatures of> 120 ° C. The latter is due to the destruction of the polymerization-active metallocene cocatalyst complex at high temperatures. In addition, only very short polymer chains are formed at very high temperatures due to the then likewise accelerated chain termination reaction, which are no longer sufficient for a good cohesion of the material (waxy character). Another disadvantage is the high pressure level in the polymerization reactor at high temperatures, which requires high demands on the material used and thus greatly increases the cost of the process.

at the inventive method for polymerization in solvent and / or in the initially charged monomer Use of a discontinuous or continuous stirred tank and / or a continuous stirred tank cascade is - with functioning Evaporative cooling - the pressure in the reaction space in the stationary reaction state at 5-40 bar, preferably at 8-35 bar, more preferably at 10 bis 30 bar and more preferably at 12-28 bar. It is particularly preferred in the present process that to none Time of reaction at the same time critical pressure and critical Temperature of the solvents and monomers used exceeded become. This has the advantage that the technical effort to control the reaction is limited, leading to the economic advantage of inventive method compared with supercritical Procedure contributes.

Becomes as the reaction space a continuous flow tube or a continuous flow tube with forced delivery (For example, a screw machine) used, so can within this Reaction space of the pressure well above 30 bar and significantly below 5 bar, if this procedurally necessary is. Lower pressures occur especially when degassing takes place within this reactor / reactor part, in this case, the (absolute) pressure is in this reactor / reactor section preferably at <4 bar, more preferably <3 bar and particularly preferred at <1 bar. The residence time of the polymerization in areas of increased pressure is in proportion to total residence time in the reaction part very low, which is why no negative influences occur.

By the implementation of the polymerization as a solution polymerization in the submitted liquid monomer is achieved that the no technical effort to separate and work up the solvent, which brings economic benefits, and in addition one Contamination of the product polymer by solvent components excludes.

The Control of the molar mass can be above the selected polymerization temperature and / or the addition and mixing of gaseous hydrogen take place in the polymerization, more preferably carried out the control of the molecular weight without the use of gaseous Hydrogen only via the choice of the corresponding polymerization temperature. In the event that hydrogen is used to control the molecular weight is used, this is preferably in the liquid Reaction phase dosed, with the dosage over the ground the reaction space and / or a mixing element used z. B. a stirrer takes place. The use of toxic heavy metal containing Chain transfer reagents (eg tin organyls) for the regulation of Molecular weight is excluded in the process according to the invention.

following the process according to the invention becomes closer without limiting it.

The molar ratio of catalyst to cocatalyst (expressed by the molar ratio of the central transition metal atom of the metallocene to the cocatalyst constituent aluminum) is between 1: 1 and 1: 10,000. The activity of the catalyst used is between 10,000 and 10,000,000 g of polymer / g of catalyst. The monomer ethene is used in gaseous form, while the monomers propene and 1-butene can be used both gaseous and liquid. Higher homologs are used liquid. If propene and / or 1-butene are used in liquid form, a pressure corresponding to the reaction conditions must be maintained in the reactor used, which ensures a sufficient monomer concentration in the liquid phase. The mass ratio of polymer to solvent in the case of polymerization in a stationary state solvent is between 1: 100 and 1: 0.01, preferably between 1:50 and 1: 0.1 and particularly preferably between 1:10 and 1: 0.2. In a specific embodiment, in particular, when the polymerization takes place completely or partially in a continuous flow tube with forced delivery, it is preferably between 1: 1 and 1: 0.01. Catalyst and cocatalyst are decomposed at the end of the reaction in a suitable manner, for example by the addition of water or steam, or aliphatic alcohols in liquid and / or gaseous form wherein the decomposed catalyst components either remain in the polymer or are removed via a washing step. In practice, the decomposition usually takes place in such a way that the in unreactive components converted decomposed catalyst components at least partially remain in the polymer. In this case, the polymer is not colored by the decomposed catalyst components converted into unreactive constituents in the production process according to the invention. On the contrary, the proportion of catalyst decomposition products is so low that no appreciable macroscopic effects are present. According to the prior art, the polymers prepared according to the invention can be chemically stabilized either in the form of their reaction solution or at a later time in order to protect them from the influence of solar radiation, atmospheric moisture and oxygen. For example, stabilizers containing hindered amines (HALS stabilizers), hindered phenols, phosphites and / or aromatic amines can be used. The effective amount of stabilizers is in the range of 0.1 to 3 wt .-%, based on the polymer.

In special cases may be called antifogging substances be used as additives. This z. B. Fatty acid esters are used; the effective concentration is usually in the range of 0.1 to 2 wt .-%, based on the Polymer. The polymer obtained according to the invention is after polymerization either by precipitation in a counterpolar precipitant (such as water and / or Alcohols such. B., ethanol, isopropanol or butanol) or by direct degassing with subsequent melting process receive. In both cases both Rührkessel as well as stirred tank cascades or flow tubes or tubular reactors with forced delivery (For example, a screw machine) can be used. In the latter case is in particular the use of multi-shaft screw machines prefers.

in the Following the degassing, the polymer produced may be another Be subjected to confectioning, which is in the packaging to an additive and / or a pulverization and / or a Pelleting and / or granulation. The direct filling of the molten polymer in accompanying heated transport containers is also possible.

In the case of granulation, it is a strand granulation or an underwater granulation, in particular underwater strand or underwater Vorkopfgranulierung. Optionally, the use of a surfactant and / or dispersing agent or a release agent emulsion is necessary in this case. The use of liquefied or cryogenic gases, such. As CO ₂ and / or N ₂ , as a coolant is possible. Pulverization can be done either by a separate milling step or by using a spraying method. In both cases, the use of supercritical fluids such. As CO ₂ , water or propane possible. In this, z. B. under the name PGSS, known methods, the polymer melt is mixed with a supercritical medium and then atomized in a spray tower. The grain sizes can be controlled by the nozzle and tower geometry. The milling process can also be done using cryogenic gases such. As CO ₂ and / or N ₂ , take place.

Around the flowability of the granules and / or powder to ensure that in the polymer field usually flow aids used are used. these can both inorganic and organic, as well as both contain low and high molecular weight components, wherein in in all cases both crystalline and amorphous flow aids can be used. The flow aids can with the inventively prepared Polymers in terms of thermodynamic miscibility both compatible as also be incompatible. Particularly preferred are Flow aids, which are produced with the invention Polymer are compatible, and the adhesive properties of Polymers due to their chemical nature and / or their low Proportion with respect to the mass of the invention Do not interfere with polymer. As a flow aid can z. B. polyolefin waxes (both on polyethylene as also based on polypropylene) and Fischer-Tropsch waxes become. Polyolefin waxes based on 1-butene can also be used. Likewise, the use of micro waxes is possible. Next Can also grow olefin polymers such. Polyethylene, Polypropylene and / or poly (1-butene), in particular isotactic or syndiotactic polypropylene. Both waxes as well as polymers can also be used in modified form (e.g. As modified with maleic anhydride) can be used. The use of crosslinked polymers such. B. crosslinked polyolefins or crosslinked styrene-divinylbenzene polymers in the pulverized Condition is possible. Come as inorganic materials z. As MgO, talc, silica, etc. in question.

Likewise provided by the present invention are polyolefins containing not more than 20% by mass of ethylene, either 50-100% by mass or not more than 15% by mass of propylene and / or either 85% to 100% by mass or not more than 55% by mass of 1-butene Sum of proportions is 100% by mass, characterized in that the determined by ¹³ C-NMR triad distribution for Propentriaden, in the case the propene is contained as a monomer, a syndiotactic portion of 32-90 ma-%, an isotactic portion of maximum 25 ma-% and an atactic proportion of not more than 65 ma-% and / or the triad distribution determined by ¹³ C-NMR for 1-butene-tri Aden, in the case of 1-butene is contained as a monomer, have a syndiotactic portion of up to 96% by mass and an isotactic content of not more than 45% by mass.

Especially the polymers of the invention are available by methods as described above in the present invention. The use of the inventive method for Preparation of the polymers of the invention is particularly preferred and allows easy access to the desired polymers.

Preferably, the triadium distribution for propene trienes determined by ¹³ C-NMR (assuming that the polymer contains propene triads) has a syndiotactic fraction of 32-90% by mass, preferably of 34-88% by mass, particularly preferably of 36-86% by mass. % and in particular 38-85 ma-%, based on the Propentriaden on.

Thereby is achieved that the polymers of the invention a high degree of flexibility and transparency have at the same time a good strength (without the disadvantage the brittleness) is reached.

Likewise preferably, the triene distribution for propene triimines determined by ¹³ C-NMR (assuming that the polymer contains propene triads) has an isotactic content of not more than 25 m%, preferably from 0 to 23 m%, particularly preferably from 1 to 20 m. % and in particular 2-18 ma-%, based on the Propentriaden on.

Thereby is achieved that polymers are provided can, depending on the (co) polymer composition and selected Polymerization conditions either next to a high transparency and flexibility over additional (isotactic) have crystalline units that further improved Cohesion and a higher softening point, or flexible by an absence of isotactic units Have material properties at extremely high transparency.

The propylene triad distribution determined by ¹³ C-NMR (assuming that the polymer contains propene triad) preferably has an atactic content of not more than 65% by mass, preferably from 1-63% by mass, particularly preferably from 5-61% by mass. and in particular from 7-60 m%, based on the propene triages.

Thereby is achieved that the polymers of the invention depending on the (co) polymer composition and the chosen polymerization conditions high transparency in addition to the dominant flexible and cohesive Properties also specifically adjustable adhesive properties have.

In a particularly preferred embodiment of the polymers according to the invention, the propene triad distribution determined by ¹³ C-NMR (assuming that the polymer contains syndiotactic and atactic propene triads) has a ratio of syndiotactic to atactic propene diions between 1: 0.1 and 1: 2, preferably between 1: 0.12 and 1: 1.75, more preferably between 1: 0.14 and 1: 1.5 and particularly preferably between 1: 0.16 and 1: 1.35. It is thereby achieved that, depending on the (co) polymer composition and selected polymerization conditions, the polymers according to the invention have an optimum balance between the dominating flexible and cohesive material properties and the specifically adjustable adhesive material properties with high to extremely high transparency, whereby a certain basic adhesion is always guaranteed.

Particularly preferably, the triad distribution determined for 1-butene triads by ¹³ C-NMR (assuming that the polymer contains 1-butene triads) has a syndiotactic content of not more than 96% by mass, preferably from 0-94% by mass, more preferably from 1 -92mA% and especially 2-90mA%, based on the 1-butene triads, with further preferred ranges between 2 and 20mA% and 75 to 90mA%. In the case where 0 ma-% syndiotactic 1-butene triads are present, the polymers according to the invention have> 60 m% atactic triads.

Thereby is achieved by that depending on the (co) polymer composition and selected polymerization conditions are the same or strongly different tactics of propene and 1-butene triads provide additional control is present for the material properties, the optimal Adaptation of the polymers of the invention to the different material requirements.

Further preferably, the triad distribution determined for 1-butene triads by ¹³ C-NMR (assuming that the polymer contains 1-butene triads) has an atactic proportion of at most 100% by mass, preferably from 4 to 99% by mass, more preferably from 6 -98mA% and especially 8-96mA% of the 1-butene triads, with further preferred ranges between 9 and 35mA% and between 60 and 95mA%.

This ensures that z. B. at very high syndio and isotactic proportions of the sample segments and thus high softening points, the adhesion of the polymers of the invention targeted can be adjusted via the 1-butene portion, while at high atactic proportions of the sample segments at lower softening points a basic cohesion over correspondingly low atactic portions of the 1-butene segments can be ensured.

In addition, the triad distribution determined by ¹³ C-NMR in the investigation of poly (ethylene-co-propylene-co-1-butene) terpolymers according to the invention for ethylene contents of up to 20% by mass has a proportion of ethylene triads of <1% by mass. , preferably <0.8% by mass, more preferably <0.6% by mass, particularly preferably <0.5% by mass, so that the monomer ethylene is thus incorporated essentially in a statistically distributed manner. It is thereby achieved that a very specific adjustment of the material properties, in particular the softening point and the needle penetration is possible by the ethylene content of the polymers according to the invention, because the statistical distribution an optimal "disorder" of crystalline monomer units takes place, with only small amounts of ethylene must be used.

The Polymers according to the invention preferably contain not more than 20% by mass, preferably not more than 18% by mass, and more preferably maximum 15% by mass of ethylene.

The Polymers according to the invention preferably contain either 50-100 m% or at most 15 m% propylene, wherein particularly preferred ranges at 52-99 m%, 55-98 ma-% and 57-95 ma-%, or at 0-14 ma-%, 1-12 ma-% and 2-10 ma-%.

The Polymers according to the invention preferably contain either 85-100 m% or at most 55 m% 1-butene, where particularly preferred ranges at 87-99mA%, 89-97 ma-% and 90-96 ma-% or at 0-54 ma-%, 1-50 ma-%, 2-45 m%, 5-35 m% and 37-44 ma-% lie.

In a preferred embodiment of the present invention the polymers according to the invention contain 100% by mass Propylene.

In a further particular embodiment include the polymers according to the invention 100% by mass of 1-butene.

In Another preferred embodiment of the present invention Invention are the inventive Polymers to copolymers of ethylene, propylene and / or 1-butene, in particular either a poly (ethylene-co-propylene) copolymer, a poly (ethylene-co-1-butene) copolymer, or a poly (propylene-co-1-butene) copolymer is.

For the case of poly (ethylene-co-propylene) copolymers include the Polymers of the invention a maximum of 25% by mass, preferably 1-23% by mass, more preferably 2-20% by mass, and especially preferred 3-15% by volume of ethylene. The proportion of propylene results accordingly, so that there is a total of 100 ma-% (100 ma-% minus ethylene content).

For the case of poly (ethylene-co-1-butene) copolymers include the invention Polymers at most 17% by mass, preferably 1-15% by mass especially preferably 2-13% by mass, and particularly preferably 3-11 ma-% ethylene. The butene content results accordingly, so in total 100% by mass (100% by mass minus ethylene content).

For the case of poly (propylene-co-1-butene) copolymers include the Polymers of the invention either a maximum of 47 ma-%, preferably 1-45 m%, more preferably 2-43 m%, and particularly preferably 3-40 m%, or 85-99 m%, preferably 87-98% by mass and more preferably 89-97 ma-% 1-butene. The proportion of propylene results accordingly, so in total 100% by mass (100% by mass minus butene content). In a particular embodiment of the present invention the copolymers are two comonomers selected from ethylene, Propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-hexene, 3-methyl-1-heptene, 4-methyl-1-pentene and 6-methyl-1-heptene wherein the maximum proportion of the branched 1-olefin in the copolymer at most 50% by mass, preferably at most 40% by mass, and especially preferably not more than 30% by mass.

For also contains the preferred case of a terpolymer this particular ethylene, propylene and 1-butene, with a maximum of 25 ma-%, preferably 1-20 m%, more preferably 2-18 m%, and particularly preferably 3-15 m% of ethylene, at most 95% by mass, preferably 40-92% by mass, more preferably 45-90 m%, and particularly preferably 50-87 m% of propylene and at most 25% by mass, preferably 1-23% by mass, more preferably 2-21mA%, more preferably 3-20mA% 1-butene.

In a particular embodiment of an inventive Terpolymers contains this selected three comonomers from ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-hexene, 3-methyl-1-heptene, 4-methyl-1-pentene and 6-methyl-1-heptene the maximum proportion of the branched 1-olefin in the copolymer is maximum 50% by mass, preferably at most 40% by mass, and most preferably at most 30 ma-%.

The polymers according to the invention are preferably present in the form of a powder after preparation, in the form of pellets or in the form of granules. Particularly preferred are Pul ver, pellets and / or granules which are free-flowing, and can be dosed automatically. The direct further processing of molten polymer to the products of the invention is also possible.

The polymers of the invention preferably contain no aromatic compounds (ie, <100 μg / g). In addition, they contain substantially no organic halogenated compounds derived from the polymerization process. It is likewise preferred that the polymers (with the exception of the decomposition products derived from the catalyst decomposition) do not contain impurities by suspending oils (release agents), no residues of inorganic support materials, in particular no inorganic oxides and / or alkaline earth halides (such as MgCl ₂ ), no inorganic salts or organic boron compounds, no talcites and / or hydrotalcites and / or their degradation products, no impurities by alcohols, in particular by methanol. This on the one hand ensures that the polymers of the invention are free of toxic compounds and optimally suitable for use in sensitive areas such. As food packaging, medical supplies, children's toys, clothing, carpet / floor coverings, automotive interior applications, etc. are suitable. On the other hand, the negative effects of the above auxiliaries and by-products on the thermal stability (in particular color stability) and the adhesive properties of the polymers are excluded.

The Molecular weight distribution of the polymers according to the invention, determined by high-temperature gel permeation chromatography with universal calibration, can be monomodal or bimodal, where also with bimodal distributed polymers a narrow Molmassenverteilung with a polydispersity of <3. Especially preferred the molecular weight distribution is monomodal. Polymers with a narrow molecular weight distribution are characterized by a low variance of the material properties out. For example, they have a clearly defined melting and Setting behavior on. For very narrow molecular weight distribution leaves a defined melting / setting behavior also with bimodal reach distributed polymers, especially when longer open times are required and / or no sharp melting peaks may occur (eg with long joining times or fluctuating application temperature).

Farther the polymers according to the invention have a polydispersity, determined by high-temperature gel permeation chromatography with universal calibration of 1.3-3, preferably 1.4-2.7 on. This area is particularly advantageous, especially for the application in the adhesive sector. The crystallization or melting behavior at Polymers, especially polyolefins, are known a function of the molecular weight, with linear polyolefins in particular the chain length. So z. B. of classical amorphous Polyolefins, as currently in the field of hot melt adhesives be used, known to have a polydispersity of 4-6 (or even higher) to a very wide melting range on the one hand and to a delayed physical curing / crystallization on the other hand leads. The latter is for hot melt glue, which are to be used in the packaging sector, particularly disadvantageous because the polymers thereby a sometimes extremely long open time (This is the time when a strong stickiness of the polymer due not or not completely crystallized Constituents present). For processing in Fast-running packaging machines are not such polymers suitable. An additional disadvantage of the known systems is that polymers with a broad molecular weight distribution due to the described Crystallization deficiencies often also poor tensile strengths show what packaging adhesives also undesirable is. In general, a broad molecular weight distribution is a sign that that is not a uniform polymer but rather a polymer blend (or a polymer blend) is present, which is known to be Restrictions on the material properties leads.

The weight-average molar mass of the polymers according to the invention, determined by high-temperature gel permeation chromatography with universal calibration, is usually in the range from 15,000 to 400,000 g / mol, preferably from 17,000 to 200,000 g / mol, more preferably in the range from 20,000 to 100,000 g / mol, and in particular preferably in the range of 22,000 to 95,000 g / mol. This range is particularly advantageous, especially for use in the adhesive sector. Due to their molecular weight and their molecular weight distribution, the polymers according to the invention have an optimum melt viscosity in the relevant application window, so that optimum wetting of the surface to be bonded can take place. The relatively low melt viscosity also allows penetration into macroscopic and microscopic surface structures, which significantly improves the adhesion of the adhesive layer. The polymers according to the invention having weight-average molar masses of> 75,000 g / mol are also particularly suitable for use in molding compositions, geomembranes and films. Polymers of higher molecularity have, especially in the case of linear polyolefins, a high to very high melt viscosity. This is for many applications, such as. As the production of moldings or the production of films and films quite desirable, because they give the products a high rigidity and high tensile strength. For use as raw materials for hot However, hot-melt adhesives, especially for those intended for use in packaging applications, are completely unsuitable for such materials.

Especially show an only hesitant crystallization (as a result of Kettenverschlaufungen) and a poor applicability (in particular a poor atomizability and a bad profile also when caterpillar or doctor blade order. This is u. a. on too the more pronounced with increasing molecular weight Attributed to structural viscosity. she can also be combined with the usual processing or Application machines in hot melt adhesive area on Do not process the reason of their high melt viscosity, because in many cases pumpability at reasonable temperatures not given and also a very high pressure build-up in the pipes to be recorded. In contrast, polymers with very lower show Molecularity even in the cold state is not sufficient Cohesion, and exhibit a waxy behavior. she are therefore not in particular for use in the field the hot melt adhesives suitable. Low molecular components tend in addition to "bleeding" by diffusion, what strongly weakens an adhesive bond and leads to its failure. In areas with demanding requirements regarding the Release of organic volatiles, such. B. at Food packaging and in the field of automotive interior bonding, can be adhesive systems containing high levels of low molecular weight compounds often, even for legal reasons be used.

Farther characterized polymers are characterized from being an ALPHA VALUE as determined by high temperature gel permeation chromatography with universal calibration, in the range of 0.6 to 1.2, preferred in the range of 0.62 to 1.17, more preferably in the range of 0.65 to 1.15, and more preferably in the range of 0.7 to 1.12 exhibit.

The Polymers according to the invention are thus distinguished by a low branching tendency, in particular included she prefers no Langkettenverzeigungen. Branched polymers show a highly complex due to their molecular structure rheological behavior, resulting in poor applicability from the melt and a bad course, especially at Doctor and spray application, leads.

Preferably is that when examined by high temperature gel permeation chromatography with universal calibration found proportion of low molecular weight Ingredients with a molecular weight of 500 to 1000 daltons at a maximum of 0.75mA%, preferably at a maximum of 0.5mA%, especially preferably at a maximum of 0.4% by mass, in particular at a maximum of 0.3% by mass. Very particularly preferred may be described by the described Method no ingredients with a molecular weight of 500 to 1000 daltons are detected. This ensures that the inventive Polymers contain no polymer constituents that are required for migration z. B. to the surface and / or the interface tend. Such a migration (also called "bleeding") leads due to the separation effect of low molecular weight polymer components to a strong weakening of an adhesive joints, the contains this polymer. On top of that, in the range of Food packaging (especially for direct and / or indirect Food contact) Substances with migrating components due to may not be used by legal regulations.

Farther preferred is that when examined by high temperature gel permeation chromatography with universal calibration found proportion of low molecular weight Constituents with a molecular weight <500 daltons with a maximum of 0.75 m%, preferably at a maximum of 0.5% by mass, more preferably at maximum 0.4mA%, especially at a maximum of 0.3mA%. Very particularly preferred can by the method described no components with a molecular weight <500 Dalton be detected. In the vehicle interior there is the problem that low molecular weight polymer components with very low molecular weights emerge from the adhesive layer and evaporate, causing undesirable "fogging" phenomenon leads. For such applications are polymers contain the low molecular weight components with low molecular weights therefore not suitable, there are very strict limits of Automakers. The same applies to the area of food packaging.

Furthermore, the polymers of the invention are characterized in that they have a complex melt viscosity of 700 to 400,000 mPa · s, preferably from 800 to 300,000 mPa · s at a temperature of 190 ° C, a maximum deformation of 1% and a measurement frequency of 1 Hz , more preferably from 900 to 250,000 mPa · s, and more preferably from 1,000 to 150,000 mPa · s, with further preferred ranges between 1100 and 25,000 mPa · s, between 26,000 and 65,000 mPa · s and between 66,000 and 140,000 mPa · s. Depending on the desired application, different regions are very particularly preferred. So z. B. for use in the field of spray application and for naps and Filamenteinbindung the polymers of the invention having a melt viscosity of 1250 to 10,000 mPa · s particularly preferred, while for use in molding compositions polymers having a melt viscosity of> 50,000 mPa · s and for the use in films or geomembranes of> 100000 mPa · s particularly before are awarded. As a measure of the intrinsic viscosity of the polymers of the invention, the ratio of melt viscosity measured at 190 ° C and a maximum deformation of 1% at a shear rate of 10 Hz and a shear rate of 0.1 Hz serve. This ratio is between 1: 1 and 1: 100, preferably between 1: 1.05 and 1:50, more preferably between 1: 1.075 and 1:25 and particularly preferably between 1: 1.1 and 1 for the polymers according to the invention. 10th

The Polymers according to the invention thus have an optimum Balance between processability and flow properties and are characterized by a moderate structural viscosity out. In particular, the processability of a polymer melt in the hot-melt adhesive area (eg during spraying) important that the viscosity in the application tool (eg. B. spray gun) in the usually high shear rates prevail, is low, and thus transport the material well and distribute it. For the course of the applied Polymer melt on the substrate, on the other hand, is an increase the viscosity at the loss of shear important, so no course of the polymer melt over the sprayed Area takes place. The increase, however, must be in narrow limits, otherwise no coagulation of the individual Spray particles takes place.

A important parameter for hotmelt adhesives or adhesive raw materials is the temperature-dependent rheological Behavior. This is for example by measuring a cooling curve being accessible in the oscillation rheometer, taking on a very low deformation (max 1%) and a slow cooling rate (1.5 K / min) is to be respected. The ones available from the cooling curve Measured values are those obtained from heating curves (in particular Curves at first heating) with respect to their reproducibility clearly superior, because of the previous melting on the one hand leveled the thermal history of the polymer sample and, on the other hand, optimum wetting of the measuring body surface through the melt, creating friction and slip effects between measuring body and sample are excluded. Come in addition, that at the high temperatures at the start of the measurement (ie in the melt) the susceptibility to deformation (i.e. an irreversible morphology change) of the polymer sample significantly lower than in the solid state, so only on this Remain within the linear viscoelastic region the polymer sample is to be ensured. Furthermore, it should be stated that the rheological material states during Bonding by means of hot melt adhesives anyway only realistically depicted over a cooling curve can be as this is the present state during the bonding is.

The Polymers of the invention are characterized that by oscillatory rheometry (cooling curve, 1.5 k / min) at a shear frequency of 1 Hz and a deformation from 1% certain minimum processing temperature (Crosspoint = Intersection of memory module and loss modulus) at a maximum of 160 ° C, preferably at a maximum of 150 ° C, more preferably at a maximum of 145 ° C and particularly preferably between 50 and 120 ° C. The polymers of the invention accordingly optimal rheological processing properties in the Hot melt adhesives relevant processing range of 100-220 ° C. Is the loss module over The memory module can be sheared using the polymer made to flow and permanently deformed. Lies By contrast, the storage modulus higher are the elastic restoring forces so big that no trouble-free application is possible.

When rheological characteristic of the optimal processing window can the ratio of storage and loss modulus in the temperature range of 220 ° C are used at the end of the melting point. For a trouble-free application from the melt must in the processing window the loss modulus G '' (as a synonym for the viscous material properties) clearly above the storage modulus G ' (as a synonym for the elastic material properties) lie. The ratio of storage modulus G 'to loss modulus G '' is for the claimed polymers at a shear rate of 1 Hz and a deformation of 1% in the temperature range from the end of the highest melting peak (offset / DSC) up to about 220 ° C between 1: 1 and 1: 10000, preferably between 1: 1.25 and 1: 5000, more preferably between 1: 1.5 and 1: 2500 and more preferably between 1: 2 and 1: 1000.

Also Preferably, the at processing temperature by Oszillationsrheometrie with a deformation of 1% certain minimum shear rate from where the loss module is above the storage module (Crosspoint) and thus a rheological processability of the melt is present at a maximum of 1 Hz, preferably at a maximum of 0.5 Hz, more preferably at a maximum of 0.1 Hz and more preferably at a maximum of 0.01 Hz. This ensures that the inventive Polymers at processing temperature even with relatively lower Scherenergie can be brought into the flow state. This is especially true when processing the melt by spraying important, both within the processing machine (where thereby a trouble-free transport of the melt without excessive Pressure build-up is ensured) as well as on the application surface (where at low shear stresses the course of the adhesive take place got to).

The Needle penetration of the polymers of the invention is in the range of 1-50 x 0.1 mm, preferably from 2-45 x 0.1mm, more preferably 3-30 x 0.1 mm, and more preferably from 4 to 28 x 0.1 mm., value ranges between 5 and 15 x 0.1 mm and between 16 and 27 x 0.1 mm are most preferred. Thereby is achieved that the polymers of the invention despite high strength, a sufficient degree of plasticity exhibit. This is especially important in application areas in which a dynamic stress of the bond takes place. Highly crystalline polyolefins have a needle penetration of <1 x 0.1 mm and are therefore very hard and not in the unmelted state plastically deformable so inflexible. Predominantly amorphous Polyolefins have a needle penetration of> 60 · 0.1 mm and therefore show no sufficient strength.

The Polymers according to the invention are predominant semicrystalline nature, so have a significant crystalline Share on. This is reflected in melting peaks at the first and / or second heating of the polymers in the DSC. All inventive Polymers show at least the first melting in the DSC at least a melting peak.

It it is preferred that when measuring in the differential calorimeter (DSC) at first heating 1-3 melting peaks detected can be, wherein in the case of three melt peaks the first melting peak maximum at temperatures of 40-60 ° C the second at temperatures of 65-110 ° C and the third at temperatures of 80-140 ° C, particularly preferred at temperatures of 85-130 ° C. If only two melting peaks occur, this is the first melting peak maximum between 40 and 115 ° C, the second between 50 and 140 ° C, especially preferably from 55 to 135 ° C. If only one melting peak occurs, so the melting peak maximum is between 40 and 140 ° C.

at the second heating in Differentialkalorimeter exhibit the polymers according to the invention preferably 0, 1 or 2 melting peaks, wherein in the case of two Melting peaks the first melting peak maximum at 80 to 125 ° C, the second melting peak maximum at 90-140 ° C, more preferred from 95-135 ° C. If there is only one melting peak, so the melting temperature is 80 to 145 ° C, especially preferably from 85-142 ° C. Depending on the copolymer composition the polymers have a pronounced tendency to cold crystallization , wherein (if present) the exothermic cold crystallization peak at the 2nd heating between 30 and 75 ° C lies. Assign that polymers according to the invention during the second melting no melting peak, this does not mean that they have no Possess crystallinity. Rather, only the existing one Crystallinity due to the DSC standard measurement method used not detectable.

The Polymers according to the invention have an optimum Ratio of crystalline and non-crystalline units on show and both in the load and in the processing case optimal thermal properties. In case of stress it comes up elevated temperatures depending on the polymer composition a more or less pronounced partial melting before the adhesive joint melts altogether. This is also without complete dissolution (melting) of the adhesive bond a plastic deformation possible, especially in structural Bonding and temporary fixation is beneficial. If this is not desired then the polymers of the invention by changing the polymer composition and polymerization conditions also be run until just before the melting point no significant partial melting takes place. In the latter Case can be very high heat resistance of the Bonding can be realized, the heat deflection temperature very close to the softening temperature.

Different as highly crystalline polyolefins which are a very sharp one Have melting peak, show the inventive Polymers in the 2nd heating curve of the DSC measurement at a heating rate of 10 K / min. either a melting peak, or two melting peaks, these melting peaks have different intensities can have. Is in the 2nd heating curve of the DSC at least a melting peak detectable, so is the end of the melting area (so-called peak offset) for the inventive Polymers between 85 ° C and 150 ° C, preferably between 87 ° C and 148 ° C, more preferably between 89 ° C and 146 ° C, and more preferably between 90 ° C and 145 ° C. If the end of the melting range is at low temperatures, This is especially true for the bonding of thermolabile Materials of advantage. If the end of the melting range is high, This results in a particularly high heat resistance.

The polymers preferably have an endothermic enthalpy of fusion of 0 to 35 J / g, preferably 1-33 J / g, particularly preferably 2-30 J / g and particularly preferably 3-28 J / g, measured in the DSC during the second heating with the ranges of 1-15 J / g and 16-28 J / g being most preferred. This ensures that the polymers of the invention have a crystallinity which, although high enough to ensure a high initial strength of a bond, but remains so low that the flexibility of the polymers of the invention is not impaired becomes. Depending on the polymer composition and the chosen polymerization conditions, it is possible to provide polymers for whose melting only one (in comparison with highly crystalline polyolefins) very low or a moderate energy contribution is necessary.

The exothermic cold crystallization enthalpy measured on the second heating in the DSC is preferably at most 20 J / g, preferably from 0-18 J / g, more preferably 1-17 J / g. This will achieve that polymers can be made available their use in bonds completely new possibilities in relation to the joining techniques used. So it is the polymers of the invention depending after polymer composition and polymerization conditions used possible after joining and cooling to plastically deform the adhesive bond for a certain period of time and then via a storage at elevated Cure temperature (recrystallization). on the other hand For example, recrystallization may also be carried out by heat treatment (i.e., storage at elevated temperature) immediately after the joining be accelerated.

The by DSC (2nd heating curve, 20 K / min.) Specific glass transition temperature the polymers of the invention is at maximum 0 ° C, preferably between -2 and -50 ° C, more preferably between -3 and -45 ° C, in particular the value ranges between -3 and -25 ° C as well as between -26 and -45 ° C especially are preferred. This ensures that the inventive depending on the polymer composition and the chosen polymerization conditions can also be used in applications that require high low-temperature flexibility and therefore highly crystalline Polyolefins (such as isotactic polypropylene) stay. It is particularly noteworthy that for the polymers of the invention the low glass transition temperatures without the use of expensive comonomers such. 1-pentene, 1-hexene, 1-octene, 1-nonene and / or 1-decene can be achieved.

Farther is depending on the polymer composition and the polymerization process used Softening point, measured according to the Ring & Ball method, at a maximum of 160 ° C, preferably at 80-155 ° C, more preferably at 83-145 ° C and especially at 85 to 140 ° C. This ensures that polymers are provided can be, whose bonds increased Have heat resistance.

Farther preferably differs in the polyolefins according to the invention, depending on the polymer composition and polymerization conditions used the found softening temperature (according to Ring & Ball method) of the in the DSC at 2. melting determined upper melting temperature (maximum Melting peak) by 1-40 K, preferably 2-35 K, especially prefers 3-30 K. Very particularly preferred is the found softening temperature (by ring & ball method) 1-40 K, preferably 2-35 K, more preferably 3-30 K above the in the DSC at the 2nd melting determined upper melting temperature (maximum melting peak). This ensures that polymers for Can be provided, which is also above their melting point still have a good material cohesion, so that high heat resistance can be achieved.

In a particular embodiment, the inventive Polymers in the 2nd heating curve of DSC no detectable melting peak but a softening temperature determined by ring and ball method of at least 80 ° C, preferably at least 83 ° C, more preferably at least 85 ° C and in particular preferably from 85-160 ° C. There are thus polymers provided only a very small amount of energy need to reach the molten liquid, but still have a high heat.

The Polymers according to the invention preferably have a solubility in xylene at room temperature up to 100% by mass, preferably 60-100% by mass, more preferably of 70-100mA% and more preferably of 80-100 ma-% on. This has the advantage that polymers with good to very good solubility in xylene provided be, in contrast to previously known systems with this Property a very narrow molecular weight distribution with extreme low low molecular weight fraction and one with regard to Solubility high crystallinity and high Have softening point and moderate needle penetration. The Polymers of the invention having high solubility in xylene allow the preparation of solution formulations with good handling and low toxic hazard potential.

The polymers according to the invention furthermore preferably have a solubility in tetrahydrofuran at room temperature of up to 100% by mass, preferably at least 10% by mass, preferably at least 25% by mass, more preferably at least 40% by mass and most preferably at least 50% -% on. This has the advantage that non-polar polymers with moderate to very good solubility can be provided in a polar solvent (eg for solvent applications) which, in contrast to previously known systems with this property, has a very narrow molecular weight distribution with extremely low low molecular weight Shares and one with regard to Solubility high crystallinity and have a high softening point and a moderate needle penetration, so that polymers are provided, which despite their solubility in tetrahydrofuran have a very good material cohesion. The polymers according to the invention with high solubility in tetrahydrofuran also make it possible to prepare solution formulations which, owing to the low boiling point of THF, permit the realization of very short drying / drying times.

additionally characterized polymers are characterized from being added to untreated isotactic without further additions Polypropylene after at least 24 hours of storage an adhesive shear strength of at least 0.2 MPa, preferably at least 0.4 MPa, especially preferably of at least 0.5 MPa, and more preferably of have more than 0.6 MPa. In the case of untreated polyethylene and without further additives is an adhesive shear strength after at least 24 hours storage time of at least 0.1 MPa, preferably at least 0.15 MPa, more preferably at least 0.2 MPa and more preferably more than 0.25 MPa. For untreated beech test specimens is the adhesive shear strength without further additives at least 24 hours storage at least 1.0 MPa, preferably at least 1.5 MPa, more preferably at least 2.0 MPa and particularly preferably more than 2.5 MPa.

The open time of the polymers of the invention can depending on the polymer composition and the polymerization conditions used up to 30 minutes.

Especially preferred in particular for the use of the invention Polymers in packaging adhesives is the open time without further additives a maximum of 300 seconds, preferably a maximum 250 seconds, more preferably at most 200 seconds and in particular preferably 1-180 seconds.

Farther characterized polymers are characterized from that without further additives after at least 24 hours Storage time in the tensile test a tensile strength of 1-25 MPa, preferably from 1.5 to 23 MPa, more preferably from 2 to 21 MPa and in particular from 2.5 to 20 MPa and / or an absolute Elongation at break of at least 10%, preferably of at least 15%, especially preferably from 20-1500% and most preferably from 25 to 1250%, with the ranges of 50-750%, 100-650% and 150-600% as well as the ranges of 150-1200%, 250-1100% and 350 to 1000% are also particularly preferred are.

One Another object of the present invention is the use the polymers according to the invention in molding compositions, as or in adhesives, in marking compounds, coating compounds, geomembranes or roofing membranes, as primers or in primer formulations and / or in aqueous dispersions, suspensions and / or emulsions. Corresponding molding compounds, adhesives, marking compounds, coating compounds, Geomembranes or roof membranes, primers or primer formulations, aqueous dispersions, suspensions and / or emulsions containing the polymers of the invention are also the subject of the present invention.

in the Traps of molding compositions contain these substantially the invention Polymer. In addition, the molding compounds contain further ingredients.

The other constituents can in particular other polymers include, wherein these other polymers to a or several ethylene polymers, and / or isotactic propylene polymers and / or syndiotactic propylene polymers and / or isotactic Poly-1-butene polymers and / or syndiotactic poly-1-butene polymers can act.

in this connection is particularly preferably between the invention contained Polymers and the additionally contained polymers significant difference in melt viscosity, measured by Oszillationsrheometrie at 190 ° C, the additional contained at least twice as high melt viscosity as the polymers of the invention, preferred at least 3 times as high, more preferably at least one 4 times as high, and more preferably one at least 5 times as have high melt viscosity.

The mentioned molding compositions can be used for the production of finished parts (eg by injection molding) or for the production of films and / or Slides are used.

Preferably be the polymers of the invention as or used in adhesives, particularly preferably in adhesive formulations. In essence, the invention contain preferred adhesive formulations the inventive Polymer.

In addition to the polymers according to the invention, further constituents may be present in the adhesive formulations according to the invention. In the case of other constituents, solution formulations in particular may be cyclic and / or linear aliphatic and / or aromatic hydrocarbons, including halo geniated hydrocarbons. This proves the good solubility of the polymers of the invention in different solvents such. As xylene and tetrahydrofuran are particularly advantageous. It is therefore not necessary to choose halogenated solvents in order to prepare a solution formulation. Preferably, no halogenated hydrocarbons are used. In the adhesive formulations which are liquid at room temperature, the abovementioned hydrocarbons have a formulation proportion of not more than 90% by mass, preferably not more than 80% by mass, more preferably not more than 75% by mass, and particularly preferably not more than 50% by mass.

All it is particularly preferable for the inventive Adhesive formulation around a hot melt adhesive formulation, for all known to the expert types of bonds can be used, for example, for bonding of packaging materials.

The Hot melt adhesive formulation according to the invention may contain other ingredients necessary to achieve special Properties such. B. deformability, adhesion, Processing ability, (melting or solution) Viscosity, strength, crystallization rate, Stickiness, storage stability, etc. are necessary. The share of other ingredients is in a particular embodiment of the present invention particularly preferably at a maximum of 10 % by mass. This has the advantage that, the material properties of the adhesive formulation essentially those of the invention used Polymers are. Such an adhesive formulation leaves to produce with very little effort. Alternatively, in one Another embodiment of the present invention of Proportion of other ingredients> 10 ma-%. In this case, make the other ingredients not more than 80% by mass of the total formulation, preferably not more than 60% by mass, more preferably at most 50% by mass, especially preferably at most 40 ma-% off.

at the other components may be inorganic and / or organic fillers which are optionally electrically conductive or may be insulating, inorganic and / or organic Pigments which are optionally electrically conductive or insulating can, synthetic and / or natural resins, in particular Adhesive resins, synthetic and / or natural oils, inorganic and / or organic, synthetic and / or natural Polymers that are either electrically conductive or insulating may be inorganic and / or organic, synthetic and / or natural fibers, optionally electrically conductive or may be insulating, inorganic and / or organic Stabilizers, inorganic and / or organic flame retardants act.

In particular, the other constituents comprise resins, the resins being used to adapt certain properties of the adhesive layer, in particular the tackiness and / or adhesion, the flow and creep behavior of the adhesive layer and / or the adhesive viscosity, to particular requirements. These may be natural resins and / or synthetic resins. In the case of natural resins, these natural resins contain abietic acid as the main component (eg rosin). Furthermore, the resins may be terpene or polyterpene resins, petroleum resins and / or kumarone-indene resins, in particular so-called C ₅ resins and / or C ₉ resins and / or copolymers of C ₅ - / 10 ₉ resins acts. The proportion of the resins in the hot-melt adhesive formulation according to the invention is in particular at most 45% by mass, preferably between 1 and 40% by mass, more preferably between 2 and 30% by mass, and particularly preferably between 3 and 20% by mass, based on the total formulation.

Farther can in the hot melt adhesive formulations of the invention classical amorphous poly (α-olefins) (so-called APAOs) as further constituents be included. In the case of the abovementioned amorphous poly (α-olefins) may be homo- / co- and / or terpolymers of ethylene, propylene, 1-butene or linear and / or branched 1-olefins with 5-20 Carbon atoms which z. B. by classical Ziegler-Natta catalysis or Metallocene catalysis are available. The proportion of amorphous Poly (α-olefins) is in particular at most 50% by mass preferably at a maximum of 40% by mass and more preferably at maximum 30% by mass, based on the total formulation. Preferably it is the other ingredients to crystalline or partially crystalline polyolefins, in particular isotactic polypropylene, syndiotactic polypropylene, polyethylene (HDPE, LDPE and / or LLDPE), isotactic poly (1-butene), syndiotactic poly (1-butene) their copolymers and / or their copolymers with linear and / or branched 1-olefins having 5 to 10 carbon atoms. Furthermore is preferred that it is the crystalline or semi-crystalline Polyolefins to chemically modified polyolefins, wherein the chemical modification, especially those caused by maleic anhydride, Itaconic anhydride, acrylic acid, acrylates, methacrylates, unsaturated epoxy compounds, silane acrylates, silanes and Hydroxyalkylsilane includes.

Furthermore, the other ingredients may include polymers having polar groups. Polymers having polar groups include polystyrene copolymers (eg, with maleic anhydride, acrylonitrile, etc.), polyacrylates, polymethacrylates, (co) polyesters, polyurethanes, (co) polyamides, polyether ketones, polyacrylic acid, polycarbonates, and chemically modified Polyolefins (such as poly (propylene-graft-maleic anhydride) or poly (propylene-graft-alkoxyvinylsilane)

Farther the other constituents can be homopolymers and / or copolymers based on ethylene, propylene, acrylonitrile, butadiene, styrene and / or Isoprene include, in particular, these polymers to block copolymers, in particular rubbers such. Example Natural and synthetic rubber, poly (butadiene), poly (isoprene), styrene-butadiene rubber and nitrile rubber. The proportion of polymers based on butadiene, Styrene, and / or isoprene is at most 20% by mass, preferably 1-15mA%, more preferably 1.5-10mA% and in particular 2-9 ma-%, based on the hot melt adhesive formulations.

Farther For example, the other ingredients may include elastomeric polymers Base of ethylene, propylene, a diene and / or cis, cis-1,5-cyclooctadiene, exo-dicyclopentadiene, endo-dicyclopentadiene and the like 1,4-hexadiene and 5-ethylidene-2-norbornene include, in particular, these are ethylene-propylene rubber, EPM (double bond free, ethylene content 40-75 m%) and / or EPDM. The proportion of polymers based on ethylene, propylene, a Diene and / or cis, cis-1,5-cyclooctadiene, exo-dicyclopentadiene, endo-dicyclopentadiene and 1,4-hexadiene and 5-ethylidene-2-norbornene is usually not more than 20% by mass, preferably 1-15% by mass, more preferably 1.5-10% by mass and especially 2-9% by mass on the hot melt adhesive formulations.

alternative For example, the other ingredients may include waxes, in particular modified and unmodified waxes, these being preferably crystalline, semi-crystalline and / or amorphous polyolefin waxes based on polyethylene, polypropylene and / or poly (1-butene), Paraffin waxes, metallocene waxes, microwaxes, polyamide waxes, polytetrafluoroethylene waxes and / or Fischer-Tropsch waxes. The proportion of waxes is not more than 50% by mass, preferably 1-40% by mass, more preferably 2-30mA% and especially preferably 3-20mA%, based on the hot melt adhesive formulations.

Farther the further constituents may comprise fillers, where the fillers are used to give specific property profiles the adhesive layer, such. B. the temperature application area, the Strength, shrinkage, electrical conductivity, the magnetism and / or the thermal conductivity specifically adapted to specific requirements. General acts it is the fillers to inorganic and / or organic Fillers. The inorganic fillers are in particular selected from silicic acids (incl. hydrophobized silicic acids), quartz flour, chalks, barite, Glass particles (in particular spherical particles to increase light reflection), glass fibers, carbon fibers, asbestos particles, asbestos fibers and / or metal powders. Organic fillers are for example Carbon black, bitumen, cross-linked polyethylene, cross-linked rubber or rubber mixtures synthetic fibers such. For example, polyethylene fibers, polypropylene fibers, Polyester fibers, polyamide fibers, aramid fibers, saran fibers, MP fibers or natural fibers such as straw, wool, cotton, silk, flax, hemp, Jute, and / or sisal. The proportion of fillers is not more than 80% by mass, preferably 1-60% by mass, more preferably 5-40mA%, and more preferably 7-30mA%, based on the hot melt adhesive formulations.

Also the other constituents may comprise stabilizers, these are used to prepare the adhesive formulation external influences such. B. the influence of (processing) heat, Shear stress, solar radiation, humidity and oxygen to protect. Suitable stabilizers are, for example, hindered Amines (HALS stabilizers), hindered phenols, phosphites and / or aromatic amines. In the above formulations is the proportion of stabilizers maximum 3% by mass, preferably between 0.05 and 2.5mA%, and more preferably between 0.1 and 2mA%, based on the hot melt adhesive formulations.

About that In addition, the other ingredients may include one or more oils include, which are natural and / or synthetic oils can act. These one or more oils preferably at the processing temperature, a viscosity of 1 to 1000 mPa.s, preferably from 2-750 mPa.s, most preferably from 3-500 mPa.s. Suitable oils are, for example, mineral oils, (medicinal) white oils, Isobutene oils, butadiene oils, hydrogenated butadiene oils and / or paraffin oils. The proportion of one or more oils is not more than 50% by mass, preferably 1-45% by mass, more preferably 3-40 m% and especially 5-38 ma-%, based on the hot melt adhesive formulations.

Farther can in the hot melt adhesive formulations inorganic and / or organic pigments, UV-active substances, organic and / or inorganic nucleating agents that crystallize accelerate the polymers and thus the open time of the bond reduce, be included.

In a further preferred form of the invention Hot melt adhesive formulations are the formulations described above to multiphase blends.

The hot-melt adhesive formulations according to the invention can in particular by means of spray application, as Caterpillar (s) and / or by doctoring on the surface to be bonded be applied. Particularly preferably, the order is carried out by spray application.

One Another object of the present invention are adhesions containing one or more polymers of the present invention. In particular, the bonds are packaging bonds, Bonding of hygiene articles, wood bonds, adhesions of glass surfaces, label laminating laminating, Carpet or artificial turf gluing, shoe gluing, pressure-sensitive Gluing, book gluing or textile gluing.

In the case of packaging bonds, the packaging materials may include the materials wood, cardboard, paper, plastic, metal, ceramics, glass, synthetic and / or natural fibers and / or textiles. The packaging materials are preferably non-polar plastics, in particular polyethylene, polypropylene, poly (1-butene) or their copolymers with linear and / or branched C _2-20 1-olefins, for example uncrosslinked polyethylene such as. As LDPE, LLDPE and / or HDPE, and / or to (eg silane) crosslinked polyolefin, in particular silane-crosslinked polyethylene. Furthermore, it may be in the non-polar plastics in particular polystyrene, polybutadiene, polyisoprene homo- and / or copolymers, and / or their copolymers with linear and / or branched C _2-20 1-olefins or dienes, such as. As EPDM, EPM or EPR, and / or synthetic or natural rubber.

in the Traps of polar plastics are in particular polyacrylates, in particular polyalkyl methacrylates, to polyvinyl acetate to polyester and / or copolyesters, in particular polyethylene terephthalate and / or Polybutylene terephthalate, polyamides and / or copolyamides, acrylonitrile copolymers, in particular acyl nitrile / butadiene / styrene copolymers and / or styrene / acrylonitrile copolymers, maleic anhydride copolymers, in particular S / MSA copolymers and / or MSA-grafted polyolefins such as. As polypropylene and / or Polyethylene, polyvinyl chloride and / or polycarbonates. As a general rule the packaging materials can be used as a box, box, container, sheet, Disc, film and / or foil present. For example, you can corresponding plastic films via extrusion, calender, Blow molding, casting technique, solution drawing, deep drawing or a combination of several of these techniques become. For example, it is the plastic films single-layer films that are oriented or not oriented. In the case of orientation of the monolayer film, a single, two- or multi-axial orientation, with the orientation axes can be at any angle to the film take-off direction.

alternative the plastic films may be multilayer films, the film layers being of the same as well as different ones Material can be made. The multilayer films can be oriented or not oriented. In case of orientation The multilayer plastic films may have a single, dual or multi-axial Orientation are available, with the orientation axes in any Can stand angle to the film take-off direction. In particular, acts the bonds are gluing of transparent plastic films.

In a particular embodiment is in the Multilayer plastic film around a composite film. When bonding of composite films may comprise one or more of the film layers Composite material, wherein the composite materials in continuous Mold (eg paper, aluminum foil or the like) and / or discontinuous Form (eg., Particles and / or fibers) may be present.

Especially are in the bonding of plastic packaging materials according to the present invention generally no chemical and / or energetic Pretreatments of the plastic surfaces (eg plasma, Corona treatment, etching, sulfonation, etc.) for the achievement of liability necessary.

in the Trapping of wood packaging materials may occur in the wood packaging to solid real wood to real wood laminates to Plastic laminates to MDF boards and / or similar woody Substances act. Both resin and oil can be used Woods such. B. beech, oak, etc., but also resin or oil rich Woods such as teak, pine etc. can be used.

at the said packaging bonds preferably has at least one of the polymers according to the invention contained an open time of less than 30 seconds.

at The bonding of toiletries is basically no restrictions, for example, it can be here to act on diapers, bandages, etc. As a rule, by the invention Bonding built a multi-layered structure, the different Materials such. As polymer films and nonwoven covers. About that In addition, moisture-absorbing substances, such as z. As polyacrylic acid particles contained in the bond be.

One further field of application of the invention Bondings are structural wood bonds, in particular Kantenumleimungen and / or Decorative paper coatings and / or decorative film laminations and / or Assembly bonding.

One another essential field of application of the invention Bondings are bonds involving a glass surface. there the bond can moisture absorbing substances such. As silica gel, polyacrylic acid particles, etc. included. Preferably this is a multi-pane insulating glass composite. For this suitable are all types of multi-pane insulating glass composites known to the person skilled in the art, regardless of the individual structure, for example with or without additional spacer.

Farther can in bonding according to the invention under Involvement of a glass surface performed a lamination become. In addition, it may be at the glass surface to act on the surface of glass fibers, such as the Surface of a fiber optic cable, as z. Eg for data and / or telephone lines is used.

In another embodiment of the present invention it is the object to be bonded to a label. The label can be made of a paper, plastic, metal and / or Multilayer film exist and in particular for labeling painted, coated, anodised and / or otherwise surface-treated metal, in particular tinplate cans and glass or plastic (especially PET) - bottles used become. In particular, it may be in the adhesive for Label bonding around a so-called "pressure-sensitive" adhesive (PSA) act.

In another embodiment of the present invention when the bonds are a lamination, wherein it is the surface to be laminated around the surface an inorganic and / or organic substance, preferably of metals (eg steel, aluminum, brass, copper, Tin, zinc, enamel), of glass, of ceramics and / or inorganic Building materials, such. B. open or closed-pored concrete. About that In addition, the surface may be wood, paper, Cardboard and / or plastics act. The surface can itself a composite of inorganic and organic materials (eg glass fiber composites). This can be counter-laminated Laminating material of inorganic and / or organic nature. Examples of counter-laminated inorganic laminating materials are ultra-thin glass panes, ceramic membranes and / or metal foils (eg aluminum foil). Corresponding examples gegenkaschierter organic laminating materials are paper, cardboard, wood veneer, Plastics, natural and / or synthetic textiles, Nonwoven synthetic leather and / or natural leather.

Of course it may be in the bonds according to the invention also a bonding in the vehicle interior (eg screens, headliner etc.).

In another particular embodiment of the present invention Invention are adhesives for the production of carpets and / or Artificial grass. In particular, the bond for nubs and filament binding used. It may be in the fibers to be incorporated or Fiber composites around natural and / or synthetic fibers act. Examples of natural fibers or fiber composites are wool, cotton, sisal, jute, straw, hemp, flax, silk and / or Blends of these fibers.

Examples synthetic fibers or fiber composites to be incorporated are (co) polyamide fibers, polyethylene fibers, Co (polyester fibers), polypropylene fibers and / or mixtures of these fibers. In the case of Kunstrasenverklebungen are by the Bonding embedded filaments selected from polypropylene filaments, Polyethylene filaments, polyamide filaments, polyester filaments or Mixed filaments of the listed plastics.

Preferably as the bond used for carpet backing. In addition, a textile substrate can additionally be counter laminated. The carpet elements obtained are, for example, carpet tiles or a subsequently deformable car carpet. In the aforementioned applications for nubbed and filament incorporation, the polyolefin according to the invention contained has a melt viscosity at 190 ° C. of not more than 10,000 mPa.s, preferably from 500 to 8,000 mPa.s, more preferably from 600 to 6,000 mPa.s and most preferably from 750 up to 4000 mPa · s. The proportion of polyolefins according to the invention is in particular 60-98 ma-%. The application weight is in particular 20-1500 g / m ² . Other examples are within the skill of one of ordinary skill in the art.

Farther it may be in the bonds according to the invention to act shoe bonding, for example, in the field of Sport shoes and / or for the production of so-called split leather used can be.

Likewise, adhesions according to the invention are so-called "pressure-sensitive adhesions" (PSA) nes of the inventive polymers and / or formulation constituents contained a "cold flow" (that is, a melting point below room temperature) has.

Formulation ingredients with cold flow are, for example, poly (1-hexene), poly (1-octene), poly (1-hexene-co-1-octene), Polyacrylates, etc.

in the Traps of book bindings are usually one Bonding made in the process of bookbinding.

In the case of textile adhesives, a plurality of textile layers can be connected to one another selectively or in a planar manner, wherein textile elements to be bonded can comprise natural or synthetic materials. In particular, the natural textile elements are wool, horsehair, cotton, linen fabric, hemp, jute, sisal, flax, straw and / or leather. Preferred synthetic textile elements as constituents polypropylene, polyethylene, (co) polyamides, (co) polyester, nylon, perlon and / or Kevlar ^®. In particular, one or more of the elements to be bonded may be an insert. In a particular embodiment, the adhesive formulation according to the invention is introduced in the form of a powder between the textile layers to be bonded and activated by thermal energy (eg with the aid of an ironing press).

In an embodiment of the invention also of the present invention, the inventive Polymers in marking compounds, coating compounds, geomembranes or roofing membranes are used.

The marking compositions according to the invention can already in the description of the molding compositions or adhesive formulations contain listed further ingredients. For example, you can the marking compositions of the invention as road marking compounds be used.

in the Case of coating compositions may be, for example, a Trade coating material for cardboard or paper coating.

Farther the polymers of the invention are suitable for Use in geomembranes. In addition to the invention Polymers can be further constituents in the geomembranes be included, in particular, it is the other ingredients to other polymers, fillers and bitumen. In case of Geomembranes is the proportion of the invention Polymers at a maximum of 30% by mass, preferably at a maximum of 27% by mass, especially preferably at a maximum of 25% by mass and especially preferably at maximum 22% by mass, based on the geomembrane.

Especially If the geomembranes are roofing membranes. In the event of the roofing membranes has at least one of the invention Polymers have a glass transition temperature of at most -10 ° C, preferably from a maximum of -15 ° C, more preferably of at most -18 ° C, and more preferably from maximum -20 ° C.

Farther the polymers of the invention are suitable for Use as primer, adhesion promoter or in primer formulations and / or in primer formulations, in particular the The absence of halogenated organic constituents is advantageous. Especially are primer and adhesion promoter formulations which are the inventive Polymers used to provide adhesion of organic coatings and / or Adhesives on untreated polyolefin surfaces, in particular to achieve on untreated polypropylene. In a special Case, the primer and / or primer formulations as Primer on polypropylene moldings such. B. car bumpers and / or trim panels applied to better adhesion to achieve the subsequent painting.

Farther the polymers of the invention are suitable for Use in aqueous dispersions, suspensions and / or Emulsions. In addition to the polymers of the invention may be surface-active in the dispersions, suspensions and / or emulsions Substances (for example, inorganic and / or organic surfactants of ionic and / or nonionic nature) as well as other polymers, in particular those with polar monomeric units (such as poly (propylene-graft-maleic anhydride) be included. Preferably, the preparation of the aqueous Dispersions, suspensions and / or emulsions using a solution of the polymers according to the invention, especially in tetrahydrofuran or xylene. Also a production using a melt of the invention Polymers are possible, in which case polymers are preferred with a melting / softening temperature of <100 ° C, particularly preferably used of <90 ° C. become.

In the said aqueous dispersions, suspensions and / or Emulsions is the proportion of the invention Polyolefins more than 10% by mass based on the total formulation.

Even without further statements, it is assumed that a person skilled in the art can use the above description to the greatest extent. The preferred embodiments and examples are therefore only as a descriptive, in no way limiting, disclosure specific.

following The present invention will become more apparent by way of example explained. Alternative embodiments of the present invention Invention are available in an analogous manner.

Examples:

analytics:

a) high temperature ¹³ C NMR

The polymer composition is determined by high temperature ¹³ C NMR. The ¹³ C NMR spectroscopy of polymers is described, for example, in the following publications:

• [1] S. Berger, S. Braun, H.-O. Kalinowski, 13C-NMR spectroscopy, Georg Thieme Verlag Stuttgart 1985
• [2] AE Tonelli, NMR Spectroscopy and Polymer Microstructure, Verlag Chemie Weinheim 1989
• [3] JL Koenig, Spectroscopy of Polymers, ACS Professional Reference Books, Washington 1992
• s [4] JC Randall, Polymer Sequence Determination, Academic Press, New York 1977
• [5] A. Zambelli et al: Macomolecules, 8, 687 (1975)
• [6] A. Filho, G. Galland: J. Appl. Polym. Sci., 80, 1880 (2001)

b) high temperature GPC

The Determination of the molecular weight is carried out via high-temperature GPC. The determination is carried out in accordance with ASTM D6474-99, However, at a higher temperature (160 ° C instead 140 ° C) and a lower injection volume of 150 μl instead of 300 μl. As further literature on the GPC analysis of Polymers are mentioned:

• HG Elias: "Macromolecules"; Vol. 2; Wiley-VCH; Weinheim 2001 ;
• Z. Grubisic, P. Rempp, H. Benoit; Polym. Lett .; 5; 753 (1967) ;
• KA Bonuses, FA Sliemers, PB Stickney; J. Polym. sci .; A2; 6; 1579 (1968) ;
• D. Goedhart, A. Opschoor; J. Polym. Sci .; A2; 8th; 1227 (1970) ;
• A. Rudin, HLW Hoegy; J. Polym. Sci .; A1; 10; 217 (1972) ;
• G. Samay, M. Kubin, J. Podesva; Angew. Makromol. Chem .; 72; 185 (1978) ;
• B. Ivan, Z. Laszlo-Hedvig, T. Kelen, F. Tüdos; Polym. Bull .; 8th; 311 (1982) ;
• K.-Q. Wang, S.-Y. Zhang, J. Xu, Y. Li, HP Li; J. Liqu. Chrome.; 5; 1899 (1982) ;
• TG Scholte, HM Schoffeleers, AMG Brands; J. Appl. Polym. Sci .; 29; 3763 (1984) ,

When Solvent is trichlorobenzene used. The measurement takes place at a column temperature of 160 ° C. The used for the evaluation of the elution curves Universal calibration is based on polyolefin standards carried out. The results are not comparable to measurements their calibrations based on foreign polymers -. B. on polystyrene-based - was, or without universal Calibration is done, otherwise an invalid Comparison of different three-dimensional polymer structures or hydrodynamic radii takes place. Also the comparison with measurements, use the other solvent than specified, is not allowed in different solvents different three-dimensional polymer structures or hydrodynamic Radii may be present, resulting in a different result lead in the determination of molecular weight.

The polydispersity P _d is defined as the quotient of number average and weight average molecular weight. In particular, it is a measure of the width of the present molecular weight distribution, which in turn allows conclusions to be drawn about the present polymerization behavior. It is determined by high temperature GPC. The polydispersity is characteristic within certain limits for a particular catalyst-cocatalyst combination. The polydispersity has a relatively strong influence on the tackiness of the material at room temperature and on the adhesion.

When determining the molecular weights by means of gel permeation chromatography (GPC), the hydrodynamic radius of the polymer chains present in solution plays a special role. In addition to thermal conductivity, RI (refractive index) or UV / VIS and FTIR or light scattering detectors, viscosity detectors are also used as detection mechanisms. Looking at the polymer chain as an undistorted ball, the relationship between its intrinsic viscosity and molecular weight can be empirically determined by the so-called KMHS equation [η] = K v M v α describe ( H.-G. Elias, Macromolecules, Volume 2, 6th Edition, Wiley-VCH, Weinheim 2001, pp. 411-413 ). K _v and α are constants which are influenced by the constitution, configuration and molar mass of the polymer as well as by the solvent and the temperature. The essential meaning of the alpha value in the present invention is that of the hydrodynamic radius, which depends more or less on the branching sites on the polymer chains. With a low branch the alpha value is high, with a higher branch the value is low.

c) rheology

The melt viscosity is determined by Oszillationsrheometrie, working at a shear rate of 1 Hz. The maximum deformation of the sample is chosen so that the sample is in the linear viscoelastic region during the entire measurement period. Viscoelastic materials are characterized by their ability to dissipatively dissipate stresses resulting from a deformation over a certain time compared to Hook's solid bodies (relaxation). In contrast to Newtonian fluids, which undergo exclusively irreversible deformation under the effect of shear / strain, viscoelastic fluids can regain some of the deformation energy after the shear force has been removed (so-called "memory effect") [ NP Cheremisinoff; "An Introduction to Polymer Rheology and Processing"; CRC Press; London; 1993 ]. Another characteristic of polymeric melts is the occurrence of a so-called intrinsic viscosity. As such, a behavior is described in which the shear stress as occurring force degrades the initial structure of the material as a function of the shear rate. Since this degradation process requires a minimum shear rate, the material flows below this shear rate like a Newtonian fluid. An explanation can be found in the Le Chatelier principle, where the "evasion" of the pseudoplastic fluid (prior to mechanical stress) in alignment along the thrust surfaces results in the reduction of frictional resistance. In polymer melts, the Newtonian range is perceptible only at very low shear rates or small shear amplitudes and is determined by rheometric test methods (amplitude "sweeps", ie measurement at a fixed frequency as a function of the shear amplitude) is possible and necessary if the measurement is to be carried out in the reversible, ie reproducible range [ RS steering; "Rheology of plastics"; C. Hanser Verlag; Munich; 1971 ; J. Meissner; "Rheological behavior of plastic melts and solutions" in: "Practical rheology of plastics VDI-Verlag; Dusseldorf; 1978 ; J.-F. Jansson; Proc. 8th. Int. Congr. Rheol .; 1980; Vol. 3 ]. The vibrational rheometry is due to their low force, their low deformation and thus low impact on the sample morphology particularly well suited for the investigation of materials that show pseudoplastic behavior.

d) Needle penetration

The needle penetration is according to DIN EN 1426 certainly.

e) DSC

The determination of the enthalpy of fusion, the glass transition temperature and the melting range of the crystalline portion is carried out by differential scanning calorimetry (DSC) according to DIN 53 765 from the 2nd heating curve at a heating rate of 10 K / min. The inflection point of the heat flow curve is evaluated as the glass transition temperature.

f) xylene solubility

It is a mixture of xylene isomers used, wherein the polymer under Dissolved backflow and then the solution is cooled to room temperature. 2 g of polyolefin in 250 ml of xylene with stirring and heating to the boiling point solved by xylene. After 20 min under reflux was boiled, leaves the polymer solution on Cool to 25 ° C. Unsolved or failed Polyolefin is sucked off (15 cm suction filter, Sartorius 390 filter paper) and dried. The remaining polymer solution becomes in a 5-fold excess of methanol (with a drop 37% aqueous HCl added) precipitated. The resulting precipitate is filtered off with suction and at 80 ° C. dried in a drying oven (vacuum).

g) solubility in THF

The Solubility in THF is a characteristic of semi-crystalline Polyolefins. The procedure is analogous to the solution experiments in xylene.

h) tensile strength and elongation at break

The determination of the tensile strength and elongation at break is carried out after DIN EN ISO 527-3 ,

i) softening point (ring & ball)

The determination of the softening point according to the ring and ball method is carried out according to DIN EN 1427 ,

j) adhesive shear strength

The determination of the adhesive shear strength is carried out according to DIN EN 1465 ,

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

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• BA Krentsel, YV Kissin, VI Kleiner, LL Stotskaya; "Polymers and Copolymers of higher 1-olefins", pages 19/20; Hanser Publ .; Munich; 1997 [0010]
• - YV Kissin; "Isospecific polymerization of olefins"; Springer Verlag, New York; 1985 [0010]
• H. El Mansouri, N. Yagoubi, D. Scholler, A. Feigenbaum, D. Ferrier; J. Appl. Polym. Sci .; 71 (1999); 371ff [0010]
• - S. Davison, GL Taylor; Br. Polym. J .; 4 (1972); 65ff [0015]
• - S. Berger, S. Braun, H.-O. Kalinowski, 13C NMR Spectroscopy, Georg Thieme Verlag Stuttgart 1985 [0173]
• AE Tonelli, NMR Spectroscopy and Polymer Microstructure, Verlag Chemie Weinheim 1989 [0173]
• - JL Koenig, Spectroscopy of Polymers, ACS Professional Reference Books, Washington 1992 [0173]
• JC Randall, Polymer Sequence Determination, Academic Press, New York 1977 [0173]
• A. Zambelli et al: Macomolecules, 8, 687 (1975) [0173]
• A. Filho, G. Galland: J. Appl. Polym. Sci., 80, 1880 (2001) [0173]
• - HG Elias: "Macromolecules"; Vol 2; Wiley-VCH; Weinheim 2001 [0174]
• Z. Grubisic, P. Rempp, H. Benoit; Polym. Lett .; 5; 753 (1967) [0174]
• - KA Bonuses, FA Sliemers, PB Stickney; J. Polym. Sci .; A2; 6; 1579 (1968) [0174]
• - D. Goedhart, A. Opschoor; J. Polym. Sci .; A2; 8th; 1227 (1970) [0174]
• - A. Rudin, HLW Hoegy; J. Polym. Sci .; A1; 10; 217 (1972) [0174]
• G. Samay, M. Kubin, J. Podesva; Angew. Makromol. Chem .; 72; 185 (1978) [0174]
• B. Ivan, Z. Laszlo-Hedvig, T. Kelen, F. Tüdos; Polym. Bull .; 8th; 311 (1982) [0174]
• - K.-Q. Wang, S.-Y. Zhang, J. Xu, Y. Li, HP Li; J. Liqu. Chrome.; 5; 1899 (1982) [0174]
• TG Scholte, HM Schoffeleers, AMG Brands; J. Appl. Polym. Sci .; 29; 3763 (1984) [0174]
• - H.-G. Elias, Macromolecules, Volume 2, 6th Edition, Wiley-VCH, Weinheim 2001, pp. 411-413 [0177]
• - NP Cheremisinoff; "An Introduction to Polymer Rheology and Processing"; CRC Press; London; 1993 [0178]
• - RS steering; "Rheology of plastics"; C. Hanser Verlag; Munich; 1971 [0178]
• - J. Meissner; "Rheological behavior of plastic melts and solutions" in: "Practical rheology of plastics VDI-Verlag; Dusseldorf; 1978 [0178]
• - J.-F. Jansson; Proc. 8th. Int. Congr. Rheol .; 1980; Vol. 3 [0178]
• - DIN EN 1426 [0179]
• - DIN 53 765 [0180]
• - DIN EN ISO 527-3 [0183]
• - DIN EN 1427 [0184]
• - DIN EN 1465 [0185]

Claims (42)

A process for preparing polyolefins comprising contacting a metallocene compound, at least a first solvent, wherein the first solvent is a non-halogenated aliphatic solvent, at least one alkyl group-modified methylaluminoxane component optionally dissolved and / or suspended in a second solvent, wherein the second solvent may be the same as or different from the first solvent, and at least one 1-olefin monomer in a reaction space and subsequent polymerization of the at least one 1-olefin monomer at a reaction temperature to form polyolefins, characterized in that the reaction temperature above the Boiling temperature of the first or the solvent is. Process according to claim 1, characterized characterized in that the first solvent is a boiling temperature of not more than 101 ° C at ambient pressure (normal pressure) having. Method according to claim 1 or 2, characterized that it is the non-halogenated aliphatic solvents to linear and / or cyclic aliphatic compounds with not more than 7 carbon atoms. Method according to one or more of claims 1 to 3, characterized in that the non-halogenated aliphatic solvents selected is from the group comprising propane, butane, pentane, cyclopentane, Methylcyclopentane, hexane, cyclohexane, methylcyclohexane, heptane or mixtures thereof. Method according to one or more of claims 1 to 4, characterized in that the metallocene compound is selected from compounds according to the formula I. XR ¹ ₂ (CpR ² R ³ R ⁴ R ⁵ ) (FluR ⁶ R ⁷ R ⁸ R ⁹ R ¹⁰ R ¹¹ R ¹² R ¹³ ) MCl ₂ I wherein M is a transition metal selected from the group comprising Zr, Hf and Ti, wherein Cp is cyclopentadienyl and Flu is fluorenyl, and wherein XR ¹ ₂ (with X = Si or C) bridges the cyclopentadienyl and fluorenyl ligands, R ^{1 is} selected from linear or branched alkyl groups having 1 to 6 C atoms, alkoxylalkyl groups having 1 to 6 C atoms, aryl groups or alkoxyaryl groups and R ² to R ¹³ selected from the group comprising H and / or linear or branched alkyl groups 1 to 10 carbon atoms. Method according to one or more of claims 1 to 5, characterized in that it is in the metallocene compound, dimethylmethylene (cyclopentadienyl) - (fluorenyl) zirconium dichloride, Dimethylmethylene (3-tert-butylcyclopentadienyl) - (fluorenyl) zirconium dichloride, Dimethylsilyl (cyclopentadienyl) - (fluorenyl) zirconium dichloride, Diphenylmethylene (cyclopentadienyl) - (fluorenyl) zirconium dichloride, Diphenylsilyl (cyclopentadienyl) - (fluorenyl) zirconium dichloride or di (paramethoxyphenyl) -methylene (2,7-di-tert-butylfluorenyl) - (cyclopentadienyl) -zirconium dichloride is. Method according to one or more of claims 1 to 6, characterized in that the at least one 1-olefin monomer is selected from Group comprising ethylene and linear 1-olefins. Process according to claim 7, characterized characterized in that the linear 1-olefin is selected from the group comprising 1-propene and / or 1-butene. Method according to one or more of claims 1 to 8, characterized in that the metallocene compound and the at least one alkyl-modified methylaluminoxane component be fed to the reaction space in a homogeneous form. A method according to claim 9, characterized in that the metallocene compound and the at least an alkyl group-modified methylaluminoxane component dissolved in the second solvent. Method according to one or more of claims 1 to 10, characterized in that it in the reaction space to a stirred tank, a stirred tank cascade with at least two stirred tanks, one flow tube and / or a flow tube with forced delivery is. Method according to one or more of claims 1 to 11, characterized in that the Polymerization temperature is 60-120 ° C. Method according to one or more of claims 1 to 12, characterized in that the Pressure in the reaction chamber at 5-40 bar. Method according to one or more of claims 1 to 13, characterized in that the Polymerisation temperature in the stationary reaction state is below the softening temperature of the polymers produced Polyolefins containing not more than 20% by mass of ethylene, either 50-100 or at most a maximum of 15% by mass of propylene and either 85-100% by mass or not more than 55% by mass of 1-butene, the sum of the proportions being 100% by mass, characterized in that the propene triad distribution determined by ¹³ C-NMR has a syndiotactic fraction of 32-90% by mass, an isotactic fraction of maximum 25 ma-% and an atactic proportion of not more than 65 ma-%, and / or the triad distribution determined for 1-butene triads by ¹³ C-NMR has a syndiotactic fraction of not more than 96 m%, an isotactic fraction of not more than 45 m% exhibit. Polyolefins according to claim 15, obtainable by a method according to or more of claims 1 to 13. Polyolefins according to claim 15 or 16, characterized in that the needle penetration of the polyolefins in the range of 1-50 x 0.1 mm. Polyolefins according to one or more of claims 15 to 17, characterized in that it are copolymers of ethylene, propylene and / or 1-butene. Polyolefins according to one or more of claims 15 to 18, characterized in that it They are poly (ethylene-co-propylene) copolymers or poly (propylene-co-1-butene) copolymers is. Polyolefins according to one or more of claims 15 to 19, characterized in that they a polydispersity as determined by gel permeation chromatography of 1.3-3. Polyolefins according to one or more of claims 15 to 20, characterized in that the weight average molecular weight of the invention Polymers determined by high-temperature gel permeation chromatography with universal calibration, in the range of 15,000 to 400,000 g / mol is located. Polyolefins according to one or more of claims 15 to 21, characterized in that the found on examination by gel permeation chromatography Proportion of low molecular weight components with a molecular weight from 500 to 1000 daltons at a maximum of 0.75 m%. Polyolefins according to one or more of claims 15 to 22, characterized in that they at a temperature of 190 ° C, a maximum deformation 1% and a measurement frequency of 1 Hz, a complex melt viscosity from 700 to 400,000 mPa · s. Polyolefins according to one or more of claims 15 to 23, characterized in that the by DSC certain glass transition temperature of the polyolefins at a maximum of 0 ° C. Polyolefins according to one or more of claims 15 to 24, characterized in that they have an endothermic enthalpy of fusion of 0 to 35 J / g at the second heat up in the DSC. Polyolefins according to one or more Claims 15 to 25, characterized in that their Solubility in xylene and tetrahydrofuran at room temperature up to 100% by mass. Use of polymers according to one or several of claims 15 to 26 in molding compositions, as or in adhesives, in marking compounds, coating compounds, geomembranes or roofing membranes, as primers or in primer formulations and / or Adhesion promoter formulations and / or in aqueous dispersions, Suspensions or emulsions. Molding compounds, adhesives, marking compounds, coating compounds, Geomembranes or roofing membranes, primers, primer formulations, primer formulations, aqueous dispersions, suspensions and / or emulsions containing one or more polymers according to one or more of claims 15 to 26. Molding compositions according to claim 28, characterized in that it additionally one or more Ethylene polymers, and / or isotactic propylene polymers and / or syndiotactic propylene polymers and / or isotactic Poly-1-butene polymers and / or syndiotactic poly-1-butene polymers contain. Adhesives according to claim 28, characterized in that they are hot melt adhesive formulations is. Adhesives according to claim 28 or 30, characterized in that they additionally inorganic and / or organic fillers, inorganic and / or organic Pigments, synthetic and / or natural resins, inorganic and / or organic, synthetic and / or natural polymers, inorganic and / or organic, synthetic and / or natural Fibers, inorganic and / or organic stabilizers, inorganic and / or organic flame retardants, resins, amorphous poly (α-olefins), Polymers with polar groups, polymers based on ethylene, butadiene, styrene and / or isoprene, elastomeric polymers based on ethylene, propylene, Acrylonitrile, a diene and / or a cyclic diene, styrene, Waxes, one or more synthetic or natural ones and / or Contain UV-active substances. Geomembranes according to claim 28, characterized in that they additionally contain other polymers, Fillers and bitumen included. Geomembranes according to claim 28 or 32, characterized in that the proportion of polymers according to one of claims 15 to 26 maximum 30 ma-%, based on the geomembrane. Adhesives containing one or more polymers according to one or more of the claims 15 to 26. Adhesive bonds according to claim 34, characterized in that the bonds are packaging bonds, Bonding of hygiene articles, wood gluing, gluing of Glass surfaces, label laminating laminating, Carpet or artificial turf gluing, shoe gluing, pressure-sensitive Bonding, book gluing or Textilgeschiebungen acts. Packaging bonds according to claim 35, characterized in that the packaging materials are the materials Wood, cardboard, paper, plastic, metal, ceramics, glass, artificial and / or natural fibers and / or textiles. Packaging adhesive according to claim 34 or 35, characterized in that at least one of the contained Polyolefins has an open time of less than 30 seconds. Packaging bonding according to a or more of claims 35 to 37, characterized that it is a bonding of transparent plastic films. Carpet bonding for nap and filament binding according to claim 35, characterized in that a coating weight of 20 to 1500 g / m ² is used. Artificial grass bonding according to claim 35 characterized in that the integrated by the bonding Filaments are selected from polypropylene filaments, polyethylene filaments, Polyamide filaments, polyester filaments or mixed filaments of listed plastics. Primer and / or primer formulation according to Claim 28, containing one or more polyolefins according to one or more of claims 15 to 26 characterized that it is used to treat a polyolefin surface. Aqueous dispersions, suspensions and / or Emulsions according to claim 28 comprising one or more polyolefins according to one or more of the claims 15 to 26, characterized in that the proportion of polymer more is 10mA%, based on the total formulation.