CA2024715A1 - Impact modified thermoplastic polyurethane-polyester molding materials and preparation thereof - Google Patents
Impact modified thermoplastic polyurethane-polyester molding materials and preparation thereofInfo
- Publication number
- CA2024715A1 CA2024715A1 CA002024715A CA2024715A CA2024715A1 CA 2024715 A1 CA2024715 A1 CA 2024715A1 CA 002024715 A CA002024715 A CA 002024715A CA 2024715 A CA2024715 A CA 2024715A CA 2024715 A1 CA2024715 A1 CA 2024715A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- thermoplastic polyurethane
- graft
- impact modified
- molding material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Abstract
- 34 - O.Z. 0050/41133 Abstract of the Disclosure: Impact modified thermoplastic polyurethane-polyester molding materials containing, based on 100 parts by weight of (A) to (C), A) from 30 to 90 parts by weight of at least one thermoplastic polyurethane elastomer, B) from 5 to 65 parts by weight of at least one thermo-plastic polyester, preferably a polyalkylene tereph-thalate, and C) from 5 to 30 parts by weight of at least one graft rubber based on a polybutadiene (C1) or polyacrylate (C2) or a mixture of these graft rubbers and D) from 0 to 60 % by weight of at least one fibrous or particulate filler and E) from 0 to 10 % by weight of at least one assistant, the weight percentages being based on the weight of (A) to (C), are prepared by homogenizing the formative components at 190-250°C.
Description
2~2i~
O.Z. ~050/41133 Impact modified thermoplastic poly~rethane-polyester molding materials and preparation thareof The present invention relate~ to impact modified thermoplastic polyurethane-polyester molding materials which contain A) at lea~t one thermoplastic polyurethane elastomer, hereinafter abbreviated to TPU, B) at least one thermoplastic polye~ter, hereinafter abbreviated to PES, and lQ C) at least one graft rubber ba ed on a polybutadiene (C1) or polyacxylate (C2), and optionally D) fillers and/or E) assi~tant~.
Thermoplastic molding materials from TPU and PES
are known.
Material~ of improved low temperature impact toughness as de~cribed in DE-A-26 46 647 (GB 1 513 197) con~ist of an .intimate mixture of from 50 to 75 part~ by weight of TPU and from 25 to 50 % by weight of a poly-butylene terephthalate, al30 known ~ PBT. CA-A-l lll 984 likewi~a describes TPU/PBT matsrial~ which, however, based on the total weight, consi~t of from 5 to 95 ~ by weight of TPU and from 95 to 5 ~ by weight of PBT. These TPU/PBT molding materials, however, have the disadvantage of inadequate notched impact ~trength and insufficient multiaxial touyhne~, in particular at low temperature~.
TPU mixtures which contain processing aid~ and are composed of from 4~ to 100 ~ by weight of TPV, from O to 60 % by w~ight of a thermoplastic polymer selected from the group consl~ting of polycarbon~tas, polyoxy-methylene~, acrylonitrile-butadiene-styrene graftcopoly-mar~, P~r polyethylene terephthalate and mixture~
thereof, and from 0.5 to 10 % by weight, based on the total weight of TPU and th~ other thermoplast1c polymer, of a polyacrylata-based processing ~id ~elected from the group conaisting of a ~ethyl m0thacrylate homopol~er, a methyl msthacrylata/n-butyl methac~ylato or methyl 7 ~ -~
- 2 - o.Z. 0050J~1133 methacrylate/ethyl acrylate copolymer and a terpolymer of methyl methac~ylate, n~butyl acrylate and styrene are known from US-A-4 179 479. Howev~r, th~se materials based on TPU, PBT or polyethylene terPphthalate and the e~qen-tially linear (meth)acrylate homopolymer or copolymar possess unsati~factory toughne~ at low temperature~ and are difficult to process.
It i~ an object of the present invention to remove the aforementioned disadvantages as completely as possible and to develop TPU/PES molding materials which posses a distinctly Lmproved low temperature toughness and ara ea~y to proce~s into shaped article3.
We have found, surprisingly, that this object is achieved by introducing at least one graft rubber (C) based on a polybutadiene (Cl) or polyacrylate ~C2) into TPU/PES molding material~ of defined composition.
The preqent invention accordingly provideR ~mpact modified thermopla~tic polyurethane-polyester molding materials which contain or preferably con3ist of, based on 100 parts by weight of (A) to (C), A) from 30 to 90 part~ by weight, preferably from 40 to 80 parts by weight, of at least one TPU (A), B) from 5 to 65 part~ by weight, preferably from 10 to 50 parts by weight, of at least one PES (B) and C) from S to 30 parta~ by weight, preferably from 5 to 20 p~rt~ by weight, of at least one graft rubber (C) based on a Cl) polybutadiene or C2) polyacrylate or ~ mixture of graft rubbers based on (C1) and (C2) and al~o, based on the total weight of (A) to (C), D) from 0 to 60 % by weight, preferably from 2 to 50 %
by weight, of at lea~t one fibrou~ or particulate filler and E) from 0 to lO % by weight, preferably from 0 to 5 %
by w~ight, of at least one assistant.
The present in~ention further provide~ a proces~
7~1 ~
O.Z. ~050/41133 Impact modified thermoplastic poly~rethane-polyester molding materials and preparation thareof The present invention relate~ to impact modified thermoplastic polyurethane-polyester molding materials which contain A) at lea~t one thermoplastic polyurethane elastomer, hereinafter abbreviated to TPU, B) at least one thermoplastic polye~ter, hereinafter abbreviated to PES, and lQ C) at least one graft rubber ba ed on a polybutadiene (C1) or polyacxylate (C2), and optionally D) fillers and/or E) assi~tant~.
Thermoplastic molding materials from TPU and PES
are known.
Material~ of improved low temperature impact toughness as de~cribed in DE-A-26 46 647 (GB 1 513 197) con~ist of an .intimate mixture of from 50 to 75 part~ by weight of TPU and from 25 to 50 % by weight of a poly-butylene terephthalate, al30 known ~ PBT. CA-A-l lll 984 likewi~a describes TPU/PBT matsrial~ which, however, based on the total weight, consi~t of from 5 to 95 ~ by weight of TPU and from 95 to 5 ~ by weight of PBT. These TPU/PBT molding materials, however, have the disadvantage of inadequate notched impact ~trength and insufficient multiaxial touyhne~, in particular at low temperature~.
TPU mixtures which contain processing aid~ and are composed of from 4~ to 100 ~ by weight of TPV, from O to 60 % by w~ight of a thermoplastic polymer selected from the group consl~ting of polycarbon~tas, polyoxy-methylene~, acrylonitrile-butadiene-styrene graftcopoly-mar~, P~r polyethylene terephthalate and mixture~
thereof, and from 0.5 to 10 % by weight, based on the total weight of TPU and th~ other thermoplast1c polymer, of a polyacrylata-based processing ~id ~elected from the group conaisting of a ~ethyl m0thacrylate homopol~er, a methyl msthacrylata/n-butyl methac~ylato or methyl 7 ~ -~
- 2 - o.Z. 0050J~1133 methacrylate/ethyl acrylate copolymer and a terpolymer of methyl methac~ylate, n~butyl acrylate and styrene are known from US-A-4 179 479. Howev~r, th~se materials based on TPU, PBT or polyethylene terPphthalate and the e~qen-tially linear (meth)acrylate homopolymer or copolymar possess unsati~factory toughne~ at low temperature~ and are difficult to process.
It i~ an object of the present invention to remove the aforementioned disadvantages as completely as possible and to develop TPU/PES molding materials which posses a distinctly Lmproved low temperature toughness and ara ea~y to proce~s into shaped article3.
We have found, surprisingly, that this object is achieved by introducing at least one graft rubber (C) based on a polybutadiene (Cl) or polyacrylate ~C2) into TPU/PES molding material~ of defined composition.
The preqent invention accordingly provideR ~mpact modified thermopla~tic polyurethane-polyester molding materials which contain or preferably con3ist of, based on 100 parts by weight of (A) to (C), A) from 30 to 90 part~ by weight, preferably from 40 to 80 parts by weight, of at least one TPU (A), B) from 5 to 65 part~ by weight, preferably from 10 to 50 parts by weight, of at least one PES (B) and C) from S to 30 parta~ by weight, preferably from 5 to 20 p~rt~ by weight, of at least one graft rubber (C) based on a Cl) polybutadiene or C2) polyacrylate or ~ mixture of graft rubbers based on (C1) and (C2) and al~o, based on the total weight of (A) to (C), D) from 0 to 60 % by weight, preferably from 2 to 50 %
by weight, of at lea~t one fibrou~ or particulate filler and E) from 0 to lO % by weight, preferably from 0 to 5 %
by w~ight, of at least one assistant.
The present in~ention further provide~ a proces~
7~1 ~
- 3 - O.Z. 0050/41133 for preparing the TPU/PES molding materials according to the present invention by homogenizing the formative components at 190-250C in a quitable mixing apparatus as mentioned in claim 12.
S As mentioned, th~ TPU/PES molding materials according to the present invention have very good low temperature toughness. It i~ also worth mentioning their very good proce~ibility into shaped article~ by means of the in~ection molding techniqua, the ~hort cycle tLmes required for this purpo~e and the good demoldability. The TPU/PES molding materials also po~ses~ excellent re~is-tan~e to organic solvent~.
The TPUs tA) u~able for preparing the TPU/PES
molding materials according to the pre~ent invention correspond to the prior art and can be prepared by reacting a) organic, preferably aromatic, diisocyanate~, in particular 4,4'-diphenylmethane diisocyanate, with b) polyhydroxy compounds, preferably e~sentially linear polyhydroxy compounds, having molecular weight~ of from 500 to 8000, in particular polyalkylene glycol polyadipates having from 2 to 6 carbon atom~ in the alkylene moiety and molecular weight~ of from 500 to 6000 or hydroxyl-containing polytetrahydrofuran having a molecular weight of from 500 to 8000, and c) diols as chain extenders haviny molecular weights of from ths 60 to 400, in particular 1;4-butanediol, in the prQsence ef d) cataly~ts and optionally e) a~d~ and/or f) additives at elevated temperature~.
The TPU-forming component~ ta) to (d~ and option-ally (e) and~or (f) may b~ d~scribed in datail as follows~
a) Suitable organic dii~oc~anates (a) are for example aliphatic, cycloaliphatic-and pref~rably aromatic 2 ~ 2 ~
_ 4 _ o. æ . 0050/41133 dii~ocyanate~. Specific examples are: aliphatic dii~o-cyanate~ ~uch a~ 1,6-hexamethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 2-ethyl-1,4-butylene diisocyanate and mixture~ of at least two of said aliphatic diisocyanateR, cycloaliphatic dii~ocyan-ates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, l-methyl-2,4-cyclohexane diisocyanate and 1-methyl-2,6 cyclohexane diisocyanate and the corre~pond-ing isomeric mixtures, 4,4'-, 2,4'- or 2,2'-dicyclohexyl-methane diisocyanate and the corre~ponding isomericmixtures and preferably aromatic dii~ocyanate~ such as 2,4-toluylene dii~ocyanate, mixture of 2,4- and 2,6-toluylene dii~ocyanate, 4,4'-, 2,4'~ and 2,2'-diphenyl-methane diisocyanate, mixtures of 2,4'- and 4,4'-di-phenylmsthane diisocyanate, urethane-modified liquid 4,4'- and/or 2,4~-diphenylmethane diisocyanates, 4,4'-diisocyanato-1,2-diphenylethane, mixtures of 4,4'-, 2,4'-and 2,2'-diisocyanato-1,2-diphenylQthane, preferably those having a 4,4'-diisocyanato-1,2-diphenylethane content of at least 95 ~ by w~ight, and 1,5-naphthylene dii~ocyanate. Preference i~ given to u~ing diphenyl-methane diisocyanate isomer mixtures having a 4,4'-diphenylmethane diisocyanate content of greater than 96 %
by weight and in particular essentially pure 4,4'-di-phenylmethan~ diisocyanate.
The organic diisocyanate may be replaced to aminor extent, for examp~e in an amount of up to 3 mol %, preferably up to 1 mol %, ba~ed on the organic diisocyan-ate, by a trifunctional or more highly functional poly-isocyanate, the amount of which, however, must bo limitedin such a way as to produce a still thermoplastic poly-urethsne. A ma~or amount of such tri- or more highly functional isocyanates is advantageously balanced by the inclusion of les~ than difunctional compound~ having reactive hydrogen atom~, in order that excessive chemical crosslinking of the polyurethane may be avoided. Examples of more than difunctional i~ocyanates are mixtures of 7 ~ -~
_ 5 - o.Z. 0~50/41133 diphenylmethan0 diisocyanat~ and polyphenylpolymethylene polyisocyanate~, so-called cr~de MDI, and liquid 4,4~-and/or 2,4'-diphenylmethane diisocyanates modifi~d with isocyanurate, urea, biuret, allophanate, urethane and/or carbodiimid~ groups.
Suitable monofunctional compounds having reactive hydrogen atoms which are also u~able a~ molecular weight regulators are for example: monoamine~ such 2s butyl-amine, dibutylamine, octylamine, ~tearylamine, N-methyl-stearylamine, pyrrolidone, piperidine and cyclohexylamineand monoalcohols such as butanol, amyl alcohol, l~ethyl-hexanol, octanol, dodecanol, _yclohexanol and ethylene glycol monoethyl ether.
b) Preferred polyhydroxy compound~ (b) having molecular weights of from 500 to 8000 are polyetherol~
and in particular polye~terol~. ~owever, it i~ al~o pos~ible to use other hydroxyl-containing polymer~
con~aining ether or ester groups as bridge member~, for example polyacetals, such as polyoxymethylenes and in particular water-soluble formal3, eg. polybutanediol formal and polyhexanediol formal, and polycarbonates, in particular tho~e formed from diphenyl carbonate and 1,6~
hexane~iol, prepared by transe~terification. ~he poly-hydroxy compound mus~ be at least predominantly linear, ie. difunctional within the meaning of the isocyanate reaction. The polyhydroxy compQunds mentioned may be used as individual component~ or in the form of mixture~.
5uitable polyetherols can be prepared from ons or more alkylene oxides having from 2 tD 4 ca~bon atom~ in the alkylene moiety in a conventional manner, for example by anionic polymerization with alkali metal hydroxides, such as sodium hydroxide or potas 8 ium hydroxide, or alkali metal alcoholates, ~uch as sodium methoxide, ~odium ethoxide, pota~sium ethoxide or potassium isoprop-oxide, as catalysts and in the presence of at least oneinitiator molecule which contains a or 3, preferably 2 reactivo hydrogen atom~, or by cationic polymerization 2 ~ 2 .~
- 6 - O.Z. 0050/41133 with Lewis acids, such a~ antimony pentachloride, boron fluoride etherate, etc. or bleaching earth, as cataly8t8.
Preferred alkylene oxides ar~ for example tetra-hydrofuran, 1,3-propylene oxide, 1,2-butylene oxide, 2,3-5butylene oxide and in particular ethylene oxide and 1,2-propylena oxide. The alkylene oxide~ may be u~ed indi-vidually, alternately in succession or a~ mixtures.
Suitable initiator molecules are for example: water, organic dicarboxylic acidR, such a~ ~uccinic acid, adipic 10acid and~or glutaric acid, alkanolamines, such a~ ethan-olamine, N-~lkylalkanolamine~, N-alkyldialkanolamine~, eg. N~methyl- and N-ethyl~diethanolamine, and preferably dihydric alcohol~ which may contain ether linkages, eg.
ethanediol, 1,2-propanediol~ 1,3-propanediol, 1,4-butane-15diol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, 2-methyl-1,5-pentanediol and 2-ethyl-1,4-butanediol. Th~ initiator molecules may be used individually or a~ mixture~.
Preference i3 give~ to using polyetherol~ from 201,2 propylene oxide and ethylene oxid~ in which more than 50 ~, p-eferably from 60 to 80 ~, of the OH group~ are prLmary hydroxyl groups and where at least some of the ethylene oxide units are present as a terminal block.
Such polyetherol~ can be obtained ~y, for example, 25polymerizing onto the initiator molecula first the 1,2-propylene oxide and then the ethylene oxide, or first the entire 1,2-propylene oxide mixed with ~ome of the ethyl-ene oxide and then the remainder of the ethylene oxide, cr step by 8t5p first some of the ethylene oxide, then 30the entire 1,2-propylene oxide and then the remainder of the ethylene oxide.
Other preferre~ possibilities are the ~Iydroxyl-containing polymerization product~ of tetrahydrofuran.
The e~sentially linear polyetherol~ have mole-35cular weight~ of from 500 to 8000, preferably from 600 to 6000, in particular from 800 to 3500, th~ polyoxytetra-methylene glycol~ preferably having molecular weights of ~ ~ 2 ~ ~ ~ ? ~
- 7 - o.z. 0050/41133 from 500 to 2800. ~hey can be used not only individually but also in the form of mixtures with one another.
Suitable polyest~rols may be prepared for example from dicarboxylic acid~ of from 2 to 12, preferably from 4 to 6, carbon atoms and polyhydric alcohols. Suitable dicarboxylic acid~ are for example: aliphatic dicar-boxylic acid~, such as succinic acid, glutaric acid, adipi~ acid, suberic acid, azelaic acid and sebacic acid, and aromatic dicarboxylic acids, such as phthalic acid, i~ophthalic acid and terephthalic acid. The dicarboxylic acid~ can be used individually or as mixtures, for exampie in the form of a mixture of ~uccinic acid, glutaric acid and adipic acid. ~o prepare the poly-e~terol~ it may be advanta~eous to u~e instead of the dicarboxylic acids the corresponding dicarboxylic acid derivatives, ~uch a~ dicarboxylic monoe~ter~ or diesters having from 1 to 4 carbon atom~ in the alcohol moiety, dicarboxylic anhydrides or dicarbonyl dichlorides.
ExampleR of polyhydric alcohol~ are glycols of from 2 to 10, preferably from 2 to 6, carbon atom~, cuch as ethyl-ene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2-di-methylpropane-1,3-diol, 1,3-propanediol and dipropylene glyeol. Depending on the properties which are desired, the polyhydric alcohol~ may be used alone or optionally mixed with one another.
It is also possible to use e~ter~ of carbonic acid with the diols mentioned, in particular those having from 4 t~ 6 carbon atom~, such a~ 1,4-butanediol and/or 1,6-hexanediol, conden~tion products of ~-hydroxycar-boxylic acids, eg. ~-hydroxycaproic acid, and preferably polymerization product~ of lactones, for example sub~ti-tuted or un~ubstituted ~ caprolactones.
Preferred polye~tQrols are ethanediol poly-adipats~, 1,4-butanediol polyadipates, etha~ediGl/1,4-butanediol polyadipate~, 1,6-hexansdi~l/neopentylglycol polyadipates, 1,6-hexanediol~1,4-butanediol polyadipate~
2 ~
- 8 - O.Z. 0050/41133 and polycaprolactones.
The polyesterols have molecular weigh~ of from 500 to 6000, preferably from 800 to 3500.
c~ Suitable chain extender~ (c) having molecular weight~ of from 60 to 400~ preferably from 60 to 300, are preferably aliphatic diols of from 2 to 12 carbon atoms, preferably of 2, 4 or 6 carbon atoms, eg. ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and in particular 1,4-butanediol. However, it is also pos-sible to use diester~ of terephthalic acid with glycols of from 2 to 4 carbon atom~, eg. bisethylene glycol terephthalate, 1,4-butanediol terephthalate, and hydroxy-alkylene ethers of hydroquinone, eg. 1,4-di-(~-hydroxy-ethyl)-hydroquinone, and al~o polytetramethylene glycols having molscular weights of from 162 to 378.
To set the hardnes~ and the melt flow index, the formative components can be varied within relatively wide molar ratios bearing in mind that the hardne~s and melt visco~ity increase with an increa~ing level of chain extenders (c) while the melt flow index decrease~.
To prepare relatively ~oft TPUs (A), for example those having a Shore A hardness of le~# ~han 95, prefer-ably from 95 to 75, it is advantageous for example to use the es~entially difunctional polyhydroxy compounds (b) and the diols ~cJ in a molar ratio of from 1:1 to 1:5, preferably fro~ 1:1.5 to 1: 4 . 5, 80 that the resulting mixtures of (b) and (c) have a hydroxy equivalent weight of greater than 20U, n parti~ular from 230 to 450, while harder TPUs (a), for exa~ple tho~e having a Shore A
hardness of greater than 98, preferably from 55 to 75 Shore D, are prepared using molar ratios of (b)s(c) within the range from 1~5.5 to ls15, preferably from 1:6 to lsl~, 80 that the resulting mix~ure~ of (b) and (c) have a hydroxy equivalent weight of from 110 to 200, preferably from 120 to 180.
d) Suitable cataly~t3, in particular for the.reaG-tion between tho NCO group8 of the dii~ocyanates (a) and ~ gJ 2 - g - o.z. 0050/41133 the hydroxyl group~ of the formative components (b) and (c), are the customary tertiary amines, such a~ triethyl-amine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, diazabicyclo[2.2.2]octane and the like, in particular organic metal compounds ~uch a~
tit~nic e~ters, iron compound~, tin compounds, eg. tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salt~ of aliphatic carboxylic acids ~uch a~
dibutyltin diacetate, dibutyltin dilaurate and the like.
The cataly~ts are customarily used in amount~ of from 0.001 to 0.1 part by weight per 100 parts by weight of the m xture of polyhydroxy compound~ (b) and diols (c).
In addition to cataly~ts, the formative compo-nents may al30 contain aid~ (e) and/or additive~ (f).
Example~ are lubricants, inhibitor~, stabilizers again~t hydrolysis, light, heat or discoloration, flame retar-dantR, dyes, pigment~, inorganic and/or orqani~ fillers and reinforcing agents.
The aids (e) and/or additive~ (f) may be intro-duced into the formative components or into the reactionmixture for preparing the TPUs (A). Alternatively~ the aids (e) and/or additives (f), which may be identical to the assi~tant (E), may be mixed with the TPU (A), the PES
(B) and/or the graft rubber (C) and then melted, or they are incorporated directly into the melt of components tA), (B) and (C). The latter method is also adopted in particular for incorporating the fibrous and/or particulate filler3 (D).
Where, in what follow~, no details are provided concerning the usable aid~ or additives, they can be discerned from the relevant technical literature, for example J.H. Saunders and K.C. Frisch's monograph, ~igh Polymers, volume XVI, Polyurethanes, parts 1 and 2 (Interscience Publisher~ 1962 and 1964 re~pectively), Kunst~toff ~andbuch, volum~ 7, Polyurethanes, l~t and 2nd editions (Carl Han er Verlag 1966 and 1983 respectively), or DE-A-2,901,774.
- 10 - O. Z . 0050/41133 To prepare the TPU~ (A), the formati~e component~
~a), (b) and (c) are made to react in the pr~ence of a cataly~t (d) and in the pre~ence or absenc~ of aid~ (e) and/or additives (f) in ~uch amount~ that the equivalance ratio of the diisocyanate NCO groups to the total number of hydroxyl groups of components (b) and (c) iB from 0.95 to 1.10:1, preferably 0.98 to 1.08:1, in particular approximately l.0 to 1.05:1O
The TPUs (A~ which are usable according to the present invention and which customarily contain from 8 to 20 % by weightt preferably from 8 to 16 % by weight, ba ed on the total weight, ef urethane groups and have a melt flow index at 210C of from 500 to 1, preferably from 100 to 1, can be prepared by the extruder technique or preferably the belt technique by batchwise or con-tinuou~ mixing of formative components (a) to (d) and optionally (e) and~or (f3, reacting the mixture in an extruder or on a ~upport belt a$ from 60 to 250C, preferably at from 70 to 150C, and then granulating the resulting TPUs (A). It may be advantageou3 to heat the resulting TPU (A) at ~rom 80 to 120C, preferably at from 100 to llODC, for a period of from 1 to 24 hour~ before further processing into the TPU/PES molding materials according to the present invention.
The TPUs (A) are, as mentioned, preferably prepared by the belt technique. To this end, the forma-tive components (a) to (d) and optionally (e) andJor (f) are continuously mixed with the aid of a mixing head at above the melting point of formative components (a) to (c). Tho reaction mixture i8 brought out onto a support, preferably a conveyor belt, for example a metal belt, and is pa~sed at 1-20 m/min, preferably 4-10 m/min, through a hot zone from 1 to 20 m, preferably from 3 to 10 m, in l~ngth. The temperature in the hot zone i~ 60-200C, preferably 80-180C. Depending on the dii30cyanate content of the reaction mixture, the reaction i8 con-trolled by cooling or heating in such a way that at least ~2~7~
~ O.Z. 0050/41133 90 ~ preferably at leas~ 98 %, of the i~ocyanate groups of the diisocyanatas react and the reaction mixtur~
solidifies at the chosen reaction temperature. Cwing to the free isocyanate gxoups in the solidified reaction product~ which based on the total weight are within the range from 0.05 to 1 ~ by weight, preferably from 0.1 to O.5 % by weight, the TPUs (A) obtained have a very low melt vi~c08ity or a high melt flow index.
B) Formative component (B) of the TPU/PES molding materialS according to the pre3ent invention is, as mentioned, an amoun~, based on 100 parts by weight of (A), (B) and (C), of from 5 to 65 parts by weight, preferably from 10 to 60 parts by weight, in particular 12 to 50 parts by weight~ of one or more thermoplastic polyester~ Polyester~ suikable for this purpose are described in the literature. They contain in the polycon-den~ate main chain at leaYt one aromatic ring derived from an aromatic dicarboxylic acid. The aromatic ring may also be substituted, for example by halogen, eg. chlorine or bromine, or/and by linear or branched alkyl, prefer-ably of from 1 to 4 carbon atoms, in particular of 1 or 2 carbon atoms,.eg. methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl or tert-butyl.
The polye~ters can be prepared by polyconden~a-tion of aromatic dicarboxylic acids or mixture~ ofaromatic and ali.phatic and/or cycloaliphatic dicarboxylic acids and the corresponding e~ter-forming derivatives, for example dicarboxylic anhydride~, monoester~ and/or die~ter~ having advantageou~ly not more than 4 carbon atomx in the alcohol moiety, with aliphatic dihydroxy compounds st elevated temperature~, for example at from 160 to ~60C, in the presence or absence of esterifica-tion cataly8t8~
The preferred aromatlc dicarboxylic acid~ axe the naphthalenedicarbo~ylic acids, isophthalic acid and in particular terephthalic acid or mixture3 of these dicarb-oxylic acid~. Ifmixture~ of aromatic and (cyclo~aliphatic ~ ~ 2 ~
- 12 - O.Z. 0050/41133 dicarboxylic ~cid~ are used, up to 10 mol % of the aromatic dicarbo~ylic acids may be replaced by aliphatic and/ox cycloaliphatic dicarboxylic acids of advantage-ously 4-14 carbon atoms, eg. succinic, adipic, azelaic, sebacic or dodecanedioic acid and/or cyclohexanedicar-boxylic acid.
The p_eferred aliphatic dihydroxy compounds are alkanediols of from 2 to 6 carbon atom~ and cycloalkane-diols of from 5 to 7 carbon atQms. Specific examples of preferred aliphatic dihydroxy compoundæ are 1,2-ethane-diol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol and ~ cyclohexanediol and mixture~ of at least two of ~aid diols.
Particularly suitable PES'~ (B) are ~pecifically tne polyalkylene terephthalate~ of alkanediol~ of from 2 to 6 carbon atom~, 80 that polyethylene ~erephthalate and in particular polybutylene terephthalate are preferred.
The relative viscosity of the PES'~ (B) i~ in general within the range from 1.2 to 1.8, measured in a 0.5 ~ ~trength by weight solution in l:l wJw phenol/o-dichlorobenzene at 25C.
C) The TPU/PES molding material~ according to the present invention contain one or more graft rubber~ (C) based on a polybutadiene (Cl) or polyacrylate (C2) or a mixture of graft rubber~ based on (C1) and (C2) a~ an additional formative component for Lmproving the toush-ness, in particular the low-temperature Lmpact toughness, and the proces~ibility. A8 mentioned, the proportion of graft rubber (C) is, based on 100 parts by weight of the molding ma~2rial~ consisting of (A), (~) and (C), from 5 to 30 parts by weight, preferably from-5 to 20 part~ by weight, in particular from 10 to 20 part by weiyht.
Suitable graft rubber~ based on polybutadiene (Cl) axe compo~ed of a grafting base (Cll) which advan-tageously consi~ts of a polybutadiene, a polyisoprene, abutadiene-styren~ copolymer or 8 copolymer of ~tyrene or an alkylstyrene, eg. ~-methyl~tyrene, and con~ugated 2 ~ 2 ~ 7 - 13 - O.Z. 0~50/41133 dienes (high impact polystyrenes), and a graft (C12) prepared by polymerization of styrene, alkyl~tyrene, eg.
~-methylstyrenQ, acrylonitxile, alkyl acrylate or meth-acrylate, haYing from 1 to 8 carbon atoms in the alkyl 5moiety, preferably methyl (meth)acrylate, or vinyl acetate or by copol~merization of at least two of said monomers, eg. styrene and/or acrylonitrile and/or (meth)-acrylic e ters. Graft rubber~ of the type mentioned (Cl) are described for example in DE-A-16 ~4 173 (US-A-3 564 077) and DE-A-23 48 377 (US-A-3 919 353). It is also possible to use ABS polymer~ as de~cribed for e~ample in DE-A-20 35 390 (US-A-3 644 574) and in DE-A-22 48 242 (GB-A-l 409 275).
Preference i8 given to u~ing graft rubbers based 15on polybutadiene (Cl) and composed of Cll) ~0~90 ~ by weight, preferably 65-90 % by weight, in particular 75-85 % by weight, based on the weight of (Cll) and (C12), of a butadiene polymer containing at least 50 % by weight, preferably at least 70 ~ by weight, based on (Cll), of butadiene radical~ as grafting base and C12) 10-40 % by weight, preferably 10-35 ~ by weight, in particular 15-25 % by weight, based on the weight of (Cll) and ~C12), cf a graft or ~heath prepared by graft polymerization of an alkyl acrylate or meth-acrylate or graft copolymerization of a mixture consi3ting o~
10-35 ~ by weight, preferably 20-35 % by w~ight, ba~ed on th~ weight of the mixture, of acrylonitrile and 65-90 % by weight, preferably 65-80 % by weight, ba~ed on the weight of the mixture, of styrene or by graft copolymerization of th~ aforementioned acrylo-nitxil~-~tyrene mixture with at least one alkyl acrylate and/or methacrylate, the alkyl (meth)ac~rlates being mon~e~ters of acrylic or methacryiic acid with alcohol~ which hav~
- 14 - O.Z. 0050/41133 from 1 to 8 carbon atom~ and may contain further functional groups, eg. ether group~ or praferably epoxy or hydroxyl groups.
The grafting base (Cll) advantageously contains, 5as mentioned above, at lea~t 50 % by weight, based on (C11) r of butadiene radical~, in which case the preferr~d grafting base consists of pure polybutadiene. If the grafting base con~ists of a polybutadiene copolymer, the re~idues of othsr ethylenically un aturated monomer~
10present therein are advantageou~ly: styrene, acrylo-nitrile and ac~ylate or methacrylate radical~ of alkyl (meth~2crylates containing from 1 to 4 carbon atoms in the alkyl moiety, eg. methyl (meth)acrylate or ethyl (meth)acrylate. The grafting ba~e ~C11) preferably ha~ a 15gel content of from 70 % by weight, measured in toluene.
The polybutadiene-ba~ed graft rubber~ (Cl) have a median particle diameter d50 of from 0.05 to 0.6 ~m, preferably of from 0.08 to 0.5 ~m, and exhibit a degree of grafting G of from 0.15 to 0.55, preferably of from 200.2 to 0.4. The degree of grafting G indicate~ the weight ratio of grafted-on monomer to the gxafting base and i~
dimen~ionless. The median particle diameter d50 i~ that diameter which .i8 less than the diameter posses~ed by 50 % by weight of the particles and greater than the 25diameter pos~essed by 50 % by weight of the particles. It can ba determined by mean~ of ultracentrifuge mea~ure-mQnts (W. Scholtan, H. Lange, Kolloid. Z. and Z. Polym~re 25Q (1972~, 782-796) or by mean~ of electron microscopy and 8ub8equent particle counting (G. ~mpf, H. Schuster, 30Angew. Makromolekulare Chemie 14 (1970), 111-129) or by means of light scattering measurements.
Since, as wlll be known, the grafting monomer~
(C12) are not completely gxafted onto the grsfting base (Cll), the polybutadiene-based graft rubber~ (Cl) u~able 35according to the present invention a}~o contain homopoly-mer~ and po8Bibly copolymer~ of the grafting mono~ers (C12) as well as th~ actually grafted polymars.
~ ~ 2 ~
- 15 O.z. 0~50/41133 C2) Suitabl~ graft rubbers ba ed on polyacrylate~
(C2) are compo~ed of C21) a grafting base consisting of an acrylate rubber having a glas~ transition temperature of below -20C and C22) a graft prepared by graft polymerization of at least one polym~rizable ethylenically unsatura-ted monomer whose homopolymer or copolymers formed in the ab~ence of ~C21) would have a glass tran~ition temperature of above 25C.
Preferred grafting monomer~ for forming ths graft (C22) are ~tyrene, alkyl~tyrene, eg. ~-methyl3tyrene, acrylonitrile, alkyl acrylate~ or methacrylates, eg.
methyl methacrylate, and mixtures of at least two of ~aid monomer~. Preferred grafting monomer mixtures are tho e between styrene and acrylonitrile in a weight ratio of from 90.10 to 50:50.
The polyacrylate-based graft rubber~ [C2) con~ist advantageou31y of C21~ 2S-98 % by weight, preferably 50-90 % by weight, based on the total weight of (C2), of (C21) and C22) 2-75 % by weight, preferably 10-50 % by weight, based on the total weight of (C2), of ~C22).
The acrylate rubber~ (C21) which come into consideration Eor use as grafting bases are preferably polymers of alkyl acrylate3 which may contain up to 50 %
by weight, ba3ed on the total weight, of units of other polymerizable, ethylenically unsaturated monomer~ as copolymerized units. If the acrylat2 rubbers used as grafting base (C21) in turn are already graft polymer~
having a diene rubber core, the diene rubber coro i8 not included in the calculation o~ the af orementioned per-centage. The preferred polymerizable alkyl acrylates include those having from 1 to 8 carbo~ atom3 in the alkyl moiety, eg~ methyl, ethyl, butyl, octyl or 2-ethylhexyl acrylate. It i8 al80 po3~ible to u~e ~, q~
- 16 - o.z. 0050/41133 haloalkyl acrylate~, preferably halo-Cl-C~-alkyl acry-lates, ~g. chloro~thyl acrylate, and arylalkyl acrylate~, eg. benzyl or phenylethyl a~rylate. The alkyl acrylates mentioned can be used individually or in the form of 5 mixturPs.
The acrylate rubbers (C21) may be uncrosslinked, crosslinked or preferably partially cros~linked.
The cros31inking may be brought about by copoly-merizing the alkyl acrylate~ with suitable monomer~ which have more than one copolymerizable double bond. Example~
of uch cros31inking monomers are carboxylic ester~
prepared from olefinically unsaturated monocarboxylic acids of from 3 to 8 carbon atoms and olefinically un~aturated monohydric alcohol~ of from 3 to 12 carbon atom~ or saturat2d at least dihydric, preferably di-hydric, trihydric or tetrahydric, alcohol~ of from 2 to 20 carbon atoms, eg. allyl methacrylate or an alkylene glycol di(meth)acrylate. It i~ al o possible to u~e polyunsaturated heterocyclic compounds, ~uch a~ trivinyl or triallyl cyanurate or i~ocyanurate, tri~acryloyl-~-triazines, polyfunctional vinyl compounds, eg. di- and trivinylbenzene a~d al50 triallyl phosphater dicyclodi-hydropentadienyl acrylate or/and diallyl phthalate.
It i~ pelrticularly advantageous and hence prefer-able to use butanediol diacrylate, dicy~lopentadienyl acrylate and butadiene.
The amount of cro~slinkin~ monomer i8 preferably from 0.02 to 10 # by weight, in particular from 0.05 to 5 %
by weight,ba~ed on the weight of the grafting ba~e (C21).
If cyclic cro~slinking monomers having at lea8t hree ethylenically un~aturated groups are u~ed, it i8 advantageous to limit their amount to 1 % by weight of the qrafting ba~a (C21).
Other suita~le polymerizabla ethylenically un~aturated monomer~ which may be used for preparing the grafting bas~ ~21) beside~ alkyl acrylats~ are for example acrylonitrile, styrene, ~-mathylstyrene, J
- 17 - O.Z. 0050~41133 acrylamldes and vinyl Cl-C6-alkyl ether~.
The acrylate rubberR preferably used a~ grafting base (C21) are emulsion polymers which have a gel content of 60 % by w~ight, meaRured at 25C in dimethylformamide ~M. ~offmann, H. Rromer, R. Kuhn, Polymeranalytik I and II, Georg-Thieme-Verlag Stuttgart 1977).
A grafting base (C21) may alRo be acrylate rubber with a core compri~ing a diene rubber formed from one or more conjugated diene~, such as polybutadiene, or a copolymer of a conjugated diene with an ethylenically unsaturat~d monomer, such as ~tyrene and/or acrylo nitrile.
The polydiene cors content of the grafting base (C21) may range from 0.1 to 50 % by weight, preferably from 10 to 40 % by weight, based on (C21). Her8 the grafting ba3e (C21) and the graft or 3heath may each be independently of the other uncrocslinked or partially or compl~tely crosslinked.
Par~icularly preferred grafting ba~e~ (C21) for polyacrylate-ba~ed graft rubbers (C2) are thus: alkyl acrylate homopolymers and copolymers without a core of diene rubber and alkyl acrylate homopolymers and copoly-mers with a core of diene rubber.
The graft yield, ie. the ratio of the weight of grafted-on monomer (or the weight of the graft ~heath) to the weight of the grafting monomer~ used, iB in general from 20 to 80 %, preferably from 40 to 80 ~. The graft yiald is det~rmined a~ de~cribed by M. ~offmann, H. Kromer and R. Kuhn in Polymeranalytik, volume 1, &eorg-Thieme-Verlag Stuttgart 1977.
Graft rubbers ~C) based on polyacrylate~ (C.2) which are usable according to the pre~ent invention are dsscribed for example in DE-~-24 44 584 (US-A-4 022 748) and DE-A-27 26 256 (US-A-4 096 202).
Polyacrylat~-ba~ed graft rubbers (C2) of thi~
kind can al~o be obtained by grafting 2-20 % by weight, pr~erably 2-15 % by weight, ba~ed on 2 ~ 2 ~
~ o.Z. 0050/41133 the weight of (C2)~ of a grafting monomer s~lected from the group con~i~ting of the alkyl acrylate~, alkyl methacrylate~ having from 1 to 8 carbon atoms in the alkyl moiety, styrene, ~-methylstyrene, acrylonitrile and S vinyl acetate and mix~ures of at least two grafting monomer~ onto 80-98 % by weight, preferably 85-g8 % by weight, ba~ed on th~ weight of (C2), of a completely broken, aqueous latex of the grafting base (C21) in the absence of a suspending aid. The re~ulting pulverulent graft rubber (C2) may then be dried and homogenized in the desired ratio with the forma~ive component~ (A) and (B) by the action of shear-ing force in ~uch a way that ths median particle ~ize d50 of (C2) in a TPU/PES molding material according to the present invention i8 from 0.05 to 3 ~m, preferably from 0.1 to 2 ~m, in particular from 0.2 to 1 ~m.
The expression ~in the absence of a ~u~pending aid" indicates for the purposes of the pre~ent invention the absence of substances which, by quality and quantity, are capsble of Yu~pending the aforementioned grafting monomers in the aqueoua phasa. However, thi~ definition does not rule out the presence of substance~ which may have had a ~uspending effect for example in the prepara-tion of a grafted grafting base (C21). In such case~ the coagulant or precipitant used for breaking the latex of the grafting base (C21) must be added in an amount which outweighs the 3uspendiny effect of ~ubstances used for foxming the grafted grafting base (C21); that i~t care must be .taken to en~ure that the grafting monomar~ for forming the graft do not form stable emul~ions in the aqueous phase.
The grafting ba~e (C21) may al80 compri~e an acrylate rubbar in the form of an aqueous emulsion (latex) wher~ the latex particles contain as copolymer-ized units 1 to 20 ~ by weight, prefsrably from 1 to 10 %
by w~isht, based on-(C21), o~ monomers previously graft ed-on in aquoous emulsion, prefer~bly alkyl (meth)acryla-~, 7 ~ rj - lg - O.Z. 0050/41133 te~r styrene, ~-methyl~tyren~, acrylonitrile and/or vinyl acetata, which in the form of their homopolymer~ or copolymer3 would have a gla~s transition temperature of O~C.
Such grafting base~ (C21) are obtained for example by emulsion graft polymerization. Alternatively, the acrylate rubbers can be prepared by solution or bulk polymerization, the grafting monomers can be gra~ted on, and the resulting rubber~ can then be converted into an aqueou3 emulsion suitable for further graft polymeriza tion processes.
Suitable grafting bases (C21) for polyacrylate-based graft rubber~ prepared by thi~ particular embodi-ment are thus not only the above-de~cribed grafting base~
but alco graft polymer~ prepared in aqueou~ emul ion from acrylate polymers and copolymers which may contain a core of diene rubber and ethylenically un~aturated polymer-izable monomers.
The graft rubbers based on a polybutadiene ~Cl) or on a graft acrylate (C2) which are usable according to the present invention for impact modification can be used alon~ or as mixture~. It i~ also pos3ible to use mixture~
of graft rubbers based on (C1) and (C2).
The impact modified thermopla~tic TPU/PES molding matarial~ according to the present in~ention may in addition to th~ essential components (A), (B) and (C) optionally also contain fibrous and/or particulate fillers (D) and~or assi~tant~ ~E).
D) The proportion of filler (D) i8 customarily from 0 to 60 % by w~ight, preferably from 2 to 50 % by weight, in particular from 5 to 30 % by weight, based on the total weight of components (A) to (C).
Suitable particulate filler~ are for example:
organic fillers, ~uch as. carbon black, chlorinated p~lyethylene~ and melamine, and inorganic fillers such a3 wollastonite, calcium carbonate, magnesium carbonate, amorphous silica, calcium ~ilicats, calcium metasilicatQ, ~ ~ 2 f- 7 3 - 20 - O.~. 0050/41133 quartz powder, talc, kaolin, mica, feld~par, gla~
Rph~re~, 8ilicon nitride, boron nitride and mixture~
thereof.
Particularly ~uitabl~ reinforcing fillars which are therefore preferred are fiber~, for example carbon fibers and in particular gla3s fibers, with or without an adhe~ion promoting or/and ~ize finish. Suitable gla~s fibars, which are al80 for example in the form of glas~
weaves, mats, w~bs and~or preferably gla~s fil~ment roving~ or chopped glas~ filament formed from low-alkali E-glasses from 5 to 200 ~m, preferably from 6 to 15 ~m, in diameterr generally have a mean fiber length of from O.05 to 1 mm, preferably from 0.1 to 0.5 mm, after incorporation into the TPU/PES molding materials.
Of the aforementioned parti~ulatQ or fibrous reinforcing filler~, gla 8 fiber~ in particular are advantageous, in particular when a high heat resiRtanca or very high Rtiffnes~ i~ required.
E) A~ mentioned, the TPU/PES molding materials according to the present invention may also contain aq~istant~ (E). The assi~tant~ can be identical to the customary aids (c) or additive~ (f) used for preparing TPUs and therefore already be present in the TPU (A). The proportion of a~ tant (E) i~ in general from 0 to lO ~
by weight, preferably from 0 to 5 % by weight, based on the total weight of formative components (A) to (C). Such a~ tants are for QXample: nucleating agents, anti-oxidants, stabilizers, lubricantq, damolding agen~ and dyes.
The nucleating agent used can be for example talc, calcium fluoride, ~odium phenylphosphinate, alumi-num oxide or ~inely-divided polytetra~luoroethylene in an amount of up to 5 % by weight, based on the weight of formative component~ (A) to (C).
Suitable antioxidants and heat stabilizer~ which may be added to the TPU/~'ES molding materials are for example halides of metal~ of group I of the periodic - 21 - O.Z. 0050/41133 table, for example halides of sodium, pota~sium or lithium, alone or combined with copper(I) halideY, eg.
chloride~, bromide~ or iodides, terically hindered phenols, hydroquinones and also ~ubstituted compounds of these group~ and mixture~ thereof, which are preferably used in concentration~ of up to 1 ~ by weight, based on the weight of formative components (A) to (C).
Examples of W stabilizers are various sub~titu-ted resorcinol~, ~alicylates, benzotria~oles and benzo-phenones and also sterically hindered amines, which ingeneral are used in amount~ of up to 2.0 % by weight, ba~ed on the weight of fonmatiYe components (A) to (C).
Lubricants and demolding agents which in general are likewise added in amount~ of up to 1 % by weight based on the weight of formative component~ (A) to (C), are Cl2-C38-fatty acids, for example ~tearic acids, fatty alcohols, eg. stearyl alcohol, fatty acid esters or amides, eg. ~tearic e~ter~ and ~tearamides, and al80 the fatty acid esters of pentaarythritol and montan e~ter waxe~.
It i8 also pos~ible to add organic dyQs, eg.
nigro~ine, and piçments, eg. titanium dioxide, cadmium sulfide, cadmium ulfide selenide, phthalocyanine~, ultramarine blue or carbon black, in amounts of for example up to S % by weight, ba~ed on formative compo-nents (A) to (C)-The impact modified thermoplAstic TPU/PES moldingmaterials accordlnq to the pre~ent invention can be prepared by any desired method for forming an essentially homogeneou~ composition from the TPU (A), the PES (B) and the graft rubber (C) and optlonally the fillers (D) and as~istant~ (E)~ For ax~mple, the formative component~ (A) to (C) and optionally (D) andJor (E) can be mixed at from 0 to 150C, pref2rably at from 15 to 30~C, and then m~lted, or the componentA csn be mixed directly in the melt. Alternatively, (A) can be mixed with (C) or (B) w~ith (C) and tha~e mixtures be incorporated into (B) or 2 ~ 2 ~
- 22 - O.Z. 0050/41133 (A) respecti~ely, in which ca~e (D) and/or (E) may already be present in one of the fQrmati~e components (A) to (C) or may be added subsequently.
The TPU/PES molding material~ according to the present invention ar~ prepared at from 190 to 250C, preferably from 210 to 240C, in the cour~e o a resi-dence time of from 0.5 to 10 minutas, preferably of from 0.5 to 3 minute~, in for example the fluant, ~oftened or preferably molten state of formative component~ (A) to (C), for examplQ by stirring, rolling, kneading or preferably extruding, using for example cu~tomary pla8ti-ca~ins apparatus, eg. Brabender or Banbury mLlls, kneader~ and extruders, preferably a twin-~crew ~truder or a mixing extruder for transfer molding.
In the mo~t con~enient and therefore preferable method of preparation, the TPU (A), the PES (B) and tha graft rubber (C~ are mixed with or without (D) andtor tE) and melted together at 190-250C, preferably in an extruder, the melt ha~ incorporated into it any component (D) and~or (E) not introduced earlier and i8 then cooled, and the resulting TPU~PES molding material i comminuted.
The TPU~PES molding materials obtained according to the pre~ent invention are ea~y to process into ~haped articles pos~essing good surface properties and L~proved impact toughness combined with high ~tiffness, in par-ticular at low temperatures, without separation into component~ (A) or (B) or (C) occurring in the melt or in the molding.
The TPU/PES molding materials are also suitable for the extrusion of ~heets, in particular thermoforming sheets.
EXAMPLES
Impact modified thermoplastic TPUJPES molding matarials according to the pre~ent invention are prepared using the following component~s A) Thermoplastic polyur~thane elastomers Al: TPU having a ~hore D hardness of 69 prepared by ~2~
- 23 - 0.2. 0050/41133 reaction of a mixture of 0.5 mol of 1,4-butansdiol polyadipate of molecular weight 2000 and 5.86 mol of 1,4~butanediol with 4,4~-diphenylmethane ~iisocyan-ate in an NCO:OH group ratio of 1 at 80-170 C by the belt technique.
A2: TPU having a Shore D hardnes~ of 74 prepared in the same way aQ Al except that he NCO:OH group ratio u~ed waQ 1 . 04.
A3: TPU having a Shore D hardnes~ of 64 prepared in the ~ame way a~ Al except that 3.87 mol of 1,4-butane-diol w~re used.
A4: r'PU having a Shore A hardne~ of 90 prepared in the same way a~ Al, except that 1.7 mol of 1,4-butane-diol were used.
A5: TPU having a Shore D hardness of 74 prepared by reacting a mixture of 0.5 mol of 1,4-butanediol/
ethylene glycol polyadipate having a 1,4-butane-diol:ethylene glycol molar ratio of 1:1 and a molecular weight of 2000 and 5.66 mol of 1,4-butane-diol with 4,4'-diphenyLmethane diisocyanate in an NCO:OH group ratio of 1.
The above-described TPUB A1 to A5 each contain, based on the alkanediol polyadipa~e weight, 1 % by weight of diisopropylphenylcarbodiimide a~ hydrolysis stabilizer.
A6~ TPU havinS~ a Shore D hardness of 64 prepared by reaction of a mixture of 1 mol of polytetramethylene glycol of molecular weight 1~00 and 3.87 mol of 1,4-butanediol wLth 4,4'-diphenylmethane diisocyanate in an NCOsOH group ratio of 1 at 90-170C by the belt technique.
B) Thermoplastic polye~ters Bl: Polyethylene terephthalats having a relative visco-sity of l.38 (measured on a 0.5 % strength by weight solution in 1~1 w/w phenol/o-dichlorobenzene).
B2: Polybutylene terephthalate haYing ~ relati~e vi~co-~ity of 1.4, measured in the ~ame way as Bl~
~ 7 ~t - 24 - o.z. 0050~41133 Cl) Graft rubbers based on polybutadiene ClI: Graft rubber having a grafting base (75 % by weight) of polybutadiene and a graft (2s % by weight) of a copolymer of styrene and acrylonitrile in a weight ratio of 75:25, prepared by emulsion polymerization in a conventional manner. Th~ median particle diameter d50, defined a~ the diameter which i8 respectively le~s than and yreater than the diameter posses~Qd by 50 % of the particle~, was 250 nm.
ClII: Graft rubber prepared in the ~ame way as ClI, except that the graft i8 a copolymer of ~-methyl-~tyren~ and acrylonitrile in a weight ratio of 75:25.
ClIII: Graft rubber having a grafting ba~e (70 % by weight) of polybutadiene and a two-stage graft (in total 30 % by weight), the 18t stage (10 % by weight) being poly~tyrene and the 2nd stage (20 %
by weight) being a copolymer of methyl methacry-late, n-butyl acrylate and glycidyl methacrylate in a weight ratio of from 89:10:1. The graft polymar, which was prepared by emulsion polymer-ization in a conventional manner, had a median particle diamster d50 of 240 ~m.
C2) Graft rubber based on polyacrylate C2I: Graft rubber having a grafting ba~e (75 % by weight) of a cro~slinked poly-n-butyl acrylate and a graft (25 % by weight) of a copolymer o~ styrene and acrylonitrile in a weight ratio of 75s25, prepared by emulsion polymerization in a conventional manner.
The graft rubbsr had a median particle diameter d~o of 210 ~m.
C2IIs Graft rubb~r having a gr~fting b~se (75 % by w~ight) comprising a poly-n-~utyl ac~ylate cro~slinked with butanediol diacrylate and a graft (25 % by weight) compo~ed of a copolymer of ~tyrene, acrylonitrile and tert-butyl acrylate in a weight ratio of 73~24:3. Th~ graft rubber, - ~5 - O.Z. 0050/41133 which wa~ prepared by emulsion polymerization in a conventional manner, had a median particle diameter d50 of 420 ~m.
D) Filler~
E-Gla~ fiber~ in the form of a roving or in the form of chopped fiber. The gla~s fiber diameter was 1 0 ,~
Preparation of the Lmpact modified thermoplastic TPU/PES
molding material~
1 O EXAMPLES 1 TO 3 0 ~ND
CO~D?~ATIVE EX~?LES I TO IV
To prepare the TPU/PES molding materials, com-ponents ~A), (B) and (C) ara intensively mixed at ~3C, the mixture is introduced into a twin-screw e~truder and melted at 230C, and the melt i~ homogenized for ~ min-ute~ and then extruded into a watar bath.
If E-gla~ fibers wera used, these were incor-porated into the homogenized malt in tha form of chopped fibers or rovings.
Following granulation and drying, the TPU/PES
molding materials were in~ection molded at 230C into test ~pecimens on which measurements were carried out, without further aftertreatment, of the notched impact strength according to ~erman Standard Specification DIN
53 453, the breaking exten~ion according to German Standard Spe~ific~tion DIN 53 455 and the modulu~ of elasticity accordLng to German Standard Specification DIN
53 457.
The identity and quantity of the TPUs (A), PES's (B) and graft rubbers (C1) and (C2) used and of any reinforcing filler~ (D) and the meehanical propertie~
measured on the test specimens are summarized below in Table~ I to IV.
.. ... .. .
~2li 7 L~;
- 26 - O. Z . 00~0/41133 cnC
3,X~ _ooo ooooo~ooU~oo ~ ~ ~O 0 ~ ~ ~ ~ ~D 1--C~ In ~0 U
c ~ ~ o ~ ~ ~ r~ ` ~ ~ ~ ~ ~o o~
Y~, o ~--~ O 0~ i ~i ~ o o Cl~ _ o ~ ~
.-~Z ~3 U~ o U~ C ~ ~ ~ C
~ ~ r~ o ~ ~ o u~ ~ ~ ~ I 1 O o 2 a~ ~ ~ ~ X ~ O ~ Ct~ O O O
________~
~-- I I I I _ _ _ _ _ _ _ _ _ _ _ ~, 3 ~ I I I o o o o C~ o o o o o o _~ ~ ~ ~ ~ ~ ~ eo ~ ~ c a~ a~ ~ ~ ~
V~
o o o o ~ o o ~o o o o o o~
--~ ~- ~ ~ ~--~ ~ ~ ~ u~ ~ ~ r~
oooo oo~oooo~ooo ~ .. ' o ~. ~ U
~U ~ ~ o _ U ~ 1-~2'i7~
- 27 - O . Z . 0050/41133 C~ **.
C ,~ ~q ~ O q~
~ C_ C ' C
L
~C~ O
~ ~, q_~8~ o o o C~ o H
_ _ _. _ _ _ _ _ _ _ ~-- _ _ _ _ _ " 3 ~
~ ~ L 0 ~ i~
_~~ ~ ~ ~ ~
c~ tS~ D
C L C ~ ~ 1 ~ t~7 1~
'2 ~L3 ~
Vl 01 _ ~ ~ ~9 _ ~ 3OOOO-D
C ~U~
L
q_ x_ _ _ _ _ a 2 v ~ 7 ~ ~
- 28 - O. Z .005ût~1133 _ V) a:l ~ ~ O O e~ o o o o ~ o O ~o ~o ~ ao ~c~ ~ a~ I`
, ~ ~ I~ o ~
.~ U~ O
_ o ~ ~ ~ O ~ C~' D ;r O
,~ ~ _ U~ C~U~
O ~ U~ O u~
~ t~ ~ Co ~--~C~ ~ ~ O ~ o, H
~.
~,~ o~ooooo~o . ~ ~-~ ~ 0 ~ ~ CD ~D In ~ C~
e v e O o o o o c: O o O
~ ~ ----~
~ o o o o o o o o o o c ~ ~' U~
n I~
~ ___~ "c 2 ~
- 29 - O. Z . 005~/41133 C Crl C C 1-- C
'EN
._ ~ ~ C C ~ ~ C
L
v Ct Ct Ct Ct g _ ~ ao ~ Cl~
_ ~ ~
~-- O ~ _ u) ~ ~ c et o o o o ~ C L ~
oJ _ _ _ _ _ , t~
~ ~ ~ r~ r~ ~ I~ ~
~ N 1~
y ut c ~ ~ ~ ~ a~
- ~
O t ~ ~ qS
IC--~ 3_. o o o o u c o~ c t~ t~
~._ C~
. t r~ ~ c~ O o ~ . C
S As mentioned, th~ TPU/PES molding materials according to the present invention have very good low temperature toughness. It i~ also worth mentioning their very good proce~ibility into shaped article~ by means of the in~ection molding techniqua, the ~hort cycle tLmes required for this purpo~e and the good demoldability. The TPU/PES molding materials also po~ses~ excellent re~is-tan~e to organic solvent~.
The TPUs tA) u~able for preparing the TPU/PES
molding materials according to the pre~ent invention correspond to the prior art and can be prepared by reacting a) organic, preferably aromatic, diisocyanate~, in particular 4,4'-diphenylmethane diisocyanate, with b) polyhydroxy compounds, preferably e~sentially linear polyhydroxy compounds, having molecular weight~ of from 500 to 8000, in particular polyalkylene glycol polyadipates having from 2 to 6 carbon atom~ in the alkylene moiety and molecular weight~ of from 500 to 6000 or hydroxyl-containing polytetrahydrofuran having a molecular weight of from 500 to 8000, and c) diols as chain extenders haviny molecular weights of from ths 60 to 400, in particular 1;4-butanediol, in the prQsence ef d) cataly~ts and optionally e) a~d~ and/or f) additives at elevated temperature~.
The TPU-forming component~ ta) to (d~ and option-ally (e) and~or (f) may b~ d~scribed in datail as follows~
a) Suitable organic dii~oc~anates (a) are for example aliphatic, cycloaliphatic-and pref~rably aromatic 2 ~ 2 ~
_ 4 _ o. æ . 0050/41133 dii~ocyanate~. Specific examples are: aliphatic dii~o-cyanate~ ~uch a~ 1,6-hexamethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 2-ethyl-1,4-butylene diisocyanate and mixture~ of at least two of said aliphatic diisocyanateR, cycloaliphatic dii~ocyan-ates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, l-methyl-2,4-cyclohexane diisocyanate and 1-methyl-2,6 cyclohexane diisocyanate and the corre~pond-ing isomeric mixtures, 4,4'-, 2,4'- or 2,2'-dicyclohexyl-methane diisocyanate and the corre~ponding isomericmixtures and preferably aromatic dii~ocyanate~ such as 2,4-toluylene dii~ocyanate, mixture of 2,4- and 2,6-toluylene dii~ocyanate, 4,4'-, 2,4'~ and 2,2'-diphenyl-methane diisocyanate, mixtures of 2,4'- and 4,4'-di-phenylmsthane diisocyanate, urethane-modified liquid 4,4'- and/or 2,4~-diphenylmethane diisocyanates, 4,4'-diisocyanato-1,2-diphenylethane, mixtures of 4,4'-, 2,4'-and 2,2'-diisocyanato-1,2-diphenylQthane, preferably those having a 4,4'-diisocyanato-1,2-diphenylethane content of at least 95 ~ by w~ight, and 1,5-naphthylene dii~ocyanate. Preference i~ given to u~ing diphenyl-methane diisocyanate isomer mixtures having a 4,4'-diphenylmethane diisocyanate content of greater than 96 %
by weight and in particular essentially pure 4,4'-di-phenylmethan~ diisocyanate.
The organic diisocyanate may be replaced to aminor extent, for examp~e in an amount of up to 3 mol %, preferably up to 1 mol %, ba~ed on the organic diisocyan-ate, by a trifunctional or more highly functional poly-isocyanate, the amount of which, however, must bo limitedin such a way as to produce a still thermoplastic poly-urethsne. A ma~or amount of such tri- or more highly functional isocyanates is advantageously balanced by the inclusion of les~ than difunctional compound~ having reactive hydrogen atom~, in order that excessive chemical crosslinking of the polyurethane may be avoided. Examples of more than difunctional i~ocyanates are mixtures of 7 ~ -~
_ 5 - o.Z. 0~50/41133 diphenylmethan0 diisocyanat~ and polyphenylpolymethylene polyisocyanate~, so-called cr~de MDI, and liquid 4,4~-and/or 2,4'-diphenylmethane diisocyanates modifi~d with isocyanurate, urea, biuret, allophanate, urethane and/or carbodiimid~ groups.
Suitable monofunctional compounds having reactive hydrogen atoms which are also u~able a~ molecular weight regulators are for example: monoamine~ such 2s butyl-amine, dibutylamine, octylamine, ~tearylamine, N-methyl-stearylamine, pyrrolidone, piperidine and cyclohexylamineand monoalcohols such as butanol, amyl alcohol, l~ethyl-hexanol, octanol, dodecanol, _yclohexanol and ethylene glycol monoethyl ether.
b) Preferred polyhydroxy compound~ (b) having molecular weights of from 500 to 8000 are polyetherol~
and in particular polye~terol~. ~owever, it i~ al~o pos~ible to use other hydroxyl-containing polymer~
con~aining ether or ester groups as bridge member~, for example polyacetals, such as polyoxymethylenes and in particular water-soluble formal3, eg. polybutanediol formal and polyhexanediol formal, and polycarbonates, in particular tho~e formed from diphenyl carbonate and 1,6~
hexane~iol, prepared by transe~terification. ~he poly-hydroxy compound mus~ be at least predominantly linear, ie. difunctional within the meaning of the isocyanate reaction. The polyhydroxy compQunds mentioned may be used as individual component~ or in the form of mixture~.
5uitable polyetherols can be prepared from ons or more alkylene oxides having from 2 tD 4 ca~bon atom~ in the alkylene moiety in a conventional manner, for example by anionic polymerization with alkali metal hydroxides, such as sodium hydroxide or potas 8 ium hydroxide, or alkali metal alcoholates, ~uch as sodium methoxide, ~odium ethoxide, pota~sium ethoxide or potassium isoprop-oxide, as catalysts and in the presence of at least oneinitiator molecule which contains a or 3, preferably 2 reactivo hydrogen atom~, or by cationic polymerization 2 ~ 2 .~
- 6 - O.Z. 0050/41133 with Lewis acids, such a~ antimony pentachloride, boron fluoride etherate, etc. or bleaching earth, as cataly8t8.
Preferred alkylene oxides ar~ for example tetra-hydrofuran, 1,3-propylene oxide, 1,2-butylene oxide, 2,3-5butylene oxide and in particular ethylene oxide and 1,2-propylena oxide. The alkylene oxide~ may be u~ed indi-vidually, alternately in succession or a~ mixtures.
Suitable initiator molecules are for example: water, organic dicarboxylic acidR, such a~ ~uccinic acid, adipic 10acid and~or glutaric acid, alkanolamines, such a~ ethan-olamine, N-~lkylalkanolamine~, N-alkyldialkanolamine~, eg. N~methyl- and N-ethyl~diethanolamine, and preferably dihydric alcohol~ which may contain ether linkages, eg.
ethanediol, 1,2-propanediol~ 1,3-propanediol, 1,4-butane-15diol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, 2-methyl-1,5-pentanediol and 2-ethyl-1,4-butanediol. Th~ initiator molecules may be used individually or a~ mixture~.
Preference i3 give~ to using polyetherol~ from 201,2 propylene oxide and ethylene oxid~ in which more than 50 ~, p-eferably from 60 to 80 ~, of the OH group~ are prLmary hydroxyl groups and where at least some of the ethylene oxide units are present as a terminal block.
Such polyetherol~ can be obtained ~y, for example, 25polymerizing onto the initiator molecula first the 1,2-propylene oxide and then the ethylene oxide, or first the entire 1,2-propylene oxide mixed with ~ome of the ethyl-ene oxide and then the remainder of the ethylene oxide, cr step by 8t5p first some of the ethylene oxide, then 30the entire 1,2-propylene oxide and then the remainder of the ethylene oxide.
Other preferre~ possibilities are the ~Iydroxyl-containing polymerization product~ of tetrahydrofuran.
The e~sentially linear polyetherol~ have mole-35cular weight~ of from 500 to 8000, preferably from 600 to 6000, in particular from 800 to 3500, th~ polyoxytetra-methylene glycol~ preferably having molecular weights of ~ ~ 2 ~ ~ ~ ? ~
- 7 - o.z. 0050/41133 from 500 to 2800. ~hey can be used not only individually but also in the form of mixtures with one another.
Suitable polyest~rols may be prepared for example from dicarboxylic acid~ of from 2 to 12, preferably from 4 to 6, carbon atoms and polyhydric alcohols. Suitable dicarboxylic acid~ are for example: aliphatic dicar-boxylic acid~, such as succinic acid, glutaric acid, adipi~ acid, suberic acid, azelaic acid and sebacic acid, and aromatic dicarboxylic acids, such as phthalic acid, i~ophthalic acid and terephthalic acid. The dicarboxylic acid~ can be used individually or as mixtures, for exampie in the form of a mixture of ~uccinic acid, glutaric acid and adipic acid. ~o prepare the poly-e~terol~ it may be advanta~eous to u~e instead of the dicarboxylic acids the corresponding dicarboxylic acid derivatives, ~uch a~ dicarboxylic monoe~ter~ or diesters having from 1 to 4 carbon atom~ in the alcohol moiety, dicarboxylic anhydrides or dicarbonyl dichlorides.
ExampleR of polyhydric alcohol~ are glycols of from 2 to 10, preferably from 2 to 6, carbon atom~, cuch as ethyl-ene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2-di-methylpropane-1,3-diol, 1,3-propanediol and dipropylene glyeol. Depending on the properties which are desired, the polyhydric alcohol~ may be used alone or optionally mixed with one another.
It is also possible to use e~ter~ of carbonic acid with the diols mentioned, in particular those having from 4 t~ 6 carbon atom~, such a~ 1,4-butanediol and/or 1,6-hexanediol, conden~tion products of ~-hydroxycar-boxylic acids, eg. ~-hydroxycaproic acid, and preferably polymerization product~ of lactones, for example sub~ti-tuted or un~ubstituted ~ caprolactones.
Preferred polye~tQrols are ethanediol poly-adipats~, 1,4-butanediol polyadipates, etha~ediGl/1,4-butanediol polyadipate~, 1,6-hexansdi~l/neopentylglycol polyadipates, 1,6-hexanediol~1,4-butanediol polyadipate~
2 ~
- 8 - O.Z. 0050/41133 and polycaprolactones.
The polyesterols have molecular weigh~ of from 500 to 6000, preferably from 800 to 3500.
c~ Suitable chain extender~ (c) having molecular weight~ of from 60 to 400~ preferably from 60 to 300, are preferably aliphatic diols of from 2 to 12 carbon atoms, preferably of 2, 4 or 6 carbon atoms, eg. ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol and in particular 1,4-butanediol. However, it is also pos-sible to use diester~ of terephthalic acid with glycols of from 2 to 4 carbon atom~, eg. bisethylene glycol terephthalate, 1,4-butanediol terephthalate, and hydroxy-alkylene ethers of hydroquinone, eg. 1,4-di-(~-hydroxy-ethyl)-hydroquinone, and al~o polytetramethylene glycols having molscular weights of from 162 to 378.
To set the hardnes~ and the melt flow index, the formative components can be varied within relatively wide molar ratios bearing in mind that the hardne~s and melt visco~ity increase with an increa~ing level of chain extenders (c) while the melt flow index decrease~.
To prepare relatively ~oft TPUs (A), for example those having a Shore A hardness of le~# ~han 95, prefer-ably from 95 to 75, it is advantageous for example to use the es~entially difunctional polyhydroxy compounds (b) and the diols ~cJ in a molar ratio of from 1:1 to 1:5, preferably fro~ 1:1.5 to 1: 4 . 5, 80 that the resulting mixtures of (b) and (c) have a hydroxy equivalent weight of greater than 20U, n parti~ular from 230 to 450, while harder TPUs (a), for exa~ple tho~e having a Shore A
hardness of greater than 98, preferably from 55 to 75 Shore D, are prepared using molar ratios of (b)s(c) within the range from 1~5.5 to ls15, preferably from 1:6 to lsl~, 80 that the resulting mix~ure~ of (b) and (c) have a hydroxy equivalent weight of from 110 to 200, preferably from 120 to 180.
d) Suitable cataly~t3, in particular for the.reaG-tion between tho NCO group8 of the dii~ocyanates (a) and ~ gJ 2 - g - o.z. 0050/41133 the hydroxyl group~ of the formative components (b) and (c), are the customary tertiary amines, such a~ triethyl-amine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, diazabicyclo[2.2.2]octane and the like, in particular organic metal compounds ~uch a~
tit~nic e~ters, iron compound~, tin compounds, eg. tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salt~ of aliphatic carboxylic acids ~uch a~
dibutyltin diacetate, dibutyltin dilaurate and the like.
The cataly~ts are customarily used in amount~ of from 0.001 to 0.1 part by weight per 100 parts by weight of the m xture of polyhydroxy compound~ (b) and diols (c).
In addition to cataly~ts, the formative compo-nents may al30 contain aid~ (e) and/or additive~ (f).
Example~ are lubricants, inhibitor~, stabilizers again~t hydrolysis, light, heat or discoloration, flame retar-dantR, dyes, pigment~, inorganic and/or orqani~ fillers and reinforcing agents.
The aids (e) and/or additive~ (f) may be intro-duced into the formative components or into the reactionmixture for preparing the TPUs (A). Alternatively~ the aids (e) and/or additives (f), which may be identical to the assi~tant (E), may be mixed with the TPU (A), the PES
(B) and/or the graft rubber (C) and then melted, or they are incorporated directly into the melt of components tA), (B) and (C). The latter method is also adopted in particular for incorporating the fibrous and/or particulate filler3 (D).
Where, in what follow~, no details are provided concerning the usable aid~ or additives, they can be discerned from the relevant technical literature, for example J.H. Saunders and K.C. Frisch's monograph, ~igh Polymers, volume XVI, Polyurethanes, parts 1 and 2 (Interscience Publisher~ 1962 and 1964 re~pectively), Kunst~toff ~andbuch, volum~ 7, Polyurethanes, l~t and 2nd editions (Carl Han er Verlag 1966 and 1983 respectively), or DE-A-2,901,774.
- 10 - O. Z . 0050/41133 To prepare the TPU~ (A), the formati~e component~
~a), (b) and (c) are made to react in the pr~ence of a cataly~t (d) and in the pre~ence or absenc~ of aid~ (e) and/or additives (f) in ~uch amount~ that the equivalance ratio of the diisocyanate NCO groups to the total number of hydroxyl groups of components (b) and (c) iB from 0.95 to 1.10:1, preferably 0.98 to 1.08:1, in particular approximately l.0 to 1.05:1O
The TPUs (A~ which are usable according to the present invention and which customarily contain from 8 to 20 % by weightt preferably from 8 to 16 % by weight, ba ed on the total weight, ef urethane groups and have a melt flow index at 210C of from 500 to 1, preferably from 100 to 1, can be prepared by the extruder technique or preferably the belt technique by batchwise or con-tinuou~ mixing of formative components (a) to (d) and optionally (e) and~or (f3, reacting the mixture in an extruder or on a ~upport belt a$ from 60 to 250C, preferably at from 70 to 150C, and then granulating the resulting TPUs (A). It may be advantageou3 to heat the resulting TPU (A) at ~rom 80 to 120C, preferably at from 100 to llODC, for a period of from 1 to 24 hour~ before further processing into the TPU/PES molding materials according to the present invention.
The TPUs (A) are, as mentioned, preferably prepared by the belt technique. To this end, the forma-tive components (a) to (d) and optionally (e) andJor (f) are continuously mixed with the aid of a mixing head at above the melting point of formative components (a) to (c). Tho reaction mixture i8 brought out onto a support, preferably a conveyor belt, for example a metal belt, and is pa~sed at 1-20 m/min, preferably 4-10 m/min, through a hot zone from 1 to 20 m, preferably from 3 to 10 m, in l~ngth. The temperature in the hot zone i~ 60-200C, preferably 80-180C. Depending on the dii30cyanate content of the reaction mixture, the reaction i8 con-trolled by cooling or heating in such a way that at least ~2~7~
~ O.Z. 0050/41133 90 ~ preferably at leas~ 98 %, of the i~ocyanate groups of the diisocyanatas react and the reaction mixtur~
solidifies at the chosen reaction temperature. Cwing to the free isocyanate gxoups in the solidified reaction product~ which based on the total weight are within the range from 0.05 to 1 ~ by weight, preferably from 0.1 to O.5 % by weight, the TPUs (A) obtained have a very low melt vi~c08ity or a high melt flow index.
B) Formative component (B) of the TPU/PES molding materialS according to the pre3ent invention is, as mentioned, an amoun~, based on 100 parts by weight of (A), (B) and (C), of from 5 to 65 parts by weight, preferably from 10 to 60 parts by weight, in particular 12 to 50 parts by weight~ of one or more thermoplastic polyester~ Polyester~ suikable for this purpose are described in the literature. They contain in the polycon-den~ate main chain at leaYt one aromatic ring derived from an aromatic dicarboxylic acid. The aromatic ring may also be substituted, for example by halogen, eg. chlorine or bromine, or/and by linear or branched alkyl, prefer-ably of from 1 to 4 carbon atoms, in particular of 1 or 2 carbon atoms,.eg. methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl or tert-butyl.
The polye~ters can be prepared by polyconden~a-tion of aromatic dicarboxylic acids or mixture~ ofaromatic and ali.phatic and/or cycloaliphatic dicarboxylic acids and the corresponding e~ter-forming derivatives, for example dicarboxylic anhydride~, monoester~ and/or die~ter~ having advantageou~ly not more than 4 carbon atomx in the alcohol moiety, with aliphatic dihydroxy compounds st elevated temperature~, for example at from 160 to ~60C, in the presence or absence of esterifica-tion cataly8t8~
The preferred aromatlc dicarboxylic acid~ axe the naphthalenedicarbo~ylic acids, isophthalic acid and in particular terephthalic acid or mixture3 of these dicarb-oxylic acid~. Ifmixture~ of aromatic and (cyclo~aliphatic ~ ~ 2 ~
- 12 - O.Z. 0050/41133 dicarboxylic ~cid~ are used, up to 10 mol % of the aromatic dicarbo~ylic acids may be replaced by aliphatic and/ox cycloaliphatic dicarboxylic acids of advantage-ously 4-14 carbon atoms, eg. succinic, adipic, azelaic, sebacic or dodecanedioic acid and/or cyclohexanedicar-boxylic acid.
The p_eferred aliphatic dihydroxy compounds are alkanediols of from 2 to 6 carbon atom~ and cycloalkane-diols of from 5 to 7 carbon atQms. Specific examples of preferred aliphatic dihydroxy compoundæ are 1,2-ethane-diol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol and ~ cyclohexanediol and mixture~ of at least two of ~aid diols.
Particularly suitable PES'~ (B) are ~pecifically tne polyalkylene terephthalate~ of alkanediol~ of from 2 to 6 carbon atom~, 80 that polyethylene ~erephthalate and in particular polybutylene terephthalate are preferred.
The relative viscosity of the PES'~ (B) i~ in general within the range from 1.2 to 1.8, measured in a 0.5 ~ ~trength by weight solution in l:l wJw phenol/o-dichlorobenzene at 25C.
C) The TPU/PES molding material~ according to the present invention contain one or more graft rubber~ (C) based on a polybutadiene (Cl) or polyacrylate (C2) or a mixture of graft rubber~ based on (C1) and (C2) a~ an additional formative component for Lmproving the toush-ness, in particular the low-temperature Lmpact toughness, and the proces~ibility. A8 mentioned, the proportion of graft rubber (C) is, based on 100 parts by weight of the molding ma~2rial~ consisting of (A), (~) and (C), from 5 to 30 parts by weight, preferably from-5 to 20 part~ by weight, in particular from 10 to 20 part by weiyht.
Suitable graft rubber~ based on polybutadiene (Cl) axe compo~ed of a grafting base (Cll) which advan-tageously consi~ts of a polybutadiene, a polyisoprene, abutadiene-styren~ copolymer or 8 copolymer of ~tyrene or an alkylstyrene, eg. ~-methyl~tyrene, and con~ugated 2 ~ 2 ~ 7 - 13 - O.Z. 0~50/41133 dienes (high impact polystyrenes), and a graft (C12) prepared by polymerization of styrene, alkyl~tyrene, eg.
~-methylstyrenQ, acrylonitxile, alkyl acrylate or meth-acrylate, haYing from 1 to 8 carbon atoms in the alkyl 5moiety, preferably methyl (meth)acrylate, or vinyl acetate or by copol~merization of at least two of said monomers, eg. styrene and/or acrylonitrile and/or (meth)-acrylic e ters. Graft rubber~ of the type mentioned (Cl) are described for example in DE-A-16 ~4 173 (US-A-3 564 077) and DE-A-23 48 377 (US-A-3 919 353). It is also possible to use ABS polymer~ as de~cribed for e~ample in DE-A-20 35 390 (US-A-3 644 574) and in DE-A-22 48 242 (GB-A-l 409 275).
Preference i8 given to u~ing graft rubbers based 15on polybutadiene (Cl) and composed of Cll) ~0~90 ~ by weight, preferably 65-90 % by weight, in particular 75-85 % by weight, based on the weight of (Cll) and (C12), of a butadiene polymer containing at least 50 % by weight, preferably at least 70 ~ by weight, based on (Cll), of butadiene radical~ as grafting base and C12) 10-40 % by weight, preferably 10-35 ~ by weight, in particular 15-25 % by weight, based on the weight of (Cll) and ~C12), cf a graft or ~heath prepared by graft polymerization of an alkyl acrylate or meth-acrylate or graft copolymerization of a mixture consi3ting o~
10-35 ~ by weight, preferably 20-35 % by w~ight, ba~ed on th~ weight of the mixture, of acrylonitrile and 65-90 % by weight, preferably 65-80 % by weight, ba~ed on the weight of the mixture, of styrene or by graft copolymerization of th~ aforementioned acrylo-nitxil~-~tyrene mixture with at least one alkyl acrylate and/or methacrylate, the alkyl (meth)ac~rlates being mon~e~ters of acrylic or methacryiic acid with alcohol~ which hav~
- 14 - O.Z. 0050/41133 from 1 to 8 carbon atom~ and may contain further functional groups, eg. ether group~ or praferably epoxy or hydroxyl groups.
The grafting base (Cll) advantageously contains, 5as mentioned above, at lea~t 50 % by weight, based on (C11) r of butadiene radical~, in which case the preferr~d grafting base consists of pure polybutadiene. If the grafting base con~ists of a polybutadiene copolymer, the re~idues of othsr ethylenically un aturated monomer~
10present therein are advantageou~ly: styrene, acrylo-nitrile and ac~ylate or methacrylate radical~ of alkyl (meth~2crylates containing from 1 to 4 carbon atoms in the alkyl moiety, eg. methyl (meth)acrylate or ethyl (meth)acrylate. The grafting ba~e ~C11) preferably ha~ a 15gel content of from 70 % by weight, measured in toluene.
The polybutadiene-ba~ed graft rubber~ (Cl) have a median particle diameter d50 of from 0.05 to 0.6 ~m, preferably of from 0.08 to 0.5 ~m, and exhibit a degree of grafting G of from 0.15 to 0.55, preferably of from 200.2 to 0.4. The degree of grafting G indicate~ the weight ratio of grafted-on monomer to the gxafting base and i~
dimen~ionless. The median particle diameter d50 i~ that diameter which .i8 less than the diameter posses~ed by 50 % by weight of the particles and greater than the 25diameter pos~essed by 50 % by weight of the particles. It can ba determined by mean~ of ultracentrifuge mea~ure-mQnts (W. Scholtan, H. Lange, Kolloid. Z. and Z. Polym~re 25Q (1972~, 782-796) or by mean~ of electron microscopy and 8ub8equent particle counting (G. ~mpf, H. Schuster, 30Angew. Makromolekulare Chemie 14 (1970), 111-129) or by means of light scattering measurements.
Since, as wlll be known, the grafting monomer~
(C12) are not completely gxafted onto the grsfting base (Cll), the polybutadiene-based graft rubber~ (Cl) u~able 35according to the present invention a}~o contain homopoly-mer~ and po8Bibly copolymer~ of the grafting mono~ers (C12) as well as th~ actually grafted polymars.
~ ~ 2 ~
- 15 O.z. 0~50/41133 C2) Suitabl~ graft rubbers ba ed on polyacrylate~
(C2) are compo~ed of C21) a grafting base consisting of an acrylate rubber having a glas~ transition temperature of below -20C and C22) a graft prepared by graft polymerization of at least one polym~rizable ethylenically unsatura-ted monomer whose homopolymer or copolymers formed in the ab~ence of ~C21) would have a glass tran~ition temperature of above 25C.
Preferred grafting monomer~ for forming ths graft (C22) are ~tyrene, alkyl~tyrene, eg. ~-methyl3tyrene, acrylonitrile, alkyl acrylate~ or methacrylates, eg.
methyl methacrylate, and mixtures of at least two of ~aid monomer~. Preferred grafting monomer mixtures are tho e between styrene and acrylonitrile in a weight ratio of from 90.10 to 50:50.
The polyacrylate-based graft rubber~ [C2) con~ist advantageou31y of C21~ 2S-98 % by weight, preferably 50-90 % by weight, based on the total weight of (C2), of (C21) and C22) 2-75 % by weight, preferably 10-50 % by weight, based on the total weight of (C2), of ~C22).
The acrylate rubber~ (C21) which come into consideration Eor use as grafting bases are preferably polymers of alkyl acrylate3 which may contain up to 50 %
by weight, ba3ed on the total weight, of units of other polymerizable, ethylenically unsaturated monomer~ as copolymerized units. If the acrylat2 rubbers used as grafting base (C21) in turn are already graft polymer~
having a diene rubber core, the diene rubber coro i8 not included in the calculation o~ the af orementioned per-centage. The preferred polymerizable alkyl acrylates include those having from 1 to 8 carbo~ atom3 in the alkyl moiety, eg~ methyl, ethyl, butyl, octyl or 2-ethylhexyl acrylate. It i8 al80 po3~ible to u~e ~, q~
- 16 - o.z. 0050/41133 haloalkyl acrylate~, preferably halo-Cl-C~-alkyl acry-lates, ~g. chloro~thyl acrylate, and arylalkyl acrylate~, eg. benzyl or phenylethyl a~rylate. The alkyl acrylates mentioned can be used individually or in the form of 5 mixturPs.
The acrylate rubbers (C21) may be uncrosslinked, crosslinked or preferably partially cros~linked.
The cros31inking may be brought about by copoly-merizing the alkyl acrylate~ with suitable monomer~ which have more than one copolymerizable double bond. Example~
of uch cros31inking monomers are carboxylic ester~
prepared from olefinically unsaturated monocarboxylic acids of from 3 to 8 carbon atoms and olefinically un~aturated monohydric alcohol~ of from 3 to 12 carbon atom~ or saturat2d at least dihydric, preferably di-hydric, trihydric or tetrahydric, alcohol~ of from 2 to 20 carbon atoms, eg. allyl methacrylate or an alkylene glycol di(meth)acrylate. It i~ al o possible to u~e polyunsaturated heterocyclic compounds, ~uch a~ trivinyl or triallyl cyanurate or i~ocyanurate, tri~acryloyl-~-triazines, polyfunctional vinyl compounds, eg. di- and trivinylbenzene a~d al50 triallyl phosphater dicyclodi-hydropentadienyl acrylate or/and diallyl phthalate.
It i~ pelrticularly advantageous and hence prefer-able to use butanediol diacrylate, dicy~lopentadienyl acrylate and butadiene.
The amount of cro~slinkin~ monomer i8 preferably from 0.02 to 10 # by weight, in particular from 0.05 to 5 %
by weight,ba~ed on the weight of the grafting ba~e (C21).
If cyclic cro~slinking monomers having at lea8t hree ethylenically un~aturated groups are u~ed, it i8 advantageous to limit their amount to 1 % by weight of the qrafting ba~a (C21).
Other suita~le polymerizabla ethylenically un~aturated monomer~ which may be used for preparing the grafting bas~ ~21) beside~ alkyl acrylats~ are for example acrylonitrile, styrene, ~-mathylstyrene, J
- 17 - O.Z. 0050~41133 acrylamldes and vinyl Cl-C6-alkyl ether~.
The acrylate rubberR preferably used a~ grafting base (C21) are emulsion polymers which have a gel content of 60 % by w~ight, meaRured at 25C in dimethylformamide ~M. ~offmann, H. Rromer, R. Kuhn, Polymeranalytik I and II, Georg-Thieme-Verlag Stuttgart 1977).
A grafting base (C21) may alRo be acrylate rubber with a core compri~ing a diene rubber formed from one or more conjugated diene~, such as polybutadiene, or a copolymer of a conjugated diene with an ethylenically unsaturat~d monomer, such as ~tyrene and/or acrylo nitrile.
The polydiene cors content of the grafting base (C21) may range from 0.1 to 50 % by weight, preferably from 10 to 40 % by weight, based on (C21). Her8 the grafting ba3e (C21) and the graft or 3heath may each be independently of the other uncrocslinked or partially or compl~tely crosslinked.
Par~icularly preferred grafting ba~e~ (C21) for polyacrylate-ba~ed graft rubbers (C2) are thus: alkyl acrylate homopolymers and copolymers without a core of diene rubber and alkyl acrylate homopolymers and copoly-mers with a core of diene rubber.
The graft yield, ie. the ratio of the weight of grafted-on monomer (or the weight of the graft ~heath) to the weight of the grafting monomer~ used, iB in general from 20 to 80 %, preferably from 40 to 80 ~. The graft yiald is det~rmined a~ de~cribed by M. ~offmann, H. Kromer and R. Kuhn in Polymeranalytik, volume 1, &eorg-Thieme-Verlag Stuttgart 1977.
Graft rubbers ~C) based on polyacrylate~ (C.2) which are usable according to the pre~ent invention are dsscribed for example in DE-~-24 44 584 (US-A-4 022 748) and DE-A-27 26 256 (US-A-4 096 202).
Polyacrylat~-ba~ed graft rubbers (C2) of thi~
kind can al~o be obtained by grafting 2-20 % by weight, pr~erably 2-15 % by weight, ba~ed on 2 ~ 2 ~
~ o.Z. 0050/41133 the weight of (C2)~ of a grafting monomer s~lected from the group con~i~ting of the alkyl acrylate~, alkyl methacrylate~ having from 1 to 8 carbon atoms in the alkyl moiety, styrene, ~-methylstyrene, acrylonitrile and S vinyl acetate and mix~ures of at least two grafting monomer~ onto 80-98 % by weight, preferably 85-g8 % by weight, ba~ed on th~ weight of (C2), of a completely broken, aqueous latex of the grafting base (C21) in the absence of a suspending aid. The re~ulting pulverulent graft rubber (C2) may then be dried and homogenized in the desired ratio with the forma~ive component~ (A) and (B) by the action of shear-ing force in ~uch a way that ths median particle ~ize d50 of (C2) in a TPU/PES molding material according to the present invention i8 from 0.05 to 3 ~m, preferably from 0.1 to 2 ~m, in particular from 0.2 to 1 ~m.
The expression ~in the absence of a ~u~pending aid" indicates for the purposes of the pre~ent invention the absence of substances which, by quality and quantity, are capsble of Yu~pending the aforementioned grafting monomers in the aqueoua phasa. However, thi~ definition does not rule out the presence of substance~ which may have had a ~uspending effect for example in the prepara-tion of a grafted grafting base (C21). In such case~ the coagulant or precipitant used for breaking the latex of the grafting base (C21) must be added in an amount which outweighs the 3uspendiny effect of ~ubstances used for foxming the grafted grafting base (C21); that i~t care must be .taken to en~ure that the grafting monomar~ for forming the graft do not form stable emul~ions in the aqueous phase.
The grafting ba~e (C21) may al80 compri~e an acrylate rubbar in the form of an aqueous emulsion (latex) wher~ the latex particles contain as copolymer-ized units 1 to 20 ~ by weight, prefsrably from 1 to 10 %
by w~isht, based on-(C21), o~ monomers previously graft ed-on in aquoous emulsion, prefer~bly alkyl (meth)acryla-~, 7 ~ rj - lg - O.Z. 0050/41133 te~r styrene, ~-methyl~tyren~, acrylonitrile and/or vinyl acetata, which in the form of their homopolymer~ or copolymer3 would have a gla~s transition temperature of O~C.
Such grafting base~ (C21) are obtained for example by emulsion graft polymerization. Alternatively, the acrylate rubbers can be prepared by solution or bulk polymerization, the grafting monomers can be gra~ted on, and the resulting rubber~ can then be converted into an aqueou3 emulsion suitable for further graft polymeriza tion processes.
Suitable grafting bases (C21) for polyacrylate-based graft rubber~ prepared by thi~ particular embodi-ment are thus not only the above-de~cribed grafting base~
but alco graft polymer~ prepared in aqueou~ emul ion from acrylate polymers and copolymers which may contain a core of diene rubber and ethylenically un~aturated polymer-izable monomers.
The graft rubbers based on a polybutadiene ~Cl) or on a graft acrylate (C2) which are usable according to the present invention for impact modification can be used alon~ or as mixture~. It i~ also pos3ible to use mixture~
of graft rubbers based on (C1) and (C2).
The impact modified thermopla~tic TPU/PES molding matarial~ according to the present in~ention may in addition to th~ essential components (A), (B) and (C) optionally also contain fibrous and/or particulate fillers (D) and~or assi~tant~ ~E).
D) The proportion of filler (D) i8 customarily from 0 to 60 % by w~ight, preferably from 2 to 50 % by weight, in particular from 5 to 30 % by weight, based on the total weight of components (A) to (C).
Suitable particulate filler~ are for example:
organic fillers, ~uch as. carbon black, chlorinated p~lyethylene~ and melamine, and inorganic fillers such a3 wollastonite, calcium carbonate, magnesium carbonate, amorphous silica, calcium ~ilicats, calcium metasilicatQ, ~ ~ 2 f- 7 3 - 20 - O.~. 0050/41133 quartz powder, talc, kaolin, mica, feld~par, gla~
Rph~re~, 8ilicon nitride, boron nitride and mixture~
thereof.
Particularly ~uitabl~ reinforcing fillars which are therefore preferred are fiber~, for example carbon fibers and in particular gla3s fibers, with or without an adhe~ion promoting or/and ~ize finish. Suitable gla~s fibars, which are al80 for example in the form of glas~
weaves, mats, w~bs and~or preferably gla~s fil~ment roving~ or chopped glas~ filament formed from low-alkali E-glasses from 5 to 200 ~m, preferably from 6 to 15 ~m, in diameterr generally have a mean fiber length of from O.05 to 1 mm, preferably from 0.1 to 0.5 mm, after incorporation into the TPU/PES molding materials.
Of the aforementioned parti~ulatQ or fibrous reinforcing filler~, gla 8 fiber~ in particular are advantageous, in particular when a high heat resiRtanca or very high Rtiffnes~ i~ required.
E) A~ mentioned, the TPU/PES molding materials according to the present invention may also contain aq~istant~ (E). The assi~tant~ can be identical to the customary aids (c) or additive~ (f) used for preparing TPUs and therefore already be present in the TPU (A). The proportion of a~ tant (E) i~ in general from 0 to lO ~
by weight, preferably from 0 to 5 % by weight, based on the total weight of formative components (A) to (C). Such a~ tants are for QXample: nucleating agents, anti-oxidants, stabilizers, lubricantq, damolding agen~ and dyes.
The nucleating agent used can be for example talc, calcium fluoride, ~odium phenylphosphinate, alumi-num oxide or ~inely-divided polytetra~luoroethylene in an amount of up to 5 % by weight, based on the weight of formative component~ (A) to (C).
Suitable antioxidants and heat stabilizer~ which may be added to the TPU/~'ES molding materials are for example halides of metal~ of group I of the periodic - 21 - O.Z. 0050/41133 table, for example halides of sodium, pota~sium or lithium, alone or combined with copper(I) halideY, eg.
chloride~, bromide~ or iodides, terically hindered phenols, hydroquinones and also ~ubstituted compounds of these group~ and mixture~ thereof, which are preferably used in concentration~ of up to 1 ~ by weight, based on the weight of formative components (A) to (C).
Examples of W stabilizers are various sub~titu-ted resorcinol~, ~alicylates, benzotria~oles and benzo-phenones and also sterically hindered amines, which ingeneral are used in amount~ of up to 2.0 % by weight, ba~ed on the weight of fonmatiYe components (A) to (C).
Lubricants and demolding agents which in general are likewise added in amount~ of up to 1 % by weight based on the weight of formative component~ (A) to (C), are Cl2-C38-fatty acids, for example ~tearic acids, fatty alcohols, eg. stearyl alcohol, fatty acid esters or amides, eg. ~tearic e~ter~ and ~tearamides, and al80 the fatty acid esters of pentaarythritol and montan e~ter waxe~.
It i8 also pos~ible to add organic dyQs, eg.
nigro~ine, and piçments, eg. titanium dioxide, cadmium sulfide, cadmium ulfide selenide, phthalocyanine~, ultramarine blue or carbon black, in amounts of for example up to S % by weight, ba~ed on formative compo-nents (A) to (C)-The impact modified thermoplAstic TPU/PES moldingmaterials accordlnq to the pre~ent invention can be prepared by any desired method for forming an essentially homogeneou~ composition from the TPU (A), the PES (B) and the graft rubber (C) and optlonally the fillers (D) and as~istant~ (E)~ For ax~mple, the formative component~ (A) to (C) and optionally (D) andJor (E) can be mixed at from 0 to 150C, pref2rably at from 15 to 30~C, and then m~lted, or the componentA csn be mixed directly in the melt. Alternatively, (A) can be mixed with (C) or (B) w~ith (C) and tha~e mixtures be incorporated into (B) or 2 ~ 2 ~
- 22 - O.Z. 0050/41133 (A) respecti~ely, in which ca~e (D) and/or (E) may already be present in one of the fQrmati~e components (A) to (C) or may be added subsequently.
The TPU/PES molding material~ according to the present invention ar~ prepared at from 190 to 250C, preferably from 210 to 240C, in the cour~e o a resi-dence time of from 0.5 to 10 minutas, preferably of from 0.5 to 3 minute~, in for example the fluant, ~oftened or preferably molten state of formative component~ (A) to (C), for examplQ by stirring, rolling, kneading or preferably extruding, using for example cu~tomary pla8ti-ca~ins apparatus, eg. Brabender or Banbury mLlls, kneader~ and extruders, preferably a twin-~crew ~truder or a mixing extruder for transfer molding.
In the mo~t con~enient and therefore preferable method of preparation, the TPU (A), the PES (B) and tha graft rubber (C~ are mixed with or without (D) andtor tE) and melted together at 190-250C, preferably in an extruder, the melt ha~ incorporated into it any component (D) and~or (E) not introduced earlier and i8 then cooled, and the resulting TPU~PES molding material i comminuted.
The TPU~PES molding materials obtained according to the pre~ent invention are ea~y to process into ~haped articles pos~essing good surface properties and L~proved impact toughness combined with high ~tiffness, in par-ticular at low temperatures, without separation into component~ (A) or (B) or (C) occurring in the melt or in the molding.
The TPU/PES molding materials are also suitable for the extrusion of ~heets, in particular thermoforming sheets.
EXAMPLES
Impact modified thermoplastic TPUJPES molding matarials according to the pre~ent invention are prepared using the following component~s A) Thermoplastic polyur~thane elastomers Al: TPU having a ~hore D hardness of 69 prepared by ~2~
- 23 - 0.2. 0050/41133 reaction of a mixture of 0.5 mol of 1,4-butansdiol polyadipate of molecular weight 2000 and 5.86 mol of 1,4~butanediol with 4,4~-diphenylmethane ~iisocyan-ate in an NCO:OH group ratio of 1 at 80-170 C by the belt technique.
A2: TPU having a Shore D hardnes~ of 74 prepared in the same way aQ Al except that he NCO:OH group ratio u~ed waQ 1 . 04.
A3: TPU having a Shore D hardnes~ of 64 prepared in the ~ame way a~ Al except that 3.87 mol of 1,4-butane-diol w~re used.
A4: r'PU having a Shore A hardne~ of 90 prepared in the same way a~ Al, except that 1.7 mol of 1,4-butane-diol were used.
A5: TPU having a Shore D hardness of 74 prepared by reacting a mixture of 0.5 mol of 1,4-butanediol/
ethylene glycol polyadipate having a 1,4-butane-diol:ethylene glycol molar ratio of 1:1 and a molecular weight of 2000 and 5.66 mol of 1,4-butane-diol with 4,4'-diphenyLmethane diisocyanate in an NCO:OH group ratio of 1.
The above-described TPUB A1 to A5 each contain, based on the alkanediol polyadipa~e weight, 1 % by weight of diisopropylphenylcarbodiimide a~ hydrolysis stabilizer.
A6~ TPU havinS~ a Shore D hardness of 64 prepared by reaction of a mixture of 1 mol of polytetramethylene glycol of molecular weight 1~00 and 3.87 mol of 1,4-butanediol wLth 4,4'-diphenylmethane diisocyanate in an NCOsOH group ratio of 1 at 90-170C by the belt technique.
B) Thermoplastic polye~ters Bl: Polyethylene terephthalats having a relative visco-sity of l.38 (measured on a 0.5 % strength by weight solution in 1~1 w/w phenol/o-dichlorobenzene).
B2: Polybutylene terephthalate haYing ~ relati~e vi~co-~ity of 1.4, measured in the ~ame way as Bl~
~ 7 ~t - 24 - o.z. 0050~41133 Cl) Graft rubbers based on polybutadiene ClI: Graft rubber having a grafting base (75 % by weight) of polybutadiene and a graft (2s % by weight) of a copolymer of styrene and acrylonitrile in a weight ratio of 75:25, prepared by emulsion polymerization in a conventional manner. Th~ median particle diameter d50, defined a~ the diameter which i8 respectively le~s than and yreater than the diameter posses~Qd by 50 % of the particle~, was 250 nm.
ClII: Graft rubber prepared in the ~ame way as ClI, except that the graft i8 a copolymer of ~-methyl-~tyren~ and acrylonitrile in a weight ratio of 75:25.
ClIII: Graft rubber having a grafting ba~e (70 % by weight) of polybutadiene and a two-stage graft (in total 30 % by weight), the 18t stage (10 % by weight) being poly~tyrene and the 2nd stage (20 %
by weight) being a copolymer of methyl methacry-late, n-butyl acrylate and glycidyl methacrylate in a weight ratio of from 89:10:1. The graft polymar, which was prepared by emulsion polymer-ization in a conventional manner, had a median particle diamster d50 of 240 ~m.
C2) Graft rubber based on polyacrylate C2I: Graft rubber having a grafting ba~e (75 % by weight) of a cro~slinked poly-n-butyl acrylate and a graft (25 % by weight) of a copolymer o~ styrene and acrylonitrile in a weight ratio of 75s25, prepared by emulsion polymerization in a conventional manner.
The graft rubbsr had a median particle diameter d~o of 210 ~m.
C2IIs Graft rubb~r having a gr~fting b~se (75 % by w~ight) comprising a poly-n-~utyl ac~ylate cro~slinked with butanediol diacrylate and a graft (25 % by weight) compo~ed of a copolymer of ~tyrene, acrylonitrile and tert-butyl acrylate in a weight ratio of 73~24:3. Th~ graft rubber, - ~5 - O.Z. 0050/41133 which wa~ prepared by emulsion polymerization in a conventional manner, had a median particle diameter d50 of 420 ~m.
D) Filler~
E-Gla~ fiber~ in the form of a roving or in the form of chopped fiber. The gla~s fiber diameter was 1 0 ,~
Preparation of the Lmpact modified thermoplastic TPU/PES
molding material~
1 O EXAMPLES 1 TO 3 0 ~ND
CO~D?~ATIVE EX~?LES I TO IV
To prepare the TPU/PES molding materials, com-ponents ~A), (B) and (C) ara intensively mixed at ~3C, the mixture is introduced into a twin-screw e~truder and melted at 230C, and the melt i~ homogenized for ~ min-ute~ and then extruded into a watar bath.
If E-gla~ fibers wera used, these were incor-porated into the homogenized malt in tha form of chopped fibers or rovings.
Following granulation and drying, the TPU/PES
molding materials were in~ection molded at 230C into test ~pecimens on which measurements were carried out, without further aftertreatment, of the notched impact strength according to ~erman Standard Specification DIN
53 453, the breaking exten~ion according to German Standard Spe~ific~tion DIN 53 455 and the modulu~ of elasticity accordLng to German Standard Specification DIN
53 457.
The identity and quantity of the TPUs (A), PES's (B) and graft rubbers (C1) and (C2) used and of any reinforcing filler~ (D) and the meehanical propertie~
measured on the test specimens are summarized below in Table~ I to IV.
.. ... .. .
~2li 7 L~;
- 26 - O. Z . 00~0/41133 cnC
3,X~ _ooo ooooo~ooU~oo ~ ~ ~O 0 ~ ~ ~ ~ ~D 1--C~ In ~0 U
c ~ ~ o ~ ~ ~ r~ ` ~ ~ ~ ~ ~o o~
Y~, o ~--~ O 0~ i ~i ~ o o Cl~ _ o ~ ~
.-~Z ~3 U~ o U~ C ~ ~ ~ C
~ ~ r~ o ~ ~ o u~ ~ ~ ~ I 1 O o 2 a~ ~ ~ ~ X ~ O ~ Ct~ O O O
________~
~-- I I I I _ _ _ _ _ _ _ _ _ _ _ ~, 3 ~ I I I o o o o C~ o o o o o o _~ ~ ~ ~ ~ ~ ~ eo ~ ~ c a~ a~ ~ ~ ~
V~
o o o o ~ o o ~o o o o o o~
--~ ~- ~ ~ ~--~ ~ ~ ~ u~ ~ ~ r~
oooo oo~oooo~ooo ~ .. ' o ~. ~ U
~U ~ ~ o _ U ~ 1-~2'i7~
- 27 - O . Z . 0050/41133 C~ **.
C ,~ ~q ~ O q~
~ C_ C ' C
L
~C~ O
~ ~, q_~8~ o o o C~ o H
_ _ _. _ _ _ _ _ _ _ ~-- _ _ _ _ _ " 3 ~
~ ~ L 0 ~ i~
_~~ ~ ~ ~ ~
c~ tS~ D
C L C ~ ~ 1 ~ t~7 1~
'2 ~L3 ~
Vl 01 _ ~ ~ ~9 _ ~ 3OOOO-D
C ~U~
L
q_ x_ _ _ _ _ a 2 v ~ 7 ~ ~
- 28 - O. Z .005ût~1133 _ V) a:l ~ ~ O O e~ o o o o ~ o O ~o ~o ~ ao ~c~ ~ a~ I`
, ~ ~ I~ o ~
.~ U~ O
_ o ~ ~ ~ O ~ C~' D ;r O
,~ ~ _ U~ C~U~
O ~ U~ O u~
~ t~ ~ Co ~--~C~ ~ ~ O ~ o, H
~.
~,~ o~ooooo~o . ~ ~-~ ~ 0 ~ ~ CD ~D In ~ C~
e v e O o o o o c: O o O
~ ~ ----~
~ o o o o o o o o o o c ~ ~' U~
n I~
~ ___~ "c 2 ~
- 29 - O. Z . 005~/41133 C Crl C C 1-- C
'EN
._ ~ ~ C C ~ ~ C
L
v Ct Ct Ct Ct g _ ~ ao ~ Cl~
_ ~ ~
~-- O ~ _ u) ~ ~ c et o o o o ~ C L ~
oJ _ _ _ _ _ , t~
~ ~ ~ r~ r~ ~ I~ ~
~ N 1~
y ut c ~ ~ ~ ~ a~
- ~
O t ~ ~ qS
IC--~ 3_. o o o o u c o~ c t~ t~
~._ C~
. t r~ ~ c~ O o ~ . C
Claims (12)
1. An impact modified thermoplastic polyurethane-polyester molding material containing, based on 100 parts by weight, A) from 30 to 90 parts by weight of at least one thermoplastic polyurethane elastomer (A), B) from 5 to 65 parts by weight of at least one ther-moplastic polyester (B) and C) from 5 to 30 parts by weight of at least one graft rubber (C) based on a C1) polybutadiene or C2) polyacrylate or a mixture of graft rubbers based on (C1) and (C2) and also, based on the total weight of (A) to (C), D) from 0 to 60 % by weight of at least one fibrous or particulate filler and E) from 0 to 10 % by weight of at least one assistant.
2. An impact modified thermoplastic polyurethane-polyester molding material consisting of A) from 30 to 90 parts by weight of at least one thermoplastic polyurethane elastomer (A), B) from 5 to 65 parts by weight of at least one ther-moplastic polyester (B) and C) from 5 to 30 parts by weight of at least one graft rubber (C) based on a C1) polybutadiene or C2) polyacrylate or a mixture of graft rubbers based on (C1) and (C2), the proportions by weight of (A) to (C) adding up to 100 parts by weight, and also, based on the total weight of (A) to (C), D) from 0 to 60 % by weight of at least one fibrous or particulate filler and E) from 0 to 10 % by weight of at least one assistant.
3. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1 or 2, wherein the thermoplastic polyurethane elastomer (A) is - 31 - O.Z. 0050/41133 prepared by reaction of a) an organic diisocyanate with b) a polyhydroxy compound having a molecular weight of from 500 to 8000 and c) a diol having a molecular weight of from 60 to 400 in an equivalence ratio of NCO groups of organic diiso-cyanate (a) to the total number of hydroxyl groups of components (b) and (c) of from 0.95:1.0 to 1.1:1Ø
4. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1 or 2, wherein the thermoplastic polyurethane elastomer (A) is prepared by reaction of a) an aromatic diisocyanate, preferably 4,4'-diphenyl-methane diisocyanate, with b) an essentially linear polyhydroxy compound, prefer-ably a polyalkylene glycol polyadipate, having from 2 to 6 carbon atoms in the alkylene moiety and a molecular weight of from 500 to 6000 or a hydroxyl-containing polytetrahydrofuran having a molecular weight of from 500 to 8000, and c) 1,4-butanediol.
5. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1 or 2, wherein the thermoplastic polyurethane elastomer (A) has a hardness within the range from Shore A 75 to Shore D 75 and is prepared by the belt technique.
6. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1 or 2, wherein the thermoplastic polyester (B) has a relative viscosity within the range from 1.2 to 1.8, measured in a 0.5 % strength by weight solution in 1:1 w/w phenol/o-dichlorobenzene at 25°C, and is prepared by polyconden-sation of an aromatic dicarboxylic acid with an alkane-diol having 2 to 6 carbon atoms in the alkylene moiety.
7. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1 or 2, wherein the thermoplastic polyester (B) is polyethylene - 32 - O.Z. 0050/41133 terephthalate or preferably polybutylene terephthalate.
8. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1 or 2, wherein the graft rubber (C) based on a polybutadiene (C1) is composed of C11) a grafting base consisting of a polybutadiene, a polyisoprene, a butadiene-styrene copolymer or a copolymer of styrene or alkylstyrene and a con-jugated diene, and C12) a graft prepared by polymerization of styrene, alkylstyrene, acrylonitrile, alkyl methacrylate or acrylate or vinyl acetate or by copolymerization of at least two of said monomers.
9. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1 or 2, wherein the graft rubber (C) based on a polybutadiene (C1) is composed of C11) 60-90 % by weight, based on the weight of (C11) and (C12), of a polybutadiene as grafting base and C12) 10-40 % by weight, based on the weight of (C11) and (C12), of a graft prepared by polymerization of an alkyl acrylate or methacrylate or copolymerization of a mixture of acrylonitrile and styrene in a weight ratio of from 10:90 to 35:65.
10. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1 or 2, wherein the graft rubber (C) on the basis of a polyacry-late (C2) is composed of C21) a grafting base consisting of an acrylate rubber having a glass transition temperature of below -20°C
and C22) a graft prepared by polymerization of styrene, alkylstyrene, acrylonitrile, an alkyl acrylate or methacrylate or copolymerization of at least two of said monomers.
and C22) a graft prepared by polymerization of styrene, alkylstyrene, acrylonitrile, an alkyl acrylate or methacrylate or copolymerization of at least two of said monomers.
11. An impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1 or 2, - 33 - O.Z. 0050/41133 wherein the graft rubber (C) based on a polyacrylate (C2) is composed of C21) 25-98 % by weight, based on the weight of (C21) and (C22), of an acrylate rubber having a glass transi-tion temperature of below -20°C and C22) 2-75 % by weight, based on the weight of (C21) and (C22), of a graft prepared by polymerization of styrene, alkylstyrene, acrylonitrile or an alkyl acrylate or methacrylate or copolymerization of at least two of said monomers, preferably a mixture of styrene and acrylonitrile in a weight ratio of from 90:10 to 50:50.
12. A process for preparing an impact modified thermoplastic polyurethane-polyester molding material as claimed in claim 1 or 2, which comprises homogenizing components (A) to (C) and optionally (D) and/or (E) in a suitable mixing apparatus, preferably a twin-screw extruder, at 190-250°C for 0.5-10 minutes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3932359A DE3932359A1 (en) | 1989-09-28 | 1989-09-28 | IMPACT MODIFIED THERMOPLASTIC POLYURETHANE-POLYESTER MOLDING MATERIALS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DEP3932359.5 | 1989-09-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2024715A1 true CA2024715A1 (en) | 1991-03-29 |
Family
ID=6390367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002024715A Abandoned CA2024715A1 (en) | 1989-09-28 | 1990-09-06 | Impact modified thermoplastic polyurethane-polyester molding materials and preparation thereof |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5237000A (en) |
| EP (1) | EP0420016A3 (en) |
| JP (1) | JPH03131654A (en) |
| CA (1) | CA2024715A1 (en) |
| DE (1) | DE3932359A1 (en) |
| FI (1) | FI904687A0 (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4017571A1 (en) * | 1990-05-31 | 1991-12-05 | Bayer Ag | THERMOPLASTIC, FLEXIBLE POLYURETHANE COMPOSITIONS AND METHOD FOR THEIR PRODUCTION |
| US5620696A (en) * | 1992-02-26 | 1997-04-15 | Fermenta Animal Health Company | Polyurethane insecticidal ear tag and method of use |
| EP0618265A3 (en) * | 1993-03-29 | 1995-03-01 | Bayer Ag | Flame retardant thermoplastic moulding compositions with improved thermal stability, flow behaviour and thoughness. |
| JPH09503794A (en) * | 1993-06-25 | 1997-04-15 | リファック インターナショナル リミテッド | Thermoplastic urethane elastomer alloy |
| DE19528191A1 (en) * | 1995-08-01 | 1997-02-06 | Basf Ag | Impact-resistant thermoplastic molding compounds |
| GB2306909B (en) * | 1995-11-09 | 2000-03-29 | Panel Holdings Ltd | Moulded articles their production and use |
| CA2217904A1 (en) * | 1996-10-31 | 1998-04-30 | Donald P. Nardi | A thermoplastic article having low gloss and a composition for its preparation |
| US5731380A (en) * | 1997-04-11 | 1998-03-24 | Hoechst Celanese Corporation | Elastomeric compositions |
| US5932353A (en) * | 1997-12-19 | 1999-08-03 | Basf Corporation | Rigid thermoplastic article having soft covering |
| DE10019893C2 (en) * | 2000-04-20 | 2003-05-28 | 3M Espe Ag | Device in the form of a dynamic mixer or a cartridge front and their use |
| US20040167277A1 (en) * | 2003-02-26 | 2004-08-26 | Chang Moh-Ching Oliver | Thermoplastic molding compositions having good properties |
| ATE297249T1 (en) | 2003-08-14 | 2005-06-15 | 3M Espe Ag | MIXING ELEMENT FOR A MULTI-COMPONENT PASTE MIXER, AND MIXER WITH THIS MIXING ELEMENT |
| US7041741B2 (en) * | 2004-01-08 | 2006-05-09 | Teknor Apex Company | Toughened polymer compositions |
| US7557162B2 (en) * | 2004-01-08 | 2009-07-07 | Teknor Apex Company | Toughened polymer compositions |
| EP1561880A1 (en) * | 2004-02-09 | 2005-08-10 | Forbo-Giubiasco Sa | Flat covering material comprising filled thermoplastic polyurethane elastomer |
| EP1588779A1 (en) * | 2004-04-19 | 2005-10-26 | 3M Espe AG | Dynamic mixer |
| EP1640060A1 (en) | 2004-09-22 | 2006-03-29 | 3M Espe Ag | Mixer for multi-component pastes, kit, and method of mixing paste components |
| US8322909B2 (en) | 2004-09-22 | 2012-12-04 | 3M Deutschland Gmbh | Mixer for multi-component pastes, kit, and method of mixing paste components |
| AU2006226818B2 (en) * | 2005-03-24 | 2011-05-12 | Medtronic, Inc. | Modification of thermoplastic polymers |
| WO2010031792A1 (en) | 2008-09-18 | 2010-03-25 | Basf Se | Polyurethanes based on polyester diols with improved crystallization behavior |
| WO2013101626A1 (en) * | 2011-12-30 | 2013-07-04 | Ticona Llc | Molded polymer articles for use in low temperatures having a low rigidity factor |
| WO2013169351A1 (en) * | 2012-05-09 | 2013-11-14 | Ticona Llc | Polymer composition and articles for use in low temperature environments that are wear resistant |
| EP2810986B1 (en) * | 2013-06-05 | 2017-04-19 | Carl Freudenberg KG | Thermoplastic elastomer compound and its use |
| CN106928693B (en) * | 2015-12-31 | 2020-04-10 | 万华化学集团股份有限公司 | Low-gloss thermoplastic polyurethane composition and preparation method and application thereof |
| WO2017144502A1 (en) * | 2016-02-22 | 2017-08-31 | Basf Se | Nucleating agent for compact thermoplastic polyurethanes |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1694173A1 (en) * | 1967-07-22 | 1971-06-09 | Hoechst Ag | Thermoplastic polyester molding compounds |
| IT963692B (en) * | 1972-08-03 | 1974-01-21 | Montedison Spa | SHOCK-RESISTANT POLYESTERS |
| US4279801A (en) * | 1975-07-02 | 1981-07-21 | General Electric Company | Thermoplastic molding compositions of a linear polyester and a poly(ester urethane) |
| DE2646647A1 (en) * | 1975-10-20 | 1977-04-21 | Mobay Chemical Corp | POLYBUTYLENE TEREPHTHALATE / POLYURETHANE MIXTURES |
| CA1098239A (en) * | 1977-05-05 | 1981-03-24 | Shell Canada Limited | Compositions containing hydrogenated block copolymers and engineering thermoplastic resins |
| CA1111984A (en) * | 1978-04-13 | 1981-11-03 | Herbert L. Heiss | Polybutylene terephthalate/thermoplastic polyurethane molding compositions |
| US4179479A (en) * | 1978-04-20 | 1979-12-18 | Mobay Chemical Corporation | Thermoplastic polyurethane blends containing a processing aid |
| DE3810078A1 (en) * | 1988-03-25 | 1989-10-05 | Bayer Ag | THERMOPLASTIC POLYMER BLEND AND METHOD FOR THE PRODUCTION THEREOF |
| DE3827568A1 (en) * | 1988-08-13 | 1990-02-15 | Basf Ag | KAELTESCHLAGZAEHE THERMOPLASTIC POLYESTER MOLDING |
| DE3905008A1 (en) * | 1989-02-18 | 1990-08-23 | Basf Ag | MOLDS OF THERMOPLASTIC POLYURETHANE |
-
1989
- 1989-09-28 DE DE3932359A patent/DE3932359A1/en not_active Withdrawn
-
1990
- 1990-09-06 CA CA002024715A patent/CA2024715A1/en not_active Abandoned
- 1990-09-07 US US07/578,687 patent/US5237000A/en not_active Expired - Fee Related
- 1990-09-19 EP EP19900117974 patent/EP0420016A3/en not_active Withdrawn
- 1990-09-24 FI FI904687A patent/FI904687A0/en not_active IP Right Cessation
- 1990-09-28 JP JP2257604A patent/JPH03131654A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE3932359A1 (en) | 1991-04-11 |
| JPH03131654A (en) | 1991-06-05 |
| EP0420016A3 (en) | 1991-05-15 |
| EP0420016A2 (en) | 1991-04-03 |
| US5237000A (en) | 1993-08-17 |
| FI904687A0 (en) | 1990-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2024715A1 (en) | Impact modified thermoplastic polyurethane-polyester molding materials and preparation thereof | |
| US5519094A (en) | Fiber-reinforced thermoplastic molding compositions using a modified thermoplastic polyurethane | |
| KR100203020B1 (en) | Fiber-reinforced thermoplastic molding compositions | |
| US5258445A (en) | Fiber-reinforced thermoplastic molding compositions using a copolyester | |
| EP0265790A2 (en) | Thermoplastic molding blends of polycarbonates and polyurethanes | |
| US5260375A (en) | Thermoplastic moldings materials of improved green strength and low-temperature toughness based on a thermoplastics polyurethane copolymer mixture, preparation thereof and use thereof | |
| US5859146A (en) | Impact-resistant thermoplastic molding materials | |
| US5539054A (en) | Polyurethane elastomer blends | |
| US5216062A (en) | Thermoplastic polyurethane molding composition | |
| EP0396245A2 (en) | Thermoplastic polyblends of aromatic polycarbonates and thermoplastic polyurethanes | |
| US5785916A (en) | Process for making molded thermoplastic polyurethane articles exhibiting improved UV and heat resistance | |
| US5202385A (en) | Polymer mixture having aromatic polycarbonate, polyester and thermoplastic elastomer, article formed therefrom | |
| CA2136125A1 (en) | Heat-stable, highly resilient, abrasion-resistant polyurethane/polyester three-block polyadducts, their preparation and their use | |
| DE4126499A1 (en) | Flatting agents for thermoplastic polyurethane elastomers - comprise non-polar homo- or co-polyolefin(s) which are incompatible with the elastomers and provide improved anti-blocking properties | |
| US5162461A (en) | Thermoplastic polyblends of aromatic polycarbonates and thermoplastic polyurethanes | |
| DE3932360A1 (en) | IMPACT MODIFIED THERMOPLASTIC POLYURETHANE-POLYESTER MOLDING MATERIALS, METHOD FOR THEIR PRODUCTION AND THEIR USE | |
| US5639826A (en) | Thermoplastic molding materials based on polycarbonates thermoplastic polyurethanes and styrene copolymers | |
| EP0387590B1 (en) | Impact-resistant modified thermoplastic polyurethane moulding compositions, process for their preparation and their use | |
| EP0440442A1 (en) | Polymer blend compositions containing a styrenic copolymer, an acetal polymer and a thermoplastic polyester or polycarbonate resin ingredient | |
| JP4545269B2 (en) | Urethane composition | |
| EP0769527A1 (en) | Thermoplastic polyurethane compositions exhibiting improved UV and heat resistance | |
| JPH032253A (en) | Thermoplastic resin composition | |
| JPH07100763B2 (en) | Thermoplastic resin composition | |
| JPH04213349A (en) | Composition comprising blend of synthetic copolymer, polyacetal, and thermoplastic polyurethane or elastomeric copolyester | |
| CA2134244A1 (en) | Fiber-reinforced thermoplastic molding compositions using a modified thermoplastic polyurethane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |