CA1240449A - Process for making low crystallinity polyolefins - Google Patents

Abstract

Process for Making Low Crystallinity Polyolefins Abstract of the Disclosure Disclosed is a solution polymerization process for obtaining high yields of high molecular weight, low crystal-linity polymers of propylene and higher 1-olefins at low catalyst levels. The polymerization is carried out using a catalyst system containing a soluble transition metal compon-ent derived from magnesium carboxylate and a salt of titanium, zirconium or hafnium, and specified alkyl aluminum halide activators.

Description

This invention relates to the polymerization of olefins and particularly relates to the preparation of low crystal-linity polyolefins using a Ziegler-Natta catalyst system~
It is well known in the art that Ziegler-Natta catalyst systems, such as those obtained by combining a transition metal compound of group IVB of the Periodic Table with an activator that is an organometallic compound of ~roup IIIA of the Table, are effective catalyst syste~s for polymerization of l-olefins . Catalyst systems containing TiCl~ or TiC13 and aluminum alkyl or aluminum alkyl chloride activators are known to provide mixtures of crystalline and low crystallinity polypropylene~ However, low crystallinity polyolefins having levels of crystallinity on the order of only 10 to 20~ are difficult to obtain using these catalysts, and high levels of catalysts are required to obtain satisfactory yields of polymer, thus necessitating special techniques in recovering the product to remove residual catalyst.
The use of TiC13 and TiC14-treated magnesium-chloride-supported catalyst components, or hydrocarb~n-insoluble reaction products of a tetravalent halogenatedtitanium compound and a magnesium alcoholate, with organo-aluminum compounds, to polymerize l-olefins, is also dis-closed in the art. Supported catalyst components of these types generally provide polyolefins having high crystallinity, on the order of 65% or more.
Further, it i5 known from U.S. Patent 3,933,934 to Bailly et al. khat atactic waxes can be produced with a Zle~ler-Natta ; catalyst sy~tem wherein the transltion metal component Ls formed by the reaction of metallic magnesium, an alkyl halide and a titanium compound and the activator is an organoaluminum compound. The magnesium based titanium compound used by Bailly et al. as the transition metal component of the cata-lyst is a hydrocarbon insoluble material which must be sepa-rately prepared and isolated before use in the polymerization.Also, due to the insoluble nature of the catalyst component, some residue accumulates in the resulting polymer, thus necessitating costly and labor intensive clean-up procedures to obtain polymers of good clarity, color and stability.
Recently, catalyst systems that are soluble in the reac-tion mediu~ have been described in the art. For exampLe, van den Berg in U.SO Patent 4,319,010 teaches using a catalyst obtained by mixing in the reaction solvent a titanium com-pound, a soluble magnesium salt or complex, and an organo-aluminum halide, to obtain high yields of high molecular ~eight crystalline homopolymers of ethylene at low catalyst levels. See also British publication 2,039,501 A which teaches using a catalyst system containing a magnesium halide which has been solubilized with an electron donor, a transi-tion metal compound and an organoaluminum compound in the con-tinuous polymerization of ethylene or mixtures of ethylene with small amounts of other alpha-ole-Eins in hydrocarbon solvents.
It would be desirable to produce high yields of low crystallinity polyolefins having high molecular weight with catalysts of the ~iegler-~atta type that are soluble in the reaction medium, and thereby avoid the disadvantages asso-ciated with use of the insoluble type.
According to the invention, there is provided a process for polymerizing a l-olefin containing at least 3 carbon atoms, in the presence of a catalyst of the Ziegler-Natta type at low catalyst levels, to produce polyolefins having a degree of crystallinity less than about 25%, in an inert liquid hydrocarbon diluent, the process being characterizecl in that the polymerization is carried out at a temperature ranging from about 25C to about 90C; the catdlyst mixture consists essentially of:

(a) the hydrocarbon-soluble reaction-product of (1) a hydrocarbon-soluble, halide free maynesium carboxylate and (2~ a hydrocarbon-soluble salt of a transition metal selected from the group consisting of tetravalent titanium, zirconium and hafnium, in an inert liquid hydrocarbon, and (b) an alkylaluminum halide activator having the general formula RnAlX3_n where R is a 1 to 18 carbon alkyl group and n is a number from 1.5 to 2.5;
the molar ratio of transition metal salt to magnesium carboxylate is 0.003 to 3; -the molar ratio of alkylaluminum halide activator to transition metal salt is at least 1; and the molar ratio of alkylaluminum halide activator to magnesium carboxylate is greater than 2.5.
The present invention also provides a process for the production of high molecular weight polyolefins having a degree of crystallinity less than about 25%, which process comprises polymerizing at least one l-olefin containing at least 3 carbon atoms or a mixture of at least one of said olefins with up to about 67 weight ~ of ethylene in an inert liquid hydrocarbon diluent at a temperature ranging from about 25C to about 9OC. in the presence of catalytic amount of a catalyst system consisting essentially of:
(a) a hydrocarbon soluble transi-tion metal component derived by contacting in an inert liquid hydrocarbon (1) a soluble, halide free rnagnesium-carboxylate having the general formula Mg(OOCR')2 where each R' is alike or different and is derived from a carboxylic acid containing at least 2 carbon a-tom~ wi-th

(2) a soluble salt of a transition met.al selected from the group consisting oE tetravalent titanium, zirconium and hafnium, and (b) an alkylalumi.num halide activator having the general formula RnAlX3 n where R is a 1 to 18 carbon alkyl g:roup and n is a number from 1.5 to 2.5.
the molar ratio of transition metal salt to magnesium carboxylate being 0.003 to 3, the molar ratio of alkylaluminum halide activator to transition metal salt being a-t least 1 and the molar ratio of alkylaluminum halide activator to magnesium carboxylate being greater than 2.5.
The transition metal component of the catalyst system used in the invention is a hydrocarbon soluble reaction product or complex formed by contacting (1) a hydrocarbon-soluble magnesium carboxylate with (2) a hydrocarbon-soluble salt of a transition metal of group IVB of the Periodic Table.
The magnesium carboxylates which provide hydrocarbon soluble reaction products or complexes are halide free and are soluble in hydrocarbon diluents that are used as solvents in solution polymerization reactions. Representative magnesium compounds have the general formula Mg(OOCR')2 where each R' is alike or diEferent and is derived from a carboxyl:ic ~cld containing at least 2 carbon atoms and preferably is an a.lkyl -3a-,. ~;, group containing from 5 to 17 carbon atoms. The preferred magneslum carboxylates are those derived from 2-methyl-,

3-methyl-, 2,2-dimethyl- and 2,2,4,4,- tetramethyl-pentanoic acids; 2-ethyl-, 2-methyl- and 3,5,5-trimethyl-hexanoic acids;
2-ethyl-2-methylbutyric acid, 2,3-dimethyl-2-isopropyl-butyric acid; 2,2-dimethyl- heptanoic acid; 2,2-dimethyl-octanoic acid;
2,2--dimethylnonanoic acid; decanoic acid; 2,2-dimethyl decanoic acid; undecanoic acid; 2,2-dimethyl-undecanoic acid; dodecanoic acid; 2,2-dimethyldodecanoic acid; tridecanoic acid;
2,2-dimethyltridecanoic acid; 2,2-dimethyl-pentadecanoic acid;
oleic acid, phenylacetic acid, 4-cyclo--3b-~ ' f~

hexylphenylacetic acid; alpha-cyclopentylphenylacetic acid;
3-cyclohexyl-3-cyclo- pentyl- and 3-phenylpropionic acids; 2-, 3- and 4-cyclohexyl- and phenyl-butyric acids; and 5-cyclohexyl- and phenyl- pentanoic acids. Mixtures o~ these acids can be used in the formation of the hydrocarbon-soluble magnesium carboxylates, as for example the naphthenic acids recovered as by-products of the refining of petroleum distil-lates. The most preferred acids are the monocarboxylic acids containing an alpha-quaternary carbon atom available commer-cially as the "Neo'~acids of Exxon Chemical Co. and the"Versatic"~acids of Shell Chemical Co., and particularly neodecanoic acid.
The magnesium carboxylates are readily prepared by heating essentially stoichiometric amounts o~ magnesium oxide or hydroxide and the desired carboxylic acid, preferably in a high boiling hydrocarbon diluent such as kerosene in order to azeotrope the water of reaction. The magnesium carboxylate can be recovered from the diluent, if desired, but preferably is diluted to the desired concentration and used as such.
The transition metal component of the catalyst system described in this invention is derived by contacting in a hydrocarbon diluent the magnesium carboxylate and a hydro-carbon soluble salt of a transition metal of group IVB of the Periodic Table. Tetravalent transition metal compounds havin~
the general formula Me(X4_n) (OR )n or Me(X4_m) (OOCR")~ where Me represents a titanium, zirconium or haf-nium atom; X represents a halogen atom, pre~erably chlorine;
R" represents an alkyl, preferably containing ~rom l to about 10 carbon atoms; and n and m represent ~hole numbers or frac-tions of any value rcrom O to 4 are preferred. The abovetransition metal compounds are well Xnown Ziegler-~atta catalyst components. Examples of particularly preferred transition metal compounds include titanium tetrachloride, butoxy titanium trichloride, titanium tetrabromicle and titanium tetraiodide. The most preEerred transition metal compound ls titanium tetrachloride.
The magnesium carboxylate and the transition metal com-pound are contacted in an inert liquid hydrocarbon diluent at ~J~

a relative concentration which will provide a molar ratio of transition metal salt to magnesium carboxylate in the range of 0.003:1 to 3:1, preferably in the range! of 0.01:1 to 2:1.
The contactinc~ can take place at any convenient temperature 5 such as 20C to 80C, and is preferably conducted at 50C to 60C Because no workup is required, the contacting can also occur in situ, i.e. by adding the magnesium salt and then the transition metal compound, as such or in solution, to a poly-merization vessel charged with diluent containing the alkyl aluminum halide activator. In the preferred procedure, separate solutions of the magnesium carboxylate and the trans-ition metal compound at suitable concentrations are prepared, and the solutions or portions of the solutions are combined to give a premix containing the transition metal component of the catalyst system in solution in a desired solvent.
The hydrocarbons used as solvents in the polymerization can be any liquid hydrocarbon or mixtures thereof. Represen-tative hydrocarbon solvents are the three carbon to twelve carbon aliphatic hydrocarbons, the five to twelve carbon cycloaliphatic hydrocarbons, the six to twelve carbon mono-cyclic aromatic hydrocarbons or ~heir halogenated derivatives and mixtures o~ any of these hydrocarbons. rrhe preferred hydrocarbon solvents are isobutane and hexane. Alternatively, in some embodiments, the l-olefin which is to be polymerized can be employed as the hydrocarbon solvent.
The alkyl aluminum halide activator which makes up the other compound o the catalyst system has the general formula RnAlX3_n, where R represents an alkyl containing 1 to 18 carbon atoms; X represents a halogen, preferably chlorine; and n represents a whole or a fraction o~ any value in the range of 1.5 to 2.5 and preferably in the range of 1.7 to 2.20 R
can be, for example, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, isoamyl, n-hexyl, n-heptyl or n-octyl. rrhe activator is used in ~uantities such that the molar ratio o~ the aluminum metal in the activa-tor to the transition metal is at least 1, preferably between 1 and abollt 500~, and more pre~erably be-tween about 10 and about 500. rrhe molar rati~ o~ aluminum to ma~nesium is greater than 2.5:1, preferably between about 3:1 and about 20:1, and more preferably between about 3.S:l and about ln:l.
The amount of catalyst employed in this invention is an amount sufficient to catalyze the polymerization of l-olefins containing at least 3 carbon atoms into low crystallinity homopolymers and copolymers. In general the amount of cata-lyst used will provide a concentration of transition metal during the polymerization reaction between about 0.02 and about 0~4 millimole per liter o~ hydrocarbon solvent.
Low crystallinity homopolymers are preferably prepared from the three carbon to twelve carbon l-olefins and more preferably from the three to eight carbon l-olefins, with propylene and l-butene being most preferred. Copolymers are prepared by polymerizing 2 or more monomers selected from the group of ethylene and three to twelve carbon l-olefins. In those copolymers which contain ethylene, ethylene should be present in an amount less than about 67 weight percent and preferably less than about 60 ~eight percent. The other monomers can be incorporated into copolymers in any ratio.
Representative of the low crystallinity copolymers advanta-geously produced are copolymers of ethylene and propylene, ethylene and l-butene and propylene and l-butene.
The polymerization is carried out in a conventional manner in the hydrocarbon solvent. The solution polymerization temperature is between about 25 and about 90C, preferably between 30 and 75~C. The polymerization is typically carried out at a pressure generally below 30 bars.
~ hen the polymeri~ation is carried out in the presence of more than one monomer, the monomers may be introduced into the reactor either as a constant composition mixture or the compo-sition of the mixture may be varied during the course of poly-merization.
The polymerization is quenched by conventional means such as by steam treatment or by venting and pouring out the reac-tion mixture. The polymeric product consists o~ solverlt-soluble polymer in solution in the diluenk and in some instances a small amount of solvent-insoluble polymer. The solvent-soluble fraction is conveniently recover~d ~rom the diluenk by conventional ~eans such as by eva~oratioll.

The polyole~ins produced in accordance with this invention generally contain less than 20 parts per million (ppm) by weight transition metal and, therefore, for most applications, do not require any further purification. The polyolefins are high molecular weight, low crystallinity polymers and contain less than about 25~ crystallinity as determined by X-ray diffraction or thermal analysis on the total product. The portion of the polymer which is soluble (measured in hexane at 60C) makes up at least 75% by weight of the total product.
The intrinsic viscosity (measured in decahydronaphthalene at 135C) of the soluble raction of the polymer is typically in the range of rom about 0.5 to about 1.8. It is possible to reduce the molecular weight of the polymer by employing con-ventional methods such as by adding hydrogen to the monomer 1~ prior to the monomer's introduction into the reaction vessel.
The polyolefins produced in accordance with this invention have a wide variety of uses, particularly in industrial appli-cations. Representative applications include use in aahe-sives, as viscosity index improvers, as impact modifiers, as wax modifiers, as non-volatile plasticizers and as replace-ments for plasticized polyvinyl chloride.
The best mode now contemplated of carrying out this in~en-tion is exemplified by the following working examples of pre-ferred specific embodiments. This invention is not limited to these specific examples.
The magnesium neodecanoate used in the examples is pre-pared by adding to an agitated mixture containing 64.1~ grams (1.10 moles) of magnesium hydroxide and 800 ml of kerosene ~Isopar H), 344.6 grams (2.0 moles~ of neodecanoic acid over a 1.5 hour period while heating to 115C. The mixture is gradually heated to reflux and maintained under reflux condi-tions until no more water is collected, ater which time the mixture is cooled to 100C, dilutea with additional Isopar H
and ~iltered, i~ necessary, to remove any insoluble material.
The mixture is next diluted to about 0.3 molar magne~ium neodeconate with hexane, analyzed and stored. This magnesiulll neodecanoate solution is used to prepare the premixes described in the examples by mixing, in the desired ratios, the magnesium neodecanoate solution with a 0.1 molar solution of titanium tetrachloride in hexane and diluting, if necessary, to a desired concentration.
Examples 1-3 -Examples 1-3 illustrate preferred embodiments of the preparation of low crystallinity polyprop~ylene with a cata]yst system which is the hydrocarbon soluble reaction product of magnesium neodecanoate and TiCl~ and varying proportions of an activator which is diethylaluminum chloride 5Et2AlCl).
In each example, 400 ml of hexane is placed in a 28 oz.
pop bottle containing a magnetic stirring bar and then sparged at 60C with an inert gas. Sufficient Et2AlCl as a 0.4 molar solution in hexane is added to the sparged diluent to produce the aluminum to magnesium ratio shown in Table 1.
Next, 10 ml of a premix 2.0 mmolar with respect to TiC14 and 10.0 mmolar with respect to magnesium neodecanoate is added.
The inert gas is sparged from the pop bottle using propyl-ene and the pressure of the propylene is adjusted to 40 psig.
The polymerization is continued at 60C for 3 houxs. The reaction product is filtered, the hexane evaporated from each fraction and the diluent-soluble polypropylene is recovered.
Table 1 provides further details for each example and polymer-ization data. In Table 1 and subsequent Tables, "yield, g"
refers to the total amount, in grams, of polymeric product recovered, "soluble" refers to the fraction of the total product which is soluble in the diluent at 60C, "Mileage"
refers to the grams of polymer produced per millimole of titanium "I.V." is the intrinsic viscosity measured at 135C
in decahydronaphthalene, and "Cryst ~" is the percent of the polymeric product which is crystalline, as determined by x-ray diffraction, unless otherwise specified.

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Examples 4-8 ___ Examples 4-8 exhibit preferred embodiments of the prepa-ration of low crystallinity polypropylene using a catalyst system which is a premix formed by contacting varied propor-tions of a hexane solution of magnesium neodecanoate (Mg(ND)2)and a hexane solution of titanium tetrachloride, and an acti-vator which is diethylaluminum chloride (Et2AlCl) dissolved in hexane.
400 ml of hexane is placed in a 2~ o~. pop bottle con-taining a magnetic stirrer and sparged at 60C with an inert gas. The amount of Et2AlCl shown in Table 2 is added to the hexane. Next is added the magnesium neodecanoate and titanium tetrachloride in the amounts shown in Table 2. The inert gas is sparged from the vessel using propylene. The pressure of the propylene is raised to 40 psig. The reactions are carried out until stirring is no longer possible. The times at 60~C.
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Examples 9-16 These examples illustrate the preparation of Low crystal-linity polypropylene using as catalyst a premix of magnesium neodecanoate and titanium tetrachloride prepared as in Examples 1-3 and activators containing various alkylaluminum halides.
In each example ~00 ml of hexane is placed in a 28 oz.
pop bottle containing a magnetic stirrin~ bar. The hexane is sparged at 60C with an inert gas. Mext, the activator is added to the pop bottle. The composition and amount of acti-vator axe shown in Table 3. A sufficient amount of activator is added so that the total concentration of aluminum in the hexane is 1 mmolar. ~ext is added 1 ml of a premix solution which is 20 mmolar with respect to TiCl~ and 100 mmolar with respect to magnesium neodecanoate. The inert gas is removed from the vessel by sparging with propylene and the pressure of the propylene is brought to ~0 psig. The polymerization is continued for the time shown in Table 3, until stirring is not possible. The resulting low crystallinity propylene polymers (less than 20~ crystallinity) are recovered as in Examples 1-3. Polymerization data for these examples are reported in Table 3.
For the sake of comparison, the above procedure is re-peated except that the activator is ethylaluminum dichloride, diethylaluminum hydride, a 50/50 weight mixture of diethyl-aluminum chloride and diethylaluminum hydride or diethyl-aluminum ethoxide. Little, if any, polymerization occurs in each case and recoverable amounts of polymer are not obtained.

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Examples 17-20 These examples illustrate preferred embodiments of the synthesis of low crystallinity copolymers frorn various combi-nations of athylene~ propylene and l-butene using the catalyst 5 system of Examples 1-3~
In each example a dry l~gallon stirred autoclave is purged with argon and sealed. Then, 1635 ml dry oxygen-free isobutane is charged to the autoclave and the contents are heated to 60Co Next, 8 ml of a 25 weight: percent solution of diethylaluminum chloride (equivalent to 12.2 millimoles) in hexane is added, followed by the addition of sufficient premix to provide 0.4 mmole titanium tetrachloride and 2 mmoles of magnesium neodecanoate. After 20 minutes, the amount of mono-mers shown in Table 4 is added to the reactor and the pressure noted. Additional monomers in the weight ratios shown in Table 4, are added as necessary to maintain constant pressure.
Each polymerization is continued for the time shown in Table

4 and then terminated by venting to atmosphere pressure. The resulting low crystallinity copolymers are recovered from the isobutane by evaporation.

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Example 21 This example illustrates a large scale preparation of a low crystallinity copolymer of ethylene and butene-l.
The general procedure of Examples 17 to 20 is repeated on a large scale using a 10 gallon autoclave charged with S350 grams of isobutane. The charge is heated to 60C and 19.8 millimoles of diethylaluminum chloride are added as a 25~
solution in hexane. Next 1.0 millimole o~ titanium tetra-chloride and 5.92 millimoles of magnesium neodecanoate are added as separate solutions in hexane and the charge is agi-tated for 20 minutes, after which time 5150 grams of liquid 1 butene and 206 grams of ethylene are added and the pressure noted. Additional monomer at a butene:ethylene weight ratio of 2:1 is added as necessary to maintain a constant pressure.
The polymerization is continued for 55 minutes and then termi-nated by venting to atmospheric pressure. The yield is 1700 grams of copolymer containing 32 mole ~ of l-butene by NMR and having a crystalline content of 2.2%, as ethylene. The co-polymer has an IV of 3.1, a glass transition temperature of -67C and a melting point range of 0 to 120C., as determined by DTA.
Examples 22-23 -These examples illustrate the preparation of copolymers of propylene and hexene-l (Example 22) or propylene and octene-l (Example 23) using the general procedure of Examples 1 to 3 except that the Et2AlCl, TiC14 and magnesium neo-decanoate are added to the hexane in the form of a pr~activat-ed premix which provides 0.2 millimole of Et2AlCl, 0.01 millimole of TiC14, 0.05 millimole of magnesium neodecanoate and 2.0 grams of hexene-l or octene-1 and the polymerization is continued for 5.3 hours.
The preactivated premixes used in these examples are prepared by placing in 8 oz. pop bottles containing magnetic stirring bars 120 ml of nitrogen sparged hexane and 12.0 grams of hexene-l or octene-l, and, while stirring under nitrogen, adding first 1.2 millimoles oE Et2AlCl a3 a hexane ~olution and then sufficient hexane premix to provide 0~06 millimole c~f riC14 and 0.3 millimole oE magnesium neodecanoate and con-tinue the 3tirring over night at room temparature.

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The polymerization data for these examples is reported in Table 5.

Table 5 Polymerization Data

5 Examp]e Cryst Mile-No Yield,g % Age Soluble %
.
22 57.7 21 5770 82.8 23 55.4 21 5540 82.9 Example 24 This example illustrates the preparation of a high molecular weight, essentially non-crystalline homopolymer of octene-l.
An 8 oz. pop bottle containing a magnetic stirrer bar and sparged with nitrogen is charged with 50 ml of octene-l and 0.2 millimole of diethylaluminum chloride and placed in a 60C
bath. ~ext is added sufficient of the premix of Examples 9-16 to provide 0.01 millimole of titanium tetrachloride and 0.05 millimole of magnesium neodecanoate and the polymeri~ation is carried out for 1.7 hours, at which time stirring is discon-tinued and the product is diluted with hexane. The productdoes not contain any insoluble polymer. The hexane soluble polymer (recovered by evaporation) is 20.41 grams of poly (octene-l) having a weight average molecular weight of 262,000, a number average molecular weight of 4900, a molecu-lar weight distribution, Mw/Mn, of 53.38, and a glas~ transi-tion temperature of -69C.
Example 25 -This example lllustrates the preparation of a low crystallinity copolymer of propylene and ethylene using the general procedure of Examples 17-20.
In this example the autoclave is charged with 2000 ml dry, oxygen-free isobutane and the charge is heated to 60~C.
~ext, the diethylaluminum chloride solution (12~2 millimoles) and then the premix (equivalent to 0.4 milLimole of t:itanium tetrachloride and 2 millimoles of magnesium neodecanoate) are added. After 20 minutes 92 grams of propylene and 0.45 gram of ethylene are added and the pressure noted. Additional monomers in the weiyht ratio of propylene:ethylene of about 20:1 are added as necessary to maintain constant pressure.
The polymerlzation is continued for 7.5 hours and terminated by venting. The resulting copolymer (1175 grams) contains 4.3~ ethylene, is 10.3~ crystalline, has an I.V. of 2.26, a glass transition temperature of 23~C., a melting point of 144C. and a heat of fusion of 0.8.

Claims (21)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for the production of polyolefins by poly-merizing a 1-olefin containing at least 3 carbon atoms in an inert liquid hydrocarbon diluent in the presence of a catalytic amount of a catalyst mixture containing the reaction product of a transition metal compound, a magnesium compound, and an alkylaluminum halide activator, characterized in that the polymerization is carried out at a temperature ranging from about 25°C to about 90°C; the catalyst mixture consists essentially of:
(a) the hydrocarbon-soluble reaction-product of (1) a hydrocarbon-soluble, halide free magnesium carboxylate and (2) a hydrocarbon-soluble salt of a transition metal selected from the group consisting of tetravalent titanium, zirconium and hafnium, in an inert liquid hydrocarbon, and (b) an alkylaluminum halide activator having the general formula RnAlX3-n where R is a 1 to 18 carbon alkyl group and n is a number from 1.5 to 2.5;
the molar ratio of transition metal salt to magnesium carboxy-late is 0.003 to 3; the molar ratio of alkylaluminum halide activator to transition metal salt is at least 1; and the molar ratio of alkylaluminum halide activator to magnesium carboxylate is greater than 2.5.

2. A process as claimed in claim 1 further characterized in that the 1-olefin is propylene.

3. A process as claimed in claim 1 or 2, further characterized in that the transition metal salt is titanium tetrachloride.

4. A process as claimed in claim 1, 2 or 3, further characterized in that the alkylaluminum halide activator is diethylaluminum chloride.

5. A process for the production of high molecular weight polyolefins having a degree of crystallinity less than about 25%, which process comprises polymerizing at least one 1-olefin containing at least 3 carbon atoms or a mixture of at least one of said olefins with up to about 67 weight % of ethylene in an inert liquid hydrocarbon diluent at a temperature ranging from about 25°C. to about 90°C. in the presence of a catalytic amount of a catalyst system consisting essentially of:
(a) a hydrocarbon soluble transition metal component derived by contacting in an inert liquid hydrocarbon (1) a soluble, halide free magnesium-carboxylate having the general formula Mg(OOCR')2 where each R' is alike or different and is derived from a carboxylic acid containing at least 2 carbon atoms with (2) a soluble salt of a transition metal selected from the group consisting of tetravalent titanium, zirconium and hafnium, and (b) an alkylaluminum halide activator having the general formula RnAlX3-n where R is a 1 to 18 carbon alkyl group and n is a number from 1.5 to 2.5.
the molar ratio of transition metal salt to magnesium carboxylate being 0.003 to 3, the molar ratio of alkylaluminum halide activator to transition metal salt being at least 1 and the molar ratio of alkylaluminum halide activator to magnesium carboxylate being greater than 2.5.

6. The process of Claim 5 wherein at least one 1-olefin is propylene.

7. The process of Claim 6 wherein the transition metal salt is titanium tetrachloride.

8. The process of Claim 7 wherein the alkylaluminum halide activator is diethylaluminum chloride.

9. The process of Claim 8 wherein each R' of the formula Mg(OOCR')2 independently is an alkyl group containing from 5 to 17 carbon atoms.

10. The process of Claim 9 wherein the magnesium carboxylate is magnesium neodecanoate.

11. The process of Claim 9 wherein the polyolefin is polypropylene.

12. The process of claim 9 wherein the polyolefin is a copolymer of propylene and 1-butene.

13. The process of Claim 9 wherein the polyolefin is a copolymer of propylene and ethylene.

14. The process of Claim 5 wherein at least one 1-olefin is 1-butene.

15. The process of Claim 14 wherein the transition metal salt is titanium tetrachloride.

16. The process of Claim 15 wherein the alkylaluminum halide is diethylaluminum chloride.

17. The process of Claim 16 wherein each R' of the formula Mg(OOCR')2 independently is an alkyl group containing from 5 to 17 carbon atoms.

18. The process of Claim 17 wherein the magnesium carboxylate is magnesium neodecanoate.

19. The process of Claim 18, wherein the polyolefin is a copolymer of 1-butene and ethylene.

20. The process of Claim 9 wherein the amount of catalyst system provides a titanium concentration between about 0.02 and about 0.4 millimole per liter of hydrocarbon diluent.

21. The process of Claim 17, wherein the amount of catalyst system provides a titanium concentration between about 0.02 and about 0.4 millimole per liter of hydrocarbon diluent.