DE1520567A1 - Process for the production of crystalline polyolefins - Google Patents

Description

Process for the production of crystalline polyolefins.

============================================================================= ====== The present The invention relates to a method for producing a kridtalline polyolefin In particular, the invention relates to a polymer of a mono-1-olefin with a low amorphous content.

The polymerization; of mono-1-olefins in the presence of heterogeneous initiator systems which contain a heavy metal component such as itane trichloride and an organometallic compound such as a trialkylaluminum or a alkylaluminum halide is known, and the polymers produced in this way have found numerous applications. Many processes have been proposed for the polymerization of these mono-1-olefins in the presence of the initiator systems mentioned above, such as, for example, the so-called solution and slurry polymerization systems and the bulk polymerization system accompanied by low molecular weight materials, which after removal range from viscous liquids to soft sticky solids. With processing and happen procedure an undesirable color is often formed using these polymers which contain considerable amounts of these materials. The reason for this color formation is not fully understood, but it is believed that it arises from the presence of these low molecular weight components, since it does not occur in their absence under the same conditions over about 6% by weight, bleeding can occur in the finished product Has torm and fiber-forming properties as well as the color.

It has now been found that certain materials described in the following be zeschnet as adjuvants, interact with the catalyst to create a polymer to give the enen reduced content of these low molecular weight fractions Has. to these adjuvants include quaternary ammonium halides, tertiary amines, ketones, diaryl ethers and certain phosphorus compounds.

The present invention relates to a method of polymerization a 1-olefin monomer to a normally solid polymer with a reduced Amorphous content, which consists of this monomer in a polymerization zone the action of a catalyst composition is exposed by adding of an organic adjuvant in finely divided form to a crystalline transition metal compound of the metals of groups IVa, Va, VIa and VIII of the periodic systems of the elements according to Mendelj'eff and subsequent combination of an organometallic compound according to groups 1, II and III is thus produced.

These goals are broadly achieved by dissolving the adjuvant in one suitable solvent for this prior to contacting the adjuvant with the catalyst achieved.

In one embodiment of the invention, the adjuvant solution is with mixed with the metal halide part of the catalyst and at a temperature and for a period of time sufficient to remove the pentane-soluble content of the polymer belittle older.

The invention is broadly to the polymerization of olefins applicable, which correspond to the formula R-CH = CH2 where R is an alkyl radical with 1 to including 4 carbon atoms. To be preferred, after the inventive process polymerizable olefins include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene and the like. The term "polymer" as used herein includes both homopolymers and copolymers, for simplicity the invention is made with particular reference to the manufacture of polypropylene described, but it is by no means limited thereto.

The inventive polymerization process is carried out in the presence of known coordination catalyst system carried out by mixing two or more components is produced, wherein one component is an organometallic Compound including compounds in which one or more, however not all organic groups through halogen, a metal hydride or a metal der Groups I, II or III are replaced, and the second component is a metal compound of groups IV, V, VI or VIII of the periodic table.

The invention is particularly advantageous when the adjuvant is used in conjunction with an initiator system obtained by mixing an alkyl aluminum and a titanium trihalide, e.g. B. a trialkylaluminum or a dialkylaluminum halogen nide and a titanium halide such as titanium trichloride.

The preferred initiator system, especially for polymerization of propylene in bulk, is made by mixing a dialkyl aluminum halide, in particular a dialkyl aluminum chloride, e.g. B. Diethylaluminum chloride and the reaction product of -TiCl4 and aluminum, this product roughly having the formula 3TiCl3. AlCl3 has manufactured.

The adjuvant used in conjunction with the catalyst can be any material which cooperates with the catalyst to form a polymer having a lower content of pentane solubles (as defined below) than would be obtained under identical polymerization conditions without the use of an adjuvant. These adjuvants include: 1. the quaternary ammonium halides of the general formula R4NX, in which the radicals R are identical or different hydrocarbon groups with 1 to 20 carbon atoms from the group consisting of alkyl, aryl and cycloalkyl groups and combinations thereof, such as alkaryl, aralkyl and the like Groups represent or where the nitrogen atom can optionally be part of a 5- or 6-membered heterocyclic ring or such a ring in a bicyclic compound in which the other ring is carbocyclic and in which X is chlorine, bromine or iodine, the tertiary amines including the alkyl, ArZl and heterocyclic amines with 5 to 30 carbon atoms per molecule, 7. the aryl ethers of the formula R'O (-R "O-) nR"', in which Rt, R and Bn' are aromatic hydrocarbon groups which May have alkyl or aryl substituents and in which n is an integer from up to and including 4, 4. the alisyclic, acyclic and aromatic ketones and polyks clays with 1 to 14 carbonyl groups and a total of 3 to 30 carbon atoms and so phosphorus compounds, namely phosphines and phosphine oxides, sulfides and imides and their derivatives of the following structural formulas: where R is hydrogen, E is an alkyl group with 1 to 5 carbon atoms or an aryl group with 6 to 12 carbon atoms, the radical A can be the same as the radical R or (if both radicals A together form a double bond) the same as the radical Y and where Y is oxygen , Represents sulfur, the imino (NH) group or a substituted imino (NR) group.

Suitable quaternary ammonium halides include di- (hydrogenated Tallow) dimethylammonium chloride, N-ethylohinolinium iodide, N-cyclopentylpyridinium bromide, Tetramethylammonium iodide, tetraethylammonium iodide, tetrabutylammonium iodide, tetradecylammonium iodide, Hexadecyltrimethylammonium iodide, tetraethylammonium chloride, tetraamylammonium bromide, Tetraoctylammonium chloride, tetraundecylaxmonium bromide, hexadocyltrimothylammonium bromide, Tetraicosylammonium chloride and the like.

Suitable amines include tribenzylamine, 1,2,4-trimethyl piperazine, Tri-n-propylamine, N, N-dimethylaniline, pyridine, N, N, N ', N'-tetraphenylparaphenylenediamine, N, N-diethyl-1-napthylamine, tri-n-hexylamine, 1,1,3,3-tetraphenyl-2-methylguanidine, N, N, N ', N'-tetraethyl-p-phenylenediamine, 1-isobutylpyrrole and the like.

Suitable aryl ethers include diphenyl ethers, dinaphthyl ethers, phenyl naphthyl ethers, Di- (4-biphenyl) -ether, 4-biphenylphenylether, bis-m-phenoxyphenylether, 2,3-diethyl-4-m- (m-tolylphenoxy) -phenyl-4-benzylphenylether, m- (m-phenoxyphenoxy) -phenyl-mphenoxyphenyl ether, m-phenyl-p- (o-isopentylphenoxy) -phenyl-oisobutyl-p-phenoxyphenyl ether, 3- (2,4-Dimethyl-5-ethylphenoxy) -S-phenethylphenyl-2-3-n-heptyl-S- (3-ethylpentyl) -phenylj-4 (4-phenylphenoxy) -phenyl ether, bis-L4- (4-phenoxyphenoxy) -phenyL ether, bis- (3-phenoxyphenyl) -ether, 3- (3-Phenylphenoxy) -phenyl-3- (2-phenoxyphenoxy) -phenyl ether, 2- [2-phenoxy- (2-phenoxy) -phenoxy] -phenyl-2 - [(2-phenoxy) -phenoxy] - phenyl ether, 2-phenoxyphenyl-2-biphenyl ether, 2-phenoxyphenyl-2-n-propyl-4,5-diethylphenyl ether, [2-p-Tolyl-4- (3-methyl-4-ethyl-5-benzyl) -phenoxy-5-phenyl-6-n-hexyl-7-phenyl-3, 4,5-trtieopropylphenylither, 2-n-heptyl-3- [3-methyl-5- (3-isopentyl-5-n-butyl) -phenoxy-6-phenyl] phenoxyphenyl-3- (3,4,6-triisobutyl) -phenoxy-5- (3-biphenyl) -phenyl = ether, 3- [3-methyl-5- (3-phenylphenoxy)] - phenoxy-5-ethylphenyl- 3- [2- (3-benzylphenoxy) -4-n-propyl] phenoxy-5-ethylphenyl ether and the like

Suitable ketones include acetone, 2-butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2,4-dimethyl-3-pentanone, cyclohexanone, benzophenone, benzyl, 2,3-pentanedione, 2,4-pentanedione, 2,5-hexanedione, 2,5,6,8-nonantetron, 2,4,6,8,10,12,14,16,18,20, 22,24,26,28-tricontante tetradecone and the like.

Suitable phosphorus compounds include phosphine, thionophosphine, Oxopropylphosphine, iminophosphine, propyl- (n-pentyl) -phosphine, butyl- (phenyl) -phosphine, Triphenylphosphine, ethyl- (propylimino) -phosphine, (methylimino) -phenyl-phosphine oxide, Butylthionophosphine oxide, (phenyl) imino phosphine sulfide, isopentyl (propylimino) phosphine sulfide, Iminophosphinimide, (phenyl) - @ minophosphinimide, (butylimino) propylphosphinimide, (Phenylimino) phenylphosphine oxide and the like.

It has also been found that the beneficial effects of these catalyst adjuvants can be increased significantly if the adjuvant is with the heavy metal compound of the catalyst is milled prior to introduction into the reaction zone. With this procedure .can use the amorphous polymer components, sometimes called pentanoic materials are designated, for example in polypropylene by more than 60% compared to the Values that are obtained in the absence of this grinding stage are reduced.

The polymer removed from the reaction vessel contains changing d @ e amounts of amorphous material often in the vicinity of 10% by weight when the usual Organometallic and titanium halide catalysts disturb without the inventive Adjuvant can be used; The allowable content of amorphous fraction in the polymer product @ depends on the end use of the polymer, but the content should be general to a level below about 4 wt .- *, based on the polymer, preferably below about 3% by weight, to result in deleterious effects resulting therefrom avoid.

The present invention provides this desired result. r refers to the term "polymer" on the polymer of an olefin, such as polypropylene, as it is in the reaction vessel is formed, and includes trapped diluent, catalyst residues, low and high molecular weight amorphous and crystalline homopolymers and copolymers and the like

The term "amorphous polymer" as used herein relates on that part of the polymer of a 1-olefin that is in the presence of a heterogeneous catalyst system described here is prepared, @@@ that in pentane is soluble based on the determination described in Example 1. "Amorphous Polymerisat1, is usually called "pentane-like proportions, the ratio of The catalyst components used in the present process can be quite extensive vary, depending on the particular monomers used and the operating conditions.

The molar ratio of the organometallic compound, the metal hydride or the metal of groups I, II or III to the metal compound the Groups IV, V, VI or VIII is usually in the range of 1: 1 to 10: 1, preferably 2: 1 to 5: 1. The concentration of catalyst in the polymerization zone is usually in the range from 0.01 to 5% by weight, based on the monomer used in this zone, however, smaller or larger amounts can also be used.

The amount of adjuvant used is in the range @@@ between about 0.1 and about 15, preferably between about 0.1 and about 5 moles and in particular between 0.25 and 1.25 mol / mol Metallver Utlg of groups IV, V, VI or VIII. im Within the scope of the present invention it has now been found that by dissolving of the adjuvant in a suitable solvent prior to contacting it with the catalyst system a still further reduction in the content of pentane-soluble Proportions is obtained 5 The solvent can be any liquid that the adjuvant within a reasonable period of time, preferably at room temperature, dissolves and that does not detrimentally affect the polymerization catalyst or the polymer poisoned or otherwise significantly affected O The solutions used are preferably of such a high concentration as to avoid appreciable amounts of solvent in the Avoid product, for example about 0.05 to 0.5 molar.

Among the examples of a preferred method for making Polyolefins belong to the polymerization in a 8yetem in Cup using a monomer as a reaction diluent and carrying out the reaction at a temperature at which the polymer is more powdery Solid forms, i.e. where it is not soluble in the olefin diluent, While this is not essential, it is preferred that the reaction be in the presence carried out by elemental hydrogen0 The preferred catalyst system contains Diethyl aluminum chloride and titanium trichloride It is also preferred when used Titanium trichloride to use a complex of the approximate formula 3TiCl3 @ llCl3, which can be produced by reducing titanium tetrachloride with aluminum0 The milling stage is carried out in a ball mill or other suitable mechanical Device which can be operated in such a way that air, Moisture or other impurities can be excluded, The grinding time usually ranges from 30 minutes to 20 hours and depends to some extent on the effectiveness of the matil device.

It is not essential, but it is often useful, a small one Add amount of inert hydrocarbon at the end of milling to remove of the ground product to facilitate. Even in cases where a liquid adjuvant is used is the addition of a small amount of hydrocarbon, e.g. Cyclohexane, in the grinding batch often expedient.

The mechanism by which this grinding exerts the action of the Adjuvant improved is not fully understood, however, it is believed to be due to this Working method, the metal salt and the adjuvant are mixed more intimately, this intimate mixing may be accompanied by an actual chemical reaction ist0 According to another embodiment of the invention, the metal halide part is of the catalyst, preferably that formed by reacting TiCl4 with aluminum Complex, diapered in the adjuvant solution and at an elevated temperature and Aged for so long that the capacity of this adjuvant to decrease the pentane-soluble fractions is further improved. The temperature can vary from room temperature up to the boiling point of the solvent, preferably from 38 to 95 ° C., in particular 38 to 650C (100 to 2000F or 100 to 150 ° F) range. The aging takes place appropriately overnight or the aging time is 1 to 20 hours because moisture and oxygen @ For the catalytic converter are harmful, the aging stage is preferably without contact carried out with the atmosphere.

Suitable solvents include chlorobenzene and others Aryl hydrocarbons (which are particularly useful for quaternary ammonium holgenides are), propane, isobutane, n-pentane, n-heptane, isooctane, n-dodecane, cyclopentane, cyclohexane, Methylcyclopentane, ethylcyclopentane, dimethylcyclopentane, ethylcyclohexane, benzene, Toluene, xylene, xthylbenzene, naphthalene, mixtures such as hydrocarbon fractions and the like

The polymerization of the 1-olefin with the catalyst and adjuvant can be carried out in any suitable manner, such as in a solution process or in bulk, and under known conditions. As is known, the polymerization of the α-olefins can be carried out in the presence of a hydrocarbon diluent. that which is inert and liquid under the process conditions and has no deleterious effect on the catalyst. Suitable diluents include paraffinic, cycloparaffinic and / or aromatic hydrocarbons. Examples of such diluents include propane, butane, pentane, hexane, cyclohexane, methylcyclohexane, senzene, toluene, the xylenes, mixtures of hydrocarbon fractions, and the like. The relative amounts of diluent and olefin used in the polymerization will depend on the particular conditions or procedures are generally dictated by the capacity of the device to be effective Be un aBuw and to effect heat dissipation. The polymerization can be carried out at a temperature which varies over a fairly wide range, e.g. at a temperature of -75 to +26000 (-100 to + 5000F). In general, pressures which are sufficient to keep the reaction mixture practically in the liquid phase are satisfactory. as discussed earlier, is preferably contacted in the presence of hydrogen. When using propylene as the monomer and diluent, a suitable temperature is in the range of about -20 to + 120 ° C (0 to 250 ° F).

The process can be carried out on a batch basis, for example by pressing the olefin to be polymerized into a reaction vessel that contains a Catalyst system which contains adjuvant and optionally a diluent. In addition, the process can be carried out kow @ inuierlich by the reactants a suitable residence time must be maintained in the reaction vessel.

The residence time used in the continuous process can be in vary widely, depending to a large extent on the temperature and the particular Depends on olefin. However, the residence time is a continuous process usually in the range v @@ 2 seconds to 5 hours0 or more0 in a rudimentary manner Procedure can also vary the response time widely, for example from 15 Minutes up to 25 hours or more0 The treatment of the polymer is then carried out to the Polymerisa- @ lonsstufe depends on the type of used for the polymerization Procedure. In the case of a solution process, e.g. after the end of the polymerization, according to a suitable method blown off any excess olefin, and the contents of the reaction vessel is treated in such a way that the catalyst is inactivated and the catalyst residue removed will. The polymer is then precipitated and removed from the diluent by decanting, Filter or separate in some other suitable manner and then dry A suitable method in the bulk polymerization process is the polymer Poured from the reaction vessel into a suitable vessel and the catalyst residue by contact with an extractant such as a diketone, e.g. acetylacetone, removed in the presence of propylene oxide So far it was generally necessary to to wash the effluent with an extractant for the amorphous polymer, such as with propylene, propane or other hydrocarbons or mixtures thereof 1 at a temperature preferably less than 27 ° C (80 ° S). To the polymerizate is dried after the separation. One of the advantages of the present Invention is that a polymer with a very low content of amorphous Components is generated. The amorphous materials are generally in Hydrocarbons are soluble and can be removed by extraction, however such procedures are time consuming and require manpower and manpower extensive tmd expensive additional facility. Hence, a satisfactory A method of preventing their formation during polymerization is an essential one Improvement.

The olefins polymerized in the present process include Propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Copolymers such olefins with each other and the like. The resulting polymers are valuable for the production of films, foils, molded products and numerous other objects0 The following examples serve to explain the invention in more detail without adding to it restrict0 Example I A series of tests was carried out using propylene in the presence of a mixture of diethyl aluminum chloride and the reaction product of Al and TiCl4 of the approximate formula 3TiCl3. AlCl3 with tetrabutylammonium iodide, Di- (dihydrogenated taly) -dimethylammonium chloride, benzophenone, m-bis- (m-phenoxyphenoxy) -benzene, @riphenylphosphine or 1,2,4-trimethylpiperazine was polymerized as an adjuvant. These experiments were carried out in a 1 liter stainless steel reaction vessel, which was purged with propylene before filling. The reaction product of Al and TiCl4 was filled in first, followed or accompanied by the adjuvant, then the diethylaluminum chloride component introduced as a solution in cyclohexane (0.183 g / ml). One liter (NTP) of hydrogen was made then added, followed by the propylene charge (150 g ': the polymerization was carried out Performed 2 1/2 hours at 54 ° C (130 ° F).

Unreacted propylene was blown off and the polymer became transferred to a graduated 500 com cylinder in which 450 ml of pentane was added The cylinder was closed and shaken about once every 4 or 5 hours. After that he became left to stand overnight. An aliquot share of 200 ml of the liquid was removed into a weighed dish from which the Pentane was removed by evaporation. The polymer residue was left on for 15 minutes 110 ° C heated, cooled and weighed. The pentane-soluble proportions in the overall polymer were calculated from the obtained weight. The values of these trials are as follows specified.

Table I AlCl3. (B) Adjuvanslösl. Vermin- @ ers. Adjuvant DÄAC (a) 3TiCl3 adjuvant added proportions of derung N @. (g) (g) (g) as: (%) (%) TBAJ (c) 0.210 0.090 0.413 solution (d) 0.63 85.8 2 TBAJ 0.226 0.097 0.060 crystals (e) 2.32 48.0 TBAJ 0.234 0.100 0.060 ball-shaped 0.87 80.5 grind (f) 4 DTDMAC (g) 0.241 0.103 1.00 Solution 2.0 55.5 5 DTDMAC (g) 0.229 0.098 0.50 Solution 2.3 49.2 6 Piperazine (@) 0.234 0.100 0.20 solution 3.9 13.4 7 PPB (i) 0.239 0.102 0.50 solution 1.9 58.2 8 PPB (i) (j) 0.229 0.098 0.20 solution 1.2 73.7 9 benzophenone 0.236 0.101 0.99 solution 2.7 40.2 10 none 0.243 0.104 - - 4.47 - (a) Diethylaluminum chloride.

(b) Reaction product of Al and TiCl4 (c) tetrabutylammonium iodide (d) Solution in chlorobenzene (0.02 g / ml) in the reaction vessel after filling of the Al-TiCl4 reaction product introduced.

(e) In the reaction vessel after filling the Al-TiCl4 reaction product brought in.

(f) Ball milled with Al-TiCl4 reaction product before filling and filled with it.

(g) Di (hydrogenated tallow) dimethylammonium chloride solution in cyclohexane.

(h) 1,2,4-trimethylpiperazine in solution in cyclohexane.

(j) m-Bis- (m-phenoxyphenoxy) -benzene in solution in cyclohexane.

(j) solution in cyclohexane.

These values show that the lowest pentane-soluble content Proportions when using a catalysis adjuvant can be observed when the addition is introduced as a solution.

Example II A series of experiments were based on that described in Example I. Way carried out using other adjuvants0 In the inventive In experiments, the adjuvant material was dissolved in cyclohexane and with the Al-TiCl4 reaction product blended before filling. The mixtures thus prepared were 15 hours at different Temperatures aged before filling. These experiments were carried out in a 1 liter reaction vessel stainless steel at 5400 (130 ° F) using 150 grams of propylene and 1 1 (NTP) hydrogen carried out. The reaction time was 2.5 hours. The pentane-soluble Proportions were determined in the same manner as shown in Example I. The values these tests are given in Table II.

Table II AlOl soluble vers. DÄAC (@) 3TiCl3 (b) Adjuvant aged Part No. (g) (g) Compound Amount Temp. Time (%) (g) (° F) ° C hrs.

1 0.234 0.10 tribenzylamine, solid 0.02 - - - 3.1 2 0.234 0.10 tribenzylamine (c) 0.02 (75) 24-1.5 (c) 3 0.234 0.10 tribenzylamine (c) 0.01 (75) 24-2.6 4 0.234 0.10 tribenzylamine 0.02 (122) 50 15 1.1 5 0.234 0.10 tribenzylamine (c) 0.02 (75) 04 15 1.7 6 0.234 0.10 triphenylphosphine (d) 0.02 (122) 50 15 1.2 7 0.234 0.10 triphenylphosphine (d) 0.02 (75) 24 15 1.5 8 0.211 0.09 triphenylphosphine, solid 0.05 - - - 6.9 9 0.234 0.10 diphenyl ether (s) 0.02 (122) 50 15 2.4 10 0.234 0.10 diphenyl ether (s) 0.02 (75) 24 15 3.0 11 0.234 0.10 diphenyl ether (f) - - - - 3.2 12 0.234 0.10 triphenylphosphine oxide 0.02 (122) 50 15 2.1 13 0.234 0.10 none - - - - 4.5 (a) diethyl aluminum chloride (Solution in cyclohexane @@ (0.183 g / ml) (b) reaction product of Al and TiCl4 (c) solution in cyclohexane @@ (0.02 g / ml) (d) solution in cyclohexane @@ (0.004 g / ml) (e) solution in Cyclohexane @@ (0.004 g / ml) (f) solution in cyclohexane @@.

These values show the benefit of aging at elevated temperatures and further that aging at room temperature has no advantage over immediate Filling gives, Example III A series of experiments were carried out at which propylene polymerizes in a 1 liter stainless steel reaction vessel became. The reactions were carried out for 2 1/2 hours at 54 ° C (1300F) when the adjuvant was used Tetrabutylammonium iodide used for the ground catalyst composition a glass container containing steel balls was dried and in a hot state evacuated, then flushed with dry nitrogen and then 2.5 g Titanium trichloride complex (3TiCl3.AlCl3) and 1.5 g of adjuvant are added to the container was sealed and rolled for 5 hours, after which 100 ml of dry cyclohexane were added admitted. For the polymerization, 1.0 ml of this slurry, the 0.1 g Contained TiCl3 complex and 0.06 g of adjuvant, together with 0.234 g of diethylaluminum chloride used. 200 g of propylene and 1 liter (NTP) of hydrogen were then placed in the reaction vessel Filled in0 As a control experiment, an experiment using the same Charge, but without tetrabutylammonium iodide, and a second attempt in which the adjuvant was added without ball milling.

At the end of each experiment the polymer was recovered and without washing investigated for @ pentane solubles. Polymerisa. t ir placed in a measuring cylinder, in which 450 ml of pentane were then poured. Of the The cylinder was stopped with a stopper and shaken once every hour for 4 hours and then left to stand overnight. Then 200 ml of the measuring cylinder were Liquid removed. The liquid was evaporated to dryness and then 15 Heated to 110 ° C. for minutes. The weight of the Residue was determined and the percentage of solubles in the total polymer is calculated. There were the following results are obtained:% Soluble ground catalyst 0.87 TBAJ added, not ground 2.32 no additive 4.47 Example IV A series of attempts were made performed to determine the effect of ball milling on other adjuvants. In these experiments, the polymerization and the filling took place in practically the same way, as shown in Example III The ratio of adjuvant to titanium trichloride complex, the ball milling time and catalyst loads along with the final values for the pentane-soluble parts are given below, pentar Vers.- g g Geschwindgkt. soluble no. Addition Addition TiCl3AA (a) Method g / g TiCl3 AA / pc% 1 tribenzyl 0.020 0.095 solid in the 343 2.06 amine action vessel 2 0.019 0.097 ball-milled 294 0.84 3 BuPh3PBr 0.020 0.095 firmly in the 296 1.08 action vessel 4 "0.020 0.100 ball milled 256 0.83 5 triphenyl 0.020 0.100 solid into the Re-278 1.80 phosphine Action vessel 6 "0.0202 0.1008 ball-milled (b) 332 0.88 7 Diphenyl 0.020 0.101 Solution in the 283 3.7 ether action vessel s "0.020 0.100 ball-ground 172 2.49 9 triphenyl 0.020 0.097 solid in the Re- 270 1.59 phosphine oxide action vessel Continuation: Pentane Vers.- g g Velocity. soluble no. additive additive TiCl3AA (a) method g / g TiCl3AA / hour % 10 triphenyl 0.0198 0.0992 ball milled 296 0.96 phosphine oxide 11 Ethylchino- 0.020 0.101 firmly in the Re- 277 1.52 linium iodide action vessel 12 0.0197 0.0983 ball milled 155 1.11 (a) diethyl aluminum chloride by weight of 2.34: 1 TiCl3AA was used in these experiments0 (b) 1 ml solution in cyclohexane.

When diphenyl ether was used as an additive, it became the TiCl3AA in 10 ml of dry cyclohexane added and ball milled0 after ball milling 90 ml of dry cyclohexane were added, an aliquot was mixed with a Injection syringe removed and placed in the reaction vessel0 With these The following procedure was used for experiments: A 200 cc bottle was filled at about 12000 dried 0 steel balls (10 pieces of 9.525 mm (3/8 ") and 15 pieces of 3.175 mm (1/8 ")) was removed from an oven at 110-1200C and placed in the beverage bottle brought in. The bottle was then placed in the vacuum lock of a drying cabinet brought where they are evacuated and repressurized with dry nitrogen became. After the bottle had cooled, 2.5 g of titanium trichloride complex was added to the The bottle was weighed in the drying cabinet and 0.5 g of additive was added. The bottle was removed from the drying cabinet and immediately sealed. Then the bottle on a bottle rolling device rolled overnight (15 to 16 Hours.). The bottle was put back in the drying cabinet, in a dry one The storage tube was emptied, and the steel balls were segregated. Part of the ball-milled Mixture was transferred to a small tube. The tube was drained before and after its contents weighed into the reaction vessel. Diethyl aluminum chloride and hydrogen was added, 150 g of propylene was charged, and the reaction became 2 1/2 Performed at 54 ° O (130 ° F) for hours.

The results of the above examples clearly show that the favorable Effect of the catalyst adjuvants by grinding with the heavy metal component of the catalyst is significantly increased before filling into the reaction zone.

Of course, deviations and modifications of the listed -listed details possible without leaving the scope of the invention

Claims (1)

P a t e n t a n s p r ü c h e =============================== 1. Procedure for polymerizing a 1-0 olefin monomer into a normally solid polymer with a reduced content of amorphous fractions, characterized in that the monomer subjected to the action of a catalyst composition in a polymerization zone becomes that-by adding an organic adjuvant in finely divided form to a crystalline transition metal compound of metals of groups IVa, Va, VIa and others VIII of the Periodic System according to Medeljeff and subsequent combination of one organometallic compound of the metals of groups @, II and III produced therewith is, 2. The method according to claim 1, characterized in that the adjuvant by Ball milling is added with the crystalline transition metal. 3. The method according to claim 1, characterized in that the adjuvant by forming a solution thereof and contacting the catalyst composition thus admitted. 40 The method according to any one of the preceding claims, characterized in that that as an adjuvant tetrabutylammonium iodide, tribenzylamine, diphenyl ether or m-bis- (m-phenoxyphenoxy) -benzene is used 0