DE1420544A1 - Polymerization process - Google Patents

Description

DIpI ₁ -ClKm.

DR.ILSERUCH

PATENT ADVOCATE

Telephone 23251

. Telcfrimmidietsc: Palm

Poststhtdckonto: Möndien H5964

MUNICH. Rekhcnba Aslraße 47/49

Dr. BxpL

A £

2/2/1

fhe MV Kellogg Company. Jersey Oity. Hew Jersey. USA .

Polymerization process

The present invention relates to a method for polymerizing polymerizable äthylenisoh unsaturated Compounds hereinafter referred to as "vinyl compounds" are designated.

There has been one in the field of vinyl polymerization Demand for the development of a simplified and

improved process for the polymerization of tiny compounds that can be controlled and good conversions of the monomer to polymer / em leads, which are essentially free of trapped catalyst particles. Have been for some time Ziegler catalysts, such as alkyl aluminum compounds, used to polymerize certain 1-olefins such as ethylene to normally solid polymers In practice, however, the main problem with such catalysts is that they are difficult to remove from the polymers could be so that special methods and measures for the cleaning of the final product were required In addition, such catalysts could practically only be used in a heterogeneous environment, whereby the useful life of the catalyst and its effectiveness were reduced and the process became more difficult to control.

In the following, polymerization is to be understood as meaning the polymerization of a single monomer and the interpolymerization of dissimilar monomers.

The German patent (patent application K 32 329 IVb / 39o) concerns the production of a

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Catalyst which contains an organometallic compound of a metal from group III A _1, a halide of a transition ohmic metal and an organo-chlorine-containing compound. The present invention relates to the use of a solo catalyst for the polymerization of vinyl compounds. The organometallic compounds preferred for the preparation of the catalyst are the compounds of aluminum, indium and gallium in which the metal is bonded to at least one alkyl radical, such as, for example, in the dialkyl aluminum halides and the trialkyl aluminum compounds. Of the halides of a transition heavy metal, the halides and especially the chlorides of metals of groups IVB and VIII are preferred, and the organic compound containing chlorine is an aliphatic or aromatic chlorine-containing compound which preferably contains only chlorine or chlorine and hydrogen bonded to carbon.

The molar ratio of the inorganic metal halide to the organometallic compound can be quite

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wide limits vary and generally lies within the area τοη about 0.03 * 1 and about 2 t 1 and, in some cases, τοη about 0.1 ι 1 and about 0.8 ι 1. Baa ratio of the number of organic compounds containing chlorine to the total number of moles τοη organometallic Compound plus inorganic halide can also be used in a fairly wide range, such as τοη about 0.8 s to about 200 t 1, vary, the number of moles of carbonaceous organic compounds, such as carbon tetrachloride, preferably at least equal to the total amount of the other two starting materials is in the mole · For practical reasons, the example is used Carbon tetrachloride is generally not used in excess of 100 moles and usually 50 moles.

The use of this liquid catalyst offers numerous advantages, including the dafi Ale polymerization in a homogeneous medium, d. H. in a medium in which the monomers to be polymerized and the catalyst are in the same phase, can be carried out. This homogeneity is not only at the beginning of the polymerization, but during the entire implementation gate, since the catalyst τοη beginning up to the end of each flat »polymerization

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remains in a completely liquid and dissolved state. Due to the homogeneity of the reaction medium, this can The polymerization process of the present invention can be controlled and is therefore general a simplified process that can be carried out in a simple system and also in continuous operation. Sa these active catalysts in stable liquid state »is easy to use. Another advantage of this stable liquid Catalysts lies in the fact that, with their use for the polymerization of various vinyl compounds, such as ethylene, obtained polymers cannot be included in the catalyst, and that the catalyst, in turn, which remains in the liquid state, is not in any significant or detrimental manner Amount can be included in the polymer. This makes it easier to work up the polymer, and achieved the highest possible effectiveness of the procedure. The polymer is made by simply washing, for example with carbon tetrachloride, of essentially all color freed.

Furthermore, when using this catalyst, the polymerization is carried out in a homogeneous medium.

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can be performed, the conversion of the monomer used to polymer is higher than that of the the same reaction conditions, such as time, pressure and temperature in the presence of the solid catalyst, the duroh contacting of the organometallic compound and the metal halide in the absence of the chlorine-containing organic compound, such as carbon tetrachloride, is obtained, scored.

The monomers which can be polymerized by the process of the invention include the monoolefins and polyolefins, namely the unsubstituted ones Hydrocarbons as well as those substituted with halogen, for example with fluorine, chlorine or bromine, and olefins containing the aryl, carboxylate, alkoxy, amido and nitrile groups or combinations thereof They contain monomers used according to the invention 2 to about 20 carbon atoms and preferably no more than 12 carbon atoms per molecule.

A class of monomers that are advantageously classified according to the Processes of the present invention which can be polymerized are the aliphatic hydrocarbon monoolefins, including the 1-olefins, 2-olefins,

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a- iind isoolefins, such as ethylene, propylene, butene-1, butene-2, isobutylene, cyolobutene, pentylene, and homologues and isomers of higher molecular weight. A second class of monomers that can be polymerized using this process are the aliphatic hydrocarbon polyolefins, such as bees with conjugated double bonds, typical representatives of which are butadiene, 2-methylbutadiene, 2,3-diethylbutadiene and cyclopentadiene.

As mentioned, halogen-substituted olefins, including the partially halogenated and perhalogenated monoolefins and polyolefins, can be polymerized with the catalyst of the present invention. Bine class of halogen-containing monomers are those that contain only other halogen than fluorine, such as chlorine and Contain bromine and combinations thereof as the only halogen. Typical examples of single monomers are Vinyl chloride, 2,3-dichloropropene, dichloroethylene, vinyl bromide, vinylidene bromide and 2-chlorobutadiene.

Typical examples of fluorine-containing vinyl compounds that can be used are the partially halogenated fluoromonoolefins, such as vinyl fluoride, vinylidene fluoride, tri-

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fluoroethylene, 1,1-chlorofluoroethylene, 1,1-difluoro-2-chloroproethylene, 1,1-difluoropropene, 5,3 »3-trifluoropropene, 2,3» 3 »3-tetrafluoropropene, 2 -! - <Jhlor-3 »3,3-trifluoropropene, 3 _f 3,3-trifluoroisobutene, 1,1,1-trifluoro-3-trifluoromethylbutene, and the like. Typical examples of suitable perhalogenated fluoromonoolefins include trifluorochloroethylene, bromotrifluoroethylene, tetrafluoroethylene, 2-chloropropylene, 2-chloropropylene difluoroethylene , Perfluorieobutene, 2,3-biohlorhexafluorobutene, 4,4-dichloroperfluoroyolobutene and perfluoroyolobutene. Typical examples of the fluorine-containing polyolefins include 2-fluorobutadiene, 2-trifluonethyl-butadiene; 1,1-difluorobutadiene | 1,1,2-trifluorobutadiene; 1,1,3-trifluorobutadiene; 1,1-difluoro-3-methyl-butadiene and 1,1,4,4-tetrafluorobutadiene.

As Bohon mentioned, the vinyl compounds that can be polymerized naoh the process of the present invention, also contain alkoxy and aryl groups. The alkoxy-substituted olefins which can be used include vinyl ethers, such as vinyl ethyl ether and vinyl butyl ether. Typical examples of aryl-substituted vinyl compounds which can be polymerized naoh the process described are styrene and oc-methylstyrene.

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Di · monomers can have any combination of substituents such as halogen, alkoxy and aryl groups. For example, the following ethylenically unsaturated compounds can advantageously be used according to the process of the present invention are polymerized: phenyltrifluoroethylene, Vinyl-2-chloroethyl ether, 1,1,2,2-tetrafluoroethyl vinyl ether, Fluoro-1,1-dihydroalkyl vinyl ether, α-difluoromethystyrene and α-trifluoromethylstyrene.

According to the method of the present invention however, not only homopolymerizations of the above-mentioned monomers but also interpolymerization of these Vinyl compounds are carried out. For example can use the following monomer mixtures in the presence of new catalysts of the present invention are polymerized to valuable Xi & rpolymers: ethylene and Propylene! Ethylene and butylene; Propylene and butylene; Butadiene and styrene; Butadiene and acrylonitrile; Butadiene and trifluorochloroethylene * butadiene and tetrafluoroethylenej Ethylene and letrafluoroethylene / irifluorochloroethylene and vinylidene fluoride; Tetrafluoroethylene and vinylidene fluoride; Hexafloropropene and vinylidene fluoride; Hexafluoropropene and TetrafluoroethyXene? 1,1,2-tetrafluoroethyl vinyl ether lind 1,1,2-trifluorobutadiemt 1,1,2-Sri-

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fluorobutadiene and 1,1,3-trifluorobutadiene; phenyltrifluoroethylene and 1,1,3-trifluorobutadiene; 2-trifluoromethylbutadiene and 2-chloro-3,3f3-trifluoropropene, 2-fluorobutadiene and 2-chloro-3 _s 3 »3-trifluoropropene, trifluorobluoroethylene, vinylidene fluoride and vinyl chloride.

The ratio of the number of moles to be polymerized Monomers to the total number of moles of liquid catalyst can vary within relatively wide limits. This molar ratio can be, for example, between about 1: J and about 5000 t 1 and is preferably between about 100 ι 1 and about 1800: 1.

The polymerization process of the present invention is carried out at a temperature between about -100% and about + 200 ° and preferably between about -20 and about 100 °. In particular, a temperature between about -20 and about 65 ° is preferred. Also the applied pressure can vary within relatively wide limits, such as from about atmospheric pressure to about 1000 atmospheres, and no oh higher or lower pressures can be applied. Become general, if the polymerization is to be carried out at a temperature above the boiling point of the liquid catalyst, pressures higher than atmospheric pressures may be used. The one for a particular polymerization

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preferred reaction conditions depend largely on the type of polymerizing yinyl compound. For example, it has been found that ethylene is relatively high in a pressure of only atmospheric pressure Ower can be polymerized, rapidly and in almost quantitative conversion at essentially atmospheric pressure and at a temperature below 40 °, for example at room temperature (about 25 °) to a solid Polymers are polymerized kajfrin if you can do it easily put the new ones in an open polymerisation vessel liquid catalysts of the present invention conducts. Also the fluorine-containing monomers, such as trifluorohloräthylen, can also be polymerized at about Atmoapärandruok and room temperature, but are at Using such honomers gives the best results and conversions when taking the polymerization autogenous pressure in a closed polymerization vessel and at a temperature between about 0 ° and about 63 ° is carried out. The speed of the The conversion varies and generally depends on the monomers or mixture of monomers used. Generally the reaction or contact side varies roughly one minute and about seven taps. To polymerize the halogenated olefins, longer reaction times, for example times of more than one hour, applied.

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The liquid catalysts of the present invention have greater catalytic efficiency for the polymerization of the above vinyl compounds as the organometallic compound alone, the inorganic halide alone or the precipitate formed when the organometallic compound is mixed with the inorganic halide alone. the enhanced catalytic effect of the composition of the present invention results from the fact that, for example, isobutylene in the presence of the organic Aluminum compounds alone can be difficult to homopolymerize while it is in the presence of the new liquid catalysts of the present invention very rapidly to relatively high molecular weight materials is homopolymerized. Also 2-olefins, such as sutene-2, are unexpectedly homopolymerized to polymers of relatively high molecular weight by the process of the present invention.

When the polymerization of, for example, ethylene in the presence of the solid precipitate that forms when Siäthylaluminiumbromid and litantetrachlorid are mixed together, carried out and then If the carbon tetrachloride is injected into the reaction medium, the catalyst will not be homogeneous and

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no homogeneous reaction medium obtained, but a catalyst and Bt action media remain heterogeneous. aside from that possesses the polymer obtained by polymerizing a vinyl compound in the combination of diethylaluminum bromide and titanium tetrachloride suspended in hexane is obtained due to the inclusion of solid catalyst a brown to black color and this contamination can be removed by simply washing the polymer with it Carbon tetrachloride cannot be completely removed.

The invention is to be explained in more detail below with the aid of examples.

Example 1-3

These examples illustrate the polymerization of trifluorochloroethylene by the process of the present invention Invention.

A number of experiments were carried out using different amounts of one according to the method of

mentioned patent specification · (patent application

K 32 329) from 100 ml of anhydrous carbon tetrachloride, 2 ml of diethyl aluminum and 0.1 ml of titanium tetrachloride stable liquid catalyst in 300 ml polymerization tubes made of glass previously with

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Flushed with nitrogen. Of the The contents of the well were then frozen at the temperature of liquid nitrogen and 100 g of trifluorochloroethylene were added to each tube condensed into it. The tube was sealed in each pail, and the tubes were left for seven days stand at 25 °. After this time, solid polymer particles were found in each tube and the tubes were opened to unreacted monomer to the atmosphere to drain. In each case, 200 ml of carbon tetrachloride were added to the contents of the tube with stirring. Then the reaction mixture was filtered and the solid polymer was once more with carbon tetrachloride washed until essentially all of the red color was removed from the polymer. With every attempt it was the solid white polymer dried for 8 hours at 190 °. The amount of liquid used in each experiment Catalyst as well as the physical properties4.es white resinous homopolymeric polytrifluorohydroethylene are compiled in Table I. In each run the conversion of the monomer used was too Polymer good. For example, in example? one 45 # conversion achieved.

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! Table I.

Viscosity of the

Volume of liquid dilute solution ZSI example catalyst (ml) / a / (Gensietokes) / b / (seconds)

Λ 40 .... ... 2 1,812 818 3 10 1.204 312

/ a / liquid catalyst from CCl ₄ , (C ₂ Hc) ₂ AlBr and in a volume ratio of 100 t 2: 0.1.

/ b / Determined in a 0.75 solution in dichlorobenzene trifluoride of 130 °.

Example 4-7

Various stable liquid catalysts have been used produced by separately adding 2 ml of dietary aluminum bromide and various amounts of titanium tetrachloride added to each 25 ml of anhydrous carbon tetrachloride, as described in Example 5-8 of the German patent ... .... (patent application K 32 329 ITb / 39o). Then were according to the method described in Example 1-3 PoIy-

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mere made. In each example, an essentially pure white polytrifluorohydroethylene was produced in good yield obtained of high molecular weight. The physical properties of the polymer obtained in each case are given in Table II.

Table II CCl ₄ Used Viscosity-the ml Amount of flow. diluted lo 25th catalyst sung / b / Catalyst / a / 25th ml 1.505 example TiCl ₄ 25th CVl 1.279 4th ml 25th 2 1.486 5 0.02 ία contained 2 1,345 / c / 6th 0.05 2 IMTnIT) I ₁ IlItIh-PO- 7th 0.1 2.0 ml diethvla / a / Every 2 0.25 Subfertuz

mid, 25 ml each of CCl ₄ and the specified amount of TiCl ₄ .

/ b / Determined on a 0.75 # solution in dichlorobenzotrifluoride at 130 °.

/ c / ZST = 373 seconds.

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Example 8

'A liquid catalyst was prepared by adding 1 ml of diethylaluminum bromide and 0.25 ml of titanium tetrachloride to 25 ml of essentially anhydrous Added carbon tetrachloride. 2 ml of this red liquid were placed in a polymerization tube. Bann were 300 g of freshly distilled trifluorochloroethylene added. The tube was closed and left to stand at 25 ° for 7 days. Then it was opened so as not to to allow converted honey to escape. and the pipe content was stirred with 200 ml of carbon tetrachloride. This reaction mixture was filtered and the solid polymer was dried at 190 °. Ss became 80% conversion of the monomer used to form an essentially pure white polytrifluorochloroethylene of high molecular weight achieved. The polymer had a ZST of 547 seconds. A dilute solution had a viscosity of 1j35 centistokes, determined on an O.75 solution in Dichlorobenzotrifluoride at 130 °.

Example 9

A 300 DLH polymerization tube made of glass was evacuated after flushing with nitrogen and treated with 0.68 g of diethylaluminum.

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charged with minium bromide. The contents of the pipe were frozen out at the temperature of liquid nitrogen. Then 0.28 g of titanium tetrachloride was added. After the contents of the tube were frozen out again, 100 g of trifluorochloroethylene were condensed into the tube in the absence of air and moisture. The tube was closed and left to stand at 25 ° for 5 days. 10 $> of the monomers used were then converted to homopolymeric polytrifluorocarbon ethylene with a ZSX of 95 seconds. The viscosity of a dilute solution of the polymer was 0.40 centistokes, determined in a 0.75 # solution in dichlorobenzotrifluoride at 130 °.

Compare Example y with Examples 4-8 found that with the liquid catalysts of the present invention, better conversions on trifluorochloroethylene to polymers and polymers of higher molecular weight than if the catalyst were essentially consists of titanium tetrachloride and diethyl aluminum bromide.

Example 10

This example illustrates the polymerization of ethylene according to the process of the present invention.

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A vertical pyrex wash tower with a length Clay 1.2 m and 5 cm in diameter, which had a sintered glass gas dispersion inlet near its lower end, was filled with 200 ml of carbon tetrachloride and 500 ml of n-hexane were charged, after which 4 ml of diethylaluminum bromide and 1 ml of titanium tetrachloride were added separately. Then rasoh ethylene was obtained in the clear red catalyst initiated at 25 ° and atmospheric pressure. A solid polymer formed immediately. The exothermic reaction warmed up the reaction mixture to about 40-50 °. The ethylene supply was regulated so that although the monomer was quickly introduced into the system at the bottom of the tower, no bubbles arrived at the top, d. H. it became a quantitative conversion of ethylene almost instantly to polyethylene achieved. The polymer separated out as it was formed and gradually filled the tube. After 2 For hours, the ethylene supply was stopped and the polymer was repeatedly added and removed washed free of liquid catalyst by η-hexane. The solid polyethylene was washed several times and then dried and pressed. The solid homopolymeric polyethylene obtained had a ZST of 138 seconds and a transition temperature of 136 °.

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Example 11

This Teransohau example shows the polymerization τοη Propylene according to the process of the present invention.

Un rertical Yasoh tower made of Pyrez clay 1.2 m long and 5 The Suroh knife, which had a sintered glass dispersion insert near its lower drawer, was also used 700 ml of carbon tetrachloride were charged, to which 4 ml of siethylaluminum bromide and 1 ml of titanium tetra chloride were added separately. Then it quickly became teohnisohes Propylene passed into the resulting red liquid catalyst at a rate of about 0.1 Hol per minute at JLtmospharendruok. Implementation was initiated by placing a bowl of hot water under the beactor set, where the exothermic reaction resulted in the temperature of the reaction medium remaining at 40-50 °. It formed a solid bottom layer of homopolymeric polypropylene and the liquidity.tsTOlumen rose by about 30 ml. The polymer has a broad molecular weight distribution in the range of easily distillable oils to hard-like solid materials τοη high molecular weight

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Example 12

4 ml of triisobutylaluminum were added separately to 200 ml of carbon tetrachloride at room temperature and 1 ml of titanium tetrachloride was added. The resulting red colored stable liquid catalyst was then in a 2.4m glass column containing 2 liters of technical, freshly dried η-hexane »was added · There was none Separation of solid material. This liquid catalyst was then sintered through a disk Glass introduced at the bottom of the column ethylene at a rate of about 12 moles per hour. Bas Ethylene was quantitatively absorbed for 20 minutes, the temperature rising to 35-40 °. Then the catalyst-containing solution was drained from the bottom of the column, while fresh carbon tetrachloride was continuously added through the top of the column. The process was continued until the solid polyethylene remaining in the tower was essentially pure white. Ban became the polymer removed from the bottom of the reactor, treated with methanol and dried overnight at 100 ° * A total of 120 g of white, solid, homopolymeric polyethylene were obtained.

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Example 13

This example illustrates the polymerization τοη Isobutylene according to the process of the present invention.

After purging with nitrogen, 12 ml of anhydrous n-hexane were placed in a 300 μl glass polyaerization vessel and 50 ml of anhydrous carbon tetrachloride were introduced, where 0.5 al (0.0045 mol) diethylaluminum bromide and 0.1.2 al 0.0011 mol) titanium tetra chloride were added separately. A wine-red, stable, liquid catalyst was obtained. Then 40 g of isobutylene was added to the liquid catalyst at room temperature. The polymerization jar was closed and the polymerization was stopped for about 15 minutes at 25 ° run autogenous pressure. Then the glass jar was opened. An elastic, rubbery hoaopolyeresis polyisobutylene was obtained. Ss was a quantitative conversion of the introduced monomers to form polymers (about 40 g).

Example 14 This example illustrates the polymerization of BADORIQINAL

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2-olefins according to the process of the present invention.

Hn polymer! was old nitrogen purged. Then there were 12 au. anhydrous · η-hexane and 50 ml of anhydrous carbon tetrachloride were introduced and separated from one another 0.5 ml (0.0045 Hol) of diethyl aluminum bromide and 0.12 ml (0.0011 moles) of titanium tetra chloride are added. One received a clear wine red liquid catalyst. 40 g of 2-butene were then added to the liquid catalyst at a temperature of 25 ° Gesohloeeen and the polymerization was run for about 15 minutes at 25 ° under autogenous pressure. Then the pressure was released to atmospheric pressure. Ss was a quantitative conversion of the 2-butene and solid homopolymeric olybutene-2 (about 40 g) was achieved.

Example 15

This Yeransoha example shows copolymerization ▼ on ethylene and! Propylene according to the invention.

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In a 3-JJ-Polyfflerieationsreaktor, which was previously old Was flushed with nitrogen, 200 ml of anhydrous Tetracfilorkohlenatoff and 2500 ml of anhydrous n-Htxan and 4 al (0.033 mol) of ethylaluminum bromide and 1 al (0.009 mol) of titanium tetrahedral chloride were then introduced separately from one another. A wine-red liquid was obtained, τοη der sioh no firm ·· material parting. In these liquid The catalyst was a gaseous mixture of 95 mol £ Ethylene and 5 mol- ^ propylene in Ataosphärendruok old one speed τοη about 12 moles per hour slides. she Polymerization took place quantitatively at room temperature (25 °) and gave 128 g of white, solid after 20 minutes Oopolyaeres τοη ethylene and propylene, which is a ZSf τοη 152 seconds at 160 ° and a transition temperature tone 127t9 °. During the implementation none did not escape uagesetites ethylene and propylene from the reactor.

Example 16

This example is intended to continue the copolymerization τοη ethylene and propylene according to the procedure described above Illustrate the invention.

In a polymerization reactor τοη 3 liters were, after flushing with nitrogen, add 200 ml of water-

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free carbon tetrachloride, 2500 ml anhydrous n-hexane and then separately from each other 4 ml Trueobuty! aluminum and 1 ml (0.009 mole) of titanium tetra chloride. A clear, wine-red liquid was obtained from which none can be seen solid material absohied. In the liquid catalyst then became a gaseous mixture at i.tmosphärendruok from 95 M0I-3C ethylene and 5 mol-? C propylene introduced at a rate of about 12 pounds per hour. the Copolymerization took place quantitatively at room temperature and atmospheric pressure and resulted in about 20 minutes HO g of a solid copolymer of ethylene and propylene with a ZST of 106 seconds at 160 ° and a transition temperature of 118.8 °.

Example 17

This example illustrates the polymerization a polyolefin naoh. the procedure of the present Invention.

A polymerization tube made of glass with a volume of 300 ml was flushed with nitrogen and boiled with 12 ml anhydrous η-hexane and 50 ml anhydrous carbon tetrachloride, after which 0.5 ml (0.0045 Mol) diethylaluminum bromide and 0.12 ml (0.0011 mol) titanium

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tantetraohlorid sugeaetst were. Kan received a clear wine-red liquid catalyst. After adding τοη 40 g The pipe became the 1,3-butiene-diene for the liquid catalyst closed. The polymerization was allowed to take place under autogenous Advance pressure for 15 minutes at 25 °. Then the drill was opened. The solid polymeric product was collected, Washed with carbon tetrachloride and dried * Xs a quantitative conversion of the 1,3-butadiene-1,3% solid homopolymeric polybutadiene introduced into the polymerization ion was obtained, which up to the temperature below 450 ° was thermally stable.

Example 18

This example is intended to rehabilitate the polymerization of a boron-containing olefin according to the method of the present invention.

A 300 ml polymerisation tube from the fllas was naoh Flush with nitrogen with 10 ml anhydrous fetra ·? Carboniferous carbon, where separate from each other 1 ml (0.00825 Hol) of diethylaluminum bromide and 0.5 ml (0.0045 mol) of titanium tetrachloride were added. The drilling contents were frozen out at the temperature τοη liquid nitrogen and 50 g vinyl chloride were in the drilling hiti-

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condensed in, whereupon it was closed. The RealrifensgemiBoh was left to stand for 7 days at 25 °, after which about 42 g of solid polyvinyl chloride were obtained and isolated as a process product.

Example 19

This example is intended to polymerize an aryl substituted olefin according to the method of the present invention Discovery of Teransohauliohen.

A 300 ml glass polymerization tube was fitted with Stiok Rinsed fabric and then charged with 10 ml of anhydrous carbon tetrachloride, after which 1 ml (0.00825 mol) of Diftthylaluminiumbroaid and 0.5 ml (0.0045 mol) of titanium tetrachloride were added. The drilling content was at the Temperature τοη liquid nitrogen frozen out, and 50 g of styrene were condensed into the tube, after which it was closed. The reaction mixture was left for 7 days 25 ° stand, after which about 42 g of homopolymer polystyrene were obtained and isolated as a Yerfahrenproduct.

Example 20 This example is intended to illustrate the polymerization of an alkoxy

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Illustrate substituted olefins according to the process of the present invention.

To 10 ml of anhydrous carbon tetrachloride were added 100 ml of η-hexane and then 1 al (0.00825 Hol) Diäthylaluminiumbromld and 0 _r 5 ml (0.0045 mol) Titantetraohlorid added lin portion of 20 ml of this clear red liquid was then added dropwise with stirring placed at a temperature of about 0 ° in a glass flask containing 50 g of yinyl isobutyl ether. A rapid exothermic polymerization took place, whereby a resinous homopolymeric polyvinyl butyl ether was obtained in quantitative yield.

Example 21

A glass polymerization vessel with a volume of 300 ml was purging with nitrogen with 25 ml of anhydrous η-hexane and 25 ml of anhydrous chloroform, after which 1 ml of diethylaluminum bromide and 0.2 ml of titanium tetra chloride were added separately. Han received a clear wine-red liquid, from which no solid material separated even after standing for a long time. Sann were at room temperature (25 °) and atmospheric pressure 25 g of Ithyles

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passed into this liquid catalyst. After this reaction mixture for about 10 minutes "at 25 ° had left to stand, there was a quantitative conversion of the ethylene introduced into about 25 g of solid homopolymer Polyethylene.

Example 22

In a polymerisation reactor made of glass of approx 50 cm in length were 100 ml of pentachloroethane and 100 ml given η-hexane, after which 0.5 flil separately Diisobutylaluminum hydride and 0.1 ml of titanium tetrachloride were added at room temperature. One received clear dark red liquid, from which no solid material separated. Then it was at 25 and atmospheric pressure Ethylene passed into this stable liquid catalyst for 15 minutes. The forming solid Polymers were allowed to settle and then washed with n-hexane to remove the red color and dried it. Han received about 10g of white solid homopolymer Polyethylene.

Example 25

This example aims to polymerize a

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fluorine-containing polyethylene by the method of illustrate the present invention.

To 0.5 ml of carbon tetrachloride were added at room temperature separately from each other 0 ^ .02 ml of diethyl aluminum bromide and 0.002 ml of titanium tetra chloride added. The obtained red liquid was poured into a 10 ml polymerization tube given. The tube was cooled in a bath of liquid nitrogen. Then about 10g 1,1,3-trifluorobutadiene added. The ear was locked and left to stand for 30 minutes at 25 ° under autogenous pressure. Then it was put in a bath of liquid Nitrogen transferred and the positive pressure vented to the atmosphere. The solid polymeric product was filtered off, washed with η-hexane and placed in a vacuum oven dried at 80 °. In quantitative conversion of the monomer used, a white, Yes, homopolymer of 1, 1, 3-trifluorobutadiene.

Following the procedures described in the above examples, the same polymerizations can be carried out by, for example Ethylene, propylene and isobutylene to polymers also using the remaining liquid ca-

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catalysts dee patents ... ... (patent application K 32 329), i.e. H. Bit the liquid catalysts by, separate addition of diethylaluminum bromide and ierrlohlorid to carbon tetrachloride; by separately adding diethyl aluminum bromide and titanium tetra chloride to a mixture of chloroform and Hezanf or by separately adding diethyl aluminum bromide and titanium tetra chloride to a mixture of 1,2,3-trlohloropropane and hexane; and the like are, for the production of the stable liquid catalyst besides η-hexane also other hydrocarbons, such as pentane, isopentane, gyolohexane, kerosene, tetrahydronaphthalene, decahydronaphthalene, and aromatic compounds such as benzene, toluene and xylene can be used can.

The polymerization process of the present invention can be carried out batchwise or continuously. When carried out continuously, for example, ethylene is continuously converted into a liquid Catalyst initiated, which consists for example of diethyl bromide, titanium tetrachloride and carbon tetrachloride, while the suspension of solid polyethylene in the XaBe in which it is formed, deducted and the Tlüesigkelts level in the polymerization zone duroh add

would give up from hexane or further ·· carbon tetrachloride the desired height is maintained · The solid polymer can be separated by decanting or filtering and the so recovered Tetraohlorkohlenetofflöeuag can be fed to the polymerization zone after further diethylaluminumbronide and litantetraohlorid have been added separately from one another or without such a further addition taking place, whereby "I the necessity of the addition of further bromide or Metal chloride results from the rate at which the ethylene is converted to solid polymer. the The effectiveness of the process described here is the greatest possible, since the chlorine-containing organic compounds and the hydrocarbon, if such is used, are recovered and the polymerization zone can be recycled and since essentially no catalyst is lost through inclusion in the polymeric product.

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Claims (1)

U20544 Claims 1 * process zxtx production of a polymer by polymerizing a polymerizable © !! Ethylenically unsaturated compound in the presence of a liquid catalyst which contains a chlorine-containing organic compound, an organic compound of a metal of Group IIIA and a halide of a transition ohmic metal, if desired mixed with an inert liquid diluent. 2. The method according to claim 1, characterized in that that the polymerization temperature between about -100 ° 0 and about 200 ° C, preferably between about -20 ° C and about 100 ° C. 3 * Process according to Claim 1 or 2, characterized in that a monoolefin such as ethylene, propylene, isobutylene or butene-2 is polymerized. 4. The method according to claims 1 or 2, characterized in that a polyolefin such as butadiene is polymerized. 809806/0579 5 · Method according to claim 1 or 2, characterized in that » draws that an aryleuo-substituted olefin, such as styrene, is polymerized 6. Method according to claim 1 or 2, characterized in that that an alkoxy-substituted olefin, such as vinyl isobutyl ether, is polymerized. 7. The method according to claim 1 or 2, characterized by that a halogen-containing olefin, such as vinyl chloride, is polymerized " 8. The method naoh one of the preceding claims, characterized in that a solid copolymer is formed will. 809806/0579