DE1468276A1 - Process for the polymerization of olefins - Google Patents

Description

DR. E. WIEGAND

MÖNCHEN DIPL.-ING. W. NIEMANN

HAMBURG PATENTANWXLTE

Mönchen is, July 26, 1963

NUSSBAUMSTRASSE 10 TELEFON = 55547 «

V. 11 457/63 11 / Bn

Monsanto Chemical Company St. Louis, Missouri (V.St.A.)

Process for the polymerization of olefins

The invention relates to a process for the polymerization of polymerizable olefinic hydrocarbons. In particular, the invention relates to a method of polymerizing polymerizable bar olefinic hydrocarbons under thermal polymerization conditions. The invention still further relates to a process for the polymerization of polymerizable olefinic hydrocarbons to form polymers

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relatively low molecular weights in the presence a "modifying" compound and under specific thermal polymerization conditions.

The polymerization of polymerizable olefinic Hydrocarbons at high temperatures and pressures under non-catalytic conditions are known. In general, large amounts of High molecular weight polymers produced by the condensation of many of the molecules used at the beginning polymerizable olefinic monomers are formed

Also through careful regulation of working conditions. such as temperature and pressure, can be different olefinic Hydrocarbons with the formation of polymeric products, which result from the condensation of two olefinic Hydrocarbons, molecules or monomer units result, are thermally polymerized. Such products are commonly referred to as dimers. In general, however, such working methods have become due to the very low yields of total polymer formed under the conditions necessary for the formation of dimers « de, found to be inadequate

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Another feature of the known procedures for making dimers by thermal routes is that they are proportionate large amount of branched chain polymeric products formed. In some cases they are just straight chain Products desired. In such cases it is often only a matter of a simple distillation to get the branched chain Separate products from straight chain products. In many cases, however, different the branched-chain polymers by simple distillation or other economic means are not removed from the straight-chain polymers are separated · An example of this are the n-hexenes and 2-mdfchyl-1-pentene, which formed by the dimerization of propylene. Sooind, if it is desired to obtain relatively straight-chain polymers as polymerization products, the known working methods quite poor.

One purpose of the invention is to provide a new and improved process for the polymerization of polymerizable olefinic hydrocarbons "Another purpose of the invention is to provide a new one and improved processes for the polymerization of polymerizable olefins under thermal polymerization conditions. Another purpose of the invention is the sheep-

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fung of a new and improved process for the production of polymers of relatively low molecular weight by the polymerization of polymerizable olefinic hydrocarbons under thermal polymerization conditions. The particular purpose of the invention is to provide a process for dimerization and trimerization of polymerizable olefinic hydrocarbons under thermal polymerization conditions · A It is a specific purpose of the invention to provide

from

Process for the preparation of dimers and trimers of polymerizable olefinic hydrocarbons by polymerizing polymerizable olefinic hydrocarbons under the polymerization conditions of high temperature and low pressure and in the presence of a modifying compound. Another special purpose of the invention .; is creating a new and improved one Process for the dimerization of olefinic hydrocarbons under thermal polymerization conditions, wherein higher yields of straight chain isomers can be obtained · Further purposes of the invention are from the following Description visible.

According to the invention, polymerizable olefinic hydrocarbons are used under polymerization conditions of temperature and pressure in the presence of lower

Amounts of a modifying agent, which sulfur, a · Comprises sulfur-containing compound or a halogen-containing compound in which the halogen is selected from bromine, Chlorine or iodine is subject. Ib has been found that when you have polymerizable olefinic hydrocarbons elevated temperatures and pressures in the presence subject to lower amounts of such funds, much higher ones. Yields of polymers of low molecular weights, such as dimers and trimers, are generated. These increased yield of low molecular weight polymers and linear polymers is obtained while a relatively high yield of total polymer formed is maintained.

The terms "dimers" and "trimerea", such as ei · here used to describe the products of the method according to the invention, refer to compounds, which are formed by the condensation of 2 or 3 molecules or monomer units of a particular polymerizable olefinic hydrocarbon.

Si · invention is illustrated below by way of examples illustrated in more detail.

Example 1 Two separate polymerizations were carried out.

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using a propylene feed having a composition of 97 wt% propylene and 3 wt% propane in each experiment. Both experiments were carried out in a 1.7-liter jacketed autoclave. One experiment was carried out in the presence of 1-bromohexane in an amount equivalent to a weight ratio of 1-bromohexane to propylene of about 0.036; 1. In the other experiment, no modifier was used. In each experiment ^ de wu the temperature within the ranges τοη held 325-350 ° 0th The pressures in each experiment reached a maximum when the reaction reached a temperature τοη 350 * C, and then fell in the course to a minimum final pressure. The pressures were as follows: a maximum of 274 atmospheres (3,900 psig) and a minimum of 162 atmospheres (2,300 psig) on the no modifier test and a maximum of 253 atmospheres (3,600 psig) and a minimum of 183 atm. (2,600 psig), in the experiment modified with 1-bromohexane, The reaction carried out in the presence of 1-bromohexane was terminated after only one hour, while the unmodified experiment took about 3,., *. Has been allowed to run for hours. After completion of the reaction period in each experiment, the autoclave was cooled to room temperature and opened to the atmosphere. The liquid product was recovered and the mol

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lecularly accredited distribution determined. The transformation and the Molecular weight distribution or scatter are given in the table below *

Non-Modified Modified Yersuoh. Weight 1 » Trial. Weight

Conversion into liquid
total product 42.3 34.0 distribution Cg Dimer · » 17.9 33.3 Cq trimeres 21.2 29.1 C ₁₂ tetrameres 20.0 19.0 C.
15 pentameres 18.9 5.5 rest 22.0 13.1

In the above example, the conversion to liquid product in the presence of 1-bromohexane represents a decrease in conversion of about 19.1 #. However, it is to note that the reaction time in the attempt at which 1-bromohexane was used was only one hour compared to 3 hours for the Versuoh which contained no modifying compound. The advantage that achieved by the process according to the invention is clearly illustrated by the increase in the yield of Cg dimers and Cq tromers in the experiment carried out in the presence of 1-bromohexane. The total increase in the yield of these two polymeric products

increased from 39 »1 56 to 62.4 J * of the polymeric product. It represents a 59.6 # increase in yield two preferred polymers when using the method according to the invention of the invention produces a larger amount of dimers and trimers from a given amount of monomers, and this in less time than similar conventional thermal polymerization processes and without a substantial amount Loss of the total amount of polymeric product

Example 2

A number of tests were carried out with various halogen-containing compounds as modifying agents. In each of the tests, about 0.84 g of propylene were used the same composition used in example 1 in • introduced into a stainless steel tube, in which a · Halogen-containing compound in an amount equivalent to about 1.5 mole-ji of the total charge to the tube has been introduced. The stainless steel tube was 4.3 ml in length and 0.07 cm (0.05 inch) inside diameter. The pipe was suitable for this. Withstand pressures of about 352 atmospheres (5,000 psig). Tue Tubes were sealed and raised to a temperature

80981 3/1 3? Il

brewed * The pressure was not used in each of the attempts measured, but it can easily be calculated from the temperature and the amount of product in the closed pipe. In the table below are the percent conversion, the weight percent of dimer in the product that The length of time during which the reaction is carried out and the temperature given

Modification a medium

2-bromopropane 1-bromohexane 1-chloropropane

2-bromopropane benayl bromide 1-bromopropane Brombene

Gew. JG conversion
development of C-zBV
in liquid ⁰
product Weight? 6
Witches in
liquid
product ⁰ C Minutes 18th 66.6 375 7.5 22nd 51.6 350 30th 13th 46.0 350 SO 44 41.9 375 30th 48 41, d 350 120 31 41.5 350 60 39 41.2 350 60 32 31.1 350 SO Example 3

In order to demonstrate the usefulness of the process according to the invention as a continuous process , two continuous polymerization experiments were carried out under similariohea

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Conditions when using propylene in Example 1 specified composition executed. An experiment was carried out in the presence of 2-bromopropane as a modifying compound while the other was done in the absence of any modifying agent. In the following The table shows the conditions of the two tests and the results obtained from them »

conditions Not-
modified Modified with
2-bromopropane Amount of modification
funds none 1 MoI- * Pressure, atü (psig) 211 (3,000) 211 (3,000) Temperature, ° C 450 450 IHSV 12.7 36 Medium · feed
speed,
g / min 3.4 5.6 Results Conversion into liquid
total product, weight 3 * 26.0 16.0 Ratio straight chain
ger su ver * weigtketti
ger 0.73 6.16 Analysis of the product
Oew.jC
^C 5
^C 6 7.6
25.3 no
72.1

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Mioht- Modified with modified 2-lrompropane 11.8 no 20.2 21.9 11.0 no 24.1 6.0

Analysis of the product Gew.jfc

C ₇ , C ₈

^C 9

^C 10 » ⁰ II C ₁₉ plus

The above comparison reveals the unexpected pie parts using the method according to the invention As can be seen, the non-modified test produces significantly higher amounts of polymers with a higher molecular weight than the modified test Test obtained · Also of importance is the fact that by using the method according to the invention block or Bulk polymers (multiple of the bosohickungsolefine) are formed, while in the unmodified Versuoh Polymers of various molecular weights are formed.

As stated above, there is the main advantage which the method according to the invention offers is achieved in the very considerable increase in the yield of low molecular weight polymers, i.e. Dlmeren in the product. This is particularly clear from the following table, which shows a tergleioh of the yield. Seigt in Og dimers at different conversion levels, what duroh polymerization of propylene with and without addition «

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of a halogen-containing modifying compound received hurdle. When used as a modification compound The compound is isopropyl bromide

Gew.jC hexene in the liquid product

in liquid product
Modified Example 4 »Eht modified ♦ 5 21.0 17.8 35 38.5 18.2 25th 56.0 19.4 15th 73.5 20.8 10 82.5 21.5

There were five separate polymerization runs carried out, with a propylene charge bit with a composition of 97 wt. ^ Propylene and 3 ffew.jC Propane was used. These attempts were made in one 4.3 ml stainless steel tube with a pressure of withstands about 352 atmospheres (5,000 psig), performed ♦ The The diameter of the stainless steel tube was about 0.07 ob (0.03 inch). In four attempts was sulfur or • a sulfur-bearing compound as a modifier admitted. The fifth attempt was one without the hat

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executed. In all four experiments, the amount of propylene introduced into the reaction tube was about 0.85 g. The temperature was kept at about 375 ° C. in all experiments. The amount of modifier used in each jar, if one was used. , corresponded to a molar ratio of propylene to modifier of 75 t 1. The pressure was not recovered in any of the tests; however, the experiments were carried out in a closed container «The pressures can therefore easily be calculated from the temperature and the amount of the reaction components added to the reaction _{tube Φ} The results of these experiments and the modifying agents used are shown in Table Z below»

ORIGINAL INSPECTED
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Table I. No aodifi- 2-Haphtha- tert.-Ootyl ·,

decorative linthiol mercaptan sulfur S + DPEA

bond )

Wt * O ₃ H ₆

Conversion to

liquid product 20

0ew «£ witches im

liquid product 19.8

Composition of witches graiction

2-methylpentane 3.41

2,3-DSiethylbutane 0.49

4-methyl-1-pentene 24.89

4-methyl-2-pentene 2.92 (;tear)

2 _f 3-Biaetnyl-1-butene -

1-hexene 42.72

trans-2-hexene 1.95

Methylcyolopentane 2.92 2-methyl-2-pentene

ols-2-witches -

3-Jlethylpiehten ^

2-methyl-1-pentene 2o, 70

linear ·, Η # χ · ηβ 44.67

18th ν «.? ;; 22.70 19.7 32.2 5.46 ^{1 of} 0.61 ²⁸ » ⁵ 3.33 1.23 10.23 20.00 ^v 52.78 1.14 13.89 1.21 . "■ f.-. -4.29- .. 13.07 i; 66 1.21 6.13 1.70 - " W, 9y 0.57 53.88 6.67 59.68 11.13 4.85. 3.41 10, PO 7.96

6.11 ""

1.84

f-i S

63.64

2.27

Cl, 0 60.13 £ 5.36

X)

3ohulphur. dissolved in diisopropylethanolamine (ÄlThaltei 11)

ORIGINAL fNSf »ECTED 809813 / Ϊ12Ρ

The gate part of the method according to the invention let aue of the advisory table slightly ereiohtlloh ·

The average conversion τοη propylene into polymer is actually greater in two of the reddening modifiers and only slightly reduced in the other two. Sable the gewlohteprosentuale proportion of di- or ■ Hezenen was in the polymer product τοη 19.8 i "τοη in the absence Sohwefel to 32.2 jC 2-Baphthalinthiol risen. The increase in the amount of linear hexene product τοη 44.67 Ji without the use of a modifier to 71.12 i » when using τοη 2-naphthalenediol shows the accompanying improvement that can be achieved in the process according to the invention for the production of τοη linear polymers. It must also be noted that the formation of 2-methyl-1-pentene is influenced when the sulfur-containing modification compounds are used.

The modifying agents which can be used to carry out the process according to the invention include compounds in which the halogen · chlorine, bromine, iodine or combinations thereof -present · Such a compound can either be an organic or inorganic compoundIn addition to these halogens, other elements such as carbon, Hydrogen, sulfur, oxygen or nitrogen in the

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Modifying compounds are not available ₉ In the case of an organic compound, this can be saturated or unsaturated, aliphatic or aromatic, straight-chain, branched-chain or of a cyclic structure.Generally, it should be noted that the halogen-containing modifiers are compounds which are decomposable under the conditions of the reaction chamber or form hydrogen halides, HBr, HCl and HJ »This includes not only those compounds that contain bromine, chlorine and iodine as part, but also the halogen gases Cl ₂ , Br? and J ₂ · halogen-containing compounds within the scope of the invention include the following non-limiting examples.

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Column I.

2-bromopropane 2-chloropropane 1-iodopropane 1-bromobutane 1-chlorobutane 2-iodobutane 1-bromopentane 2-bromopentane 3-chloropentane 2-iodopentane 3-bronnexane 2-bromohexane 2-iodohexane 2-bromo-4-methylhexane

3-chloroheptane 3-bromoheptane 2-iodoheptane ¹ 2-bromo-4-ethylhexane 4-bromooctane 3-chlorooctane 2-iodootane

Column II

Bromobenzene Chlorobenzene

m-dichlorobenzene

2-diochlorobenzene

2-diochlorobenzene

m-Di "bromobenzene

o_-dibromobenzene

^ -Dibromobenzene

Iodobenzene

£ - iodotoluene

m-iodotoluene

£ -iodotoluene

2-chlorotoluene

m-chlorotoluene

£ -Ohlortoluene

jo-bromotoluene

m-bromotoluene

p-bromoluene

1.5 »5-dibromotoluene

<o-bromobenzene sol

m-bromochlorobensol Column III

Chiorethane acid Dibrosaethanoic acid

dl-iodoethane acid 4 α-ghloraoetamide a-bromoacetanilide '

Benzoyl chloride Benzoyl bromide Benzoyl iodide Butanoylochloride Butanoyl bromide Butanoyl iodide

2-chloro-1,4-benaoldiol 2-bromo-1,4-benzenediol

l-chloro-4-nitronaphthalene

Benzoloarbonylochloride Benzene carbonyl bromide Suocinyl chloride

4-chloromnoline

Ethanoyl iodide Hexanoylochloride Deoanoylohlinride ORIGINAL INSPECTED

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Column I.

η,
1-bromonane

2-chlorodeoane 2-bromodeoane 2-bromo-6-methyldecane 313-bromomethyl decane 4-iodo-undecane 1-bromododeoane Hydrogen chloride Hydrogen bromide Hydrogen iodide

Column II

Jg-Br omehlorb enzol

2-bromonaphthalene

1-chloronaphthalene

1,3-dichloronaphthalene

2-bromodiphenyl

2-chlorodiphenyl

4-chlorodipheny1

Ghlorgas

Bromine gas

Iodine gas

Column III

2-chloroethano1

Bis-ß-chloroethyl ether

Chloromethoxymethane

Gyclohexyibtoniid

Carbon tetrachloride

2-chloro-3-hexene

2-bromo-2-pentene

3-bromo-4-octene

Most useful halogen-containing compounds for carrying out the process according to the invention are those that contain a halogen from the group consisting of bromine, chlorine and iodine and the elements carbon and / or oxygen contain. These compounds are the halogen-substituted hydrocarbons and hydrogen halides. It exists no critical limitation on the molecular weight of the modifying compound other than that of a practical one Handling. From a purely practical standpoint, the use of such compounds, the are usually liquid, somewhat preferred, whereby the usual

ORiGINAL INSPECTED 809813 / 13W

U68276

Borrowed gaseous compounds are even more preferred »You preferred in carrying out the method according to the invention Compounds are the mono- and di-halo substituted ones Hydrocarbons of no more than 6 carbon atoms and the hydrogen halides. Although all of them Halogens from the group consisting of bromine, chlorine and iodine are useful for carrying out the process, the general use will be those compounds containing chlorine and bromine are preferred, with bromine being preferred over chlorine.

Modifying compounds useful in carrying out the process of the invention include elemental sulfur as well as sulfur-containing compounds. The sulfur-containing compounds can be either organic or inorganic. Biβ can be of virtually any molecular weight, the limitations being given by practical considerations, ie, ease of handling in the process. When using organic compounds, the modifying compounds can be straight-chain, branched-chain or cyclic, aromatic or non-aromatic, saturated or unsaturated. When elemental sulfur is used as the modifying compound, any of its forms can be used. In general, the requirements for the modifying compound are to be formulated in such a way that it must be a compound which, if it is in

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the reaction chamber is brought under the tea temperature and pressure conditions of the reaction calibrated or delayed Schwefelwaaaeratoff forms. For the procedure according to Sulfur-containing compounds useful in the invention include those listed above.

Allyl sulfide Benzyl disulfide

2-methyl-1-butanethiol 2-methyl-2-butanethiol

Butyl disulfide

1,2-ithandithiol

Ethylene sulfide Ethyl sulfide

1-heptane_thiol

Ieoamyl disulfide I «obutylaulf id Methyl sulfide

1-naphthalene thiol

Phenylene sulfide

2-methyl-propanethiol 2.2 * shio diethanol

Aoetyl disulfide

, o-Br oabenzo laulf onaäur e j> -chlorobenzenesulfona aure e

Bensoyl disulfide Benayla sulfide

3-methyl-1-butanethiol tert-octanethiol

Butyl sulfide Ethanethiol Ethyl disulfide Purfuryl mercaptan

1-hexanethiol

Iaoamyla sulfide Methyl sulfide

2-naphthalenediol 1-pentanethiol 1-propanethiol 2-propanethiol Thiophene

Benzenesulfonic acid

jg-bromobenzenesulfonic acid £ -Formylbenzenesulfonic acid

8098 Ί 3/1

Methylbenzenesulfonic acid

2.2 ^f -ithiophane

Butyl sulfone Dtthiooarbamic acid Thiocarbamic acid Dithiolo carbonic acid Dodecyl sulfate Ethionic anhydride Ethyl sulfone Ethylaohulphuric acid Methyl sulfoxide

2-Bronthlophs 2, 5-dibromothiophene 2,3-dimethylthiophene 1-decanol sulfate

Methyl sulfite Ootyl sulfate Bia- (ß-dichloroethyl) sulfide Tetradeoyl sulfate Thlonaphthenohinone

3-methylthiophene elemental sulfur

Benzyl sulfoxide Butyl sulfate Butyl sulfoxide Thioloarbamic acid Irithloo carbonic acid Cetyl sulfate

1,2-ethanedi eulfona acid

Ethyl sulfite Ethyl sulfozyme Methanethiol

β, β · -Diohloroethyl sulfide 2-chlorothiophene 2,5-diiodothiophene

Vinyl sulfide Methyl sulfate

llethylaulfone

Diolophenylphoaphine sulfide Ethyl methyl sulfide Thionaphthene

2-methylthiophene «<-Toluene thiol

Sulfur dissolved in dialkyl alkanols

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Wit also the above list of compounds As can be seen, the sulfur-containing modifiers can contain elements other than sulfur, such as carbon, hydrogen, oxygen, nitrogen, chlorine, bromine, Iodine or the like. Preferred soulfur modifying agents include soehulphur and such sohulfur Carrying compounds, such as mercaptans, or thiols, aliphatic such as aromatic, sulfur, hydrogen and thiol ethers. In the list of preferred compounds are also contain those obtained by dissolving soh sulfur in tertiary amines at elevated temperatures · Other preferred sulfur modifiers are sulfur and carbonaceous compounds that additionally contain elements such as carbon and / or hydrogen contain. When using sulfur-bearing compounds, which contain carbon and hydrogen, will generally preferred that they contain no more than 20 carbon atoms.

You amount of to perform the procedure according to Modifying compound useful in the invention relates to the ratio of hydrogen halide or Hydrogen sulfide obtained by decomposition of the modification compound or its formation the polymerizable olefinic hydrocarbons.

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In general, the molar ratio between the amount of hydrogen halide or hydrogen sulfide present and the polymerizable olefinic hydrocarbons in the feed will be within the range of 10 held until 1: 500. Preferably this molar ratio is in the range of It50 to 10000.

The way of working, according to which the modifying Compound fed to the reaction zone is not critical and can be done in virtually any manner will. The only critical feature of this addition is that there be thorough and intimate contact between the polymerizable olefinic hydrocarbons and the modifying compound. The modifying compound can be introduced at the same time as the olefin coating or it can be introduced in opposite directions or as a transverse stream with respect to the flow of the Olefinbesohiokung are given. When using liquid or liquefiable modification compounds these can either be called within the reaction chamber a liquid bed or in fora of heat exchange pellets or the like. be dispersed. The best way of working by which the modifying compound is in contact with the Reaction will, of course, vary depending on the physical properties of the modifying

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Link. For example, a modifying agent which is gaseous or which can easily be converted into the gaseous state Compound is most advantageously introduced in cocurrent, cross-flow or countercurrent to the charge flow, while a more viscous liquid or a liquefiable solid is introduced in is more advantageously added to the reaction chamber as a dispersed bed as described above. Finding the best way of working to achieve contact between the modifier and the reaction components is within the capabilities of a person skilled in the art.

The polymerization process according to the invention can can be carried out either batchwise or continuously. The equipment required for each type of operation can be any conventional equipment ■ one that can withstand the extraordinarily high pressures developed during the process. The residence time of the reactants in the polymerization zone is generally in the range from ο, οοΐ to 240 to 300 Out there. Preferably, however, the residence time should not be less than 0.05 and not more than 120 minutes.

Indeed, any polymerizable olefin can be thermally polymerized by the process according to the invention. In general, such olefins should contain 2 to 2o carbon atoms. The expression "olefin ^{11" used below}

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does not only contain mono-olefinic hydrocarbons, but also diolefins. Further, the method according to the invention can see effective polymerization of aoetylenis Hydrocarbons are used »Preferably, the process according to the invention is based on polymerization τοη olefinic hydrocarbons used which contain 2 to 6 carbon atoms «Examples of such hydrocarbons are ethylene, propylene, butylene, pentylene, Isopentylene, Hexene, Isohezene, Butadiene, Hexadiene and Ieohexadienes · The process according to the invention is particularly brewable when it is based on thermal polymerization of ethylene, propylene and butylene and mixtures thereof is used. The polymerizable olefinic hydrocarbon content according to the invention does not have to be a pure one Be a stream, but generally contains not less than 40 moles of polymerizable olefin. This limitation, however, is primarily concerned with technical expediency and not on feasibility. Impurities which can be tolerated in the feed in the process according to the invention include saturated hydrocarbons, such as n- and isoparaffins or the like.

The thermal polymerization of. olefinic hydrocarbons in the presence of the modifislerenden compounds

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According to the invention, at elevated temperatures usually 1 ion within the range of 250 ° C to crack temperature of the special hydrocarbons in the barrier Implementation of the method according to the invention are however within the range of about 300 to 500 ° C. Temperatures of 325 to 475 ° C provide for polymerization of the preferred feeds of the process according to the invention generally the optimum in yield of dimeric product.

The Arbeltswelse described here is at increased Pressures generally at a pressure of more than 14 ·, 1 atm (200 pslg) run · The upper gkrence of pressures at the Execution of the method according to the invention is only through the strength of the leakage vessel is given · general The higher the pressure, the better the results of the polymerization reaction. The preferred pressures for carrying out the method according to the invention are above 70.3 atmospheres (1000 psig). The optimal pressures for execution of the method according to the invention are generally to be indicated as the minimum pressure that is caused by the partial pressures of the Reaction participants within a closed polymerization zone at the particular temperature at which the

80 9813 / 132p

Polymerization is carried out can be obtained.

The device used to carry out the procedure can be used according to the invention can be practical be designed in any way. Of course it must be like that be designed and made of such materials, that it can withstand relatively high pressures and temperatures "

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Claims (1)

Claims 1 «Procedure for polymerisation η τοη olefins, daduroh characterized that one has a polymerizable jjt olefinic Kohlenwaeeeretoff in the presence of a modifying agent, welohee sulfur, a sulfur-bearing Compound or a halogen-containing compound in which the halogen can consist of bromine, chlorine or iodine, comprises, leads to a polymerization ion maintained at an elevated temperature and an elevated pressure 2.Veroh naoh Anspruoh 1, daduroh characterized, that a temperature swisohen about 250 ° C and the Kraok temperature of the olefinic hydrocarbon in the feed and a pressure τοη not less than 14.1 atm f * (200 psig) applies » 3 · The method according to claim 1 or 2, characterized by the fact that the polymerizable material is a olefinic hydrocarbon with 2-20 carbon atoms Terwendet · 4 «i method according to one of claims 1 to 3, daduroh characterized in that the polymerizable olefinic hydrocarbon is ethylene, propylene, butylene or Mixtures used * 809813/1320 5. The method according to any one of claims 1 to 4 _9, characterized in that the modifying agent used is halogen-substituted hydrocarbons or hydrogen halide β. 6. The method according to any one of claims 1 to 4, daduroh characterized that one is used as a modifier a bromine-containing compound, in particular HBr, isopropyl bromide, bromine hexane, or bromobensol, a chlorine-containing compound, sulfur, mercaptans, in particular Alleyl mercaptan, soh sulfur dissolved in a tertiary amine, Hydrogen sulfide, thioether or naphthalenethiol used 7 · Method according to one of Claims 1 to 6, characterized in that a temperature is wiped off 300 and 500 ° G and if necessary a pressure of not less than 70 atU (1000 peig) applies 809813/1320