CS271861B1 - Method of cationically polymerizing monomers polymerization and copolymerization - Google Patents

Abstract

The solution concerns the method of polymerisation and copolymerisation of cationically polymerising monomers. The advantage of this technique is based on the fact that polymerisation and copolymerisation are carried out at a temperature of +20 to -120 degrees C in the presence of the starting system, the single component of which is low-molecular alkyl halide, oligomer or polymer, in the chains of which at least two atoms of chlorine occur, which are bound to the secondary carbon atoms containing molecules with the following number of carbon atoms: C >= 5. The second component is Lewis acid such as boron trichloride, titanium(IV) chloride, aluminium trichloride, vanadium tetrachloride or their mutual mixture, or even the mixture of these Lewis acids with iron(III) chloride, while the molecular ratio of Lewis acids to monomer is 50 to 10<-5> at the rise of the products containing the chemically bound starting component that corresponds with used low-molecular alkyl halide, oligomer or polymer, or in the ambient medium of polar halogenated solvents or their mixtures with non-polar cyclic or even aromatic solvents. According to the solution, the method enables to prepare functionalised polymers, or respectively copolymers with various contents of polymer starters, e.g. PVC and these grafted materials can be further modified chemically and/or directly used as modifying agents, or even as compatibilizer for incompatible polymer mixtures.

Description

The invention relates to a process for the polymerization and copolymerization of cationic polymerizing monomers.

In the basic research of cationic polymerization, alkyl halides and telechelic polyieobutylenes containing chlorine bound to tertiary carbon have long been considered unreactive substances when using Lewie kyeeline boron trichloride (BClg), titanium tetrachloride (TiCl ₄ ) and aluminum chloride (AlClg) as co-initiators. In the case of AlClg, which has been used in initiation systems for more than 40 years, especially in the production of butyl rubbers, ie copolymers of ieobutylene with 18Pren (annual production in the US alone exceeds a quarter of a million tons) Pleeh's view of auto-ionization of AlClg and rejecting initiation by an alkyl halide: Al ₂ Cl ₆ = = Alcl ® AlC 4 (PH Plesh, Makromol. Chem., 175,

1065 (1974)). This so-called direct initiation * is referred to in the literature as Korshak-Pleeh-Merkov theory (P.P. Kennedy, E. Maréchal, Carbooationio Polymerization, A. Wiley-Interecience Publioation, 0. Wiley and Sons, New York 1982, etr. 113). Kennedy, on the other hand, is of the opinion that the initiator is methyl chloride, which is found in the reaction eyetem as a medium: CHgCl + AlCl ₃ ;? = ± CH * AlCl 4 - *. CH ₃ CH ₂ (/ ⁵ (CH ₃ ) ₂ AlCl®.

(P. P. Kennedy and RM Thomas, 0, polym, Soi., 45, 227 (1960). When using the BCl-j co-initiator, only in 1984 according to the author's certificate No. 239 995 ('Method preparation of aliphatic halinifers *, L. Toman), the initiation of an alkyl halide in tert-butyl chloride (t-BuCl) / BClg system during the polymerization of ieobutylene was revealed, where the initiation and transfer reactions were favorably influenced by This new hitherto undisclosed knowledge was then utilized in the synthesis of heterothelechelic polyisobutylene at -20 ° C, where no protogenic initiation by water in the presence of BClg (L. Toman no. 246 647) was made. polyisobutylene β reactive groups in the polymer chain *)

L. Toman, S. Pokorny, 3. Singer, 3. Ohanhelka, Polymer 27,1121 (1986).

In the synthesis of the radical mechanism, polyvinyl chloride (PVC) is one of the most important commercially produced thermoplastics. 3enom in the US annual production exceeds 3 million tons (Chem. Eng. News, 36, May 5, (1980)). Polyvinyl chloride and polyisobutylene or butyl rubber are not miscible, but their mutual copolymers would be widely used as compatibilizing materials for the preparation of polymer blends, and in the case of a butyl rubber tercolymer a new type of rapidly vulcanizable chlorinated elastomer would be formed.

However, it is not easy to initiate cationic polymerizing PVC monomers, since the polymer chain contains only a very small amount of Hyl-bonded chlorine atoms (about 0.1 mol%), which are referred to in the literature as the only possible reactive groups capable of forming anchored ketone centers in the chain . The grafting of cationic polymerizing PVC monomers was performed by Pleeh in nitrobenzene, which mixed AlClg and TiCl ₄ β PVC at room temperature (H. H. Plesh, Chem, Ind., 1958, 954) Ρ. H. Plesh, GB 817, 684 December 5 (1956). In the presence of these strong Lewie acids at room temperature, PVC dehydrochlorination occurs and, due to the high sensitivity of AlClg and TiCl ₄ to protogenic substances, the rapid synthesis of homopolymers proceeds mainly by protogenic initiation, for example: HCl + AlClg-> Tr \ 1Cl ₄ ® HM®, is a cationic polymerizing monomer. However, protogenic incorporation greatly reduces the proportion of grafting to PVC, as Kennedy previously pointed out (3rd Kennedy, Cationic Graft Copolymerization, 3rd Appl. Polym, Sci., Appl. Polym. Symp, 30, Akron).

Later, alkyl aluminum compounds such as EtgAlCl, EtgAl were used as co-initiators for PVC grafting, and PVC grafting was performed both in solution and solid state on PVC powder or film (3rd P. Kennedy, Appl, Polym. Symp., No. 30 (1977)) A. Vidal, 3. B. Donnet, 3. P. Kennedy, 3. Polym. sci. polym. Lett. Ed., 15, 585 (1977)). Iván,

3. P. Kennedy, Z. Kelen, F., Tudos, 3. Macromol. Sci. Chem., A16, 1473 (1981)). However, the alkylaluminum compound in the termination of the counterions undergoes alkylation or hydridation of the growing end of the polymer chain in the termination reaction, and the graft becomes unreactive again. This is a disadvantage (O. Kennedy, Catlonnlc A. Wiley-Interscience Publication, New York (1975) p. 245) P. Kennedy and Maréchal, Carbocationic Polymerization, Oohn Wiley and Sons, A. wiley-Interscience Publication, New York (1982), p. 221- 223)).

Other possible silver-containing co-initiators such as AgSbFg silver hexafluoroantimonate (E. Franta, F. Afshar-Taromi, p. Rempp, Makromol, Chem., 177, 2191 (1976)) are too expensive for industrial PVC grafting applications.

Almost 10 years ago, Kennedy performed PVC isobutylene grafting in the presence of the BClg co-initiator, at -75 ° C in dichloromethane using a 2% PVC solution at a monomer concentration of 0.9 mol / l and a 10 ^-2 mol / l BClg concentration ( SN Gupta, 3rd Kennedy, Polym Bull., 1,233 (1979)). The authors described that in the open system (dry box) PVC grafting was not performed under these experimental conditions. Therefore, partial dehydrochlorination of PVC with sodium hydroxide was performed, which resulted in a substantial increase in the reactive allyl chlorine content, which in turn had a beneficial effect on the PVC grafting process. However, dehydrochlorination of PVC is disadvantageous since it involves dissolving the polymer in an organic solvent, reacting with a base, thoroughly washing it with water to neutral, and thoroughly drying.

It has now been found that the interaction of at least two chlorine atoms bonded to the secondary carbons of an initiator, an alkyl halide, an oligomer or polymer containing chlorine atoms, by Lewis acid such as BClg, Tid ₄ , Alclg, vanadium chloride (VCl ₄ ) or mixtures thereof , optionally in admixture with ferric chloride (Fec1g), leads to the formation of cationic active centers anchored in the chain of the chloro derivative used as initiator. SUMMARY OF THE INVENTION The present invention provides a process for the polymerization and copolymerization of cationic polymerizing monomers, characterized in that the polymerization or copolymerization is carried out at a temperature of +20 ° C to -120 ° C in the presence of an initiation system of which one component is a low molecular weight alkyl halide, oligomer or polymer containing molecules having a carbon number of 5, in which at least two chlorine atoms are attached to the secondary carbons and the other is a Lewis acid such as boron trichloride, titanium tetrachloride, aluminum chloride, vanadium trichloride, or a mixture thereof or a mixture of these Lewis acids ferric chloride, the molar ratio of Lewis acid to monomer is 50 to ⁵ as well as to products including chemical bonding aložku initiator corresponding to the low molecular weight alkyl halide, oligomer or polymer, optionally in the environ diluents of polar halogenated solvents or mixtures thereof with non-polar or aromatic solvents. The interaction found leading to the initiation of cationic polymerizable monomers and a mixture thereof makes it possible to synthesize the respective functionalized polymers or copolymers or to produce a product comprising a mixture of functionalized and non-functionalized polymer.

In carrying out the process of the invention, the monomer or monomer mixture may be batchwise and / or continuously metered into a preformed initiator system (initiator + Lewis acid) or by mixing the initiator system with the monomer or monomer mixture, optionally by adding Lewis acid as the last component to the monomer / initiator mixture.

According to the invention, the polymerization can be carried out without a co-solvent or in the environment of polar halogenated solvents such as methyl chloride, methylene chloride, ethyl chloride or mixtures thereof with non-polar solvents such as heptane, carbon tetrachloride, cyclohexane, optionally in admixture with aromatic solvents such as benzene. or toluene.

Všechny all low molecular weight alkyl halides, oligomeric and polymeric fluxes containing at least two chlorine atoms attached to secondary carbons and containing C 5 carbon atoms, such as 2,4-dichloropentane, 2,4,6-trichloroheptane, chlorinated paraffins, can be used as initiators , cyclic hydrocarbons, olefins, polyolefins, PVC.

CS 271861 Bl

If vanadium chloride is used and the polymerization or copolymerization is carried out, optionally, using the effect of ultraviolet or visible light.

For example, isobutylene, styrene, n-methylstyrene, isoprene, butadiene, or mixtures thereof, such as isobutylene / isoprene, may be used cationically polymerizing monomers.

According to the present invention, low molecular weight chlorine or chlorine-containing oligomers or polymers are used as cationic initiators and / or initiator-transfer substances (inifery-polyinifers). Depending on the activation time of the corresponding chlorine-containing substance with Lewis acid, depending on the type of Lewis acid, either functionalized polymers or copolymers can be synthesized, for example using BClg, or a mixture of functionalized and non-ruralized polymers or copolymers, e.g. AlClg initiator. Substances containing chlorine atoms on secondary carbons become initiators when Lewis acid is metered into their mixtures with the monomer as the last eloz. On the other hand, when a pre-prepared initiation system composed of, for example, PVC and BC1 ₃ in dichloromethane medium is metered into the monomer or monomer mixture, the chlorine-containing polymer used, in this case PVC, has a distinct iniferous, in this case polyiniferous character.

In order to demonstrate the mechanism of initiation by an organic substance containing chlorine or secondary carbon atoms, the polymerization of isobutylene initiated with 2,4-dlchlorpentane in the presence of BClg was studied in detail. These polymerizations were carried out in dichloromethane at two temperatures, -70 ° C and -20 ° C. At -20 ° C, it is generally known that the polymerization of isobutylene with boron trichloride does not occur, even in the presence of H ₂ O or hydrogen chloride (O. Kennedy, Y. Huang, SC Feinberg, O. Sci., 15, 2801 (1977) 3, P. Kennedy, O. FY Chem. Polym. Bull., 15, 201 (1986) In our initiation system, however, the isobutylene polymerization proceeded at both temperatures, the isolated polymers were subjected to gel permeation chromatography. GPC) and 1 H-NMR analysis.

The results showed that both -70 ° C and -20 ° C produced polymers with almost the same molecular weight, only the polymer prepared at -70 ° C had a bimodal GPC record, indicating a small amount of molecular weight fraction (about It is also evident from Figure 1 that this molecular weight fraction was due to protogenic initiation, as shown by comparison with curve 2, which characterizes the GPC record of polyisobutylene prepared by the protogenic HgO / BClg initiation at -70 ° C The conclusions of the GPC analysis are consistent with the results obtained by 1 H-NMR analysis. NMR spectra showed that there was no resonant band in the 4.5-5.3 'p' region to indicate the presence of a double bond in the polymer. It is therefore apparent that the polymerization was carried out in the absence of monomer transfer. A low resonance in the region of 1.047 belonging to the t-butyl groups was demonstrated for polyisobutylene prepared at -70 ° C. A resonance band was found in the 3.5 Φ * range, which can be assigned to the -CHCI · methine guide. ** The ratio of the intensities of the bands of the methanol and t-butyl protons was in good agreement with the fraction of mass fractions determined from GPC chromatograms. Since the polymerization temperature does not have a major effect on the molecular weights of the polyisobutylenes obtained, it is clear that 2,4-dichloropentane (X), after interaction with BClg, behaves in the polymerization system as a typical initiator-transfer substance, inifer, according to the following scheme:

Initiation:

+ BCl _q

Cl Cl (I) activation

BCI4

II (II)

II + ch ₂ = c (ch ₃ ) ₂ ^ 7-012-0 (013) 2 _n , _{CH 2 = c (CH 3} ) ₂

- C1 polymerization

CS 271861 Bl

CH

Transmission

CH,

PIB-CH ₂ -C--Cl + / /

Cl

Since 2,4-dichloropentane is a model PVC (dimer), it can be assumed that a similar mechanism of initiation and transfer occurs with PVC and other oligomeric or polymeric materials containing chlorine atoms on secondary carbons. Due to the high concentration of these chlorine atoms in, for example, PVC, this polymer becomes a polyinifer upon interaction with BClg.

An advantage of the polymerization process of the present invention is that polymerizations conducted in the presence of polyinifers (i.e. polymers such as PVC, which was activated by BCl ₃ before use, for example) run at a higher rate to produce functionalized products compared to protonically initiated polymerization (e.g. ₂ o / BCl ₃ ). When using polymeric initiators (i.e. polymers such as PVC, which has been premixed with β monomer and BCl ₃ added as the last component), preferably higher molecular weight products are synthesized according to the invention as compared to products prepared by classically cationic synthesis, which allows, for example, to substantially increase the polymerization temperature of butyl rubber synthesis from -100 ° C to -60 ° C while maintaining the same molecular weight and unsaturation of the rubber. In this case, the presence of, for example, a PVC initiator favorably influences the suspension process used in the production of butyl rubber. Even at higher temperatures, the stickiness of the precipitated product does not increase. A polymeric initiator, for example of the PVC type, introduces, for example, chlorine atoms into butyl rubber, which can be advantageously used in vulcanization which proceeds faster and β higher efficiency, the increase in polymerization rate according to the invention is apparent Fig. 2, wherein curve 1 is the GPC recording of the polyisobutylene prepared according to the invention and curves 2, 3 are polyisobutylenes prepared by protonic polymerization under otherwise comparable conditions (as shown in Example 3).

Table I

The process according to the invention makes it possible to prepare graft copolymers which can be further chemically modified and / or already used directly as modifiers or compatibilizers of incompatible polymer mixtures.

The process for preparing the polymers and copolymers of the present invention is illustrated in several examples. In all the examples below, the polymerizations were carried out in glass ampoules fitted with a 30 ml piercing cap or in a 150 ml glass reactor equipped with a stirrer. Mixtures of an initiator (e.g. PVC) with a coiniclator (e.g. BCl ₃ ) in dichloromethane were prepared in glass ampoules equipped with a three-way Teflon cap for dispensing the components in a nitrogen stream, respectively removing the initiator system after activation. The polymerizations and copolymerizations were carried out under dry conditions under nitrogen. The drying of ampoules and the reactor has been described previously (L. Toman, M. Marek, Makromol. Chem. 177,3325 (1976)). Drying of the chemicals and monomers was carried out according to known methods. Molecular weights were determined by gel permeation chromatography in tetrahydrofuran solution. Polystyrene standards were used to easily compare the molecular weights of polymers and copolymers. Molecular weights were subtracted from the peaks of the GPC curves and these values are therefore apparent relative to polystyrene. The initiators were dried in dichloromethane (e.g. PVC) using molecular sieves. The PVC was dissolved in dichloromethane 24 hours before use.

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Table I Comparison of Polyisobutylene / PVC copolymers recovery of isobutylene polymerization initiated from PVC in the presence of BC1 as a co-initiator in dichloromethane at -70

CS 271861 Bl

Example 1

A dichloromethane solution containing 1.4 mol / L 2,4-dlchlorpentane and 0.9 mol / L BClg was prepared at -40 ° C. After warming to room temperature, the solution was stirred for 48 hours (the initiator interaction time of, for example, 2,4-dichloro-pentane 8 with a collector such as BClg will be generally referred to as activation time in other examples). It was then cooled to -70 ° C or -20 ° C in the solution and metered into isobutylene in dichloromethane. After mixing, the concentration in the batch was as follows: (i-butylene) 4.6 mol (l), 2,4-dlchloropentane (= 0.3 mol) and (BClg) = 0.21 mol (1). The polymerizations carried out at -70 ° C and -20 ° C, respectively, were terminated by the addition of methanol after 12 h at a conversion> 90%. A 6PC analysis of polyisobutylene (PIB) prepared at -70 ° C is shown in Figure 1 (curve 1). The PIB contained about 80 wt. The PIB prepared at -20 ° C had only a monomodal GPC chromatogram, and the molecular weight M was 4 4000 Example 2

The isobutylene polymerization was carried out at -20 ° C as in Example 1, but 2,4,6-trichloroheptane was used as the initiator. The activation time of the initiator with the co-initiator at 25 ° C was 24 hours. The composition of the batch was as follows: [isobutylene] = 4.6 mol / l, 2,4,6-trichloroheptane = 0.2 mol / l (Belg) * 0.2 ipol / l. polymerization performed at -20 ° C was terminated by the addition of methanol after 12 h at 100% conversion. Molecular weight of product M 4 000.

Example 3

Isobutylene Polymerization Initiated from PVC in dichloromethane at -70 ° C was carried out by a method of feeding the initiator system into the monomer. The initiator system containing laboratory-prepared PVC (hereinafter referred to as PVC (I) and BClg in dichloromethane) was activated for 20 min at room temperature and then, after cooling to -70 ° C, was metered into the monomer. : (Ieobutylene) »4.6 mol / l, Belgian» 0.14 mol / l, PVC (l) · 8.8 g / l The polymerization was terminated after 35 min by the addition of methanol Product conversion 28% with M and 450 000. GPC analysis of the product showed that the PVC / BClg initiation system resulted in a higher molecular weight polydispersity copolymer of polyisobutylene / PVC under the above experimental conditions as compared to the PIB produced by comparative polymerization under the same conditions and without PVC. in these cases, they were initiated by the residual water present in the system (the protonation initiation of HgO / BClg), the results are shown in Table I and the comparison of GPC records is reported Fig. 2. Curves 2, 3 are GPC records of PIB samples prepared by protonic initiation to 1.5% conversion and 4.5% conversion respectively, and Curve 1 is the GPC record of the PVC initiation product (I).

Example 4

Polymerizations of Isobutylene are initiated by PVC at -70 ° C by adding boron trichloride to the polymerization feedstocks as the last component. The monomer solution was metered in with PVC (I) in dichloromethane and BClg was added after stirring for 5 min. After mixing, the concentration of the ingredients in the batch was as follows: (i -butylene) &lt; 4.6 mol / l, Belg / 0.14 mol / l, PVC (I) + 12.3 g / l. The polymerizations were stopped by addition of methanol for 15 min, 30 min and 45 min. Polymerization was performed at the same monomer and PVC concentration with a lower BClg concentration of 0.046 mol / l. The yield versus polymerization time and BClg concentration is compared in Table I. GPC analysis of the products showed that after 30 minutes of polymerization all PVC had reacted with isobutylene as shown in Figure 3, where the curve is a PVC (I) initiator of M- 150,000, curve 2 is the polymerization product stopped after 15 min and curve 3 is the product polymerization stopped after 30 min of M / v 450,000.

CS 271861 Bl

Example 5

The isobutylene polymerizations are initiated by PVC at -70 ° C by adding a PVC (I) -BClg or PVC (II) initiator system to a monomer solution in dichloromethane is a commercial product with an apparent M AJ 170 000). The initiator system in Dichloromethane is activated for 48 h at room temperature. The monomer and PVC concentrations are the same as in Example 4. The yield versus time is compared in Table i, which also shows that the products show a significant increase in molecular weight (Μ / v 1.0.10 ®) when activated. PVC.

example 6

The polymerization of PVC-initiated isobutylene is carried out as in Example 3. After mixing the components, the concentration in the feed was as follows: (isobutylene) 4.5 mol / l, (BClg) 0.06 mol / l PVC (I) 8.8 g / 1. After 3 h the product was isolated at 41% β M AJ 440 000 conversion. A comparison of GPC records with the initial PVC initiator is shown in Figure 4, where curve 1 is PVC, curves 2 and 3 are polyisobutylene / PVC copolymers. Syntheses lasting 12 hours lead to conversions> 80%. When the BClg concentration was increased to 0.12 mol / l, the conversion / V was 95% in 12 h.

Example 7

The PVC-initiated copolymerization of isobutylene with isoprene in dichloromethane was performed at -75 ° C. In the monomer mixture, PVC (X) was added first and only then as the last BClg component. Dosing of PVC and BClg was carried out in dichloromethane, after mixing at -75 ° C, the concentration of the components in the feed was as follows: (isobutylene) 4.5 ° / isoprene / 0.135 mol / l / BClg / 0.09 mol / l, PVC ® 8.8 g / l. After 12 h a product of M A 430 000 and an unsaturation of 1.5 mol% was obtained at a conversion> 90%.

Example 8

The PVC-initiated copolymerization of isobutylene with isoprene in dichloromethane was performed at -60 ° C. The initiator system PVC (XI) - BClg in dichloromethane, which was activated as in Example 5, was added to the monomer mixture. After mixing, the concentration of the components in the feed was as follows: (isobutylene) > 4.3 mol / l, / isoprene / 0.2 mol / l, PVC 9 g / l. After 12 h a product of M A of 320,000 and an unsaturation of 2.0 mol% was obtained at a conversion> 90%.

Example 9

The PVC-BClg mixture in die-chloromethane was activated according to Example 5. After cooling to -50 ° C, the concentration of the components was as follows: PVC (XI) 6 g / l, (BClg).

0.05 mol / l. To the mixture under stirring was added continuously or styrene -methyIstyren in Dichloromethane 1,8.1ο rate of ² moles of monomer / min. after 1 h, dosing was terminated at a conversion> 90%. GPC analysis showed polystyrene / PVC copolymers and methyletyrene / PVC copolymers by comparing the refractometric (RI) and ultraviolet (UV) at 254 nm.

Example 10

Styrene copolymerization or. -methylstyrene with PVC was performed according to Example 9. In addition, 0.03 mol / l ferric chloride powder was present in the activation of PVC (II), GPC analysis showed the formation of polystyrene / PVC and poly-styrene / PVC copolymers.

Example 11

The copolymerization of styrene or gC-methylstyrene from PVC was carried out at temperature

-50 ° C. The mixture of PVC with titanium tetrachloride and ferric chloride in dichloromethane was mixed at

-50 ° C for 3 h. The concentration of the components was as follows: (TiCl 4) 0.05 mol / l PVC (I)

6.6 g (l, FeCl2) 0.1 mol / l. The monomer in dichloromethane was then added to the mixture

CS 271861 B1 according to Example 9. GPC analysis showed the formation of polystyrene / PVC and poly-oC-methylstyrene / PVC copolymers.

Example 12

Copolymerization of i-butylene with 1,3-butadiene and 2,3-dimethylbutadiene -1,3, respectively, initiated from PVC was carried out at -60 ° C. A mixture of PVC (I) and PVC (II) and vanadium chloride in dichloromethane, respectively, was stirred for 3 h at -20 ° C. The resulting initiator system was then added to a mixture of monomers in dichloromethane at -60 ° C. After mixing the reactants, the batch contained 6.0 mol / l of isobutylene, 0.9 mol / l of the dlolefinic monomer, 9.0 g / l of PVC and 9.10 of ³ mol / l of vanadium chloride. The copolymerizations were stopped by the addition of methanol for 30 min at a conversion of 31%. Products with molecular weight M < V450,000 and an unsaturation of 1.6 mol% were formed.

Example 13

The copolymerizations of i-butylene with diolefinic monomers were carried out as in Example 12. After the initiation system was fed into the monomer mixture, the polymerization rate was increased by UV or visible light. The polymerizations were stopped after 25 min at conversions> 35%. The resulting copolymers had a molecular weight M r of 450,000 at an unsaturation of 1.6 mol%.

Example 14

PVC-initiated copolymerization of isobutylene with isoprene in the presence of aluminum chloride co-initiator was performed at -78 ° C. the PVC (I) and PVC (II) blends were mixed with aluminum chloride in ethyl chloride at -20 ° C for 3 h. After cooling to -78 ° C, this initiation system was added to the monomer mixture in methyl chloride. After mixing the reactants, the batch contained; isobutylene · 4,0 mol / l, iaoprene «

0.18 mol / l, PVC »9.0 g / l, AlClg» 0.2 g / l. After 35 min they were. copolymerizations were completed by the addition of methanol at a conversion of 41%. Products having a molecular weight M of 350,000 and an unsaturation of 1.5 mol% were obtained.

Example 15

The PVC-initiated copolymerization of isobutylene with isoprene was carried out as in Example 14. Aluminum chloride was dissolved in toluene or benzene for 48 hours before being mixed with PVC (I) and PVC (XI) in ethyl chloride, respectively. After activation for 3 h at -20 ° C, the initiation system thus prepared was dosed into the monomer mixture of Example 14. After 30 min, the products were attracted at conversions>. 44% with a molecular weight of about 330,000 with a 1.5 mole% unsaturation.

Claims (6)

A process for the polymerization and copolymerization of cationic polymerizing monomers, characterized in that the polymerization or copolymerization is carried out at a temperature of 420 ° C to -120 ° C in the presence of an initiator system of which one component is a low molecular weight alkyl halide, oligomer or the C> 5 atoms in which the chains contain at least two chlorine atoms attached to the secondary carbons and the second component is a tewis acid selected from the group consisting of boron trichloride, titanium tetrachloride, aluminum chloride, vanadium tetrachloride or a mixture thereof or a mixture of these Lewis acids 8 ferric chloride, the molar ratio of Lewis acid to monomer is 50 to lo ^'5 to give products containing chemically bound initiator component corresponding to the low molecular weight alkyl halide, oligomer or polymer, optionally in a polar halogenated solvents or mixtures thereof with non-polar or aromatic solvents. CS 271861 Bl 2. A method according to claim 1, wherein the ae (co) polymerization is carried out by feeding the monomer or monomer mixture discontinuously and / or continuously into a preformed initiator system, or by mixing the initiator system with the monomer or monomer mixture, optionally by adding Lewis acids as the last component in the mixture of initiator and monomer. 3. The process of claim 1, wherein the cationic polymerizing monomers are isobutylene, isoprene, 1,3-butadiene, 2,3-dimethylbutadiene-1,3, styrene, p-methylstyrene or mixtures thereof. 4. A process according to any one of claims 1 to 3, wherein the low molecular weight alkyl halides, oligomers or polymers containing at least two chlorine atoms in the chain are bonded to secondary carbons containing C-5 molecules such as 2,4-dichloropentane, 2,4 6-trichloropentane, polyvinyl chloride, chlorinated paraffins, or cyclic hydrocarbons or olefins, chlorinated polyolefins and chlorinated polyvinyl chloride. 5. A process as claimed in any one of claims 1 to 4, wherein the polar halogenated solvents are methyl chloride, methylene chloride or ethyl chloride, the nonpolar solvents are heptane, carbon tetrachloride or cyclohexane and the aromatic solvents are benzene or toluene. 6. A method according to any one of claims 1 to 6, characterized in that, when using vanadium tetrachloride and polymerization or copolymerization, it optionally performs ultraviolet or visible light effects.