BE704956A - - Google Patents

Description

  

   <Desc / Clms Page number 1>
 



  "Process for the production of high molecular weight homopolymers or copolymers of isoolefins and products obtained"
The present invention relates to a process for the production of homopolymers or copolymers of isoolefins using a novel catalyst composition. The invention also relates to the products obtained by means of such a process.



   It is well known that a homopolymer or copolymer of isobutylene having a high molecular weight can be obtained by polymerization of an isoolefin, in particular isobutylene, or by copolymerization of isobutylene with copolymerizable comonomers.

 <Desc / Clms Page number 2>

 with it, in the presence of metal halides, of the Friedel'-Crafts type.



   However, in the polymerization reaction using such a catalyst, the transfer and termination reactions are too violent at high temperatures, and therefore good high polymers can only be obtained by using a very high temperature. low.



   By way of example, Japanese Patent Publication No. 7943/1956 to Esso Research & Engineering Co. discloses that a temperature as low as -100 ° C. is required for the production of butyl rubber by the copolymerization of isobutylene with. a small amount of diolefin, using a catalyst formed by a metal halide of the Friedel-Crafts type, for example aluminum chloride, titanium tetrachloride and aluminum bromide.

   In addition, it has been described on pages 98-99 of "Polyisobutylen und Isobutylén -Mischpolymerizate" (1959) by H. GUterboch that in the production of polymers of high molecular weight, such as "Oppanol B" and "Vistanex" (registered trademarks), the polymerization is carried out using boron trifluoride or aluminum chloride at a temperature of -80 to -100 C.



   U.S. Patent No. 2,440,498 describes the use of a catalyst in the form of double salts, for example
 EMI2.1
 AIC13.Ti (OC2HS) 4 or TiBr4.Ti0 (oC2H5) 2, which are soluble in commonly used solvents, unlike Friedel-Crafts type metal halide catalysts, such as aluminum trichloride, aluminum tribromide, aluminum triiodide and titanium tetrabromide, which have poor solubility in hydrocarbon solvents, as well as in polar halogenated solvents, such as methyl chloride and ethyl chloride.



   However, even with a modification as mentioned above, the performance of the catalyst is practically the same as that of aluminum trichloride alone, or even lower.

 <Desc / Clms Page number 3>

 and further the requirement of a low temperature for obtaining a high molecular weight polymer is not decreased.



   The requirement of a severe temperature condition is obviously undesirable to wood from a commercial and an economic point of view and, therefore, it is very desirable to obtain a polymer of raised molar weight at a relatively higher temperature. high. Therefore, many attempts have been made to meet this requirement.



   By way of example, the use of (C2H5) 2AlCl has been proposed as a catalyst in the polymerization of isobutylene® in a polar solvent, and this as described in Japanese Patent No. 1,144 / 1963; the use of a catalyst comprising boron trifluoride and an organometallic compound, as disclosed in Japanese Patent No. 15,489 / 1962; the use of A1 (OH) 2 (secondary O-butyl) .2BF3.TiC14 as a catalyst, as reported in IUPC Symposium on Macromolecules, Wiesbaden, Section III A - 13 (1959), J. Polymer Sci., 53 ; 281 (1961); and the use of SnC14- (C2H5) 2A21C1, as described in U.S. Patent No.
3,066,123.



   Although these mentioned processes are recognized as producing a high molecular weight polymer at a relatively high temperature, they are not of practical application in the production of valuable high polymers on an industrial scale.



   When using a catalyst, such as aluminum chloride and boron trifluoride, which is commonly employed in the industrial production of polymers, the presence of a small amount of water and / or alcohol in the polymerization system is essential for the activation of the catalyst and, indeed, it is known that these catalysts do not show any catalytic activity in the complete absence of water and alcohol [cf. pH

 <Desc / Clms Page number 4>

      
 EMI4.1
 



  9Í '- eeaaen, J. #heta Sos. (1947J /.



   Water and / or alcohols, which are essential for the proper activation of a catalyst of the Friedel-Crafts type, only act effectively in a favorable direction when they are present in small quantities. quantities. the presence of excessive amounts of these substances tending to lower the degree of polymerization and being able to prevent this polymerization.



   As the amount of water and alcohol is critical, and the polymerization reaction is strongly affected even for a slight change only in the amount of these substances, very strict control of the amount of water and alcohol is required. required in the polymerization system. The requirement for such strict control over the amount of water and alcohol raises a very difficult problem from a technical point of view. Therefore, it is desired to obtain a stable catalyst allowing the polymerization reaction without requiring the presence of water, alcohols, etc.



   Accordingly, it is an object of the present invention to provide a process for the production of a high molecular weight isoolefin homopolymer free from the disadvantages of the prior art described above.



   Another object of the invention is to provide an effective catalyst composition, having high catalytic efficiency and good stability, to be useful in the production of an isoolefin homopolymer or copolymer. 'high molecular weight.



   These objects are achieved, according to the present invention, by a process which comprises the polymerization of an isoolefin or the copolymerization of an isoolefin with at least one diolefin copolymerizable therewith, in the presence of a new one. composi-
 EMI4.2
 An analytical reaction comprising boron trifluoride and a compound of a metal of Groups II-VII of the Periodic Table.



   The Applicant has carried out extensive studies to resolve the problems described above. This is how she found

 <Desc / Clms Page number 5>

 a novel catalyst composition comprising boron trifluoride and a compound of a metal of Groups II-VII of the Periodic Table, represented by the general formula M (OR1) p. (OR) Q. Xr a p Q r such a composition making it possible to obtain a polymer having a markedly higher molecular weight compared with those of the polymers obtained using the catalysts known hitherto.



  For example, a polymer having a molecular weight can be produced. cular of 200,000 or more at an elevated polymerization temperature, for example 0 ° C., according to the process of the invention. The catalyst composition of the invention exhibits stable and high catalytic activity without requiring the presence of water, alcohol, etc. in the polymerization system.



   Taking into account the remarkable and surprising characteristics mentioned above, the catalyst composition of the invention is clearly distinguished from catalysts, such as aluminum chloride and boron trifluoride, previously known.



   The catalytic composition used in the process of the invention is therefore composed of deobre trifluoride and of a metal compound of the general formula
M (OR1) p. (OR2) q.Xr in which R1 and R2, which may be the same or different, represent alkyl groups, such as methyl, ethyl, n-propyl,, isopropyl, n-butyl, sec-butyl, tert-butyl , n-amyl, isoamyl, n-hexyl, isohexyl, heptyl and octyl; cycloalkyl groups, such as cyclopentyl, methylcyclopentyl and cyclohexyl; aryl groups, such as phenyl, tolyl, naphthyl,: xylyl, mesityl and cumenyl; aralkyl groups, such as benzyl and phenethyl; and the groups mentioned above substituted with halogen;

   X represents a halogen atom, M represents a metal of groups II-VII of the Periodic Table, p, q and r represent

 <Desc / Clms Page number 6>

 an integer, and the sum of p, q and r is the valence. metal, provided that p and q are not simultaneously equal to 0.



   As described above, when polymerizing or copolymerizing an isoolefin, for example isobutylene, with at least one diolefin copolymerizable with the isoolefin, employing the catalyst composition of the invention, a polymer having an extremely higher molecular weight is obtained as compared to those of the polymers obtained by using known catalysts, such as aluminum chloride and boron trifluoride.



   Therefore, when the catalyst composition of the present invention is used, an interesting solid elastomer can be obtained even at a high temperature reaching above 0 C, that is, a temperature at which it is not obtained. Usually a liquid or semi-solid type polymer of low industrial value, having a low molecular weight, when a known catalyst is used, such as aluminum chloride or boron trifluoride.

   Further, when the catalyst according to the invention is employed, a large amount of polymer can be produced even in a highly purified, almost water-free reaction system, in which no polymer could be obtained on the process. use of a prior art catalyst, such as aluminum chloride or boron trifluoride.



   This clearly demonstrates the superiority of the catalyst composition of the invention, both in operation and in efficiency.



   Although the chemical structure and the catalytic mechanism of the composition of the present invention are not clearly understood, it can be assumed, while taking into account that the invention is obviously not bound by any particular theory. whatever, that, because the catalyst according to the invention provides a catalytic effect which is quite unexpected if we consider

 <Desc / Clms Page number 7>

 aluminum chloride and boron trifluoride, an active catalyst, having a completely new active species, hitherto unknown, is formed by boron trifluoride and by a metal compound of the formula M (OR1 ) p. (OR2) q.Xr.



   The amount of catalyst which is used in the process of the invention is from 10 to 0.001 mol% of boron trifluoride and from 5 to 0.001 mol%, in particular 1-0.01 mol% of a compound. metallic M (OR1) p. (OR2) q.Xr per mole of monomer used. p q r
The process of the invention can be carried out continuously or batchwise, in a bulk or solution polymerization process. The process of the invention is particularly well suited for continuous operation, since no strict control of water and / or alcohol concentrations is necessary in the reaction system.



   Solvents which can be employed in the solution polymerization according to the process of the present invention are, in particular, aliphatic or aromatic hydrocarbons, halogenated alkyls and halogenated aryls, or mixtures thereof.



   Iso-olefins which can be polymerized according to the process of the invention are, for example, isobutylene, 2-methylbutene-1, 2-methylpentene-1, etc. Diolefins which can be copolymerized with iso-olefins according to the process of the invention are those which contain from 4 to 10 carbon atoms, in particular butadiene, isoprene, 2,4-dimethylbutadiene, piperylene, cyclopentadiene, dicyclopentadiene, hexadiene, divinylbenzene, cyclohexadiene and vinylcyclohexene.



   As previously pointed out, one of the characteristics of the process of the invention is that a polymer having a high molecular weight can be obtained as compared to those of the polymers obtained using known catalysts. By way of example, a solid elastomer with a high molecular weight can be obtained even at a temperature of up to 0 C. In this way, no particular restriction is imposed on the polymer temperature.

 <Desc / Clms Page number 8>

 risation and this can be optionally chosen according to the 'desired properties of the product.



   The accompanying drawing illustrates the comparison of the results of the polymerization of isobutylene according to the process of the invention versus the results obtained with prior art processes.



   It can be seen from the drawing that a polymer having a high molecular weight is obtained in a relatively higher temperature range, and that the process of the invention provides a polymer having a molecular weight. higher than those of the polymers obtained according to the prior art.



   In this drawing, the references (1), (2), (3) and (4) respectively denote the following (1) the process of the invention (2) a process using an A1 (OH) 2 system (OR) .2BF3-TiC14, cited in IUPC Symposium on Macromomecules, Wiesbaden, Section IIIA-
13 (1959) (3) a process using boron trifluoride as a catalyst, as described in Polymer, 6,579 (1965) (4) a process using aluminum trichloride, as described in Polymer, 6,579 (1965).



   The high molecular weight polymer obtained by the process of the invention can be vulcanized by the vulcanization process which is commonly used for the vulcanization of an iso-olefin copolymer obtained by the current processes and the product thus vulcanized exhibits the same physical properties, such as tensile strength, elongation, modulus, etc. than those of current products.



   In carrying out the process according to the present invention, the methods of feeding the materials and the catalyst

 <Desc / Clms Page number 9>

 are as follows: (i) the boron trifluoride and the metal compound are first mixed and then the resulting mixture is introduced into the reaction system; (ii) the boron trifluoride is introduced into the mixture of the monomer, the solvent and the metal compound: and (iii) the boron trifluoride and the metal compound are introduced into the mixture of monomer and the solvent, and this separately. one of the other.



   Among these three methods, methods (ii) and (iii), are more favorable than method (i), with regard to the efficiency, stability and activity of the catalyst, as well as with regard to the reproductive character of the reaction.



   Boron trifluoride can be supplied in gaseous or liquid form, or it can also be supplied as a solution in a solvent.



   It is possible to feed the metal compound M (OR1) p. (OR2) q.



  Xr as is or preferably in the form of a solution.



   Various examples of implementation of the invention are given below, these examples showing preferred embodiments but not, however, in any way limiting.



    EXAMPLES 1-4
Into an autoclave with a capacity of one liter, 500 cc of an n-hexaic solution, containing various amounts of isobutylene, as specified below, and various amounts of di-butpxyl chloride, are charged. secondary-aluminum A1) o-secBu) 2C1, as specified below, and then various amounts of boron trifluoride, also mentioned below, are added to the resulting mixture, with cooling and stirring.



  After the polymerization reaction has developed for 1 hour, the reaction is terminated by adding ethanol and the polymer.

 <Desc / Clms Page number 10>

   resulting is lyophilized overnight to give a white rubber-like polymer. The results are given in the following Table I, as well as the results obtained in Comparative Examples 1 and 2, in which boron trifluoride was used alone.



   TABLE 1
 EMI10.1
 
<tb> Examples
<tb> comparative
<tb>
 
 EMI10.2
 Example, n ¯¯ 1 2 3 4 1 2 Amount of Al (0-secBu) ZCl (mmok4) 0.5 2.0 0.5 0.5 -
 EMI10.3
 
<tb> Quantity <SEP> of <SEP> trifluoride
<tb> of <SEP> bore <SEP> (mmolei) <SEP> 1.5 <SEP> 4.0 <SEP> 2.5 <SEP> 1.25 <SEP> 1.5 <SEP> 4.0
<tb>
<tb> Isobutylene <SEP> (gr) <SEP> 33 <SEP> 33 <SEP> 33 <SEP> 65 <SEP> 33 <SEP> 33
<tb>
<tb> Temperature
<tb> polymerization <SEP> (OC) <SEP> -45 <SEP> -45 <SEP> -75-20 <SEP> -45 <SEP> -45
<tb>
<tb> Efficiency <SEP> (% <SEP> in <SEP> weight) <SEP> 98.5 <SEP> 67 <SEP> 99.2 <SEP> 92.5 <SEP> 30 <SEP> 74.4
<tb>
<tb> Molecular <SEP> weight <SEP> to <SEP> 4.
<tb> average <SEP> viscosity <SEP> (x104) <SEP> 110 <SEP> 105 <SEP> 240 <SEP> 48 <SEP> 15 <SEP> 10
<tb>
<tb> EXAMPLES <SEP> 5-7
<tb>
 
500 cm3 of a hexane solution containing 1,

  2 mole per liter of isobutylene and 0.023 mole per liter of isoprene, as well as the various amounts of chlo-
 EMI10.4
 di-butoxy secraluminum A1 (o-secBu) Cl and boron trifluoride, which is added with cooling and stirring. The polymerization reaction is carried out for one hour.



   The results are given in the following Table II, as well as the results obtained in a Comparative Example 3, in which boron trifluoride was used alone.

 <Desc / Clms Page number 11>

 



  TABLE II
 EMI11.1
 
<tb> Example
<tb>
<tb> Example, <SEP> n <SEP> 5 <SEP> 6 <SEP> 7 <SEP> comparative <SEP> 3 <SEP>
<tb>
<tb>
<tb>
<tb> Quantity <SEP> of <SEP> (A1 (O-secBu) 2C1 <SEP> (mmol / 1) 2,0 <SEP> 2,0 <SEP> 2,0 <SEP> -
<tb>
<tb>
<tb> Quantity <SEP> of <SEP> trifluoride <SEP> of <SEP> boron
<tb>
<tb> (mmol / 1) <SEP> 3, <SEP> 4 <SEP> 3, <SEP> 6 <SEP> 3, <SEP> 8 <SEP> 4.0 <SEP> '
<tb>
<tb>
<tb>
<tb> Isobutylene <SEP> (mole1) <SEP> 1,2 <SEP> 1, <SEP> 2 <SEP> 1, <SEP> 2 <SEP> 1,2
<tb>
<tb>
<tb>
<tb> Isoprene <SEP> (mole / 1) <SEP> 0.023 <SEP> 0.023 <SEP> 0.023 <SEP> 0.023
<tb>
<tb>
<tb>
<tb> Temperature <SEP> of <SEP> polymerization, <SEP> C <SEP> -45-45 <SEP> -45-45
<tb>
<tb>
<tb>
<tb> Efficiency, <SEP>% <SEP> 27.2 <SEP> 34.9 <SEP> 57.4 <SEP> 25.3
<tb>
<tb>
<tb>
<tb> Molecular <SEP> weight <SEP> (x10) <SEP> 13.9 <SEP> 18.6 <SEP> 12.8 <SEP> 2,

  8
<tb>
<tb>
<tb>
<tb> Degree <SEP> of unsaturation <SEP> x <SEP> (mole <SEP>%) <SEP> 0.92 <SEP> 1.16 <SEP> 1.71 <SEP> 1.27
<tb>
 * the degree of unsaturation was measured by an iodine titration method, using a solution of mercury acetate, as described in Analytical Chemistry, 29,751 (1857) by
R. McNall et al.



  EXAMPLES 8-9
Into an autoclave, a solution in methyl chloride containing isobutylene or a mixture of isobutylene and isoprene, and a solution in benzene containing various amounts of secondary di-isopropoxy-monobutoxide are successively charged. aluminum A1 (O-iPr) 2 (secBu), as specified below, and with cooling and stirring, various quantities of gaseous boron trifluoride are blown into it, as specified below.



   After the polymerization reaction for one hour, the reaction is terminated by adding isopyl alcohol and the resulting polymer is dissolved in benzene and freeze-dried overnight to obtain a white rubbery-like polymer.



   The results are given in the following Table III, as well as those obtained in Comparative Example 4, in which boron trifluoride was used alone.

 <Desc / Clms Page number 12>

 



  TABLE III
 EMI12.1
 
<tb> Example
<tb>
<tb>
<tb> comparative
<tb>
<tb>
<tb>
<tb> Example, <SEP> n <SEP> 8 <SEP> 4
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Quantity <SEP> of <SEP> A1 (O-Ipr) 2 (O-secBu), mmol / 1. <SEP> 2.0 <SEP> 0.5 <SEP> 0
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Quantity <SEP> of <SEP> trifluoride <SEP> of <SEP> boron <SEP> (ce) <SEP> 30 <SEP> 18 <SEP> 20
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Isobutylene <SEP> (% <SEP> in <SEP> vol.) <SEP> 10 <SEP> 30 <SEP> 10
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Isoprene <SEP> (% flight) <SEP> 0.2 <SEP> 0 <SEP> 0
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Temperature <SEP> of <SEP> polymerization, <SEP> C <SEP> -45-45 <SEP> -45
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Randement <SEP> (% <SEP> in <SEP> weight) <SEP> 68.9 <SEP> 90,

  2 <SEP> 80
<tb>
<tb>
<tb>
<tb> average
<tb>
<tb>
<tb>
<tb>
<tb> Molecular <SEP> weight <SEP> to <SEP> viscosity / (x104) <SEP> 20.0 <SEP> 40.0 <SEP> 12.0
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Degree <SEP> of unsaturation <SEP> (moles%) <SEP> 1,1- <SEP> -
<tb>
 
The foregoing Examples 1-9 show that the process of the present invention provides a polymer having a higher molecular weight than that of a polymer obtained by using boron trifluoride alone as a catalyst.



  EXAMPLE 10
Has a hexane solution containing 30 gr of isobutylene. 0.3 mmol of trichlorotitane-n-butylate Ti (O-nC4H9) C13 and 0.4 mmol of boron trifluoride are added, the polymerization being carried out at -45 C. 17.2 g of a polymer are obtained. having a molecular weight of 1,250,000.



  EXAMPLE 11
To a mixture comprising 34 g of isobutylene, 0.5 g of isoprene and 200 cc of ethyl chloride, which has been cooled to -45 ° C., 0.4 mmol of aluminum n-butoxide is added. and 1.3 mniole of boron trifluoride, and stirred for one hour to obtain 29.4 g of a polymer having a polecular weight of 230,000.



  The degree of unsaturation of the resulting polymer was 1.21%.



  EXAMPLE 12
In a mixture comprising 33 g of isobutylene, 6 g of butadiene and 100 cc of n-hexane, which has been cooled to -45 C, we

 <Desc / Clms Page number 13>

 0.5 mmol of trichlorotitane-n-butoxide Ti (O-nBu) C13 and 1.4 mmol of boron trifluoride are added, and the polymerization reaction is carried out for 30 minutes to obtain 26.8 g of a poly- mother having a molecular weight of 150,000. The degree of unsaturation of the resulting polymer was 1.06%.



  EXAMPLE 13
In an autoclave loaded with 10 g of isobutylene and 120 cc of methyl chloride, which was cooled to -45 C, 2 cc of a mixture prepared by mixing 20 mmoles of Ti (O-ipr) are added. 2 (O-nBu) C1 and 40 mmol of gaseous boron trifluoride in 100 cc of n-hexane, the polymerization reaction being carried out for one hour. This resulted in a white rubber-like polymer having a molecular weight of 510,000, the yield being 94.7%.



  EXAMPLE 14
To a solution in n-hexane, containing 10% by volume of isobutylene, 0.5 mmol of monobromotitanium tri-n-butoxide is added and, into the resulting mixture which is cooled to -25 C, is blown 40 cm3 of boron trifluoride gas with stirring. After the polymerization reaction for one hour, the reaction is completed by adding isopropyl alcohol and the resulting polymer is dissolved in benzene, followed by lyophilization to obtain a white rubber-like polymer having a molecular weight at viscosity average of 200,000.



  EXAMPLE 15
In a solution in toluene, containing 30 g of isobutylene, 0.3 mmol of zinc diethoxide is added, and 30 cm3 of boron trifluoride are introduced therein at -20 C, the polymerization reaction being carried out for one hour. A white rubbery type polymer is obtained.

 <Desc / Clms Page number 14>

    EXAMPLE 16 '
In a solution in dutoluene containing 0.7 mmol of diethoxy vanadium dichloride and 33 g of isobutylene, 125 cm 3 of boron trifluoride are infused at -60 ° C. A polymer of the rubber type is obtained.



  EXAMPLE 17
0.3 mmol of manganese diethoxide and 30 cm3 of boron trifluoride at -40 ° C. are charged in 500 ml of a solution in n-hexane, containing 33 g of isobutylene, a solid polymer is obtained. of the catouchouc type.



  EXAMPLE 18
In a solution in n-hexane, containing 30 g of isobutylene, 1.0 mmol of chromium ethoxide is added and, in the resulting mixture, 60 cm3 of boron trifluoride is introduced at -55 C. This gives a white rubber-like polymer.



  EXAMPLE 19
In 500 ml of a solution in n-hexane, containing
15 g of isobutylene, a mixture of 120 cm3 of boron triflucride and 2 mmoles of magnesium diethoxide is added. A solid polymer of the rubbery type is obtained.



  EXAMPLE 20
To 500 ml of a solution in n-hexane, containing
1.0 mmol of tri-meta-cresylaluminum A1 (OC6H4-CH3) 3 and 30 g of isobutylene, 5 mmoles of boron trifluoride are charged at -50 ° C., the polymerization reaction being carried out for one hour. A rubber-type polymer having a molecular weight of 600,000 is obtained.



   EXAMPLE 21
In a solution in n-butyl chloride, containing 33 g of isobutylene, 0.5 mmol of titanium tetrabenzyloxide Ti (OCH2C6H5) 4 and 115 cm3 of boron trifluoride are added at -45 C, the reaction of polymerization being carried out for one hour.

 <Desc / Clms Page number 15>

 



  This results in a white rubbery-like polymer having a molecular weight of 200,000.



  EXAMPLE 22
To a solution in toluene, containing 30 g of isobutylene, which is cooled to -60 C, is introduced a mixture of 0.3 mmol of tris- (2-chloroethoxy) titanium monochloride
 EMI15.1
 Ti (OCH2-CH2Cl) 3Cl and 50 cm3 of boron trifluoride. This results in a white, rubbery-like polymer.



  EXAMPLES 23-24
60 g of strongly dehydrated and purified isobutylene, 310 g of n-hexane, di-sec chloride are charged in a liter autoclave, which has been sufficiently dried under vacuum.
 EMI15.2
 butoxyaluminum Al (O-secBU) 2Cl, and various amounts of boron trifluoride, as specified below, are added to the resulting mixture with cooling and stirring, the polymerization then being carried out.



   The results are given in Table IV, as well as those obtained in Comparative Examples 5, 6 and 7, in which boron trifluoride was used alone,
TABLE IV
 EMI15.3
 
<tb> Examples
<tb> comparative
<tb>
 
 EMI15.4
 Example, n "¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ 2 24 5 6 7x Amount of Al (O-secBu) Cl (mmolel.) 0, O, 5
 EMI15.5
 
<tb>
<tb>
<tb> Quantity <SEP> of <SEP> trifluoride <SEP> of
<tb>
 
 EMI15.6
 boron (mmol / 1) 1, 25 1.5 2, O 4, O 2, 0
 EMI15.7
 
<tb> Temperature <SEP> of <SEP> polymerization, <SEP> C <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0
<tb> Efficiency, <SEP>% <SEP> 79.2 <SEP> 92.3 <SEP> traces <SEP> traces'21.2
<tb>
<tb> Molecular <SEP> weight <SEP> to <SEP> viscosity
<tb> average <SEP> (xlo4) <SEP> 18.0 <SEP> 18.5 <SEP> 0.83
<tb>
 x In this example,

   incompletely dehydrated and purified isobutylene was used,

 <Desc / Clms Page number 16>

 
As can be seen by considering Comparative Examples 5, 6 and 7, the polymerization proceeds difficult when using known Friedel-Crafts type catalysts, when there is practically no water, and furthermore, the yield of the polymer produced is strongly affected by the presence of a small. amount of water.



   On the other hand, when using the catalyst composition of the invention, as shown by Examples 23 and 24, the polymer can invariably be obtained in a good yield, even though there is virtually no waste. 'water. In addition, the resulting polymer exhibits a remarkably high molecular weight even when the polymerization reaction is carried out at a temperature up to OOC.



  .EXAMPLES 25 to 27
In an autoclave with a capacity of one liter, charged with various amounts of isobutylene and isoprene, as specified below, and of methyl chloride, various amounts of A1 (O-secBu) are charged. 2C1 and boron trifluoride, as specified below, with cooling and stirring, the polymerization being carried out for one hour. The results are given in Table V below.



   TABLE V
 EMI16.1
 
<tb> Example, <SEP> N <SEP> 25 <SEP> 26 <SEP> 27
<tb>
<tb> Quantity <SEP> of <SEP> A1 (O-secBu) 2C1 <SEP> (mmol / 1) <SEP> 1.5 <SEP> 1.5 <SEP> 1.5 <SEP>
<tb>
<tb> Quantity <SEP> of <SEP> trifluoride <SEP> of <SEP> boron <SEP> (mmol / 1) <SEP> 4.5 <SEP> 3.0 <SEP> 4.5
<tb>
<tb> Isobutylene <SEP> (mole / 1) <SEP> 1,2 <SEP> 2,4 <SEP> 1, <SEP> 2 <SEP>
<tb>
<tb> Isoprene <SEP> (mole / 1) <SEP> 0.024 <SEP> 0.072 <SEP> 0.096
<tb>
<tb> Temperature <SEP> of <SEP> polymerization, <SEP> C <SEP> -65 <SEP> -74-80
<tb>
<tb> Viscosity <SEP> Mooney <SEP> (ML-8-100) <SEP> 43.0 <SEP> 83.5 <SEP> 45.5
<tb>
<tb> Efficiency, <SEP>% <SEP> 99.1 <SEP> 74.3 <SEP> 98.2
<tb>
<tb> Degree <SEP> of unsaturation <SEP> (moles <SEP>%) <SEP> 1.21 <SEP> 2.34 <SEP> 3.05
<tb>
 

 <Desc / Clms Page number 17>

 
The polymers obtained according to Examples 25,

   26 and 27 were combined according to the formulation given in the following Table VI and vulcanized at 150 ° C. The physical properties of the samples thus prepared were measured and the results given in Table VII were obtained.



   TABLE VI
 EMI17.1
 
<tb> Compounds <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb> Polymer <SEP> 100
<tb>
<tb> Black <SEP> from <SEP> flue <SEP> from <SEP> type <SEP> to <SEP> easy <SEP> processing <SEP> 50
<tb>
<tb> Zinc <SEP> <SEP> <SEP> <SEP> 5
<tb>
<tb> Stearic acid <SEP> <SEP> 3
<tb>
<tb> Mercaptobenzothiazole <SEP> 0.5
<tb>
<tb> Tetramethylthiuram <SEP> disulfide <SEP> <SEP> 1
<tb>
<tb> sulfur <SEP> 2
<tb>
 TABLE VII
 EMI17.2
 
<tb> Exen, ple <SEP>, <SEP> n <SEP> 25 <SEP> 26 <SEP> 27
<tb>
<tb> Time <SEP> scorching <SEP> (121 C) <SEP> 34'40 "<SEP>. <SEP> 16'00" <SEP> 22'20 "
<tb>
<tb> viscosity <SEP> Mooney <SEP> (ML-8-150) <SEP> 52.0 <SEP> 77.5 <SEP> 55.0
<tb>
<tb> Resistance <SEP> to <SEP> the <SEP> traction
<tb> vulcanized <SEP> for <SEP> 40 <SEP> min.

   <SEP> (kg / cm2) <SEP> 212 <SEP> 221 <SEP> 187
<tb> vulcanized <SEP> for <SEP> 80 <SEP> min. <SEP> (kg / cm2 <SEP> 209 <SEP> 213 <SEP> 200
<tb>
<tb> Elongation
<tb> vulcanized <SEP> for <SEP> 40 <SEP> min. <SEP> (%) <SEP> 760 <SEP> 580 <SEP> 490
<tb> vulcanized <SEP> for <SEP> 80 <SEP> min. <SEP> (%) <SEP> 760 <SEP> 590 <SEP> 580
<tb>
<tb> Module <SEP> 300%
<tb> vulcanized <SEP> for <SEP> 40 <SEP> min. <SEP> (kg / cm2) <SEP> 48 <SEP> 81 <SEP> 96
<tb> vulcanized <SEP> for <SEP> 80 <SEP> min.

   <SEP> (kg / cm2) <SEP> 51 <SEP> 75 <SEP> 78
<tb>
<tb> Hardness <SEP> 64 <SEP> 67 <SEP> 68
<tb>
 
Examples 25, 26 and 27 clearly show that the synthetic polymers according to the process of the invention are copolymers of isobutylene and isoprene and that elastomers having excellent physical properties can be obtained by vulcanization. of the resulting copolymers.



  EXAMPLES 28-30
In an autoclave with a capacity of one liter, we

 <Desc / Clms Page number 18>

 charge 500 ml of a solution in n-hexane, containing isobutylene and various amounts of Al (O-secBu) 3, as specified below, and there are blown into various amounts of trifluoru- re of boron gas, as specified below, with cooling and agitation.

   After the polymerization reaction for one hour, the reaction is terminated by adding ethanol and the resulting polymer is lyophilized overnight to obtain a white rubbery-like polymer. The results are given in Table VIII, as well as those obtained in Comparative Examples 8 and 9, in which boron trifluoride was used alone.



   TABLE VIII
 EMI18.1
 
<tb> Examples
<tb>
<tb> comparative
<tb>
<tb>
<tb>
<tb> Example, <SEP> n <SEP> 28 <SEP> 29 <SEP> 30 <SEP> 8 <SEP> 9
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Quantity <SEP> of <SEP> A1 (O-secBu) 3
<tb>
<tb>
<tb> (mmol / 1) <SEP> 0.5 <SEP> 0.5 <SEP> 1.0 <SEP> - <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb> Quantity <SEP> of <SEP> trifluoride
<tb>
<tb>
<tb> of <SEP> boron <SEP> (mmol / 1) <SEP> 1.5 <SEP> 2.0 <SEP> 3.0 <SEP> 1.6 <SEP> 4.1
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Isobutylene, <SEP> gr <SEP> 34 <SEP> 34 <SEP> 34 <SEP> 32 <SEP> 35
<tb>
<tb>
<tb>
<tb>
<tb> <SEP> temperature of <SEP> polymerization,
<tb>
<tb>
<tb> C <SEP> -45-45 <SEP> -20 <SEP> -45-45
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Efficiency, <SEP>% <SEP> in <SEP> weight <SEP> 67.4 <SEP> 70.5 <SEP> 77.6 <SEP> 31 <SEP> 75,

  3
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Molecular <SEP> weight <SEP> to <SEP> viscosity
<tb>
<tb>
<tb> average <SEP> (x104) <SEP> 109 <SEP> 110 <SEP> 25.8 <SEP> 14 <SEP> 11
<tb>
<tb>
<tb>
<tb>
<tb> EXAMPLES <SEP> 31-33
<tb>
 
In an autoclave loaded with 500 ml of a solution in methyl chloride containing 1.2 moles per liter of isobutylene and 0.023 moles per liter of isoprene, a solution which has been cooled, a predetermined amount is added. of A1 (O-secBu) 3 dissolved in methyl chloride and various amounts of boron trifluoride gas, as specified below, slowly over a period of 20 minutes and separately, the reaction polymerization being carried out for one hour.

 <Desc / Clms Page number 19>

 



   The results are given in the following Table IX, as well as the results obtained in Comparative Example 10 in which boron trifluoride was used alone.
 EMI19.1
 
<tb>



  TABLE <SEP> IX <SEP> Example <SEP> co
<tb>
<tb> comparative
<tb>
 
 EMI19.2
 Example, n, "31 32 33 there Quantity of 1T. (0-z3.) 3 (mmQlef.) 1.5 1.5 1.5 Quantity of boron triluoride (mmOlQ4) 4.5 3, O 3, 4 4, Q Isobutylene (m4J.) Z 1, 2 cl, 2 1, 2 Isoprene (mo>, 1) 0.023 0.023 0.023 0.023 Polymerization temperature, C -78 -6o -78 -78
 EMI19.3
 
<tb> Efficiency, <SEP>% <SEP> approx. 100 <SEP> 58.8 <SEP> 60.5 <SEP> 97.8
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Molecular <SEP> weight <SEP> (x104) <SEP> 92 <SEP> 31.1 <SEP> 102 <SEP> 10.5
<tb>
<tb>
<tb>
<tb>
<tb> Degree <SEP> of unsaturation <SEP> (mole <SEP>%) <SEP> 1.20 <SEP> 1.07 <SEP> 1.15 <SEP> 1,

  27
<tb>
 
The preceding Examples 28-33 show that the process of the present invention provides a polymer having a molecular weight far greater than that of a polymer obtained using boron trifluoride alone as a catalyst.



  EXAMPLES 34 - 35
In a solution in methyl chloride, containing 2-methylbutene-1 or a mixture of 2-methylbutene-1 and isoprene, which has been cooled and stirred, different amounts of di-isopropoxy are added. aluminum mono-sec-butoxide
 EMI19.4
 Al (O-iPr) 2 (0-seaBu), as specified herein, prs. Then, boron trifluoride gas is introduced into the polymerization system and the polymerization reaction is carried out for one hour. At the end of this period, the reaction is completed by adding isopropyl alcohol and the resulting polymer is dissolved in benzene, then lyophilized to obtain a white polymer. The results are given in the following Table X.

 <Desc / Clms Page number 20>

 



  PAINTINGS
 EMI20.1
 
<tb> Example, <SEP> n <SEP> 34 <SEP> 35
<tb>
<tb>
<tb>
<tb>
<tb> Quantity <SEP> of <SEP> A1 (O-iPr) 2 (O-secBu) <SEP> (mmol / 1) <SEP> 2.1 <SEP> 0.6
<tb>
<tb>
<tb>
<tb> Quantity <SEP> of <SEP> trifluoride <SEP> of <SEP> boron <SEP> (cm3) <SEP> 30 <SEP> 19
<tb>
<tb>
<tb>
<tb>
<tb> 2-methylbutene-1 <SEP> (% <SEP> in <SEP> vol.) <SEP> 11 <SEP> 30
<tb>
<tb>
<tb>
<tb>
<tb> Isoprene <SEP> (% <SEP> in <SEP> vol.) <SEP> 0.2 <SEP> -
<tb>
<tb>
<tb>
<tb> Temperature <SEP> of <SEP> polymerization, <SEP> C <SEP> -45-45
<tb>
<tb>
<tb>
<tb>
<tb> Molecular <SEP> weight <SEP> to <SEP> average <SEP> viscosity,
<tb>
<tb> (10,000) <SEP> 16 <SEP> 30
<tb>
<tb>
<tb>
<tb>
<tb> Degree <SEP> of unsaturation <SEP> (moles%) <SEP> 0.8
<tb>
<tb>
<tb>
<tb>
<tb> EXAMPLES36-38
<tb>
 
In an autoclave with a capacity of one liter,

   isobutylene, various amounts of isoprene as specified below, and methyl chloride are charged, cooled and stirred, followed by various amounts of Al (O-secBu) 3 and boron trifluoride, as specified hereinafter separately, and the polymerization reaction is carried out for one hour. The results are given in Table XI below.



   TABLE XI
 EMI20.2
 
<tb> Example, <SEP> n <SEP> 36 <SEP> 37 <SEP> 38
<tb>
<tb>
<tb>
<tb>
<tb> Quantity <SEP> of <SEP> A1 (O-secBu) 3, <SEP> mmol / 1. <SEP> 1.6 <SEP> 1.4 <SEP> 1.5
<tb>
<tb>
<tb>
<tb>
<tb> Quantity <SEP> of <SEP> trifluoride'de <SEP> boron
<tb>
<tb>
<tb> (mmol / 1) <SEP> 4.0 <SEP> 4.0 <SEP> 4.5
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Isobutylene <SEP> (mole / 1) <SEP> 2.4 <SEP> 2.4 <SEP> 2.4
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Isoprene <SEP> (mole / 1) <SEP> 0.072 <SEP> 0.030 <SEP> 0.096
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Temperature <SEP> of <SEP> polymerization, <SEP> C <SEP> -70 <SEP> -55 <SEP> -78
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Visited <SEP> Mooney <SEP> 80.0 <SEP> 46.5 <SEP> 47.0
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Efficiency, <SEP>% <SEP> 74.0 <SEP> 80.3 <SEP> 84.1
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Degree <SEP> of unsaturation <SEP> (moles%)

   <SEP> 1.78 <SEP> 0.81 <SEP> 2.20
<tb>
 
The polymers obtained in Examples 36, 37 and
38 were combined according to the formulation given in Table XII following qflk they were vulcanized at 150 C.

 <Desc / Clms Page number 21>

      



   The physical properties of the samples thus prepared were measured and obtained. the results given in Table XIII.



   TABLE XII
 EMI21.1
 
<tb> compounds <SEP> Parts <SEP> in <SEP> weight
<tb>
<tb> Polymer <SEP> 100
<tb>
<tb> Black <SEP> from <SEP> flue <SEP> from <SEP> type <SEP> to <SEP> easy <SEP> processing <SEP> 50
<tb>
<tb> Carbon <SEP> <SEP> <SEP> oxide 5.0
<tb>
<tb> Stearic acid <SEP> <SEP> 3.0
<tb>
<tb> Mercaprobenzothiazole <SEP> 0.5
<tb>
<tb> Disulfide <SEP> of <SEP> tetramethylthiuram <SEP> 1.0
<tb>
<tb> Sulfur <SEP> 2.0
<tb>
 TABLE XIII
 EMI21.2
 EXemh.e.

   n 36 37 38
 EMI21.3
 
<tb> <SEP> index of <SEP> vulcanization <SEP> (1210C) <SEP> 7'10 "<SEP> 11'10" <SEP> 6'00 "
<tb>
<tb>
<tb>
<tb> Viscosity <SEP> Mooney <SEP> (ML-8-121) <SEP> 75 <SEP> 60 <SEP> 56
<tb>
<tb>
<tb>
<tb> Resistance <SEP> to <SEP> the <SEP> traction
<tb>
<tb> vulcanization <SEP> during <SEP> 40 <SEP> min. (kg / cm2) <SEP> 205 <SEP> 212 <SEP> 186
<tb>
<tb> vulcanization <SEP> during <SEP> 80 <SEP> min. (kg / cm2) <SEP> 205 <SEP> 205 <SEP> 170
<tb>
<tb>
<tb>
<tb> Elongation
<tb>
<tb> vulcanization <SEP> for <SEP> 40 <SEP> min. <SEP> (kg / cm2) <SEP> 590 <SEP> 760 <SEP> 520
<tb>
<tb> vulcanization <SEP> during <SEP> 80 <SEP> min. (kg / cm2) <SEP> 630 <SEP> 770 <SEP> 570
<tb>
<tb>
<tb>
<tb> Module <SEP> 300%
<tb>
<tb> vulcanization <SEP> for <SEP> 40 <SEP> min.

   <SEP> (kg / cm2) <SEP> 97 <SEP> 45 <SEP> 98
<tb>
<tb> vulcanization <SEP> for <SEP> 80 <SEP> min. <SEP> (kg / cm2) <SEP> 71 <SEP> 46 <SEP> 78
<tb>
<tb>
<tb>
<tb> Hardness <SEP> 62 <SEP> 61 <SEP> 63
<tb>
 
Examples 36, 37 and 38 clearly show that the synthetic polymers according to the process of the invention are copolymers of isobutylene and isoprene, and that it is possible to obtain elastomers having excellent physical properties, by vulcanization of the resulting copolymers.



   The IUPC publications IIIA-13 (1959) by 0.



  Wichterle et al. And J. Polymer Sci., 53, 281 (1961) are the only literature currently available regarding observations on iso-olefin polymerization.

 <Desc / Clms Page number 22>

 related to the catalytic activities in the cationic polymerization of iso-olefins, in which certain catalysts obtained by reacting boron trifluoride as a member of the metal halides with an aluminum alkoxide as a part have been used. member of metal alcoholates.



   As described by Orienter et al, when an aluminum alkoxide is dissolved in n-hexane and a large quantity of boron trifluoride is introduced therein at normal temperature, a material is produced. isolable. The property of such insoluble material varies depending on the type of aluminum alcoholate used. For example, the combination of an aluminum alkoxide containing a primary alkyl group and boron trifluoride leads to a heterogeneous reaction and a precipitate of a complex of aluminum fluoride and boron trifluoride is formed.



   Further, O. Wichterle et al also believe that when A1 (O-secC4H9) 3 is reacted with boron triflucride, a gel-like material is formed, probably having structures
 EMI22.1
 such as A7 .- (O-secCli9) 3, 2BF3 and A1 (0-aecCH9j (OH) 2. 2BF3, and this according to the chemical equation given below; Al (o-secC4H9) 3 + BF3 --- 2> A1 (0-secCI3) 3. 2BF3 - Ai (O-serCI39). (OIïj 2. 2Hf3 + 2CeS
However, 0. Wichterle et al report in IUPC IIIA-13 1959, page 1, that such insoluble materials do not show catalytic activity in the polymerization or copolymerization of isobutylene, and that they cannot be used for as polymerization catalysts in the synthesis of any polymer.



   Further, 0. Wichterle et al report that, if titanium tetrachloride is added to the reaction mixture of an aluminum alcoholate and boron trifluoride, catalytic activity is manifested for the first time and one can l 'use in the polymerization of isobutylene as a ca-

 <Desc / Clms Page number 23>

 
 EMI23.1
 .



  1aS2sa3s.pOX-- xe 3'rc t taaec xun ieonog.e a re d '"s- Oiei3w, .1 having a pal" akr3drela m-. pAK de. ossre de 3 t 'm sse d "-x'! s s ee
 EMI23.2
 J1 aC 3 au ttSIangtB dlise-alftlm, dImm dtolâflom copolywà- r isabi.e s s.ee t de i. 9; 1 r os llsre is: s lm d 8E31.0. tH d ... 8 l, / Le <) êlamg <s <am noMamÈBe tBa t.Aema6 ei-afantm <Bt. At xeamtb 1, vagw + Mdepo% Ax- + poµ> ID.dâ'3 âlev6. apti eozpema the C. loo- olefin preau- a% ne n + -b> m ¯ olàfine in prCjteaM-c <a * <me ecaOtBit.iom of catalapaBawr sl 0 il I!. '$ I.'. ' 3 SfE '.' 3 NtO in ie 3 re sm es s "1- 2 d Table * er> i- * B + '. Fl4F> l ** cm diffdm% -, mm 90ouï abam le! Olmqui oms- prenamt the alkylm. IBac # d & NM MahM tBeMamaNM who can be s! TBts! T3Xaa6sB aac za TiEBBasg & Bi6 X Mt <j <& B''t <o azn a ù'haZëe.

   P, q and r Taaa & aeattaeaBt n #! BNtahce tjBdt & eo: eett the sum of P. q and x d 3 a e sa a, r, e P q ae si; 3.m II ,. '2. a YVOMM of Il Zn Rmaimmum at 7 molïcxaaire 3 ". Asmd a nüam al 3i, ae-, éi m a:' e o'e aüe a & e afiets3ey.



  = Sn 'l Imdârisaffiam avem oen2oe, oen Isseear e ye a $ 9'ee aa 71] BBMMnM4rf? <TiiaBQ L 3. Zn WmugM mdmamtt la aae "a'as 11a- qmi lLndmo-mamLmm autt um mm &, m eau amu WIJJBI35) 11ttîr- &#.% Fl% - + fl1t lµe Sa << aS;% t ') mUm D

** ATTENTION ** end of DESC field can contain start of CLMS **.

 

Claims (1)

<Desc / Clms Page number 24> 4. A method according to claim 2, in the EMI24.1 which i80-016fin is a member of the group consisting of i80bat: ylhe, 2-methylbutene-1 and 2-thylpentene-1, and the diolefin is a member of the group consisting of butadiene, i, srer 2,4-dimethylbutadiene, piperylene, cyclopentadlene, dieyelopentadiene, hexadiene, diviaylbenzene, e3eeacadie and vinylcyclohexene. 5. A process according to claim 1, wherein the amount of the catalyst used is 10 to 0.001% boron trifluoride and 5 to 0.001 mole%, preferably 1 to 0.01 mole%, of boron trifluoride. a metal compound M (OR1) p (OR2) qXr per mole of the monomer used. 6. A process according to claim 2, wherein the amount of the catalyst used is 10 to 0.001 mole% of boron trifluoride and 5 to 0.001 mole%, preferably 1 to 0.01 mole%, of a compound. metallic M (OR1) p (OR2) qxr per mole of the monomer used. 7. A process for the production of high molecular weight polymers which comprises polymerizing a fine iso-key by introducing boron trifluoride into a mixture of monomeric iso-olefin, a solvent and a compound. aluminum EMI24.2 of the formula AL (DR) 3 in laquel3eJR, .1 which may be idestigaet or different, represent a member selected from the group comprising EMI24.3 nant alkyls, cycloalkyls, arylea and ara / ±% 1es. which can be substituted by a halogen. 8. A process for producing high molecular weight polymers which comprises polymerizing an iso-olefin by introducing boron trifluoride and an aluminum compound of the general formula A1 (OR) 3 'in which the Rs, which may be the same or different, represent a member selected from the group comprising alkyls. cycloalkyls, aryls and aralkyls, which can be substituted by a <Desc / Clms Page number 25> halogen, in a mixture of the isoolefin and a solvent, this introduction being done separately. 9. A process for the production of high molecular weight copolymers, which comprises the copolymerization of an isolefin with at least one diolefin of 4 to 10 carbon atoms, copolymerizable therewith, by introducing boron trifluoride into a mixture of the isoolefin, the diolefin and an aluminum compound of the general formula a1 (OR) 3 'in which the Rs, which may be the same or different, represent a member selected from the group comprising alkyls, cycloalkyls, aryls and aralkyls, which may be substituted with halogen. 10. A process for the production of high molecular weight copolymers which comprises copolymerizing an isolefin with at least one diolefin of 4 to 10 carbon atoms, copolymerizable therewith, by introducing boron trifluoride and d. 'an aluminum compound of the general formula A1 (OR) 3 in which the Rs, which may be the same or different, represent a member of the group comprising alkyls, cycloalkyls, aryls and aralkyls, which may be substituted with a halogen, in a mixture of the isoolefin, of the diolefin and of a solvent, this introduction being done separately. 11. A process according to any one of claims 7 to 10, wherein the isoolefin is a member of the group consisting of isobutylene, 2-methylbutene-1 and 2-methylpentene-1. 12. A process according to either of claims 9 and 10, wherein the isoolefin is a member of the group consisting of isobutylene, 2-methylbutene-1 and 2-methylpentene. -1, and the diolefin is a member of the group comprising butadiene, isoprene, 2,4-dimethylbutadiene, hexadiene, <Desc / Clms Page number 26> divinylbenzene, cyclohexadiene and vinylcyclohexene. 13. A process according to any one of claims 7 to 10, wherein the boron trifluoride is used in an amount of 10 to 0.001 mole%. and the aluminum compound Al (OR) 3 is used in an amount of 5 to 0.001 mole%, preferably 1 to 0.01 mole%, per mole of the monomer used. 14. A process according to any one of claims 7,8,9 and 10, wherein the solvent is wethyl chloride. 15. A process for the production of high molecular weight polymers and co-polymers, as described above, especially in the examples given. 16. High molecular weight polymers and copolymers, when obtained by a process according to any one of the preceding claims.