CA1077464A

CA1077464A - Polymerization of olefins

Info

Publication number: CA1077464A
Application number: CA250,500A
Authority: CA
Inventors: Erwin R. Ruckel; Long S. Wang
Original assignee: Arizona Chemical Co LLC
Current assignee: Kraton Chemical LLC
Priority date: 1975-05-12
Filing date: 1976-04-20
Publication date: 1980-05-13
Also published as: DE2620597A1; FR2311034A1; JPS523680A; JPS51137784A; BR7602911A; FR2311034B1

Abstract

A B S T R A C T
The present invention relates to a method for polymerizing difficulty polymerizable olefins or mixtures thereof to obtain polymers in good yields. Still more par-ticularly, it is concerned with a method for polymerizing olefins, such as .alpha.-pinene, isoprene, isobutylene, terpenes or mixtures of same, utilizing a catalyst system comprising an aluminum halide an alkyl germanium or an aryl germanium halide or alkoxide and optionally a (lower) alkyl, alkenyl or aralkyl halide to obtain polymers having softening points of at least 100°C. and possessing relatively high molecular weights.

Description

:
: ~077 , -The present invention relates to a method for polymer-izing difficultly polymerizable olefins or mixtures thereof to obtain polymers in good yields. Still more particularly, it is concerned with a method for polymerizing olefins, such as ~-pinene, isoprene, isobutylene, terpenes or mixtures of same, utilising a catalyst system comprising an aluminum halide an alkyl germanium or an aryl germanium halide or alkoxide and optionally a (lower) alkyl, alkenyl or aralkyl halide to obtain polymers having softening points of at least 100C and possess-. 10 ing relatively high molecular weights.
, Alpha-pinene has been subjected to isomerization and polymerization utilising catalyst systems, such as aluminum chloride alone or in conjunction with either a trialkyl silicon halide or a dialkyl tin dichloride, attention being directed to ' United States Patent Nos. 3,354,132 and 3,478,007. However, ~! none of the prior methods is entirely satisfactory. The yields obtained are poor and softening points low. Moreover, even to obtain such unsatisfactory yields, such prior procedures require rigorous drying of the olefin monomer and solvent prior to polymerization. If a simple process could be provided to insure ' high yields hitherto unobtainable, and without scrupulously dry-!, ing of the materials present, such a process would fulfill a need long recognized in the art.
Thus, according to the present invention there is pro-vided a catalyst system for the polymerization of an olefin i monomer which comprises: a minor amount of an admixture of an alkyl germanium halide or an aryl germanium halide and an alkyl, alkenyl or aralkyl halide and (2) a major amount of aluminum chloride or aluminum bromide or mixtures thereof.
The present invention also provides a process for ~ polymerizing olefin monomers which comprise the steps of:
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;`'` , establishing a catalyst system comprising (a) a minor amount ; of a mixture of (a) an alkyl germanium halide, alkyl germanium .;~ alkoxide or an aryl germanium halide (b) and from 0 to about ; 1% based on the weight of the monomer of an alkyl halide, , alkenyl or aralkyl halide, (2) a major amount of aluminum chloride or aluminum bromide or mixtures of the latter in an inert solvent, adding at a temperature between about minus 30 C and about plus 30 C the olefin incrementally with agitation adjusting and maintaining the temperature of the mixture at about minus 30C to about plus 30C for from about one to about four hours, quenching the latter mixture with an aqueous sol- :
.': ution, separating the phases, and recovering a solid polymer .
:- from the hydrocarbon phase.
Particularly the present invention provides the above process wherein the olefin monomer is a alpha-pinene.
. In a preferred embodiment of the aforesaid catalyst ~, system the alkyl germanium halide is trimethyl germanium ;
chloride ranging from about 0.08% to 0.1% and the alkyl halide . is t-butyl-chloride ranging from 0.4% to 1.0%.
The aforementioned catalyst system is first prepared :: .
in an inert solvent and the undried or dried olefin is then added incrementally with vigorous stirring while .
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1 maintaining the reaction mixture at from about minus (-) 30C.
to about plus (+) 30C. and, preferably, between about -20C.
to +20C., to insure maximum yield of resin of high softening point. After the olefln has been added, stirring and cooling S are continued for at least fifteen minutes or until the amount i - of unreacted monomer is substantially reduced. Thereafter, j the reaction temperature is permitted to rise slowly to a temperature of about 20C. over a period of one to four hours.
The reaction mixture is then quenched with water or dilute hydrochloric acid with the production of an organic phase and an aqueous phase. Resultant polymer is then recovered as a residue from the organic phase after removal of the sol-` vent, as by steam distillation.
., .
Illustrative of the olefins which can be employed herein are: linear aliphatic mono- or di-olefins, such as isobutylene, isoprene, or piperylene, and terpenic olefins, such as ~-pinenee, B-pinene, camphene, dipentenè, limonene, and mixtures of the same, such as ~-pinene and isoprene or a-pinene and limonene, so as to obtain either homopolymers j 20 or copolymers.
Exemplary solvents or diluents include: aromatic hydrocarbons such ao toluene, mixed xylenes, mesitylene, and diethyl benzenes. Other solvents that can be employed here-.
in are halogenated hydrocarbons, such as methylene chloride, 25 ethyl chloride or chlorobenzene. ~- -Advantageously, the ratio of the organo germanium halide to aluminum chloride or bromide in the catalyst ~ystem may vary within wide limits. The amount of aluminum chloride or bromide may vary from 2-10% and the alkyl germanium halide ~30 from 0.1 to 1.5%, both based on the weight of monomer. ~t has been found that particularly satisfactory results are attained with catalyst systems comprising 3 to 5 weight per-' cent of aluminum chloride and 0.6 weight percent of a trialkyl ' . .

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germanium halide or a triaryl geDanium halide, The organo germanium halide or alkoxide utilized in the process of this invention can be represented by the formula:
RnGeXy where R is lower alkyl or aryl, X is halogen or lower alkoxide, y is an integer from l to 3 and n is 4-y. Illustrative of the organo germanium halide or alkoxide co-catalyst component employed are: trimethyl germanium chloride, trimethyl ge Danium methoxide, triethyl germanium chloride, tri- ~-butyl germanium chloride, iodide, tri-t-butyl ge Danium chloride, dimethyl ge Danium dichloride, diethyl germanium dibromide, monoethyl germanium trichloride, monopropyl germanium trifluoride, diphenyl geDanium dibromide, triphenyl germanium chloride and tri-n-propyl ge Danium chloride.
Due to the present high cost of organo geDanium halide the process can be appropriately modified whereby the cost is substantially reduced -~
without dramatically decreasing yield of resin. This modification employs a -co-catalyst.
Exemplary co-catalysts are: lower alkyl halides such as t-butyl chloride, allyl chloride, benzyl chloride, benzyl bromide, sec-butyl bromide, isopropyl chloride, n-propyl bromide and equivalents thereof.
The ratio of mixture of the alkyl, alkenyl or aralkyl halide and the organo germanium synergist to aluminum chloride or bromide may vary within wide limits. A ratio of 0.08 to 1.5%, and preferably 0.2 to 0.8% -geDanium compound; 2 to 10% and preferably 3 to 5% aluminum chloride or bromide; and 0.4 to 1.0% of an alkyl, alkenyl or aralkyl halide co-catalyst all based on the weight of the monomer used. It has been found that satisfactory results are particularly attained with a catalyst system com-prising 5 weight percent of aluminum chloride and 0.6 weight percent of a triaryl ger-E - 3 _ -.' , :
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1(~774~4 1 manium halide synergist plus .8 weight percent of an alkyl, alkenyl, aralkyl halide.
Advantageously, in the production of the high yields of high softening point resin which characterizes the S present invention, both the terpenic olefin reactant and the inert solvent can be utilized without the removal of water therefrom. For instance, it is known that a solvent can con-tain as much as 400 ppm. water and the monomer as much as 200 ppm. water under ambient conditions. Greater amounts of water, however, cannot be tolerated without concomitant reductions in yields of polymer. Alternatively, the solvent and monomer can be dried prior to reaction.
In a preferred practice of the invention, monomeric olefin such as, for instance, ~-pinene, and solvent are each employed undried, i.e. with respectively 100 and 300 ppm.
; ; detectable water. The overall system is flushed with an in-ert gas, suitably nitrogen. ~he solvent and catalyst system are introduced into the vessel and the monomeric olefin is then added incrementally and progressively, while vigorously stirring the reaction medium. As soon as the monomeric ole-fin addition begins, an exotherm occurs and cooling is ap-plied to maintain the reaction medium at -15C. to -20C.
Stirring and temperature control at this level are continued for a period of time, generally 30 minutes, after all o} the olefin has been added. Thereafter, the temperature is al-lowed to gradually rise over a period of one to two hours to +20C. to +25C,, where it is maintained for two to four hours. Normally, reaction is continued until essentially all monomer is converted.
me reaction mixture is then quenched to inactivate the catalyst, as by adding a volume of water equal to the volume of a-pinene used. Alternatively, a dilute solution of an acid or base may be used. In all cases two layers are `

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1 formed, one of which constitutes a hydrocarbon phase and the other an aqueous phase. After separation, the hydrocarbon ~-phase is washed repeatedly with equal amounts of water until neutral.
- 5 The polymerization reaction may be carried out con-tinuously by utilizing two reactors, the first held at -15 to -20C. and the second at +20C. The overflow from the second reactor is continuously quenched and the polymer iso-lated by a suitable technique. For instance, a-pinene of -95 percent purity is commercially available and will give excellent results The following examples illustrate the invention.
Unless otherwise noted, the parts and percentages are by weight.
-~ 15 Example 1 To a suitable three-neck flask are introduced 210 parts of xylene and there are next added 9 parts of aluminum chloride and 1.8 parts of triethyl germanium chloride, (C2H5)3GeCl, providing a weight ratio of 5:1. The resultant mixture is vigorously stirred. 300 Parts of a-pinene are then introduced over a period of 30 minutes. The reaction mixture is held at minus 15C. to minus 20C. by a cooling bath. Thereafter, the contents of the flas~ are maintained in an inert nitrogen atmosphere at this temperature for one-half hour. Thereafter, the temperature is allowed to risegradually with controlled cooling while finally reaching +20C.
to +25C. after two and one-half hours. There is next add-ed water equal in volume to the ~-pinene, to inact1vate the catalyst system, and to cause separation of the aqueous and organic phases. The phases are separated, and the organic one is washed three times with equal amounts of water. It is then charged to a flask provided with a heater, thermom-eter and nitrogen atmosphere, and the temperature raised to ` lf~7746~

; 1 210C., thereby removing the solvent and recovering a sub-stantial amount of the volatile germanium constituent in the distillate. The introduction of~nitrogen is discontinued and in its place steam is passed in and the temperature in-creased to 230C. Steaming is continued until the resin soft-ening point reaches the desired limit. Application of vac-`j uum removes any trace of moisture and the molten resin is obtained in 96.7% yield and having:
Softening point 120C., ring and ball .
Color Gardner 2 ; No. average molecular 820 weight .j .
Example 2 i ~ Repeating Example l in every detail except that trimethyl germanium chloride, trimethyI germanium bromide or triphenyl germanium chloride is substituted for triethyl ¦ germanium chloride, there i 8 obtained a-pinene polymer in oxcellent yields.
Example 3 The procedure of Example 1 is repeated in every de-tail except that trimethyl germanium bromide in lieu of tri-~
ethyl germanium chloride is dissolved directly in the monomer ~ feed rather than in the solvent. There resules a yield of i 95% a-pinene resin having a softening point of 113C.
~ 25 Ex~e~c_4 f: The procedure of Example 1 is followed in every ,; detail except that the monomeric a-pinene reactant and the ~ solvent are carefully dried. There is obtained a resin yield ,~ . . .
(polymer) of 91.0%, based on the weight of the monomer, and a softening point of 125C.

Examples 5 - 27 The procedure of Example 1 is followed in every re-spect except that the specific solvent, temperature, catalyst .

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`-' 1077464 1 system and polymeric product are set and summarized in Table I below.

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~1 Examples 29 - 38 The following examples all illustrate the AlC13/RnGeXy catalyst system, where R, X, n and y are defined above, as useful for the preparation of homopolymers and co- --5 polymers derived from a variety of monomers by utilizing the -:~
procedure of Example 1. The modifications and results are :-summarized in Table II below.

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`~" 1077464 1 ~ Example 39 ` ~ a-Pinene and a-pinene-limonene resins, as prepared in accordance with Examples 1 and 33, respectively, are ex-tremely light in color and show exceptionally wide compat- -ibility with commonly used polymers and film formers. They have -the ability to tackify other materials with which they are compatible, such as styrene-butadiene rubber, natural rubber, ethylene-propylene elastomers chlorobutyl and butyl rubbers.
The following table lists results of test evalua-tions of pressure-sensitive adhesives employing a-pinene resin and a 1:1 a-pinene-limonene copolymer as tackifier with pale crepe natural rubber and styrene-butadiene-styrene block co-~`~ polymer, respectively.

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; 1 The tackifiers listed above are employed in the following formulation:
100 parts elastomer 75 parts tackifying resin 1 part antioxidant Polyisoprene natural rubber is milled to a Mooney viscosity of 50 prior to use. Kraton 1102~ a linear block styrene- --butadiene-styrene, is used as received.
Example 40 a-pinene-isobutylene copolymer as prepared in ac-cordance with Example 34, is a resin having a softening point of 35C. In addition to its use in pressure-sensitive tapes as shown in Example 39, the low molecular weight polymer ha~
a large variety of applications, such as an oil additive, viscosity index improver, sealant, caulking agent, special lubricant, soundproofing compound, ink, or as a waterproofing, leather impregnating, and paper coating agent.
Example 41 The procedure of Example 17 is repeated in every detail except that trimethyl germanium bromide in lieu of triethyl germanium chloride is dissolved directly in the mo~-, omer feed rather than in the solvent. There results an 84.0%
yield of a-pinene resin having a softening point of 113C.
Example 42 The procedure of Example 17 is followed in every dètail except that the a-pinene monomer and the solvent are carefuily dried. There is obtained a resin yield (polymer) of 83%, based on the weight of the monomer, and a softening point of 115C.
a-Pinene polymers prepared as in Examples 1 to 10, and 12-28, have molecular weights of from about 700 to 900 by vapor pressure osmometry, and a softening point of at least about 110C. These polymers are soluble in solvents, such .
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1 as hexane, benzene, heptane, toluene, xylene and mineral spir-its. However, the latter differ from other related polymers, namely the ~-pinene polymers, in exhibiting solubility in methyl ethyl ketonef dioxane, ethyl acetate and cyclohexanol.
Example 43 ~-Pinene resin as prepared in accordance with Ex- -ample 17 is extremely light in coior and shows exceptionally ; wide compatability with commonly used polymers and film form-- ers. It has the ability to tackify other materials with which it is compatible, such as styrene-butadiene rubber, natural - rubber, ethylene-propylene elastomers chlorobutyl and butyl rubber by method5 well known in the art. -.: ' ' ' ' ~ ' ~ ' . -., .
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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for polymerizing olefin monomers which comprise the steps of: establishing a catalyst system comprising (1) a minor amount of a mix-ture of (a) an alkyl germanium halide, alkyl germanium alkoxide or an aryl germanium halide and (b) from 0 to 1% based on the weight of the monomer of an alkyl halide, alkenyl or aralkyl halide, (2) a major amount of aluminum chloride or aluminum bromide or mixtures of the latter in an inert solvent, adding at a temperature between about minus 30°C. and about plus 30°C. the olefin incrementally with agitation, adjusting and maintaining the temperature of the mixture at about minus 30°C. to about plus 30°C. for from about one to about four hours, quenching the latter mixture with an aqueous solution, separating the phases, and recovering a solid polymer from the hydrocarbon phase.

2. The process according to claim 1 wherein the inert solvent and olefin monomer in admixture contains from about 200 ppm. to about 400 ppm.
water.

3. The process according to claim 1 wherein the catalyst system com-prises from 2 to 10 weight percent of aluminum chloride, and a mixture of from 0.08 to 1.5 weight percent of an alkyl germanium chloride or an aryl germanium chloride and from 0.4 to 1.0 weight percent of an alkyl halide, alkenyl halide or aralkyl halide, said weight percentages being based upon the weight of monomer.

4. The process according to claim 1 wherein the alkyl germanium halide is trimethyl germanium chloride ranging from about 0.08% to 0.1% and the alkyl halide is t-butyl-chloride ranging from 0.4% to 1.0%.

5. The process according to claim 3 wherein the alkyl germanium halide is dimethyl germanium dichloride and the halide is t-butyl-chloride.

6. The process according to claim 1 wherein the alkyl germanium halide is tri-n-propyl germanium chloride.

7. The process according to claim 1 wherein the alkyl germanium halide is triethyl germanium bromide.

8. The process according to claim 1 wherein the aryl germanium halide is triphenyl germanium chloride.

9. A process according to claim 1 wherein the olefin monomer is alphapinene.

10. A catalyst system for the polymerization of an olefin monomer which comprises: (1) a minor amount of an admixture of an alkyl germanium halide or an aryl germanium halide and an alkyl, alkenyl or aralkyl halide and (2) a major amount of aluminum chloride or aluminum bromide or mixtures thereof.

11. A process according to claim 1 wherein the aluminum chloride or bromide is present in an amount from 3 to 5 weight % of monomer, the alkyl germanium halide is present in an amount from 0.2 to 0.8 weight % of monomer and the alkyl, alkenyl or aralkyl halide is present in an amount from 0.4 to 1 weight % of monomer.

12. A process according to claim 11 wherein the alkyl germanium halide is selected from the group trimethyl germanium chloride, triethyl germanium chloride, tributyl germanium chloride, iodide, tri-t-butyl germanium chloride, dimethyl germanium dichloride, diethyl germanium dibromide, monoethyl germanium trichloride and monopropyl germanium trifluoride.

13. A process according to claim 12 wherein the alkyl, alkenyl or aralkyl halide is selected from t-butyl chloride, allyl chloride, benzyl chloride, benzyl bromide, sec-butyl bromide, isopropyl chloride, n-propyl bromide,

14. A catalyst system according to claim 10 wherein the aluminum chloride or bromide is present in an amount from 3 to 5 weight % of monomer, the alkyl germanium halide is present in an amount from 0.2 to 0.8 weight %
of monomer and the alkyl, alkenyl or aralkyl halide is present in an amount from 0.4 to 1 weight % of monomer.

15. A catalyst system according to claim 14 wherein the alkyl germanium halide is selected from the group trimethyl germanium chloride, triethyl germanium chloride, tributyl germanium chloride, iodide, tri-t-butyl germanium chloride, dimethyl germanium dichloride, diethyl germanium dibromide, mono-ethyl germanium trichloride and monopropyl germanium trifluoride.

16. A catalyst system according to claim 15 wherein the alkyl, alkenyl or aralkyl halide is selected from t-butyl chloride, allyl chloride, benzyl chloride, benzyl bromide, sec-butyl bromide, isopropyl chloride, n-propyl bromide.

17. A process according to claim 11, 12 or 13 wherein the monomer is selected from isobutylene, isoprene, piperylene, .alpha.-pinene, .beta.-pinene, cam-phene, dipentene, limonene, and mixtures thereof.