Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Patent
1995-01-15
1995-05-23
Teskin, Fred
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
526335, 526339, 526901, 526902, 526904, 524576, 524579, C08F23620, C08F21006
Patent
active
054183081
DESCRIPTION:
BRIEF SUMMARY
This invention relates to copolymers of alpha-olefins and in particular propylene with non-conjugated diene or triene monomers.
Ethylene-propylene-diene monomer copolymers (EPDM rubbers) are a well known class of elastomeric copolymers. They are used in blends with thermoplastic polymers to increase the toughness of the thermoplastic. Additionally, the EPDM rubbers are unsaturated (one of the double bonds in the diene monomer is present in the polymer) and this enables ready cross-linking (vulcanisation). Unfortunately, the typical diolefins used poison highly stereospecific Ziegler-Natta olefin polymerisation catalysts and, thus, EPDM rubbers are made using non-stereospecific catalysts, typical of those used to homopolymerise ethylene.
The present invention is directed to providing a copolymer of propylene and optionally ethylene with a specific class of non-conjugated diene or triene monomers. The copolymers have high stereoregularity and are generally mainly thermoplastic rather than elastomeric as with EPDM rubbers.
The present invention accordingly provides a random copolymer of: from 0.1 to 40, particularly 0.5 to 15, mole % units derived
from a non-conjugated diene or triene of the formula (I):
R.sup.1 is a hydrogen atom or an alkyl group, particularly a C.sub.1 to C.sub.10 alkyl group;
R.sup.2 is independently a group as defined for R.sup.1 (above), provided that R.sup.1 and R.sup.2 are not both hydrogen atoms;
R.sup.3 is an alkyl group, particularly a C.sub.1 to C.sub.10 alkyl group or is an alkenyl group of the formula (II): (above), provided that R.sup.5 and R.sup.6 are not both hydrogen atoms; each R.sup.8 is independently a group as defined for R.sup.4 (below); and integer of from 2 to 5, in particular 2, 3 or 4; propylene.
The invention includes a method of making a copolymer of the invention comprising polymerising the respective monomers in the presence of a highly stereospecific Ziegler-Natta olefin polymerisation catalyst.
The monomer of general formula (I) (the diene or triene monomer) includes an alpha-olefinic double bond which will polymerise under Ziegler-Natta conditions. The two carbon atoms of the second double bond of the diene or triene monomer have at least 3 substituent carbon atoms (including the main chain of the compound) bonded to them. This is necessary to avoid deactivating the highly stereospecific Ziegler-Natta catalysts where there are only one or two carbon based substituents. Of course, all four substituents can be carbon based. In terms of the general formula (I) this means that at least two of the groups R.sup.1, R.sup.2 and R.sup.3 are alkyl groups (or for R.sup.3 an alkenyl group of the formula II).
When R.sup.1 and/or R.sup.2 are alkyl groups it is particularly convenient if they are short chain alkyl, especially C.sub.1 to C.sub.3 and most conveniently methyl, groups. R.sup.3 can also conveniently be such a short chain alkyl especially methyl group or it can be a longer chain straight or branched chain alkyl group. When R.sup.3 is an alkenyl group, the double bond is not conjugated with the --CR.sup.1 =R.sup.2 R.sup.3 double bond of the diene or triene monomer and, like the 'second' double bond it has at least 3 carbon based substituents. Of course, when R.sup.3 is an alkenyl group the diene monomer is technically a non-conjugated triene, however, for clarity and brevity this possibility is encompassed by the general term 'diene or triene monomer'as applied to the monomer of the formula (I). Within R.sup.3, when the groups R.sup.5 and/or R.sup.6 and/or R.sup.7 are alkyl groups they are particularly short chain alkyl, especially C.sub.1 to C.sub.3 and most conveniently methyl, groups. The groups R.sup.4 and R.sup.8 (when R.sup.3 is an alkenyl group) can all be hydrogen atoms. When at least some of them are alkyl groups it is desirable that such alkyl groups do not unduly crowd the main chain of the alkyl substituted diene or triene monomers. Accordingly, when there are two or more such alkyl substituents, they will generally be separated by at least one unsubst
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Patent Abstract of Japan, vol. 14, No. 220, May 1990.
BASF - Aktiengesellschaft
Teskin Fred
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