US 5,401,805 AGranted

Olefin graft copolymers prepared using borane-containing olefin backbone polymers

AssigneeThe Penn State Research Foundation

InventorsT. C. Chung, G. J. Jiang, D. Rhubright

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Abstract

Graft copolymers are disclosed which comprise an olefin borane-containing homopolymer or copolymer backbone polymer having radically polymerized polymeric segments chemically bonded as side chains or as a chain end. A borane-containing diene homopolymer or a copolymer of a diene and/or at least one alpha-olefin having from about 2 to 22 carbon atoms copolymerized with another monomer containing organoborane functional groups can be used as a backbone polymer to prepare the graft copolymers of the present invention. Under oxidation conditions, the borane group becomes the reaction site for the radical polymerization and copolymerization. Radical polymerizable monomers, such as methyl methacrylate, styrene, alpha-methylstyrene, acrylonitrile and the like, can be polymerized to yield high molecular weight graft copolymer. By this synthetic route, high graft efficiency is observed with only a very low concentration of homopolymer being produced.

Claims59

Dependent claims

A process for preparing a graft copolymer having the formula I ##STR9## wherein R.sub.1 and R.sub.2 are the same or different and are selected from H, C.sub.1 to C.sub.20 linear or branched alkyl, phenyl and alkyl substituted phenyl;

R.sub.3 is a direct linkage or a divalent linear or branched hydrocarbon having from 1 to 20 carbon atoms;
W is a polar substituent;
M is the residue of a free radically polymerizable monomer;
n and p are the same or different and are the degree of polymerization of M ranging from 1 to about 70,000;
(M).sub.n and (M).sub.p comprise polymer segments chemically bonded as side chains or chain ends;
x ranges from about 50 to about 70,000;
(a) ranges from 0 to 20,000;
(b) ranges from 1 to about 20,000;
(c) ranges from 0 to about 20,000;
and the sum of (b)+(c) ranges from at least 1 to about 20,000, which comprises:
(i) contacting in the presence of a Ziegler-Natta polymerization catalyst a mixture of at least one C.sub.2 to C.sub.22 alpha-monoolefin and a borane-containing monomer having the structure CH.sub.2 .dbd.CH(CH.sub.2).sub.m --BR.sub.4 R.sub.5, wherein m is an integer ranging from 3 to 12 and R.sub.4 and R.sub.5 are the same or different and are selected from the group consisting of C.sub.1 to C.sub.10 alkyl groups and C to C.sub.10 cycloalkyl groups;
(ii) subjecting the mixture from step (i) to polymerization conditions to form a copolymer product containing borane units;
(iii) contacting the copolymer of step (ii) with at least one free radically polymerizable monomer in the presence of a free radical catalyst capable of converting said borane units into free radicals;
and
(iv) subjecting the mixture of step (iii) to free radical polymerization conditions to convert at least a portion of said borane units to free radicals and to thereby initiate graft polymerization and the formation of a graft copolymer product containing polymeric side chains based on said free radically polymerizable monomer.

12 more elements

A process for preparing a graft copolymer having a formula selected from formulas II and III:

##STR10## wherein R.sub.1 and R.sub.2 are the same or different and are selected from H, C.sub.1 to C.sub.20 linear or branched alkyl, phenyl and alkyl substituted phenyl;
R.sub.3 ' is a direct link or a linear, cyclic, or branched hydrocarbon having from 1 to 20 carbon atoms;
(diene) is a recurring segment of a polymerized diolefin monomer;
W is a polar substituent;
M is the residue of a free radically polymerizable monomer;
n and p are the same or different and are the degree of polymerization of M ranging from 1 to about 70,000;
y ranges from 0 to about 70,000;
(a') ranges from 0 to about 20,000;
(b') ranges from 1 to about 20,000;
(c') ranges from 0 to about 20,000;
(d') ranges from about 0 to about 70,1000;
y' and z' are the same or different and range from about 100 to about 50,000;
and the sum of (b' )+(c') ranges from at least 1 to about 20,000, which comprises:
(i) contacting a backbone polymer selected from the group consisting diene homopolymer and diene copolymer derived from diene monomer and at least one C.sub.2 to C.sub.22 monoolefin monomer with a hydroboronation reagent under hydroboronation conditions to incorporate borane groups on the backbone polymer;
(ii) contacting the borane-group containing polymer of step (i) with at least one free radically polymerizable monomer in the presence of a free radical catalyst capable of converting said borane groups to free radicals;
(iii) subjecting the mixture of step (ii) to free radical polymerization conditions to convert at least a portion of said borane groups to free radicals and to thereby initiate graft polymerization and the formation of a graft copolymer product containing polymeric side chains based on said free radically polymerizable monomer.

13 more elements

Dependencies are inferred from the claim text.

Facts

Application: 08/146,861Filed 3 Nov 1993 · continuation in part
Priority: 6 Apr 1992
Granted: 28 Mar 1995
Term ends: Not estimatedThe source records don’t support an estimate.

Classification6 codes

C07F 5/027
Boron compounds: organoboranes and organoborohydrides
C08C 19/00
Chemical modification of rubber
C08F 291/00
Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to
C07F
Acyclic, carbocyclic or heterocyclic compounds containing elements other than carbon, hydrogen, halogen