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US5286800A Expired / Lapsed US ⏱️ 0.0 years remaining

Olefin graft copolymers prepared using borane-containing olefin backbone polymers

Assignee: Pennsylvania Research Corp
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Filing: 1992-04-06
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Granted: 1994-02-15
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Expires: 2012-04-06
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Abstract

Abstract Polyolefin graft copolymers are disclosed which comprise a polyolefin homopolymer or copolymer backbone polymer having a plurality of free radically polymerized polymeric segments chemically bonded as side chains. It has been found that the use of a borane-containing polyolefin comprising a copolymer of 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 free radical polymerization and copolymerization. Numerous free radical polymerizable monomers, such as methyl methacrylate, styrene, alpha-methylstyrene, acrylonitrile and the like, can be polymerized to yield high molecular weight graft copolymers. By this synthetic route, high graft efficiency is observed with only a very low concentration of homopolymer being produced.

Inventors

  • 👤 T. C. Chung
  • 👤 G. J. Jiang
  • 👤 D. Rhubright

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-05 02:46
CPC Classifications
C; C07; C07F; C07F5/00; C07F5/02; C07F5/027; C08; C08C; C08C19/00; C08F; C08F291/00

Claims Analysis

Total Claims: 18
Claim 1
Independent Claim 446 words
A graft copolymer having the formula selected from: ##STR3## wherein R 1 and R 2 are the same or different and are selected from the group consisting of H, C 1 to C 20 alkyl, phenyl and alkyl substituted phenyl; R 3 is a direct link or a divalent hydrocarbon having from 1 to 20 carbon atoms of linear or branched structure and comprises the residue from a group having the structure --R 3 BR 4 R 5 , where R 4 and R 5 are the same or different alkyl or cycloalkyl group containing from 1 to about 10 carbon atoms and R 3 is as defined above; W is a polar substituent group; M is the residue of a free radically polymerizable monomer; n is the degree of polymerization of M ranging from 1 to about 70,000; (diene) is a recurring segment of a polymerized diolefin monomer; x ranges from about 50 to about 70,000; (a) ranges from 0 to about 20,000; and the sum of (b) and (c) ranges up to about 20,000 with the proviso that (b) or (c) is at least 1 when the other of (b) or (c) is 0; wherein said graft copolymer having the formula I is prepared by: (i) contacting in the presence of a Ziegler-Natta catalyst a mixture of at least one C 2 to C 22 alpha-monoolefin and a borane-containing monomer having the structure CH 2 ═CH(CH 2 ) m --BR 4 R 5 wherein m is an integer of from 3 to 12 and R 4 and R 5 are as described above, to form a copolymer product having borane-containing units in the copolymer chain; and (ii) contacting the copolymer formed in step (i) with at least one free radically polymerizable monomer in the presence of an oxidative reagent to convert at least one of said borane-containing units to a free radical which, in turn, initiates free radical polymerization of said free radically polymerizable monomer, thereby forming said graft copolymer having the formula I; and, wherein said graft copolymer having the formula II is prepared by: (iii) reacting a diene copolymer of at least one C 2 to C 22 alpha olefin and at least one conjugated or non-conjugated diene with a hydroboration reagent to incorporate borane-containing units into the diene copolymer chain; and (iv) contacting the borane-containing diene copolymer formed in step (iii) with at least one free radically polymerizable monomer in the presence of an oxidative reagent to convert at least one of said borane-containing units to a free radical which, in turn, initiates free radical polymerization of said free radically polymerizable monomer, thereby forming said graft copolymer having the formula II.
Claim 2
Dependent Claim 446 words
A graft copolymer having the formula selected from: ##STR3## wherein R 1 and R 2 are the same or different and are selected from the group consisting of H, C 1 to C 20 alkyl, phenyl and alkyl substituted phenyl; R 3 is a direct link or a divalent hydrocarbon having from 1 to 20 carbon atoms of linear or branched structure and comprises the residue from a group having the structure --R 3 BR 4 R 5 , where R 4 and R 5 are the same or different alkyl or cycloalkyl group containing from 1 to about 10 carbon atoms and R 3 is as defined above; W is a polar substituent group; M is the residue of a free radically polymerizable monomer; n is the degree of polymerization of M ranging from 1 to about 70,000; (diene) is a recurring segment of a polymerized diolefin monomer; x ranges from about 50 to about 70,000; (a) ranges from 0 to about 20,000; and the sum of (b) and (c) ranges up to about 20,000 with the proviso that (b) or (c) is at least 1 when the other of (b) or (c) is 0; wherein said graft copolymer having the formula I is prepared by: (i) contacting in the presence of a Ziegler-Natta catalyst a mixture of at least one C 2 to C 22 alpha-monoolefin and a borane-containing monomer having the structure CH 2 ═CH(CH 2 ) m --BR 4 R 5 wherein m is an integer of from 3 to 12 and R 4 and R 5 are as described above, to form a copolymer product having borane-containing units in the copolymer chain; and (ii) contacting the copolymer formed in step (i) with at least one free radically polymerizable monomer in the presence of an oxidative reagent to convert at least one of said borane-containing units to a free radical which, in turn, initiates free radical polymerization of said free radically polymerizable monomer, thereby forming said graft copolymer having the formula I; and, wherein said graft copolymer having the formula II is prepared by: (iii) reacting a diene copolymer of at least one C 2 to C 22 alpha olefin and at least one conjugated or non-conjugated diene with a hydroboration reagent to incorporate borane-containing units into the diene copolymer chain; and (iv) contacting the borane-containing diene copolymer formed in step (iii) with at least one free radically polymerizable monomer in the presence of an oxidative reagent to convert at least one of said borane-containing units to a free radical which, in turn, initiates free radical polymerization of said free radically polymerizable monomer, thereby forming said graft copolymer having the formula II.
Claim 3
Dependent Claim 16 words
The graft copolymer of claim 1, wherein (c) is 0 and (b) is at least one.
Claim 4
Dependent Claim 28 words
The graft copolymer of claim 2 wherein the x units are derived from one or a mixture of alpha monoolefins having from 2 to about 22 carbon atoms.
Claim 5
Dependent Claim 24 words
The graft copolymer of claim 3 wherein said monoolefins are selected from the group consisting of ethylene, propylene, 1-butene, 1-octene, isobutylene and mixtures thereof.
Claim 6
Dependent Claim 11 words
The graft copolymer of claim 4 wherein said monoolefin is propylene.
Claim 7
Dependent Claim 11 words
The graft copolymer of claim 4 wherein said monoolefin is isobutylene.
Claim 8
Dependent Claim 11 words
The graft copolymer of claim 4 wherein said monoolefin is 1-octene.
Claim 9
Dependent Claim 16 words
The graft copolymer of claim 4 wherein said monoolefin is a mixture of ethylene and propylene.
Claim 10
Dependent Claim 21 words
The graft copolymer of claim 2 wherein R 3 is a divalent hydrocarbon containing from 3 to about 12 carbon atoms.
Claim 11
Dependent Claim 10 words
The graft copolymer of claim 2 wherein (a) is 0.
Claim 12
Dependent Claim 25 words
The graft copolymer of claim 2 having formula II wherein the x units are derived from isobutylene and the diene units are derived from isoprene.
Claim 13
Dependent Claim 33 words
The graft copolymer of claim 2 having the formula II wherein the x units are derived from a mixture of ethylene and propylene and the diene units are derived from a non-conjugated diolefin.
Claim 14
Dependent Claim 50 words
The graft copolymer of claim 2 wherein said M units are based on a free radically polymerized monomer selected from the group consisting of alkyl acrylates and methacrylates, acrylic and methacrylic acid, vinyl aromatic compounds, vinyl amides, vinyl pyridines, acrylonitriles, vinyl acetates, vinyl chloride and vinylidene chloride and mixtures thereof.
Claim 15
Dependent Claim 23 words
The graft copolymer of claim 13 wherein said M units are selected from the group consisting of styrene, methyl methacrylate and t-butyl methacrylate.
Claim 16
Dependent Claim 40 words
The graft copolymer of claim 2 having a number average molecular weight in the range of from about 50,000 to about 3,000,000 and wherein said (M)n units comprise from about 5 to about 95% by weight of the copolymer composition.
Claim 17
Dependent Claim 28 words
The graft copolymer of claim 2 wherein (a) is greater than 0 and W is selected from the group consisting of NH 2 , CHO, OH and halogen.
Claim 18
Dependent Claim 40 words
The graft copolymer of claim 2 wherein (a) is greater than 0 and W is BR 4 R 5 wherein R 4 and R 5 are the same or different alkyl or cycloalkyl groups containing 1 to 10 carbon atoms.

References Cited (Backward Citations)

US3862102A Cited
US4638092A Cited
US4806581A Cited
US4751276A Cited
US5180788A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1997-02-14 1997-08-16 1998-02-15 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 2001-02-14 2001-08-16 2002-02-15 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 2005-02-14 2005-08-16 2006-02-15 $7700.00 Window Closed / Lapsed

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