The Penn State Research Foundation

T C Chung

D Rhubright

H L Lu

G J Jiang

M Chasmawala

Functionalized copolymers of .alpha.-olefin and para-alkylstyrene having the formula: ##STR1## in which in which R, R' and R', independently, are hydrogen or primary or secondary alkyl groups; X comprises a functional group, such as --COOH, --OH, --SH, --NH.sub.2, --Cl, --Br, --M, --COOM (M=metals, e.g. Li, Na, K and Ca) and anhydrides; P comprises a polymer having the molecular weight of at least about 500, which can be derived from both step and chain polymerization reactions; Y is a chemical linkage between polymer P and para-alkystyrene side chain, which is also a residue derived from graft reaction; and the combination of a+b+c+d represents the empirical formula of a substantially random functional polymer, where a ranges from about 50 to about 100,000, b, c and d range from 0 to about 10,000, and the sum of c+d is at least 1, and processes for preparing the funcitonalized copolymers are disclosed.

Functionalized .alpha.-olefin/para-alkylstryne copolymers

Copolymers comprising poly(.alpha.-olefin) having at least few p-alkylstyrene (para-alkylstyrene) groups or/and p-alkylstyrene derivatives within the structure therein, said polymer having monomer units represented by the structural formula: ##STR1## in which R, R' and R' are, independently, either hydrogen, alkyl, or primary or secondary alkyls. Preferably, R is hydrogen and C.sub.1 to C.sub.10 linear and branched alkyl, and most preferably R is hydrogen, C.sub.1 and C.sub.2. R' and R' are hydrogen, C.sub.1 to C.sub.5 alkyl, or C.sub.1 to C.sub.5 primary or secondary alkyl, and most preferably R' and R' are hydrogen. F comprises a hydrogen or a functional group, such as --COOH, --OH, --NH.sub.2, --Cl, --Br, --M, --COOM (M=metals, e.g. Li, Na, K and Ca) etc., or a mixture of functional group and hydrogen. In the copolymer composition, the .alpha.-olefin mole % (m) is between about 5 and 99.9. Preferably, m is between 85 and 99.9, and most preferably m is between 95 and 99.9. The sum of m and n (mole % of p-alkylstyrene) is 100. The copolymer having a number average molecular weight (Mn) of at least about 1,000, and preferably at least about 10,000. The copolymers also preferably have a ratio of weight average molecular weight (Mw) to number average molecular weight, or Mw/Mn of less than about 8, more preferably less than about 4, most preferably less than about 2.5. Also disclosed are polymerization process, involving transition metal catalysts (especially metallocene compounds with constrained ligand geometry) for producing .alpha.-olefin/p-alkylstyrene copolymers, and subsequently derivatization processes for producing functionalized copolymers of .alpha.-olefin and p-alkylstyrene by the functionalization of benzylic protons in p-alkylstyrene units of copolymer.

.alpha.-olefin/para-alkylstyrene copolymers

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.

Olefin graft copolymers prepared using borane-containing olefin backbone

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.

Polymeric hydrocarbons having reactive borane groups at chain ends or in the polymer chain are described. These types of polymers can be used as intermediate materials for preparing a broad range of polymers which have functional groups located at both ends of the polymer chain (telechelic polymers). The process of preparing the borane-containing polymers involves metathesis degradation of the polymer at the double bond locations in the backbone and simultaneous functionalization of the broken chain ends by borane monomers. Depending on the nature of the borane monomer, the location of boron atoms can be controlled to be at either the chain ends (telechelic) or in the polymer backbone. The concentration of boron in the resulting polymer is related to the reaction time and the mole ratio between borane monomer and the double bonds in the starting hydrocarbon polymer. In turn, the borane groups are interconvertible to various functional groups, such as OH, NH.sub.2, and halides, under mild reaction conditions. Overall, the chemistry is very general and is applicable to most hydrocarbon polymers. A wide variety of telechelic polymers are obtained.

Growing community of inventors

State College, PA, United States of America

T C Chung