FIELD OF THE INVENTION This invention relates to a novel catalyst that is suitable for use in the homopolymerization of norbornenes, in the homopolymerization of acrylates, and in the copolymerization of norbornenes with acrylates. The invention relates, further, to a process for homopolymerizing norbornenes and acrylates using the present catalyst, to a process for copolymerizing norbornenes with acrylates using the present catalyst, and to novel copolymers of norbornenes with acrylates.

BACKGROUND OF THE INVENTION Considerable interest has existed in the copolymerization of acrylates with norbornenes because of the potential benefits of combining the useful properties of the homopolymers of the two monomers. For example, polyacrylates are valued for their extreme hardness and adhesive properties, and are used to form clear, glass-like materials like Lucite0 and Plexiglas0. Polynorbornenes, on the other hand, are capable of resisting high temperatures and, thus, typically are employed in applications that necessitate high-temperature stability.

Typically, acrylates polymerize in the presence of radical or anionic initiators, whereas norbornene derivatives do not follow radical pathways and normally are polymerized by cationic, insertion, or ring-opening metathesis mechanisms. Therefore, in order to effect the copolymerization of acrylates with norbornenes, it was necessary to develop a catalyst system that would be effective for polymerizing both types of monomers. Attempts to copolymerize acrylates with norbornenes generally have been unsuccessful because of the aforementioned disparity in the mechanisms by which the respective monomers polymerize. Recently, however, as disclosed in the Sen et al

copending U. S. Patent Application Serial No. 09/099,070, filed on June 18,1998, the disclosure of which is incorporated herein by reference, successful copolymerization of acrylates with norbornene has been achieved with the use of certain Pd (II) dimer catalysts. Nonetheless, there exists a need for developing still other catalyst systems that are capable of effectively polymerizing acrylate homopolymers, norbornene homopolymers and copolymers of acrylates with norbornenes.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a catalyst system that is capable of copolymerizing acrylates with norbornenes.

It is another object to provide a catalyst system that is useful for the homopolymerization of both acrylate monomers and norbornenes.

It is yet another object to provide a novel catalyst system that is useful both for the homopolymerizing of acrylate monomers and norbornene monomers, and for copolymerizing acrylates with norbornenes.

Still another object of the invention is to provide novel copolymers of acrylates with norbornenes.

DETAILED DESCRIPTION OF THE INVENTION The above and other objects and advantages of the invention are accomplished in one embodiment by providing a Pd (II)-based catalyst system which homopolymerizes acrylates to high molecular-weight polymers, which homopolymerizes norbornenes, and which copolymerizes acrylates with norbornenes to high molecular weight polymers.

The copolymers prepared in accordance with this invention are characterized by advantages and properties attributable to the respective acrylate and norbornene monomers from which they are derived. The copolymers can be tailored in norbornene to acrylate ratio by varying the ratio of the respective monomers in the reaction mixture and by varying the ligands utilized in the catalyst system.

As used in the specification and claims, the term"acrylates"is meant to include compounds of the general formula H2C=CHCOOR, where R includes, but is not limited to, alkyl groups such as methyl (CH3), ethyl (CH2CH3), propyl (CH, CH, CH3), n-butyl (CH2CH2CH2CH3) and t-butyl (C- (CH3) 3), and aryl groups such as phenyl (C6H5) and p- tolyl (C7H8). Other acrylates that do not conform to this formula, but which nonetheless

are suitable for use in the present invention and are intended to be included within the scope of the term"acrylates", include such acrylates as 2-hydroxy ethyl methacrylate and methyl methacrylate. Specific non-limiting examples of acrylates contemplated for use in the present invention include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, acrylamide, 2-hydroxy ethyl acrylate, methyl methacrylate, ethyl methacrylate, acryloyl chloride and phenyl acrylate.

The term"norbornenes"is meant to include norbornene, as well as norbornene derivatives, such as norbornadiene, dicyclopentadiene and compounds conforming to the general formulas 5-norbornene-2-R'a, 5-norbornene-2, 2-R'a, 5-norbornene-3-R'a, 5- norbornene-3, 3-ruz 5-norbornene-2, 3-R'a, or 5-norbornene-2,-Rla-3-'b, where R'a and R'b, independently, represent an alkyl or aryl group or an alcohol or carboxylic acid derivative. Specific non-limiting examples of norbornenes contemplated for use in the present invention include, norbornene, 5-norbornene-2-methanol, cis-5-norbornene-endo- 2,3-dicarboxylic anhydride, 5-norbornene-2, 2-dimethanol, 5-norbornen-2-ol, norbornadiene, 5-norbornene-2, 3-diphenyl, cis-5-norbornene-endo-2, 3-dicarboxylic acid dimethyl ester, 5-norbornen-2-yl-acetate and 5-norbornene-2-carboxyaldehyde.

The Pd (II)-based catalyst system of the present invention is a catalyst that may be characterized by either of the following formulas: (L), 2Pd (R) (X) (I) or (L') Pd (R) (X), (II) where L is a monodentate phosphorus or nitrogen ligand, L'is a bidentate phosphorus or nitrogen ligand, R is an alkyl or aryl group, and X is an anionic group.

Non-limiting examples of the monodentate phosphorus or nitrogen ligand (L) include triphenyl phosphine (PPh3), tricyclohexyl phosphine (PCy3), trimethyl phosphine (PMe3), triethyl phosphine (PEt3), tri-n-propyl phosphine (P (n-Pr) 3), tri-n-butyl phosphine (P (n-Bu) 3), tri-t-butyl phosphine (P (t-Bu) 3), tri-p-tolyl phosphine (P (p-Tol) 3), or pyridine.

Non-limiting examples of the bidentate phosphorus or nitrogen ligand (L') include bis (diphenylphosphino) ethane, bis (diphenylphosphino) propane, bis (diphenylphosphino) butane, bis (dimethylphosphino) propane, bis (diphenylphosphino)- 1,1'-binaphthyl, bis (diphenylphosphino) amine, bis (diphenylphosphino) acetylene, bis (dimethylphosphino) methane, or bipyridine.

Anionic groups (X) contemplated for use in the present invention include, for example, chloride or bromide, or a carboxylate, such as acetate, propionate, trifluoroacetate, and benzoate. Non-limiting examples of alkyl or aryl groups contemplated for use in the present invention include methyl (CH3), ethyl (CHCH3), propyl (CH2CH2CH3), n-butyl (CH2CH, CH2CH3), t-butyl (C- (CH3) 3), phenyl (C6H6), or p- tolyl (C7H8).

The catalyst may be formed by reaction of 2 equivalents of the monodentate ligand or 1 equivalent of the bidentate ligand with [ (1, 5 cyclooctadiene) Pd (Me) (X)], as illustrated by the equation (where Me is CH3 and X is Cl): The catalyst may be formed in situ as used as such. Alternatively, the catalyst can be isolated and characterized by phosphorus or nitrogen NMR to establish its purity, and then used in its pure form.

The relevance of the alkyl (or aryl) group in the present catalyst system was explored by attempting to homopolymerize methyl acrylate using a catalyst that was devoid of alkyl (or aryl) groups. It was found that methyl acrylate would not polymerize when reacted in the presence of a Pd (II) catalyst that was prepared by reacting [ (1, 5- cyclooctadiene) Pd (CI) 2] with two equivalents of tricyclohexylphosphine (PCy3). This indicates that the alkyl (or aryl) group is essential to the polymerization mechanism.

As indicated above, and as will be more readily apparent in view of the following examples, the copolymers can be tailored in norbornene to acrylate ratio by varying the ratio of the respective monomers in the reaction mixture and by varying the ligands utilized in the catalyst system. Typically, the ratio of norbornene monomer to acrylate monomer in the starting mixture is from about 100: 1 to 1: 100. In preferred aspects of the invention, the ratio of norbornene monomer to acrylate monomer that is added to the

reactor is from about 10: 1 to about 1: 10.

Varying the ratio of monomer affects the properties of the copolymer in that increasing the ratio of one of the monomer reactants increases its presence in the copolymer product. Polymer products with a high methyl acrylate content tend to be somewhat tacky, while those with higher norbornene content are powdery white substances. Both varying the ligand used in the reaction and varying reactant monomer ratio affect the molecular weight of the polymer product obtained.

The polymerization preferably is carried out in the liquid phase using a solvent such as dichloromethane (CH2Cl2), benzene (C6H6), chlorobenzene (C6H5Cl) or hexane (C6H, 4). Other solvents that may be used as the polymerization medium include, for example, pentane (C5HI2), toluene (C7H9), and chloroform (CHCl3).

The polymerization in accordance with this invention may be carried out at temperatures ranging from about 0 to about 200° C. Typically, however, the polymerization will be carried out at a temperature of from about 30 to about 70° C, e. g., about 60° C. The pressure at which the polymerization is carried out is not critical, with pressures ranging from 0.5 to 2.0 atm being suitable.

The various aspects of the invention will be appreciated more fully in light of the following illustrative examples: Example 1: [(PPh3) 2Pd (Me) (Cl)]/norbornene in C6H5Cl In a glove box, under an inert atmosphere (nitrogen), [(PPh3) 2Pd (Me) (Cl)] (0. 050 g, 7.34 x 10-5 mol) was placed into a 25 mL round bottom flask. To this was added about 5 mL of chlorobenzene (C6HSCl) to form a suspension. Next, 2 g norbornene (0.021 mol) was added to the flask. The flask was sealed with a rubber septum and stirred at 60° C for 24 hours. 0.081 g of poly (norbornene) was obtained. Polymer product was obtained by precipitating in methanol, then decanting off liquid and drying under reduced pressure at room temperature. The product had a peak average molecular weight (Mp) = 997, 000, and a molecular weight distribution (MW/Mn, where M, is the weight average molecular weight and Mn is the number average molecular weight) = 2. 9.

Example 2: [(PPh3) 2Pd (Me) (Cl)]/t-butyl acrylate/norbornene in C6H5C' (10: 1 t- BA/NB ratio) In a glove box, under an inert atmosphere (nitrogen), [(PPh3) 2Pd (Me) (Cl)] (0. 050

g, 7.34 x 10-5 mol) was placed into a 25 mL round bottom flask. To this was added about 5 mL of chlorobenzene (C6H^CI) to form a suspension. Next, 1.881 g (1.47 x 10-2 mol) of t-butyl acrylate and 0.138 g (1.47 x 10-3 mol) of norbornene were dissolved in each other in a beaker, and the resulting solution was added to the flask containing the (PPh3) 2PdMeCI. The flask was sealed with a rubber septum and stirred at 60° C for 24 hours. Polymer product was obtained by precipitating in methanol, then decanting off liquid and drying under reduced pressure at room temperature. 0.419 g polymer was obtained. The composition of the polymer obtained was largely poly (t-butyl acrylate) with a few norbornene units.

Example 3: [(PPh3)2Pd(Me)(C1)]/butyl acrylate/norbornene in C6H^CI (10: 1 BA/NB ratio) In a glove box, under an inert atmosphere (nitrogen), [(PPh3) 2Pd (Me) (Cl)] (0. 050 g, 7.34 x 10-5 mol) was placed into a 25 mL round bottom flask. To this was added about 5 mL of chlorobenzene (C6HSCl) to form a suspension. Next, 1.881 g (1.47 x 10-2 mol) of butyl acrylate and 0.138 g (1.47 x 10-3 mol) of norbornene were dissolved in each other in a beaker, and the resulting solution was added to the flask containing the (PPh3) 2PdMeCI.

The flask was sealed with a rubber septum and stirred at 60° C for 24 hours. Polymer product was obtained by precipitating in methanol, then decanting off liquid and drying under reduced pressure at room temperature. 0.470 g polymer was obtained. The composition of the polymer obtained was largely poly (butyl acrylate) with a few norbornene units. The product had a peak average molecular weight (Mp) = 209, 000.

'Example 4: [(PPh3) 2Pd (Me) (CI)]/methyl methacrylate/norbornene in C6HsCI (10: 1 MMA/NB ratio) In a glove box, under an inert atmosphere (nitrogen), [(PPh3) 2Pd (Me) (CI)] (0. 050 g, 7.34 x 10-5 mol) was placed into a 25 mL round bottom flask. To this was added about 5 mL of chlorobenzene (C6HSCI) to form a suspension. Next, 1.8 g (0. 018 mol) of methyl methacrylate and 0.169 g (1.798 x 10-3 mol) of norbornene were dissolved in each other in a beaker, and the resulting solution was added to the flask containing the (PPh3) 2PdMeCl. The flask was sealed with a rubber septum and stirred at 60° C for 24 hours. Polymer product (0.535 g) was obtained by precipitating in methanol, then decanting off liquid and drying under reduced pressure at room temperature. 0.535 g

polymer was obtained. The composition of the polymer obtained was largely poly (butyl acrylate) with a few norbornene units. The product had a peak average molecular weight (Mp) = 295,000, and a molecular weight distribution (MN,/Mn) = 3. 0.

Example 5: [(PPh3) 2Pd (Me) (Cl)]/ methyl acrylate/norbornene in C6HSCI (10: 1 MA/NB ratio) In a glove box, under an inert atmosphere (nitrogen), [(PPh3) 2Pd (Me) (CI)] (0. 050 g, 7.34 x 10-5 mol) was placed into a 25 mL round bottom flask. To this was added about 5 mL of chlorobenzene (C6HSCl) to form a suspension. Next, 2 g (2.3 x 10-2 mol) of methyl acrylate and 0.226 g (2.3 x 10-3 mol) of norbornene were dissolved in each other in a beaker, and the resulting solution was added to the flask containing the (PPh3) 2PdMeCl. The flask was sealed with a rubber septum and stirred at 60° C for 24 hours. Polymer product (0.784 g) was obtained by precipitating in methanol, then decanting off liquid and drying under reduced pressure at room temperature. The product had a peak average molecular weight (Mp) = 160,000 and a molecular weight distribution (M,/Mn) = 8.7. The polymer product consisted mainly of poly (methyl acrylate).

Example 6: [(PPh3) 2Pd (Me) (Cl)]/ methyl acrylate/norbornene in C6HsCI (5: 1 MA/NB ratio) The procedure of Example 5 was repeated, except that 1.8 g (0.021 mol) of methyl acrylate and 0.394 g (4.19 x 10-3 mol) of norbornene were added to the reaction solution.

Approximatelyl. 8 g polymer product was obtained. The product had a peak average molecular weight (Mp) = 289,000 and a molecular weight distribution (MN~/Mn) = 2. 8.

The polymer product consisted mainly of poly (methyl acrylate).

Example 7: [(PPh3) 2Pd (Me) (Cl)]/ methyl acrylate/norbornene in C6HsCI (2: 1 MA/NB ratio) The procedure of Example 5 was repeated, except that 1.5 g (0.017 mol) of methyl acrylate and 0.820 g (8.7 x 10-3 mol) of norbornene were added to the reaction solution.

1.456 g of polymer product was obtained. The product had a peak average molecular weight (Mp) = 244,000 and a molecular weight distribution (M*JMn) = 2.5. The polymer product had a methyl acrylate to norbornene ratio of 1: 0. 14.

Example 8: [(PPh3)2Pd (Me) (Cl)]/ methyl acrylate/norbornene in C6H5C' (1: 1 MA/NB ratio) The procedure of Example 5 was repeated, except that 1.000 g (1.20 x 10-2 mol) of methyl acrylate and 1.130 g (1.20 x 10-2 mol) of norbornene were added to the reaction solution. 0.400 g of polymer product was obtained. The product had a peak average molecular weight (Mp = 100,000 and a molecular weight distribution (MNV/Mn) = 2.6. The polymer product had a methyl acrylate to norbornene ratio of 1: 0. 27.

Example 9: [(PPh3) 2Pd (Me) (Cl)]/ methyl acrylate/norbornene in C6H5C' (1: 2 MA/NB ratio) The procedure of Example 5 was repeated, except that 1.5 g (0.016 mol) of methyl acrylate and 0.686 g (7.98 x10-3 mol) of norbornene were added to the reaction solution.

0.314 g of polymer product was obtained. The product had a peak average molecular weight (Mp) = 41,000 and a molecular weight distribution (MNV/Mn) = 2.2. The polymer product had a methyl acrylate to norbornene ratio of 1: 0. 49.

Example 10: [(PPh3) 2Pd (Me) (Cl)]/ methyl acrylate/norbornene in C6HsCI (1: 5 MA/NB ratio) The procedure was the same as Example 5 except that 0.329 g (3.83 x 10-3 mol) of methyl acrylate and 1.800 g (0.019 mol) of norbornene were added to the reaction solution. 0.102 g polymer product was obtained. The product had a peak average molecular weight (Mp) = 17,000 and a molecular weight distribution (M,/Mn) = 1.6. The polymer product had a methyl acrylate to norbornene ratio of 1: 0. 54.

Example 11: [(PPh3) 2Pd (Me) (Cl)]/ methyl acrylate/norbornene in C6HsCl (1: 10 MA/NB ratio) The procedure of Example 5 was repeated, except that 0.174 g (9.57 x 10-4 mol) of methyl acrylate and 1.900 g (0.020 mol) of norbornene were added to the reaction solution. 0.070 g polymer product was obtained. The product had a peak average molecular weight (Mp) = 12,000, and a molecular weight distribution (M,/Mn) = 1.5. The polymer product had a methyl acrylate to norbornene ratio of 1 : 1. 55.

Example 12: [(PCy3) 2Pd (Me) (Cl)]/methyl acrylate/norbornene in C6H, Cl (10 : 1 MA/NB ratio) In a glove box, under an inert atmosphere (nitrogen), (PCy3) (Me) (CI) (0.050 g, 6.97 x 10-5 mol) was placed into a 25 mL round bottom flask. To this was added 1 approximately 5 mL C6H5Cl, and the mixture was gently swirled to form a suspension.

Next, 2 g (2.3 x 10-2 mol) of methyl acrylate and 0.219 g (2.3 x 10-3 mol) of norbornene were dissolved in each other in a beaker, and the resulting solution was added to the flask.

The flask was sealed with a rubber septum and stirred at 60° C for 24 hours. Polymer product (1.052 g) was obtained by precipitating in methanol, then decanting off liquid and drying under reduced pressure at room temperature. The product had a number average molecular weight (Mn) = 243,000. The polymer product had a methyl acrylate to norbornene ratio of 1: 0. 09.

Example 13: [(PCy3) 2Pd (Me) (Cl)]/methyl acrylate/norbornene in C6H5C' (5 : 1 MA/NB ratio) The procedure of Example 12 was repeated, except that 1.8 g (0.021 mol) of methyl acrylate and 0.394 g (4.19 x 10-3 mol) of norbornene were added to the reaction solution. 0.540 g of polymer product was obtained. The product had a peak average molecular weight (Mp) = 407,000 and a molecular weight distribution (MN~/Mn) = 4.3. The polymer product had a methyl acrylate to norbornene ratio of 1: 0. 11.

Example 14: [(PCy3) 2Pd (Me) (Cl)]/methyl acrylate/norbornene in C6H5C' (1: 1 MA/NB ratio) The procedure of Example 12 was repeated, except that 1.00 g (1.2 x 10-2 mol) of methyl acrylate and 1.140 g (1.2 x 10-2 mol) of norbornene were added to the reaction solution. 0.382 g polymer product was obtained. The product had a peak average molecular weight (Mp) = 119,000 and a molecular weight distribution (M,/Mn) = 4.8. The polymer product had a methyl acrylate to norbornene ratio of 1: 0. 34.

Example 15: [ (P (o-methoxy phenyl) 3) 2Pd (Me) (Cl)]/methyl acrylate/norbornene in C6H5CI (10 : 1 MA/NB ratio) In a glove box, under an inert atmosphere (nitrogen), [ (P (o-methoxy phenyl) 3) 2Pd (Me) (Cl)] (0.050 g, 5.80 x 10-5 mol) was placed into a 25 mL round bottom

flask. To this was added 1 approximately 5 mL C6H5C1, and the mixture was gently swirled to form a suspension. Next, 2 g (2.3 x 10-3 mol) of methyl acrylate and 0.219 g (2.3 x 10-3 mol) of norbornene were dissolved in each other in a beaker, and the resulting solution was added to the flask. The flask was sealed with a rubber septum and stirred at 60° C for 24 hours. Polymer product was obtained by precipitating in methanol, then decanting off liquid and drying under reduced pressure at room temperature. 1.026 g polymer was obtained. The product had a number average molecular weight (Mn) = 289,000 and a molecular weight distribution (MNV/MD) = 4.3. The polymer product consisted mainly of poly (methyl acrylate).

Example 16: [ (P (o-methoxy phenyl) 3) 2Pd (Me) (Cl)]/methyl acrylate/norbornene in C6HsC1 (5: 1 MA/NB ratio) The procedure was the same as Example 15, except that 1.8 g (0.021 mol) of methyl acrylate and 0.394 g (4.19 x 10-3 mol) of norbornene were added to the reaction solution. 1.397 g of product was collected. The product had a number average molecular weight (Mn) = 348,000 and a molecular weight distribution (M,/Mn) = 4.2. The polymer product consisted mainly of poly (methyl acrylate).

Example 17: [ (P (o-methoxy phenyl) 3) 2Pd (Me) (Cl)]/methyl acrylate/norbornene in C6H5C' (1: 1 MA/NB ratio) The procedure was the same as Example 15, except that 1.00 g (1.2 x 10-2 mol) of methyl acrylate and 1.140 g (1.2 x 10-2 mol) of norbornene were added to the reaction solution. 0.530g of product was collected. The product had a number average molecular weight (Mn) = 157,000 and a molecular weight distribution (Mw/Mn) = 2.2. The polymer product had a methyl acrylate to norbornene ratio of 1: 0. 23.

Example 18: [ (P (o-methoxy phenyl) 3) 2Pd (Me) (Cl)]/methyl acrylate/norbornene in C6H^C 1 (1: 5 MA/NB ratio) The procedure was the same as Example 15, except that 0.329 g (3.83 x 10-3 mol) of methyl acrylate and 1.800 g (0.019 mol) of norbornene were added to the reaction solution. 0.441 g of product was collected. The product had a number average molecular weight (Mn) = 18,000 and a molecular weight distribution (Mw/Mn) = 1.8. The product had a methyl acrylate to norbornene ratio of 1: 0. 57.

Example 19: [ (P (o-methoxy phenyl) 3) 2Pd (Me) (Cl)]/methyl acrylate/norbornene in C6HsCI (1: 10 MA/NB ratio) The procedure was the same as Example 15, except that 0.174 g (9.57 x 10-4 mol) of methyl acrylate and 1.900 g (0.020 mol) of norbornene were added to the reaction solution. 0.243 g of product was collected. The product had a number average molecular weight (Mn) = 12,000 and a molecular weight distribution (M"lMn) = 1.6. The product had a methyl acrylate to norbornene ratio of 1: 0. 71.

Example 20: [(bis (diphenylphosphino) benzene) Pd (Me) (Cl)]/methyl acrylate/norbornene in C6H5CI (10 : 1 MA/NB ratio) In a glove box, under an inert atmosphere (nitrogen), [ (bis (diphenylphosphino) benzene) Pd (Me) (Cl)] (0.050 g, 8.28 x 10-5 mol) was placed into a 25 mL round bottom flask. To this was added 1 approximately 5 mL C6H5CI, and the mixture was gently swirled to form a suspension. Next, 2 g (2.3 x 10-3 mol) of methyl acrylate and 0.219 g (2.3 x 10-3 mol) of norbornene were dissolved in each other in a beaker, and the resulting solution was added to the flask. The flask was sealed with a rubber septum and stirred at 60° C for 24 hours. Polymer product (1.635 g) was obtained by precipitating in methanol, then decanting off liquid and drying under reduced pressure at room temperature. The product had a number average molecular weight (Mn) = 270,000. The product consisted mainly of poly (methyl acrylate).

Example 21: [(bis (diphenylphosphino) benzene) Pd (Me) (Cl)]/methyl acrylate/norbornene in C6HsCI (5: 1 MA/NB ratio) The procedure of Example 20 was followed, except that 1.8 g (0.021 mol) of methyl acrylate and 0.394 g (4.19 x 10-3 mol) of norbornene were added to the reaction solution. 0.570 g of product was collected. The product had a number average molecular weight (Mn) = 260,000 and a molecular weight distribution (M,/Mn) = 4.3. The product consisted mainly of poly (methyl acrylate).

Example 22: [(bis (diphenylphosphino) benzene) Pd (Me) (Cl)]/methyl acrylate/norbornene in C6HsCI (1: 1 MA/NB ratio) The procedure was the same as Example 20, except that 1.00 g (1.2 x 10-2 mol) of methyl acrylate and 1.140 g (1.2 x 10-2 mol) of norbornene were added to the reaction

solution. 0.434 g of product was collected. The product had a number average molecular weight (Mn) = 178,000 and a molecular weight distribution (M/Mn) = 3. 9.

The product had a methyl acrylate to norbornene ratio of 1: 0. 20.

Example 23: [ (P (o-methoxy phenyl) 3) 2Pd (Me) (Cl)]/methyl acrylate/norbornene in C6HsCI (1 : 5 MA/NB ratio) The procedure was the same as Example 20, except that 0.329 g (3.83 x 10-3 mol) of methyl acrylate and 1.800 g (0.019 mol) of norbornene were added to the reaction solution. 0.051 g of product was collected. The product had a number average molecular weight (Mn) = 28,000 and a molecular weight distribution (Mw/Mn) = 1.7. The product had a methyl acrylate to norbornene ratio of 1: 0.74. The results of Examples 1- 11 are summarized in Table 1 under designation (A) (I), the results of Examples 12-14 are summarized in Table 2 under designation (A) (II), the results of Examples 15-19 are summarized in Table 3 under the designation (A) (III), and the results of Examples 20-23 are summarized in the Table 4 under the designation (B) (I).

Table 1: Catalytic System Results for Examples 1-11 A. L2PdMeCl System I. (PPh3) 2PdMeCl reactions Ex. No. Yieldb Molecular Polydispersity Compositiond 1H NMR Monomer WeightC (MJMn) integratione FeedRatioa Ex. 1 0. 081 g Mp=997, 000 2.9 poly (NB)--- Norbornene Ex. 2 0. 419 g not available not available poly (t-BA) 10 t-BA: 1 NB Ex. 3 0. 470 g Mp= not poly (BA) --- 10 BA: 209,000 available 1 NB Ex. 4 0. 535 g Mp= 3.0 poly (MMA)--- 10 MMA: 295, 000 1 NB Ex. 5 0. 784 g Mp= 8.7 poly (MA) 10 MA: 160, 000 1 NB Ex.6#1.8g Mp = 2.8 poly(MA) --- 5 MA : 1 NB 289, 000

Ex. 7 1. 456 g MP 4.5 copolymer 1: 0. 14 2 MA : 1 NB 244, 000 Ex. 8 0. 400 g Mp= 2.6 copolymer 1: 0. 27 1 MA : 1 NB 100, 000 Ex. 9 0. 314 g Mp=41, 000 2.2 copolymer 1: 0. 49 1 MA: 2 NB Ex. 10 0. 102 g Mp=17,000 1.6 copolymer 1: 0. 54 1 MA: 5 NB EX. 11 0. 070 g Mp=12, 000 1.5 copolymer 1: 1. 55 1 MA:10 NB a. MA= methyl acrylate, NB= norbornene, t-BA= t-butyl acrylate, MMA= methyl Methacrylate, BA= butyl acrylate b. Out of approximately 2 grams total monomer feed c. In CHCl3, calibrated to poly (styrene) standards d. Determined by'H NMR and GPC e. Ratio of methyl acrylate to norbornene Table 2: Catalytic System Results for Examples 12-14 A. L2PdMeCl System II. (PCy3) 2PdMeCl Reactions Ex. No. Yieldb Molecular Polydispersity Compositiond H NMR Monomer WeightC (MW/Mn) Integratione FeedRatioa Ex. 12 1. 052g Mp= not available Copolymer 1: 0. 09 10 MA: 1 243, 000 NB Ex. 13 0. 540g Mp= 4.3 Copolymer 1: 0. 11 5 MA : 1 407, 000 NB Ex. 14 0. 382g Mp= 4.8 Copolymer 1: 0. 34 1 MA : 1 119, 000 NB a. MA=methyl acrylate, NB=norbornene b. Out of approximately 2 grams total monomer feed c. In CHCl3, calibrated to poly (styrene) standards d. Determined by'H NMR and GPC e. Ratio of methyl acrylate to norbornene

Table 3: Catalytic System Results for Examples 15-19 A. L2PdMeCl System III. [(P(o-methoxy phenyl)3)2PdMeCl] Reactions Ex. No. Yieldb Molecular Polydispersity Composition 1H NMR Monomer'Weight (M) Integratione Ex. 15 1. 026 g Mp= 289, 000 4.3 poly(MA) --- 10 MA: 1 NB Ex. 16 1.397 g Mp= 348, 000 4. 2 poly (MA)--- 5 MA: 1 NB Ex. 17 0.530 g Mp= 157,000 2.2 Copolymer 1: 0. 23 1 MA : 1 NB Ex. 18 0.441 g Mp= 18,000 1.8 Copolymer 1: 0. 57 1 MA : 5 NB Ex. 19 0.243 g Mp= 12,000 1.6 Copolymer 1: 0. 71 1 MA : 10 NB a. MA=methyl acrylate, NB=norbornene b. Out of approximately 2 grams total monomer feed c. In CHCl3, calibrated to poly (styrene) standards d. Determined by'H NMR and GPC e. Ratio of methyl acrylate to norbornene Table 4: Catalytic System Results for Examples 20-23 B. LPdMeCl System Results I. (dppb) PdMeClf Reactions Ex. No. Yieldb Molecular Polydispersity Compositiond 1H NMR Monomer Weightc (Mw/Mn) Integratione FeedRatio' Ex. 20 1. 635 g Mp= 270, 000 17 poly (ma) 10 MA: 1 NB Ex. 21 0.570 g Mp= 260,000 4.3 poly (ma) 5 MA : 1 NB Ex. 22 0.434 g Mp= 178, 000 3.9 Copolymer 1 : 0. 20 1 MA: 1 NB Ex. 23 0.051 g Mp= 28,000 1.7 copolymer 1: 0. 74 1 MA : 5 NB

a. MA=methyl acrylate, NB=norbornene b. Out of approximately 2 grams total monomer feed c. In CHCtj, calibrated to poly (styrene) standards d. Determined by'H NMR and GPC e. Ratio of methyl acrylate to norbornene f. dppb= bis (diphenylphosphino) benzene While the present invention has been described and exemplified above, it is to be understood that the invention is not limited to the details of the illustrative embodiments and examples, and that it may be embodied with various changes and modifications which may occur to those skilled in the art, without departing from the invention defined in the following claims.