Catalyst composition and process for preparing norbornene-type homopolymers or copolymers

A catalyst composition and process for preparing norbornene-type homopolymers or copolymers. The norbornene-type homopolymers or copolymers can be prepared using an in-situ catalyst composition including: (a) a transition metal compound of ML4, wherein M is a Group 10 metal and L is a neutral electron donor ligand; (b) a hydrocarbyl halogen containing a double bond or a triple bond; and (c) a salt of a non or weakly coordinative anion that can replace a halogen bonded to a metal. The catalyst composition is in a mixing state of components (a), (b), and (c), or in a mixing state of a reaction product of components (a) and (b) together with component (c).

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a catalyst composition for preparing norborene-type homopolymers or copolymers, and more particularly to a process for preparing norborene-type homopolymers or copolymers using an in-situ catalyst composition.

2. Background of the Invention

Polynorbornenes have high temperature resistance and high transparency. In addition, polynorbornenes with particular functional groups are valuable in optoelectronic products. Therefore, it is very important to develop a catalyst suitable for preparing norbornene-type homopolymers and copolymers.

Many researchers have used various metal catalysts to synthesize norbornene-type polymers. For example, Goodall et al. in U.S. Pat. No. 5,468,819 use allyl-Ni COD (weakly coordinating anion), wherein COD cyclooctadiene. Lipian et al. in WO 00/20472 use (R ) z M(L ) x (L ) y b WCA d , wherein (R ) z M(L ) x (L ) y is a cation complex where M represents a Group 10 transition metal; R represents an anionic hydrocarbyl containing ligand; L represents a Group 15 neutral electron donor ligand; L represents a labile neutral electron donor ligand; x is 1 or 2; y is 0, 1, 2, or 3; and z is 0 or 1, wherein the sum of x, y, and z is 4; and WCA represents a weakly coordinating counteranion complex; and b and d are numbers representing the number of times the cation complex and weakly coordinating counteranion complex are taken to balance the electronic charge on the overall catalyst complex. A representative example is (allyl)palladium(tricyclohexylphosphine)triflate. Sen et al. in WO 01/21670 use (L) 2 Pd(R)(X) and L Pd(R)(X), wherein L is a monodentate phosphorus or nitrogen ligand, L is a bidentate phosphorus or nitrogen ligand, X is an anionic group, and R is an alkyl or aryl group. A representative example is (PPh 3 ) 2 Pd(CH 3 )(Br).

However, the catalysts used in the above patents are a reaction product of different components. Procedures for isolating the catalyst are required, causing inconvenience.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a catalyst composition for preparing norbornene-type homopolymers or copolymers. The catalyst composition is in a mixing state of each component, rather than an isolated state of the reaction product of each different components.

Another object of the present invention is to provide a process for preparing norbornene-type homopolymers or copolymers. Norbornene-type polymers can be directly synthesized using the above-mentioned catalyst in situ. Since the catalyst composition needs not be isolated and can be directly used in situ, the procedures are simple and costs are saved.

Another object of the present invention is to provide a catalyst product for preparing norbornene-type homopolymers or copolymers. The present invention also provides a process for preparing norbornene-type homopolymers or copolymers using the catalyst product.

To achieve the above-mentioned objects, according to a first aspect of the present invention, the first kind of catalyst composition includes the following components: (a) a transition metal compound of ML 4 , wherein M is a Group 10 metal and L is a neutral electron donor ligand; (b) a hydrocarbyl halogen containing a double bond or a triple bond; and (c) a salt of a non or weakly coordinative anion that can replace a halogen bonded to a metal. The catalyst composition is in a mixing state of components (a), (b), and (c), or in a mixing state of a reaction product of components (a) and (b) together with component (c).

According to a second aspect of the present invention, the second kind of catalyst composition includes the following components: (a) a transition metal compound of ML 4 , wherein M is a Group 10 metal and L is a neutral electron donor ligand; and (c) a salt of a non or weakly coordinative anion that can replace a halogen bonded to a metal; and optionally (e) a solvent containing a halogen atom. The catalyst composition is in a mixing state of components (a) and (c), or in a mixing state of components (a), (c), and (e).

The two above-mentioned kinds of catalyst compositions can be used to prepare norbornene-type homopolymers or copolymers in situ.

According to a third aspect of the present invention, the catalyst product is a reaction product of the following components: (a) a transition metal compound of ML 4 , wherein M is a Group 10 metal and L is a neutral electron donor ligand; (b) a hydrocarbyl halogen containing a triple bond; (c) a salt of a non or weakly coordinative anion that can replace a halogen bonded to a metal; and (d) a proton source provider that can react with an eta-3-propargyl group.

DETAILED DESCRIPTION OF THE INVENTION

The present invention develops two kinds of catalyst compositions and one kind of catalyst product, all of which are suitable for preparing norbornene-type homopolymers or copolymers.

The first kind of catalyst composition of the present invention includes the following components: (a) a transition metal compound of ML 4 , wherein M is a Group 10 metal and L is a neutral electron donor ligand; (b) a hydrocarbyl halogen containing a double bond or a triple bond; and (c) a salt of a non or weakly coordinative anion that can replace a halogen bonded to a metal. The catalyst composition is in a mixing state of components (a), (b), and (c), or in a mixing state of a reaction product of components (a) and (b) together with component (c).

The first catalyst composition of the present invention can be used to prepare norbornene-type homopolymers or copolymers in situ. At least one norbornene-type monomer is polymerized in the presence of the catalyst composition. The catalyst composition amount can be 0.02 to 0.2 mole % based on the total monomers amount. The so-called in situ indicates that the first catalyst composition of the present invention needs not be purified or isolated in advance, and can be directly used in a mixing state of each component to polymerize the monomer. The so-called mixing state can be a mixing state of components (a), (b), and (c). Or, alternatively, components (a) and (b) can be first reacted, and then the reaction product of components (a) and (b) is mixed with component (c).

According to the present invention, the salt of a non or weakly coordinative anion that can replace a halogen bonded to a metal can be a salt of an alkaline metal (such as lithium) or a salt of silver, preferably a salt of silver. The non or weakly coordinative anion can be BF 4 , PF 6 , CF 3 SO 3 , SbF 6 , B(C 6 F 5 ) 4 , B C 6 H 3 (CF 3 ) 2 4 , NO 3 , and CH 3 COO . Representative examples of the salt include AgBF 4 , AgSbF 6 , LiB(C 6 F 5 ) 4 , silver nitrate, and silver acetate.

According to the present invention, the hydrocarbyl halogen containing a double bond or a triple bond can be reacted with the transition metal compound ML 4 . When the hydrocarbyl halogen contains a double bond, representative examples include CH 3 CH CHCH 2 Cl, CH 2 CCH 3 CH 2 Cl, CH 2 CHCHCH 3 Cl, CH 2 CHCH 2 Cl, preferably CH 3 CH CHCH 2 Cl. When the hydrocarbyl halogen contains a triple bond, representative examples include HCCCH 2 Br(propargyl bromide) and H 3 CCCCH 2 Br(1-bromo-2-butyne).

As to the first catalyst composition of the present invention, when the hydrocarbyl halogen contains a triple bond, the first catalyst composition can further include component (d) a proton source provider that can react with an eta-3-propargyl group. The proton source provider is a nucleophilic group or compound that has a proton/hydride active group. The proton source provider can be an amine and representative examples include H 2 NCH 2 CH 2 NH 2 and HN(C 2 H 5 ) 2 , preferably H 2 NCH 2 CH 2 NH 2 .

The second catalyst composition of the present invention includes the following components: (a) a transition metal compound of ML 4 , wherein M is a Group 10 metal and L is a neutral electron donor ligand; (c) a salt containing a non or weakly coordinative anion that can replace a halogen bonded to a metal; and optionally (e) a solvent containing a halogen atom. The catalyst composition is in a mixing state of components (a) and (c), or in a mixing state of components (a), (c), and (e).

The solvent containing a halogen atom can be CH 2 Cl 2 , C 6 H 5 Cl, and CHCl 3 .

The second catalyst composition of the present invention can also be used to prepare norbornene-type homopolymers or copolymers in situ. At least one norbornene-type monomer is polymerized in the presence of the catalyst composition. The catalyst composition amount can be 0.02 to 0.2 mole % based on the total monomer amount. The so-called in situ indicates that the second catalyst composition of the present invention needs not be purified or isolated in advance, and can be directly used in a mixing state of components (a) and (c), or in a mixing state of components (a), (c), and (e) to polymerize the monomer.

The above-mentioned first or second catalyst composition of the present invention can further include a scavenger in order to remove residual donor ligands from transition metal compound ML 4 ), thus increasing catalytic activity. Representative examples of the donor scavenger include B(C 6 H 5 ) 3 , Ni(COD) 2 , and CuCl.

The catalyst product of the present invention is a reaction product of the following components: (a) a transition metal compound of ML 4 , wherein M is a Group 10 metal and L is a neutral electron donor ligand; (b) a hydrocarbyl halogen containing a triple bond; (c) a salt of a non or weakly coordinative anion that can replace a halogen bonded to a metal; and (d) a proton source provider that can react with an eta-3-propargyl group.

In order to make the content of the present invention more fully understood, a representative example is taken to describe the reaction of synthesizing the catalyst product of the present invention. When the transition metal compound ML 4 is Pd(PPh 3 ) 4 , the triple bond-containing hydrocarbyl halogen is H 3 CCCCH 2 Br, the salt of a non or weakly coordinative anion that can replace a halogen bonded to a metal is AgBF 4 , the proton source provider is H 2 NCH 2 CH 2 NH 2 , the synthetic reaction equation is depicted in FIG. 1 . The detailed reaction procedures are described in the following Examples 3 to 5.

The first and second catalyst compositions and the catalyst product of the present invention are suitable for use to polymerize at least one norbornene-type monomer, obtaining norbornene-type homopolymers or copolymers. The norbornene-type monomer suitable for use in the present invention is not limited and can be norbornene or norbornene derivatives. A representative example of the norbornene derivative is NB Si(OMe) 3 5-(bicycloheptenyl)trimethoxysilane .

According to the present invention, more than two kinds of norbornene-type monomers can be polymerized to obtain a norbornene-type copolymer using the first or second catalyst compositions or the catalyst product of the present invention. For example, norbornene and NB Si(OMe) 3 are polymerized to obtain a norbornene-type copolymer.

According to the present invention, a norbornene-type monomer and a monomer different from the norbornene can be polymerized using the first or second catalyst compositions or the catalyst product of the present invention. For example, a norbornene-type monomer and an acrylic monomer are polymerized. Suitable acrylic monomer can be t-butyl acrylate (t-BA), butyl methacrylate (BMA), and methyl acrylate (MA).

The following examples are intended to illustrate the process and the advantages of the present invention more fully without limiting its scope, since numerous modifications and variations will be apparent to those skilled in the art.

Preparation Of Catalyst Composition

5 g of PdCl 2 (28.2 mmol) and 37 g of PPh 3 (141 mmol) were charged in DMSO (200 ml) and heated to 140 C. for dissolution. After PdCl 2 and PPh 3 were dissolved, heating was stopped. After 15 minutes, H 2 NNH 2 .H 2 O (6 ml) was added and stirred at room temperature. The reaction mixture was quickly filtered through an oxygen-free filter. The crude product was washed with degassed ethanol and degassed ether two times respectively, filtered, and dried to collect an yellow powdery solid Pd(PPh 3 ) 4 (31 g, yield 95%)

Pd(PPh 3 ) 4 (5 g, 4.3 mmol) obtained from Example 1 was dissolved in benzene (50 ml), had propargyl bromide (0.8 g, 6.7 mmol) added, and stirred at room temperature for 30 minutes. After the reaction was complete, the reaction mixture was concentrated under reduced pressure to remove most solvent. Ether was slowly added to the reaction mixture to precipitate the product. A yellowish brown solid Pd(PPh 3 ) 2 (Br)( 1 -CHCCH 2 ) (2.8 g, Yield 87%) was obtained after filtration.

The reaction schemes of Examples 3 to 5 are shown in FIG. 1 .

Process of Preparing Norbornene-Type Homopolymers and Copolymers

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.81 g).

The same procedures as described in Example 7 were employed, except that AgBF 4 was replaced by 0.085 g (0.25 mmol) of AgSbF 6 and the solvent was changed to C 6 H 5 Cl. The product was 2.28 g.

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.009 g (0.012 mmol) of Pd(PPh 3 ) 2 (Br)( 1 -CHCCH 2 ) obtained from Example 2 was dissolved in 3 ml of C 6 H 5 Cl in a 20 ml sample vessel. 0.007 g (0.02 mmol) of AgSbF 6 was dissolved in 2 ml of C 6 H 5 Cl in a 5 ml sample vessel. The AgSbF 6 solution was added dropwise to the Pd(PPh 3 ) 2 (Br)( 1 -CHCCH 2 ) solution and stirred for 40 minutes. 0.006 g (0.022 mmol) of Ni(COD) 2 was dissolved in 2 ml of toluene and then added to the above solution. Stirring proceeded for 5 minutes.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight, the polymer was obtained (0.23 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.009 g (0.012 mmol) of Pd(PPh 3 ) 2 (Br)( 1 -CHCCH 2 ) obtained from Example 2 was dissolved in 3 ml of CH 2 Cl 2 in a 20 ml sample vessel. 0.004 g (0.021 mmol) of AgBF 4 was dissolved in 2 ml of CH 2 Cl 2 in a 5 ml sample vessel. The AgBF 4 solution was added dropwise to the Pd(PPh 3 ) 2 (Br)( 1 -CHCCH 2 ) solution and stirred for 40 minutes. 0.005 g (0.051 mmol) of CuCl was dissolved in 1 ml of CH 2 Cl 2 and then added to the above solution. Stirring proceeded for 10 minutes.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (1.06 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (1.97 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (1.27 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (1.69 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (2.56 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.037 g (0.048 mmol) of Pd(PPh 3 ) 2 (Br)( 1 -C(Me)CCH 2 ) obtained from Example 3 was dissolved in 3 ml of CH 2 Cl 2 in a 20 ml sample vessel. 0.016 g (0.082 mmol) of AgBF 4 was dissolved in 2 ml of CH 2 Cl 2 in a 5 ml sample vessel. The AgBF 4 solution was added dropwise to the Pd(PPh 3 ) 2 (Br)( 1 -C(Me)CCH 2 ) solution and stirred for 30 minutes. 0.022 g (0.08 mmol) of Ni(COD) 2 was dissolved in 5 ml of toluene and then added to the above solution. Stirring proceeded for 5 minutes.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (2.38 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.037 g (0.048 mmol) of Pd(PPh 3 ) 2 (Br)( 1 -C(Me)CCH 2 ) obtained from Example 3 was dissolved in 3 ml of CH 2 Cl 2 in a 20 ml sample vessel. 0.016 g (0.082 mmol) of AgBF 4 was dissolved in 2 ml of CH 2 Cl 2 in a 5 ml sample vessel. The AgBF 4 solution was added dropwise to the Pd(PPh 3 ) 2 (Br)( 1 -C(Me)CCH 2 ) solution and stirred for 30 minutes. 0.009 g (0.081 mmol) of CuCl was dissolved in 2 ml of CH 2 Cl 2 and then added to the above solution. Stirring proceeded for 10 minutes.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (2.19 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.009 g (0.012 mmol) of Pd(PPh 3 ) 2 (Br)( 1 -C(Me)CCH 2 ) obtained from Example 3 was dissolved in 3 ml of C 6 H 5 Cl in a 20 ml sample vessel. 0.007 g (0.02 mmol) of AgSbF 6 was dissolved in 2 ml of C 6 H 5 Cl in a 5 ml sample vessel. The AgSbF 6 solution was added dropwise to the Pd(PPh 3 ) 2 (Br)( 1 -C(Me)CCH 2 ) solution and stirred for 40 minutes. 0.005 g (0.051 mmol) of CuCl was dissolved in 2 ml of C 6 H 5 Cl and then added to the above solution. Stirring proceeded overnight.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (1.22 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.044 g (0.038 mmol) of Pd(PPh 3 ) 4 was dissolved in 3 ml of Et 2 O. 0.015 g (0.126 mmol) of C 3 H 3 Br was dissolved in 2 ml of Et 2 O and was then added to the Pd(PPh 3 ) 4 solution. Stirring proceeded for 1.5 hours. The mixed solution was allowed to stand for 1 minute. The solid in the lower layer was collected and 3 ml of CH 2 Cl 2 was added. 0.016 g (0.082 mmol) of AgBF 4 was dissolved in 2 ml of CH 2 Cl 2 , which was then added dropwise to the above solution. Stirring was conducted for 1 minute.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (2.17 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.011 g (0.0095 mmol) of Pd(PPh 3 ) 4 was dissolved in 3 ml of Et 2 O. 0.004 g (0.033 mmol) of C 3 H 3 Br was dissolved in 2 ml of Et 2 O and was then added to the Pd(PPh 3 ) 4 solution. Stirring proceeded for 1.5 hours. The mixed solution was allowed to stand for 1 minute. The solid in the lower layer was collected and 3 ml of CH 2 Cl 2 was added. 0.004 g (0.021 mmol) of AgBF 4 was dissolved in 2 ml of CH 2 Cl 2 , which was then added dropwise to the above solution. Stirring was conducted for 1 hour. 0.005 g (0.051 mmol) of CuCl was dissolved in 2 ml of CH 2 Cl 2 , added to the above solution, and then stirred for 10 minutes.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (1.74 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.011 g (0.0095 mmol) of Pd(PPh 3 ) 4 was dissolved in 3 ml of toluene. 0.004 g (0.033 mmol) of C 3 H 3 Br was dissolved in 2 ml of toluene and was then added to the Pd(PPh 3 ) 4 solution. Stirring proceeded for 1.5 hours. 0.004 g (0.021 mmol) of AgBF 4 was dissolved in 5 ml of CH 2 Cl 2 , which was then added dropwise to the above solution. Stirring was conducted for 1 hour.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (1.32 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.011 g (0.0095 mmol) of Pd(PPh 3 ) 4 was dissolved in 3 ml of Et 2 O. 0.004 g (0.033 mmol) of C 3 H 3 Br was dissolved in 2 ml of Et 2 O and was then added to the Pd(PPh 3 ) 4 solution. Stirring proceeded for 1.5 hours. The mixed solution was allowed to stand for 1 minute. The solid in the lower layer was collected and 3 ml of CH 2 Cl 2 was added. 0.004 g (0.021 mmol) of AgBF 4 was dissolved in 2 ml of CH 2 Cl 2 , which was then added dropwise to the above solution. Stirring was conducted for 1 hour. 0.012 g (0.023 mmol) of B(C 6 F 5 ) 3 was dissolved in 1 ml of CH 2 Cl 2 , added to the above solution, and then stirred for 10 minutes.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (1.42 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.022 g (0.019 mmol) of Pd(PPh 3 ) 4 was dissolved in 3 ml of Et 2 O. 0.008 g (0.066 mmol) of C 3 H 3 Br was dissolved in 2 ml of Et 2 O and was then added to the Pd(PPh 3 ) 4 solution. Stirring proceeded for 1 hour. The mixed solution was allowed to stand for 1 minute. The solid in the lower layer was collected and 3 ml of C 6 H 5 Cl was added. 0.014 g (0.041 mmol) of AgSbF 6 was dissolved in 2 ml of C 6 H 5 Cl, which was then added dropwise to the above solution. Stirring was conducted for 3 hours.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (1.28 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.011 g (0.0095 mmol) of Pd(PPh 3 ) 4 was dissolved in 3 ml of Et 2 O. 0.002 g (0.022 mmol) of C 4 H 7 Cl was dissolved in 2 ml of Et 2 O and was then added to the Pd(PPh 3 ) 4 solution. Stirring proceeded for 1.5 hours. The mixed solution was allowed to stand for 1 minute. The solid in the lower layer was collected and 3 ml of CH 2 Cl 2 was added. 0.004 g (0.021 mmol) of AgBF 4 was dissolved in 2 ml of CH 2 Cl 2 , which was then added dropwise to the above solution. Stirring was conducted for 1 hour.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.37 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.24 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.21 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (1.72 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.41 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.83 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe and the reaction proceeded at 50 C. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (1.52 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe and the reaction proceeded at 50 C. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (1.86 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe and the reaction proceeded. After 1 hour of reaction, 0.012 g (0.023 mmol) of B(C 6 F 5 ) 3 was dissolved in 2 ml of CH 2 Cl 2 and then injected into the above reaction solution for further reaction. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.31 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe and the reaction proceeded. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.26 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe and the reaction proceeded. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.018 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.21 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (1.76 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.49 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.011 g (0.0095 mmol) of Pd(PPh 3 ) 4 was dissolved in 3 ml of C 6 H 5 Cl. 0.005 g (0.026 mmol) of AgBF 4 was dissolved in 2 ml of C 6 H 5 Cl, added dropwise to the above solution, and stirred for 30 minutes.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (1.12 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.011 g (0.0095 mmol) of Pd(PPh 3 ) 4 was dissolved in 3 ml of toluene. 0.005 g (0.026 mmol) of AgBF 4 was dissolved in 2 ml of toluene, added dropwise to the above solution, and stirred for 30 minutes.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.18 g).

Step 1 (Monomer): 20 ml of purified toluene (20 ml) and 4 ml of norbornene (85 wt %) were charged in a 50 ml reactor.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe and the reaction proceeded at 60 C. After the reaction was complete, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (1.58 g).

Copolymerization of Norbornene

Copolymerization of NB and MA

Step 1 (Monomer): 1 ml of purified norbornene (85 wt %) and 4 ml of MA (methyl acrylate) were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.011 g (0.0095 mmol) of catalyst obtained from Example 1 was dissolved in 3 ml of Et 2 O. 0.004 g (0.033 mmol) of C 3 H 3 Br was dissolved in 2 ml of Et 2 O, added dropwise to the above solution, and stirred for 1 hour. The mixed solution was allowed to stand for 1 minute. The solid in the lower layer was collected and 3 ml of C 6 H 5 Cl was added. 0.007 g (0.02 mmol) of AgSbF 6 was dissolved in 2 ml of C 6 H 5 Cl, added dropwise to the above solution, and stirred for 30 minutes.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe and the reaction proceeded at 50 C. After 1 hour of reaction, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.421 g).

Copolymerization of NB and BMA

Step 1 (Monomer): 1 ml of purified norbornene (85 wt %) and 4 ml of BMA (butyl methacrylate) were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.011 g (0.0095 mmol) of catalyst obtained from Example 1 was dissolved in 3 ml of Et 2 O. 0.004 g (0.033 mmol) of C 3 H 3 Br was dissolved in 2 ml of Et 2 O, added dropwise to the above solution, and stirred for 1 hour. The mixed solution was allowed to stand for 1 minute. The solid in the lower layer was collected and 3 ml of C 6 H 5 Cl was added. 0.007 g (0.02 mmol) of AgSbF 6 was dissolved in 2 ml of C 6 H 5 Cl, added dropwise to the above solution, and stirred for 30 minutes.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe and the reaction proceeded at 50 C. After 1 hour of reaction, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.587 g).

Copolymerization of NB and t-BA

Step 2 (Catalyst): 0.011 g (0.0095 mmol) of catalyst obtained from Example 1 was dissolved in 3 ml of Et 2 O. 0.004 g (0.033 mmol) of C 3 H 3 Br was dissolved in 2 ml of Et 2 O, added dropwise to the above solution, and stirred for 1 hour. The mixed solution was allowed to stand for 1 minute. The solid in the lower layer was collected and 3 ml of C 6 H 5 Cl was added. 0.007 g (0.02 mmol) of AgSbF 6 was dissolved in 2 ml of C 6 H 5 Cl, added dropwise to the above solution, and stirred for 30 minutes.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe and the reaction proceeded at 50 C. After 24 hours of reaction, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.248 g).

Copolymerization of NB and t-BA

Step 2 (Catalyst): 0.011 g (0.0095 mmol) of catalyst obtained from Example 1 was dissolved in 3 ml of Et 2 O. 0.004 g (0.033 mmol) of C 3 H 3 Br was dissolved in 2 ml of Et 2 O, added dropwise to the above solution, and stirred for 1 hour. The mixed solution was allowed to stand for 1 minute. The solid in the lower layer was collected and 3 ml of C 6 H 5 Cl was added. 0.004 g (0.021 mmol) of AgBF 4 was dissolved in 2 ml of C 6 H 5 Cl, added dropwise to the above solution, and stirred for 30 minutes.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe and the reaction proceeded at 50 C. After 1 hour of reaction, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.434 g).

Copolymerization of NB and NB Si(OMe) 3

Step 1 (Monomer): 1 ml of purified norbornene (85 wt %) and 1 ml of NB Si(OMe) 3 were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.011 g (0.0095 mmol) of Pd(PPh 3 ) 4 was dissolved in 3 ml of Et 2 O. 0.004 g (0.033 mmol) of C 3 H 3 Br was dissolved in 2 ml of Et 2 O, added dropwise to the above solution, and stirred for 1 hour. The mixed solution was allowed to stand for 1 minute. The solid in the lower layer was collected and 3 ml of C 6 H 5 Cl was added. 0.007 g (0.02 mmol) of AgSbF 6 was dissolved in 2 ml of C 6 H 5 Cl, added dropwise to the above solution, and stirred for 30 minutes.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After 2 hours of reaction, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (2.81 g).

Step 1 (Monomer): 1 ml of purified norbornene (85 wt %) and 1 ml of NB Si(OMe) 3 were charged in a 50 ml reactor.

Step 2 (Catalyst): 0.011 g (0.0095 mmol) of Pd(PPh 3 ) 4 was dissolved in 3 ml of Et 2 O. 0.004 g (0.033 mmol) of C 3 H 3 Br was dissolved in 2 ml of Et 2 O, added dropwise to the above solution, and stirred for 1 hour. The mixed solution was allowed to stand for 1 minute. The solid in the lower layer was collected and 3 ml of C 6 H 5 Cl was added. 0.005 g (0.026 mmol) of AgBF 4 was dissolved in 2 ml of C 6 HsCl, added dropwise to the above solution, and stirred for 30 minutes.

Step 3: The catalyst solution obtained from step 2 was injected into the monomer solution with a syringe. After 2 hours of reaction, methanol was added to the reaction mixture to precipitate the product. After filtration and drying overnight in an oven, the polymer was obtained (0.29 g).