KR20040009614A - Reaction injection molding of polycycloolefins using zwitterionic catalysts - Google Patents

Abstract

PURPOSE: A method for reaction injection molding a polycyclic olefin is provided, to allow a catalyst to be dissolved in a polycyclic olefin monomer easily and to suppress the steric hindrance problem of a polycyclic olefin monomer by using a zwitterion compound as a catalyst. CONSTITUTION: The method comprises the steps of polymerizing a reactant (A) comprising a polycyclic olefin monomer and a zwitterion transition metal compound precursor and a reactant (B) comprising a polycyclic olefin monomer and a Lewis acid; and injection molding the obtained polymer. Preferably the zwitterion transition metal compound precursor is represented by the formula 1, 2, 3, 4 or 5, wherein X is a substituted or unsubstituted p-allyl group or a substituted or unsubstituted p-benzyl group; Y is N or P; Z is CH2 or O; M is Ni, Pd or Pt; Rs are H or a substituted or unsubstituted hydrocarbyl group and are identical or different one another; L is a neutral monovalent ligand capable of substituted by olefins; L' is an anionic monovalent ligand; and L and L' can be linked to form an anionic divalent ligand.

Description

Reaction injection molding of polycycloolefins using zwitterionic catalysts

The present invention relates to a reaction injection molding method for a multicyclic olefin using a zwitterion compound catalyst, and more particularly, a reactant (A) containing a multicyclic olefin monomer and a zwitterion transition metal compound precursor, and a multicyclic olefin. By mixing together the reactant (B) containing the monomer and the Lewis acid in one mold, the zwitterion catalyst used is easily dissolved in the polycyclic olefin monomer, while the anions of the catalyst used in the past revolve around the catalyst. The problem of steric hindrance, which hindered the access of the polycyclic olefin monomer, can be effectively suppressed, and a zwitterionic compound catalyst can be prepared by producing a zwitterion catalyst and simultaneously initiating polymerization to produce a polymer having a certain form. The present invention relates to a reaction injection molding method of a polycyclic olefin.

Recently, single-site homogeneous catalyst development has been actively conducted in academia and industry [G. J. P. Britovsek, V. C. Gibson, D. F. Wass, Angew. Chem., Int. Ed. Eng. 38 (1999) 429. The structural features of almost all single site catalysts, including metallocene catalysts already commercially available, consist of ion pairs of cations and anions. Indeed, where the polymerization takes place is cationic central metal, which is cationic due to its electrophilicity, increasing the bond of ethylene. In order to exhibit high polymerization activity, the anion should not be coordinated with the cationic core metal. As the anionic activity catalyst, bulky compounds such as methylaluminoxane (MAO) or tris (pentafluorophenyl) boron are mainly used. When anions derived from these compounds are used, they are not coordinating with the central metal and thus have high activity. You can get it.

However, catalysts in which cations and anions exist as ion pairs can inhibit the polymerization process by preventing the anion from circulating the central metal and the monomers from accessing the central metal. This interference will be more severe, especially for monomers with high steric hindrance, such as polycyclic olefins.

In order to overcome this problem, attempts have been made to use a zwitterion catalyst having both a cation and an anion in a molecule, and the representative zwitterion metal compound catalysts developed to date are as follows.

The compound A is a catalyst developed by Bazan et al. In the initial stage, and only a reaction of producing 1-butene by the dimerization reaction of ethylene has been reported [Z. J. A. Komon, X. Bu, G. C. Bazan, J. Am. Chem. Soc., 2000, 122, 1830; Z. J. A. Komon, X. Bu, G. C. Bazan, J. Am. Chem. Soc., 2000, 122, 12379]. Subsequently, a catalyst has been developed which can be represented as compound B which is a zwitterion nickel compound and can polymerize ethylene to produce polyethylene [B. Y.Lee, G. C. Bazan, J. Vela, Z.J. A. Komon, X. Bu, J. Am. Chem. Soc., 2001, 123, 5352; B. Y. Lee, X. Bu, G. C. Bazan, Organometallics, 2001, 20, 5425]. Compounds C and D can likewise be made from polyethylene from ethylene [Y. H. Kim, TH Kim, BY Lee, D. Woodmansee, X. Bu, GC Bazan, Organometallics, 2001, 21, ASAP], although a patent has been filed which may include Compound C [WO 01/92348]. It is limited to manufacturing polar copolymers.

In recent years, ring-opening metathesis (hereinafter referred to as 'DCPD') using more than 99% of ultra high-purity dicyclopentadiene, which is one of precision polymer design techniques, has been developed due to the development of metathesis catalyst. 'ROMP' enables the technology of reaction injection molding (RIM). Products based on one-step RIM technology by ROMPD catalysis of DCPD have been used for various purposes such as automobile parts, construction materials, electronic parts, etc., since they have superior heat resistance and impact resistance compared to existing products, and have recently become a major core technology. For example, U.S. Patent No. 6,204,347 to Hafner et al. Discloses that a polyDCPD of desired form can be obtained by mixing DCPD and a catalyst component with DCPD and a promoter mixture in a mixer and injecting them into the reaction frame to cause polymerization. Doing. However, the above DCP polymerization product by ROMP has the unsaturation of the starting monomer in the basic skeleton due to the reaction characteristics. On the other hand, addition polymerization has properties that are distinct from ROMP even if they are produced in the same monomer. Because of a fundamentally different mechanism from ROMP, addition polymerization does not have a double bond in the backbone.

The structural differences between the products of ROMP and addition polymerizations also make a difference in physical properties. For example, in the case of norbornene, the additive polymer has a glass transition temperature (Tg) of 350 ° C., while the ROMP polymer has a glass transition temperature of 35 ° C., and exhibits low thermal stability at high temperatures of 200 ° C. or higher due to unsaturation of the basic skeleton. .

Meanwhile, a patent for polymerizing norbornene-type monomers using a Group 10 transition metal catalyst for RIM has already been registered [US Pat. No. 6,350,832]. In the case of this patent, a complex salt catalyst composed of Group 10 compounds is used as a catalyst. It is limited.

On the other hand, much of the use of C ₅ oil as a by-product of naphtha cracking has not been developed, and many parts have not been used. However, efforts to maximize the economics of naphtha cracking have been actively made. In particular, polycyclic olefins can be readily obtained by Diels-Alder reaction from cyclopentadiene, which accounts for 20% of the C ₅ fraction. Since these compounds have a double bond can be used as a monomer raw material of the polymer product, the recent development of polymerization technology using this as a raw material has attracted great attention.

Accordingly, as a result of research efforts to solve the above problems, a reactant (A) containing a polycyclic olefin monomer and a zwitterion transition metal compound precursor, and a reactant (B) containing a polycyclic olefin monomer and Lewis acid as a single When mixed in the mold, the present invention was completed by knowing that the zwitterion used can be easily dissolved in a solution composed of a polycyclic olefin monomer and can suppress problems of steric hindrance of the monomer.

Accordingly, an object of the present invention is to provide a reaction injection molding method for a multi-cyclic olefin using a zwitterion compound catalyst which can start polymerization and simultaneously produce a zwitterion catalyst to produce a polymer having a certain form.

1 shows X-ray crystal images of compound 6 prepared according to Example 7.

Figure 2 shows an X-ray crystal photograph of compound 7 prepared according to Example 8.

The present invention is a zwitterion which is polymerized by injection of a reactant (A) comprising a polycyclic olefin monomer and a zwitterion transition metal compound precursor, and a reactant (B) comprising a polycyclic olefin monomer and a Lewis acid. A reaction injection molding method for a multi-cyclic olefin using a compound catalyst is featured.

The present invention will be described in detail as follows.

The present invention is carried out by mixing together a reactant (A) comprising a precursor of a multicyclic olefin monomer and a zwitterion transition metal compound and a reactant (B) comprising a multicyclic olefin monomer and a Lewis acid together in one mixer. The bitter ion catalyst is easily dissolved in the polycyclic olefin monomer, and at the same time, the anion of the conventional catalyst can be effectively hovered around the catalyst, thereby effectively suppressing the problem of steric hindrance that prevented the access of the polycyclic olefin monomer. The present invention relates to a reaction injection molding method for a multi-cyclic olefin using a zwitterionic compound catalyst capable of producing a polymer having a certain form by initiating polymerization simultaneously with the formation of an ion catalyst.

The present invention will be described in more detail as follows.

In the present invention, the zwitterion transition metal compound is used as a catalyst and applied to the monomer polymerization of norbornene type.

Zwitterion catalysts can be prepared by a variety of methods, generally by adding Lewis acid to a transition metal compound having a Lewis basic site in one of the ligands of the catalyst. That is, when Lewis acid binds to the Lewis base, electrons of the metal are attracted to the Lewis acid by the resonance structure of the ligand, so that the metal becomes positive and the central atom constituting the Lewis acid becomes negative. Catalysts of this type are well illustrated in Compound A and the references cited above. The transition metal that can be used in the zwitterion transition metal compound of the present invention is not particularly limited.

The zwitterion transition metal compound that can be used in the present invention may be represented by the following Chemical Formulas 1 to 5, and the Lewis acid that may be used may be represented by the following Chemical Formulas 6 to 8.

Wherein X is p-allyl, substituted p-allyl, p-benzyl or substituted p-benzyl group, Y is nitrogen or phosphorus atom, Z is CH ₂ or oxygen atom, M is nickel, palladium or platinum Is an atom, R is a hydrogen radical, hydrocarbyl or substituted hydrocarbyl and may be the same or different from each other, L is a neutral monodentate ligand which may be substituted by an olefin, L 'is a monodentate ligand of an anion and L and L' May be linked to each other to form a bidentate ligand of an anion.

R ^1- [Al (R ¹ ) -O] _a -AlR ¹ ₂ AlX ¹ _n (R ¹ ) _3-n BX ¹ _n (R ¹ ) _3-n

(6) (7) (8)

Wherein X ¹ is hydrogen, halogen, alkoxy or aryloxy, R ¹ is a hydrocarbyl substituted with a halogen radical, hydrocarbyl or halogen, a is an integer from 1 to 5 and n is an integer from 0 to 3. When _n of X ¹ _n is 2 or more, X ¹ may be the same as or different from each other, and when a is 2 or more or (R ¹ ) ₃ n is 0 or 1, R ¹ may be the same or different.

The polycyclic olefin monomers that can be used in the present invention include norbornene, norbornadiene, dicyclopentadiene and derivatives thereof, and the like based on norbornene as follows. It may include all polycyclic olefins. Formula 9 represents norbornene, formula 10 represents norbornadiene, formula 11 represents dicyclopentadiene, and formulas 12 and 13 represent substituted norbornene.

Here, the ^{R 2, R 3, R 4} , R 5 are each H, an alkyl group, a vinyl group independently, halogen, -COOH, -CN or -COOCH ₃ one, n is an integer from 1-5.

The present invention relates to a method of simultaneously molding a desired form simultaneously with polymerization of a polycyclic olefin monomer by reaction injection molding using a zwitterion as a catalyst.

More specifically, examples of the RIM using the zwitterion precursor and Lewis acid which can be used in the present invention are as follows.

In the polymerization technique of the present invention, the zwitterion transition metal compound precursor and the Lewis acid are mixed with a monomer to be polymerized in a separate container, and mixed immediately before the polymerization so that a catalyst is automatically generated, followed by addition polymerization to a mold of a certain form. Reaction Injection Molding In other words, a single or two or more polycyclic olefin monomers are mixed and injected into a mold of a certain form in a state of mixing with a catalyst to obtain a crosslinkable polymer having a form of the die by monopolymerization or copolymerization.

Referring to the polymerization method of the present invention in detail as follows. A reactant (B) prepared by dividing one or two or more polycyclic olefin monomers into two parts and mixing a Lewis acid component in one place, and a premixed catalyst of a zwitterion precursor metal compound in another place (A ), Two liquid streams are made through the mixing chamber to form a highly active zwitter ion catalyst, which initiates polymerization, and is then injected into a closed mold, whereby the liquid component polymerizes into the mold to polymerize the polymer compound. Forming at the same time as forming. In this method, fillers for resin reinforcement such as glass fibers or mica may be injected together with the reactants to modify the strength and properties of the molded article.

The temperature at which the polymerization method is carried out is about -50 to 200 캜, preferably 20 to 150 캜. At this time, if the polymerization temperature is less than -50 ℃ polymerization rate is too slow, if it exceeds 200 ℃ it is inconvenient to utilize the reaction injection molding. Although the pressure at which the polymerization is carried out is not critical, there is a problem in that the atmospheric pressure to about 50 atm is an appropriate range, and if it is below the atmospheric pressure or exceeds 50 atm, it is complicated to constitute the actual process.

In the present invention, the amount of the catalyst used for the polycyclic olefin monomer is not important, but it is appropriate to mix at a ratio of 10 to 100,000 kg of monomer per mole of catalyst, wherein the proportion of monomer used is less than 10 kg per mole of catalyst. In this case, the polymerization rate is too slow, and if it exceeds 100,000 kg, there is a problem that too much catalyst is contained in the product. The mixing ratio of the zwitterion transition metal compound precursor and the Lewis acid in the catalyst may be used in a 1: 0.1 to 10 molar ratio, and when used in a ratio of 1: 1, a preferable effect may be obtained. At this time, if the mixing ratio of the Lewis acid is less than 0.1, or more than 10, there is a problem that can not obtain the proper catalytic activity.

As described above, when using a zwitterion transition metal compound when compared to using a catalyst of the ion pair form commonly used [US Patent No. 6,350,832] has the following advantages.

First, the catalyst must be dissolved in the monomer when manufacturing the product by the RIM process. Monomers obtained from the above-mentioned cyclopentadiene are generally nonpolar and thus have limitations in dissolving the catalyst in the complex salt form. In general, the zwitterionic compound is a neutral compound when the molecule itself is viewed, so it is more soluble in nonpolar solvents than the ion-pair compound, which is more advantageous for use in the RIM process. Second, the monomers obtained from dicyclopentadiene are generally monomers with significantly higher steric hindrance. As mentioned above, catalysts composed of ion pairs can cause anions to hover around the catalyst, preventing the monomers from accessing it. However, in the case of the zwitterion catalyst used in the present invention, such interference can be eliminated.

Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited to the following examples.

Example 1

In a dry box, a mixture of 5.0 μmol of zwitterion transition metal compound precursor and 2.5 g of norbornene, which is represented by the following Chemical Formula 3a, was prepared, and in a separate container, 5.0 μmol of B (C ₆ F ₅ ) ₃ and norbornene 2.5 g of the mixture was prepared. The two mixtures prepared above were injected and mixed in one bay, and then immersed in a thermostat set to 60 ° C. in a preset temperature to 60 ° C., and then left for 10 hours to obtain a solid polymer. TGA (Thermogrametric analysis) The yield by measurement was 88.7%.

Example 2

The experiment was carried out in the same manner as in Example 1, but the polymerization was carried out for 5 hours at 80 ° C., and the yield by TGA measurement was 92.4%.

Example 3

The experiment was carried out in the same manner as in Example 1, but the polymerization was carried out for 5 hours at 90 ° C., and the yield by TGA measurement was 95.4%.

Example 4

The experiment was carried out in the same manner as in Example 1, but 10 μmol of B (C ₆ F ₅ ) ₃ was used, the polymerization was carried out for 3 hours at a reaction temperature of 90 ℃, yield by TGA measurement 95.7%.

Example 5

The experiment was carried out in the same manner as in Example 1, but 20 μmol of B (C ₆ F ₅ ) ₃ was used, the polymerization was carried out for 3 hours at a reaction temperature of 90 ℃, the yield by TGA measurement is 96.4%.

Example 6

The experiment was carried out in the same manner as in Example 1, but instead of B (C ₆ F ₅ ) ₃ , 10 μmol of Al (C ₆ F ₅ ) ₃ was used, and the polymerization was performed at 90 ° C. for 14 hours. The yield by TGA measurement was 89.1%.

Example 7:

Synthesis of Bis (h3-metall) bis {m-[(2-diphenylamino) benzoate-O: O ']} Dikeel (II): catalyst precursor (Formula 5a)

As shown in Scheme 1, according to bis (metall) nickel (II) (0.300 g, 1.82 mmol) and 2- (diphenylamino) benzoic acid (Goldberg, I. Ber. 1907, 40, 2448) Preparation, 0.474 g, 1.63 mmol) was quantified in a dry box, put in a flask, and cold toluene (20 mL, -30 ° C) was added thereto, and the mixture was stirred at room temperature for 12 hours. All volatiles were removed under reduced pressure in vacuo to give a dark yellow crystalline solid (yield 0.600 g, 92%), and the structure of this compound was determined by X-ray crystallography. Found equality.

Spectral data and crystal structure are as follows. ¹ H NMR (400 MHz, C ₆ D ₆ ): δ 7.65 (br d, J = 6 Hz, 1 H, H3 or 6), 7.12 (d, J = 7.6 Hz, 4 H, o-Ph), 7.06 to 7.00 (m, 4H, m-Ph), 6.97 to 6.70 (m, 2H, p-Ph), 6.80 (br, 1H, H3 or 6), 6.77 (tt, J = 7.2, 1.2 Hz, 2 H, H 4 and 5), 2.36 (br s, 2 H, methallyl-CH ₂ ), 2.33 (br s, 3 H, methallyl-CH ₃ ), 1.71 (br s, 2 H, methallyl-CH ₂ ) ppm. ¹³ C {1H} NMR (100 MHz, C ₆ D ₆ ): δ 178.19 (carbonyl), 148.84, 145.39, 136.66, 131.69, 131.61, 131.46, 129.44, 125.83, 123.36, 122.82, 121.83, 50.23 (methallyl-CH ₂₎ ), 23.39 (methallyl-CH ₃ ) ppm.

Example 8:

Synthesis of [(2-diphenylamino) benzoate tris (pentafluorophenyl) borate-k2N, O] (h3 -metall) nickel (II): zwitter ion catalyst (Formula 2a)

As shown in Scheme 1, Chemical Formulas 5a (0.100 g, 0.124 mmol) and B (C ₆ F ₅ ) ₃ (0.127 g, 0.248 mmol) were weighed into a flask, and toluene (10 g) was added thereto for 12 hours. Was stirred. The solvent was removed to obtain the desired solid compound quantitatively, and X-ray crystallography showed that the zwitterion compound as shown in FIG. 2 was obtained by X-ray crystallography.

Spectral data and crystal structure are as follows. ¹ H NMR (400 MHz, C ₆ D ₆ ): δ 8.69 (dd, J = 7.6, 1.6 Hz, 1 H, H3 or 6), 6.85 (t, J = 7.2 Hz, 2 H, p-Ph), 6.82 (td, J = 7.6, 1.2 Hz, 1 H, H4 or 5), 6.76 (t, J = 8.4 Hz, 4 H, m-Ph), 6.68 (ddd, J = 8.0, 7.6, 1.2 Hz, 1 H, H4 or 5), 6.66 (d, J = 7.6 Hz, 4 H, o-Ph), 6.18 (dd, J = 8.0 Hz, 1.2 Hz, 1 H, H3 or 6), 1.82 (s, 3 H , methallyl-CH ₃ ) 1.1 to 1.7 (br, 4H, methallyl-CH ₂ ) ppm. ¹³ C {1H} NMR (100 MHz, C ₆ D ₆ ): δ 172.52 (carbonyl), 148.8 (dm, 1JCF = 240 Hz, p-CF), 149.0 (br, methallyl-CCH ₃ ), 148.34, 140.0 ( dm, 1JCF = 250 Hz, o-CF), 137.5 (dm, 1JCF = 250 Hz, m-CF), 134.91, 134.11, 129.31, 129.30, 128.76, 127.65, 127.12, 126.84, 124.87, 56.73 (br, methallyl- CH ₂ ), 21.73 (methallyl-CH ₃ ) ppm. ¹⁹ F NMR (376 MHz, C ₆ D ₆ ), -77.0 (d, 3JFF = 19 Hz, ortho-F), -102.30 t, 3JFF = 20Hz, para-F), -107.76 (br t, 3JFF = 18Hz , meta-F) ppm. ¹¹ B NMR (C ₆ D ₆ , 128 MHz): δ −3.1 ppm. Anal. Calcd. for C ₄₁ H ₂₁ BF ₁₅ NNiO ₂ x C ₆ H ₆ x 1/2 (C ₅ H ₁₂ ): C, 57.8; H, 3.24. Found: C, 57.6; H, 3.10.

Scheme 1

Example 9

In a dry box, 1 mol of precursor compound 6 of a zwitterion catalyst was previously added to 2.5 g of norbornene in one portion. Furthermore, 1 mol of B (C ₆ F ₅ ) ₃ was added to 2.5 g of norbornene in another portion. After the two components were injected and mixed into one bayer, the bayer was immersed in a thermostat pre-set to a temperature of 40 ° C. and allowed to rise to that temperature, and left for 16 hours to obtain solid polymers after a given time. The yield by was 92.3%.

Example 10

The experiment was carried out in the same manner as in Example 9, but the yield was 94.8% by TGA measurement after the polymerization was carried out at a reaction temperature of 50 ℃.

Example 10

The experiment was carried out in the same manner as in Example 9, but the yield was 96.5% by TGA measurement after the polymerization was carried out at a reaction temperature of 70 ℃.

Example 11

In a dry box, the precursor formula 5a of a 5.0 μmol zwitterion catalyst was previously added to 2.5 g of a portion of dicyclopentadiene (purity 95%). Furthermore, 5.0 mol of B (C ₆ F ₅ ) ₃ was added to 2.5 g of dicyclopentadiene (purity-95%) in the other part. Inject and mix the two components into one vial, immerse the vial in a thermostat pre-set to 40 ° C, allow it to rise to that temperature and allow to stand for 24 hours, after which time a very viscous solution is obtained. It can be seen that the polymerization takes place.

Example 12

The experiment was carried out in the same manner as in Example 11, but the reaction was carried out using a dicyclopentadiene having a purity of 99% as a monomer to obtain a solid polymer, and the yield by TGA measurement was 91.2%.

As described above, when the zwitterion transition metal compound is used as in the method of the present invention, the solubility in nonpolar solvents is superior to that of the catalyst composed of conventional ion-pair compounds, which is more advantageous for use in the RIM process. It works. In addition, by solving the problem of the steric hindrance caused by disturbing the access of the catalyst and the monomer by the anion of the catalyst consisting of ion pairs, obtained from dicyclopentadiene containing a monomer of the polycyclic olefin that was poorly used There is an effect that can increase the utilization of the monomer.

Claims (9)

Zwitter, characterized in that the reactant (A) comprising a multi-cyclic olefin monomer and a zwitterion transition metal compound precursor, and the reactant (B) containing a multi-cyclic olefin monomer and Lewis acid are mixed and polymerized and injection molded Reaction injection molding method of polycyclic olefin using ionic compound catalyst. The method of claim 1, wherein the zwitterion transition metal compound precursor may be represented by the following Chemical Formulas 1-5: The reaction injection molding method of a multi-cyclic olefin using a zwitterionic compound catalyst. Wherein X is p-allyl, substituted p-allyl, p-benzyl or substituted p-benzyl group, Y is nitrogen or phosphorus atom, Z is CH ₂ or oxygen atom, M is nickel, palladium or platinum Is an atom, R is a hydrogen radical, hydrocarbyl or substituted hydrocarbyl and may be the same or different from each other, L is a neutral monodentate ligand which may be substituted by an olefin, L 'is a monodentate ligand of an anion and L and L' May be linked to each other to form a bidentate ligand of an anion. The method of claim 1, wherein the Lewis acid may be represented by the following Chemical Formulas 6 to 8. R ^1- [Al (R ¹ ) -O] _a -AlR ¹ ₂ AlX ¹ _n (R ¹ ) _3-n BX ¹ _n (R ¹ ) _3-n (6) (7) (8) Wherein X ¹ is hydrogen, halogen, alkoxy or aryloxy, R ¹ is a hydrocarbyl substituted with a halogen radical, hydrocarbyl or halogen, a is an integer from 1 to 5 and n is an integer from 0 to 3. When _n of X ¹ _n is 2 or more, X ¹ may be the same as or different from each other, and when a is 2 or more or (R ¹ ) ₃ n is 0 or 1, R ¹ may be the same or different. The method of claim 1, wherein the polycyclic olefin monomer is a polycyclic olefin monomer using a zwitterionic compound catalyst, characterized in that the polycyclic olefin monomer based on norbornene, norbornadiene, dicyclopentadiene or norbornene Reaction injection molding method. The method of claim 1, wherein the multi-cyclic olefin monomer may be represented by the following Chemical Formulas 9 to 13. Here, the ^{R 2, R 3, R 4} , R 5 are each H, an alkyl group, a vinyl group independently, halogen, -COOH, -CN or -COOCH ₃ one, n is an integer from 1-5. The method of claim 1, wherein the zwitterion transition metal compound precursor and the Lewis acid are mixed at a ratio of 1: 0.1 to 10 molar ratio. The method of claim 1, wherein the multi-cyclic olefin monomer solution is mixed at a ratio of 10 to 100,000 kg per 1 mole of zwitterion catalyst used. The reaction injection molding method of polycyclic olefin using a zwitterionic compound catalyst according to claim 1, wherein the polymerization is carried out at a temperature of -50 to 200 ° C. The reaction injection molding method for polycyclic olefins using a zwitterionic compound catalyst according to claim 1, wherein the pressure at which the polymerization is carried out is from atmospheric pressure to 50 atm.