TWI224114B - Method for purifying cycloolefin copolymer - Google Patents

Abstract

The present invention relates to a method for purifying cycloolefin copolymer, especially for removing metallic components in cycloolefin copolymer. The method of the present invention basically involves the following steps: mixing cycloolefin copolymer with an organic solvent and water, allowing the precipitation of metallic components to form solid compounds, and removing the metallic solid compounds from cycloolefin copolymer solution by filtration or centrifugation. The previously mentioned organic solvent is selected from the group consisting alcohol, ketone, ester, and ether. The method of the present invention reduces the content of metallic components of mCOC to the standard for optical uses without producing large quantity of waste.

Description

1224114 _ Case No. 90130791 _ Month Day _ Amendment _ V. Description of the invention (1) Field of the invention: The present invention relates to a method for removing metal components from cycloolefin copolymers. The method of the present invention mainly uses organic solvent and water and mc oc solution to fully stir, so that the metal component contained in COC forms a solid compound to facilitate separation. Among them, the organic solvents are selective alcohols, ketones, and S-types. And ethers. The method of the present invention can reduce the metal content of mCOC to a purity specification as an optical material without generating a large amount of waste. Background of the invention:

Cyclic olefin copolymers (metallocene based cyclic olefin copoiymers (hereinafter referred to as mCOC)) is a copolymer with excellent performance, which has good light transmission, low birefringence, high heat resistance, good chemical resistance, low water absorption, and dimensional stability. Jia 'can be used as optical, medical equipment, electrical, and electronic materials. mCOC is an excellent optical material, suitable for the application of optical products such as optical discs and optical waveguides. In the field of optical applications, in order to have good optical properties, the purity of the material is quite high. mCOC must be purified and reduced. Miscellaneous, for example, its metal content must be reduced to less than 0.

mC0C is a copolymer of ethylene and norbornene catalyzed by arylene metal (metal locene) catalyzed copolymerization. mC0CT is a pure white powder precipitated from ketones, alcohols, or esters from the reaction solution. The catalyst used in mC〇c polymerization ^ 1〇cene catalyst and co-catalyst methyl aluminoxane (MAO) are metal compounds, so the mC〇c polymerized contains aluminum and Hammer-based residual metal components, these metal components must be removed from mCOc * to avoid impact; performance of mCOC products. The conventional method for removing metal components from mCOC is to use a filter aid such as diatom 1224114 _ Case No. 90130791 _ year and month revision _ 'V. Description of the invention (2) Soil or HC1 aqueous solution to separate metal components from mCOC Out. As described in US Patent No. 5, 6 3 7, 4 0 0, one of the methods for removing metal components from mCOC is to combine a polymerization reaction solution (total about 28 kg) containing 4.2 kg mCOC with 50 0 g of diatomaceous earth or cellulose-based filter aid, 200 m 1 of water, 0.5 g of antioxidant and 50 L of hydrogenated diesel are mixed and stirred at 60 ° C for 30 minutes, and then filtered through a filter press . The filter press has been pre-suspended in 10 liters of Exsol containing 500 g of diatomaceous earth to form a filter aid layer. After the mCOC solution processed by the filter press is filtered through a 5 // m filter, the metal component can be removed. The biggest disadvantage of this method is that it produces a large amount of solid waste, and this method has a capacity of 12 kg per 100 kg of mCOC. Another method mentioned in the same patent to remove the metal component of mCOC is to precipitate the mCOC solid with acetone, stir with ethanol / HC1 (1: 2) solution to remove the metal component, and then filter the solid mCOC and use water Wash until neutral. This method produces 3100 liters of 3N HC 1 waste acid containing aluminum and tritium and subsequent washing wastewater for each 100 kg of mCOC. It also has the disadvantage of generating a large amount of waste acid and wastewater. U.S. Patent No. 5,498,6 77 also uses diatomaceous earth or 10MC1 to remove metal components in mCOC, which also has the problem of generating a large amount of solid waste or waste acid and wastewater. In order to avoid the problems caused by the above methods, the present invention provides a method which can effectively remove the metal components in in C 0 C without using celite or H C 1 ′ and does not generate a large amount of waste. Detailed invention description:

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The purpose of the present invention is to provide a method for reducing the metal content of mCOC to another aspect of the present invention. To provide a method for removing the metal components in mCOC as a method of purifying optical materials, which sometimes does not generate a large amount of waste. specification. In the same way, the method of the present invention uses organic solvents and water to effectively remove metal components in mC0C solution. The organic solvent is selected from the group consisting of alcohols, ketones, esters, and ethers. Among the ethnic groups, the best is acetone. Organic solvent toilet water has a weight ratio of 0: 100 to 80: 20, and more preferably: 90 to 25: 75. The method of the present invention is that the mC0G solution is fully mixed with the above organic solvent and water, and the reaction temperature is 3 (TC to 25 (TC, preferably 8 叱 to 5 ot), so that the metal components in the mCOC reaction solution are formed. Solid metal compounds. Most of the solid metal compounds will have an aqueous phase, and a small amount of the organic phase can be removed by filtration or centrifugation. The metal content of mC〇c treated by this method can be reduced to less than 10 ppm. And the organic solvent and water can be recycled and reused 'to save costs and resources. The technological breakthrough of this invention is that an appropriate amount of organic solvent is added to the water. Because the organic solvent and the mCoC reaction solution have good mutual solubility, washing is greatly improved. Effect, so that the metal component in the mCoC reaction solution forms a solid metal compound whose main body is a metal oxide or hydroxide, and is separated from the mCOC reaction solution. ~ The method of the present invention can use 1 to 3 in series with a clip Set the tank out, stir the mCOC solution, acetone, and water into the above mixing tank to make a mixture. The liquid is vented into the jacket to control the operating temperature until the metal is oxidized or hydroxided. After precipitation, the mixed solution is pumped to a phase separation tank, and the mixed solution is then divided into an upper layer; an organic phase and a lower aqueous phase. The upper organic phase contains mCOC, and most of the formed metal oxides or hydroxides will exist. Lower layer

1224114 Amendment No. 90130791 V. Description of the invention (4) _ Water phase, a small part of which is in the upper organic phase. The aqueous phase solution is then guided to a single machine, and the solid metal oxide or hydroxide is separated from the lower aqueous phase solution with an organic solvent at a centrifugal acceleration of 1000 g to 1500 blur which can be achieved industrially. 0 0 0 g After the water phase of the lower layer of water is adjusted by the adjustment tank, it can return to 3. Repeated use with mixing tank. On the other hand, the upper organic phase containing mCOC can be used to remove solid metal oxides or hydroxides by stirring, and the amount of mCOC that meets the specifications can be obtained or centrifuged. 1 Metal Containing In order to further clarify the method, structure and characteristics of the present invention, the preferred embodiments of the present invention will be described in more detail. In the following Example 1, the reaction solution after polymerizing mCOC was 266 g, Ηg C class g water: about 15: 85) in a 1 liter pressure-resistant glass stirring tank and 11,1 into a mixed solution, The mC0c reaction solution contained polycycloolefin 3 and the rest was methylbenzyl and thousands of ppm of norbornene. The mixture was heated by 1%, and stirred at 120 ° C for 2 hours, then allowed to stand to cool down to normal pressure, and the upper hydration reaction mixture was taken out. The mixture was centrifuged in a centrifuge at 3,000 g for 2 minutes. The micro-precipitation at the bottom of the C-body centrifuge tube was separated, and then acetone was added, and the two were filtered and dried to obtain solid mCOC. With the sensitivity of η ς, from the ▲ · 13 Ppm system, the metal content of the solid mCoc is measured as follows: the aluminum content of 73 PPm cannot be detected, so it is less than 0.5 ppm. The lower aqueous phase was centrifuged in a 3000 g centrifuge for 2 minutes to obtain a Shen Huan of about 0.07 g, and the number of people belonged to the brothers. The compounds were in the aqueous phase. Example 2

1224114 __Case No. 90130791 Rev. ____ V. Description of the invention (5) g of water (acetone: water is about 16: 8 4) in a 1 liter pressure-resistant glass mixing tank, search and mix into a mixed solution, of which 3 wt% ， mCOC reaction solution contains polycycloolefin

The rest is methylbenzyl and thousands of ppm of norbornene. The mixture was heated to 120 ° C, stirred for 2 hours, and then allowed to stand to cool down to normal pressure. The mCOC polymerization reaction mixture in the upper layer was taken out and filtered through a paper towel. Then, acetone was added to precipitate mCOC, and then filtered and dried to obtain solid mCOC. Using an analysis system with a sensitivity of 0.5 ppm, the metal content of the solid ro C 0 C was measured as follows: the content was 5.2 ppm, which could not be detected, so it was less than 0.5 p p m. The lower aqueous phase was centrifuged at 300 g for 2 minutes to obtain a precipitate of about 0.075 g. Most of the metal compounds were in the aqueous phase. W Example 3 The mCOC / ΜA0 toluene solution and the washing solution were stirred in a pressure-resistant glass stirring tank to form a mixed solution. The mCOC / MAO methylbenzyl solution contained 5% mCOC and about 60 ppm A1. The washing solution contained pure water and acetone ( The weight ratio is 92: 8). The mixture is heated to 120 ° C, stirred for 1 hour, then allowed to stand to cool down to normal pressure, and the upper mCOC methylbenzyl solution is taken out, filtered through filter paper, and then acetone is added to precipitate mCOC, filtered and dried, that is, MCOC was obtained as a solid. An analysis system with a sensitivity of 0.5 p p in was used to measure the metal content of this solid ni C 0 C as Cui Lu content of 5.9 ppm. g Example 4 The mCOC / ΜA0 toluene solution and the washing solution were stirred in a pressure-resistant glass stirring tank to form a mixed solution. The mCOC / MAO toluene solution contained 5% mCOC and about 40 ppm A1. The washing solution contained pure water and acetone (weight The ratio is 86:14). The above-mixed solution was heated to 12 ° C, stirred for 1.5 hours, and then allowed to stand to cool down to normal pressure. The upper mCOC solution was removed and filtered with filter paper. This solution was measured.

Page 10 1224114 ___Case No. 90130791_ ^ Ά ^ __—— V. Description of the Invention (6) Contains 0 · 17 ppm A1, which is 3.4 PPm relative to mCOC. Example 5 The mCOC / ΜA0 methylbenzyl solution was washed with The liquid was stirred in a pressure-resistant glass stirring tank to form a mixed liquid, in which the mCOC / MAOf solution contained 5% mC0C and about 240 pp in A 1, and was washed; the strip liquid contained pure water and acetone (weight ratio 9 2 · 8). The mixture was heated to 100 ° C, stirred for 1.5 hours, and then allowed to stand to cool down to normal pressure. The mCOC solution was removed from the upper layer and filtered with filter paper. This methylbenzyl solution was found to contain 0.14 ppm of A1, which was 2.8 ppm relative to mCOC. Example 6

The mCOC / ΜA0 methylbenzyl solution and the washing solution are mixed into a pressure-resistant glass mixing tank to form a mixed solution. The mCOC / Μ A 0 toluene solution contains 5% mCOC and about 240 ppm A 1, and the washing solution contains pure water and acetone. (The weight ratio is 9 0: 1 0). The mixture was heated to 120 ° C, stirred for 2 hours, and then allowed to stand to cool down to normal pressure. The mCOC solution in the upper layer was taken out and passed through filter paper. This toluene solution was found to contain 0.1 ppm of A 1 at 2.8 ppm relative to mCOC. Although the present invention has been disclosed as above with a preferred embodiment, it is not intended to limit the present invention. Anyone skilled in the art can make changes and retouches without departing from the spirit and scope of the present invention, so the protection of the present invention The scope shall be determined by the scope of the attached patent application. stomach

1224114 Case No. 90130791 ^ _η amendment

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Claims (1)

1224114 _ Case No. 90130791_Year_Day_ Charm_ VI. Application for patent scope 1. A method for removing metal components from cyclic olefin copolymers, including the following steps: A cyclowomen copolymer solution and an aqueous solution containing organic solvents Stir well into a mixed solution to make the metal components of the cyclic olefin copolymer solution _ form a solid metal compound. The organic solvent is compatible with the cyclic olefin copolymer solution, and free ketones, alcohols, esters, In the group consisting of ethers; the mixed liquid is left to stand to separate the phases into an upper organic phase and a lower aqueous phase, wherein the cycloolefin copolymer exists in the upper organic phase and the solid metal compound exists in the The upper organic phase and the lower aqueous phase; removing the solid organic compound by filtering or high-speed centrifugation to obtain a cycloolefin copolymer solution; and separating the cycloolefin copolymer solution by precipitation or concentration method A solid cyclic olefin copolymer; wherein the weight ratio of the organic solvent to water is 1: 1 0 to 80 to 20, and the suitable reaction temperature is 30 ° C to 250 ° C. 2. The method according to item 1 of the scope of patent application, further comprising the steps of removing the solid metal 'compound in the lower aqueous phase by filtration or centrifugation; and recovering and reusing the solution of the lower aqueous phase. 3. The method as described in claim 1 or 2, wherein the organic solvent is acetone. 4. The method according to item 1 or 2 of the scope of patent application, wherein the weight ratio of the organic solvent to water is 10:90 to 25:75. > 5. The method described in item 1 or 2 of the scope of patent application, its reaction Page 13 1224114 Page 14 I ^ 1 4 / X / Modal, 口 A of this application ^ ψο one ": one / Z ---- Application number: 90130791 -------------------- 11 = · ^. Sound change $ Correction J3- 1224114 Invention name in Chinese English1 · 魏玉 暖 2 · Xing Shuiqin Name (Chinese) Name (English) 1. Yuh-Yuan Wei2. Shoei-Chin Wu Inventor (total 2 persons) Applicant (total 1 person) Nationality (Chinese and English) Residence Address (Chinese residence (English j name or name (Chinese) Name or name (English) Nationality / Domicile if business office) (L text) / Main residence Jf business office) Turkish) Representative (Chinese) 1 · China Republic of China ROC 2. ROC J. No. 321, Section 2, Guangfu Road, Hsinchu City 2 No. 321, Section 2, Guangfu Road, Hsinchu City 2. 1. Industrial Technology Research Institute 1. Industrial technology research institute 1. ROC 1 · No.195, Section 4, Zhongxing Road, Zhudong Town, Hsinchu County (this address is different from the previous applicant) 1. Weng Zhengyi ' page 1