CN101831052A - Production method of low-residue tetrabromobisphemol A brominated epoxy resin - Google Patents
Production method of low-residue tetrabromobisphemol A brominated epoxy resin Download PDFInfo
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- CN101831052A CN101831052A CN 201010154179 CN201010154179A CN101831052A CN 101831052 A CN101831052 A CN 101831052A CN 201010154179 CN201010154179 CN 201010154179 CN 201010154179 A CN201010154179 A CN 201010154179A CN 101831052 A CN101831052 A CN 101831052A
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Abstract
The invention relates to a production method of low-residue tetrabromobisphemol A brominated epoxy resin, comprising an etherification step, a ring-closure reaction step, a step of acquiring brominated epoxy resin oligomer and a synthesis step. The synthesis step comprises the following steps of: heating, stirring and melting the brominated epoxy resin oligomer in a synthesis kettle; adding the tetrabromobisphemol A according to the mass ratio of the tetrabromobisphemol A and the brominated epoxy resin oligomer of 1:1.1 to 1.4; after the materials are melted completely, adding compound auxiliaries accounting for 0.3 to 0.8% of the total mass of the brominated epoxy resin oligomer and the tetrabromobisphemol A in the step, and carrying out the synthesis reaction for 3 to 5h at the temperature of 150 to 200 DEG C and the pressure of 0.3 to 0.5 Pa. The invention greatly reduces the energy consumption and reduces the production cost; meanwhile, the product fills up the blank of the domestic product and meets the international requirements of environmental protection.
Description
Technical field
The present invention relates to a kind of production method of brominated epoxy resin, relate in particular to a kind of production method of low-residue tetrabromobisphemol A brominated epoxy resin.
Background technology
Brominated epoxy resin is divided into basic, normal, high three major types by relative molecular mass, can be divided into EP type, EC type again by end-group structure, can be applied to respectively in the different plastic materials.In recent years, homemade brominated epoxy resin development rapidly, especially changed that brominated amount is low, relative molecular mass is little, can only be as shortcomings such as insulating encapsulating materials, can handle the relative molecular mass of superpolymer according to fire-retardant requirement, produce the product that is complementary with it, with produce good heat resistance, photostabilization is good, has simultaneously the flame retardant plastics of resistance to impact shock preferably again.Nowadays, national brominated epoxy resin demand is more than 20,000 tons, and with annual 20% speed increment.The world market total volume has reached more than 100,000 tons.But generate the cigarette and the toxic gas of more amount during as the burning of the tetrabromo-bisphenol of brominated epoxy resin synthesis material, environmental pollution is bigger; Add this material in addition and can reduce the stability of polymkeric substance UV-light.Therefore to be lower than 100ppm be that can brominated epoxy resin reach an important indicator of environmental requirement in recent years to the residual volume of tetrabromo-bisphenol.
Domestic relevant report: Shandong brother Science and Technology Ltd. and Weifang Brother Chemical Co., Ltd.'s (Chinese patent 200910016470.6), Shandong marine chemical industry research institute (" chemical propellant and macromolecular material "), Chemical Engineering College, Dalian Univ. of Science and Engineering's (" Chinese sizing agent "), Ba Ling petrochemical complex limited liability company (" chemical industry progress "), units such as (Chinese patents 200410075424.0) of Yutai Salt Chemistry Co., Ltd., Guangrao County has reported the production method of the brominated epoxy resin of various molecular weight in succession, the existing part of the product that its different production technique is produced is gone into operation and is approved by market, but the production technique of low-residue tetrabromobisphemol A brominated epoxy resin yet there are no report so far.
Summary of the invention
The production method that the purpose of this invention is to provide a kind of low-residue tetrabromobisphemol A brominated epoxy resin, this method greatly reduces energy consumption, has reduced production cost, and product has been filled up domestic blank again simultaneously, has reached international environmental requirement.
The technical solution used in the present invention is:
The production method of low-residue tetrabromobisphemol A brominated epoxy resin,
Step 1, etherification reaction: is 1 with epoxy chloropropane and tetrabromo-bisphenol by mass ratio: (1.1-1.3) drop into etherifying reactor, add and to account for always the feed intake quaternary ammonium salt catalyst of quality 0.5% of epoxy chloropropane and tetrabromo-bisphenol, etherification temperature 90-95 ℃, etherification reaction 3-4h;
Step 2, ring-closure reaction: vacuumize and remove unnecessary epoxy chloropropane, drop into and account for the feed intake toluene of quality 20-35% of tetrabromo-bisphenol, controlled temperature divides three inputs to account for the feed intake NaOH of mass concentration 45% of quality 42-52% of tetrabromo-bisphenol about 70 ℃ to carry out ring-closure reaction 5.5-6.5h;
Step 3 obtains the brominated epoxy resin oligopolymer: drop into and account for the feed intake water of quality 30-40% of tetrabromo-bisphenol, add and account for the feed intake toluene of quality 50-60% of tetrabromo-bisphenol, regulating the pH value with SODIUM PHOSPHATE, MONOBASIC is 7-8, toluene is reclaimed in extraction, distillation, gets the brominated epoxy resin oligopolymer;
Step 4, synthesis step: with the brominated epoxy resin oligopolymer after the synthesis reactor internal heating stirs fusion, by tetrabromo-bisphenol and brominated epoxy resin oligopolymer mass ratio is 1: 1.1～1.4 adding tetrabromo-bisphenols, add after the fusion fully and account for that the composite assistant of brominated epoxy resin oligopolymer and tetrabromo-bisphenol total mass 0.3～0.8% carries out building-up reactions in this step, temperature of reaction is 150～200 ℃, reaction times is 3～5h, and reaction pressure is 0.3～0.5Mpa;
Step 5, the finished product of cooling curing step 4 are pulverized then, are packed.
Composite assistant in the described step 4 be quaternary ammonium salt, season phosphonium salt and the mixture of polyethers, described quaternary ammonium salt: season phosphonium salt: the mass ratio of polyethers is (0.29-0.32): 1: (0.011-0.014).
Described quaternary ammonium salt is a benzyl triphenyl brometo de amonio, described season phosphonium salt be benzyl triphenyl bromide phosphine, described polyethers is a polyethyleneglycol diglycidylether.
Brominated epoxy resin (EP) the average mark quality that the present invention produces is 14000～22000, and the residual volume of tetrabromo-bisphenol is lower than 100ppm.Present method has adopted than the reasonable raw material proportioning, and has selected composite assistant for use, and quality product is improved, and reaches environmental requirement, reduces product cost simultaneously.
Description of drawings
Fig. 1 is a reaction process block diagram of the present invention.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment and reaction process block diagram.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention professor, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Reaction formula of the present invention is:
Embodiment 1
The production method of low-residue tetrabromobisphemol A brominated epoxy resin,
Step 1, etherification reaction: 450.3Kg epoxy chloropropane and 540.5Kg tetrabromo-bisphenol are dropped into etherifying reactor, add 4.95Kg catalyzer benzyl triphenyl brometo de amonio, 94 ℃ of etherification temperatures, etherification reaction 3.5h.
Step 2, ring-closure reaction: vacuumize and remove unnecessary epoxy chloropropane, drop into 150.3Kg toluene again, controlled temperature divides the NaOH that drops into the mass concentration 45% of 260.5Kg for three times to carry out ring-closure reaction 6h about 70 ℃.
Step 3 obtains the brominated epoxy resin oligopolymer: input 198.7Kg water, add 300.5Kg toluene, and regulating the pH value with SODIUM PHOSPHATE, MONOBASIC is 7-8, toluene is reclaimed in extraction, distillation, gets brominated epoxy resin oligopolymer 619.3Kg.
Step 4, synthesis step: with the brominated epoxy resin oligopolymer after the synthesis reactor internal heating stirs fusion, add the 476.4Kg tetrabromo-bisphenol, add the 8.76Kg composite assistant fully after the fusion and carry out building-up reactions, temperature of reaction is 150～200 ℃, reaction times is 3～5h, and reaction pressure is 0.3～0.5Mpa; Composite assistant is for by quaternary ammonium salt: season phosphonium salt: the mass ratio of polyethers is 0.31: 1: 0.014 mixture of forming, and quaternary ammonium salt is a benzyl triphenyl brometo de amonio, season phosphonium salt be benzyl triphenyl bromide phosphine, polyethers is a polyethyleneglycol diglycidylether.
Step 5, the finished product of cooling curing step 4 are pulverized then, are packed.
The brominated epoxy resin that above-mentioned steps obtains (EP) average mark quality is 17600, the residual volume 94ppm of tetrabromo-bisphenol.
Embodiment 2
The production method of low-residue tetrabromobisphemol A brominated epoxy resin,
Step 1, etherification reaction: 512.8Kg epoxy chloropropane and 615.4Kg tetrabromo-bisphenol are dropped into etherifying reactor, add 5.64Kg catalyzer benzyl triphenyl brometo de amonio, 95 ℃ of etherification temperatures, etherification reaction 3.5h.
Step 2, ring-closure reaction: vacuumize and remove unnecessary epoxy chloropropane, drop into 179.3Kg toluene again, controlled temperature divides the NaOH that drops into the mass concentration 45% of 298.6Kg for three times to carry out ring-closure reaction 6h about 70 ℃.
Step 3 obtains the brominated epoxy resin oligopolymer: input 226.3Kg water, add 341.4Kg toluene, and regulating the pH value with SODIUM PHOSPHATE, MONOBASIC is 7-8, toluene is reclaimed in extraction, distillation, gets brominated epoxy resin oligopolymer 705.2Kg.
Step 4, synthesis step: with the brominated epoxy resin oligopolymer after the synthesis reactor internal heating stirs fusion, add the 546.2Kg tetrabromo-bisphenol, the composite assistant that adds 10.12Kg after the fusion carries out building-up reactions fully, temperature of reaction is 150～200 ℃, reaction times is 3～5h, and reaction pressure is 0.3～0.5Mpa; Composite assistant is for by quaternary ammonium salt: season phosphonium salt: the mass ratio of polyethers is 0.32: 1: 0.012 mixture of forming, and quaternary ammonium salt is a benzyl triphenyl brometo de amonio, season phosphonium salt be benzyl triphenyl bromide phosphine, polyethers is a polyethyleneglycol diglycidylether.
Step 5, the finished product of cooling curing step 4 are pulverized then, are packed.
The brominated epoxy resin that above-mentioned steps obtains (EP) average mark quality is 20130, the residual volume 98ppm of tetrabromo-bisphenol.
Embodiment 3
The production method of low-residue tetrabromobisphemol A brominated epoxy resin,
Step 1, etherification reaction: 1000.2Kg epoxy chloropropane and 1200.3Kg tetrabromo-bisphenol are dropped into etherifying reactor, add 11.02Kg catalyzer benzyl triphenyl brometo de amonio, 93 ℃ of etherification temperatures, etherification reaction 3.5h.
Step 2, ring-closure reaction: vacuumize and remove unnecessary epoxy chloropropane, drop into 340.3Kg toluene again, controlled temperature divides the NaOH that drops into the mass concentration 45% of 542.7Kg for three times to carry out ring-closure reaction 6h about 70 ℃.
Step 3 obtains the brominated epoxy resin oligopolymer: input 430.1Kg water, add 609.2Kg toluene, and regulating the pH value with SODIUM PHOSPHATE, MONOBASIC is 7-8, toluene is reclaimed in extraction, distillation, gets brominated epoxy resin oligopolymer 1380.6Kg.
Step 4, synthesis step: with the brominated epoxy resin oligopolymer after the synthesis reactor internal heating stirs fusion, add the 1061.5Kg tetrabromo-bisphenol, add the 15.62Kg composite assistant fully after the fusion and carry out building-up reactions, temperature of reaction is 150～200 ℃, reaction times is 3～5h, and reaction pressure is 0.3～0.5Mpa; Composite assistant is for by quaternary ammonium salt: season phosphonium salt: the mass ratio of polyethers is 0.29: 1: 0.011 mixture of forming, and quaternary ammonium salt is a benzyl triphenyl brometo de amonio, season phosphonium salt be benzyl triphenyl bromide phosphine, polyethers is a polyethyleneglycol diglycidylether.
Step 5, the finished product of cooling curing step 4 are pulverized then, are packed.
The brominated epoxy resin that above-mentioned steps obtains (EP) average mark quality is 19530, the residual volume 97ppm of tetrabromo-bisphenol.
Embodiment 4
The production method of low-residue tetrabromobisphemol A brominated epoxy resin,
Step 1, etherification reaction: 500Kg epoxy chloropropane and 649.3Kg tetrabromo-bisphenol are dropped into etherifying reactor, add 5.75Kg catalyzer benzyl triphenyl brometo de amonio, 90 ℃ of etherification temperatures, etherification reaction 3h.
Step 2, ring-closure reaction: vacuumize and remove unnecessary epoxy chloropropane, drop into 129.9Kg toluene again, controlled temperature divides the NaOH that drops into the mass concentration 45% of 272.7Kg for three times to carry out ring-closure reaction 5.5h about 70 ℃.
Step 3 obtains the brominated epoxy resin oligopolymer: input 194.8Kg water, add 389.6Kg toluene, and regulating the pH value with SODIUM PHOSPHATE, MONOBASIC is 7-8, toluene is reclaimed in extraction, distillation, gets brominated epoxy resin oligopolymer 739.6Kg.
Step 4, synthesis step: with the brominated epoxy resin oligopolymer after the synthesis reactor internal heating stirs fusion, add the 672.4Kg tetrabromo-bisphenol, add the 4.24Kg composite assistant fully after the fusion and carry out building-up reactions, temperature of reaction is 150～200 ℃, reaction times is 3～5h, and reaction pressure is 0.3～0.5Mpa; Composite assistant is for by quaternary ammonium salt: season phosphonium salt: the mass ratio of polyethers is 0.29: 1: 0.011 mixture of forming, and quaternary ammonium salt is a benzyl triphenyl brometo de amonio, season phosphonium salt be benzyl triphenyl bromide phosphine, polyethers is a polyethyleneglycol diglycidylether.
Step 5, the finished product of cooling curing step 4 are pulverized then, are packed.
The brominated epoxy resin that above-mentioned steps obtains (EP) average mark quality is 20530, the residual volume 106ppm of tetrabromo-bisphenol.
Embodiment 5
The production method of low-residue tetrabromobisphemol A brominated epoxy resin,
Step 1, etherification reaction: 500Kg epoxy chloropropane and 549.5Kg tetrabromo-bisphenol are dropped into etherifying reactor, add 5.25Kg catalyzer benzyl triphenyl brometo de amonio, 92 ℃ of etherification temperatures, etherification reaction 4h.
Step 2, ring-closure reaction: vacuumize and remove unnecessary epoxy chloropropane, drop into 192.3Kg toluene again, controlled temperature divides the NaOH that drops into the mass concentration 45% of 285.7Kg for three times to carry out ring-closure reaction 6.5h about 70 ℃.
Step 3 obtains the brominated epoxy resin oligopolymer: input 219.8Kg water, add 302.2Kg toluene, and regulating the pH value with SODIUM PHOSPHATE, MONOBASIC is 7-8, toluene is reclaimed in extraction, distillation, gets brominated epoxy resin oligopolymer 627.6Kg.
Step 4, synthesis step: with the brominated epoxy resin oligopolymer after the synthesis reactor internal heating stirs fusion, add the 448.3Kg tetrabromo-bisphenol, add the 8.61Kg composite assistant fully after the fusion and carry out building-up reactions, temperature of reaction is 150,180 or 200 ℃, reaction times is 3,4 or 5h, and reaction pressure is 0.3,0.4 or 0.5Mpa; Composite assistant is by quaternary ammonium salt: season phosphonium salt: the mixture that the mass ratio of polyethers is formed at 0.3: 1: 0.01, quaternary ammonium salt are benzyl triphenyl brometo de amonio, season phosphonium salt be benzyl triphenyl bromide phosphine, polyethers is a polyethyleneglycol diglycidylether.
Step 5, the finished product of cooling curing step 4 are pulverized then, are packed.
The brominated epoxy resin that above-mentioned steps obtains (EP) average mark quality is 14530, the residual volume 101ppm of tetrabromo-bisphenol.
The present invention is with existing starting material, use by composite assistant, optimization production technology, make low-residue tetrabromobisphemol A brominated epoxy resin (EP), and can be widely used in making it have good flame-retardant effect in the production of engineering plastics, the inventive method greatly reduces energy consumption, reduced production cost, product has been filled up domestic blank again simultaneously, has reached international environmental requirement.
Claims (3)
1. the production method of low-residue tetrabromobisphemol A brominated epoxy resin is characterized in that:
Step 1, etherification reaction: is 1 with epoxy chloropropane and tetrabromo-bisphenol by mass ratio: (1.1-1.3) drop into etherifying reactor, add and to account for always the feed intake quaternary ammonium salt catalyst of quality 0.5% of epoxy chloropropane and tetrabromo-bisphenol, etherification temperature 90-95 ℃, etherification reaction 3-4h;
Step 2, ring-closure reaction: vacuumize and remove unnecessary epoxy chloropropane, drop into and account for the feed intake toluene of quality 20-35% of tetrabromo-bisphenol, controlled temperature divides three inputs to account for the feed intake NaOH of mass concentration 45% of quality 42-52% of tetrabromo-bisphenol about 70 ℃ to carry out ring-closure reaction 5.5-6.5h;
Step 3 obtains the brominated epoxy resin oligopolymer: drop into and account for the feed intake water of quality 30-40% of tetrabromo-bisphenol, add and account for the feed intake toluene of quality 50-60% of tetrabromo-bisphenol, regulating the pH value with SODIUM PHOSPHATE, MONOBASIC is 7-8, toluene is reclaimed in extraction, distillation, gets the brominated epoxy resin oligopolymer;
Step 4, synthesis step: with the brominated epoxy resin oligopolymer after the synthesis reactor internal heating stirs fusion, by tetrabromo-bisphenol and brominated epoxy resin oligopolymer mass ratio is 1: 1.1～1.4 adding tetrabromo-bisphenols, add after the fusion fully and account for that the composite assistant of brominated epoxy resin oligopolymer and tetrabromo-bisphenol total mass 0.3～0.8% carries out building-up reactions in this step, temperature of reaction is 150～200 ℃, reaction times is 3～5h, and reaction pressure is 0.3～0.5Mpa;
Step 5, the finished product of cooling curing step 4 are pulverized then, are packed.
2. the production method of low-residue tetrabromobisphemol A brominated epoxy resin according to claim 1, it is characterized in that: the composite assistant in the described step 4 be quaternary ammonium salt, season phosphonium salt and the mixture of polyethers, described quaternary ammonium salt: season phosphonium salt: the mass ratio of polyethers is (0.29-0.32): 1: (0.011-0.014).
3. the production method of low-residue tetrabromobisphemol A brominated epoxy resin according to claim 1 and 2, it is characterized in that: described quaternary ammonium salt is a benzyl triphenyl brometo de amonio, described season, phosphonium salt was a benzyl triphenyl bromide phosphine, and described polyethers is a polyethyleneglycol diglycidylether.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553887A (en) * | 2013-10-11 | 2014-02-05 | 镇江市高等专科学校 | Method for preparing bisphenol A-type fire retardant epoxy resin |
| CN103923300A (en) * | 2014-04-17 | 2014-07-16 | 开美化学科技(南通)有限公司 | Preparation method of brominated epoxy resin with low bromine content |
| CN103923301A (en) * | 2014-04-17 | 2014-07-16 | 开美化学科技(南通)有限公司 | Preparation method of electronic-grade brominated epoxy resin with low bromine content |
| CN104017171A (en) * | 2014-06-16 | 2014-09-03 | 山东天一化学股份有限公司 | Production method of high-thermal-stability brominated epoxy resin |
| CN106117536A (en) * | 2016-07-22 | 2016-11-16 | 山东润科化工股份有限公司 | A kind of synthetic method of flame retardant polyether polyol |
| CN107286321A (en) * | 2017-06-02 | 2017-10-24 | 开美化学科技(南通)有限公司 | The preparation method of environment-friendly type brominated epoxy resin high polymer |
| CN108598567A (en) * | 2018-04-26 | 2018-09-28 | 吉林大学 | A kind of fire-retardant gel electrolyte, preparation method and its application in lithium ion battery and ultracapacitor |
| CN108752566A (en) * | 2018-05-02 | 2018-11-06 | 苏州博瑞达高分子材料有限公司 | A kind of production technology of flame-retarded resin |
| CN110041507A (en) * | 2019-05-07 | 2019-07-23 | 安徽美佳新材料股份有限公司 | A kind of preparation method of environmental protection UV resistance linear epoxy resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1298154B1 (en) * | 2001-09-28 | 2004-05-19 | Dainippon Ink And Chemicals, Inc. | Process for preparing epoxy resin |
| CN101481490A (en) * | 2009-01-19 | 2009-07-15 | 东莞联茂电子科技有限公司 | Thermosetting resin composition and use |
-
2010
- 2010-04-23 CN CN2010101541798A patent/CN101831052B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1298154B1 (en) * | 2001-09-28 | 2004-05-19 | Dainippon Ink And Chemicals, Inc. | Process for preparing epoxy resin |
| CN101481490A (en) * | 2009-01-19 | 2009-07-15 | 东莞联茂电子科技有限公司 | Thermosetting resin composition and use |
Non-Patent Citations (3)
| Title |
|---|
| 《中国胶粘剂》 20090630 于棚等 溴化环氧树脂合成新工艺 第18－21页 1-3 第18卷, 第06期 2 * |
| 《化工生产与技术》 20061025 李凤 我国特种环氧树脂生产和研究进展 第43－45页 1-3 第13卷, 第05期 2 * |
| 《绝缘材料通讯》 19300713 刘守贵 固体双酚A型环氧树脂合成工艺述评 第28－34页 1-3 , 第06期 2 * |
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| CN103553887A (en) * | 2013-10-11 | 2014-02-05 | 镇江市高等专科学校 | Method for preparing bisphenol A-type fire retardant epoxy resin |
| CN103923300A (en) * | 2014-04-17 | 2014-07-16 | 开美化学科技(南通)有限公司 | Preparation method of brominated epoxy resin with low bromine content |
| CN103923301A (en) * | 2014-04-17 | 2014-07-16 | 开美化学科技(南通)有限公司 | Preparation method of electronic-grade brominated epoxy resin with low bromine content |
| CN103923301B (en) * | 2014-04-17 | 2016-06-15 | 开美化学科技(南通)有限公司 | The preparation method of the brominated epoxy resin of the low bromine content of a kind of electronic-grade |
| CN104017171A (en) * | 2014-06-16 | 2014-09-03 | 山东天一化学股份有限公司 | Production method of high-thermal-stability brominated epoxy resin |
| CN106117536A (en) * | 2016-07-22 | 2016-11-16 | 山东润科化工股份有限公司 | A kind of synthetic method of flame retardant polyether polyol |
| CN107286321A (en) * | 2017-06-02 | 2017-10-24 | 开美化学科技(南通)有限公司 | The preparation method of environment-friendly type brominated epoxy resin high polymer |
| CN108598567A (en) * | 2018-04-26 | 2018-09-28 | 吉林大学 | A kind of fire-retardant gel electrolyte, preparation method and its application in lithium ion battery and ultracapacitor |
| CN108598567B (en) * | 2018-04-26 | 2020-03-10 | 吉林大学 | Flame-retardant gel electrolyte, preparation method and application thereof in lithium ion battery and supercapacitor |
| CN108752566A (en) * | 2018-05-02 | 2018-11-06 | 苏州博瑞达高分子材料有限公司 | A kind of production technology of flame-retarded resin |
| CN108752566B (en) * | 2018-05-02 | 2020-11-17 | 苏州博瑞达高分子材料有限公司 | Production process of flame-retardant resin |
| CN110041507A (en) * | 2019-05-07 | 2019-07-23 | 安徽美佳新材料股份有限公司 | A kind of preparation method of environmental protection UV resistance linear epoxy resin |
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