CN105968071A - Method for producing tetrabromobisphenol A diglycidyl ether - Google Patents
Method for producing tetrabromobisphenol A diglycidyl ether Download PDFInfo
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- CN105968071A CN105968071A CN201610301702.2A CN201610301702A CN105968071A CN 105968071 A CN105968071 A CN 105968071A CN 201610301702 A CN201610301702 A CN 201610301702A CN 105968071 A CN105968071 A CN 105968071A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
- C07D303/30—Ethers of oxirane-containing polyhydroxy compounds in which all hydroxyl radicals are etherified with oxirane-containing hydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
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Abstract
The invention discloses a method for producing tetrabromobisphenol A diglycidyl ether. The method comprises the following synthesis steps: tetrabromobisphenol A and excessive epichlorohydrin are thrown into a reaction vessel and heated to 50-70 DEG C, an aqueous solution of an initiator is added dropwisely, and a reaction is carried out for 4-5 hours; the aqueous solution of the initiator is added dropwisely in a vacuum condition again, in the process of the reaction, epichlorohydrin is dewatered by distillation for backflow to the reaction vessel, the reaction is continuous to carry out for 4-5 hours, reduced pressure distillation is carried out in order to obtain unreacted epichlorohydrin, nitrogen is filled for removing vacuum, water and methyl isobutyl ketone are added, an aqueous phase is discharged by extraction, an organic phase is distilled at 110-120 DEG C, filtering is carried out while hot, filtrate is transferred to a crystallization kettle, crystallization is carried out at 0-35 DEG C, after crystallization, centrifugal filtering is carried out in order to obtain precipitation, the precipitation is transferred to the reaction vessel for carrying out reduced pressure distillation, a colorless transparent organic matter is obtained, and cooling solidification, crushing and package are carried out. The method substantially reduces energy consumption and reduces production cost, at the same time the product fills the domestic blank, and international environmental protection requirements are achieved.
Description
Technical field
The present invention relates to the production method of a kind of tetrabromobisphenol A bisglycidyl ether.
Background technology
Tetrabromobisphenol A bisglycidyl ether monomer be water white transparency solid, theoretical molecular be 656, fusing point be 120 ~ 122 DEG C, there is the features such as heat-resist, light resistance is good, light transmission is strong, may be directly applied in plastics, casting glue, the field such as glasses lens plated.Due to technological problems, present stage, each producer was in tetrabromobisphenol A bisglycidyl ether production process, it is easily generated by-product and polyreaction occurs, the mean molecule quantity causing tetrabromobisphenol A bisglycidyl ether is 660 ~ 680, fusing point is only 45 ~ 54 DEG C, it is impossible to be applied directly in plastics, casting glue, the field such as glasses lens plated.Though the brominated epoxy resin that tetrabromobisphenol A carries out 2000 ~ 3000 molecular weight that polymerization generates can state field with application first, but this type of brominated epoxy resin colourity is poor and has remained a small amount of tetrabromobisphenol A raw material, and generate more cigarette and toxic gas during tetrabromobisphenol A burning, environmental pollution is relatively big, affects its application;It is greatly increased production cost simultaneously.
The production method of the domestic brominated epoxy resin the most in succession reporting various molecular weight, the product that its different production technology is produced part puts goods on the market and gets the nod, but the production technology as the tetrabromobisphenol A bisglycidyl ether monomer of brominated epoxy resin base resin is not reported so far, also have no the tetrabromobisphenol A bisglycidyl ether monomer report as production marketing.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides the production method of a kind of tetrabromobisphenol A bisglycidyl ether.The method greatly reduces energy consumption, decreases production cost, and the product simultaneously produced has filled up again domestic blank, has reached International Environmental Protection requirement.
The present invention is by the following technical solutions: the production method of a kind of tetrabromobisphenol A bisglycidyl ether, comprise the following steps: (1) etherification reaction: tetrabromobisphenol A and epoxychloropropane are put in reactor for 1:0.8 ~ 1.2 in mass ratio and be heated to 50 ~ 70 DEG C, the aqueous solution of dropping initiator, reaction 4 ~ 5h, wherein, the mass ratio of tetrabromobisphenol A and initiator is 1:(0.02 ~ 0.03);
(2) ring-closure reaction: under vacuum condition (vacuum is 15 ~ 30Kpa), continue for heating, again drip the aqueous solution of initiator, keep thermotonus 4 ~ 5h, in this course of reaction, after epoxychloropropane is distilled out removing water layer, again it is back in reactor continue to participate in reaction;Wherein, the initiator again added is (0.2 ~ 0.3) with the mass ratio of tetrabromobisphenol A: 1;
(3) purify: decompression distills out unreacted epoxychloropropane, after being filled with nitrogen removing vacuum, add water and methyl iso-butyl ketone (MIBK), stirring 1 ~ 2h, stand 1 ~ 2h, extracting and demixing, after discharging aqueous phase, organic facies is distilled at 110 ~ 120 DEG C, filtered while hot removes insoluble matter, gained filtrate is transferred to crystallization kettle, slowly regulation and control crystallization temperature is to 0 ~ 35 DEG C, add crystal seed, solution slowly separates out the crystallization of tetrabromobisphenol A diglycidyl ether, it is filtrated to get precipitation after machine (hanging bag type centrifugal machine) is centrifugal by centrifugation, precipitation is transferred to reactor decompression distillation, obtain water white Organic substance;Wherein, the water, the methyl iso-butyl ketone (MIBK) that add in extraction process are 0.6 ~ 0.7:1 ~ 1.3:1 with the mass ratio of tetrabromobisphenol A;
(4) the water white transparency Organic substance that cooling and solidifying step (3) obtains, then carries out pulverizing, packing.
The aqueous solution of the initiator added in described step (1) and step (2) is NaOH aqueous solution.
Beneficial effects of the present invention: during cyclization, distills the water that the water in initiator and reaction generate, reduces by-product and the generation of polyreaction;Recrystallization method is used to be removed by the impurity such as the macromolecule brominated epoxy resin of by-product and polymerization generation.The inventive method greatly reduces energy consumption, decrease production cost, the product average molecular mass obtained is 654 ~ 656, fusing point 121 ~ 122 DEG C, colourity 0.0 ~ 0.2(APHA), more existing same specification product has the advantages such as high-melting-point, high-weatherability and low colourity, can be widely used in the Material Fields such as plastics, casting glue and lens coating;Fill up domestic blank simultaneously, reached International Environmental Protection requirement, be greatly saved production cost.
Accompanying drawing explanation
Fig. 1 is the reacting flow chart of the present invention.
Detailed description of the invention
In order to deepen the understanding of the present invention, below in conjunction with embodiment and accompanying drawing, the invention will be further described, and this embodiment is only used for explaining the present invention, is not intended that the restriction to protection scope of the present invention.
Embodiment 1
The production method of a kind of high purity tetrabromobisphenol A bisglycidyl ether, comprises the following steps:
(1) etherification reaction: 450.7kg tetrabromobisphenol A and 370.4kg epoxychloropropane are put in reactor and be heated to 60 DEG C, dropping 18.7kgNaOH aqueous solution (NaOH is 9kg), react 4.5h;
(2) ring-closure reaction: vacuum is maintained at 19Kpa, and continuous heating, dropping 187.5kgNaOH aqueous solution (NaOH is 90kg), keep thermotonus 4.5h, in this course of reaction, after epoxychloropropane is distilled out removing water layer, again it is back in reactor continue to participate in reaction;
(3) purify: decompression distills out unreacted epoxychloropropane, it is filled with nitrogen and removes vacuum, add 272.3kg water and 460.7kg methyl iso-butyl ketone (MIBK), stirring 1h, stand 1h, extracting and demixing, after discharging aqueous phase, organic facies is distilled at 115 DEG C, filtered while hot removes insoluble matter, gained filtrate is transferred to crystallization kettle, slowly regulation and control crystallization temperature is to 15 DEG C, add crystal seed, solution slowly separates out the crystallization of tetrabromobisphenol A diglycidyl ether, it is filtrated to get precipitation after hanging bag type centrifugal machine is centrifugal, precipitation is transferred to reactor decompression distillation, obtain water white Organic substance;
(4) the water white transparency Organic substance that cooling and solidifying step (3) obtains, then carries out pulverizing, packing.
It is 663 that above-mentioned steps obtains tetrabromobisphenol A bisglycidyl ether mean molecule quantity, fusing point 111 ~ 114 DEG C, and tetrabromobisphenol A residual volume is ND, and colourity is 1.4(APHA).
Embodiment 2
The production method of a kind of high purity tetrabromobisphenol A bisglycidyl ether, comprises the following steps:
(1) etherification reaction: 890.1kg tetrabromobisphenol A and 1052.2kg epoxychloropropane are put in reactor and be heated to 62 DEG C, dropping 55.3kgNaOH aqueous solution (NaOH is 26.3kg), react 4.5h;
(2) ring-closure reaction: vacuum is maintained at 21Kpa, and continuous heating, dropping 545.1kgNaOH aqueous solution (NaOH is 261.9kg), keep thermotonus 4h, in this course of reaction, after epoxychloropropane is distilled out removing water layer, again it is back in reactor continue to participate in reaction;
(3) purify: decompression distills out unreacted epoxychloropropane, it is filled with nitrogen and removes vacuum, add 620.4kg water and 1157.1kg methyl iso-butyl ketone (MIBK), stirring 1h, stand 1h, extracting and demixing, after discharging aqueous phase, organic facies is distilled at 117 DEG C, filtered while hot removes insoluble matter, gained filtrate is transferred to crystallization kettle, slowly regulation and control crystallization temperature is to 10 DEG C, add crystal seed, solution slowly separates out the crystallization of tetrabromobisphenol A diglycidyl ether, it is filtrated to get precipitation after hanging bag type centrifugal machine is centrifugal, precipitation is transferred to reactor decompression distillation, obtain water white Organic substance;
(4) the water white transparency Organic substance that cooling and solidifying step (3) obtains, then carries out pulverizing, packing.
It is 655 that above-mentioned steps obtains tetrabromobisphenol A diglycidyl ether mean molecule quantity, fusing point 115 ~ 118 DEG C, and tetrabromobisphenol A residual volume is ND, and colourity is 0.8(APHA).
Embodiment 3
The production method of a kind of high purity tetrabromobisphenol A bisglycidyl ether, comprises the following steps:
(1) etherification reaction: 2640.5kg tetrabromobisphenol a and 2750.1kg epoxychloropropane are put in reactor and be heated to 58 DEG C, dropping 121.0kg NaOH aqueous solution (NaOH is 58.1kg), react 4.5h;
(2) ring-closure reaction: vacuum is maintained at 24Kpa, and continuous heating, dropping 1212.3kg NaOH aqueous solution (NaOH is 581.9kg), keep thermotonus 5h, in this course of reaction, after epoxychloropropane is distilled out removing water layer, again it is back in reactor continue to participate in reaction;
(3) purify: decompression distills out unreacted epoxychloropropane, it is filled with nitrogen and removes vacuum, add 1770.4kg water and 2904.8kg methyl iso-butyl ketone (MIBK), stirring 1h, stand 1h, extracting and demixing, after discharging aqueous phase, organic facies is distilled at 118 DEG C, filtered while hot removes insoluble matter, gained filtrate is transferred to crystallization kettle, slowly regulation and control crystallization temperature is to 9 DEG C, add crystal seed, solution slowly separates out the crystallization of tetrabromobisphenol A diglycidyl ether, it is filtrated to get precipitation after hanging bag type centrifugal machine is centrifugal, precipitation is transferred to reactor decompression distillation, obtain water white Organic substance;
(4) the water white transparency Organic substance that cooling and solidifying step (3) obtains, then carries out pulverizing, packing.
It is 657 that above-mentioned steps obtains tetrabromobisphenol A diglycidyl ether mean molecule quantity, fusing point 120 ~ 122 DEG C, and tetrabromobisphenol A residual volume is ND, and colourity is 0.35(APHA).
Embodiment 4
The production method of a kind of high purity tetrabromobisphenol A bisglycidyl ether, comprises the following steps:
(1) etherification reaction: 145.5kg tetrabromobisphenol A and 161.8kg epoxychloropropane are put in reactor and be heated to 67 DEG C, dropping 8.4kg NaOH aqueous solution (NaOH is 4.1kg), react 4.5h;
(2) ring-closure reaction: vacuum is maintained at 28Kpa continuous heating, dropping 191.8kgNaOH aqueous solution (NaOH is 44.1kg), keep thermotonus 4.5h, in this course of reaction, after epoxychloropropane is distilled out removing water layer, be again back in reactor continue to participate in reaction;
(3) purify: decompression distills out unreacted epoxychloropropane, it is filled with nitrogen and removes vacuum, add 99.0kg water and 177.7kg methyl iso-butyl ketone (MIBK), stirring 1.5h, stand 1.5h, extracting and demixing, after discharging aqueous phase, organic facies is distilled at 118 DEG C, filtered while hot removes insoluble matter, gained filtrate is transferred to crystallization kettle, slowly regulation and control crystallization temperature is to 9 DEG C, add crystal seed, solution slowly separates out the crystallization of tetrabromobisphenol A diglycidyl ether, it is filtrated to get precipitation after hanging bag type centrifugal machine is centrifugal, precipitation is transferred to reactor decompression distillation, obtain water white Organic substance;
(4) the water white transparency Organic substance that cooling and solidifying step (3) obtains, then carries out pulverizing, packing.
It is 656 that above-mentioned steps obtains tetrabromobisphenol A diglycidyl ether mean molecule quantity, fusing point 120 ~ 122 DEG C, and tetrabromobisphenol A residual volume is ND, and colourity is 0.15(APHA).
Embodiment 5
The production method of a kind of high purity tetrabromobisphenol A bisglycidyl ether, comprises the following steps:
(1) etherification reaction: 8990kg tetrabromobisphenol A and 10338.5kg epoxychloropropane are put in reactor and be heated to 65 DEG C, dropping 430.7kg NaOH aqueous solution (NaOH is 206.1kg), react 4.5h;
(2) ring-closure reaction: vacuum is maintained at 21Kpa, and continuous heating, dropping 5056.9kg NaOH aqueous solution (NaOH is 2427.3kg), keep thermotonus 4h, in this course of reaction, after epoxychloropropane is distilled out removing water layer, again it is back in reactor continue to participate in reaction;
(3) purify: decompression distills out unreacted epoxychloropropane, it is filled with nitrogen and removes vacuum, add 5483.4kg water and 10788.7kg methyl iso-butyl ketone (MIBK), stirring 1h, stand 1h, extracting and demixing, after discharging aqueous phase, organic facies is distilled at 118 DEG C, filtered while hot removes insoluble matter, gained filtrate is transferred to crystallization kettle, slowly regulation and control crystallization temperature is to 11 DEG C, add crystal seed, solution slowly separates out the crystallization of tetrabromobisphenol A diglycidyl ether, it is filtrated to get precipitation after hanging bag type centrifugal machine is centrifugal, precipitation is transferred to reactor decompression distillation, obtain water white Organic substance;
(4) the water white transparency Organic substance that cooling and solidifying step (3) obtains, then carries out pulverizing, packing.
It is 656 that above-mentioned steps obtains tetrabromobisphenol A diglycidyl ether mean molecule quantity, fusing point 120 ~ 121 DEG C, and tetrabromobisphenol A residual volume is ND, and colourity is 0.05(APHA).
Claims (4)
1. the production method of a tetrabromobisphenol A bisglycidyl ether, it is characterized in that, comprise the following steps: (1) etherification reaction: tetrabromobisphenol A and epoxychloropropane are put in reactor for 1:0.8 ~ 1.2 in mass ratio and be heated to 50 ~ 70 DEG C, the aqueous solution of dropping initiator, reaction 4 ~ 5h, wherein, the mass ratio of tetrabromobisphenol A and initiator is 1:(0.02 ~ 0.03);
(2) ring-closure reaction: under vacuum condition, continues for heating, again drips the aqueous solution of initiator, keeps thermotonus 4 ~ 5h, in this course of reaction, is again back in reactor continue to participate in reaction after epoxychloropropane distills out removing water layer;Wherein, the initiator again added is (0.2 ~ 0.3) with the mass ratio of tetrabromobisphenol A: 1;
(3) purify: decompression distills out unreacted epoxychloropropane, after being filled with nitrogen removing vacuum, add water and methyl iso-butyl ketone (MIBK), stirring 1 ~ 2h, standing 1 ~ 2h, extracting and demixing, after discharging aqueous phase, organic facies being distilled at 110 ~ 120 DEG C, filtered while hot removes insoluble matter, and gained filtrate is transferred to crystallization kettle, slowly regulation and control crystallization temperature is to 0 ~ 35 DEG C, add crystal seed, solution slowly separates out the crystallization of tetrabromobisphenol A diglycidyl ether, after machine is centrifugal by centrifugation, is filtrated to get precipitation, precipitation is transferred to reactor decompression distillation, obtains water white Organic substance;Wherein, the water, the methyl iso-butyl ketone (MIBK) that add in extraction process are 0.6 ~ 0.7:1 ~ 1.3:1 with the mass ratio of tetrabromobisphenol A;
(4) the water white transparency Organic substance that cooling and solidifying step (3) obtains, then carries out pulverizing, packing.
The production method of a kind of tetrabromobisphenol A bisglycidyl ether the most according to claim 1, it is characterised in that the aqueous solution of the initiator added in described step (1) and step (2) is NaOH aqueous solution.
The production method of a kind of tetrabromobisphenol A bisglycidyl ether the most according to claim 1, it is characterised in that in described step (2), the vacuum of vacuum condition is 15 ~ 30Kpa.
The production method of a kind of tetrabromobisphenol A bisglycidyl ether the most according to claim 1, it is characterised in that the centrifuge in described step (3) is hanging bag type centrifugal machine.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109456464A (en) * | 2018-12-13 | 2019-03-12 | 山东鲁源化工科技有限公司 | A kind of synthetic method for the tetrabromo bisphenol-a epoxy resin that coloration is low, transparency is high |
CN109608618A (en) * | 2018-12-13 | 2019-04-12 | 山东鲁源化工科技有限公司 | A kind of preparation method of low molecular weight tetrabromo bisphenol-a epoxy resin |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1039601A (en) * | 1988-07-20 | 1990-02-14 | 三井石油化学工业株式会社 | Polyhydroxypolyether, and manufacture method thereof and purposes |
CN102234256A (en) * | 2010-04-30 | 2011-11-09 | 本州化学工业株式会社 | Novel diepoxide |
CN104592168A (en) * | 2013-10-30 | 2015-05-06 | 青岛旺裕橡胶制品有限公司 | Preparation method fire retardant tetrabromobisphenol A bis-glycidyl ether |
-
2016
- 2016-05-09 CN CN201610301702.2A patent/CN105968071A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1039601A (en) * | 1988-07-20 | 1990-02-14 | 三井石油化学工业株式会社 | Polyhydroxypolyether, and manufacture method thereof and purposes |
CN102234256A (en) * | 2010-04-30 | 2011-11-09 | 本州化学工业株式会社 | Novel diepoxide |
CN104592168A (en) * | 2013-10-30 | 2015-05-06 | 青岛旺裕橡胶制品有限公司 | Preparation method fire retardant tetrabromobisphenol A bis-glycidyl ether |
Non-Patent Citations (6)
Title |
---|
于棚: "溴化环氧树脂的合成与性能研究", 《中国学位论文全文数据库》 * |
成乐琴等: "四溴双酚A双缩水甘油醚的合成研究", 《合成化学》 * |
梁平辉: "高纯度双酚A二缩水甘油醚的分离制备", 《热固性树脂》 * |
贾修伟等: "反应型阻燃剂四溴双酚A双缩水甘油醚的精制", 《河南大学学报(自然科学版)》 * |
贾修伟等: "四溴双酚A二缩水甘油醚的合成", 《河南化工》 * |
贾修伟等: "四溴双酚A二缩水甘油醚的合成与表征", 《河南大学学报(自然科学版)》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109456464A (en) * | 2018-12-13 | 2019-03-12 | 山东鲁源化工科技有限公司 | A kind of synthetic method for the tetrabromo bisphenol-a epoxy resin that coloration is low, transparency is high |
CN109608618A (en) * | 2018-12-13 | 2019-04-12 | 山东鲁源化工科技有限公司 | A kind of preparation method of low molecular weight tetrabromo bisphenol-a epoxy resin |
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