CN105175363A - Preparation method of epoxy cyclohexylmethyl-3,4-(methyl)acrylate - Google Patents
Preparation method of epoxy cyclohexylmethyl-3,4-(methyl)acrylate Download PDFInfo
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- CN105175363A CN105175363A CN201510732070.0A CN201510732070A CN105175363A CN 105175363 A CN105175363 A CN 105175363A CN 201510732070 A CN201510732070 A CN 201510732070A CN 105175363 A CN105175363 A CN 105175363A
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- methyl
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- vinylformic acid
- acrylate
- carbon
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004593 Epoxy Substances 0.000 title abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 150000002576 ketones Chemical class 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 239000012429 reaction media Substances 0.000 claims abstract description 5
- 238000000605 extraction Methods 0.000 claims abstract description 4
- -1 (methyl) vinylformic acid ester Chemical class 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- OXQXGKNECHBVMO-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound C1C(C(=O)O)CCC2OC21 OXQXGKNECHBVMO-UHFFFAOYSA-N 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical group 0.000 abstract description 2
- 239000012425 OXONE® Substances 0.000 abstract 1
- ILHCNKVSURBSFC-UHFFFAOYSA-N cyclohexen-1-ylmethyl but-2-enoate Chemical compound CC=CC(=O)OCC1=CCCCC1 ILHCNKVSURBSFC-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 abstract 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 238000005809 transesterification reaction Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- HVAZUMBELNLIGM-UHFFFAOYSA-N cyclohex-3-en-1-ylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1CCC=CC1 HVAZUMBELNLIGM-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- NPDDCAZCWJWIBW-UHFFFAOYSA-N dioxiran-3-one Chemical compound O=C1OO1 NPDDCAZCWJWIBW-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
Abstract
The invention relates to a preparation method of epoxy cyclohexylmethyl-3,4-(methyl)acrylate. The invention is characterized in that the method comprises the following steps: carrying out ester exchange on 3-cyclohexenyl-1-methanol and methyl(ethyl) (methyl)acrylate used as raw materials to obtain an intermediate cyclohexenylmethyl-3-(methyl)acrylate; carrying out C=C selective epoxidation reaction under milder reaction conditions by using potassium monopersulfate as an oxidizer and low-carbon-number ketone as a reaction medium; and after the reaction finishes, carrying out extraction, distillation and the like to obtain the product. Compared with the traditional method, the method provided by the invention is simple to operate, and has the advantages of favorable reaction selectivity and high product yield and purity.
Description
[technical field]
The present invention relates to one (methyl) vinylformic acid-3, the preparation method of 4-epoxycyclohexanecarboxylate, first, with 3-tetrahydrobenzene-1-methyl alcohol and (methyl) vinylformic acid ester of low-carbon alcohol for raw material, organotin is catalyzer, adopts ester-interchange method to obtain intermediate (methyl) vinylformic acid-3-cyclohexenyl methyl esters, then, employing potassium hydrogen persulfate is oxygenant, and low carbon number ketone is reaction medium, carries out the obtained target product of selective epoxidation reaction.
[background technology]
(methyl) vinylformic acid-3,4-epoxycyclohexanecarboxylate is a kind of novel organic multi-functional polymerization single polymerization monomer, owing to containing the allyl double bonds of active epoxy base and polymerizability in its molecule, can be used for preparing the chemical such as anticorrosive additive material (particularly solder resist material), agricultural chemicals, medicine intermediate, softening agent, binding agent, coating resin and pressure sensitive adhesive.
The committed step of preparation (methyl) vinylformic acid-3-cyclohexenyl methyl esters is the epoxidization reaction process of intermediate (methyl) vinylformic acid-3-cyclohexenyl methyl esters, owing to containing two carbon-carbon double bonds in its molecule, therefore this reaction is the reaction of a kind of selective epoxidation, higher to the requirement of oxygenant and reaction conditions, the key of epoxidation reaction is the selection of epoxidation reagent.
Usually, epoxidised for olefinic double bond oxygenant can be used for mainly contain organic peroxide acid and hydrogen peroxide.People use organic peroxide acid as the selective epoxidation agent (Chem.Ber., 1985,118,1267-1270) of diolefine, but the oxidisability of peroxy acid is comparatively strong, causes selective oxidizing poor.Therefore, organic peroxide acid is only suitable for the epoxidation of monoolefine, is not suitable for the selective epoxidation of diolefin.In addition, reaction can generate with a large amount of organic acid by-product.
Hydrogen peroxide is a kind of environmental type oxygenant, and it is cheap and easy to get, but during for epoxidation reaction of olefines, usually the material adopting quaternary ammonium salt etc. to have phase transition ability is needed to make catalyzer (CN201180012600.4), this kind of catalyzer not only has phase transition ability, and there is high surface, cause product separation difficulty, also there is the not high problem of selective oxidizing simultaneously.
Also someone adopts organic peroxy ketone to be the epoxidation that oxygenant carries out alkene, achieves good result (JOrgChem, 2003,68 (17): 6576-6582), but this oxygenant is unstable, and valency is high is not easy to obtain.The research of this respect relates generally to the epoxidation reaction of monoolefine.
[summary of the invention]
The present invention proposes the novel preparation method of one (methyl) vinylformic acid-3,4-epoxycyclohexanecarboxylate.The method first with 3-tetrahydrobenzene-1-methyl alcohol and (methyl) vinylformic acid ester of low-carbon alcohol for raw material, organotin is catalyzer, ester-interchange method is adopted to obtain intermediate (methyl) vinylformic acid-3-cyclohexenyl methyl esters, then, employing potassium hydrogen persulfate is oxygenant, low carbon number ketone is reaction medium, carries out the obtained target product of selective epoxidation reaction.
The object of the invention is the preparation method that have developed one (methyl) vinylformic acid-3,4-epoxycyclohexanecarboxylate.It is cheap and easy to get that the method has raw material, simple to operate, good reaction selectivity, and product yield is high, transesterification catalyst can repeat the features such as reuse.Overcome that the reaction preference existed in traditional method is poor, the shortcoming such as raw material valency is highly not easy to obtain, product separation difficulty.
Temperature of reaction described in the inventive method is preferentially selected within the scope of-10 ~ 60 DEG C, more preferably selects within the scope of 0 ~ 30 DEG C.Potassium hydrogen persulfate and (methyl) vinylformic acid-3-cyclohexenyl methyl ester intermediate mol ratio are generally 0.5 ~ 3.0:1, are preferably 1.0 ~ 2.0:1.
[technical scheme]
The present invention addresses these problems by the following technical programs, first, with 3-tetrahydrobenzene-1-methyl alcohol and (methyl) vinylformic acid ester of low-carbon alcohol for raw material, organotin is catalyzer, ester-interchange method is adopted to obtain intermediate (methyl) vinylformic acid-3-cyclohexenyl methyl esters, then, potassium hydrogen persulfate cheap and easy to get is adopted to be oxygenant, low carbon number ketone is reaction medium, at a certain temperature, stirring reaction certain hour, carbon-carbon double bond on cyclohexenyl in intermediate molecule is carried out selective epoxidation reaction, after reaction terminates, through extraction, the operations such as distillation obtain product.
The reaction principle related in the present invention is as follows:
The first step: transesterification reaction
R=CH
3or H
Second step: selective epoxidation reacts
R=CH
3or H
Present method is realized by following steps:
First, catalyzer, stopper, (methyl) methyl acrylate and 3-tetrahydrobenzene-1-methyl alcohol are joined in reactor according to a certain percentage, stirring reaction certain hour at a certain temperature.After reaction terminates, be separated by rectification under vacuum and obtain intermediate (methyl) vinylformic acid-3-cyclohexenyl methyl esters, at the bottom of still, residual (being mainly catalyzer and stopper) is without any process direct reuse.
Then, a certain amount of intermediate (methyl) vinylformic acid-3-cyclohexenyl methyl esters, organic ketone, sodium bicarbonate and hydrogen persulfate potassium solution are joined in reactor, at a certain temperature, stirring reaction certain hour.After reaction terminates, filter, add a certain amount of ethyl acetate and carry out extracting and separating in filtrate, organic phase is separated through underpressure distillation and obtains product (methyl) vinylformic acid-3,4-epoxycyclohexanecarboxylate.
Present method, compared with traditional method, is characterized in: (1) adopts potassium hydrogen persulfate to be epoxidizing agent, and low carbon number ketone is medium, and raw material is cheap and easy to get; (2) good reaction selectivity, product yield is high; (3) product separation process operation is simple; (3) catalyst for ester exchange reaction can repeat reuse.
Specific implementation method:
Below in conjunction with embodiment, method of the present invention is described further, but is not limitation of the invention.
Embodiment 1: transesterification reaction: 11.8g3-tetrahydrobenzene-1-methyl alcohol, 30.3g methyl methacrylate and 0.71g dibutyl tin laurate are added in reactor successively, reaction backflow 5h at 120 DEG C, after reaction terminates, underpressure distillation obtains intermediate methacrylic acid-3-cyclohexenyl methyl esters, the transformation efficiency of 3-tetrahydrobenzene-1-methyl alcohol is 99%, and reaction preference is 100%.
Epoxidation reaction: methacrylic acid-3-cyclohexenyl methyl ester intermediate 18g, 25.2gNaHCO that transesterification reaction is obtained
3, 46.1g potassium hydrogen persulfate, acetone 133.5g and a certain amount of deionized water be added in reactor successively, stirring reaction 5h at a certain temperature.After reaction terminates, reaction solution after filtration, extraction, the treating processes such as distillation, obtain colourless transparent liquid, methacrylic acid-3-cyclohexenyl methyl ester conversion rate reaches 99.2%, product selectivity 99.8%.
Embodiment 2: implementation condition and step are with case study on implementation 1, and the raw material methyl methacrylate just in epoxidation reaction changes methyl acrylate into, and the product obtained is vinylformic acid-3,4-epoxycyclohexanecarboxylate.Vinylformic acid-3-cyclohexenyl methyl ester conversion rate reaches 99.5%, and selectivity is 99.7%.
Embodiment 3 ~ 4: implementation condition and step, with case study on implementation 1, just change the methyl methacrylate in transesterification reaction into β-dimethyl-aminoethylmethacrylate and butyl methacrylate respectively, the results are shown in Table 1.
The reaction result of table 1 case study on implementation 3 ~ 4
Embodiment 5 ~ 6: implementation condition and step, with case study on implementation 1, just change the acetone in epoxidation reaction into butanone and pimelinketone respectively, the results are shown in Table 2.
The reaction result of table 2 case study on implementation 5 ~ 6
Embodiment 7 ~ 12: transesterification catalyst dibutyl tin laurate, with case study on implementation 1, is just changed into the transesterification catalyst reclaimed in embodiment 1 by implementation condition and step, carry out repeating reuse experiment for six times, reuse the results are shown in Table 3.
The reaction result of table 3 case study on implementation 7 ~ 12
Claims (3)
1. (methyl) vinylformic acid-3, the preparation method of 4-epoxycyclohexanecarboxylate, first, with 3-tetrahydrobenzene-1-methyl alcohol and (methyl) vinylformic acid ester of low-carbon alcohol for raw material, organotin is catalyzer, ester-interchange method is adopted to obtain intermediate (methyl) vinylformic acid-3-cyclohexenyl methyl esters, then, employing potassium hydrogen persulfate is oxygenant, low carbon number ketone is reaction medium, at a certain temperature, stirring reaction certain hour, carbon-carbon double bond on cyclohexenyl in intermediate molecule is carried out selective epoxidation reaction, after reaction terminates, through extraction, the operations such as distillation obtain product.
2. method according to claim 1, (methyl) vinylformic acid ester of low-carbon alcohol wherein used is (methyl) methyl acrylate, (methyl) ethyl propenoate or (methyl) butyl acrylate.
3. method according to claim 1, low carbon number ketone wherein used is acetone, butanone or pimelinketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510732070.0A CN105175363A (en) | 2015-10-31 | 2015-10-31 | Preparation method of epoxy cyclohexylmethyl-3,4-(methyl)acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510732070.0A CN105175363A (en) | 2015-10-31 | 2015-10-31 | Preparation method of epoxy cyclohexylmethyl-3,4-(methyl)acrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105175363A true CN105175363A (en) | 2015-12-23 |
Family
ID=54897882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510732070.0A Pending CN105175363A (en) | 2015-10-31 | 2015-10-31 | Preparation method of epoxy cyclohexylmethyl-3,4-(methyl)acrylate |
Country Status (1)
| Country | Link |
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| CN (1) | CN105175363A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047402A (en) * | 2017-12-18 | 2018-05-18 | 华东理工大学 | A kind of triblock copolymer and preparation method based on ATRP mechanism |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04279575A (en) * | 1991-03-07 | 1992-10-05 | Daicel Chem Ind Ltd | Epoxidized (meth)acrylate isomer and its production |
| EP0529197A1 (en) * | 1991-08-28 | 1993-03-03 | Daicel Chemical Industries, Ltd. | A process for the preparation of a purified 3,4-epoxycyclohexyl-methyl (meth)acrylate and a stabilised composition thereof |
| WO1998045349A2 (en) * | 1997-04-10 | 1998-10-15 | Sartomer Company, Inc. | Cycloaliphatic epoxides and the method for making the same |
| WO2001047907A1 (en) * | 1999-12-27 | 2001-07-05 | Asahi Kasei Kabushiki Kaisha | Ester containing alicyclic epoxy and process for producing the same |
| CN101472908A (en) * | 2006-06-23 | 2009-07-01 | 陶氏环球技术公司 | Process for producing epoxides from olefinic compounds |
| CN104428704A (en) * | 2012-07-02 | 2015-03-18 | 松下知识产权经营株式会社 | Optical waveguide and dry film for optical waveguide production |
-
2015
- 2015-10-31 CN CN201510732070.0A patent/CN105175363A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04279575A (en) * | 1991-03-07 | 1992-10-05 | Daicel Chem Ind Ltd | Epoxidized (meth)acrylate isomer and its production |
| EP0529197A1 (en) * | 1991-08-28 | 1993-03-03 | Daicel Chemical Industries, Ltd. | A process for the preparation of a purified 3,4-epoxycyclohexyl-methyl (meth)acrylate and a stabilised composition thereof |
| WO1998045349A2 (en) * | 1997-04-10 | 1998-10-15 | Sartomer Company, Inc. | Cycloaliphatic epoxides and the method for making the same |
| WO2001047907A1 (en) * | 1999-12-27 | 2001-07-05 | Asahi Kasei Kabushiki Kaisha | Ester containing alicyclic epoxy and process for producing the same |
| CN101472908A (en) * | 2006-06-23 | 2009-07-01 | 陶氏环球技术公司 | Process for producing epoxides from olefinic compounds |
| CN104428704A (en) * | 2012-07-02 | 2015-03-18 | 松下知识产权经营株式会社 | Optical waveguide and dry film for optical waveguide production |
Non-Patent Citations (5)
| Title |
|---|
| BATOG, A. E. ET AL: "Synthesis and structure of 1-acryloyloxymethyl- and 1-acetoxymethyl-3,4-epoxycyclohexanes", 《ZHURNAL ORGANICHESKOI KHIMII》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047402A (en) * | 2017-12-18 | 2018-05-18 | 华东理工大学 | A kind of triblock copolymer and preparation method based on ATRP mechanism |
| CN108047402B (en) * | 2017-12-18 | 2020-12-18 | 华东理工大学 | Triblock copolymer based on ATRP mechanism and preparation method thereof |
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Application publication date: 20151223 |