CN103145923A - Preparation method of polymerizable oligomer based on soybean oil route - Google Patents
Preparation method of polymerizable oligomer based on soybean oil route Download PDFInfo
- Publication number
- CN103145923A CN103145923A CN2013100392696A CN201310039269A CN103145923A CN 103145923 A CN103145923 A CN 103145923A CN 2013100392696 A CN2013100392696 A CN 2013100392696A CN 201310039269 A CN201310039269 A CN 201310039269A CN 103145923 A CN103145923 A CN 103145923A
- Authority
- CN
- China
- Prior art keywords
- preparation
- polymerizable oligomer
- soybean oil
- monomer
- prepared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a preparation method of polymerizable oligomer based on a soybean oil route. The preparation method of the polymerizable oligomer based on the soybean oil route comprises reacting epoxidation soybean oil fatty acid methyl ester and maleic anhydride at the temperature with a range of 90DEG C-120DEG C to form a single body with an unsaturated double-bond, and using diisocyanate to carry out chain extension and polymerization to form the polymerizable oligomer; and copolymerizing the polymerizable oligomer with styrene, acrylic ester and metacrylic acid ester to obtain a thermosetting material which is good in flexibility. According to the polymerizable oligomer obtained in the preparation method of the polymerizable oligomer based on the soybean oil route, a raw material is renewable vegetable oil, and therefore the polymerizable oligomer has the advantages of being low in cost and environment-friendly. Due to the fact that the structure of the polymerizable oligomer is a highly branched structure, the polymerizable oligomer is low in viscosity, and good in toughness.
Description
Technical field
The present invention relates to a kind of polymerizable oligomers preparation method for preparing, belong to the polymerizable oligomers preparation field.
Technical background
Soybean oil is the triglyceride quasi-grease that a class is extracted from soybean seeds.Wherein unsaturated fatty acids accounts for 35% ~ 45% left and right.Thereby soybean oil can be by to the modification of unsaturated double-bond and as the various chemical industry products of preparation.At present, be divided into to the glyceryl ester modification application with to the modification application of unsaturated fatty acids soybean oil modified.The modification of glyceryl ester is mainly prepared by hydrolytic action the lubricating oil that monoglyceride and Diglyceride are applied to machinofacture.It is efficient utilization to soybean oil that the modification of the unsaturated double-bond of soybean oil is prepared the chemical industry product.
At present, to soybean oil not mainly containing epoxidation modification, hydroxylation modification, carboxylic acid modification with two key modifications, and be applied in Synolac, urethane resin and some elastomer material.As Zhao Yuhua etc. (polyurethane industrial, 2007,22,3,1-4) summarized soybean oil hydroxylation modification application in urethane, and its special performance be discussed.Soybean oil has lower viscosity and the structure of long aliphatic chain, and has special applications in Photopolymer System.Having prepared epoxy soybean oil acrylate photo polymerization monomer as (Chinese oil, 2011,36, Isosorbide-5-Nitrae 5-49) such as Xiuyun Zhangs uses and the low viscosity system.The present invention utilizes the characteristic of the long aliphatic chain of soybean oil, and having prepared is the polymer coated photopolymerization oligopolymer that excellent toughness is provided.
Summary of the invention
The present invention is by will be by the epoxy soybean oleic acid methyl esters of soybean oil preparation, adopts maleic anhydride open loop oxygen and prepares and have the oligopolymer that polymerizable forms cross-linking polymer system.Concrete reaction process is as follows:
Concrete operation step is as follows:
1) oligomer based on soybean oil prepares: epoxidized fatty acid methyl esters and maleic anhydride are pressed the blend of 2:1 molar equivalent in there-necked flask, add catalyzer, add 0.1% MEHQ, be warming up to 90 ~ 120 ℃, reaction 4h ~ 6h;
2) monomer that step 1) is prepared and vulcabond react under 0.1% dibutyl tin laurate catalysis and form oligopolymer
3) with step 2) prepared oligopolymer and the monomer that contains unsaturated double-bond copolymerization under suitable initiator effect, preparation has the adjustable thermosetting resin of mechanical property.
Above-mentioned steps 1) catalyzer described in can be tetramethyl ammonium chloride, triethylamine, catalyst levels 0.05% ~ 0.15%;
Above-mentioned steps 2) monomer that contains unsaturated double-bond described in is vinylbenzene, vinylformic acid and esters of acrylic acid, methyl acrylic ester reactive monomer;
Above-mentioned steps 3) vulcabond described in can be hexamethylene-diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate.
Advantage of the present invention and innovative point
1) the present invention adopts renewable vegetables oil preparation and gets, and is with low cost;
2) the prepared polymerisable oligopolymer of the present invention has long aliphatic chain and a large amount of branched structure, can be the rear material of curing good toughness is provided;
3) the prepared polymerizable oligomers of the present invention can with multiple double bond containing monomer copolymerization, thereby can obtain the adjustable solidify material of mechanical property.
Specific embodiment
Embodiment one
1) epoxidized fatty acid methyl esters and maleic anhydride are pressed the blend of 2:1 molar equivalent in there-necked flask, add 0.05% catalyzer tetramethyl ammonium chloride, add 0.1% MEHQ, be warming up to 90 ℃, reaction 6h;
2) monomer that step 1) is prepared and hexamethylene-diisocyanate react under 0.1% dibutyl tin laurate catalysis and form oligopolymer
3) with step 2) prepared oligopolymer and vinylbenzene copolymerization under 0.1% initiator dibenzoyl peroxide causes, preparation has the adjustable thermosetting resin of mechanical property.
Embodiment two
1) epoxidized fatty acid methyl esters and maleic anhydride are pressed the blend of 2:1 molar equivalent in there-necked flask, add 0.05% catalyst of triethylamine, add 0.1% MEHQ, be warming up to 100 ℃, reaction 5h;
2) monomer that step 1) is prepared and hexamethylene-diisocyanate react under 0.1% dibutyl tin laurate catalysis and form oligopolymer;
3) with step 2) prepared oligopolymer and vinylformic acid copolymerization under 0.1% initiator dibenzoyl peroxide causes, preparation has the adjustable thermosetting resin of mechanical property.
Embodiment three
1) epoxidized fatty acid methyl esters and maleic anhydride are pressed the blend of 2:1 molar equivalent in there-necked flask, add 0.1% catalyzer tetramethyl ammonium chloride, add 0.1% MEHQ, be warming up to 120 ℃, reaction 4h;
2) monomer that step 1) is prepared and hexamethylene-diisocyanate react under 0.1% dibutyl tin laurate catalysis and form oligopolymer;
3) with step 2) prepared oligopolymer and methyl acrylate copolymerization under 0.1% initiator dibenzoyl peroxide causes, preparation has the adjustable thermosetting resin of mechanical property.
Embodiment four
1) epoxidized fatty acid methyl esters and maleic anhydride are pressed the blend of 2:1 molar equivalent in there-necked flask, add 0.15% catalyzer tetramethyl ammonium chloride, add 0.1% MEHQ, be warming up to 120 ℃, reaction 5h;
2) monomer that step 1) is prepared and hexamethylene-diisocyanate react under 0.1% dibutyl tin laurate catalysis and form oligopolymer;
3) with step 2) prepared oligopolymer and the copolymerization under 0.1% initiator dibenzoyl peroxide causes of diacrylate macrogol ester, preparation has the adjustable thermosetting resin of mechanical property.
Embodiment five
1) epoxidized fatty acid methyl esters and maleic anhydride are pressed the blend of 2:1 molar equivalent in there-necked flask, add 0.15% catalyzer tetramethyl ammonium chloride, add 0.1% MEHQ, be warming up to 120 ℃, reaction 5h;
2) monomer that step 1) is prepared and hexamethylene-diisocyanate react under 0.1% dibutyl tin laurate catalysis and form oligopolymer;
3) with step 2) prepared oligopolymer and methyl methacrylate copolymerization under 0.1% initiator dibenzoyl peroxide causes, preparation has the adjustable thermosetting resin of mechanical property.Embodiment six
1) epoxidized fatty acid methyl esters and maleic anhydride are pressed the blend of 2:1 molar equivalent in there-necked flask, add 0.15% catalyzer tetramethyl ammonium chloride, add 0.1% MEHQ, be warming up to 120 ℃, reaction 5h;
2) monomer that step 1) is prepared and tolylene diisocyanate react under 0.1% dibutyl tin laurate catalysis and form oligopolymer;
3) with step 2) prepared oligopolymer and methyl methacrylate copolymerization under 0.1% initiator dibenzoyl peroxide causes, preparation has the adjustable thermosetting resin of mechanical property.Embodiment seven
1) epoxidized fatty acid methyl esters and maleic anhydride are pressed the blend of 2:1 molar equivalent in there-necked flask, add 0.15% catalyzer tetramethyl ammonium chloride, add 0.1% MEHQ, be warming up to 120 ℃, reaction 5h;
2) monomer that step 1) is prepared and diphenylmethanediisocyanate react under 0.1% dibutyl tin laurate catalysis and form oligopolymer;
3) with step 2) prepared oligopolymer and methyl methacrylate copolymerization under 0.1% initiator dibenzoyl peroxide causes, preparation has the adjustable thermosetting resin of mechanical property.
Claims (4)
1. the present invention relates to a kind of method for preparing polymerizable oligomers based on the soybean oil route, its concrete operation step is as follows:
1) oligomer based on soybean oil prepares: epoxidized fatty acid methyl esters and maleic anhydride are pressed the blend of 2:1 molar equivalent in there-necked flask, add catalyzer, add 0.1% MEHQ, be warming up to 90 ~ 120 ℃, reaction 4h ~ 6h;
2) monomer that step 1) is prepared and vulcabond react under 0.1% dibutyl tin laurate catalysis and form oligopolymer;
3) with step 2) prepared oligopolymer and the monomer that contains unsaturated double-bond copolymerization under suitable initiator effect, preparation has the adjustable thermosetting resin of mechanical property.
2. preparation method according to claim 1, is characterized in that above-mentioned steps 1) described in catalyzer can be tetramethyl ammonium chloride, triethylamine, catalyst levels 0.05% ~ 0.15%.
3. preparation method according to claim 1, is characterized in that above-mentioned steps 2) described in vulcabond can be hexamethylene-diisocyanate, tolylene diisocyanate, diphenylmethanediisocyanate.
4. preparation method according to claim 1, is characterized in that above-mentioned steps 3) described in the monomer that contains unsaturated double-bond be vinylbenzene, vinylformic acid and esters of acrylic acid, methyl acrylic ester reactive monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310039269.6A CN103145923B (en) | 2013-01-31 | 2013-01-31 | Preparation method of polymerizable oligomer based on soybean oil route |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310039269.6A CN103145923B (en) | 2013-01-31 | 2013-01-31 | Preparation method of polymerizable oligomer based on soybean oil route |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103145923A true CN103145923A (en) | 2013-06-12 |
| CN103145923B CN103145923B (en) | 2015-05-06 |
Family
ID=48544276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310039269.6A Expired - Fee Related CN103145923B (en) | 2013-01-31 | 2013-01-31 | Preparation method of polymerizable oligomer based on soybean oil route |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103145923B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107266637A (en) * | 2017-06-28 | 2017-10-20 | 常州水精灵环保设备有限公司 | A kind of preparation method of fuel thickener |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007861A (en) * | 2006-12-20 | 2007-08-01 | 中国科学院山西煤炭化学研究所 | Process for synthesis of polymer polyhydric alcohol |
| CN101314632A (en) * | 2008-07-23 | 2008-12-03 | 广州市海珥玛植物油脂有限公司 | Method for preparing hard polyurethane foam plastics with soybean oil |
| US8048949B1 (en) * | 2004-05-07 | 2011-11-01 | Drexel University | Composite repair resins containing minimal hazardous air pollutants and volatile organic compound |
-
2013
- 2013-01-31 CN CN201310039269.6A patent/CN103145923B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8048949B1 (en) * | 2004-05-07 | 2011-11-01 | Drexel University | Composite repair resins containing minimal hazardous air pollutants and volatile organic compound |
| CN101007861A (en) * | 2006-12-20 | 2007-08-01 | 中国科学院山西煤炭化学研究所 | Process for synthesis of polymer polyhydric alcohol |
| CN101314632A (en) * | 2008-07-23 | 2008-12-03 | 广州市海珥玛植物油脂有限公司 | Method for preparing hard polyurethane foam plastics with soybean oil |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107266637A (en) * | 2017-06-28 | 2017-10-20 | 常州水精灵环保设备有限公司 | A kind of preparation method of fuel thickener |
| CN107266637B (en) * | 2017-06-28 | 2019-04-30 | 辽宁永润石油制品集团有限公司 | A kind of preparation method of fuel thickener |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103145923B (en) | 2015-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| NZ590875A (en) | Process for the continuous production of polyesters from cycli ester monomers in a continueous mixing loop reactor | |
| EP2094746A4 (en) | Thermoplastic resin having uniform composition and narrow molecular weight distribution, and method for preparing the same | |
| TW200833656A (en) | Acrylic acid and water-absorbing polymer structures based on renewable raw materials and process for their production by dehydration | |
| WO2003095499A1 (en) | Styrene polymer resin and composition thereof | |
| CN102702480B (en) | Modified epoxy acrylate and preparation method thereof | |
| WO2010086217A3 (en) | Cross-linkable, in water redispersible polymer powder compound | |
| JP2011522094A5 (en) | ||
| CN103980438A (en) | Preparation of UV cured soybean oil based composite resin | |
| CN104031205B (en) | A kind of bio-based Cured up resin and preparation method thereof | |
| DE502009000580D1 (en) | Pressure-sensitive adhesives and process for their preparation | |
| WO2012027246A3 (en) | Curable compositions with moisture-curable functionality clusters near the chain ends | |
| CN110396176A (en) | Vegetable oil-based epoxy acrylate resin and preparation method and application thereof | |
| JP2013189616A5 (en) | Method for producing polymer | |
| CN101225262B (en) | Fluorocarbon compound modified polyacrylate flow agent for coating ink and production method thereof | |
| CN103145923B (en) | Preparation method of polymerizable oligomer based on soybean oil route | |
| MX362063B (en) | Wellbore strengthening composition. | |
| CN107216419A (en) | A kind of method for preparing high concentration hydroxyl polyacrylic resin and its solidification | |
| CN107955113B (en) | A kind of flexible unsaturated polyester resin of no styrene and preparation method thereof | |
| CN109096430A (en) | A kind of novel reactive quadripolymer and preparation method thereof | |
| CN103664598B (en) | A kind of preparation method of vinylformic acid dicyclopentenyloxyethyl methacrylate | |
| CN104557537B (en) | In a kind of tower, reactive distillation produces the method for butyl acrylate | |
| CN110818837A (en) | Maleate polymer, waste edible oil coagulant and preparation method thereof | |
| CN101709205A (en) | Method for preparing degradable pressure-sensitive adhesive | |
| PL2222727T3 (en) | Production of solutions of vinyl polymers in reactive monomers | |
| CN105754046B (en) | A kind of preparation method of initiator microcapsules |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150506 Termination date: 20220131 |