CN103819463A - Self-setting epoxy resin containing acid anhydride radicals and preparation method thereof - Google Patents
Self-setting epoxy resin containing acid anhydride radicals and preparation method thereof Download PDFInfo
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- CN103819463A CN103819463A CN201410014466.7A CN201410014466A CN103819463A CN 103819463 A CN103819463 A CN 103819463A CN 201410014466 A CN201410014466 A CN 201410014466A CN 103819463 A CN103819463 A CN 103819463A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4238—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof heterocyclic
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- Epoxy Resins (AREA)
Abstract
The invention relates to self-setting epoxy resin containing acid anhydride radicals and a preparation method thereof. The preparation method comprises the following steps: reacting 1 mol of unitary fatty acid containing conjugated double bonds with 6-10 mol of epoxy chloropropane in a proportion at a temperature of 100-120 DEG C for 2-6 h, cooling to a temperature of 20-60 DEG C, then adding 1 mol of solid sodium hydroxide and 0.001 mol of a phase transfer catalyst for a ring-closure reaction for 6-12 h, filtering and recycling excess epoxy chloropropane so as to obtain conjugated fatty acid glycidyl ester; enable 1 mol of the conjugated fatty acid glycidyl ester and 1 mol of maleic anhydride to perform a Diels-Alder diene addition reaction for 0.5-2 h at 90-110 DEG C so as to obtain the self-setting epoxy resin containing the acid anhydride radicals. Compared with a linear polymer formed in the prior art, the self-setting epoxy resin provided by the invention has mechanical properties of a thermosetting cross-linked polymer, and has higher modulus and strength after setting.
Description
Technical field
The present invention relates to a kind of preparation method of epoxy resin, relate in particular to a kind of self curable epoxy resin that simultaneously contains epoxy group(ing) and anhydride group and preparation method thereof.
Background technology
Epoxy resin is one of topmost thermosetting resin.And the application of epoxy resin generally all needs two components: epoxy resin and solidifying agent.Epoxy resin and solidifying agent by different chemical reactions, can be cross-linked with each other, thereby form high-intensity thermoset cured article after mixing.The kind of solidifying agent mainly contains amine, anhydrides and latent curing agent.In the mixing process of epoxy resin and solidifying agent, due to reasons such as the inhomogeneous or bubbles mixing, can cause in formed cured article and have some defects, and these defects tender spots of material just directly causes the too early destruction of material under stress.In addition, the viscosity ratio of some epoxy resin or solidifying agent is larger, need to add some organic solvents to dilute when blend, the volatilization meeting pollutant atmosphere of these organic solvents and being detrimental to health.For this reason, the epoxy curing systems of some single-components is invented, such as micro capsule curing agent.Micro capsule curing agent is that solidifying agent is wrapped in microcapsule, is uniformly distributed in epoxy resin.But microcapsule need certain condition to break, if broken not exclusively, also can cause mixing inhomogeneous, thereby cause solidifying inhomogeneous problem.
Therefore, if a kind of chemical substance can be stablized at normal temperatures, and the crosslinking reaction of self can occur under given conditions and form cured article, this just can reduce the cured article defect that the ununiformity in mixing process causes to greatest extent.Mikroyannidis has synthesized the epoxy compounds (J.A.Mikroyannidis of a series of self cure, Self-curing epoxy compounds, Journal of Applied Polymer Science, 1990,41,2613-2624.), these glycidyl ethers or glycidyl ester all contain carboxyl, amino or a phenolic hydroxyl group, thereby the in the situation that of heating, can make these compounds self that crosslinking reaction occurs, form polymkeric substance.But these compounds, owing to only containing an epoxy group(ing) and other active reactive groups, can only form linear polymeric after thermofixation, and can not form thermoset cross-linked polymkeric substance.
After the blend at normal temperatures of acid anhydride type curing agent and epoxy resin, if do not heated, be more stable.In use, be generally, after acid anhydrides and epoxy resin are mixed according to a certain percentage, to add micro-tertiary amine promotor, under the condition of heating, be cured.The present invention has provided a kind of epoxy compounds that contains anhydride group, this compound is low-viscosity (mobile) liquid at normal temperatures, adds after a small amount of promotor, the in the situation that of heating, can selfing be unified into a kind of thermoset cross-linked polymkeric substance, curing process is simple, the mechanical property excellence of cured article.
Summary of the invention
The technical problem solving: the invention provides a kind of self curable epoxy resin that contains anhydride group and preparation method thereof, this self curable epoxy resin does not need and solidifying agent blend while use, just can be under suitable condition, curing molding voluntarily
Technical scheme: a kind of self curable epoxy resin that contains anhydride group, structural formula is as follows:
The preparation method of the described self curable epoxy resin that contains anhydride group, step is: in proportion 1 mole of unary fatty acid that contains conjugated double bond is reacted to 2-6 hour with 6-10 moles of epichlorohydrin at 100-120 ℃, be cooled to 20-60 ℃, and then add the phase-transfer catalyst ring-closure reaction 6-12 hour of 1 mole of solid sodium hydroxide and 0.001 mole, filter and reclaim excessive epoxy chloropropane, obtain conjugated fatty acid glycidyl ester; 1 mole of conjugated fatty acid glycidyl ester carries out Diels-Alder Diene-addition with 1 mole of maleic anhydride at 90-110 ℃ again and reacts 0.5-2 hour, obtains a kind of self curable epoxy resin that contains anhydride group.
The described unary fatty acid that contains conjugated double bond is alpha-eleostearic acid, β-eleostearic acid or dehydrated castor oleic acid.
Described phase-transfer catalyst is benzyltriethylammoinium chloride.
Wherein the synthetic route as an example of alpha-eleostearic acid example is as follows:
Beneficial effect:
1. different from general epoxy resin, the epoxy resin of this self cure does not need and solidifying agent blend, just can be under suitable condition, and curing molding voluntarily.The epoxy resin of this self cure that compared with prior art, the present invention provides uses convenient.
2. compared with the linear polymer forming with prior art, after the epoxy resin cure of this self cure that the present invention provides, there is the mechanical characteristic of thermoset cross-linked polymkeric substance, there is higher modulus and intensity.
Accompanying drawing explanation
The nucleus magnetic resonance 1H spectrum of a kind of self curable epoxy resin that contains anhydride group preparing in Fig. 1 embodiment 1.
The nucleus magnetic resonance 13C spectrum of a kind of self curable epoxy resin that contains anhydride group preparing in Fig. 2 embodiment 1.
Embodiment
Following examples further illustrate content of the present invention, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, the modification that the inventive method, step or condition are done and replacement, all belong to scope of the present invention.If do not specialize, the conventional means that in embodiment, technique means used is well known to those skilled in the art.
Reagent used in embodiment: alpha-eleostearic acid is according to document (Hoffmann, J.S.; O'connor, R.T.; Heinzelman, D.C.; Bickford, W.G.J.Am.Oil.Chem.Soc., 1957,34,338-342.) preparation, dehydrated castor oleic acid (hydroxyl value is less than 10 for Shanghai Yi Yuan Chemical Co., Ltd., content 99%)
1 mole of alpha-eleostearic acid and 6 moles of epichlorohydrin are added to the there-necked flask that thermometer and reflux condensing tube are housed, be warming up to 117 ℃ of insulations 2 hours.Be cooled to 20 ℃, add the solid sodium hydroxide of 1 mole and the benzyltriethylammoinium chloride of 0.001 mole, stir 12 hours.Filter, obtain alpha-eleostearic acid glycidyl ester after reclaiming excessive epoxy chloropropane.Again with 1 mole of maleic anhydride of 1 mole of alpha-eleostearic acid glycidyl ester, 90 ℃ of reactions 2 hours, obtains a kind of self curable epoxy resin that contains anhydride group.
By the 2-ethyl-4-methylimidazole catalyst mix of 100 grams of the self curable epoxy resins that contains anhydride group obtaining in embodiment 1 and 0.1 gram, inject the V class mould according to ASTM D638 design, solidify 2 hours at 120 ℃, then carry out after fixing 4 hours at 160 ℃.After the demoulding, obtain 5 parallel battens, according to ASTM D638, batten is carried out to tension test.Experimental result is averaged, as shown in the table:
Table 1
1 mole of alpha-eleostearic acid and 6 moles of epichlorohydrin are added to the there-necked flask that thermometer and reflux condensing tube are housed, be warming up to 100 ℃ of insulations 6 hours.Be cooled to 60 ℃, add the solid sodium hydroxide of 1 mole and the benzyltriethylammoinium chloride of 0.001 mole, stir 6 hours.Filter, obtain alpha-eleostearic acid glycidyl ester after reclaiming excessive epoxy chloropropane.Again with 1 mole of maleic anhydride of 1 mole of alpha-eleostearic acid glycidyl ester, 110 ℃ of reactions 0.5 hour, obtains a kind of self curable epoxy resin that contains anhydride group.
1 mole of dehydrated castor oleic acid and 6 moles of epichlorohydrin are added to the there-necked flask that thermometer and reflux condensing tube are housed, be warming up to 117 ℃ of insulations 2 hours.Be cooled to 20 ℃, add the solid sodium hydroxide of 1 mole and the benzyltriethylammoinium chloride of 0.001 mole, stir 12 hours.Filter, obtain synourin oil glycidyl ester after reclaiming excessive epoxy chloropropane.Again with 1 mole of maleic anhydride of 1 mole of synourin oil glycidyl ester, 90 ℃ of reactions 2 hours, obtains a kind of self curable epoxy resin that contains anhydride group.
Claims (4)
1. contain a self curable epoxy resin for anhydride group, it is characterized in that structural formula is as follows:
2. described in claim 1, contain the preparation method of the self curable epoxy resin of anhydride group, it is characterized in that step is: in proportion, 1 mole of unary fatty acid that contains conjugated double bond is reacted to 2-6 hour with 6-10 moles of epichlorohydrin at 100-120 ℃, be cooled to 20-60 ℃, and then add the phase-transfer catalyst ring-closure reaction 6-12 hour of 1 mole of solid sodium hydroxide and 0.001 mole, filter and reclaim excessive epoxy chloropropane, obtain conjugated fatty acid glycidyl ester; 1 mole of conjugated fatty acid glycidyl ester carries out Diels-Alder Diene-addition with 1 mole of maleic anhydride at 90-110 ℃ again and reacts 0.5-2 hour, obtains a kind of self curable epoxy resin that contains anhydride group.
3. contain according to claim 2 the preparation method of the self curable epoxy resin of anhydride group, the unary fatty acid that contains conjugated double bond described in it is characterized in that is alpha-eleostearic acid, β-eleostearic acid or dehydrated castor oleic acid.
4. contain according to claim 2 the preparation method of the self curable epoxy resin of anhydride group, it is characterized in that described phase-transfer catalyst is benzyltriethylammoinium chloride.
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| CN201410014466.7A CN103819463B (en) | 2014-01-13 | 2014-01-13 | Self curable epoxy resin containing anhydride group and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146800A (en) * | 2016-06-30 | 2016-11-23 | 中国林业科学研究院林产化学工业研究所 | A kind of Oleum Verniciae fordii base flame retardant type polyamide curing agent and preparation method thereof |
| CN106749882A (en) * | 2016-12-15 | 2017-05-31 | 吴定财 | A kind of metal adhesive Nian Jie with silicon rubber and preparation method thereof |
| CN110092884A (en) * | 2019-04-28 | 2019-08-06 | 上海嘉宝莉涂料有限公司 | A kind of haze tallow oleoresin and high rigidity color inhibition wood wax oil |
| CN110105540A (en) * | 2019-05-08 | 2019-08-09 | 浙江大学 | A kind of preparation method of glycidyl ester type self curable epoxy resin |
| CN113248463A (en) * | 2021-06-03 | 2021-08-13 | 安徽农业大学 | Preparation method of tung oil-based fatty acid modified monomer, prepared tung oil-based fatty acid modified monomer and application thereof |
| CN113563564A (en) * | 2021-06-22 | 2021-10-29 | 中国林业科学研究院林产化学工业研究所 | Grease-based latent resin and preparation method and application thereof |
Citations (5)
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|---|---|---|---|---|
| US2865931A (en) * | 1953-11-03 | 1958-12-23 | Charles H Mack | Maleinated eleostearic acids |
| US2967837A (en) * | 1958-07-30 | 1961-01-10 | Tung Res And Dev League | Compositions and methods for curing epoxy resins |
| US3002950A (en) * | 1958-01-08 | 1961-10-03 | Devoe & Raynolds Co | Epoxidized adduct of a dicarboxylic acid and a trialkene, process of making and composition containing same |
| CN1631938A (en) * | 2004-11-29 | 2005-06-29 | 中国林业科学研究院林产化学工业研究所 | Method for producing low molecular polyamide from tung oi |
| CN101643452A (en) * | 2008-08-08 | 2010-02-10 | 夏恩将 | Method for preparing triglycidyl isocyanurate |
-
2014
- 2014-01-13 CN CN201410014466.7A patent/CN103819463B/en not_active Expired - Fee Related
Patent Citations (5)
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| US2865931A (en) * | 1953-11-03 | 1958-12-23 | Charles H Mack | Maleinated eleostearic acids |
| US3002950A (en) * | 1958-01-08 | 1961-10-03 | Devoe & Raynolds Co | Epoxidized adduct of a dicarboxylic acid and a trialkene, process of making and composition containing same |
| US2967837A (en) * | 1958-07-30 | 1961-01-10 | Tung Res And Dev League | Compositions and methods for curing epoxy resins |
| CN1631938A (en) * | 2004-11-29 | 2005-06-29 | 中国林业科学研究院林产化学工业研究所 | Method for producing low molecular polyamide from tung oi |
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Non-Patent Citations (5)
| Title |
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| W. G. BICKFORD，等: "The Infrared Spectra and the Structural Relationships Between Alpha- and Beta-Eleostearic Acids and Their Maleic Anhydride Adducts", 《THE JOURNAL OF THE AMERICAN 0IL CHEMISTS" SOCIETY》 * |
| 周尽花，等: "树脂催化合成桐酸甲酯-马来酸酐加合物", 《中南林业科技大学学报》 * |
| 聂小安，等: "C22三羧酸三缩水甘油酯型环氧树脂的研究", 《热固性树脂》 * |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146800A (en) * | 2016-06-30 | 2016-11-23 | 中国林业科学研究院林产化学工业研究所 | A kind of Oleum Verniciae fordii base flame retardant type polyamide curing agent and preparation method thereof |
| CN106749882A (en) * | 2016-12-15 | 2017-05-31 | 吴定财 | A kind of metal adhesive Nian Jie with silicon rubber and preparation method thereof |
| CN110092884A (en) * | 2019-04-28 | 2019-08-06 | 上海嘉宝莉涂料有限公司 | A kind of haze tallow oleoresin and high rigidity color inhibition wood wax oil |
| CN110092884B (en) * | 2019-04-28 | 2021-09-28 | 上海嘉宝莉涂料有限公司 | Wood wax oil resin and high-hardness yellowing-resistant wood wax oil |
| CN110105540A (en) * | 2019-05-08 | 2019-08-09 | 浙江大学 | A kind of preparation method of glycidyl ester type self curable epoxy resin |
| CN110105540B (en) * | 2019-05-08 | 2020-06-19 | 浙江大学 | Preparation method of glycidyl ester type self-curing epoxy resin |
| CN113248463A (en) * | 2021-06-03 | 2021-08-13 | 安徽农业大学 | Preparation method of tung oil-based fatty acid modified monomer, prepared tung oil-based fatty acid modified monomer and application thereof |
| CN113248463B (en) * | 2021-06-03 | 2023-09-05 | 安徽农业大学 | Preparation method of tung oil-based fatty acid modified monomer, prepared tung oil-based fatty acid modified monomer and application thereof |
| CN113563564A (en) * | 2021-06-22 | 2021-10-29 | 中国林业科学研究院林产化学工业研究所 | Grease-based latent resin and preparation method and application thereof |
| CN113563564B (en) * | 2021-06-22 | 2022-07-22 | 中国林业科学研究院林产化学工业研究所 | Grease-based latent resin, and preparation method and application thereof |
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