CN1371930A - Process for preparing outdoor weathe resistance epoxy resin - Google Patents
Process for preparing outdoor weathe resistance epoxy resin Download PDFInfo
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- CN1371930A CN1371930A CN 01108250 CN01108250A CN1371930A CN 1371930 A CN1371930 A CN 1371930A CN 01108250 CN01108250 CN 01108250 CN 01108250 A CN01108250 A CN 01108250A CN 1371930 A CN1371930 A CN 1371930A
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- epoxy
- epoxy resin
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- chloride
- bromide
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Abstract
The maleopimaric acid triglyceride synthesized by utilizing reaction of rosin derivative maleopimarix anhydride and epoxy chloropropane is used as main resin, and more than one kind of glycidic ether (ester or amine) type adjuvant containing C2-C25 aliphatic and alicyclic carbonchain skeletal structure are added, then the above-mentioned materials are undergone the process of chemical modification treatment so as to can obtain the invented new-type epoxy resin composition with excellent outdoor weather resistance and thick alicyclic structure. Said epoxy resin composition is specially suitable for making outdoor weather-resisting electronic insulating material, also can be used as weather-resisting adhesive, epoxy resin paint and water epoxy resin coating material.
Description
The present invention relates to a class prepares outdoor weathe resistance epoxy resin from the rosin derivative maleopimaric anhydride method.
This method is to be matrix resin with rosin derivative maleopimaric anhydride and epichlorohydrin reaction synthetic maleopimaric acid three-glycidyl ester, contains C by more than one
2～C
25The glycidyl ether of aliphatics, alicyclic carbon-chain structure (ester or amine) analog assistant prepares the neo-epoxy resin constituent that a class has thick alicyclic structure through chemical modification.
The cured article of solidifying agent such as this epoxy resin component and methyl hexahydrophthalic anhydride confirms to have excellent ultraviolet light stability, weather resistance through weathering test, be specially adapted to pour into a mould, electrical insulating materials such as moulding processs such as automatic pressure gel injection and mold pressing are made high-voltage switch gear, transformer, mutual inductor and insulator that the electrician trade outdoor environment uses down, insulating sleeve, also can be as application such as Weather-resistant epoxy tackiness agent, epoxy resin-based paint and aqueous epoxide resin paints.
Usually the Resins, epoxy that contains the saturated fat ring structure can absorb by anti-sunlight middle-ultraviolet lamp, and ultraviolet light stability is good, has the outdoor weatherability energy.At present, the outdoor weathe resistance epoxy resin of external development mainly is by cyclohexyl compound (as cyclohexanediol, cyclohexane diacid, Hydrogenated Bisphenol A etc.) or derivatives thereof and epichlorohydrin reaction synthetic, and the cycloaliphatic epoxides of being made through the superoxide oxidation by unsaturated cyclohexyl compound or derivatives thereof is also arranged.Because above outdoor Resins, epoxy is made raw materials used being difficult for and obtained, on manufacturing process, acquire a certain degree of difficulty, and price is very high, thereby is difficult to the large-scale popularization application.
Purpose of the present invention and task are from the renewable natural resource of the inexpensive rosin of China's abundant, with its derivative maleopimaric anhydride is main raw material, prepare the novel epoxy resin component of a class by easier synthetic and method of modifying, so that it obtains to use in weathering resistance material out of doors with thick alicyclic structure.
Compared with prior art, characteristics of the present invention are to have made full use of the rosin natural resource to enrich inexpensive advantage and the peculiar thick alicyclic ring cage construction feature of molecular structure thereof, and institute's synthetic Resins, epoxy has more excellent weather resistance.
The synthetic used catalyzer of general formula I Resins, epoxy of the present invention comprises having: quaternary ammonium salt is (as tetramethyl ammonium chloride, 4 bromide, etamon chloride, tetraethylammonium bromide, tetrabutylammonium chloride, Tetrabutyl amonium bromide, benzyl trimethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, methyl trioctylphosphine ammonium chloride, methyl trioctylphosphine brometo de amonio, palmityl trimethyl ammonium chloride, quaternary alkylammonium halides salt such as cetyl trimethylammonium bromide), tertiary amines is (as N, accelerine, N, the N-Diethyl Aniline, N, the N-dimethyl benzylamine, N, N-diethyl benzylamine etc.), boron trifluoride based compound (as boron trifluoride diethyl etherate etc.), metal halide is (as zinc chloride, iron(ic) chloride, aluminum chloride, tin chloride etc.), catalyst levels is 0～5%, preferentially selects the quaternary ammonium salt of catalytic amount for use.Catalytic reaction temperature range is 50～120 ℃, and the reaction times is more than 0.5 hour.
The synthetic used basic cpd of general formula I Resins, epoxy includes: strong alkali compound (as sodium hydroxide, potassium hydroxide etc.), alkaline carbonate (as yellow soda ash, salt of wormwood etc.), consumption is 0.8～1.5 times of theoretical amount, preferentially selects the strong alkali compound (as sodium hydroxide, potassium hydroxide etc.) of 1.2～1.5 times of theoretical amount for use.Range of reaction temperature is normal temperature～120 ℃, and the reaction times is more than 0.5 hour.
R in general formula I I～V modified additive
1, R
2, R
3, R
4For containing C
2～C
25The monobasic of aliphatics, alicyclic carbochain, binary or polyvalent alcohol (acid or amine) class group.The consumption of auxiliary agent is 0～250 weight % of general formula I Resins, epoxy.
Adopting the epoxy resin component oxirane value of the method for the invention preparation is 0.25～0.50eq/100g, and maximum output reaches 90～100%.
Following example has more clearly been described three kinds of approach that the present invention prepares epoxy resin component.
Embodiment 1
Maleopimaric anhydride (1 mole), epoxy chloropropane (being no less than 3 moles), water (1 mole), catalyzer (quaternary ammonium salt, tertiary amines, boron trifluoride based compound and metal halide etc.) 0.05～5%, stir, heat, reaction is extremely complete more than 0.5 hour under 50～120 ℃ of temperature.The remaining epoxy chloropropane of reaction is reclaimed in underpressure distillation, add an amount of solvent (benzene, toluene etc.) dissolving, a ℃ following gradation adds solid alkaline compound (sodium hydroxide, potassium hydroxide or yellow soda ash, salt of wormwood etc.) or dripping alkali liquid in normal temperature～120, consumption is 0.8～1.5 times of theoretical amount, keep this temperature more than 0.5 hour to reacting completely.Then, filter and wash to neutral, vacuum distillation recovered solvent.At last, under agitation add 0～250 weight % and contain C
2～C
25The glycidyl ether of aliphatics, alicyclic carbochain (ester or amine) analog assistant makes light yellow transparent epoxy resin constituent.
Embodiment 2
Maleopimaric anhydride (1 mole) adds in equivalent such as the embodiment 1 described alkali lye, is stirred to dissolving fully.Then in oven dry more than 100 ℃, porphyrize.Add epoxy chloropropane (being no less than 3 moles), solvent (benzene, toluene etc.) is an amount of, and catalyzer and consumption be as described in the embodiment 1, under 50～120 ℃ of temperature, stirring reaction more than 0.5 hour to fully.Then, filter and wash, vacuum distillation recovered solvent and reaction residual epoxide chloropropane to neutral.At last, under agitation add, make light yellow transparent epoxy resin constituent as auxiliary agent as described in the embodiment 1.
Embodiment 3
Maleopimaric anhydride (1 mole), epoxy chloropropane (being no less than 3 moles), as catalyzer 0～5% as described in the embodiment 1, solvent (benzene, toluene etc.) is an amount of, stirs, heating.Under 50～120 ℃ of temperature, by embodiment 1 described alkali and consumption gradation or be added dropwise to reaction solution, keep this temperature reaction more than 0.5 hour to fully.Then, filter and wash, vacuum distillation recovered solvent and reaction residual epoxide chloropropane to neutral.Under agitation add at last as auxiliary agent as described in the embodiment 1, make light yellow transparent epoxy resin constituent.
The epoxy resin component that adopts the method for the invention to make has excellent weather resistance, can be used for fields such as outdoor weatherability electrical insulating material, epoxy adhesive, epoxy resin-based paint and aqueous epoxide resin paint.
Claims (9)
1. be matrix resin with general formula I maleopimaric acid three-glycidyl ester, adopt auxiliary agent to prepare the epoxy resin component that a class has thick alicyclic structure through chemical modification as general formula I I～V.
2. the method for claim 1 is a raw material with the rosin derivative maleopimaric anhydride, and is synthetic as general formula I Resins, epoxy with epichlorohydrin reaction.
3. as claim 1,2 described methods, general formula I Resins, epoxy synthetic can by maleopimaric anhydride and epoxy chloropropane under the effect of catalyzer and basic cpd by three kinds of approach realizations.
4. as the described method of claim 1～3, the synthetic used catalyzer of general formula I Resins, epoxy comprises having: quaternary ammonium salt is (as tetramethyl ammonium chloride, 4 bromide, etamon chloride, tetraethylammonium bromide, tetrabutylammonium chloride, Tetrabutyl amonium bromide, benzyl trimethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammoinium chloride, benzyl triethyl ammonium bromide, methyl trioctylphosphine ammonium chloride, methyl trioctylphosphine brometo de amonio, palmityl trimethyl ammonium chloride, quaternary alkylammonium halides salt such as cetyl trimethylammonium bromide), tertiary amines is (as N, accelerine, N, the N-Diethyl Aniline, N, the N-dimethyl benzylamine, N, N-diethyl benzylamine etc.), boron trifluoride based compound (as boron trifluoride diethyl etherate etc.), metal halide is (as zinc chloride, iron(ic) chloride, aluminum chloride, tin chloride etc.), catalytic reaction temperature range is 50～120 ℃, and the reaction times is more than 0.5 hour.
5. as the described method of claim 1～3, the synthetic used basic cpd of general formula I Resins, epoxy includes: strong alkali compound (as sodium hydroxide, potassium hydroxide etc.), alkaline carbonate (as yellow soda ash, salt of wormwood etc.), range of reaction temperature is normal temperature～120 ℃, and the reaction times is more than 0.5 hour.
6. the method for claim 1 is as R in the modified additive of general formula I I～V
1, R
2, R
3, R
4For containing C
2～C
25The monobasic of aliphatics, alicyclic carbochain, binary or polyvalent alcohol (acid or amine) class group.
7. as claim 1,6 described methods are 0～250 weight % of general formula I Resins, epoxy as the consumption of general formula I I～V modified additive.
8. as the described method of claim 1～7, the cured article of solidifying agent such as prepared epoxy resin component and methyl hexahydrophthalic anhydride has excellent ultraviolet light stability and weather resistance.
9. as described in the claim 1～8, moulding processs such as prepared epoxy resin component is specially adapted to pour into a mould, automatic pressure gel injection and mold pressing are made electrical insulating materials such as high-voltage switch gear, transformer, mutual inductor and insulator that the electrician trade outdoor environment uses down, insulating sleeve, also can be as application such as Weather-resistant epoxy tackiness agent, epoxy resin-based paint and aqueous epoxide resin paints.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01108250 CN1371930A (en) | 2001-02-27 | 2001-02-27 | Process for preparing outdoor weathe resistance epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01108250 CN1371930A (en) | 2001-02-27 | 2001-02-27 | Process for preparing outdoor weathe resistance epoxy resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1371930A true CN1371930A (en) | 2002-10-02 |
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ID=4657131
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01108250 Pending CN1371930A (en) | 2001-02-27 | 2001-02-27 | Process for preparing outdoor weathe resistance epoxy resin |
Country Status (1)
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|---|---|
| CN (1) | CN1371930A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353555B (en) * | 2008-07-18 | 2011-04-27 | 中国科学院广州化学研究所 | Flame-retardant rosin epoxide resin and preparation thereof |
| CN102234268A (en) * | 2011-01-04 | 2011-11-09 | 南京工业大学 | Method for preparing ultraviolet (UV)-curable polyisocyanate modified superbranched epoxy acrylate |
| CN102675130A (en) * | 2011-11-04 | 2012-09-19 | 江苏泰特尔化工有限公司 | Phase-transfer catalyst quaternary ammonium salt and preparation method thereof |
| CN102702525A (en) * | 2012-06-21 | 2012-10-03 | 东莞市信诺橡塑工业有限公司 | Biological based long-carbon-chain semi-alicyclic polyamidoimide copolymer and synthetic method of copolymer |
| CN103382378A (en) * | 2013-07-23 | 2013-11-06 | 张运泉 | Weather-resistant epoxy adhesive |
| CN107459608A (en) * | 2017-09-14 | 2017-12-12 | 中国林业科学研究院林产化学工业研究所 | A kind of acrylic acid rosin based high molecular surfactant and its production and use |
| CN112341603A (en) * | 2020-10-28 | 2021-02-09 | 衡阳拓创聚合新材料有限公司 | Halogen-free flame-retardant rosin-based epoxy resin and preparation method thereof |
| CN114929810A (en) * | 2019-10-14 | 2022-08-19 | 瀚森公司 | Glycidyl esters of alpha, alpha-branched acids from renewable sources and formulations thereof |
-
2001
- 2001-02-27 CN CN 01108250 patent/CN1371930A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101353555B (en) * | 2008-07-18 | 2011-04-27 | 中国科学院广州化学研究所 | Flame-retardant rosin epoxide resin and preparation thereof |
| CN102234268A (en) * | 2011-01-04 | 2011-11-09 | 南京工业大学 | Method for preparing ultraviolet (UV)-curable polyisocyanate modified superbranched epoxy acrylate |
| CN102234268B (en) * | 2011-01-04 | 2013-10-30 | 南京工业大学 | Method for preparing ultraviolet (UV)-curable polyisocyanate modified superbranched epoxy acrylate |
| CN102675130A (en) * | 2011-11-04 | 2012-09-19 | 江苏泰特尔化工有限公司 | Phase-transfer catalyst quaternary ammonium salt and preparation method thereof |
| CN102702525A (en) * | 2012-06-21 | 2012-10-03 | 东莞市信诺橡塑工业有限公司 | Biological based long-carbon-chain semi-alicyclic polyamidoimide copolymer and synthetic method of copolymer |
| CN103382378A (en) * | 2013-07-23 | 2013-11-06 | 张运泉 | Weather-resistant epoxy adhesive |
| CN107459608A (en) * | 2017-09-14 | 2017-12-12 | 中国林业科学研究院林产化学工业研究所 | A kind of acrylic acid rosin based high molecular surfactant and its production and use |
| CN107459608B (en) * | 2017-09-14 | 2020-03-24 | 中国林业科学研究院林产化学工业研究所 | Acrylic acid rosin-based high-molecular surfactant and preparation method and application thereof |
| CN114929810A (en) * | 2019-10-14 | 2022-08-19 | 瀚森公司 | Glycidyl esters of alpha, alpha-branched acids from renewable sources and formulations thereof |
| CN112341603A (en) * | 2020-10-28 | 2021-02-09 | 衡阳拓创聚合新材料有限公司 | Halogen-free flame-retardant rosin-based epoxy resin and preparation method thereof |
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