CN1594425A - Epoxy resin complex with long chemical storage stability and temperature thixotropy - Google Patents
Epoxy resin complex with long chemical storage stability and temperature thixotropy Download PDFInfo
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- CN1594425A CN1594425A CN 200410020896 CN200410020896A CN1594425A CN 1594425 A CN1594425 A CN 1594425A CN 200410020896 CN200410020896 CN 200410020896 CN 200410020896 A CN200410020896 A CN 200410020896A CN 1594425 A CN1594425 A CN 1594425A
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Abstract
The invention discloses a category of epoxy resin complexes with long chemical storage stability and temperature thixotropy characterized in that the complexes are prepared by charging acetyl acetone lanthanides group transition metal complexes, methyl tetrohydrogen orthophthalic acid anhydride, silicane coupling agent, nano silica into epoxy resin base through uniform dispersion. The prepared resin system has good wettability with the reinforced material.
Description
Technical field
The invention belongs to the polymer material science technical field.Disclose a class and had long-term chemical stability in storage and the thixotropic Resins, epoxy compound of temperature.Specially refer to the Resins, epoxy compound that satisfies preimpregnation wet method fiber winding technology technology.
Background technology
Resins, epoxy is the thermosetting polymer synthetic materials that a class has performances such as good bonding, corrosion-resistant, electric insulation, high strength.It has been widely used in the manufacturing of multiple metal and nonmetallic bonding, corrosion resistant coating, insulating material, glass reinforced plastic/matrix material etc.It plays important effect in electronics, electric, machinofacture, chemical anticorrosion, aerospace, ship and other many industrial circles, become indispensable base mateiral in each industrial circle.Resins, epoxy just after becoming crosslinked three dimensional structure under the solidifying agent effect, could show its inherent premium properties.The normally used solidifying agent of Resins, epoxy has amine, anhydrides and synthetic resin etc.Because solidifying than amine, acid anhydride curable epoxy resin has excellent more dynamo-electric thermal characteristics, so use more extensive in recent years.Especially in fiber winding technology technology.But need higher curing reaction temperature and long curing reaction time.Therefore, for save energy and enhancing productivity, do promotor with tertiary amine and derivative thereof usually, yet this has shortened the storage usage period of system again greatly.There are many people to develop some new promotor in recent years and comprise phenol derivatives, metallic compound etc.It is more that Japan TOKYO company is studied, and Japanese JP5-7123-248 mentions with the inner complex of lead, copper, vanadium etc. and do promotor in epoxy-resin systems.English Patent GB1,604,942 to mention at solvent-free insulated paint be that the Acetyl Acetone inner complex with zinc, aluminium, manganese is done latent curing promotor in epoxy-anhydride system.Chinese patent CN85102264A proposes for various types of curative systems promoter action is arranged with the promotor of rare earth organic compounds as the thermofixation of Resins, epoxy, improves thermofixation speed, shortens storing time.Can make epoxy-resin systems at room temperature have long-term chemical stability in storage.Chinese patent CN1156166A proposes to drop down the pasty state epoxyn that properties-correcting agent obtains having stable sag resistance with polybutyl terapthalate or its segmented copolymer as the anti-current of Resins, epoxy, but this technology is at high temperature to heat to make polybutyl terapthalate or its segmented copolymer be dissolved in Resins, epoxy, in this process, easy and the Resins, epoxy generation transesterification reaction of polybutyl terapthalate or its segmented copolymer, rheological property can not repeat.CN1348971A proposes high isotaxy polyphenyl glycidyl ether/epoxy-resin systems can form reversible gel, and has the rheological properties of reversible gel.Wang Xia etc. have reported a kind of nanometer SiO that uses
2Make the making method of Resins, epoxy rheology modifier.But all do not provide and have long-term chemical stability in storage and the thixotropic Resins, epoxy compound of temperature.
The preimpregnation wet processing is called wet method rewinding (wet-rerool) technology again.This technological synthesis the advantage of conventional wet winding process and dry method winding process, represented contemporary high performance composite fiber to twine the development trend of manufacturing technology.Its technical matters difficult point is to seek a kind of high thixotropic resin matrix prescription that has, and this resin system should reach following requirement: 1. better with the wetting property of strongthener; 2. when soak into finish after, resin viscosity when rolling has a mutation process, can reach bigger viscosity rapidly to satisfy the requirement of rolling; Viscosity changes less, that resin does not take place migration, adhesion when 3. storing; 4. the room temperature storage phase longer, volatile content is low as far as possible; 5. curing system has high reaction activity and high.Adopt this resin system lay-up, the preimpregnation yarn is made in rolling then, stores directly debatching winding during use down in room temperature (or low temperature).
Above-mentioned first three point requires just to be meant that resin matrix will have high thixotropic, be that the wetting property of collosol state and strongthener is good under certain condition, another kind of condition is next little needs of viscosity variation when satisfying rolling requirement and storage for gel state.2 of backs require resin matrix to have chemical stability when room temperature storage, solidify rapidly when reaching the curing reaction condition.
Summary of the invention
Purpose of the present invention just provides and a series ofly satisfies preimpregnation wet method winding process technology with having the thixotropic epoxy resin-base compound of long-term stability in storage and temperature.
The Resins, epoxy compound that technical solution of the present invention provides is directly to add liquid acid anhydride type curing agent, Acetyl Acetone lanthanide transition metal complex compound promotor (being called for short Mtacac), silane coupling agent and nano silicon in epoxy resin-base.Used Resins, epoxy is general bisphenol A type epoxy resin, and wherein Acetyl Acetone lanthanide transition metal complex compound is a kind of latent curing promotor of Resins, epoxy, and its adding makes whole resin system have secular chemical stability.Nano-silica surface have great amount of hydroxy group can be each other or and Resins, epoxy between form intermolecular hydrogen bonding, under low-temperature condition, form gel state.When temperature reaches one regularly, intermolecular hydrogen bonding destroys, and whole resinite is tied to form collosol state, recovers trickling, thereby satisfies the needs of fiber impregnation.When temperature reduced once more, hydrogen bond recovered the resin system gel state, and viscosity changes less, that resin does not take place migration, adhesion during storage.The liquid acid anhydride type curing agent is a methyl tetrahydrophthalic anhydride, and silane coupling agent is two kinds of γ-An Jibingjisanyiyangjiguiwan (be called for short KH-550) and γ-glycidyl ether oxygen propyl trimethoxy silicanes (abbreviation KH-560).
It is collosol state that its temperature thixotropy of Resins, epoxy compound provided by the present invention shows as in the time of 50-60 ℃, it when low temperature or normal temperature gel state, by adding latent curing promotor, it is not reacted with resin system before curing reaction temperature, reach solidification value and then interrogate tachy steroling.Can satisfy the requirement that the system room temperature storage phase is long, the system activity of curing reaction is high.Meet of the requirement of preimpregnation wet method winding technology with resin.
Preimpregnation wet method winding technology of the present invention is compared with the conventional dry winding process, and having preimpregnation material does not need low tempertaure storage, solidifies advantage such as need not pressurize.Compare advantage such as have again that wind-up speed is fast, winding path is stable, good operational environment and winding product quality fluctuation are little with the conventional wet winding process.
Preimpregnation wet method winding technology of the present invention is compared with the conventional wet winding technology, can reduce and accurately control gel content, reduce the generation of resin and fiber waste-material, compare with the dry method winding process, do not need the autoclave cure under pressure, in addition, this preimpregnation technology is solvent-free in prepreg process, need not the solvent recuperation treatment system.Therefore can obviously reduce production costs, also be a kind of low-cost manufacturing technique.
Effect of the present invention and benefit are that preparation process is directly to add promotor in epoxy resin-base, and the back that stirs adds solidifying agent and coupling agent, adds nano silicon while stirring after stirring once more, and stirring is uniformly dispersed it and gets final product.Whole process does not need solvent, and temperature control can be below 100 ℃.Carry out the fiber preimpregnation with epoxy resin-base compound of the present invention, room temperature storage is after 60 days, still directly debatching.Reach the requirement of preimpregnation wet method winding technology.Resins, epoxy compound preparation process provided by the present invention is simple, need not solvent.Have secular chemical stability and temperature thixotropy, satisfy the preimpregnation wet method and twine the requirement of using resin matrix.
Embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme.
Embodiment 1
At E-51 epoxy resin-base (100%; below be mass ratio) the middle Acetyl Acetone lanthanide transition metal complex compound (0.2%～2.0%) that adds; under 85 ℃, stir evenly the back and add methyl tetrahydrophthalic anhydride (50%～80%) and silane resin acceptor kh-550 (0.5%～5.0%); be warming up to 90 ℃; add nano silicon (4%～20%) while stirring after stirring evenly evenly; whole then system continues to stir 5 hours, can obtain this Resins, epoxy compound.Glass fibre carries out fiber preimpregnation experiment, and after 50～60 ℃ of following thermostatically heating 10-20 minutes, dipping continuous glass fibre or carbon fiber or aramid fiber 30-60S soak into back continuous fibre prepreg and naturally cool to room temperature, rolling with resin matrix.Room temperature storage is directly debatching after 60 days.Viscosity changes less, that resin does not take place migration, adhesion during storage.Can satisfy of the requirement of preimpregnation wet method winding technology with resin matrix.Under 150 ℃～180 ℃ high temperature, can crosslinking curing, generate and have the insoluble infusible cured article of good dynamo-electric thermal characteristics, thereby satisfy the demand of multiple industrial circle.
Embodiment 2
At E-51 epoxy resin-base (100%; below be mass ratio) the middle Acetyl Acetone lanthanide transition metal complex compound (0.2%～2.0%) that adds; under 85 ℃, stir evenly the back and add methylhexahydrophthalic anhydride (50%～80%) and silane resin acceptor kh-550 (0.5%～5.0%); be warming up to 90 ℃; add nano silicon (4%～20%) while stirring after stirring evenly evenly; whole then system continues to stir 5 hours, can obtain this Resins, epoxy compound.Glass fibre carries out fiber preimpregnation experiment, and after 50～60 ℃ of following thermostatically heating 10-20 minutes, dipping continuous glass fibre or carbon fiber or aramid fiber 30-60S soak into back continuous fibre prepreg and naturally cool to room temperature, rolling with resin matrix.Room temperature storage is directly debatching after 60 days.Viscosity changes less, that resin does not take place migration, adhesion during storage.Can satisfy of the requirement of preimpregnation wet method winding technology with resin matrix.Under 150 ℃～180 ℃ high temperature, can crosslinking curing, generate and have the insoluble infusible cured article of good dynamo-electric thermal characteristics, thereby satisfy the demand of multiple industrial circle.
Embodiment 3
At E-51 epoxy resin-base (100%; below be mass ratio) the middle Acetyl Acetone lanthanide transition metal complex compound (0.2%～2.0%) that adds; under 85 ℃, stir evenly the back and add methyl tetrahydrophthalic anhydride (50%～80%) and silane coupling agent KH-560 (1.0%～4.0%); be warming up to 90 ℃; add nano silicon (4%～20%) while stirring after stirring evenly evenly; whole then system continues to stir 5 hours, can obtain this Resins, epoxy compound.Glass fibre carries out fiber preimpregnation experiment, and after 50～60 ℃ of following thermostatically heating 10-20 minutes, dipping continuous glass fibre or carbon fiber or aramid fiber 30-60S soak into back continuous fibre prepreg and naturally cool to room temperature, rolling with resin matrix.Room temperature storage is directly debatching after 60 days.Viscosity changes less, that resin does not take place migration, adhesion during storage.Can satisfy of the requirement of preimpregnation wet method winding technology with resin matrix.Under 150 ℃～180 ℃ high temperature, can crosslinking curing, generate and have the insoluble infusible cured article of good dynamo-electric thermal characteristics, thereby satisfy the demand of multiple industrial circle.
Embodiment 4
At E-54 epoxy resin-base (100%; below be mass ratio) the middle Acetyl Acetone lanthanide transition metal complex compound (0.2%～2.0%) that adds; under 85 ℃, stir evenly the back and add methyl tetrahydrophthalic anhydride (50%～80%) and silane coupling agent KH-560 (1.0%～4.0%); be warming up to 90 ℃; add nano silicon (4%～20%) while stirring after stirring evenly evenly; whole then system continues to stir 5 hours, can obtain this Resins, epoxy compound.Glass fibre carries out fiber preimpregnation experiment, and after 50～60 ℃ of following thermostatically heating 10-20 minutes, dipping continuous glass fibre or carbon fiber or aramid fiber 30-60S soak into back continuous fibre prepreg and naturally cool to room temperature, rolling with resin matrix.Room temperature storage is directly debatching after 60 days.Viscosity changes less, that resin does not take place migration, adhesion during storage.Can satisfy of the requirement of preimpregnation wet method winding technology with resin matrix.Under 150 ℃～180 ℃ high temperature, can crosslinking curing, generate and have the insoluble infusible cured article of good dynamo-electric thermal characteristics, thereby satisfy the demand of multiple industrial circle.
Claims (4)
1. one kind has long-term chemical stability in storage and the thixotropic Resins, epoxy compound of temperature; it is characterized in that: in epoxy resin-base, added Acetyl Acetone lanthanide transition metal complex compound promotor, liquid acid anhydride type curing agent respectively; they can be methyl tetrahydrophthalic anhydride or methylhexahydrophthalic anhydride or methyl carbic anhydride; silane coupling agent; they can be KH-550 or KH-560 and A-380 type nano silicon, and various material blend disperse.
2. a kind of have long-term chemical stability in storage and the thixotropic Resins, epoxy compound of temperature according to claim 1, it is characterized in that: 100 part (100% of content of epoxy resin, below be mass ratio), promotor is lanthanide transition metal complex compound consumption 0.2-2.0 part, anhydride curing agent is methyl tetrahydrophthalic anhydride consumption 50-80 part, silane coupling agent is KH-550 or KH-560 consumption 0.5-5.0 part, nano silicon consumption 4-20 part.
3. a kind of have long-term chemical stability in storage and the thixotropic Resins, epoxy compound of temperature according to claim 1, it is characterized in that: 100 part (100% of content of epoxy resin, below be mass ratio), promotor is lanthanide transition metal complex compound consumption 0.2-2.0 part, anhydride curing agent is methylhexahydrophthalic anhydride consumption 50-80 part, silane coupling agent is KH-550 or KH-560 consumption 0.5-5.0 part, nano silicon consumption 4-20 part.
4. a kind of have long-term chemical stability in storage and the thixotropic Resins, epoxy compound of temperature according to claim 1, it is characterized in that: 100 part (100% of content of epoxy resin, below be mass ratio), promotor is lanthanide transition metal complex compound consumption 0.2-2.0 part, methyl carbic anhydride solidifying agent is consumption 50-80 part, silane coupling agent is KH-550 or KH-560 consumption 0.5-5.0 part, nano silicon consumption 4-20 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100208966A CN1320020C (en) | 2004-07-02 | 2004-07-02 | Epoxy resin complex with long chemical storage stability and temperature thixotropy |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100208966A CN1320020C (en) | 2004-07-02 | 2004-07-02 | Epoxy resin complex with long chemical storage stability and temperature thixotropy |
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| CN1594425A true CN1594425A (en) | 2005-03-16 |
| CN1320020C CN1320020C (en) | 2007-06-06 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101313005B (en) * | 2005-09-02 | 2011-06-08 | 新日铁化学株式会社 | Epoxy resin composition |
| CN101466761B (en) * | 2006-04-12 | 2012-06-13 | 东洋制罐株式会社 | Oxygen-absorbing resin, oxygen-absorbing resin compositions and oxygen-absorbing containers |
| US8470918B2 (en) | 2005-09-30 | 2013-06-25 | Sumitomo Bakelite Co., Ltd. | Epoxy resin composition and semiconductor device |
| CN106751460A (en) * | 2016-11-17 | 2017-05-31 | 无锡市长安曙光手套厂 | One kind preimpregnation wet method pressure stochastic distribution |
| CN106738446A (en) * | 2016-11-17 | 2017-05-31 | 无锡市长安曙光手套厂 | One kind preimpregnation wet method pressure stochastic distribution |
| CN106905659A (en) * | 2017-01-22 | 2017-06-30 | 江苏恒神股份有限公司 | A kind of winding resin of NOL rings tensile strength high |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3624032A (en) * | 1969-04-24 | 1971-11-30 | Morton Int Inc | Epoxy compositions cured with carboxylic acid anhydrides and metallic salt of acetylacetone |
| JPS5026599B2 (en) * | 1972-10-02 | 1975-09-02 | ||
| CN1003896B (en) * | 1985-04-01 | 1989-04-12 | 菲利普光灯制造公司 | Colour kinescope |
| CN85102264B (en) * | 1985-04-01 | 1987-10-14 | 中国科学院长春应用化学研究所 | Organic compounds of rare-earth elements used as hot curing promoter of epoxy resin |
| JPS62227923A (en) * | 1986-03-31 | 1987-10-06 | Toshiba Corp | Epoxy resin composition |
| JPH06192396A (en) * | 1992-12-25 | 1994-07-12 | Nissan Chem Ind Ltd | One pack type epoxy resin composition |
| CN1181038C (en) * | 2002-12-20 | 2004-12-22 | 中国科学院广州化学研究所 | Method of catalyzing esterification of carboxylic acid and expoxy compound |
| CN100335574C (en) * | 2003-02-21 | 2007-09-05 | 中国科学院等离子体物理研究所 | High-strength epoxy impregnating varnish capable of using at ultra-low temp. and its preparation and application method |
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2004
- 2004-07-02 CN CNB2004100208966A patent/CN1320020C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101313005B (en) * | 2005-09-02 | 2011-06-08 | 新日铁化学株式会社 | Epoxy resin composition |
| US8470918B2 (en) | 2005-09-30 | 2013-06-25 | Sumitomo Bakelite Co., Ltd. | Epoxy resin composition and semiconductor device |
| CN101466761B (en) * | 2006-04-12 | 2012-06-13 | 东洋制罐株式会社 | Oxygen-absorbing resin, oxygen-absorbing resin compositions and oxygen-absorbing containers |
| CN106751460A (en) * | 2016-11-17 | 2017-05-31 | 无锡市长安曙光手套厂 | One kind preimpregnation wet method pressure stochastic distribution |
| CN106738446A (en) * | 2016-11-17 | 2017-05-31 | 无锡市长安曙光手套厂 | One kind preimpregnation wet method pressure stochastic distribution |
| CN106905659A (en) * | 2017-01-22 | 2017-06-30 | 江苏恒神股份有限公司 | A kind of winding resin of NOL rings tensile strength high |
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| Publication number | Publication date |
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| CN1320020C (en) | 2007-06-06 |
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