CN1467237A - Modified cyanate ester resin and preparation method and uses thereof - Google Patents
Modified cyanate ester resin and preparation method and uses thereof Download PDFInfo
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- CN1467237A CN1467237A CNA031145256A CN03114525A CN1467237A CN 1467237 A CN1467237 A CN 1467237A CN A031145256 A CNA031145256 A CN A031145256A CN 03114525 A CN03114525 A CN 03114525A CN 1467237 A CN1467237 A CN 1467237A
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- acid ester
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Abstract
A modified cyanate ester resin which is a low-viscosity liquid at ordinary temp and its preparing process are disclosed. It has higher comprehensive property and lower viscosity, so it can be shaped by RTM technology and ordinary temp.
Description
One, technical field:
The present invention relates to a kind of modified cyanic acid ester resin and its production and application, is a kind of low viscosity modified cyanic acid ester resin of liquid that at room temperature is specifically.Modified cyanic acid ester resin is specially adapted to resin transfer moulding (RTM) technological forming goods, and can be applied to fields such as electromagnetic wave transparent material, mechanical structure material.
Two, technical background:
In the prior art, acid ester resin has good thermotolerance, dielectric properties, mechanical property etc., and it and Resins, epoxy, bimaleimide resin belong to high performance reisn base material.Structured material, electromagnetic wave transparent material, adhesives, dielectric function material etc. be can be applied to and aerospace field, electronic information field etc. are applied to.
Because the development of advanced composite material technology of preparing-resin transfer molding (RTM) process (RTM), people have tended to come the moulding cyanate ester resin composite material with RTM technology.The cyanate resin alicyclic monomer generally is xln or semisolid under normal conditions, but under its molten state, it has lower viscosity, and (viscosity is generally 100～1000cPas).This low viscosity characteristics satisfies RTM and requires the characteristics of the resin matrix viscosity of institute's moulding less than 1000cPas, makes cyanate ester resin can adopt the RTM technological forming.
Comparatively simple RTM can be by synthetic cyanate ester monomer product and the performed polymer product thereof that obtains of industry with the cyanate ester resin matrix, as long as earlier resin matrix is heated to it more than fusing point, it is changed into by crystal form or semi-solid state liquidly just can carry out the RTM technological operation and come moulded products.Resin matrix also can be epoxide modified cyanate or bi-maleimide modified cyanate ester resin.Modified resin equally also requires to be heated it earlier more than the fusing point when carrying out the RTM technological operation, change liquid resin into after, carry out the RTM technological operation again and come moulded products.Because these RTM resin matrixes all will be operated under the condition of heating, this will increase extra energy, and make operation become complicated.
Three, summary of the invention:
The object of the present invention is to provide a kind of liquid low viscous modified cyanic acid ester resin that at room temperature is, it can directly use the RTM technological forming.
Another object of the present invention provides the preparation method of modified cyanic acid ester resin.
Another object of the present invention provides the application in Composite Preparation technology-resin transfer molding (RTM) process of modified cyanic acid ester resin.
For achieving the above object, the technical solution used in the present invention is:
A kind of modified cyanic acid ester resin, its special character is: the compositing formula of described modified cyanic acid ester resin matrix and proportioning: (b is a weight unit)
Cyanate 30～70b vinylbenzene 0～50b Vinylstyrene 0～50b
Above-mentioned cyanate is bisphenol A-type, bis-phenol L type cyanate, or its prepolymer.
Above-mentioned vinylbenzene is vinylbenzene, o-methyl styrene, a vinyl toluene, p-methylstyrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene, to t-butyl styrene, to the mixture of chloro-styrene or their arbitrary proportion.
Above-mentioned Vinylstyrene is for being ortho position, a position, contraposition Vinylstyrene, and methyl or ethyl replace Vinylstyrene and composition thereof.
The compositing formula of above-mentioned modified cyanic acid ester resin matrix adds stablizer, catalyzer and initiator.
A kind of preparation method of modified cyanic acid ester resin, its special character is:
The preparation method of modified resin cyanate is as follows:
At first cyanate ester monomer is heated to more than the fusing point, makes it change liquid state into, under condition of stirring, add vinylbenzene and the Vinylstyrene that is pre-mixed then, after waiting to stir, add an amount of stablizer, and make its naturally cooling, obtain the liquid modified resin of a homogeneous phase.
The application of a kind of preparation method of modified cyanic acid ester resin in the RTM technological operation, its special character is:
The modified resin cyanate has viscosity characteristics and the under-stream period that satisfies RTM technological operation requirement under the room temperature, catalyzer and initiator can not need be dissolved in the modified resin by any solvent, generally before carrying out the RTM technological operation, directly add, can heat in case of necessity to promote its dissolving.
The present invention is with respect to prior art, and its advantage is as follows:
Modified cyanic acid ester resin has very well kept the resistance toheat of cyanate ester resin, and some mechanical property is increased, and water-intake rate is littler.This shows that modified cyanic acid ester resin of the present invention has reasonable over-all properties.Modified cyanic acid ester resin matrix of the present invention has lower viscosity characteristics, and the RTM technological operation that can use under the room temperature comes moulded products.
Four, embodiment:
In the present invention, the modified cyanic acid ester resin matrix mainly is made up of cyanate ester monomer and performed polymer thereof, vinylbenzene, Vinylstyrene.
Component cyanate ester monomer and performed polymer thereof can be: 4,4 '-two cyanate ester based-ditans, 4,4 '-two cyanate ester based-diphenylethanes (bis-phenol L type cyanate), 4,4 '-two cyanate ester based-diphenyl propanes (bisphenol A cyanate ester), it is two that (4-cyanate ester based-3, the 5-3,5-dimethylphenyl) propane, 2, two (the cyanate ester based phenyl of the 3-methyl-4-) propane of 2-, 2,2-two (4-cyanate ester based-3-tert-butyl-phenyl) third protective embankment, 2,2-two (4-cyanate ester based-the 3-tertiary butyl-6-aminomethyl phenyl) propane, 2,2-two (4-cyanate ester based-3-allyl phenyl) propane, 1,1-two (4-cyanate ester based-the 3-tertiary butyl-6-aminomethyl phenyl) butane, 1, two (the cyanate ester based phenyl of the 4-) hexanaphthenes of 1-, 1, two (4-cyanate-3-aminomethyl phenyl) hexanaphthenes of 1-, 1, two (4-cyanate-3-cyclohexyl-6-methyl) butane of 1-with and performed polymer etc., they also can mix use.
Component vinylbenzene has no particular limits, and can directly adopt industrial goods, also can the ortho position, the vinylbenzene that replaces such as a position, contraposition methyl, ethyl.
The Vinylstyrene of component has no particular limits, and can directly adopt industrial goods, and they are by ortho position, a position, contraposition Vinylstyrene, and methyl or ethyl replace Vinylstyrene and composition thereof.
In modified resin system, vinylbenzene and Vinylstyrene can reduce the viscosity of resin system, select proper proportion crystal form or semi-solid cyanate ester monomer can be converted into liquid state.And cyanate ester monomer and performed polymer thereof can provide high thermotolerance.Show that according to The experimental results the content of cyanate ester monomer and performed polymer thereof should be greater than 50% in the modified resin system, cured resin just has ideal thermotolerance (promptly having high glass transition) like this.In order to make modified resin can not make the thermotolerance of cyanate that the reduction of big spoke degree is arranged owing to the adding of the vinylbenzene of low heat resistant and Vinylstyrene, the viscosity of modified resin system is increased, and the content of cyanate ester monomer and performed polymer thereof should be between 30～70%.
The adding of Vinylstyrene is mainly used as linking agent, and it utilizes the addition reaction of two keys, forms crosslinked network-like polymkeric substance with vinylbenzene, to improve the thermotolerance and the mechanical property of polystyrene.The content of Vinylstyrene is generally between 0～40%.
The modified resin system that is grouped into by cyanate ester monomer and performed polymer thereof, vinylbenzene, three kinds of one-tenth of Vinylstyrene, it more than 40 ℃ the liquid resin of homogeneous, phase-splitting shape is but at room temperature can take place slowly, cyanate ester monomer easily from system crystallization settle.In order to eliminate this phase-splitting shape be, the stablizer that can in modified resin system, add, its effect is the electrostatic force that weakens between the cyanate functional group.Stablizer mainly is by containing heteroatomic micromolecular compounds such as aerobic, nitrogen, phosphorus, silicon.As ether compound, phenolic compound, aminated compounds, heterocyclic compound etc.The add-on of stablizer is generally between 0～5%.
Modified cyanic acid ester resin of the present invention need add catalyzer and initiator when solidifying.Catalyzer can the catalysis cyanate curing reaction, initiator mainly causes and styrene catalyzed and polyreaction Vinylstyrene.The catalyzer that adopts mainly be transition metal salt (octylate of zinc, tin, copper, cobalt etc., naphthenate, acetylacetonate etc.) with the hybrid catalyst system of nonyl phenol (referring to US 4,608,434), the active organic transition metal composition catalyst of UV-light is (referring to US 5,215,860), and organo-tin compound catalyzer etc.The add-on of catalyzer is 50～200ppm.The initiator that adopts mainly is peroxide compound and azo compound etc., as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dilauroyl peroxide, di-isopropyl peroxydicarbonate etc.The add-on of initiator is 0.1～5%.
The preparation method of modified resin cyanate of the present invention at first is heated to cyanate ester monomer more than the fusing point, make it change liquid state into, under condition of stirring, add vinylbenzene and the Vinylstyrene that is pre-mixed then, after waiting to stir, add an amount of stablizer, and make its naturally cooling, obtain the liquid modified resin of a homogeneous phase.This resin has viscosity characteristics and the under-stream period that satisfies RTM technological operation requirement under the room temperature.
Catalyzer and initiator can not need be dissolved in the modified resin by any solvent, generally directly add before carrying out the RTM technological operation, can heat in case of necessity to promote its dissolving.
Embodiment 1
Vinylbenzene and Vinylstyrene are pre-mixed in the ratio of 100: 30 parts (weight).Take by weighing 50 parts of (weight) dihydroxyphenyl propane cyanates with beaker, heating and stirring make its fusion in 85 ℃ of oil baths.The mixture that adds 33.3 parts of vinylbenzene and Vinylstyrene again after stirring, naturally cools to 55 ℃, adds 2% stablizer, and the back that stirs is chilled to room temperature naturally and promptly obtains modified cyanic acid ester resin.
Add organotin catalysts and initiator at above-mentioned modified cyanic acid ester resin, and with resin be heated to 40 ℃ with impel catalyzer and initiator the dissolving, pour into then in the glass mold that scribbles releasing agent in advance, the technology by 90 ℃/3h+110 ℃/2h+130 ℃/2h+150 ℃/2h+180 ℃/2h+200 ℃/1h in the electronics baking oven is cured processing.The performance of modified cyanic acid ester resin and cured article thereof is listed in table 1 and table 2.
Embodiment 2
Identical with embodiment 1, but the ratio of dihydroxyphenyl propane cyanate and vinylbenzene and divinyl benzol mixture is 65: 35.The performance of modified cyanic acid ester resin and cured article thereof sees Table 1 and table 2.
Comparative Examples
Take by weighing 100 parts of dihydroxyphenyl propane cyanates, in 85 ℃ of oil baths, after the heating fusion, add 1 part of organotin catalysts, pour in the glass mold that scribbles releasing agent in advance after stirring.Curing process is identical with embodiment 1.Its performance sees Table 2.
Table 1: modified cyanic acid ester resin is formed and performance.
| Embodiment 1 | Embodiment 2 | ||
| Resin is formed (weight) | Dihydroxyphenyl propane cyanate (A) | ????50 | ????50 |
| Vinylbenzene (B) | ????20 | ????18 | |
| Vinylstyrene (C) | ????13.3 | ????9 | |
| Stablizer (D) | ????2 | ????2 | |
| Organotin catalysts | ????0.01 | ????0.01 | |
| The dibenzoyl peroxide initiator | ????0.1 | ????0.1 | |
| Resin viscosity under the room temperature (cPas) | ????90 | ????95 | |
| The storage period of resin (my god) | ????20 | ????20 | |
| The formula of resin is done the phase *(hour) | ????72 | ????72 | |
*The time that resin can keep its low viscosity characteristics behind finger adding catalyzer and the initiator.
Table 2: the performance of modified cyanic acid ester resin cured article.
| Embodiment 1 | Embodiment 2 | Comparative Examples | |
| Second-order transition temperature (Tg, ℃) | ????216 | ????235 | ????258 |
| Heat-drawn wire (HDT, ℃) | ????186 | ????198 | ????224 |
| Flexural strength (MPa) | ????105 | ????103 | ????104 |
| Modulus in flexure (Gpa) | ????3.3 | ????3.1 | ????3.1 |
| Tensile strength (Mpa) | ????89 | ????88 | ????80 |
| Elongation at break (%) | ????2.31 | ????2.22 | ????1.29 |
| Shock strength (KJ/m 2) | ????7.6 | ????7.4 | ????6.0 |
| The water-intake rate of poach 48h (%) | ????0.66 | ????0.68 | ????1.24 |
From the result of embodiment and Comparative Examples as can be seen, modified cyanic acid ester resin of the present invention has very well kept the resistance toheat of cyanate ester resin, and some mechanical property is increased, and water-intake rate is littler.This shows that modified cyanic acid ester resin of the present invention has reasonable over-all properties.Modified cyanic acid ester resin matrix of the present invention has lower viscosity characteristics, and the RTM technological operation that can use under the room temperature comes moulded products.
Claims (7)
1, a kind of modified cyanic acid ester resin is characterized in that: the compositing formula of described modified cyanic acid ester resin matrix and proportioning: (b is a weight unit)
Cyanate 30～70b vinylbenzene 0～50b Vinylstyrene 0～50b
2, modified cyanic acid ester resin according to claim 1 is characterized in that: described cyanate is bisphenol A-type, bis-phenol L type cyanate, or its prepolymer.
3, modified cyanic acid ester resin according to claim 2, it is characterized in that: described vinylbenzene is vinylbenzene, o-methyl styrene, a vinyl toluene, p-methylstyrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene, to t-butyl styrene, to the mixture of chloro-styrene or their arbitrary proportion.
4, modified cyanic acid ester resin according to claim 3 is characterized in that: described Vinylstyrene is for being ortho position, a position, contraposition Vinylstyrene, and methyl or ethyl replace Vinylstyrene and composition thereof.
5, modified cyanic acid ester resin according to claim 4 is characterized in that: the compositing formula of described modified cyanic acid ester resin matrix adds stablizer, catalyzer and initiator.
6, a kind of preparation method of modified cyanic acid ester resin is characterized in that:
The preparation method of modified resin cyanate is as follows:
At first cyanate ester monomer is heated to more than the fusing point, makes it change liquid state into, under condition of stirring, add vinylbenzene and the Vinylstyrene that is pre-mixed then, after waiting to stir, add an amount of stablizer, and make its naturally cooling, obtain the liquid modified resin of a homogeneous phase.
7, the application of a kind of preparation method of modified cyanic acid ester resin in the RTM technological operation is characterized in that:
The modified resin cyanate has viscosity characteristics and the under-stream period that satisfies RTM technological operation requirement under the room temperature, catalyzer and initiator can not need be dissolved in the modified resin by any solvent, generally before carrying out the RTM technological operation, directly add, can heat in case of necessity to promote its dissolving.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB031145256A CN100341921C (en) | 2003-03-07 | 2003-03-07 | Modified cyanate ester resin and preparation method and uses thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031145256A CN100341921C (en) | 2003-03-07 | 2003-03-07 | Modified cyanate ester resin and preparation method and uses thereof |
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| CN1467237A true CN1467237A (en) | 2004-01-14 |
| CN100341921C CN100341921C (en) | 2007-10-10 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400572C (en) * | 2005-12-14 | 2008-07-09 | 浙江大学 | Polyurethane elastomer, dicyclopentadiene cyanate ester resin modifier and method for preparing the same |
| CN102399366A (en) * | 2011-09-28 | 2012-04-04 | 哈尔滨玻璃钢研究院 | Preparation method for liquid cyanate resin |
| CN101822132B (en) * | 2007-10-16 | 2012-12-26 | 住友电木株式会社 | Substrate with semiconductor element mounted thereon |
| CN104249512A (en) * | 2013-06-28 | 2014-12-31 | 深圳光启创新技术有限公司 | Cyanate ester resin compound, composite substrate and manufacturing method of composite substrate |
| CN104987670A (en) * | 2015-07-14 | 2015-10-21 | 苏州科淼新材料有限公司 | Wear-resistant composite material |
| CN105038225A (en) * | 2015-07-28 | 2015-11-11 | 苏州科淼新材料有限公司 | Preparation method of high-hardness composite board |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0378103A3 (en) * | 1989-01-11 | 1991-12-27 | The Dow Chemical Company | Cyanate ester resin blends with brominated styrene containingpolymers |
-
2003
- 2003-03-07 CN CNB031145256A patent/CN100341921C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400572C (en) * | 2005-12-14 | 2008-07-09 | 浙江大学 | Polyurethane elastomer, dicyclopentadiene cyanate ester resin modifier and method for preparing the same |
| CN101822132B (en) * | 2007-10-16 | 2012-12-26 | 住友电木株式会社 | Substrate with semiconductor element mounted thereon |
| CN102399366A (en) * | 2011-09-28 | 2012-04-04 | 哈尔滨玻璃钢研究院 | Preparation method for liquid cyanate resin |
| CN102399366B (en) * | 2011-09-28 | 2013-07-03 | 哈尔滨玻璃钢研究院 | Preparation method for liquid cyanate resin |
| CN104249512A (en) * | 2013-06-28 | 2014-12-31 | 深圳光启创新技术有限公司 | Cyanate ester resin compound, composite substrate and manufacturing method of composite substrate |
| CN104987670A (en) * | 2015-07-14 | 2015-10-21 | 苏州科淼新材料有限公司 | Wear-resistant composite material |
| CN105038225A (en) * | 2015-07-28 | 2015-11-11 | 苏州科淼新材料有限公司 | Preparation method of high-hardness composite board |
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| Publication number | Publication date |
|---|---|
| CN100341921C (en) | 2007-10-10 |
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