CN101613459A - Cyanate resin composition and prepare application in the high modulus carbon fiber prepreg in hot melt process - Google Patents
Cyanate resin composition and prepare application in the high modulus carbon fiber prepreg in hot melt process Download PDFInfo
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- CN101613459A CN101613459A CN200910055180A CN200910055180A CN101613459A CN 101613459 A CN101613459 A CN 101613459A CN 200910055180 A CN200910055180 A CN 200910055180A CN 200910055180 A CN200910055180 A CN 200910055180A CN 101613459 A CN101613459 A CN 101613459A
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Abstract
The invention provides a kind of cyanate resin composition, form by cyanate or cyanate prepolymer, the Resins, epoxy of 30～10 weight % and the catalyzer of 100～500ppm of at least a 70～90 weight %.In addition, the invention provides the solvent-free high modulus carbon fiber prepreg that soaks into this cyanate resin composition down and form, this prepreg is in the operability of room temperature and good in the long lifetime property of room temperature, and the mechanical property of the cyanate/high modulus carbon fiber matrix material of or autoclave molding hot-forming through press significantly improves than corresponding epoxy/high modulus carbon fiber mechanical property.
Description
Technical field
The application that the present invention relates to a kind of cyanate resin composition and prepare high modulus carbon fiber prepreg in hot melt process especially provides and soaks into this cyanate resin composition under solvent-free, forms the preparation method of high modulus carbon fiber prepreg.
Background technology
Along with the continuous development of modern satellite technology, the structural system of satellite has special requirement to the rigidity and the thermal dimensional stability of structural part, thereby weight reduction, raising rigidity and thermal dimensional stability just become the key factor of enhancing product performance.High modulus carbon fiber strengthens advantages such as polymer matrix composites have specific tenacity, specific modulus height, dimensional stability is good, thermal expansivity is little, anti-space environment is good, is excellent structure candidate material of new generation.But because the high-modules carbon fibre smooth surface, active group is few, cause the interface binding ability of carbon fiber and resin relatively poor, so high modulus carbon fiber has special requirement to matrix resin.At present, the spacecraft structure of many developed countries is mostly selected the matrix resin of cyanate ester resin as high-modulus, ultra high modulus carbon-fibre composite for use, as the EX series of Bryte, 954 series of HEXEL etc. are widely used in the devices such as parabolic antenna, supporting structure, camera optics system.Cyanate ester resin is to contain in the molecule structure that (OCN) the performance resins system of group, (OCN) annulation can take place group, forms stable triazine structure under the effect of heat or catalyzer.The chemical structure of cyanate ester resin has determined it to have good heat resistance, characteristics such as rate of moisture absorption is low, and dimensional stability is good, and the radiation hardness ability is strong, can replace traditional Resins, epoxy, phenolic resin as matrix resin in aerospace with aspects such as materials, become performance resins matrix of new generation.
Domesticly over past ten years obtaining strong development aspect the study on the synthesis of cyanate ester resin, but rarely reporting in the engineering application facet, but more do not having the cyanate ester resin matrix of special-purpose hot melt dipping by today.Prepare high modulus carbon fiber prepreg with hot melt process, can make the product visual appearance better, reduced the influence of defective widely to composite element, the volatile content of prepreg is few simultaneously, unit surface fibre weight and matrix resin content control accuracy height have been saved solvent cost and to the pollution of environment with to the harm of human body.So, how to research and develop a kind of high-performance cyanate ester resin system that can be complementary, be suitable for carbon fiber hot melt process preimpregnated process that has with high modulus carbon fiber, give full play to high modulus carbon fiber high specific strength, high ratio modulus, strong corrosion resistant, the good low and programmable advantage of dimensional stability, thermal expansivity, have important science and construction value.
Summary of the invention
The purpose of this invention is to provide a kind of hot melt process that is applicable to and prepare the cyanate resin composition of high modulus carbon fiber prepreg.In order to reach this purpose, the technical scheme that the present invention takes is: a kind of cyanate resin composition, be made up of the cyanate ester resin of 70～90 weight %, the Resins, epoxy of 30～10 weight % and the catalyzer of 100～500ppm, described catalyzer is one or more of methyl ethyl diketone acid metal salt.
Cyanate is represented by formula I structure:
A
1-(OCN)
n
Formula I
Wherein, A
1Be aromatics or mixing aromatics-aliphatic alkyl, contain one or more atoms that are selected from oxygen, nitrogen, halogen, sulphur, phosphorus, boron, silicon, hydrogen and composition thereof; And n=2～5.
Described Resins, epoxy is phenol aldehyde type epoxy resin or bisphenol A type epoxy resin.
Metal in the described methyl ethyl diketone acid metal salt is selected from zinc, copper, manganese, cobalt, iron or nickel.
The softening temperature of said composition is at 30 ℃～40 ℃, its viscosity of 80 ℃ is 1500mPa.s～2500mPa.s, after 25 ℃ are placed 30 days 80 ℃ 2 times of viscosity increases or below it.And kept under 180 ℃ atmosphere 2000 seconds, viscosity reaches 1 * 10
6Pa.s.
In addition, the invention provides with hot melt process and soak into this cyanate resin composition and the high modulus carbon fiber prepreg that forms, suitable preimpregnation temperature is 85～105 ℃, suitable time 〉=2 hour.High modulus carbon fiber in its prepreg is that unidirectional paving forms, the mass content of the cyanate resin composition in the prepreg 〉=40%.Prepreg is placed in the close die, temperature is risen to 160 ℃ from room temperature with the temperature rise rate of 1 ℃/min, insulation 60min, the temperature rise rate with 1 ℃/min rises to 180 ℃ with temperature again, is forced into 5Kg/cm in this process
2, insulation, pressurize 240min heat, pressurize and be shaped down at 180 ℃.The demoulding is taken out in the formed matrix material in back, solidifies back cyanate resin composition content N to be: 25%≤N≤35%.
Because the utilization of technique scheme, the present invention compared with prior art has following advantage: this prepreg is in the operability of room temperature and good in the long lifetime property of room temperature, flood high modulus carbon fiber with hot melt process, negative impacts such as use production cost height, contaminate environment, efficient that solvent brought are low have been avoided, simultaneously can be with in the fugitive constituent introducing system, the curing molding that helps material is given full play to the excellent properties of fortifying fibre, satisfies the needs of different component.The mechanical property of the cyanate/high-modules carbon fibre matrix material of or autoclave molding hot-forming through press significantly improves than existing corresponding epoxy/high-modules carbon fibre mechanical property.
Embodiment
The invention will be further described below by embodiment, and its purpose is to understand content of the present invention better, rather than limitation of the present invention.
Embodiment 1
By weight, 70 parts of bisphenol A cyanate ester resins (intelligent peak Science and Technology Ltd. provide) and 30 parts of E51 type Resins, epoxy (Shanghai Resin Factory provides) are put in carry out pre-polymerization in the reactor, temperature of reaction is 140 ℃.The viscosity of resin system in the tracking measurement reactor.When resin after the pre-polymerization stops polyreaction when 80 ℃ viscosity reaches 1700mPa.s, in reactor, add the methyl ethyl diketone nickel catalyzator of 300ppm, stir, stand-by.
Preimpregnation hopper with 90 ℃ of above-mentioned cyanate resin composition injections, after the M40J high modulus carbon fiber is fully flooded, be laid in the mould that scribbles releasing agent by 0 ° of direction, close die, temperature rise rate with 1 ℃/min rises to 160 ℃ with temperature from room temperature, insulation 60min, the temperature rise rate with 1 ℃/min rises to 180 ℃ with temperature again, is forced into 5Kg/cm in this process
2, insulation, pressurize 240min under 180 ℃.After naturally cool to room temperature, material is got in the demoulding.
Embodiment 2
By weight, 90 parts of bisphenol A cyanate ester resins (intelligent peak Science and Technology Ltd. provide) and 10 parts of F46 type Resins, epoxy (Shanghai Resin Factory provides) are put in carry out pre-polymerization in the reactor, temperature of reaction is 140 ℃.The viscosity of resin system in the tracking measurement reactor.When resin stops polyreaction when 80 ℃ viscosity reaches 2000mPa.s, in reactor, add the methyl ethyl diketone cobalt catalyst of 100ppm, stir, stand-by.
Preimpregnation hopper with 100 ℃ of above-mentioned cyanate resin composition injections, after the M40J high modulus carbon fiber is fully flooded, be laid in the mould that scribbles releasing agent by 0 ° of direction, close die, temperature rise rate with 1 ℃/min rises to 160 ℃ with temperature from room temperature, insulation 60min, the temperature rise rate with 1 ℃/min rises to 180 ℃ with temperature again, is forced into 5Kg/cm in this process
2, insulation, pressurize 240min under 180 ℃.After naturally cool to room temperature, material is got in the demoulding.
Embodiment 3
By weight, 85 parts of dicyclopentadiene type ethylene rhodanate resins (intelligent peak Science and Technology Ltd. provide) and 15 parts of F46 type Resins, epoxy (Shanghai Resin Factory provides) are put in carry out pre-polymerization in the reactor, temperature of reaction is 140 ℃.The viscosity of resin system in the tracking measurement reactor.When resin after the pre-polymerization stops polyreaction when 80 ℃ viscosity reaches 1500mPa.s, in reactor, add the methyl ethyl diketone Mn catalyst of 200ppm, stir, stand-by.
Preimpregnation hopper with 85 ℃ of above-mentioned cyanate resin composition injections, after the M40J high modulus carbon fiber is fully flooded, be laid in the mould that scribbles releasing agent by 0 ° of direction, close die, temperature rise rate with 1 ℃/min rises to 160 ℃ with temperature from room temperature, insulation 60min, the temperature rise rate with 1 ℃/min rises to 180 ℃ with temperature again, is forced into 5Kg/cm in this process
2, insulation, pressurize 240min under 180 ℃.After naturally cool to room temperature, material is got in the demoulding.
Claims (9)
1, a kind of cyanate resin composition is characterized in that, comprising:
(a) cyanate of 70～90 weight % or cyanate prepolymer;
(b) Resins, epoxy of 30～10 weight %;
When (c) being base of calculation with the quality of (a), the catalyzer of 100～500ppm;
Described catalyzer is one or more of methyl ethyl diketone acid metal salt.
According to the cyanate resin composition of claim 1, it is characterized in that 2, after 140 ℃ of following pre-polymerizations, 80 ℃ viscosity is 1.5～2.5Pa.s with (a) and material (b), softening temperature is at 30～40 ℃.
According to the cyanate resin composition of claim 1, it is characterized in that 3, described cyanate is represented by formula I structure:
A
1-(OCN)
n
Formula I
A
1Be aromatics or mixing aromatics-aliphatic alkyl, contain one or more atoms that are selected from oxygen, nitrogen, halogen, sulphur, phosphorus, boron, silicon, hydrogen and composition thereof; And n=2～5.
According to the cyanate resin composition of claim 1, it is characterized in that 4, described Resins, epoxy is phenol aldehyde type epoxy resin or bisphenol A type epoxy resin.
According to the cyanate resin composition of claim 1, it is characterized in that 5, the metal in the described methyl ethyl diketone acid metal salt is selected from zinc, copper, manganese, cobalt, iron or nickel.
6, according to the cyanate resin composition of claim 1, it is characterized in that, 160 ℃ solidified 4 hours and more than, resin solidification degree 〉=93.8%.
7, the cyanate resin composition of claim 1～6 prepares application in the high modulus carbon fiber prepreg in hot melt process, it is characterized in that, described cyanate resin composition is injected in the hopper, hopper is heated to 85～105 ℃, high modulus carbon fiber is fully flooded in hopper, and the high modulus carbon fiber that will fully flood is unidirectional then is laid in the mould that scribbles releasing agent, forms high modulus carbon fiber prepreg, close die heats, pressurization, insulation reaction; Naturally cool to room temperature afterwards, material is got in the demoulding, promptly obtains the high modulus carbon fiber reinforced composite.
8, application according to claim 7 is characterized in that, weight percentage M 〉=40% of contained cyanate resin composition in the described high modulus carbon fiber prepreg.
9, application according to claim 7 is characterized in that, in the described high modulus carbon fiber reinforced composite after the contained curing cyanate resin composition percentage composition N be 25%≤N≤35%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910055180A CN101613459A (en) | 2009-07-22 | 2009-07-22 | Cyanate resin composition and prepare application in the high modulus carbon fiber prepreg in hot melt process |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905528A (en) * | 2010-07-16 | 2010-12-08 | 沈阳飞机工业（集团）有限公司 | Wedge-shaped autoclave forming process of composite material I-shaped section |
| CN103343868A (en) * | 2013-06-27 | 2013-10-09 | 北京卫星制造厂 | Composite material star sensor support and preparation method thereof |
| CN104448821A (en) * | 2013-09-17 | 2015-03-25 | 深圳光启创新技术有限公司 | Resin material for prepreg, prepreg, preparation method thereof, and meta-material substrate and meta-material containing the prepreg |
| CN104974521A (en) * | 2014-04-01 | 2015-10-14 | 吉坤日矿日石能源株式会社 | Prepreg, carbon-fiber-reinforced composite material, and robot hand |
| CN109486186A (en) * | 2018-12-24 | 2019-03-19 | 苏州大学 | Epoxy-modified cyanate pre-polymerization material |
| CN109593357A (en) * | 2018-12-10 | 2019-04-09 | 苏州大学 | Epoxy/cyanic acid ester group composite laminate |
| CN109762333A (en) * | 2018-12-29 | 2019-05-17 | 苏州大学 | Modified cyanic acid ester is poured plate |
| CN110041702A (en) * | 2019-04-22 | 2019-07-23 | 华东理工大学 | Hot melt prepreg lower shrinkage cyanate ester resin system and preparation method thereof |
-
2009
- 2009-07-22 CN CN200910055180A patent/CN101613459A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905528A (en) * | 2010-07-16 | 2010-12-08 | 沈阳飞机工业（集团）有限公司 | Wedge-shaped autoclave forming process of composite material I-shaped section |
| CN101905528B (en) * | 2010-07-16 | 2012-07-04 | 沈阳飞机工业（集团）有限公司 | Wedge-shaped autoclave forming process of composite material I-shaped section |
| CN103343868A (en) * | 2013-06-27 | 2013-10-09 | 北京卫星制造厂 | Composite material star sensor support and preparation method thereof |
| CN104448821A (en) * | 2013-09-17 | 2015-03-25 | 深圳光启创新技术有限公司 | Resin material for prepreg, prepreg, preparation method thereof, and meta-material substrate and meta-material containing the prepreg |
| CN104974521A (en) * | 2014-04-01 | 2015-10-14 | 吉坤日矿日石能源株式会社 | Prepreg, carbon-fiber-reinforced composite material, and robot hand |
| CN104974521B (en) * | 2014-04-01 | 2021-11-09 | 吉坤日矿日石能源株式会社 | Prepreg, carbon fiber reinforced composite material and manipulator |
| CN109593357A (en) * | 2018-12-10 | 2019-04-09 | 苏州大学 | Epoxy/cyanic acid ester group composite laminate |
| CN109593357B (en) * | 2018-12-10 | 2021-05-25 | 苏州大学 | Epoxy/cyanate ester based composite laminate |
| CN109486186A (en) * | 2018-12-24 | 2019-03-19 | 苏州大学 | Epoxy-modified cyanate pre-polymerization material |
| CN109486186B (en) * | 2018-12-24 | 2021-02-26 | 苏州大学 | Epoxy modified cyanate ester prepolymer |
| CN109762333A (en) * | 2018-12-29 | 2019-05-17 | 苏州大学 | Modified cyanic acid ester is poured plate |
| CN110041702A (en) * | 2019-04-22 | 2019-07-23 | 华东理工大学 | Hot melt prepreg lower shrinkage cyanate ester resin system and preparation method thereof |
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Open date: 20091230 |