CN107325292A - A kind of method of modifying of cyanate ester resin - Google Patents
A kind of method of modifying of cyanate ester resin Download PDFInfo
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- CN107325292A CN107325292A CN201710776773.2A CN201710776773A CN107325292A CN 107325292 A CN107325292 A CN 107325292A CN 201710776773 A CN201710776773 A CN 201710776773A CN 107325292 A CN107325292 A CN 107325292A
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- cyanate ester
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- ester resin
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- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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Abstract
The present invention relates to a kind of method of modifying of cyanate ester resin, which solve present in existing method that viscosity in prepreg manufacturing process is smaller, the technical problem that process window is narrower, operational characteristic is bad in composite material shaping process, it comprises the following steps：Chemosensitive area conditioning agent A is added in cyanate ester resin, graft reaction obtains resin solution；Add Chemosensitive area conditioning agent B and accelerator in resin solution, further prepolymerization reaction obtains prepreg cyanate ester resin system.The present invention can be used for the preparation field of prepreg cyanate ester resin system.
Description
Technical field
The present invention relates to field of compound material, a kind of method of modifying of cyanate ester resin is related in particular to.
Background technology
Resin in the processing performance of prepreg resin, including the viscosity and viscosity, and composite material shaping process of resin
Fluidity and process window, the manufacture influence for prepreg and composite are larger.First, prepreg resin has necessarily
Viscosity, it is ensured that the bonding between filament tow and prepreg；Secondly, prepreg resin meets certain viscosity, fully infiltration
Fiber and do not salivate；Require that the resin flow of prepreg is low wide with pressurization window simultaneously, it is ensured that the performance of composite.As
The cyanate ester resin of prepreg common resins matrix, the defect of operational characteristic is more obvious.
In order to improve the operational characteristic of cyanate ester resin matrix, universal method is that epoxy resin is added in cyanate ester resin
It is modified.
Publication No. CN104177640A Chinese invention patent application discloses a kind of preparation side of cyanate prepreg
Method, adds epoxy resin modification agent in melting cyanate, solves the viscosity that existing hot melt prepares cyanate prepreg
Be coated with sex chromosome mosaicism, but viscosity is smaller in prepreg manufacturing process, and the process window in composite material shaping process is narrower.
Publication No. CN105038223A Chinese patent application disclose a kind of sweat connecting material cyanate ester resin and
Its preparation method, using epoxy resin as modifying agent, thermoplastic resin and nano-particle etc. are prepared as blending toughening agent
Prepreg there is certain viscosity and viscosity, but operational characteristic is not still good enough.
The content of the invention
The present invention be exactly in order to solve present in existing method that viscosity in prepreg manufacturing process is smaller, composite into
The technical problem that process window is narrower, operational characteristic is bad during type there is provided a kind of method of modifying of cyanate ester resin, its
The gummosis in prepreg dipping process and composite material shaping process can be reduced；Molecular chain length, the viscous temperature of extension are widened simultaneously
Platform is interval, increases the process window in composite material shaping process, improves the processing performance of cyanate prepreg.
Therefore, the present invention provides the method for modifying of cyanate ester resin, it comprises the following steps：(1) count by weight, will
5-15 parts of Chemosensitive area conditioning agent A are added in 100 parts of cyanate ester resins, the graft reaction 0.5-1.5h in 120 DEG C -140 DEG C,
Obtain resin solution；(2) in the resin solution that step (1) is obtained add 20-40 parts by weight Chemosensitive area conditioning agent B and
0.01%-0.1% parts by weight accelerator, the further prepolymerization reaction 0.5-1.5h under the conditions of 90 DEG C -110 DEG C obtains prepreg
Use cyanate ester resin system；The range of number-average molecular weight of cyanate ester resin is 200-5000 dalton in resin system, and-OCN is pre-
Poly- conversion ratio is 20%-50%.
It is preferred that, Chemosensitive area conditioning agent A is the polyphenylene oxide (PPO) containing active group, polysulfones (PSF), polyether sulphone
(PPES), one or more of compositions in polyether sulfone (PES), polyether-ketone (PEK), PEI (PEI).
It is preferred that, cyanate ester resin is Bisphenol F cyanate, bisphenol A cyanate ester, phenolic cyanate, dicyclopentadiene pair
One or more of combinations in phenol cyanate, bis-phenol M cyanates or other polyfunctional group cyanates.
It is preferred that, Chemosensitive area conditioning agent B is bisphenol A epoxide resin, novolac epoxy resin, glycidyl amine epoxy tree
One or more of combinations in fat, unsaturated polyester resin.
It is preferred that, accelerator is in dibutyl tin laurate, cobalt octoate, manganese acetylacetonate, imidazoles, butyl titanate
One or more of combinations.
Effect of the present invention is that the present invention is carried by the active group of thermoplastic resin and the graft reaction of cyanate first
The initial viscosity of high resin matrix, reduces the gummosis in prepreg dipping process and composite material shaping process；Widen point simultaneously
Subchain length, the viscous warm platform of extension is interval, increases the process window in composite material shaping process.Then thermosetting resin is utilized
Good viscosity and being coated with property improve the viscosity of cyanate ester resin matrix, and by the prepolymerization reaction of appropriate level, improve cyanogen
The processing performance of acid esters prepreg.Compared to the method for modifying of traditional cyanate ester resin operational characteristic, the present invention solves pre-
The problems such as material is with cyanate ester resin system viscosity and viscosity balance, rheological behavior is soaked, can with good manufacturability and practicality
To realize the batch production of prepreg cyanate ester resin matrix.
Brief description of the drawings
Fig. 1 is the infrared figure of inventive article；
Fig. 2 is cyanate viscosity profile of the present invention.
Embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
Apply the content described by example and be merely to illustrate the present invention, without should be also without limitation on this hair described in claims
It is bright.
More detailed description is done to the present invention below by way of specific embodiment：In embodiments, the molecule of resin system
Amount is measured using gel permeation chromatograph (styrageHT2/3 types)；- OCN conversion ratios use internal standard method, according to Fourier transformation
The spectrogram that infrared spectrometer (NEXUS types) is measured is by following equation：
Calculating is obtained；Viscosity and viscous warm platform interval are obtained using rotational rheometer (AR2000 types) test；Resin flows
Degree is with reference to GB5260 standard testings.
Embodiment 1
5 parts by weight Chemosensitive area conditioning agent A (polyphenylene oxide resin) and 100 parts by weight bisphenol A cyanate ester resin are existed
Resin system temperature, is then down to after 90 DEG C by graft reaction 1.5h in 120 DEG C, adds 20 parts by weight Chemosensitive area conditioning agents
B (bisphenol A type epoxy resin) and 0.01% parts by weight accelerator (butyl titanate), further prepolymerization reaction 1.5h.Obtain pre-
Soak material cyanate ester resin system.
Embodiment 2
By 10 parts by weight Chemosensitive area conditioning agent A (polysulfone resin) and 100 parts by weight of bisphenol F type cyanate ester resins 130
Resin system temperature, is then down to after 100 DEG C by graft reaction 1h in DEG C, adds 30 parts by weight Chemosensitive area conditioning agent B (phenol
Formaldehyde epoxy resin) and 0.05% parts by weight accelerator (cobalt octoate), further prepolymerization reaction 1h.Obtain prepreg cyanate resin
Resin system.
Embodiment 3
By 15 weight chemistry rheology control agent A (polyethersulfone resin) and 100 parts by weight of phenolic type cyanate ester resins at 140 DEG C
Resin system temperature, is then down to after 110 DEG C by middle graft reaction 0.5h, adds 40 parts by weight Chemosensitive area conditioning agent B (no
Saturated polyester resin) and 0.1% parts by weight accelerator (imidazoles), further prepolymerization reaction 0.5h.Obtain prepreg cyanate
Resin system.
Comparative example
By 20 parts by weight Chemosensitive area conditioning agent B (bisphenol A type epoxy resin) and 100 parts by weight of bisphenol A type cyanate resins
Fat and 0.01% parts by weight accelerator (butyl titanate) prepolymerization reaction 1h at 130 DEG C.Obtain prepreg cyanate resin
Resin system.
The effect numerical value of above-described embodiment and comparative example is as follows：
Table 1
Table 2
Compared with comparative example, embodiment 1, embodiment 2 and embodiment 3 use Chemosensitive area conditioning agent A and cyanic acid in advance
Graft reaction occurs for ester, and number-average molecular weight peak value (as shown in table 2) occurs 3500 or so, shows by graft reaction, increase
Cyanate ester resin number-average molecular weight.Cyanate ester resin number-average molecular weight increases so that resin initial viscosity is improved, can from table 1
To find out, 80 DEG C of viscosity of comparative example resin only has 5000cP；And embodiment 1,80 DEG C of embodiment 2 and embodiment 3 viscous
Degree respectively reaches 18000cP, 19000cP and 22000cP, and viscosity lifting is obvious.Resin initial viscosity, which is improved, reduces prepreg
Gummosis in dipping process and composite material shaping process, the reduction of prepreg resin fluidity；Viscous warm platform is extended simultaneously
Interval, has widened the process window in composite material shaping process.On the other hand, Chemosensitive area conditioning agent B has good glue
Property and being coated with property, by controlling the rational extent of reaction so that prepreg prepared by embodiment 1, embodiment 2 and embodiment 3
Viscosity is substantially better than the prepreg of comparative example preparation.The present invention finally realizes prepreg cyanate ester resin system viscosity and viscosity
Balance, the problems such as solving resin rheological behavior, the manufacturability beneficial to prepreg cyanate ester resin optimizes.
Claims (5)
1. a kind of method of modifying of cyanate ester resin, it is characterized in that comprising the following steps：
(1) count by weight, 5-15 parts of Chemosensitive area conditioning agent A be added in 100 parts of cyanate ester resins, 120 DEG C-
Graft reaction 0.5-1.5h, obtains resin solution in 140 DEG C；
(2) 20-40 parts by weight Chemosensitive area conditioning agents B and 0.01%- are added in the resin solution that the step (1) is obtained
0.1% parts by weight accelerator, the further prepolymerization reaction 0.5-1.5h under the conditions of 90 DEG C -110 DEG C obtains prepreg cyanate
Resin system；
The range of number-average molecular weight of cyanate ester resin is 200-5000 dalton in the resin system, and-OCN pre-polymerization conversion ratios are
20%-50%.
2. the method for modifying of cyanate ester resin according to claim 1, it is characterised in that the Chemosensitive area conditioning agent A
To be one or more of in the polyphenylene oxide containing active group, polysulfones, polyether sulphone, polyether sulfone, polyether-ketone, PEI
Composition.
3. the method for modifying of cyanate ester resin according to claim 1, it is characterised in that the cyanate ester resin is bis-phenol
F cyanates, bisphenol A cyanate ester, phenolic cyanate, dicyclopentadiene bis-phenol cyanate, bis-phenol M cyanates or other are multifunctional
One or more of combinations in group's cyanate.
4. the method for modifying of cyanate ester resin according to claim 1, it is characterised in that the Chemosensitive area conditioning agent B
For the one or more in bisphenol A epoxide resin, novolac epoxy resin, glycidyl amine epoxy resin, unsaturated polyester resin
Combination.
5. the method for modifying of cyanate ester resin according to claim 1, it is characterised in that the accelerator is tin dilaurate
One or more of combinations in dibutyl tin, cobalt octoate, manganese acetylacetonate, imidazoles, butyl titanate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710776773.2A CN107325292A (en) | 2017-09-01 | 2017-09-01 | A kind of method of modifying of cyanate ester resin |
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| CN201710776773.2A CN107325292A (en) | 2017-09-01 | 2017-09-01 | A kind of method of modifying of cyanate ester resin |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111185130A (en) * | 2020-01-17 | 2020-05-22 | 中国航空工业集团公司济南特种结构研究所 | Industrial online control prepolymerization kettle and method for cyanate ester resin |
| CN112210209A (en) * | 2019-07-12 | 2021-01-12 | 航天长征睿特科技有限公司 | Preparation method of flow-controllable hot-melt cyanate ester composition |
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|---|---|---|---|---|
| CN102876247A (en) * | 2012-10-24 | 2013-01-16 | 黑龙江省科学院石油化学研究院 | Modified cyanate adhesive film and preparation method thereof |
| CN103087339A (en) * | 2013-01-03 | 2013-05-08 | 北京化工大学 | Method for preparing prepreg through regulating and controlling viscosity of epoxy resin system and fluidity of prepreg by chemorheology |
| 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 |
| CN104844816A (en) * | 2015-06-02 | 2015-08-19 | 长春长光宇航复合材料有限公司 | Cyanate ester preimpregnated grid and preparation method thereof |
| CN105038223A (en) * | 2015-06-02 | 2015-11-11 | 长春长光宇航复合材料有限公司 | Cyanate resin for hot-melt prepregs and preparation method thereof |
| CN106987013A (en) * | 2017-05-17 | 2017-07-28 | 中威北化科技有限公司 | The preparation method for the intermediate temperature setting epoxy prepreg that glass transition temperature is improved |
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2017
- 2017-09-01 CN CN201710776773.2A patent/CN107325292A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876247A (en) * | 2012-10-24 | 2013-01-16 | 黑龙江省科学院石油化学研究院 | Modified cyanate adhesive film and preparation method thereof |
| CN103087339A (en) * | 2013-01-03 | 2013-05-08 | 北京化工大学 | Method for preparing prepreg through regulating and controlling viscosity of epoxy resin system and fluidity of prepreg by chemorheology |
| 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 |
| CN104844816A (en) * | 2015-06-02 | 2015-08-19 | 长春长光宇航复合材料有限公司 | Cyanate ester preimpregnated grid and preparation method thereof |
| CN105038223A (en) * | 2015-06-02 | 2015-11-11 | 长春长光宇航复合材料有限公司 | Cyanate resin for hot-melt prepregs and preparation method thereof |
| CN106987013A (en) * | 2017-05-17 | 2017-07-28 | 中威北化科技有限公司 | The preparation method for the intermediate temperature setting epoxy prepreg that glass transition temperature is improved |
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| GUAN WANG等: "Study on Phenolphthalein Poly(ether sulfone)-Modified Cyanate Ester Resin and Epoxy Resin Blends", 《POLYMER ENGINEERING AND SCIENCE》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112210209A (en) * | 2019-07-12 | 2021-01-12 | 航天长征睿特科技有限公司 | Preparation method of flow-controllable hot-melt cyanate ester composition |
| CN111185130A (en) * | 2020-01-17 | 2020-05-22 | 中国航空工业集团公司济南特种结构研究所 | Industrial online control prepolymerization kettle and method for cyanate ester resin |
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