CN102887983A - Liquid phenolic-type cyanate resin suitable for RTM (resin transfer molding) process - Google Patents
Liquid phenolic-type cyanate resin suitable for RTM (resin transfer molding) process Download PDFInfo
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- CN102887983A CN102887983A CN2012101771549A CN201210177154A CN102887983A CN 102887983 A CN102887983 A CN 102887983A CN 2012101771549 A CN2012101771549 A CN 2012101771549A CN 201210177154 A CN201210177154 A CN 201210177154A CN 102887983 A CN102887983 A CN 102887983A
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Abstract
The invention discloses a liquid phenolic-type cyanate resin suitable for RTM (resin transfer molding) and a preparation method of the liquid phenolic-type cryanate resin. Thermoplastic phenolic resin with low molecular weight is taken as a matrix, and reacts with cyanogen bromide to prepare the liquid cyanate resin under base catalysis. A material with good heat resistance is obtained from the phenolic-type cyanate resin disclosed by the invention by thermocuring and catalytic curing, and the phenolic-type cyanate resin is suitable for being used as a heat-resistant composite material matrix resin.
Description
Technical field
The present invention relates to a kind of thermosetting phenolic cyanate ester resin that is suitable for room temperature forming and preparation method thereof, specifically, utilize acid catalyzed polymerisation to prepare pf resin of low molecular weight, then under base catalysis, prepare the liquid cyanate ester resin that is suitable for the RTM moulding.
Technical background
Cyanate ester resin has important application prospect in aerospace and field of electronic materials, comprises fire retardant material, rocket body material, fire-retardant fibre and carbon-carbon composite matrix.Novolac Cyanate Ester Resins is one of best high-temperature resin material of ablation resistance, have good thermotolerance, mechanical property, dielectric properties and good processing performance [Li Wenfeng, Chen Chun, kingdom builds. the research of Novolac Cyanate Ester Resins and application. and material Leader .2006,6:46].But the synthetic middle side reaction of Novolac Cyanate Ester Resins is difficult to control, and very difficult synthetic purity is high, the cyanate ester resin of stable performance; Curing process is large on the impact of degree of cure, so cyanic acid ester synthesis and application relatively lag behind, also is at home the starting stage.。
Most of cyanate ester resins are solids, and the cyanate ester resin of viscosity less (100-500cP) is less under the room temperature, therefore limited the application [W.K.Goertzen of cyanate on resin transfer molding (RTM) process (RTM), M.R.Kessler.Thermal and mechanical evaluation of cyanate ester composites with low-temperature processability.Composites Part A.2007,38:779].
The Chen Lixin of Hongchang Electronic Material Inustry Co., Ltd., Guangzhou and Northwestern Polytechnical University etc. disclose the method that a kind of water soluble method prepares the linear bisphenol A cyanate ester resin [Chen Lixin, Wang Rumin, Zheng Shuirong. a kind of water soluble method prepares the method for linear bisphenol A resin, CN02139389.3].Glass reinforced plastic graduate Feng Qing equality in Beijing discloses the blend by linear resin of phenolic cyanate and linear condensed ring Novolac Cyanate Ester Resins, and aldehyde type cyanate ester resin ablative composite material [Feng Qingping, Xue Zhongmin, Chen Chun, Hu Ping. ablative material of resin of phenolic cyanate, CN1600808A].
E.Grigat and R.Puter are extremely unstable in synthetic Novolac Cyanate Eater Resin in 1969, be heated gelation reaction namely occurs, be that carbonization is decomposed at 360 ℃, can't be as materials'use [Origat E, Cologne-Stammheim, et a1.Phenolic resins containing cyanic ester groups, US Pat, 3448079,1969].The eighties in 20th century, Japanese Patent JP 59-149918 has reported first linear phenolic resin and triethylamine reaction has been generated corresponding salt, generated corresponding monomer resin with the halogen cyan reaction again.But this method is attended by shortcoming [the Masaharu D that cigarette, gas produce when still existing the short and gel of the gel time of monomer, Hideo I, Yoshio U.Production of cyanato group-containing phenolic resin, JP58-34822,1983].
A kind of liquid phenolic cyanate ester resin and technology of preparing thereof that is suitable for room temperature RTM moulding process of this patent report has very high thermotolerance behind the resin solidification, be suitable as the resin matrix of high temperature structural composite material.
Summary of the invention
The object of the present invention is to provide a kind of liquid phenolic type cyanate ester resin of the RTM of being suitable for technique.
Another object of the present invention is to provide a kind of preparation method of pf resin of low molecular weight.
Another object of the present invention is to provide a kind of preparation method of liquid phenolic cyanate ester resin.
For achieving the above object, the preparation method of cyanate ester resin of the present invention may further comprise the steps:
1. the preparation of low molecular weight thermoplastic resol.
2. the preparation of Novolac Cyanate Ester Resins.
Above preparation method's characteristics are to be proceed step by step in pf resin of low molecular weight and the Novolac Cyanate Ester Resins reactor that is suitable for RTM technique.
The preparation of low molecular weight thermoplastic resol in the step 1 comprises following steps:: a) in reactor, add phenol, be heated to 40-70 ℃ under stirring; B) 10% aqueous sulfuric acid of adding phenol quality 0.5-2%; C) under agitation add 37% formalin of phenol mole number 40-60% in batches, and be warming up to 80-100 ℃ of reaction 4-6h, get yellow emulsion; D) close heating, add sodium hydroxide solution and be neutralized to pH value 6-7, be cooled to room temperature; E) remove water layer, unreacted phenol is removed in organic layer vacuum distilling, obtain low molecular weight thermoplastic resol.
B wherein) used acid catalyst comprises 10% dilute sulphuric acid, rare HCL, phospho-wolframic acid and phosphoric acid in; Add, catalyst levels is at 0.5-2 mass parts (per 100 parts of phenol) in batches.
C wherein) used formaldehyde consumption is 40-60 molar part (per 100 parts of phenol) in, preferably 48 to 50, should add in batches; C wherein) temperature of acid catalyzed polymerisation is controlled at 80-100 ℃ in, preferably is controlled at 85-95 ℃; 4-6h; The molecular weight of formaldehyde consumption remarkably influenced resol should accomplish that the phenolic aldehyde mol ratio is near 2.
D wherein) the ph value is neutralized to 6-7 in; Reaction is cooled to room temperature, removes water layer;
Progressively be warming up to 160 ℃ when vacuum distilling is except phenol e wherein), when by the time not having phenol steam, be cooled to room temperature and get orange red solid phenolic resin.
The molecular structure of resol of the present invention is verified at infrared spectrum shown in Figure 1.
Fig. 1 resol infrared spectrum
The preparation of Novolac Cyanate Ester Resins in the step 2 comprises following steps: f) in acetone solvent, resol and the condensation under the alkaline catalysts effect of 1-1.2 mole multiple cyanogen bromide prepare cyanate ester resin; G) remove by filter byproduct salt, acetone is removed in organic solution vacuum distilling; Remaining viscose glue with methylene dichloride dissolving, deionized water washing four times, anhydrous magnesium sulfate drying, remove by filter siccative, last vacuum is revolved to steam and is removed methylene dichloride and obtain Novolac Cyanate Ester Resins.
F wherein) used catalyzer is triethylamine, diethylamine, aniline and sodium hydroxide, adds gradually, and add-on is 1-1.2 mole multiple (based on resol).Temperature of reaction is controlled at-20-0 ℃; Reaction times is controlled at 2-3h.
Novolac Cyanate Ester Resins by above preparation method's preparation has good storage, and naturally placing more than half a year in room temperature can not affect use properties.
Novolac Cyanate Ester Resins heating self cure of the present invention obtains brittle solid, also can solidify at a lower temperature by catalytic curing.The gel time of cyanate ester resin is 60-80min in the time of 160 ℃, and gel time is 3-10min when adding 0.5% massfraction DBTDL, adds the Ni (AcAc) of 0.5% massfraction
2The time gel time be 8-15min.As shown in Figure 2, ethylene rhodanate resin curing reaction of the present invention occurs in 200-300 ℃.
The thermofixation differential thermal analysis of Fig. 2 resin of phenolic cyanate
The liquid phenolic type cyanate ester resin that the present invention is suitable for RTM technique has the following advantages
(1) viscosity is little under the room temperature, about 500cP, is fit to RTM technique;
(2) 200-300 ℃ of thermofixation, can not produce the curing small molecule by-product;
(3) good heat resistance, the heat-resisting rank of DMA is in (as shown in Figure 3) more than 350 ℃.
The dynamic thermomechanometry of Fig. 3 resin of phenolic cyanate
Embodiment
The below is enforcement embodiment of the present invention, but the present invention is not limited to following instance, and any liquid phenolic cyanate ester resin synthetic technology that does not have substantive technological improvement is all within limited range of the present invention.
Embodiment 1
After getting the fusing of 1636g phenol, be placed in three mouthfuls of glass flask that thermometer, reflux condensing tube and whipping appts are housed, be warming up to 70 ℃ and add 87g dilute sulphuric acid (10%).Add 652g formaldehyde (37% aqueous solution) in batches, be warming up to 90 ℃ of reaction 6h.Be neutralized to neutrality with 10% sodium hydroxide solution.Be cooled to room temperature, obtain the resol crude product.Crude product is begun vacuum from room temperature revolve steaming to 150 ℃, to reactive phenol steam, be cooled to room temperature and obtain brown color resol.
The molecular-weight average of gained resol is 310, and fusing point is 60 ℃.
Embodiment 2
Get 200g acetone and add in three mouthfuls of glass flask of thermometer, reflux condensing tube and whipping appts, be cooled to-10 ℃, get that resol is dissolved in the acetone in 50g cyanogen bromide and the 20g example 1.Drip gradually the 40g triethylamine, be warming up to 5 ℃ of reaction 2h after dropwising.Remove by filter salt after leaving standstill 1h, steaming obtains thick product except behind the acetone.With thick product dichloromethane extraction, extraction liquid is isolated organic phase with 5% salt acid elution; With deionized water wash three times, then use dried over mgso; The distillation desolventizing obtains the liquid cyanate ester resin after filtering.
390,20 ℃ of viscosity 600cP of resin of phenolic cyanate molecular-weight average, heat curing temperature 200-300 ℃.
Embodiment 3
Get 200g acetone and add in three mouthfuls of glass flask of thermometer, reflux condensing tube and whipping appts, be cooled to-10 ℃, get that resol is dissolved in the acetone in 50g cyanogen bromide and the 30g example 1.Drip gradually the 40g triethylamine, be warming up to 5 ℃ of reaction 2h after dropwising.Remove by filter salt after leaving standstill 1h, steaming obtains thick product except behind the acetone.With thick product dichloromethane extraction, extraction liquid is isolated organic phase with 5% salt acid elution; With deionized water wash three times, then use dried over mgso; The distillation desolventizing obtains the liquid cyanate ester resin after filtering.
380,20 ℃ of viscosity 580cP of resin of phenolic cyanate molecular-weight average, heat curing temperature 200-300 ℃.
Embodiment 4
Get two parts of cyanate ester resins, portion does not add catalyzer, and the DBTDL of a adding 0.5% puts into convection oven, be cured with following technique: ℃ (1h) ~ 250, ℃ (1h) ~ 230,120 ℃ ~ 150 ℃ ~ 180 ℃ (1h) ~ 200 ℃ (4h) are cooled to room temperature and obtain cured product.
Be brown brittle solid behind resin of phenolic cyanate self thermofixation and the catalytic curing, dynamic thermomechanometry shows that the heat resisting temperature of resin is more than 350 ℃.
Claims (9)
1. a liquid phenolic type cyanate ester resin that is suitable for the RTM technological forming adopts following method preparation: a) add phenol in reactor, be heated to 40-70 ℃ under stirring; B) 10% aqueous sulfuric acid of adding phenol quality 0.5-2%; C) under agitation add 37% formalin of phenol mole number 40-60% in batches, and be warming up to 80-100 ℃ of reaction 4-6h, get yellow emulsion; D) close heating, add sodium hydroxide solution and be neutralized to pH value 6-7, be cooled to room temperature; E) remove water layer, unreacted phenol is removed in organic layer vacuum distilling, obtain low molecular weight thermoplastic resol; F) in acetone solvent, resol and the condensation under the alkaline catalysts effect of 1-1.2 mole multiple cyanogen bromide prepare cyanate ester resin; G) remove by filter byproduct salt, acetone is removed in organic solution vacuum distilling; Remaining viscose glue with methylene dichloride dissolving, deionized water washing four times, anhydrous magnesium sulfate drying, remove by filter siccative, last vacuum is revolved to steam and is removed methylene dichloride and obtain Novolac Cyanate Ester Resins.
2. the preparation method of resol described in the claim 1, wherein b) in used acid catalyst comprise dilute sulphuric acid, dilute hydrochloric acid, phospho-wolframic acid and phosphoric acid, catalyst levels is at 0.5-2 mass parts (per 100 parts of phenol).
3. the preparation method of resol described in the claim 1, wherein c) in used formaldehyde consumption be 40-60 mole multiple (per 100 parts of phenol), add in batches.
4. the preparation method of resol described in the claim 1, wherein c) in the temperature of acid catalyzed polymerisation be controlled at 80-100 ℃, reaction times 4-6h.
5. the preparation method of resol described in the claim 1, wherein d) in the pH value should be neutralized to 6-7.
6. the preparation method of resol described in the claim 1, wherein e) in vacuum distilling progressively be warming up to 160 ℃ except phenol, resin is cooled to room temperature and gets solid thermoplastic resol.
7. novolac resin described in the claim 1, molecular-weight average is below 330, and softening temperature is below 60 ℃.
8. the preparation method of Novolac Cyanate Ester Resins described in the claim 1, wherein f) in used catalyzer be triethylamine, diethylamine, aniline and sodium hydroxide, consumption is 100-120 mole multiple (per 100 parts of phenol).
9. the Novolac Cyanate Ester Resins preparation method described in the claim 1, wherein f) in temperature of reaction be controlled at-20-0 ℃, the reaction times is controlled at 2-3h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912780A (en) * | 2017-12-13 | 2019-06-21 | 深圳市百安百科技有限公司 | A kind of preparation method of low viscosity heat resistant epoxide resin |
| CN110330612A (en) * | 2019-06-27 | 2019-10-15 | 扬州天启新材料股份有限公司 | A kind of production technology of Novolac Cyanate Ester Resins |
| CN110818933A (en) * | 2019-10-29 | 2020-02-21 | 长春长光宇航复合材料有限公司 | Ablation-resistant phenolic cyanate prepreg and preparation method thereof |
| CN111748172A (en) * | 2019-03-29 | 2020-10-09 | 中国科学院化学研究所 | Modified phenolic resin and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1600808A (en) * | 2003-07-08 | 2005-03-30 | 北京玻璃钢研究设计院 | Phenolic cyanate resin ablative material |
-
2012
- 2012-05-31 CN CN2012101771549A patent/CN102887983A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1600808A (en) * | 2003-07-08 | 2005-03-30 | 北京玻璃钢研究设计院 | Phenolic cyanate resin ablative material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912780A (en) * | 2017-12-13 | 2019-06-21 | 深圳市百安百科技有限公司 | A kind of preparation method of low viscosity heat resistant epoxide resin |
| CN111748172A (en) * | 2019-03-29 | 2020-10-09 | 中国科学院化学研究所 | Modified phenolic resin and preparation method and application thereof |
| CN111748172B (en) * | 2019-03-29 | 2021-09-28 | 中国科学院化学研究所 | Modified phenolic resin and preparation method and application thereof |
| CN110330612A (en) * | 2019-06-27 | 2019-10-15 | 扬州天启新材料股份有限公司 | A kind of production technology of Novolac Cyanate Ester Resins |
| CN110818933A (en) * | 2019-10-29 | 2020-02-21 | 长春长光宇航复合材料有限公司 | Ablation-resistant phenolic cyanate prepreg and preparation method thereof |
| CN110818933B (en) * | 2019-10-29 | 2022-06-28 | 长春长光宇航复合材料有限公司 | Ablation-resistant phenolic cyanate prepreg and preparation method thereof |
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