CN111004505A - Preparation method of modified cyanate ester resin with low volatility - Google Patents
Preparation method of modified cyanate ester resin with low volatility Download PDFInfo
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- CN111004505A CN111004505A CN201911337468.9A CN201911337468A CN111004505A CN 111004505 A CN111004505 A CN 111004505A CN 201911337468 A CN201911337468 A CN 201911337468A CN 111004505 A CN111004505 A CN 111004505A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
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Abstract
本发明公开了一种具有低挥发特性的改性氰酸酯树脂制备方法，属于高分子材料制备技术领域。本发明解决现有环氧树脂增韧改性氰酸酯树脂在空间高真空环境下可凝挥发物和质量损失较高对卫星成像系统的影响较大，且环氧树脂增韧改性氰酸酯树脂会降低其耐热性的问题。本发明选用含有苯环结构酚酞聚醚砜和玻璃化转变温度高的聚酰亚胺热塑性树脂对氰酸酯树脂进行改性，获得具有低挥发性的改性氰酸酯树脂，且该树脂的耐热性与氰酸醋树脂本体相当。使用本发明的制备方法获得的改性氰酸酯具有加工工艺好、耐热性能优异、低挥发等特性，能够满足极端环境下卫星光学成像系统使用的实际要求，可广泛应用于卫星光学遥感系统的遮光罩和光机结构构件中。The invention discloses a preparation method of a modified cyanate ester resin with low volatility characteristics, and belongs to the technical field of polymer material preparation. The invention solves the problem that the existing epoxy resin toughened modified cyanate resin has a great influence on the satellite imaging system due to the high condensable volatiles and mass loss in a high space vacuum environment, and the epoxy resin toughened modified cyanate resin has a great influence on the satellite imaging system. Ester resins reduce the problem of their heat resistance. The present invention selects phenolphthalein polyethersulfone containing benzene ring structure and polyimide thermoplastic resin with high glass transition temperature to modify the cyanate resin to obtain the modified cyanate resin with low volatility, and the resin has The heat resistance is comparable to that of the cyanate resin body. The modified cyanate ester obtained by using the preparation method of the present invention has the characteristics of good processing technology, excellent heat resistance, low volatility, etc., can meet the actual requirements for the use of satellite optical imaging systems in extreme environments, and can be widely used in satellite optical remote sensing systems. in the hood and optomechanical structural components.
Description
Technical Field
The invention relates to a preparation method of modified cyanate ester resin with low volatility, belonging to the technical field of high polymer material preparation.
Background
The cyanate ester resin has the characteristics of excellent dielectric property, mechanical property, low outgassing property and the like, and is more and more widely applied in the field of aerospace, such as a light shield of a satellite and a shipborne radome body of a radar radome. However, the cyanate ester resin has a highly symmetrical triazine ring structure inside and high crystallinity, and thus the cured product of the cyanate ester resin has high rigidity, high brittleness and insufficient toughness, which limits the application of the cyanate ester resin in a wide range.
At present, the approach for modifying cyanate ester resin mainly comprises copolymerization modification of thermosetting resin and blending modification of thermoplastic resin. However, epoxy resin is generally used for copolymerization modification, but because epoxy resin itself has high brittleness, the toughening effect is limited, and the heat resistance of epoxy resin itself is lower than that of cyanate ester resin, and the heat resistance of cyanate ester resin is reduced after the molecular structure of epoxy resin is embedded into the molecular structure of cyanate ester resin through copolymerization. And the cyanate ester resin modified by the epoxy resin has higher influence on a satellite imaging system due to higher condensable volatile matters and mass loss rate in a space high vacuum environment. Therefore, it is necessary to provide a cyanate ester resin having low volatility and good heat resistance.
Disclosure of Invention
The invention provides a preparation method of a modified cyanate ester resin with low volatility, which aims to solve the problems that the existing epoxy resin modified cyanate ester resin has large influence on a satellite imaging system due to high condensable matter and high mass loss in a space high vacuum environment and the heat resistance of the epoxy resin modified cyanate ester resin is reduced.
The technical scheme of the invention is as follows:
a preparation method of modified cyanate ester resin with low volatility comprises the following steps:
heating and melting phenolphthalein polyether sulfone and cyanate ester resin, and stirring until the mixture is uniform and transparent;
and step two, cooling, adding polyimide and a curing catalyst, continuously stirring until the mixture is uniform and transparent again, and curing after vacuum heating and bubble removal to obtain the modified cyanate ester resin material with low volatility.
Further, the cyanate ester resin is a bisphenol a type cyanate ester resin.
Further limiting, the mass ratio of the phenolphthalein polyether sulfone to the cyanate ester resin is (5-15): 100.
further limiting, the melting temperature in the step one is 150-170 ℃, and the stirring time is 30-60 min.
Further limiting, in the second step, the temperature is reduced to 110-130 ℃, and the stirring time is 60-90 min.
Further defined, the curing catalyst is aluminum acetylacetonate.
Further limiting, the mass ratio of the polyimide to the cyanate ester resin is (20-50): 100.
further limiting, the vacuum heating bubble removing temperature is 100-120 ℃, and the time is 30-60 min.
Further defined, the curing process is as follows: firstly, curing for 1-2 h at 150-170 ℃, then heating to 180-200 ℃ for curing for 1-2 h, and finally curing for 1-2 h at 210-230 ℃.
The invention has the following beneficial effects: in the existing thermoplastic resin blending modified cyanate ester resin, in order to not reduce the heat resistance of cyanate ester resin, the molecular weight of the used thermoplastic resin is generally high, almost no reactive functional group is contained or the concentration of the reactive functional group is extremely low, and only with a large addition amount, a relatively good toughening effect can be achieved, but after a large amount of thermoplastic resin is added, the viscosity is increased sharply, the manufacturability is obviously deteriorated, and even the practical value is lacked. According to the invention, phenolphthalein polyether sulfone and polyimide thermoplastic resin are selected to modify cyanate resin, the molecular structure of the phenolphthalein polyether sulfone thermoplastic resin contains a large number of benzene rings, so that the heat resistance of a copolymerization system is not reduced after the phenolphthalein polyether sulfone thermoplastic resin is copolymerized with the cyanate resin, and the content of the added phenolphthalein polyether sulfone thermoplastic resin is small, so that a sea-island structure is presented in a blend, and the structure has an energy storage effect and can prevent cracks from diffusing when the resin is stressed. The added thermoplastic polyimide resin has the properties of large molecular weight, high glass transition temperature and the like, the heat resistance of a blending system is not reduced after blending, the added mass fraction is relatively high, the thermoplastic polyimide resin becomes a continuous phase in the system, the blend forms a semi-interpenetrating network structure, the toughening effect can be further achieved, the heat resistance of the cyanate resin toughened by the two resins is equivalent to that of the cyanate resin body, the condensable volatile matter in a vacuum environment is low, and the practical requirements of the use of a satellite optical imaging system in an extreme environment can be met.
Detailed Description
The experimental procedures used in the following examples are conventional unless otherwise specified.
Embodiment mode 1:
100g of cyanate ester resin and 5g of phenolphthalein polyether sulfone were heated and melted at 170 ℃ and vigorously stirred for 30min, and the resin mixture became a uniform and transparent state.
Then cooling the resin mixture to 130 ℃, then adding 30g of polyimide and 0.3g of aluminum acetylacetonate curing catalyst, continuing to stir vigorously for 90min, changing the resin mixture to a transparent and uniform state again, removing bubbles in vacuum at 100 ℃ for 60min,
and finally, carrying out segmented curing, namely curing at 170 ℃ for 1h, then curing at 200 ℃ for 1h, and finally curing at 230 ℃ for 1h to obtain the low-volatility cyanate ester resin.
In the above experiment, the cyanate ester resin was bisphenol a type cyanate ester resin, polyimide was produced by dupont, and phenolphthalein polyethersulfone was produced by xuzhou engineering plastics factory, the institute of china and technology for the stress control of catharanthus.
The low-volatility modified cyanate ester resin obtained in the above manner had a condensable volatile content of 0.012% and a mass loss rate of 0.15 wt% as measured in a vacuum environment. Therefore, the resin completely meets the imaging use requirements of the satellite optical system.
Claims (10)
1. A preparation method of a modified cyanate ester resin with low volatility is characterized by comprising the following steps:
heating and melting phenolphthalein polyether sulfone and cyanate ester resin, and stirring until the mixture is uniform and transparent;
and step two, cooling, adding polyimide and a curing catalyst, continuously stirring until the mixture is uniform and transparent again, and curing after vacuum heating and bubble removal to obtain the modified cyanate ester resin material with low volatility.
2. The method for preparing modified cyanate ester resin with low volatility according to claim 1, wherein the cyanate ester resin is bisphenol a cyanate ester resin.
3. The preparation method of the modified cyanate ester resin with the low volatility as claimed in claim 1, wherein the mass ratio of the phenolphthalein polyethersulfone to the cyanate ester resin is (5-15): 100.
4. the preparation method of the modified cyanate ester resin with low volatility as claimed in claim 1, wherein the melting temperature in the first step is 150 ℃ to 170 ℃, and the stirring time is 30min to 60 min.
5. The method for preparing modified cyanate ester resin with low volatility as claimed in claim 1, wherein the temperature in the second step is reduced to 110-130 ℃, and the stirring time is 60-90 min.
6. The preparation method of the modified cyanate ester resin with low volatility as claimed in claim 1, wherein the mass ratio of the polyimide to the cyanate ester resin is (20-50): 100.
7. the method for preparing modified cyanate ester resin with low volatility as claimed in claim 1, wherein the curing catalyst is aluminum acetylacetonate.
8. The method for preparing a modified cyanate ester resin with low volatility according to claim 7, wherein the mass ratio of the aluminum acetylacetonate to the cyanate ester resin is (0.3-1): 100.
9. the preparation method of the modified cyanate ester resin with low volatility as claimed in claim 1, wherein the temperature of vacuum heating for removing bubbles is 100 ℃ to 120 ℃ for 30min to 60 min.
10. The method for preparing modified cyanate ester resin with low volatility as claimed in claim 1, wherein the curing process comprises: firstly, curing for 1-2 h at 150-170 ℃, then heating to 180-200 ℃ for curing for 1-2 h, and finally curing for 1-2 h at 210-230 ℃.
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| CN201911337468.9A CN111004505A (en) | 2019-12-23 | 2019-12-23 | Preparation method of modified cyanate ester resin with low volatility |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112509720A (en) * | 2020-11-26 | 2021-03-16 | 哈尔滨工业大学 | Cyanate ester radical anti-irradiation reinforced conformal coating and preparation method thereof |
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| CN101760965A (en) * | 2009-12-10 | 2010-06-30 | 中国航空工业集团公司北京航空材料研究院 | Predefinition form agent of toughening function type RTM textile powder and preparing method thereof |
| CN102040938A (en) * | 2010-12-06 | 2011-05-04 | 黑龙江省科学院石油化学研究院 | Nano-particle modified cyanate adhesive and preparation method thereof |
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2019
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112509720A (en) * | 2020-11-26 | 2021-03-16 | 哈尔滨工业大学 | Cyanate ester radical anti-irradiation reinforced conformal coating and preparation method thereof |
| CN112509720B (en) * | 2020-11-26 | 2021-10-01 | 哈尔滨工业大学 | A kind of cyanate ester-based anti-radiation reinforced conformal coating and preparation method thereof |
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Inventor after: Wu Xiaohong Inventor after: Qin Wei Inventor after: Kang Hongjun Inventor after: Lu Songtao Inventor after: Li Yang Inventor before: Qin Wei Inventor before: Kang Hongjun Inventor before: Wu Xiaohong Inventor before: Lu Songtao Inventor before: Li Yang |
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Application publication date: 20200414 |