WO2017076108A1 - 含硅改性耐高温氰酸酯树脂、其制备方法及应用 - Google Patents

含硅改性耐高温氰酸酯树脂、其制备方法及应用 Download PDF

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WO2017076108A1
WO2017076108A1 PCT/CN2016/096229 CN2016096229W WO2017076108A1 WO 2017076108 A1 WO2017076108 A1 WO 2017076108A1 CN 2016096229 W CN2016096229 W CN 2016096229W WO 2017076108 A1 WO2017076108 A1 WO 2017076108A1
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cyanate resin
anhydride
modified
silicon
resin
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PCT/CN2016/096229
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English (en)
French (fr)
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吴斌
张春琪
单升升
顾健峰
夏智峰
井丰喜
夏媛娇
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苏州太湖电工新材料股份有限公司
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Publication of WO2017076108A1 publication Critical patent/WO2017076108A1/zh
Priority to US15/972,174 priority Critical patent/US10738162B2/en

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    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
    • C08G59/3281—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/065—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon

Definitions

  • the invention belongs to the technical field of polymer materials, and particularly relates to a silicon-containing modified high temperature resistant cyanate resin, a preparation method thereof and an application thereof.
  • the inside of the carbon fiber composite core wire is a uniform solidified core layer made of carbon fiber and resin, and the material has high requirements on the curing speed, glass transition temperature and toughness of the resin.
  • the currently used resin is an epoxy resin system.
  • the general-purpose epoxy resin system has the disadvantage of low heat resistance. Although some of the resins have good heat resistance, the glass transition temperature Tg of the cured product is generally not higher than 180 ° C, and the interface properties are poor. Poor strength and toughness. Although the general-purpose epoxy resin can be modified to obtain higher heat resistance, the raw material is limited, the manufacturing process is complicated, and it is difficult to apply to large-scale production.
  • cyanate resin Although cyanate resin has high heat resistance, it is difficult to directly apply to the pultrusion process due to its own structural limitations, so it is inevitable to modify it.
  • the traditional modification method adopts external toughening.
  • the agent is compounded with a resin, but this method causes a decrease in the glass transition temperature and a decrease in partial mechanical properties and electrical properties.
  • the technical problem to be solved by the present invention is to provide a silicon-containing modified high temperature cyanate resin which satisfies the viscosity of the resin and at the same time achieves the toughening and heat resistance of the resin, a preparation method thereof and the application in the carbon fiber composite core wire.
  • the present invention adopts the following technical solutions:
  • a preparation method of a silicon-containing modified high temperature resistant cyanate resin comprising the following steps:
  • Step (1) adding a mixed solution of a hydroxy silicone oil, a silane coupling agent and an organic solvent to a mixed solution of a tetramethylammonium hydroxide aqueous solution and a polar solvent, and hydrolyzing and polycondensing at 5 to 40 ° C for 4 to 8 hours, and then passing through Distilling to obtain an epoxy group-containing silsesquioxane;
  • Step (2) pre-polymerizing the epoxy group-containing silsesquioxane and cyanate resin obtained in the step (1) at 50 to 100 ° C for 1 to 8 hours to obtain a modified cyanate resin;
  • the modified cyanate resin obtained in the step (2) and the modified acid anhydride are uniformly mixed to obtain the silicon-containing modified high temperature resistant cyanate resin.
  • the temperature of the hydrolysis polycondensation is 5 to 15 °C.
  • the prepolymerization temperature is 80 to 90 °C.
  • the tetramethylammonium hydroxide aqueous solution has a mass fraction of 5 to 20%.
  • the polar solvent is selected from n-butanol or isopropanol.
  • the silane coupling agent is selected from ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane or ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane. .
  • the organic solvent is selected from the group consisting of methanol, ethanol, benzene, toluene, xylene or cyclohexane.
  • the cyanate resin is selected from a bisphenol A type cyanate resin monomer or a prepolymer thereof, a bisphenol E type cyanate resin, a phenol cyanate resin, and a bisphenol F type cyanate.
  • the modified acid anhydride is selected from the group consisting of modified methyl tetrahydrophthalic anhydride, modified Methyl hexahydrophthalic anhydride, modified methyl nadic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, methyl endethylene hexahydrophthalic anhydride, Glutaric anhydride, terpene anhydride, methylcyclohexene tetracarboxylic dianhydride, dodecenyl succinic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, methyltetrabromophthalic anhydride
  • cyanate resin and the modified acid anhydride may be other raw materials used, and are not limited thereto.
  • the cyanate resin is one or a combination of two selected from the group consisting of a bisphenol A type cyanate resin and a bisphenol F type cyanate resin.
  • the modified anhydride is one or more compounds selected from the group consisting of modified methyltetrahydrophthalic anhydride, modified methylhexahydrophthalic anhydride, and modified methyl nadic anhydride.
  • the tetramethylammonium hydroxide aqueous solution, the polar solvent, the hydroxy silicone oil, the silane coupling agent, and the organic solvent are fed at a mass ratio of 0.5 to 10:15. ⁇ 200:1:4 to 60:3 to 6.
  • the mass ratio of the tetramethylammonium hydroxide aqueous solution, the polar solvent, the hydroxy silicone oil, the silane coupling agent, and the organic solvent is 0.5 to 2: 15 to 30: 1: 4 to 10: 3 to 6.
  • the dropping solution for controlling the mixed solution of the hydroxy silicone oil, the silane coupling agent and the organic solvent is 18 to 75 g/h.
  • the dropping rate of the mixed solution of the hydroxy silicone oil, the silane coupling agent and the organic solvent is controlled to be 55 to 70 g/h.
  • the epoxy group-containing silsesquioxane, the cyanate resin, and the modified acid anhydride are fed in a mass ratio of 1:8 to 10:13 to 15.
  • the present invention has the following advantages compared with the prior art:
  • a major feature of the present invention is that a general-purpose epoxy resin having low heat resistance and a glycidylamine series epoxy resin having high heat resistance and high cost are not used, but an existing low-cost heat-resistant high is used.
  • a new generation of cyanate resins innovatively using epoxy-containing silsesquioxanes to improve the brittleness of cyanate resins in an intrinsic toughening manner, without By sacrificing the heat resistance of the cyanate resin itself, a glass transition temperature Tg superior to that of the epoxy resin system is obtained, and a high temperature resistant resin composition for pultrusion having a Tg of 240 to 270 ° C can be prepared, which is extremely excellent. High temperature performance and good cost advantage.
  • Another feature of the present invention is that it preferentially satisfies the requirement of low viscosity of the pultrusion resin.
  • the modified resin of different viscosities is directly compounded, which is different from the traditional resin system. , to avoid the hidden dangers of other performance degradation.
  • G- POSS epoxy group-containing silsesquioxane

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

一种含硅改性耐高温氰酸酯树脂、其制备方法及应用，包括如下步骤：向四甲基氢氧化铵水溶液和极性溶剂的混合溶液中加入羟基硅油、硅烷偶联剂和有机溶剂的混合溶液，在5～40℃下水解缩聚4～8h，然后经蒸馏得到含环氧基的倍半硅氧烷；将含环氧基的倍半硅氧烷和氰酸酯树脂在50～100℃下预聚1～8h，得到改性氰酸酯树脂；将改性氰酸酯树脂和改性酸酐混合均匀，得到含硅改性耐高温氰酸酯树脂。其以本征增韧方式改善氰酸酯树脂的脆性，而没有牺牲氰酸酯树脂本身的耐热性，可制备得到Tg为240-270℃的用于拉挤成型的耐高温树脂组合物，具有极其优异的耐高温性能和良好的成本优势。

Description

[根据细则37.2由ISA制定的发明名称]　含硅改性耐高温氰酸酯树脂、其制备方法及应用 技术领域
本发明属于高分子材料技术领域，具体涉及一种含硅改性耐高温氰酸酯树脂、其制备方法及应用。
背景技术
碳纤维复合芯导线内部是一根由碳纤维与树脂复合而成的均匀固化体芯层，而此材料对树脂的固化速度、玻璃化转变温度、韧性等要求非常高。
目前常用的树脂是环氧树脂体系。而通用型环氧树脂体系存在耐热性能较低的缺点，虽然部分树脂具有较好的耐热性能，但固化物的玻璃化转变温度Tg一般不高于180℃，界面性能较差，拉伸强度和韧性差。通过对通用型环氧树脂进行改性虽然可以获得较高的耐热性能，但由于原材料受限，制造工艺复杂，难以适用于规模化生产。
由于采用环氧树脂体系在耐热等级和原材料上存在很大的难题，目前需要较环氧树脂具有更加优异耐高温特性与本征韧性的新一代树脂，于是氰酸酯树脂乘风而上，响应市场需求，必然成为全新的发展方向。
虽然氰酸酯树脂具有很高的耐热性，但它因自身结构的限制导致韧性不足难以直接应用于拉挤成型工艺，于是对它改性成为必然趋势，传统的改性方法采用外加增韧剂或是树脂复配，但是这种方法会带来玻璃化温度降低和部分机械性能和电性能下降的影响。
发明内容
本发明所要解决的技术问题是提供一种满足树脂使用粘度，同时达到树脂增韧耐热的含硅改性耐高温氰酸酯树脂及其制备方法和在碳纤维复合芯导线中的应用。
为解决以上技术问题，本发明采取如下技术方案：
一种含硅改性耐高温氰酸酯树脂的制备方法，包括如下步骤：
步骤(1)、向四甲基氢氧化铵水溶液和极性溶剂的混合溶液中加入羟基硅油、硅烷偶联剂和有机溶剂的混合溶液，在5～40℃下水解缩聚4～8h，然后经蒸馏得到含环氧基的倍半硅氧烷；
步骤(2)、将步骤(1)得到的含环氧基的倍半硅氧烷和氰酸酯树脂在50～100℃下预聚1～8h，得到改性氰酸酯树脂；
步骤(3)、将步骤(2)得到的改性氰酸酯树脂和改性酸酐混合均匀，得到所述的含硅改性耐高温氰酸酯树脂。
优选地，步骤(1)中，水解缩聚的温度为5～15℃。
优选地，步骤(2)中，预聚的温度为80～90℃。
优选地，所述的四甲基氢氧化铵水溶液的质量分数为5～20％。
优选地，所述的极性溶剂为选自正丁醇或异丙醇。
优选地，所述的硅烷偶联剂为选自γ-(2，3-环氧丙氧)丙基三甲氧基硅烷或β-(3，4-环氧环己基)乙基三甲氧基硅烷。
优选地，所述的有机溶剂为选自甲醇、乙醇、苯、甲苯、二甲苯或环己烷。
优选地，所述的氰酸酯树脂为选自双酚A型氰酸酯树脂单体或其预聚物、双酚E型氰酸酯树脂、酚醛氰酸酯树脂、双酚F型氰酸酯树脂、双酚M型氰酸酯树脂、双环戊二烯型氰酸酯树脂中的一种或多种复配；所述的改性酸酐为选自改性甲基四氢苯酐、改性甲基六氢苯酐、改性甲基纳迪克酸酐、四氢苯酐、六氢苯酐、内亚甲基四氢苯酐、甲基内亚甲基四氢苯酐、甲基内亚甲基六氢苯酐、戊二酸酐、萜烯酸酐、甲基环己烯四羧酸二酐、十二烯基丁二酸酐、四溴苯酐、四氯苯酐、甲基四溴苯酐、甲基四氯苯酐、六氯内次甲基四氢苯二甲酸酐、甘油双(脱水偏苯三酸酯)乙酸酯、均苯四甲酸二酐、苯酮四羧酸二酐中的一种或多种的复配。
当然，所述的氰酸酯树脂和所述的改性酸酐也可为其他使用的原料，并不限于此。
更为优选地，所述的氰酸酯树脂为选自双酚A型氰酸酯树脂和双酚F型氰酸酯树脂中的一种或两种复配。
更为优选地，所述的改性酸酐为选自改性甲基四氢苯酐、改性甲基六氢苯酐和改性甲基纳迪克酸酐中的一种或多种复配。
优选地，所述的四甲基氢氧化铵水溶液、所述的极性溶剂、所述的羟基硅油、所述的硅烷偶联剂、所述的有机溶剂的投料质量比为0.5～10∶15～200∶1∶4～60∶3～6。
进一步优选地，所述的四甲基氢氧化铵水溶液、所述的极性溶剂、所述的羟基硅油、所述的硅烷偶联剂、所述的有机溶剂的投料质量比为0.5～2∶15～30∶1∶4～10∶3～6。
优选地，控制所述的羟基硅油、硅烷偶联剂和有机溶剂的混合溶液的滴加速度为18～75g/h。
进一步优选地，控制所述的羟基硅油、硅烷偶联剂和有机溶剂的混合溶液的滴加速度为55～70g/h。
优选地，所述的含环氧基的倍半硅氧烷、所述的氰酸酯树脂和所述的改性酸酐的投料质量比为1∶8～10∶13～15。
由于以上技术方案的实施，本发明与现有技术相比具有如下优点：
本发明的一大特点是不使用耐热性低的通用型环氧树脂和耐热性高但价格贵的缩水甘油胺系列环氧树脂，而是使用现有的价格较低的耐热高的新一代氰酸酯树脂，创新性地采用含环氧基的倍半硅氧烷以本征增韧方式改善氰酸酯树脂的脆性，而没有 牺牲氰酸酯树脂本身的耐热性，获得比环氧树脂体系更优的玻璃化温度Tg，可制备得到Tg为240-270℃的用于拉挤成型的耐高温树脂组合物，具有极其优异的耐高温性能和良好的成本优势。
本发明的另外一个特点是优先满足拉挤成型对树脂的低粘度的要求，通过改性树脂的配方优化，选用不同粘度的改性树脂直接复配，有别于传统的树脂体系需要外加稀释剂，避免了其它性能下降的隐患。
具体实施方式
下面结合具体的实施例对本发明做进一步详细的说明，但本发明不限于以下实施例。
实施例1：
(a)在带有温度计和冷凝管的1000mL三口瓶中加入400g正丁醇和20g四甲基氢氧化铵水溶液(质量分数为10％)，搅拌混合均匀后向上述溶液中滴加20g羟基封端的聚二甲基硅氧烷和120gγ-(2，3-环氧丙氧)丙基三甲氧基硅烷与80g乙醇的混合溶液，控制滴加速度在3h滴完，控制反应温度在10℃，水解缩聚6h，反应完成后用旋转蒸发仪蒸出残留在体系中的溶剂及小分子，得到透明的室温下能流动的粘稠液体待用，即为含环氧基的倍半硅氧烷(G-POSS)。
(b)将30g上述粘稠液体(G-POSS)和270g双酚A型氰酸酯树脂倒入500mL三口瓶中并搅拌均匀，在80-90℃预聚反应2h，将改性树脂冷却至室温待用，测得改性树脂粘度为5300cps。
(c)先将420g改性甲基四氢苯酐倒入2000ml烧杯中，然后称取上述改性树脂300g加入烧杯中，均匀搅拌5-10min，进行各项性能测试。
改性树脂固化物的主要性能测试结果见表1。
实施例2：
(a)在带有温度计和冷凝管的1000mL三口瓶中加入400g正丁醇和20g四甲基氢氧化铵水溶液(质量分数为10％)，搅拌混合均匀后向上述溶液中滴加20g羟基封端的聚二甲基硅氧烷和120gγ-(2，3-环氧丙氧)丙基三甲氧基硅烷与80g乙醇的混合溶液，控制滴加速度在3h滴完，控制反应温度在10℃，水解缩聚6h，反应完成后用旋转蒸发仪蒸出残留在体系中的溶剂及小分子，得到透明的室温下能流动的粘稠液体待用，即为最终产物含环氧基的倍半硅氧烷(G-POSS)。
(b)将30g上述粘稠液体(G-POSS)和270g双酚F型氰酸酯树脂倒入500mL三口瓶中并搅拌均匀，在80-90℃预聚反应2h，将改性树脂冷却至室温待用，测得改性树脂粘度为3050cps。
(c)先将420g改性甲基四氢苯酐倒入2000ml烧杯中，然后称取上述改性树脂300g加入烧杯中，均匀搅拌5-10min，进行各项性能测试。
改性树脂固化物的主要性能测试结果见表1。
实施例3：
(a)在带有温度计和冷凝管的1000mL三口瓶中加入400g正丁醇和16g四甲基氢氧化铵水溶液(质量分数为10％)，搅拌混合均匀后向上述溶液中滴加26g羟基封端的聚二甲基硅氧烷和127gγ-(2，3-环氧丙氧)丙基三甲氧基硅烷与90g乙醇的混合溶液，控制滴加速度在3.5h滴完，控制反应温度在10℃，水解缩聚5h，反应完成后用旋转蒸发仪蒸出残留在体系中的溶剂及小分子，得到透明的室温下能流动的粘稠液体待用，即为最终产物含环氧基的倍半硅氧烷(G-POSS)。
(b)将30g上述粘稠液体(G-POSS)和270g双酚F型氰酸酯树脂倒入500mL三口瓶中并搅拌均匀，在80-90℃预聚反应2h，将改性树脂冷却至室温待用，测得改性树脂粘度为5100cps。
(c)先将420g改性甲基纳迪克酸酐倒入2000ml烧杯中，然后称取上述改性树脂300g加入烧杯中，均匀搅拌5-10min，进行各项性能测试。
改性树脂固化物的主要性能测试结果见表1。
实施例4：
(a)在带有温度计和冷凝管的1000mL三口瓶中加入400g正丁醇和25g四甲基氢氧化铵水溶液(质量分数为10％)，搅拌混合均匀后向上述溶液中滴加15g羟基封端的聚二甲基硅氧烷和130gγ-(2，3-环氧丙氧)丙基三甲氧基硅烷与80g乙醇的混合溶液，控制滴加速度在4h滴完，控制反应温度在10℃，水解缩聚7h，反应完成后用旋转蒸发仪蒸出残留在体系中的溶剂及小分子，得到透明的室温下能流动的粘稠液体待用，即为最终产物含环氧基的倍半硅氧烷(G-POSS)。
(b)将45g上述粘稠液体(G-POSS)和255g双酚F型氰酸酯树脂倒入500mL三口瓶中并搅拌均匀，在80-90℃预聚反应3h，将改性树脂冷却至室温待用，测得改性树脂粘度为4200cps。
(c)先将420g改性甲基纳迪克酸酐倒入2000ml烧杯中，然后称取上述改性树脂300g加入烧杯中，均匀搅拌5-10min，进行各项性能测试。
改性树脂固化物的主要性能测试结果见表1。
表1
Figure PCTCN2016096229-appb-000001
对比例1：
(a)在带有温度计和冷凝管的1000mL三口瓶中加入400g正丁醇和20g四甲基氢氧化铵水溶液(质量分数为10％)，搅拌混合均匀后向上述溶液中滴加20g羟基封端的聚二甲基硅氧烷和120gγ-(2，3-环氧丙氧)丙基三甲氧基硅烷与80g乙醇的混合溶液，控制滴加速度在3h滴完，控制反应温度在10℃，水解缩聚1h，反应完成后用旋转蒸发仪蒸出残留在体系中的溶剂及小分子，得到透明的室温下能流动的粘稠液体待用，即为含环氧基的倍半硅氧烷(G-POSS)。
(b)将30g上述粘稠液体(G-POSS)和270g双酚A型氰酸酯树脂倒入500mL三口瓶中并搅拌均匀，在80-90℃预聚反应2h，将改性树脂冷却至室温待用，测得改性树脂粘度为4300cps。
(c)先将420g改性甲基四氢苯酐倒入2000ml烧杯中，然后称取上述改性树脂300g加入烧杯中，均匀搅拌5-10min，进行各项性能测试。
改性树脂固化物的主要性能测试结果见表2。
对比例2：
(a)在带有温度计和冷凝管的1000mL三口瓶中加入400g正丁醇和20g四甲基氢氧化铵水溶液(质量分数为10％)，搅拌混合均匀后向上述溶液中滴加20g羟基封端的聚二甲基硅氧烷和120gγ-(2，3-环氧丙氧)丙基三甲氧基硅烷与80g乙醇的混合溶液，控制滴加速度在3h滴完，控制反应温度在0℃，水解缩聚6h，反应完成后用旋转蒸发仪蒸出残留在体系中的溶剂及小分子，得到透明的室温下能流动的粘稠液体待用，即为含环氧基的倍半硅氧烷(G-POSS)。
(b)将30g上述粘稠液体(G-POSS)和270g双酚A型氰酸酯树脂倒入500mL三口瓶中并搅拌均匀，在80-90℃预聚反应2h，将改性树脂冷却至室温待用，测得改性树脂粘度为4100cps。
(c)先将420g改性甲基四氢苯酐倒入2000ml烧杯中，然后称取上述改性树脂300g加入烧杯中，均匀搅拌5-10min，进行各项性能测试。
改性树脂固化物的主要性能测试结果见表2。
对比例3：
(a)在带有温度计和冷凝管的1000mL三口瓶中加入400g正丁醇和20g四甲基氢氧化铵水溶液(质量分数为10％)，搅拌混合均匀后向上述溶液中滴加20g羟基封端的聚二甲基硅氧烷和120gγ-(2，3-环氧丙氧)丙基三甲氧基硅烷与80g乙醇的混合溶液，控制滴加速度在3h滴完，控制反应温度在10℃，水解缩聚6h，反应完成后用旋转蒸发仪蒸出残留在体系中的溶剂及小分子，得到透明的室温下能流动的粘稠液体待用，即为含环氧基的倍半硅氧烷(G-POSS)。
(b)将30g上述粘稠液体(G-POSS)和270g双酚A型氰酸酯树脂倒入500mL三口瓶中并搅拌均匀，在60℃预聚反应1h，将改性树脂冷却至室温待用，测得改性树脂粘度为5100cps。
(c)先将420g改性甲基四氢苯酐倒入2000ml烧杯中，然后称取上述改性树脂300g加入烧杯中，均匀搅拌5-10min，进行各项性能测试。
改性树脂固化物的主要性能测试结果见表2。
表2
Figure PCTCN2016096229-appb-000002
Figure PCTCN2016096229-appb-000003
以上对本发明做了详尽的描述，其目的在于让熟悉此领域技术的人士能够了解本发明的内容并加以实施，并不能以此限制本发明的保护范围，凡根据本发明的精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围内。

Claims (10)

  1. 一种含硅改性耐高温氰酸酯树脂的制备方法，其特征在于：包括如下步骤：
    步骤(1)、向四甲基氢氧化铵水溶液和极性溶剂的混合溶液中加入羟基硅油、硅烷偶联剂和有机溶剂的混合溶液，在5～40℃下水解缩聚4～8h，然后经蒸馏得到含环氧基的倍半硅氧烷；
    步骤(2)、将步骤(1)得到的含环氧基的倍半硅氧烷和氰酸酯树脂在50～100℃下预聚1～8h，得到改性氰酸酯树脂；
    步骤(3)、将步骤(2)得到的改性氰酸酯树脂和改性酸酐混合均匀，得到所述的含硅改性耐高温氰酸酯树脂。
  2. 根据权利要求1所述的含硅改性耐高温氰酸酯树脂的制备方法，其特征在于：所述的四甲基氢氧化铵水溶液的质量分数为5～20％。
  3. 根据权利要求1所述的含硅改性耐高温氰酸酯树脂的制备方法，其特征在于：所述的极性溶剂为选自正丁醇或异丙醇；所述的有机溶剂为选自甲醇、乙醇、苯、甲苯、二甲苯或环己烷。
  4. 根据权利要求1所述的含硅改性耐高温氰酸酯树脂的制备方法，其特征在于：所述的硅烷偶联剂为选自γ-(2，3-环氧丙氧)丙基三甲氧基硅烷或β-(3，4-环氧环己基)乙基三甲氧基硅烷。
  5. 根据权利要求1所述的含硅改性耐高温氰酸酯树脂的制备方法，其特征在于：所述的氰酸酯树脂为选自双酚A型氰酸酯树脂单体或其预聚物、双酚E型氰酸酯树脂、酚醛氰酸酯树脂、双酚F型氰酸酯树脂、双酚M型氰酸酯树脂、双环戊二烯型氰酸酯树脂中的一种或多种复配；所述的改性酸酐为选自改性甲基四氢苯酐、改性甲基六氢苯酐、改性甲基纳迪克酸酐、四氢苯酐、六氢苯酐、内亚甲基四氢苯酐、甲基内亚甲基四氢苯酐、甲基内亚甲基六氢苯酐、戊二酸酐、萜烯酸酐、甲基环己烯四羧酸二酐、十二烯基丁二酸酐、四溴苯酐、四氯苯酐、甲基四溴苯酐、甲基四氯苯酐、六氯内次甲基四氢苯二甲酸酐、甘油双(脱水偏苯三酸酯)乙酸酯、均苯四甲酸二酐、苯酮四羧酸二酐中的一种或多种的复配。
  6. 根据权利要求1所述的含硅改性耐高温氰酸酯树脂的制备方法，其特征在于：所述的四甲基氢氧化铵水溶液、所述的极性溶剂、所述的羟基硅油、所述的硅烷偶联剂、所述的有机溶剂的投料质量比为0.5～10∶15～200∶1∶4～60∶3～6。
  7. 根据权利要求1或6所述的含硅改性耐高温氰酸酯树脂的制备方法，其特征在于：控制所述的羟基硅油、硅烷偶联剂和有机溶剂的混合溶液的滴加速度为18～75g/h。
  8. 根据权利要求1或6所述的含硅改性耐高温氰酸酯树脂的制备方法，其特征在于：所述的含环氧基的倍半硅氧烷、所述的氰酸酯树脂和所述的改性酸酐的投料质量比为1∶8～10∶13～15。
  9. 按照权利要求1至8中任一项所述的制备方法制得的含硅改性耐高温氰酸酯树脂。
  10. 一种如权利要求9所述的含硅改性耐高温氰酸酯树脂在碳纤维复合芯导线中的应用。
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