WO2018095357A1 - 一种含氟硅聚磷酸酯及其制备方法和应用 - Google Patents

一种含氟硅聚磷酸酯及其制备方法和应用 Download PDF

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WO2018095357A1
WO2018095357A1 PCT/CN2017/112578 CN2017112578W WO2018095357A1 WO 2018095357 A1 WO2018095357 A1 WO 2018095357A1 CN 2017112578 W CN2017112578 W CN 2017112578W WO 2018095357 A1 WO2018095357 A1 WO 2018095357A1
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fluorine
silicon
epoxy resin
polyphosphate
containing silicon
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French (fr)
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戴李宗
陈婷
刘诚
王世成
陈国荣
袁丛辉
许一婷
曾碧榕
罗伟昂
何凯斌
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厦门大学
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Priority to US16/463,697 priority Critical patent/US11046816B2/en
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  • the invention belongs to the technical field of organic flame retardant materials, and in particular relates to a fluorine-containing silicon polyphosphate ester and a preparation method and application thereof.
  • CN201410680503.8 discloses a phosphorus-silicon composite flame retardant which is applied to flame retardant of silicone rubber by using caged heptaphenyltrisilocene silsesquioxane, and plays a phosphorus flame retardant and a silicon flame retardant.
  • CN201210094955.9 discloses a phosphorus-silicon fluoride flame-retardant copolyester film, which is obtained by polycondensation to obtain a phosphorus-silicon fluorine copolyester chip, and finally processed to obtain a film having a flame retardant property of VTM-O grade.
  • most of the flame retardants still have the defects of poor compatibility with the matrix resin, and the flame retardant has a single function of modifying the matrix, and cannot extend the application fields of the flame retardant and the polymer material.
  • Another object of the present invention is to provide a process for producing the above fluorine-containing silicon polyphosphate.
  • the preparation method of the above fluorine-containing silicon polyphosphate includes the following steps:
  • an ester monomer the above silicon-containing compound is trimethylsilanol, triphenylsilanol or aminopropyl cage polysilsesquioxane (NH 2 -POSS); 2-chloro-2-oxo-1,3 , the mass ratio of 2-dioxophospholane to the first organic solvent is 1:5-50; silicon-containing compound, triethylamine and 2-chloro-2-oxo-1,3,2-diphosphorus The molar ratio of heterocyclic pentane is 1:1 to 2:1 to 2;
  • the first organic solvent is dichloromethane, toluene or ethyl acetate.
  • the second organic solvent is dichloromethane, chloroform or tetrahydrofuran.
  • the epoxy resin prepolymer is heated to 70-110 ° C, and 2 to 90 wt% of fluorine-containing silicon polyphosphate is added thereto, and stirred to be uniformly transparent. Then add the curing agent 4,4-diaminodiphenylmethane (DDM) in stoichiometric ratio until completely dissolved, then Pour into an aluminum mold and set a heating program to cure to obtain a flame retardant epoxy resin.
  • DDM 4,4-diaminodiphenylmethane
  • the epoxy resin prepolymer is an E51 bisphenol A type epoxy resin.
  • the mass ratio of the epoxy resin prepolymer to the curing agent 4,4-diaminodiphenylmethane is 8:2.02.
  • the heating procedure is: curing at 120 ° C for 4 h, curing at 140 ° C for 2 h, and curing at 180 ° C for 2 h.
  • the macromolecule obtained by ring-opening polymerization of a cyclic phosphate in the fluorine-containing silicon polyphosphate of the present invention increases the phosphorus content in the system;
  • the fluorine-containing silicon polyphosphate of the present invention is flame-retarded by using a phosphorus-fluorosilicon element, and the phosphorus element can catalyze the formation of a phosphorus-rich carbon layer, thereby functioning as a protective layer to prevent further decomposition of the epoxy resin;
  • the oxygen resin forms a carbon layer containing silica during the combustion process, which enhances the structure of the carbon layer and further enhances the protection of the carbon layer; the introduction of fluorine can improve the thermal stability of the epoxy resin, thereby improving the flame retardancy of the system. ;
  • the fluorine-containing silicon polyphosphate of the present invention incorporates fluorine and silicon elements, and the atomic specificity of the two elements not only improves the flame retardancy of the epoxy resin, but also reduces the surface energy of the epoxy resin. Making the material exhibit hydrophobic properties;
  • the preparation method of the present invention can adjust the proportion of phosphorus to silicon in the system by synthesizing different cyclic phosphate monomers or changing the type of monohydroxy compound which initiates the cyclic phosphate;
  • the method of the invention utilizes the characteristics of ring-opening polymerization of cyclic phosphate to prepare a macromolecular flame retardant integrated with phosphorus, silicon and fluorine, which is applied to the flame retardant of epoxy resin and improves the flame retardancy of epoxy resin. Performance and functionalization have a significant impact.
  • Example 1 is a structural formula of a fluorine-containing silicon polyphosphate in Example 1;
  • Figure 2 is a nuclear magnetic resonance spectrum (a), a fluorine spectrum (b) and a phosphorus spectrum (c) of the fluorine-containing silicon polyphosphate in Example 1.
  • Example 3 is a comparison diagram of the water contact angle between the pure epoxy resin and the flame-retardant epoxy resin obtained in Example 1, the upper drawing is a pure epoxy resin, and the lower drawing is the flame-retardant epoxy resin obtained in Example 1. .
  • the epoxy resin prepolymer was an E51 bisphenol A type epoxy resin.
  • the oxygen index of the above flame-retardant epoxy resin was measured according to GB/T 2406-2009 to be 32.4%.
  • the water contact angle of the above flame-retardant epoxy resin was measured according to GB/T 30693-2014 to be 87.7° (as shown in Fig. 2).
  • the oxygen index of the above flame retardant epoxy resin was measured according to GB/T 2406-2009 to be 33.1%.
  • the water contact angle of the above flame-retardant epoxy resin was measured according to GB/T 30693-2014 to be 90.5°.
  • the oxygen index of the above flame retardant epoxy resin was measured according to GB/T 2406-2009 to be 30.9%.
  • the water contact angle of the above flame-retardant epoxy resin was measured according to GB/T 30693-2014 to be 87.9°.
  • the oxygen index of the above flame retardant epoxy resin was 32.7%.
  • the water contact angle of the above flame-retardant epoxy resin was measured according to GB/T 30693-2014 to be 91.6°.
  • the oxygen index of the above flame-retardant epoxy resin was measured according to GB/T 2406-2009 to be 32.5%.
  • the water contact angle of the above flame-retardant epoxy resin was measured according to GB/T 30693-2014 to be 89.7°.
  • the preparation method of the above fluorine-containing silicon polyphosphate includes the following steps:
  • an ester monomer the above silicon-containing compound is trimethylsilanol, triphenylsilanol or aminopropyl cage polysilsesquioxane (NH 2 -POSS); 2-chloro-2-oxo-1,3 , the mass ratio of 2-dioxophospholane to the first organic solvent is 1:5-50; silicon-containing compound, triethylamine and 2-chloro-2-oxo-1,3,2-diphosphorus The molar ratio of heterocyclic pentane is 1:1 to 2:1 to 2;
  • the first organic solvent is dichloromethane, toluene or ethyl acetate.
  • the second organic solvent is dichloromethane, chloroform or tetrahydrofuran.

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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Fireproofing Substances (AREA)

Abstract

本发明公开了一种含氟硅聚磷酸酯及其制备方法和应用，其化学结构式为：其中R1为式（II）, （III）或式(IV),，R2为式（V）或式（VI）， n＝10～100。本发明的含氟硅聚磷酸酯利用磷氟硅元素进行阻燃，磷元素能够催化体系形成富磷炭层，起到保护层的作用从而阻止环氧树脂的进一步分解；含有硅的环氧树脂在燃烧过程中会形成含有二氧化硅的炭层，增强炭层结构，进一步提高炭层的保护作用；氟元素的引入能提高环氧树脂的热稳定性，从而提高体系的阻燃性能。

Description

一种含氟硅聚磷酸酯及其制备方法和应用 技术领域
本发明属于有机阻燃材料技术领域，具体涉及一种含氟硅聚磷酸酯及其制备方法和应用。
背景技术
大部分的高分子材料都具有易燃的特性，许多火灾的发生是高分子材料的燃烧造成的，给人们的生活带来极大的危害。为了改善高分子材料的阻燃性能，阻燃剂的应用也随之兴起，制备出一种高效的阻燃剂以提高材料的阻燃性能，亦或是在提高阻燃性能的同时赋予材料新性能的研究，仍然是一个富有挑战的课题。
CN201410680503.8公开了一种磷硅复合阻燃剂，其利用笼状七苯基三硅磷倍半硅氧烷应用于硅橡胶的阻燃，发挥了磷系阻燃剂与硅系阻燃剂的优势，起到防熔滴、隔热抑烟的作用。CN201210094955.9公开了一种磷硅氟阻燃共聚酯薄膜，通过缩聚得到磷硅氟共聚酯切片，最后经过加工得到阻燃性能达到VTM-O级的薄膜。然而，大部分的阻燃剂仍然存在着与基体树脂相容性差的缺陷，而且阻燃剂对基体改性的功能单一，无法扩展阻燃剂与高分子材料的应用领域。
发明内容
本发明的目的在于提供一种含氟硅聚磷酸酯。
本发明的另一目的在于提供上述含氟硅聚磷酸酯的制备方法。
本发明的再一目的在于提供上述含氟硅聚磷酸酯的应用。
本发明的技术方案如下：
一种含氟硅聚磷酸酯，其化学结构式为：
Figure PCTCN2017112578-appb-000001
其中R1为
Figure PCTCN2017112578-appb-000002
R2为
Figure PCTCN2017112578-appb-000003
n＝10～100。
上述含氟硅聚磷酸酯的制备方法，包括如下步骤：
(1)在冰浴下向反应容器中依次加入含硅化合物、三乙胺和第一有机溶剂，再缓慢滴加2-氯-2-氧-1，3，2-二氧磷杂环戊烷，室温反应4～12h，接着过滤除去三乙胺盐酸盐，将所得滤液用水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂得含硅环状磷酸酯单体；上述含硅化合物为三甲基硅醇、三苯基硅醇或氨丙基笼型聚倍半硅氧烷(NH2-POSS)；2-氯-2-氧-1，3，2-二氧磷杂环戊烷和第一有机溶剂的质量比为1∶5～50；含硅化合物、三乙胺和2-氯-2-氧-1，3，2-二氧磷杂环戊烷的摩尔比为1∶1～2∶1～2；
(2)在步骤(1)所得的含硅环状磷酸酯单体中加入含氟化合物、异辛酸亚锡和第二有机溶剂，然后升温至35℃～80℃，反应6～12h，最后将溶剂旋干，即得所述含氟硅聚磷酸酯；上述含氟化合物为3，5-双(三氟甲基)苄醇或四氟丙醇；含硅环状磷酸酯单体与第二有机溶剂的质量比为1∶5～50；含硅环状磷酸酯单体、含氟化合物何异辛酸亚锡的摩尔比为1∶0.01～0.05∶0.002～0.01。
在本发明的一个优选实施方案中，所述第一有机溶剂为二氯甲烷、甲苯或乙酸乙酯。
在本发明的一个优选实施方案中，所述第二有机溶剂为二氯甲烷、三氯甲烷或四氢呋喃。
上述含氟硅聚磷酸酯在制备阻燃性环氧树脂中的应用。
在本发明的一个优选实施方案中，具体为：取环氧树脂预聚体升温至70～110℃，在其中加入2～90wt％的含氟硅聚磷酸酯，搅拌至呈均一透明的状态，接着按化学计量比加入固化剂4，4-二氨基二苯甲烷(DDM)直至完全溶解，然后 倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
进一步优选的，所述环氧树脂预聚体为E51双酚A型环氧树脂。
进一步优选的，所述环氧树脂预聚体与固化剂4，4-二氨基二苯甲烷的质量比为8∶2.02。
进一步优选的，所述升温程序为：120℃固化4h，140℃固化2h，180℃固化2h。
本发明的有益效果是：
1、本发明的含氟硅聚磷酸酯中环状磷酸酯开环聚合所得的大分子提高了体系中的含磷量；
2、本发明的含氟硅聚磷酸酯利用磷氟硅元素进行阻燃，磷元素能够催化体系形成富磷炭层，起到保护层的作用从而阻止环氧树脂的进一步分解；含有硅的环氧树脂在燃烧过程中会形成含有二氧化硅的炭层，增强炭层结构，进一步提高炭层的保护作用；氟元素的引入能提高环氧树脂的热稳定性，从而提高体系的阻燃性能；
3、本发明的含氟硅聚磷酸酯中引入了氟、硅元素，因这两种元素的原子特殊性，不仅能提高环氧树脂的阻燃性能，还能降低环氧树脂的表面能，使材料表现出疏水的性质；
4、本发明的制备方法通过合成不同环状磷酸酯单体，或改变引发环状磷酸酯的单羟基化合物种类，可以调整体系中的磷硅氟比例；
5、本发明的制各方法利用环状磷酸酯开环聚合的特点，制备出磷、硅、氟一体的大分子阻燃剂，应用于环氧树脂的阻燃，对提高环氧树脂阻燃性能并实现功能化有着显著的作用。
附图说明
图1为实施例1中含氟硅聚磷酸酯的结构式；
图2为实施例1中含氟硅聚磷酸酯的核磁氢谱(a)，氟谱(b)和磷谱(c)；
图3为纯环氧树脂与实施例1制得的阻燃性环氧树脂的水接触角对比图，上图为纯环氧树脂，下图为实施例1制得的阻燃性环氧树脂。
具体实施方案
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
下述实施例中，环氧树脂预聚体为E51双酚A型环氧树脂。
实施例1
(1)在冰浴下向单口瓶中依次加入8.00g(9.14mmol)氨丙基笼型聚倍半硅氧烷(NH2-POSS)、1.12g(11.06mmol)三乙胺和25mL二氯甲烷，再用注射器缓慢滴加1.96g(13.75mmol)2-氯-2-氧-1，3，2-二氧磷杂环戊烷，室温反应8h；接着过滤除去三乙胺盐酸盐，将所得滤液用水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，旋蒸除去溶剂得含硅的环状磷酸酯单体。
(2)取6.08g(6.20mmol)步骤(1)中所得含硅环状磷酸酯单体于单口瓶中，加入13.60mg(0.10mmol)四氟丙醇、20.00mg(0.04mmol)异辛酸亚锡和10mL四氢呋喃，升温至80℃，反应6h，反应结束后将溶剂旋干，得到含氟硅聚磷酸酯(如图1所示)。
(3)称取20g环氧树脂预聚体升温至90℃，加入2.78g的步骤(2)中所得含氟硅聚磷酸酯，搅拌至呈均一透明的状态，接着加入5.05gDDM直至完全溶解，然后倒入铝制模具中，120℃固化4h，140℃固化2h，180℃固化2h，得到阻燃性环氧树脂。
根据GB/T 2406-2009测得上述阻燃性环氧树脂的氧指数为32.4％。
根据GB/T 30693-2014测得上述阻燃性环氧树脂的水接触角为87.7°(如图2所示)。
实施例2
(1)含硅环状磷酸酯单体的合成同实施例1。
(2)含氟硅聚磷酸酯的合成同实施例1。
(3)称取20g环氧树脂预聚体升温至90℃，加入6.26g的步骤(2)中所得含氟硅聚磷酸酯，搅拌至混合物呈均一透明的状态，加入5.05gDDM直至完全溶解，倒入铝制模具中，120℃固化4h，140℃固化2h，180℃固化2h得到阻燃性环氧树脂。
根据GB/T 2406-2009测得上述阻燃性环氧树脂的氧指数为33.1％。
根据GB/T 30693-2014测得上述阻燃性环氧树脂的水接触角为90.5°。
实施例3
(1)含硅环状磷酸酯单体的制备同实施例1。
(2)取6.08g(6.20mmol)步骤(1)中所得含硅环状磷酸酯单体于单口瓶中，加入24.41mg(0.10mmol)3，5-双(三氟甲基)苄醇、20.00mg(0.04mmol)异辛酸亚锡和10mL四氢呋喃，升温至80℃，反应6h，反应结束后将溶剂旋干，得到含氟硅聚磷酸酯。
(3)称取20g环氧树脂预聚体升温至90℃，加入2.78g的步骤(2)中所得含氟硅聚磷酸酯，搅拌至呈均一透明的状态，接着加入5.05gDDM直至完全溶解，然后倒入铝制模具中，120℃固化4h，140℃固化2h，180℃固化2h得到阻燃性环氧树脂。
根据GB/T 2406-2009测得上述阻燃性环氧树脂的氧指数为30.9％。
根据GB/T 30693-2014测得上述阻燃性环氧树脂的水接触角为87.9°。
实施例4
(1)含硅环状磷酸酯单体的制备同实施例3。
(2)含氟硅聚磷酸酯的制备同实施例3。
(3)称取20g环氧树脂预聚体升温至90℃，加入2.78g的步骤(2)中所得含氟硅聚磷酸酯，搅拌至呈均一透明的状态，接着加入5.05gDDM直至完全溶解，然后倒入铝制模具中，120℃固化4h，140℃固化2h，180℃固化2h得到阻燃性环氧树脂。
根据GB/T 2406-2009测得上述阻燃性环氧树脂的氧指数为32.7％。
根据GB/T 30693-2014测得上述阻燃性环氧树脂的水接触角为91.6°。
实施例5
(1)在冰浴下向单口瓶中依次加入1.03g(9.14mmol)三甲基硅醇、1.12g(11.06mmol)三乙胺和20mL二氯甲烷，再用注射器缓慢滴加1.96g(13.75mmol)2-氯-2-氧-1，3，2-二氧磷杂环戊烷，反应8h；接着过滤除去三乙胺盐酸盐，将所得滤液用水反复淬洗三次，取有机相用无水硫酸镁干燥，抽滤，旋蒸除去溶剂得含氟或含硅的环状磷酸酯单体含硅环状磷酸酯单体。
(2)取6.08g(6.20mmol)步骤(1)中所得含硅环状磷酸酯单体于单口瓶中，加 入24.41mg(0.10mmol)3，5-双(三氟甲基)苄醇、20.00mg(0.04mmol)异辛酸亚锡和10mL四氢呋喃，升温至80℃，反应6h，反应结束后将溶剂旋干，得到含氟硅聚磷酸酯。
(3)称取20g环氧树脂预聚体升温至90℃，加入2.78g的步骤(2)中所得含氟硅聚磷酸酯，搅拌至混合物呈均一透明的状态，加入5.05gDDM直至完全溶解，倒入铝制模具中，120℃固化4h，140℃固化2h，180℃固化2h得到阻燃性环氧树脂。
根据GB/T 2406-2009测得上述阻燃性环氧树脂的氧指数为32.5％。
根据GB/T 30693-2014测得上述阻燃性环氧树脂的水接触角为89.7°。
本领域普通技术人员可知，本发明的技术方案在下述范围内变化时，仍然能够得到与上述实施例相同或相近的技术效果，仍然属于本发明的保护范围：
一种含氟硅聚磷酸脂，其化学式结构为：
Figure PCTCN2017112578-appb-000004
其中R1为
Figure PCTCN2017112578-appb-000005
R2为
Figure PCTCN2017112578-appb-000006
n＝10～100。
上述含氟硅聚磷酸酯的制备方法，包括如下步骤：
(1)在冰浴下向反应容器中依次加入含硅化合物、三乙胺和第一有机溶剂，再缓慢滴加2-氯-2-氧-1，3，2-二氧磷杂环戊烷，室温反应4～12h，接着过滤除去三乙胺盐酸盐，将所得滤液用水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂得含硅环状磷酸酯单体；上述含硅化合物为三甲基硅醇、三苯基硅醇或氨丙基笼型聚倍半硅氧烷(NH2-POSS)；2-氯-2-氧-1，3，2-二氧磷杂环戊烷和第一有机溶剂的质量比为1∶5～50；含硅化合物、三乙胺和2-氯-2-氧-1，3，2-二氧磷杂环戊烷的摩尔比为1∶1～2∶1～2；
(2)在步骤(1)所得的含硅环状磷酸酯单体中加入含氟化合物、异辛酸亚锡和第二有机溶剂，然后升温至35～80℃，反应6～12h，最后将溶剂旋干，即得所述含氟硅聚磷酸酯；上述含氟化合物为3，5-双(三氟甲基)苄醇或四氟丙醇；含硅环状磷酸酯单体与第二有机溶剂的质量比为1∶5～50；含硅环状磷酸酯单体、含氟化合物何异辛酸亚锡的摩尔比为1∶0.01～0.05∶0.002～0.01。
所述第一有机溶剂为二氯甲烷、甲苯或乙酸乙酯。所述第二有机溶剂为二氯甲烷、三氯甲烷或四氢呋喃。
上述含氟硅聚磷酸酯在制备阻燃性环氧树脂中的应用。具体为：取环氧树脂预聚体升温至70～110℃，在其中加入2～90wt％的含氟硅聚磷酸酯，搅拌至呈均一透明的状态，接着按化学计量比加入固化剂4，4-二氨基二苯甲烷(DDM)直至完全溶解，然后倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。

Claims (9)

  1. 一种含氟硅聚磷酸酯，其特征在于：其化学式结构为：
    Figure PCTCN2017112578-appb-100001
    其中R1为
    Figure PCTCN2017112578-appb-100002
    R2为
    Figure PCTCN2017112578-appb-100003
    n＝10～100。
  2. 如权利要求1所述的一种含氟硅聚磷酸酯的制备方法，其特征在于：包括如下步骤：
    (1)在冰浴下向反应容器中依次加入含硅化合物、三乙胺和第一有机溶剂，再缓慢滴加2-氯-2-氧-1，3，2-二氧磷杂环戊烷，室温反应4～12h，接着过滤除去三乙胺盐酸盐，将所得滤液用水反复淬洗，取有机相用无水硫酸镁干燥，抽滤，最后旋蒸除去溶剂得含硅环状磷酸酯单体；上述含硅化合物为三甲基硅醇、三苯基硅醇或氨丙基笼型聚倍半硅氧烷；2-氯-2-氧-1，3，2-二氧磷杂环戊烷和第一有机溶剂的质量比为1∶5～50；含硅化合物、三乙胺和2-氯-2-氧-1，3，2-二氧磷杂环戊烷的摩尔比为1∶1～2∶1～2；
    (2)在步骤(1)所得的含硅环状磷酸酯单体中加入含氟化合物、异辛酸亚锡和第二有机溶剂，然后升温至35～80℃，反应6～12h，最后将溶剂旋干，即得所述含氟硅聚磷酸酯；上述含氟化合物为3，5-双(三氟甲基)苄醇或四氟丙醇；含硅环状磷酸酯单体与第二有机溶剂的质量比为1∶5～50；含硅环状磷酸酯单体、含氟化合物何异辛酸亚锡的摩尔比为1∶0.01～0.05∶0.002～0.01。
  3. 如权利要求2所述的制备方法，其特征在于：所述第一有机溶剂为二氯甲烷、甲苯或乙酸乙酯。
  4. 如权利要求2所述的制备方法，其特征在于：所述第二有机溶剂为二氯甲烷、三氯甲烷或四氢呋喃。
  5. 权利要求1所述的含氟硅聚磷酸酯在制备阻燃性环氧树脂中的应用。
  6. 如权利要求5所述的应用，其特征在于：具体为：取环氧树脂预聚体升温至70～110℃，在其中加入2～90wt％的含氟硅聚磷酸酯，搅拌至呈均一透明的状态，接着按化学计量比加入固化剂4，4-二氨基二苯甲烷(DDM)直至完全溶解，然后倒入铝制模具中，设置升温程序进行固化得到阻燃性环氧树脂。
  7. 如权利要求6所述的应用，其特征在于：所述环氧树脂预聚体为E51双酚A型环氧树脂。
  8. 如权利要求6所述的应用，其特征在于：所述环氧树脂预聚体与固化剂4，4-二氨基二苯甲烷的质量比为8∶2.02。
  9. 如权利要求6所述的应用，其特征在于：所述升温程序为：120℃固化4h，140℃固化2h，180℃固化2h。
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