WO2020019546A1 - 拉挤成型用环氧树脂体系及其制备的复合材料 - Google Patents
拉挤成型用环氧树脂体系及其制备的复合材料 Download PDFInfo
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- WO2020019546A1 WO2020019546A1 PCT/CN2018/111590 CN2018111590W WO2020019546A1 WO 2020019546 A1 WO2020019546 A1 WO 2020019546A1 CN 2018111590 W CN2018111590 W CN 2018111590W WO 2020019546 A1 WO2020019546 A1 WO 2020019546A1
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
Definitions
- the invention relates to the field of epoxy resins, and in particular to an epoxy resin system for pultrusion.
- Epoxy resin is an excellent thermosetting resin. Compared with unsaturated polyester resins, epoxy resin has better physical properties, electrical insulation properties, chemical resistance, heat resistance and adhesion properties. It is currently the most common and important A base material and a structural material.
- Extrusion is one of the important processing methods for thermoset fiber reinforced plastics. It is used to produce profiles with fixed cross-section shapes and unlimited lengths.
- the extrusion molding process is a unidirectional high-strength continuous reinforced plastic profile prepared by pulling continuous fibers impregnated with resin glue through a heating die, and then further curing the resin through a heating chamber.
- the epoxy carbon fiber reinforced materials prepared by the pultrusion process generally have the following problems: (1) if the curing rate of the epoxy resin is too fast, local crosslinking will occur, resulting in brittle materials; (2) if the epoxy resin If the curing rate is too slow, the epoxy resin may not be completely cured, and the sample may be cracked during the curling and storage process. Therefore, it is necessary to select an appropriate mold temperature and traction speed according to the curing rate of the epoxy resin. In order to further improve production efficiency and traction speed, epoxy resins need to be fast-curing, while still maintaining high strength and toughness.
- the present invention provides an epoxy resin system for pultrusion, comprising the following components: 100 parts by weight of epoxy resin, 30 to 60 parts by weight of isocyanate curing agent, and 2 to 10 fluorine-containing epoxy compounds Parts by weight.
- epoxy resin is a thermosetting resin containing more than two epoxy groups in the molecule.
- glycidyl ethers such as bisphenol A type, bisphenol F type, bisphenol S type, and hydrogenation.
- Bisphenol A type phenolic type, etc .
- glycidyl esters such as diglycidyl phthalate, etc .
- glycidylamines such as tetraglycidyl diaminodiphenylmethane
- alicyclic epoxy resins Epoxidized olefins, etc.
- the curing agent refers to a compound capable of curing reaction of the epoxy resin, and can be divided into addition polymerization type, catalytic type and the like according to the reaction type.
- Additive type such as polyamine type, acid anhydride type, phenolic type, polyester resin type, liquid polyurethane and polythiol type, etc .
- catalytic type such as anion catalysis type and cationic catalysis type.
- Isocyanate curing agent refers to a substance containing two or more isocyanate groups in its molecule. According to the number of isocyanate groups in the molecule, it can be divided into diisocyanate curing agent and polyisocyanate curing agent. Isocyanate curing agent has the characteristics of low curing temperature, fast curing rate and good toughness of cured epoxy resin products.
- the isocyanate curing agent is 4,4′-methylenebis (2,6-diethylphenyl isocyanate), lysine diisocyanate, and tolyl-2,4-diisocyanate blocking One or more of polypropylene glycol or 4-chloro-6-methyl-m-phenylene diisocyanate.
- the isocyanate curing agent is a mixture of tolyl-2,4-diisocyanate-terminated polypropylene glycol and 4-chloro-6-methyl-m-phenylene diisocyanate, and the tolyl group in the mixture
- the mass fraction of -2,4-diisocyanate-terminated polypropylene glycol is 25% to 60%.
- the mass fraction of tolyl-2,4-diisocyanate-terminated polypropylene glycol in the mixture is 35% to 55%.
- the fluorine-containing epoxy compound refers to a compound containing a fluorine element and an epoxy functional group in a molecule. Fluorine-containing epoxy compounds can react with isocyanate-based curing agents, and can effectively reduce the viscosity of epoxy resins and isocyanate-based curing agents, making epoxy resins more uniformly cured, and less prone to local cross-linking problems. Chemical inertness and thermal stability of epoxy resin systems.
- the fluorine-containing epoxy compound is preferably trifluoropropylene oxide, 1,4-bis (2 ', 3'-epoxypropyl) perfluorobutane, 2,2'-(2,2,3, 3,4,4,5,5,6,6,7,7-Dodecafluorooctane-1,8-diyl) bis (ethylene oxide), 3- (2,2,3,3- One or more of tetrafluoropropoxy) -1,2-propylene oxide or 3- (1H, 1H, 5H-octafluoropentyloxy) -1,2-propylene oxide, more preferably 1,4 -A mixture of bis (2 ', 3'-epoxypropyl) perfluorobutane and 3- (1H, 1H, 5H-octafluoropentyloxy) -1,2-propylene oxide, and 1,4 in the mixture -The mass fraction of bis (2 ', 3'-epoxypropyl) perfluorobutane is 20% to 50%.
- the molecular weight of the fluorine-containing epoxy compound is 250-400. The inventors found that the fluorine-containing epoxy compound in this molecular weight range can effectively reduce the viscosity of epoxy resin and isocyanate curing agent, and can ensure that the cured epoxy resin product has high strength.
- the epoxy resin system for pultrusion includes the following components: 100 parts by weight of epoxy resin, 40-50 parts by weight of isocyanate curing agent, and 4-8 parts by weight of fluorinated epoxy compound.
- the epoxy resin system for pultrusion also contains 30 to 60 parts by weight of an amine curing agent.
- Amine curing agents can further increase the curing rate of epoxy resins and the strength of cured epoxy resin products.
- the content of amine curing agent is too small, and the curing rate is slow; the content of amine curing agent is too much, and the toughness of epoxy resin products is poor.
- the epoxy resin system for pultrusion also contains 40-50 parts by weight of amine curing agent.
- the amine curing agent is N-aminoethylpiperazine, diaminodiphenylsulfone, 2- (trifluoromethyl) -1,4-phenylene diamine, 5- (trifluoro One or more of methyl) -1,3-phenylene diamine or adipic acid dihydrazide.
- the epoxy resin system for pultrusion also contains 1 to 10 parts by weight of a fluorosilicone polymer.
- Fluorosilicone polymer is a high molecular polymer containing fluorine element and silicon element in the molecule. It can improve the strength and weather resistance of epoxy resin products. Maximum performance improvement.
- the epoxy resin system for pultrusion also contains 3-7 parts by weight of fluorosilicone polymer.
- the fluorosilicone polymer is one or two of polytrifluoropropylhydroxysiloxane or polytrifluoropropylmethylsiloxane.
- the epoxy resin system for pultrusion also contains 1 to 10 parts by weight of an accelerator.
- the accelerator refers to a substance capable of reducing the curing reaction temperature of the epoxy resin and shortening the curing reaction time. According to the reaction mechanism, it can be divided into nucleophilic type such as phenol, carboxylic acid, alcohol and water, electrophilic type such as Lewis acid, metal carboxylate type such as manganese, cobalt, zinc, calcium and lead carboxylate.
- the content of the accelerator is more than 10 parts by weight, the curing rate cannot be greatly increased, but the strength and toughness of the epoxy resin cured product will be reduced.
- the epoxy resin system for pultrusion also contains 2 to 6 parts by weight of an accelerator.
- the accelerator is sodium isooctanoate, sodium stearate, amine stearate, magnesium citrate, amine citrate, ammonium lactate, ammonium ferrous sulfate, ammonium oxalate, magnesium acetate, sodium acetate, ammonium tartrate Or one or more of ammonium acetate. It is preferably one or more of amine stearate, ammonium oxalate, ammonium lactate, ammonium tartrate, amine citrate or ammonium acetate.
- the epoxy resin system of the present invention is simply mixed according to the compounding ratio of the above-mentioned raw materials and can be obtained by stirring evenly, which can be any known preparation method.
- the present invention provides an epoxy resin composite material prepared from the above-mentioned epoxy resin system for pultrusion.
- the epoxy resin composite material refers to a plastic product obtained by impregnating a fiber material with the above-mentioned epoxy resin system and curing.
- the fiber material may be any of known fiber materials such as carbon fiber, glass fiber, polyester fiber, and polyaramid fiber.
- the epoxy resin composite material contains carbon fiber.
- Carbon fiber is made of polyacrylonitrile, pitch, phenolic, viscose and other raw materials through spinning, oxidation, carbonization, and sizing. It includes carbon fiber filaments, carbon fiber bundles, chopped carbon fibers, and carbon fiber cloth.
- the epoxy resin system for pultrusion has higher curing rate, and can be used to greatly improve the traction speed when used in the pultrusion process, thereby improving work efficiency.
- the epoxy resin products prepared by the invention have excellent mechanical properties and good toughness.
- test items and measurement methods involved in the present invention are as follows. Unless otherwise specified, each test is performed at 25 ° C.
- Tensile strength and elongation at break determined according to GB / T1447-2005, the sample is cut into a type II sample, the size of the sample is 250mm long x 25mm wide x 4mm thick, and the tensile rate is 2mm / min.
- A Bisphenol A epoxy resin, GELR127 produced by Hongchang Electronic Materials Co., Ltd., epoxy equivalent 180g / eq, viscosity 8000mPa ⁇ s.
- E1 Polytrifluoropropylhydroxysiloxane, produced by Zhejiang Huanxin Fluorine Material Co., Ltd .;
- E2 Polytrifluoropropylmethylsiloxane, produced by Zhejiang Huanxin Fluorine Material Co., Ltd.
- F2 Ammonium citrate, produced by Aldrich Chemical Reagent Company.
- epoxy resin A 100 parts by weight of epoxy resin A was mixed with the raw materials and weight parts of each example shown in Table 1, and stirred to obtain the epoxy resin system for pultrusion of the present invention.
- Example 18 According to the raw material and formula of Example 18, no isocyanate-based curing agent and fluorine-containing epoxy compound were added, and other materials and parts by weight were unchanged.
- the corresponding epoxy resin system was prepared according to the same method.
- Carbon fiber filaments (T300-1000 produced by Toray Japan) and the examples and comparative examples were prepared to obtain an epoxy resin system, and a plate sample having a width of 25 mm and a thickness of 4 mm was prepared according to a pultrusion process.
- the hopper temperature of the pultrusion process is 50 ° C
- the dipping time is 15s
- the pre-forming mold temperature is 100 ° C
- the forming mold temperature is 150 ° C
- the traction rate is 2m / min.
- An epoxy resin system was prepared by using carbon fiber filaments (T300-1000 produced by Toray Japan), examples, and comparative examples, and a plate sample having a width of 25 mm and a thickness of 4 mm was prepared according to a pultrusion process.
- the pultrusion process has a tank temperature of 50 ° C, a dipping time of 15s, a preform mold temperature of 100 ° C, a molding mold temperature of 150 ° C, and a traction rate of 10m / min.
- the obtained epoxy resin plate sample was measured for the mechanical properties of the sample according to the measurement method of the present invention, and the measurement results are shown in Table 2 below.
- the epoxy resin system of the embodiment of the present invention has excellent mechanical properties of the carbon fiber reinforced epoxy resin sheet prepared by a common extrusion rate of 2 m / min and a high-draw rate of 10 m / min by extrusion molding. High bending strength and good toughness.
- the carbon fiber reinforced epoxy resin sheet prepared by the epoxy resin system of the present invention at a high traction rate of 10 m / min by a drawing process is more excellent in mechanical properties and can be applied to pultrusion of high traction rates.
- Technology improve the production efficiency of pultrusion process epoxy products, save time and cost.
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Abstract
一种拉挤成型用环氧树脂体系，包含以下组分：环氧树脂100重量份；异氰酸酯类固化剂30～60重量份；含氟环氧化合物2～10重量份。还含有胺类固化剂30～60重量份，氟硅聚合物1～10重量份，促进剂1～10重量份。还提供一种环氧树脂复合材料，根据上述拉挤成型用环氧树脂体系制备而成。上述拉挤成型用环氧树脂体系具有更高的固化速率，用于拉挤成型工艺中可以大大提高牵引速度，从而提高工作效率。同时制备得到的环氧树脂制品力学性能优异，韧性好。
Description
本发明涉及环氧树脂领域，具体涉及一种拉挤成型用环氧树脂体系。
环氧树脂是优良的热固性树脂，它与不饱和聚酯树脂相比，具有更优良的物理性能、电绝缘性能、耐化学腐蚀性能、耐热和粘合性能，是目前最普遍、最重要的一种基体材料和结构材料。
挤拉成型是热固性纤维增强塑料重要的加工方法之一，用于生产断面形状固定不变，长度不受限制的型材。挤拉成型工艺是将浸渍树脂胶液的连续纤维经加热模拉出，然后再通过加热室使树脂进一步固化而制备的单向高强度连续增强塑料型材。
挤拉成型工艺制备的环氧树脂碳纤维增强材料一般会出现如下问题：(1)若环氧树脂固化速率过快，则会出现局部的交联，导致材料性脆；(2)若环氧树脂固化速率过慢，则可能会出现环氧树脂固化不完全，样品在卷曲、存放过程中会受力开裂的情况。所以需要根据环氧树脂的固化速率，选择合适的模具温度和牵引速度。为了进一步提高生产效率，提高牵引速度，需要环氧树脂具有固化速度快的特点，同时依然保持高强度和高韧性。
发明内容
为了解决上述问题，本发明提供了一种拉挤成型用环氧树脂体系，包含以下组分：环氧树脂100重量份，异氰酸酯类固化剂30～60重 量份，含氟环氧化合物2～10重量份。
其中，环氧树脂是分子中含有两个以上环氧基团的热固性树脂，按化学结构分类，可以分为缩水甘油醚类，如双酚A型、双酚F型、双酚S型、氢化双酚A型、酚醛型等；缩水甘油酯类，如邻苯二甲酸二缩水甘油酯类等；缩水甘油胺类，如四缩水甘油二氨基二苯基甲烷；脂环族环氧树脂类、环氧化烯烃类等。
固化剂是指能使环氧树脂发生固化反应的化合物，按反应类型可分为加聚型、催化型等类型。加聚型，如多元胺型、酸酐型、酚醛型、聚酯树脂型、液体聚氨酯和聚硫醇型等；催化型，如阴离子催化型和阳离子催化型。
异氰酸酯固化剂是指分子含有两个或两个以上异氰酸酯基团的物质，按照分子中异氰酸基团数量，可以分为二异氰酸酯固化剂和多异氰酸酯固化剂。异氰酸酯固化剂具有固化温度低、固化速率快和固化后的环氧树脂产品韧性好的特点。
进一步的，所述的异氰酸酯类固化剂是4,4′-亚甲基二(2,6-二乙基苯基异氰酸酯)、赖氨酸二异氰酸酯、甲苯基-2,4-二异氰酸酯封端聚丙二醇或4-氯-6-甲基间亚苯基二异氰酸酯中的一种或多种。
优选的，所述的异氰酸酯类固化剂是甲苯基-2,4-二异氰酸酯封端聚丙二醇和4-氯-6-甲基间亚苯基二异氰酸酯的混合物，且所述的混合物中甲苯基-2,4-二异氰酸酯封端聚丙二醇的质量分数为25％～60％。进一步优选所述的混合物中甲苯基-2,4-二异氰酸酯封端聚丙二醇的质量分数为35％～55％。
含氟环氧化合物是指分子中含有氟元素和环氧官能团的化合物。含氟环氧化合物既能与异氰酸酯类固化剂反应，又能有效的降低环氧树脂和异氰酸酯类固化剂的粘度，使环氧树脂固化更加均匀，不容易出现局部交联的问题；同时可以提高环氧树脂体系的化学惰性和热稳定性。所述的含氟环氧化合物优选为三氟环氧丙烷、1,4-二(2’,3’-环氧丙基)全氟丁烷、2,2'-(2,2,3,3,4,4,5,5,6,6,7,7-十二氟辛烷-1,8-二基)双(环氧乙烷)、3-(2,2,3,3-四氟丙氧基)-1,2-氧化丙烯或3-(1H,1H,5H-八氟戊氧基)-1,2-氧化丙烯中的一种或多种，更优选为1,4-二(2’,3’-环氧丙基)全氟丁烷和3-(1H,1H,5H-八氟戊氧基)-1,2-氧化丙烯的混合物，且混合物中1,4-二(2’,3’-环氧丙基)全氟丁烷的质量分数为20％～50％。进一步优选混合物中1,4-二(2’,3’-环氧丙基)全氟丁烷的质量分数为30％～40％。
进一步的，所述的含氟环氧化合物的分子量为250～400。发明人发现，在这个分子量范围内的含氟环氧化合物，既能有效的降低环氧树脂和异氰酸酯类固化剂的粘度，又能保证固化后的环氧树脂产品具有很高的强度。
进一步的，所述的拉挤成型用环氧树脂体系中包含以下组分：环氧树脂100重量份，异氰酸酯类固化剂40～50重量份，含氟环氧化合物4～8重量份。
进一步的，以环氧树脂100重量份计，所述的拉挤成型用环氧树脂体系中还含有胺类固化剂30～60重量份。胺类固化剂可以进一步提高环氧树脂的固化速率和固化后环氧树脂产品的强度。胺类固化 剂含量太少，固化速率较慢；胺类固化剂含量太多，环氧树脂产品的韧性较差。优选的，以环氧树脂100重量份计，所述的拉挤成型用环氧树脂体系中还含有胺类固化剂40～50重量份。
进一步的，所述的胺类固化剂是N-氨乙基哌嗪、二氨基二苯基砜、2-(三氟甲基)-1,4-亚苯基二胺、5-(三氟甲基)-1,3-亚苯基二胺或己二酸二酰肼中的一种或多种。
进一步的，以环氧树脂100重量份计，所述的拉挤成型用环氧树脂体系中还包含氟硅聚合物1～10重量份。氟硅聚合物是指分子中含有氟元素和硅元素的高分子聚合物，它可以提高环氧树脂产品的强度和耐候性，并且在这个重量份范围内，氟硅聚合物对环氧树脂综合性能提高最大。优选的，以环氧树脂100重量份计，所述的拉挤成型用环氧树脂体系中还包含氟硅聚合物3～7重量份。
进一步的，所述的氟硅聚合物是聚三氟丙基羟基硅氧烷或聚三氟丙基甲基硅氧烷中的一种或两种。
进一步的，以环氧树脂100重量份计，所述的拉挤成型用环氧树脂体系中还含有促进剂1～10重量份。所述的促进剂是指能降低环氧树脂固化反应温度，缩短固化反应时间的物质。按反应机理可分为亲核型如酚、羧酸、醇和水等，亲电型如路易斯酸，金属羧酸盐型如锰、钴、锌、钙和铅的羧酸盐。当促进剂含量大于10重量份后，并不能较大地提高固化速率，但会降低环氧树脂固化产品的强度和韧性。优选的，以环氧树脂100重量份计，所述的拉挤成型用环氧树脂体系中还包含促进剂2～6重量份。
优选的，所述的促进剂为异辛酸钠、硬脂酸钠、硬脂酸胺、柠檬酸镁、柠檬酸胺、乳酸铵、硫酸亚铁铵、草酸铵、醋酸镁、醋酸钠、酒石酸铵或醋酸铵中的一种或多种。优选为硬脂酸胺、草酸铵、乳酸铵、酒石酸铵、柠檬酸胺或醋酸铵中的一种或多种。
本发明的环氧树脂体系由上述原料按照本发明所述的配比进行简单混合，搅拌均匀既可得到，可以是已知的任何一种制备方式。
进一步的，本发明提供了一种环氧树脂复合材料，由上述的拉挤成型用环氧树脂体系制备而成。环氧树脂复合材料是指由上述环氧树脂体系浸润纤维材料并固化得到塑料制品。其中纤维材料可以选择碳纤维、玻璃纤维、聚酯纤维、聚芳酰胺纤维等已知的任何一种纤维材料。
进一步的，所述的环氧树脂复合材料中含有碳纤维。碳纤维是指由聚丙烯腈、沥青、酚醛、黏胶等原料经过纺丝、氧化、碳化和上浆制成，包含有碳纤维丝、碳纤维束、短切碳纤维、碳纤维布等各种形式产品。
本发明的拉挤成型用环氧树脂体系具有更高的固化速率，用于拉挤成型工艺中可以大大提高牵引速度，从而提高工作效率。同时本发明制备得到的环氧树脂制品力学性能优异，韧性好。
下面通过实施例进一步说明本发明，并不因此将本发明限制在所述实施例范围之中。凡基于本发明上述内容所实现的技术均属于本发明的范围。对于熟悉本领域的人员而言，可容易地实现另外的修 改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节。
本发明涉及的测试项目及其测定方法如下，如无特别说明，各测试都在25℃下进行。
1、拉伸强度和断裂伸长率：按GB/T1447-2005测定，将样品裁成Ⅱ型试样，试样尺寸为长250mm×宽25mm×厚4mm，拉伸速率2mm/min。
2、弯曲强度：按GB/T1449-2005测定，样品尺寸长100mm，厚4mm，测试速度10mm/min。
本发明实施例所用原料：
<环氧树脂>
A：双酚A环氧树脂，宏昌电子材料股份有限公司产GELR127，环氧当量180g/eq，粘度8000mPa·s。
<异氰酸酯类固化剂>
B1：赖氨酸二异氰酸酯，Aldrich化学试剂公司产；
B2：甲苯基-2,4-二异氰酸酯封端聚丙二醇，Aldrich化学试剂公司产；
B3：4-氯-6-甲基间亚苯基二异氰酸酯，Aldrich化学试剂公司产，数均分子量为2300；
<含氟环氧化合物>
C1：2,2'-(2,2,3,3,4,4,5,5,6,6,7,7-十二氟辛烷-1,8-二基)双(环氧乙烷)，分子量414；
C2：3-(2,2,3,3-四氟丙氧基)-1,2-氧化丙烯，Aldrich化学试剂公司产，分子量188；
C3：1,4-二(2’,3’-环氧丙基)全氟丁烷，分子量314；
C4：3-(1H,1H,5H-八氟戊氧基)-1,2-氧化丙烯，Aldrich化学试剂公司产，分子量288。
<胺类固化剂>
D1：2-(三氟甲基)-1,4-亚苯基二胺，Aldrich化学试剂公司产；
D2：5-(三氟甲基)-1,3-亚苯基二胺，Aldrich化学试剂公司产。
<含氟硅聚合物>
E1：聚三氟丙基羟基硅氧烷，浙江环新氟材料股份有限公司产；
E2：聚三氟丙基甲基硅氧烷，浙江环新氟材料股份有限公司产。
<促进剂>
F1：柠檬酸钠，Aldrich化学试剂公司产；
F2：柠檬酸铵，Aldrich化学试剂公司产。
实施例1～18
将100重量份的环氧树脂A与表1所示的各实施例的原料及其重量份混合，搅拌均匀得到本发明的拉挤成型用环氧树脂体系。
表1：各实施例的原料及其重量份
注：“/”表示不含有该物质，括号内为混合物中各个原料的质量比。
对比例1
按照实施例18的原料和配方，不添加异氰酸酯类固化剂和含氟环氧化合物，其他物质和重量份不变，按照相同方法制备得到相应环氧树脂体系。
对比例2
按照实施例18的原料和配方，不添加异氰酸酯类固化剂，其他物质和重量份不变，按照相同方法制备得到相应环氧树脂体系。
将碳纤维长丝(日本东丽产T300-1000)和实施例和对比例制备 得到环氧树脂体系，按照拉挤成型工艺制备得到宽25mm、厚4mm的板材样品。拉挤成型工艺的料槽温度50℃，浸胶时间为15s，预成型模具温度为100℃，成型模具温度为150℃，牵引速率为2m/min。
将碳纤维长丝(日本东丽产T300-1000)和实施例和对比例制备得到环氧树脂体系，按照拉挤成型工艺制备得到宽25mm、厚4mm的板材样品。拉挤成型工艺的料槽温度50℃，浸胶时间为15s，预成型模具温度为100℃，成型模具温度为150℃，牵引速率为10m/min。
将得到的环氧树脂板材样品按照本发明的测定方法测定样品的力学性能，测定结果如下表2所示。
表2 力学性能测定结果
从表2可以看出，本发明实施例的环氧树脂体系在2m/min的普通牵引速率下和10m/min的高牵引速率下拉挤成型工艺制备的碳纤维增强环氧树脂板材的力学性能优异，弯曲强度高，韧性好。且与对比例相比，本发明的环氧树脂体系在10m/min的高牵引速率下拉挤成型工艺制备的碳纤维增强环氧树脂板材的力学性能更加优秀，能运用于高牵引速率的拉挤成型工艺，提高拉挤成型工艺环氧树脂产品的生产效率，节约时间和成本。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此。任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。
Claims (10)
- 一种拉挤成型用环氧树脂体系，其特征在于：包含以下组分：环氧树脂100重量份；异氰酸酯类固化剂30～60重量份；含氟环氧化合物2～10重量份。
- 根据权利要求1所述的拉挤成型用环氧树脂体系，其特征在于：所述的异氰酸酯类固化剂是4,4′-亚甲基二(2,6-二乙基苯基异氰酸酯)、赖氨酸二异氰酸酯、甲苯基-2,4-二异氰酸酯封端聚丙二醇或4-氯-6-甲基间亚苯基二异氰酸酯中的一种或多种。
- 根据权利要求1所述的拉挤成型用环氧树脂体系，其特征在于：所述的含氟环氧化合物的分子量为250～400。
- 根据权利要求1～3任一项所述的拉挤成型用环氧树脂体系，其特征在于：以环氧树脂100重量份计，还含有胺类固化剂30～60重量份。
- 根据权利要求4所述的拉挤成型用环氧树脂体系，其特征在于：所述的胺类固化剂是N-氨乙基哌嗪、二氨基二苯基砜、双(4-氨基环己烷)甲烷、2-(三氟甲基)-1,4-亚苯基二胺、5-(三氟甲基)-1,3-亚苯基二胺或己二酸二酰肼中的一种或多种。
- 根据权利要求1～3任一项所述的拉挤成型用环氧树脂体系，其特征在于：以环氧树脂100重量份计，还包含氟硅聚合物1～10重量份。
- 根据权利要求5所述的拉挤成型用环氧树脂体系，其特征在于：所述的氟硅聚合物是聚三氟丙基羟基硅氧烷或聚三氟丙基甲基硅氧烷中的一种或两种。
- 根据权利要求1～3任一项所述的拉挤成型用环氧树脂体系，其特 征在于：以环氧树脂100重量份计，还包含促进剂1～10重量份。
- 一种环氧树脂复合材料，根据权利要求1～8任一项所述的拉挤成型用环氧树脂体系制备而成。
- 根据权利要求9所述的环氧树脂复合材料，其特征在于：含有碳纤维。
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| WO2005080465A1 (de) * | 2004-02-23 | 2005-09-01 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Abriebbeständige und alkalibeständige beschichtungen oder formkörper mit niedrigenergieoberfläche |
| JP2009013205A (ja) * | 2007-06-29 | 2009-01-22 | Adeka Corp | 一液型シアネート−エポキシ複合樹脂組成物 |
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