WO2019011244A1 - 一种高强高韧热固性树脂基复合材料的制备方法及应用 - Google Patents

一种高强高韧热固性树脂基复合材料的制备方法及应用 Download PDF

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WO2019011244A1
WO2019011244A1 PCT/CN2018/095179 CN2018095179W WO2019011244A1 WO 2019011244 A1 WO2019011244 A1 WO 2019011244A1 CN 2018095179 W CN2018095179 W CN 2018095179W WO 2019011244 A1 WO2019011244 A1 WO 2019011244A1
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pcl
block copolymer
pdms
molecular weight
weight
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French (fr)
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邹华维
陈洋
衡正光
梁梅
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四川大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
    • C08G63/6952—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from hydroxycarboxylic acids
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • 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
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • 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

Definitions

  • the invention relates to a preparation method and application of a high molecular weight block copolymer PS-PCL-PDMS-PCL-PS modified epoxy resin.
  • thermosetting resin As an important type of thermosetting resin, epoxy resin is widely used in various fields due to its excellent properties. However, the inherent brittleness and poor damping properties brought about by high cross-linking limit its application in high-performance composites. In recent years, block copolymers have attracted much attention due to their ability to form different shapes in selective solvents. Research on modified epoxy resins has also been reported, but few reports have been made by designing block copolymers and their epoxy resins. Morphology in the matrix to obtain the desired properties for the study.
  • the core-shell structure is a relatively classic method of toughening epoxy resin.
  • the traditional core-shell structure controls the particle size by controlling the feed ratio by emulsion polymerization.
  • the rubbery flexible material is used as the core, and the rigid polymethyl methacrylate (PMMA) is used as the shell. Effectively improve the toughness of epoxy resin, but its tensile strength and modulus will be greatly reduced.
  • the present invention prepares a high molecular weight block copolymer SLDLS (polystyrene-polycaprolactone-polydimethylsiloxane-polycaprolactone-polystyrene) by controlling different dosage ratios of products during the reaction. Adding it to the epoxy resin not only increases the tensile strength of the composite, but also increases its toughness and dynamic rigidity.
  • SLDLS polystyrene-polycaprolactone-polydimethylsiloxane-polycaprolactone-polystyrene
  • the present invention provides a block copolymer of the formula I,
  • the block copolymer n is 18 to 645, t is 10 to 706, m is 5 to 100, and the number average molecular weight is 50,000 to 150,000 g/mol.
  • the block copolymer n is 46 to 60, t is 348 to 436, m is 42, and the number average molecular weight is 89162 to 104158 g/mol.
  • the block copolymer has a molecular weight distribution index of from 1 to 2, preferably from 1.23 to 1.52.
  • hydroxyl terminated polydimethylsiloxane hydroxyl terminated polydimethylsiloxane, caprolactone, 2-bromoisobutylyl bromide, styrene. Further preferably, it is prepared from the following materials:
  • PCL-b-PDMS-b-PCL is formed from hydroxyl-terminated polydimethylsiloxane and caprolactone, and the molar ratio of hydroxyl-terminated polydimethylsiloxane and caprolactone is 1.36: (140-237);
  • PCL-b-PDMS-b-PCL is reacted with 2-bromoisobutylyl bromide to obtain Br-PCL-b-PDMS-b-PCL-Br, PCL-b-PDMS-b-PCL and 2-bromo
  • the isobutyl bromide molar ratio is 1:10;
  • the invention also provides an epoxy resin composite material, which is prepared by using the above block copolymer as an additive, an epoxy prepolymer and a curing agent.
  • the block copolymer is added in an amount of from 1% by weight to 60% by weight, preferably from 5% by weight to 20% by weight, based on the epoxy prepolymer.
  • the weight ratio of the epoxy prepolymer to the curing agent is from 1.37:1 to 3:1.
  • the present invention also provides a method of preparing the aforementioned block copolymer, characterized in that it comprises the following steps:
  • the block copolymer is obtained by reacting Br-PCL-b-PDMS-b-PCL-Br with styrene.
  • the reaction method of the step (1) is: azeotropically removing water from the terminal hydroxyl polydimethylsiloxane oil and dried toluene in an anhydrous oxygen-free bottle, and distilling off excess toluene; then adding caprolactone and stannous octoate to the above After purification of the hydroxyl terminated polydimethylsiloxane oil; after three liquid nitrogen freezing-vacuum degassing-thawing cycles, the flask under negative pressure is placed in a 120 ° C constant temperature oil bath and stirred for 36 hours; after the reaction is completed, The crude product is dissolved in a dichloromethane (DCM) solution, and then dropped into a frozen methanol to precipitate, and filtered; preferably, the stannous octoate is added in an amount of 1 wt of caprolactone;
  • DCM dichloromethane
  • the reaction method of the step (2) is: adding a solution of triethylamine, PCL-b-PDMS-b-PCL and 4-dimethylaminopyridine in dichloromethane to a three-neck round bottom flask in an argon atmosphere and an ice bath. In a state of stirring, the mixture was uniformly stirred; 2-bromoisobutyl bromo bromide was dissolved in a dichloromethane solution, and the mixture was added dropwise to the above mixture through a constant pressure funnel in an ice bath, and the mixture was stirred at room temperature after completion of the dropwise addition.
  • the reaction method of the step (3) is: sequentially adding Br-PCL-b-PDMS-b-PCL-Br, styrene monomer, cuprous bromide, N, N, N', N to an anhydrous oxygen-free bottle.
  • ", N"-pentamethyldiethylenetriamine after three liquid nitrogen freezing-vacuum degassing-thawing cycles, the flask under negative pressure was placed in a 110 ° C constant temperature oil bath for magnetic stirring for 16 h; The product was exposed to air and cooled to room temperature until the reaction was stopped; the product was dissolved in DCM and passed through a neutral alumina column to remove the catalyst; the solution was concentrated by rotary evaporation and dropped into the frozen methanol to precipitate, filtered; After the precipitation-filtration process, the final product was dried to a constant weight in a vacuum oven at 30 °C.
  • the invention obtains a high molecular weight block copolymer, and the composite material with the epoxy resin has large tensile strength, good toughness, strong dynamic rigidity and good application prospect.
  • Figure 1 is an NMR of block copolymers LDL and SLDLS-L-1 according to Example 1 of the present invention.
  • Example 2 is a GPC of the block copolymer LDL and SLDLS-L-1 according to Example 1 of the present invention.
  • Example 4 is a GPC of block copolymer LDL and SLDLS-L-2 according to Example 3 of the present invention.
  • Figure 5 is a TEM photograph of an epoxy resin containing 10 wt% (a, a') and 20 wt% (b, b') SLDLS-L-1 according to Example 3 of the present invention.
  • Fig. 6 is a graph showing changes in tensile strength of block copolymers of different materials.
  • Figure 7 is a graph showing the elongation at break of different materials as a function of the amount of block copolymer added.
  • Figure 8 is a graph showing the fracture toughness (K IC ) of different materials as a function of the amount of block copolymer added.
  • HTPDMS The molecular weight of HTPDMS was 3,123, the molecular weight of caprolactone was 114, the molecular weight of 2-bromoisobutylyl bromide was 229.91, and the molecular weight of styrene was 104.
  • HTPDMS hydroxy-terminated polydimethylsiloxane
  • ⁇ -CL caprolactone
  • Sn(Oct) 2 stannous octoate
  • the solution was concentrated by rotary evaporation and dropped into a cold methanol to precipitate and filtered. After three dissolution-precipitation-filtration processes, the final product was dried to constant weight in a vacuum oven at 30 ° C in a yield of 60-70%.
  • n 46
  • t 436
  • m 42
  • HTPDMS The molecular weight of HTPDMS was 3,123, the molecular weight of caprolactone was 114, the molecular weight of 2-bromoisobutylyl bromide was 229.91, and the molecular weight of styrene was 104.
  • HTPDMS hydroxyl terminated polydimethylsiloxane
  • the solution was concentrated by rotary evaporation and dropped into a cold methanol to precipitate and filtered. After three dissolution-precipitation-filtration processes, the final product was dried to constant weight in a vacuum oven at 30 ° C in a yield of 50-60%.
  • n 60
  • t 348
  • m 42
  • the block copolymer PS-b-PCL-b-PDMS-b-PCL-b-PS (SLDLS-L1) prepared in Example 1 was added to the epoxy prepolymer (DGEBA) in the proportions shown in Table 1. Stir vigorously at 120 ° C until a homogeneously clear solution is formed, and then the curing agent MOCA is added to the system and stirred rapidly and vigorously until a homogeneous and transparent solution is obtained. The obtained blended solution was placed in a vacuum oven at 120 ° C for 1 h to remove bubbles in the system, and then poured into a polytetrafluoroethylene mold, cured at 150 ° C for 2 h, and then heated to 180 ° C for 2 h. After the curing reaction was completed, the mold was released. An epoxy thermosetting resin containing a block copolymer.
  • the block copolymer PS-b-PCL-b-PDMS-b-PCL-b-PS (SLDLS-L2) prepared in Example 2 was added to the epoxy prepolymer (DGEBA) in the proportions shown in Table 1.
  • DGEBA epoxy prepolymer
  • MOCA curing agent
  • the obtained blended solution was placed in a vacuum oven at 120 ° C for 1 h to remove bubbles in the system, and then poured into a polytetrafluoroethylene mold, cured at 150 ° C for 2 h, and then heated to 180 ° C for 2 h. After the curing reaction was completed, the mold was released.
  • the material of the present invention the composite materials prepared in Example 3 and Example 4, respectively;
  • Comparative material 2 LDL/EP composite material
  • the preparation method is as follows: the block copolymer PCL-b-PDMS-b-PCL (LDL) is added to the epoxy prepolymer (DGEBA) according to Table 2, and vigorously stirred at 120 ° C to form a uniform transparent solution, and then The curing agent MOCA was added to the system and stirred rapidly and vigorously until a homogeneously clear solution was obtained.
  • the obtained blended solution was placed in a vacuum oven at 120 ° C for 1 h to remove bubbles in the system, and then poured into a polytetrafluoroethylene mold, cured at 150 ° C for 2 h, and then heated to 180 ° C for 2 h. After the curing reaction was completed, the mold was released.
  • An epoxy thermosetting resin containing a block copolymer is added to the epoxy prepolymer (DGEBA) according to Table 2, and vigorously stirred at 120 ° C to form a uniform transparent solution, and then The curing agent MOCA was added to the system and stirred rapidly and vigorously
  • Comparative material 3 Preparation of epoxy resin containing low molecular weight block copolymer (SLDLS-S)
  • the preparation method is as follows: the preparation method of the low molecular weight block copolymer is the same as the literature Heng Z, Zeng Z, Zhang B, et al. Enhancing mechanical performance of epoxy thermosets via designing a block copolymer to self-organize into "core-shell" nanostructure [ J].RSC Advances, 2016, 6(80): 77030-77036, adding low molecular weight block copolymer PS-b-PCL-b-PDMS-b-PCL-b-PS (SLDLS-S) according to Table 3.
  • the samples were sectioned at -120 ° C using a Leica UC7 low temperature microtome to obtain a thickness of 100 to 150 nm. After 15 min of osmium tetroxide at room temperature, it was observed on a Tecnai G2F20 transmission electron microscope. The low electron beam current was less than 10 mA and the acceleration voltage was 120 keV.
  • test specimens The tensile properties of the test specimens were tested according to the GB/T 2567-2008 standard using an Instron 5567 universal material tensile tester at a test speed of 10 mm/min.
  • SLDLS-L contributes more to the tensile properties of the composite than the LDL modified epoxy resin.
  • the addition amount of SLDLS-L block copolymer is 10wt%, the tensile strength and elongation at break of the composite are higher than those of LDL/EP composite.
  • the test was carried out using a three-point bending gradient heating mode of the TA Q800 dynamic mechanical performance tester at a heating rate of 3 ° C/min and a test temperature range of 30 to 250 ° C.
  • Table 4 shows the results of dynamic mechanical properties of composites with different block copolymer contents.
  • the glass transition temperature of the composite decreases gradually, and the effective damping temperature range of the composite increases significantly.
  • the addition of the high molecular weight block copolymer increases the storage modulus of the composite and increases the dynamic rigidity. When the addition amount is 15% by weight, the storage modulus of the composite reaches a maximum.
  • the fracture toughness test sample is shown in the figure. According to the ASTM E399 standard, a three-point bending mode was used with a test rate of 2 mm/min.
  • the fracture toughness (K IC ) of the material can be calculated from the following formula:
  • the mechanical properties of the nanocomposites show that the introduction of block copolymers effectively improves the tensile strength, elongation at break and fracture toughness of nanocomposites compared to pure epoxy resins.
  • the results of dynamic mechanical properties analysis show that as the amount of block copolymer increases, the glass transition temperature of the composite decreases gradually, and the effective damping temperature range and storage modulus increase significantly.
  • Fracture toughness analysis shows that the introduction of block copolymers significantly improves the fracture toughness of nanocomposites.
  • the composite material of the high molecular weight block copolymer and the epoxy resin of the invention has a large tensile strength, and the toughness and dynamic rigidity are also obtained. improve.
  • a high molecular weight block copolymer is prepared by the method of the invention, and a composite material thereof with an epoxy resin is prepared, and the composite material has large tensile strength, good toughness, strong dynamic rigidity and application prospect. good.

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Abstract

提供了一种高分子量嵌段共聚物PS-b-PCL-b-PDMS-b-PCL-b-PS和改性环氧树脂的方法，该嵌段共聚物PS-b-PCL-b-PDMS-b-PCL-b-PS具有如式Ⅰ所示结构：用该嵌段共聚物PS-b-PCL-b-PDMS-b-PCL-b-PS改性环氧树脂时，环氧树脂的拉伸强度会大幅提高，同时韧性和动态刚性也得到了提高。

Description

一种高强高韧热固性树脂基复合材料的制备方法及应用 技术领域
本发明涉及一种高分子量嵌段共聚物PS-PCL-PDMS-PCL-PS改性环氧树脂的制备方法及应用。
背景技术
环氧树脂作为一类重要的热固性树脂，由于其优良的性能广泛的应用于各个领域。但高交联度带来的固有脆性及差的阻尼性能限制了其在高性能复合材料中的应用。近年来，嵌段共聚物因其可以在选择性溶剂中形成不同的形状而广受关注，在改性环氧树脂方面也有研究，但很少有报道通过设计嵌段共聚物及其在环氧基体中的形态来获得所需性能的研究。
壳核结构是一种比较经典的增韧环氧树脂的方法。传统的壳核结构是通过乳液聚合反应控制投料比来控制粒子的尺寸大小，一般选用橡胶态的柔性物质为核，刚性聚甲基丙烯酸甲酯(PMMA)为壳，加入到环氧树脂中可以有效的改善环氧树脂的韧性，但其拉伸强度及模量会大大降低。
目前，衡正光等(Heng Z,Zeng Z,Zhang B,et al.Enhancing mechanical performance of epoxy thermosets via designing a block copolymer to self-organize into“core–shell”nanostructure[J].RSC Advances,2016,6(80):77030-77036.)人提供了一种低分子量的嵌段共聚物PS-PCL-PDMS-PCL-PS(SLDLS-S)及环氧复合材料的制备方法。在增韧环氧树脂的同时提升了复合材料的拉伸强度，但是效果并不明显，有待进一步改进。
发明内容
本发明通过控制反应时产物不同的投量比来制备高分子量的嵌段共聚物SLDLS(聚苯乙烯-聚己内酯-聚二甲基硅氧烷-聚己内酯-聚苯乙烯)，将其加入到环氧树脂中不仅提高了复合材料的拉伸强度，同时也提升了其韧性及动态刚性。
本发明提供了式Ⅰ所示的嵌段共聚物，
Figure PCTCN2018095179-appb-000001
所述嵌段共聚物n为18～645，t为10～706，m为5～100，数均分子量为50000～150000g/mol。
优选地，所述嵌段共聚物n为46～60，t为348～436，m为42，数均分子量为89162～104158g/mol。
优选地，所述嵌段共聚物的分子量分布指数为1～2，优选为1.23～1.52。
优选地，它是由如下原料制备而成：端羟基聚二甲基硅油、己内酯、2-溴异丁基酰溴、苯乙烯。进一步优选地，它是由如下原料制备而成：
1)由端羟基聚二甲基硅油和己内酯生成PCL-b-PDMS-b-PCL，端羟基聚二甲基硅油和己内酯的摩尔比为1.36:(140～237)；
2)PCL-b-PDMS-b-PCL与2-溴异丁基酰溴反应，得Br-PCL-b-PDMS-b-PCL-Br，PCL-b-PDMS-b-PCL与2-溴异丁基酰溴的摩尔比为1：10；
3)Br-PCL-b-PDMS-b-PCL-Br与苯乙烯反应，即得所述嵌段共聚物，Br-PCL-b-PDMS-b-PCL-Br与苯乙烯的摩尔比为0.7：(540～567)。
本发明还提供了一种环氧树脂复合材料，它是以前述的嵌段共聚物作为添加剂，加上环氧预聚体与固化剂，制备得到的环氧树脂复合材料。
优选地，所述嵌段共聚物的添加量为环氧预聚体的1wt％～60wt％，优选为5wt％～20wt％。
优选地，环氧预聚体与固化剂的重量比为1.37:1～3:1。
本发明还提供了一种制备前述的嵌段共聚物的方法，其特征在于：它包括如下步骤：
(1)取端羟基聚二甲基硅油，与己内酯反应，得到PCL-b-PDMS-b-PCL；
(2)将PCL-b-PDMS-b-PCL与2-溴异丁基酰溴反应，得Br-PCL-b-PDMS-b-PCL-Br；
(3)将Br-PCL-b-PDMS-b-PCL-Br与苯乙烯反应，即得所述嵌段共聚物。
优选地，
步骤(1)的反应方法是：取端羟基聚二甲基硅油和干燥的甲苯在无水无氧瓶中共沸除水，蒸出多余的甲苯；然后将己内酯和辛酸亚锡加入到上述纯化后的端羟基聚二甲基硅油中；经过三次液氮冷冻-真空脱气-解冻循环后，将负压状态下的烧瓶置入120℃恒温油浴中搅拌反应36h；待反应结束后，将粗产物溶解于二氯甲烷(DCM)溶液中，然后逐滴滴入冷冻甲醇中沉淀，过滤；优选地，所述辛酸亚锡的添加量为己内酯的1wt‰；
步骤(2)的反应方法是：将溶有三乙胺、PCL-b-PDMS-b-PCL和4-二甲氨基吡啶的二氯甲烷溶液加入到三口圆底烧瓶中，在氩气及冰浴的状态下，搅拌混合均匀；将2-溴异丁基酰溴溶于二氯甲烷溶液中，冰浴状态下通过恒压漏斗逐滴加入到上述混合液中，滴加完成后室温继续搅拌反应24h；反应结束后将溶液旋蒸除去一半溶剂，将剩 余产物逐滴滴入冷冻甲醇中沉淀，过滤；重复此溶解-沉淀-过滤过程三次，将纯化后的产物在30℃的真空烘箱中干燥至恒重；
步骤(3)的反应方法是：向无水无氧瓶中依次加入Br-PCL-b-PDMS-b-PCL-Br、苯乙烯单体、溴化亚铜、N,N,N’,N”,N”-五甲基二乙烯三胺，经过三次液氮冷冻-真空脱气-解冻循环后，将负压状态下的烧瓶置入110℃恒温油浴中磁力搅拌16h；待反应结束后，将产物暴露在空气中冷却至室温至反应停止；将产物溶于DCM并通过中性氧化铝柱子以除去催化剂；旋蒸浓缩溶液并逐滴滴入冷冻甲醇中沉淀，过滤；经三次溶解-沉淀-过滤过程后，将最终产物在30℃的真空烘箱中干燥至恒重，即可。
本发明制备得到了一种高分子量的嵌段共聚物，其与环氧树脂的复合材料拉伸强度大，韧性好，动态刚性强，应用前景良好。
显然，根据本发明的上述内容，按照本领域的普通技术知识和惯用手段，在不脱离本发明上述基本技术思想前提下，还可以做出其它多种形式的修改、替换或变更。
以下通过实施例形式的具体实施方式，对本发明的上述内容再作进一步的详细说明。但不应将此理解为本发明上述主题的范围仅限于以下的实例。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。
附图说明
图1为根据本发明实施例1的嵌段共聚物LDL及SLDLS-L-1的NMR。
图2为根据本发明实施例1的嵌段共聚物LDL及SLDLS-L-1的GPC。
图3为根据本发明实施例2的嵌段共聚物LDL及SLDLS-L-2的NMR。
图4为根据本发明实施例3的嵌段共聚物LDL及SLDLS-L-2的GPC。
图5为根据本发明实施例3含10wt％(a，a’)和20wt％(b，b’)SLDLS-L-1的环氧树脂的TEM照片。
图6不同材料的拉伸强度嵌段共聚物添加量的变化图。
图7不同材料的断裂伸长率随嵌段共聚物添加量的变化图。
图8不同材料的断裂韧性(K IC)随嵌段共聚物添加量的变化图。
具体实施方式
实施例1、高分子量嵌段共聚物PS-PCL-PDMS-PCL-PS的制备(SLDLS-L1)
一、制备方法
高分子量嵌段共聚物SLDLS的合成过程如下：
Figure PCTCN2018095179-appb-000002
1、PCL-b-PDMS-b-PCL的制备
HTPDMS的分子量为3123，己内酯的分子量为114，2-溴异丁基酰溴的分子量为229.91，苯乙烯的分子量为104。
取4.234g端羟基聚二甲基硅油(HTPDMS，m＝42)和干燥的甲苯在250ml无水无氧瓶中共沸除水，蒸出多余的甲苯，然后将16g己内酯(ε-CL)和辛酸亚锡[Sn(Oct) 2](添加量为1wt‰ε-CL)加入到上述纯化后的HTPDMS中。经过三次液氮冷冻-真空脱气-解冻循环后，将负压状态下的烧瓶置入120℃恒温油浴中搅拌反应36h。待反应结束后，将粗产物溶解于二氯甲烷(DCM)溶液中，然后逐滴滴入冷冻甲醇中沉淀，过滤。重复此溶解-沉淀-过滤过程三次以除去体系中可能存在的副产物和残余单体。将纯化后的产物在30℃的真空烘箱中干燥至恒重，产率为90～99％。得到的PCL-b-PDMS-b-PCL的分子量为13582。
2、大分子引发剂Br-PCL-b-PDMS-b-PCL-Br的制备
将溶有447mg三乙胺(TEA)、15g HO-PCL-b-PDMS-b-PCL-OH和810mg 4-二甲氨基吡啶(DMAP)的DCM(二氯甲烷)溶液加入到三口圆底烧瓶中，在氩气及冰浴的状态下，搅拌混合均匀。将2.539g的2-溴异丁基酰溴(2-BiB)溶于DCM溶液中，冰浴状态下通过恒压漏斗逐滴加入到上述混合液中，滴加完成后室温继续搅拌反应24h。反应结束后将溶液旋蒸除去一半溶剂，将剩余产物逐滴滴入冷冻甲醇中沉淀，过滤。重复此溶解-沉淀-过滤过程三次，将纯化后的产物在30℃的真空烘箱中干燥至恒重，产率为95％～99％。Br-PCL-b-PDMS-b-PCL-Br的分子量为13732。
3、PS-b-PCL-b-PDMS-b-PCL-b-PS的制备
向无水无氧瓶中依次加入10g大分子引发剂、66g苯乙烯单体、105mg溴化亚铜(CuBr)、126mg N,N,N’,N”,N”-五甲基二乙烯三胺(PMDETA)，经过三次液氮冷冻-真空脱气-解冻循环后，将负压状态下的烧瓶置入110℃恒温油浴中磁力搅拌16h。待反应结束 后，将产物暴露在空气中冷却至室温至反应停止。将产物溶于DCM并通过中性氧化铝柱子以除去催化剂。旋蒸浓缩溶液并逐滴滴入冷冻甲醇中沉淀，过滤。经三次溶解-沉淀-过滤过程后，将最终产物在30℃的真空烘箱中干燥至恒重，产率为60～70％。
二、基本性质(PS-b-PCL-b-PDMS-b-PCL-b-PS的化学结构及分子量检测)
通过1HNMR及GPC对PS-b-PCL-b-PDMS-b-PCL-b-PS的化学结构及分子量进行表征，结果如图1及图2所示。
结果表明：PS-b-PCL-b-PDMS-b-PCL-b-PS成功合成，其数均分子量为104158，分子量分布指数1.52，其结构式为
Figure PCTCN2018095179-appb-000003
其中，n为46，t为436，m为42。
实施例2、高分子量嵌段共聚物PS-PCL-PDMS-PCL-PS的制备(SLDLS-L2)
一、制备方法
高分子量嵌段共聚物SLDLS的合成过程同实施例1。
HTPDMS的分子量为3123，己内酯的分子量为114，2-溴异丁基酰溴的分子量为229.91，苯乙烯的分子量为104。
1、PCL-b-PDMS-b-PCL的制备
取4.234g端羟基聚二甲基硅油(HTPDMS，m＝42)和一定量干燥的甲苯在250ml无水无氧瓶中共沸除水，蒸出多余的甲苯，然后将26.96g己内酯(ε-CL)和辛酸亚锡[Sn(Oct) 2](添加量为1wt‰ε-CL)加入到上述纯化后的HTPDMS中。经过三次液氮冷冻-真空脱气-解冻循环后，将负压状态下的烧瓶置入120℃恒温油浴中搅拌反应36h。待反应结束后，将粗产物溶解于适量的二氯甲烷(DCM)溶液中，然后逐滴滴入冷冻甲醇中沉淀，过滤。重复此溶解-沉淀-过滤过程三次以除去体系中可能存在的副产物和残余单体。将纯化后的产物在30℃的真空烘箱中干燥至恒重，产率为90～99％。得到的PCL-b-PDMS-b-PCL的分子量为16874。
2、大分子引发剂Br-PCL-b-PDMS-b-PCL-Br的制备
同实施例1。Br-PCL-b-PDMS-b-PCL-Br的分子量为17024。
3、PS-b-PCL-b-PDMS-b-PCL-b-PS的制备
向无水无氧瓶中依次加入12g、大分子引发剂56.896g苯乙烯单体、204mg溴化亚铜(CuBr)、247mg N,N,N’,N”,N”-五甲基二乙烯三胺(PMDETA)，经过三次液氮冷冻-真空 脱气-解冻循环后，将负压状态下的烧瓶置入110℃恒温油浴中磁力搅拌16h。待反应结束后，将产物暴露在空气中冷却至室温至反应停止。将产物溶于DCM并通过中性氧化铝柱子以除去催化剂。旋蒸浓缩溶液并逐滴滴入冷冻甲醇中沉淀，过滤。经三次溶解-沉淀-过滤过程后，将最终产物在30℃的真空烘箱中干燥至恒重，产率为50～60％。
二、基本性质(PS-b-PCL-b-PDMS-b-PCL-b-PS的化学结构及分子量检测)
通过 1HNMR及GPC对PS-b-PCL-b-PDMS-b-PCL-b-PS的化学结构及分子量进行表征，结果如图3及图4所示。
结果表明：PS-b-PCL-b-PDMS-b-PCL-b-PS成功合成，其数均分子量为89162，分子量分布指数1.23，其结构式为
Figure PCTCN2018095179-appb-000004
其中，n为60，t为348，m为42。
实施例3、环氧树脂基复合材料的制备
按表1所示比例，将实施例1制备的嵌段共聚物PS-b-PCL-b-PDMS-b-PCL-b-PS(SLDLS-L1)加入到环氧预聚体(DGEBA)中，在120℃下剧烈搅拌至形成均匀透明的溶液，再将固化剂MOCA加入体系中，快速剧烈搅拌直至获得均匀透明的溶液。将所得共混溶液放入120℃真空烘箱1h以除去体系内气泡，然后将其倒入聚四氟乙烯模具，150℃固化2h，然后升温至180℃固化2h，固化反应结束后，脱模得到含嵌段共聚物的环氧热固性树脂。
实施例4环氧树脂基复合材料的制备
按表1所示比例，将实施例2制备的嵌段共聚物PS-b-PCL-b-PDMS-b-PCL-b-PS(SLDLS-L2)加入到环氧预聚体(DGEBA)中，在120℃下剧烈搅拌至形成均匀透明的溶液，再将固化剂MOCA加入体系中，快速剧烈搅拌直至获得均匀透明的溶液。将所得共混溶液放入120℃真空烘箱1h以除去体系内气泡，然后将其倒入聚四氟乙烯模具，150℃固化2h，然后升温至180℃固化2h，固化反应结束后，脱模得到含嵌段共聚物的环氧热固性树脂。
表1：不同混合液的用料配比
Figure PCTCN2018095179-appb-000005
以下用试验例的方式来说明本发明的有益效果：
试验例1 本发明制备的嵌段共聚物及环氧树脂基复合材料所做的性质检测
一、材料制备
1、本发明材料：分别取实施例3和实施例4制备的复合材料；
2、对比材料1：不含嵌段共聚物的环氧树脂的制备
将60g环氧预聚体DGEBA、24g固化剂MOCA在120℃下剧烈搅拌，直至形成均匀透明的溶液。将所得共混溶液放入120℃真空烘箱1h以除去体系内气泡，然后将其倒入聚四氟乙烯模具，150℃固化2h，然后升温至180℃固化2h，固化反应结束后，脱模得到不含嵌段共聚物的环氧热固性树脂
3、对比材料2：LDL/EP复合材料
制备方法为：按表2将嵌段共聚物PCL-b-PDMS-b-PCL(LDL)加入到环氧预聚体(DGEBA)中，在120℃下剧烈搅拌至形成均匀透明的溶液，再将固化剂MOCA加入体系中，快速剧烈搅拌直至获得均匀透明的溶液。将所得共混溶液放入120℃真空烘箱1h以除去体系内气泡，然后将其倒入聚四氟乙烯模具，150℃固化2h，然后升温至180℃固化2h，固化反应结束后，脱模得到含嵌段共聚物的环氧热固性树脂。
表2：不同混合液的用料配比
Figure PCTCN2018095179-appb-000006
4、对比材料3：含低分子量的嵌段共聚物的环氧树脂的制备(SLDLS-S)
制备方法为：低分子量嵌段共聚物的制备方法同文献Heng Z,Zeng Z,Zhang B,et al.Enhancing mechanical performance of epoxy thermosets via designing a block copolymer to self-organize into“core–shell”nanostructure[J].RSC Advances,2016,6(80):77030-77036，按表3将低分子量嵌段共聚物PS-b-PCL-b-PDMS-b-PCL-b-PS(SLDLS-S)加入到环氧预聚体(DGEBA)中，在120℃下剧烈搅拌至形成均匀透明的溶液，再将固化剂MOCA加入体系中，快速剧烈搅拌直至获得均匀透明的溶液。将所得共混溶液放入120℃真空烘箱1h以除去体系内气泡，然后将其倒入聚四氟乙烯模具，150℃固化2h，然后升温至180℃固化2h，固化反应结束后，脱模得到含嵌段共聚物的环氧热固性树脂。
表3：不同混合液的用料配比
Figure PCTCN2018095179-appb-000007
二、检测方法
1、透射电镜
利用徕卡UC7低温超薄切片机在-120℃下对样品进行切片，所得式样厚度100～150nm。经过15min四氧化钌常温熏染后，在Tecnai G2F20型透射电镜上进行观察，低电子束流小于10mA，加速电压为120keV。
由图5可知，球状嵌段共聚物均匀的分布在环氧树脂基体内，尺寸为20～40nm。表明嵌段共聚物SLDLS-L1在环氧基体内发生微观相分离，形成以柔性PDMS为核、刚性PS为壳的“核-壳”结构，成功制备了含嵌段共聚物的环氧纳米复合材料。
2、拉伸性能
采用Instron 5567万能材料拉伸试验机，根据GB/T 2567-2008标准测试试样的拉伸性能，测试速度为10mm/min。
由图6可知，随嵌段共聚物SLDLS含量的增加，纳米复合材料的断裂伸长率先增加后基本保持不变，拉伸强度先增加后降低。比如，当SLDLS-L1添加量为10wt％时，复合材料的拉伸强度达到最大值89.45MPa；当添加量为15wt％时，复合材料的断裂伸长率达到最大值6.43％。
由图7可知，相比于LDL改性环氧树脂来说，SLDLS-L对复合材料的拉伸性能贡献 更大。当SLDLS-L嵌段共聚物的添加量为10wt％时，复合材料的拉伸强度和断裂伸长率均高于LDL/EP复合材料。
3、动态机械性能分析
采用TA Q800动态机械性能测试仪的三点弯曲梯度升温模式进行测试，升温速率为3℃/min，测试温度范围为30～250℃。
表4为添加不同嵌段共聚物含量的复合材料的动态机械性能测试结果。随着高分子量嵌段共聚物添加量的增加，复合材料的玻璃化转变温度逐渐降低，同时，复合材料的有效阻尼温域明显增加。加入高分子量嵌段共聚物，使复合材料的储能模量增加，动态刚性增加。当添加量为15wt％时，复合材料的储能模量达到最大值。
表4、不同嵌段共聚物含量的复合材料的动态机械性能测试
Figure PCTCN2018095179-appb-000008
4、断裂韧性分析
断裂韧性测试样条如图所示。按照ASTM E399标准，采用三点弯曲模式，测试速率为2mm/min。材料的断裂韧性(K IC)可由下式计算得到:
Figure PCTCN2018095179-appb-000009
Figure PCTCN2018095179-appb-000010
Figure PCTCN2018095179-appb-000011
Figure PCTCN2018095179-appb-000012
由图8可知，嵌段共聚物的加入使环氧纳米复合材料的K IC值均高于纯环氧树脂且随着嵌段共聚物含量的增加，K IC值先增加后基本保持不变。比如，当SLDLS-L1嵌段共聚物添加量为20wt％时，复合材料的K IC值达到1.43MN/m 3/2。复合材料的断裂韧性得到显著提高。
三、总结
以双端羟基聚二甲基硅氧烷,ε-己内酯和苯乙烯为原料，通过控制反应物不同的投料比，得到了一种既有柔性段(PCL和PDMS)又有刚性段(PS)的两亲性高分子嵌段共聚物PS-b-PCL-b-PDMS-b-PCL-b-PS。将上述嵌段共聚物与环氧树脂共混，制备了具有纳米结构的环氧树脂复合材料。透射电镜的结果表明嵌段共聚物在环氧树脂基体内发生微相分离，嵌段共聚物自发形成的“壳-核”结构均匀分散在环氧树脂基体内。
对纳米复合材料进行的机械性能测试结果表明：相比于纯环氧树脂，嵌段共聚物的引入有效的提高了纳米复合材料的拉伸强度、断裂伸长率和断裂韧性。动态机械性能分析结果表明，随嵌段共聚物添加量的增加，复合材料的玻璃化转变温度逐渐降低，有效阻尼温域和储能模量明显增加。断裂韧性分析表明，嵌段共聚物的引入使纳米复合材料的断裂韧性得到显著提高。
并且，与低分子量嵌段共聚物与环氧树脂的复合材料相比，本发明高分子量嵌段共聚物与环氧树脂的复合材料，其拉伸强度大幅提高，同时韧性和动态刚性也得到了提高。
综上，本发明方法制备得到了一种高分子量的嵌段共聚物，还制备得到了它与环氧树脂的复合材料，该复合材料的拉伸强度大，韧性好，动态刚性强，应用前景良好。

Claims (10)

  1. 式Ⅰ所示的嵌段共聚物，其特征在于：
    Figure PCTCN2018095179-appb-100001
    所述嵌段共聚物n为18～645，t为10～706，m为5～100，数均分子量为50000～150000g/mol。
  2. 根据权利要求1所述的嵌段共聚物，其特征在于：所述嵌段共聚物n为46～60，t为348～436，m为42，数均分子量为89162～104158g/mol。
  3. 根据权利要求2所述的嵌段共聚物，其特征在于：所述嵌段共聚物的分子量分布指数为1～2，优选为1.23～1.52。
  4. 根据权利要求1～3任意一项所述的嵌段共聚物，其特征在于：它是由如下原料制备而成：端羟基聚二甲基硅油、己内酯、2-溴异丁基酰溴、苯乙烯。
  5. 根据权利要求4所述的嵌段共聚物，其特征在于：它是由如下原料制备而成：
    1)由端羟基聚二甲基硅油和己内酯生成PCL-b-PDMS-b-PCL，端羟基聚二甲基硅油和己内酯的摩尔比为1.36:(140～237)；
    2)PCL-b-PDMS-b-PCL与2-溴异丁基酰溴反应，得Br-PCL-b-PDMS-b-PCL-Br，PCL-b-PDMS-b-PCL与2-溴异丁基酰溴的摩尔比为1：10；
    3)Br-PCL-b-PDMS-b-PCL-Br与苯乙烯反应，即得所述嵌段共聚物，Br-PCL-b-PDMS-b-PCL-Br与苯乙烯的摩尔比为0.7：(540～567)。
  6. 一种环氧树脂复合材料，其特征在于：它是以权利要求1～5任意一项所述的嵌段共聚物作为添加剂，加上环氧预聚体与固化剂，制备得到的环氧树脂复合材料。
  7. 根据权利要求6所述的环氧树脂复合材料，其特征在于：所述嵌段共聚物的添加量为环氧预聚体的1wt％～60wt％，优选为5wt％～20wt％。
  8. 根据权利要求6所述的环氧树脂复合材料，其特征在于：环氧预聚体与固化剂的重量比为1.37:1～3:1。
  9. 一种制备权利要求1～5任意一项所述的嵌段共聚物的方法，其特征在于：它包括如下步骤：
    (1)取端羟基聚二甲基硅油，与己内酯反应，得到PCL-b-PDMS-b-PCL；
    (2)将PCL-b-PDMS-b-PCL与2-溴异丁基酰溴反应，得Br-PCL-b-PDMS-b-PCL-Br；
    (3)将Br-PCL-b-PDMS-b-PCL-Br与苯乙烯反应，即得所述嵌段共聚物。
  10. 根据权利要求9所述的方法，其特征在于：
    步骤(1)的反应方法是：取端羟基聚二甲基硅油和干燥的甲苯在无水无氧瓶中共沸除水，蒸出多余的甲苯；然后将己内酯和辛酸亚锡加入到上述纯化后的端羟基聚二甲基硅油中；经过三次液氮冷冻-真空脱气-解冻循环后，将负压状态下的烧瓶置入120℃恒温油浴中搅拌反应36h；待反应结束后，将粗产物溶解于二氯甲烷(DCM)溶液中，然后逐滴滴入冷冻甲醇中沉淀，过滤；优选地，所述辛酸亚锡的添加量为己内酯的1wt‰；
    步骤(2)的反应方法是：将溶有三乙胺、PCL-b-PDMS-b-PCL和4-二甲氨基吡啶的二氯甲烷溶液加入到三口圆底烧瓶中，在氩气及冰浴的状态下，搅拌混合均匀；将2-溴异丁基酰溴溶于二氯甲烷溶液中，冰浴状态下通过恒压漏斗逐滴加入到上述混合液中，滴加完成后室温继续搅拌反应24h；反应结束后将溶液旋蒸除去一半溶剂，将剩余产物逐滴滴入冷冻甲醇中沉淀，过滤；重复此溶解-沉淀-过滤过程三次，将纯化后的产物在30℃的真空烘箱中干燥至恒重；
    步骤(3)的反应方法是：向无水无氧瓶中依次加入Br-PCL-b-PDMS-b-PCL-Br、苯乙烯单体、溴化亚铜、N,N,N’,N”,N”-五甲基二乙烯三胺，经过三次液氮冷冻-真空脱气-解冻循环后，将负压状态下的烧瓶置入110℃恒温油浴中磁力搅拌16h；待反应结束后，将产物暴露在空气中冷却至室温至反应停止；将产物溶于DCM并通过中性氧化铝柱子以除去催化剂；旋蒸浓缩溶液并逐滴滴入冷冻甲醇中沉淀，过滤；经三次溶解-沉淀-过滤过程后，将最终产物在30℃的真空烘箱中干燥至恒重，即可。
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