WO2022083024A1 - 一种光热双重固化环氧树脂 - Google Patents

一种光热双重固化环氧树脂 Download PDF

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WO2022083024A1
WO2022083024A1 PCT/CN2021/074149 CN2021074149W WO2022083024A1 WO 2022083024 A1 WO2022083024 A1 WO 2022083024A1 CN 2021074149 W CN2021074149 W CN 2021074149W WO 2022083024 A1 WO2022083024 A1 WO 2022083024A1
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epoxy resin
curing
photothermal dual
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photothermal
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刘仁
孙凯强
李小杰
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Jiangnan University
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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
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen

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  • the present invention relates to a synthesis technology, which belongs to the technical field of radiation curing materials .
  • Photothermal dual curing refers to generally first photocuring to achieve partial crosslinking of the system, so that the material has certain properties, and then thermal curing to completely react the thermal crosslinking groups in the material to form a cured material.
  • the common groups that can be photocured in photothermal dual curing are double bonds, epoxy groups, etc.
  • Groups that can undergo thermal curing such as carboxyl groups, hydroxyl groups, isocyanate groups, epoxy groups, and the like.
  • Photothermal dual curing has the following advantages: curing of adhesives between complex parts, reducing shrinkage of photocuring systems, pre-setting of materials, and improving material properties. Widely used in 3D printing and adhesive industries.
  • photothermal dual curing system such as adding reactive diluent or oligomer for photocuring and epoxy resin or polyurethane resin for thermal curing and corresponding curing agent in the system.
  • This reaction is only a simple blending of raw materials, the material properties are unstable, and the preparation process error is large.
  • Another is to use acrylic acid to consume part of the epoxy groups in the epoxy resin to synthesize a resin containing both double bonds and epoxy groups, and then add the corresponding initiator and epoxy group curing agent.
  • the raw material acrylic acid used in this method is a volatile carcinogen, which is not found to meet the requirements of the current green production process, and the material properties are relatively brittle and the scope of application is narrow.
  • This patent uses bio-based itaconic acid to introduce double bonds, and the synthesized resin molecules have both epoxy groups and double bonds. The prepared material has stable and reliable performance and is suitable for large-scale production.
  • patent CN 110791196 A uses epoxy resin E51 and hydroxypropyl-terminated polydimethylsiloxane to synthesize the methyl group matrix resin with polyhydroxy in the main chain, using isophorone diisocyanate, trimethylolpropane, acrylic acid Hydroxyethyl ester and hexamethylene diisocyanate trimer are synthesized into B-component curing agent and then formulated into a photothermal dual curing system.
  • the reaction process is complicated, the raw materials are relatively expensive, and the material properties are unstable.
  • isophorone diisocyanate and organotin catalysts used in the synthesis process are toxic substances.
  • the patent CN 110643318 A uses several acrylate reactive diluents, and then adds thermal initiators and photoinitiators in the formula. It is impossible to control the proportion of groups in the system for photocuring and thermal curing. The properties of the material after pre-curing It cannot be precisely controlled, and the resulting material has a low modulus and a narrow range of applications.
  • the object of the present invention is to provide a kind of photothermal dual curing epoxy resin, and the resin structure is as follows:
  • R1 and R2 represent a hydrogen atom or a methyl group
  • R3 represents a hydrogen atom or a glycidyl group
  • R4 represents a benzene ring or a cyclohexane structure
  • the * sign is the position of the point of attachment of the group.
  • the resin structure is as follows:
  • the second object of the present invention is to provide a method for preparing a photothermal dual-curing epoxy resin. Fully mixed to obtain the photothermal dual-curing epoxy resin under high temperature reaction;
  • the epoxy resin includes a substance having the following structure
  • R1 represents a benzene ring or a cyclohexane structure
  • R2 represents a hydrogen atom or a methyl group
  • n represents an integer of 1-3.
  • the epoxy resin comprises bisphenol A epoxy resin, bisphenol F epoxy resin, difunctional novolac epoxy resin, difunctional glycidyl ether or difunctional epoxy oligomer;
  • the difunctional epoxy oligomer includes diglycidyl ether, bisphenol A diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, poly(propylene glycol) diglycidyl ether, Polydiglycidyl ether.
  • the epoxy group of the difunctional epoxy oligomer or epoxy resin will react with the carboxyl group of itaconic acid to form a photothermal dual curing epoxy resin.
  • the polymerization inhibitor is 0.05-0.2 parts by weight.
  • the specific method is as follows: fully mixing the difunctional epoxy oligomer or epoxy resin, itaconic acid, catalyst and polymerization inhibitor, the initial reaction temperature is 95-105°C, and after 0.5 hours of reaction , the temperature is raised to 105-120° C., and the acid value is titrated at intervals of half an hour until the acid value is less than 1 mgKOH/g, and the reaction is terminated to obtain the photothermal dual-curing epoxy resin.
  • the catalyst includes triphenylphosphine, triethylamine, tetrabutylamine bromide, acetylacetonate metal complexes, phosphorus pentoxide, aluminum oxide, phosphines, and amines Catalysts, etc.;
  • the polymerization inhibitors include p-methoxyphenol, hydroquinone, and phenols.
  • the third object of the present invention is to provide an application of a photothermal dual curing epoxy resin, the application is: as a photothermal dual curing coating composition, the composition comprises: a photothermal dual curing epoxy resin, Light curing reactive diluent, epoxy resin curing agent, thermal curing initiator, light curing initiator.
  • the photocurable reactive diluent includes tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate (DPGDA), 1,6-hexanediol diacrylate (HDDA); epoxy resin
  • TPGDA tripropylene glycol diacrylate
  • DPGDA dipropylene glycol diacrylate
  • HDDA 1,6-hexanediol diacrylate
  • the curing agent includes methylhexahydrophthalic anhydride (MHHPA), polyetheramine (D230), polyetheramine (D400);
  • the catalyst for thermal curing reaction includes 1,8-diazabicycloundec-7-ene (DBU ), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN); photocuring initiators include 1173, 819, TPO, 184 and the like.
  • the coating composition is coated on a steel plate, first cured under an ultraviolet lamp to form a partially cross-linked coating film, and then placed in an oven at 130-150° C. for 4-6 hours to obtain a fully cured coating film. coating.
  • the irradiation wavelength ranges from 250 nm to 600 nm and the light intensity ranges from 400 to 1200 mJ/cm 2 .
  • the photothermal dual curing epoxy resin is prepared by one-step reaction of bio-based itaconic acid and epoxy resin.
  • the resin has epoxy groups at both ends and a photocurable double bond on the middle main chain.
  • the comparison of the modified epoxy resin prepared by one-step reaction of acid and epoxy resin shows that the introduction of double bond groups can improve the crosslinking density of the material, thereby improving the modulus, glass transition temperature and hardness of the coating film.
  • the synthesis reaction is simple and efficient, the raw materials are green and environmentally friendly, and the material after the synthesized resin is cured has a high glass transition temperature, a high storage modulus and excellent performance.
  • the epoxy resin synthesized by itaconic acid in this patent has both epoxy groups and double bonds, which avoids the defect of unstable material properties caused by simple blending of raw materials.
  • the double bond cited in this patent uses bio-based itaconic acid, which is non-toxic and volatile, and the resulting resin molecule has both double bonds and epoxy groups, and the prepared formula is uniform and stable, so that the prepared material Uniform and stable performance, suitable for large-scale industrial production.
  • Fig. 1 The synthetic route of E51-Ita in embodiment 1-3
  • FIG. 3 The resins synthesized by modifying the epoxy resin with itaconic acid and succinic acid are E51-Ita-3 and E51-Sua-3, respectively, which are characterized by infrared spectra and compared with the raw material E51 to illustrate Successful synthesis of resins.
  • FIG. 4 The resins synthesized by modifying the epoxy resin with itaconic acid and succinic acid are E51-Ita-3 and E51-Sua-3, respectively, which are characterized by NMR and compared with the raw material E51 to illustrate Successful synthesis of resins.
  • Figure 5 Characterization of the DMA phase angle of the resin synthesized in Example 2 on the splines cured according to the formulation in Table 4.
  • Figure 6 Characterization of DMA storage modulus of the resin synthesized in Example 2 on the splines cured according to the formulation in Table 4.
  • epoxy resin E51 26 g, itaconic acid (Ita): 1 g, triphenylphosphine (TPP): 0.2 g, p-methoxyphenol (MEHQ): 0.03 g and add it to the three-necked flask, and install a mechanical A stirring paddle and a hollow glass stopper were used to fix the three-necked flask in an oil bath.
  • the initial temperature was 95°C. After half an hour of reaction, the temperature was raised to 105°C, and the acid value was titrated at intervals of half an hour until the acid value was less than 1 mgKOH/g and the reaction was terminated.
  • the synthetic resin is E51-Ita-1, and the synthetic route is shown in Figure 1.
  • the synthesized resin is formulated into a formula according to the following table
  • the above two formulations were cured under a F300UVA UV lamp (total light intensity was 1600 mJ/cm 2 ), the crawler speed of the UV exposure machine was 4.5 m min -1 , and the cured samples were named E51-Sua-1-F-UV and E51-Ita-1-F-UV. Again, the above formulation was heated to 130°C for 4.5 hours after UV exposure. The cured samples were named E51-Sua-1-F-UV-Heat and E51-Ita-1-F-UV-Heat.
  • the epoxy resin modified with itaconic acid increases the crosslinking density of the resin material compared with the epoxy resin modified with succinic acid (Sua), so the stretching The strength and Young's modulus were greatly improved.
  • the elongation at break of the itaconic acid group only subjected to light curing was higher than that of the succinic acid group, but the itaconic acid group after thermal curing was lower than the succinic acid group.
  • Coating adhesion was measured by cross seam adhesion using the ASTM D3359 standard. Pendulum hardness and pencil hardness were measured using ASTM D4366 and ASTM D3363 standards. Impact resistance was characterized using the ASTM D2794 standard.
  • epoxy resin E51 26 g, itaconic acid (Ita): 3 g, triphenylphosphine (TPP): 0.2 g, p-methoxyphenol (MEHQ) 0.03 g and add it to the three-necked flask, and install mechanical stirring A paddle and a hollow glass stopper were used to fix the three-necked flask in an oil bath. The initial temperature was 95 °C. After half an hour of reaction, the temperature was raised to 105 °C, and the acid value was titrated at intervals of half an hour until the acid value was less than 1 mgKOH/g, and the reaction was terminated.
  • the synthetic resin is E51-Ita-3, and the synthetic route is shown in Figure 1.
  • a modified epoxy resin without double bonds was synthesized with succinic acid.
  • the synthesis process is as follows: Weigh epoxy resin E51: 26 g, succinic acid (Sua): 3 g, triphenylphosphine (TPP) ): 0.2 g was added to the three-necked flask, and a mechanical stirring paddle and a hollow glass stopper were also installed, and the three-necked flask was fixed in an oil bath. Titrate the acid value until the acid value is less than 1 mgKOH/g to terminate the reaction, and the synthesized resin is E51-Sua-3.
  • the resins synthesized by modifying the epoxy resin with itaconic acid and succinic acid are E51-Ita-3 and E51-Sua-3, respectively. They are characterized by infrared spectra and compared with the raw material E51 to illustrate the success of the resin. synthesis, see Figure 3.
  • the resins synthesized by modifying the epoxy resin with itaconic acid and succinic acid are E51-Ita-3 and E51-Sua-3, respectively. They were characterized by NMR spectroscopy and compared with the raw material E51 to illustrate the success of the resin. synthesis, see Figure 4.
  • the synthesized resin is formulated into a formula according to the following table
  • the above two formulations were cured under a F300UVA UV lamp (total light intensity was 1600 mJ/cm 2 ), the crawler speed of the UV exposure machine was 4.5 m min -1 , and the cured samples were named E51-Sua-3-F-UV and E51-Ita-3-F-UV. Again, the above formulation was heated to 130°C for 4.5 hours after UV exposure. The cured samples were named E51-Sua-3-F-UV-Heat and E51-Ita-3-F-UV-Heat.
  • Coating adhesion was measured by cross seam adhesion using the ASTM D3359 standard. Pendulum hardness and pencil hardness were measured using ASTM D4366 and ASTM D3363 standards. Impact resistance was characterized using the ASTM D2794 standard.
  • the results show that the glass transition temperature and storage modulus of itaconic acid-modified epoxy resin E51-Ita-3-F-UV are higher than those of succinic acid-modified epoxy resin E51 when only light-cured - Sua-3-F-UV.
  • the glass transition temperature and storage modulus of E51-Ita-3-F-UV-Heat after light curing and then thermal curing are higher than those of E51-Sua-3-F-UV-Heat, the results also show that itaconic acid can improve the Crosslink density.
  • Epoxy resin E51: 26g, itaconic acid (Ita): 5g, triphenylphosphine (TPP): 0.2g, p-methoxyphenol (MEHQ) 0.03g were weighed into the three-necked flask, and a mechanical stirring was installed. A paddle and a hollow glass stopper were used to fix the three-necked flask in an oil bath. The initial temperature was 95 °C. After half an hour of reaction, the temperature was raised to 105 °C, and the acid value was titrated at intervals of half an hour until the acid value was less than 1 mgKOH/g, and the reaction was terminated.
  • the synthetic resin is E51-Ita-5, and the synthetic route is shown in Figure 1.
  • a modified epoxy resin without double bonds was synthesized with succinic acid.
  • the synthesis process is as follows: Weigh epoxy resin E51: 26 g, succinic acid (Sua): 5 g, triphenylphosphine (TPP) ): 0.2 g was added to the three-necked flask, and a mechanical stirring paddle and a hollow glass stopper were also installed, and the three-necked flask was fixed in an oil bath. Titrate the acid value until the acid value is less than 1 mgKOH/g to terminate the reaction, and the synthesized resin is E51-Sua-5.
  • the synthesized resin is formulated into a formula according to the following table
  • Coating adhesion was measured by cross seam adhesion using the ASTM D3359 standard. Pendulum hardness and pencil hardness were measured using ASTM D4366 and ASTM D3363 standards. Impact resistance was characterized using the ASTM D2794 standard.
  • 1,4-Butanediol diglycidyl ether (DDE): 26 g, itaconic acid (Ita): 5 g, triphenylphosphine (TPP): 0.2 g, p-methoxyphenol (MEHQ) 0.03 g were weighed and added To the three-necked flask, install a mechanical stirring paddle and a hollow glass stopper, and fix the three-necked flask in an oil bath.
  • DDE 1,4-Butanediol diglycidyl ether
  • Ita itaconic acid
  • TPP triphenylphosphine
  • MEHQ p-methoxyphenol
  • the initial temperature is 95°C, and the temperature is raised to 105°C after half an hour of reaction, and the acid value is titrated at intervals of half an hour, until The reaction was terminated after the acid value was less than 1 mgKOH/g, and the synthesized resin was DDE-Ita-7.
  • a modified epoxy resin was synthesized with 1,4-butanediol diglycidyl ether (DDE).
  • DDE 1,4-butanediol diglycidyl ether
  • the synthesis process is as follows: Weigh diglycidyl ether (DDE): 12g, butyric acid (Sua) : 5g, triphenylphosphine (TPP): 0.2g was added to the three-necked flask, a mechanical stirring paddle and a hollow glass stopper were installed, the three-necked flask was fixed in an oil bath, the initial temperature was 95°C, and the reaction was performed for half an hour After that, the temperature was raised to 105° C., and the acid value was titrated at intervals of half an hour until the acid value was less than 1 mgKOH/g, and the reaction was terminated.
  • the synthesized resin was DDE-Sua-7.
  • the synthesized resin is formulated into a formula according to the following table
  • Coating adhesion was measured by cross seam adhesion using the ASTM D3359 standard. Pendulum hardness and pencil hardness were measured using ASTM D4366 and ASTM D3363 standards. Impact resistance was characterized using the ASTM D2794 standard.
  • epoxy resins modified with itaconic acid and 1,4-butanediol diglycidyl ether were compared with epoxy resins modified with succinic acid and diglycidyl ether (DDE).
  • DDE 1,4-butanediol diglycidyl ether
  • the flexibility of the material is excellent, the adhesion of the coating film reaches 5B, and the impact resistance is good.

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Abstract

本发明利用生物基衣康酸与环氧树脂一步反应制备了光热双重固化环氧树脂，该树脂两端具有环氧基团，中间主链上具有双键，可同时参与热固化和光固化反应。所述合成反应原料绿色环保，合成工艺简单高效适用于工业大规模生产，固化后的材料玻璃化转变温度高，储能模量高，强度大，适用于光-热双重固化的应用领域，如涂料、3D打印、胶黏剂等等。

Description

一种光热双重固化环氧树脂 技术领域
本发明涉及一种 合成技术，属于 辐射固化材料技术领域。
背景技术
光热双重固化指的是一般先进行光固化使体系达到部分交联，使材料具备一定的性能之后，再进行热固化使材料内的热交联基团完全反应形成固化材料。光热双重固化中可以进行光固化的基团常见的有双键，环氧基团等。能进行热固化的基团如羧基、羟基、异氰酸酯基团、环氧基团等。光热双重固化具有如下几大类优点：复杂部件之间胶黏剂的固化、降低光固化体系收缩、材料预先定型以及提升材料性能等。广泛使用与3D打印以及胶黏剂行业。目前有很多种方法来配制光热双重固化体系，如在体系中添加可用于光固化的活性稀释剂或低聚物和用于热固化的环氧树脂或聚氨酯树脂以及相应的固化剂，但这种反应只是简单的原材料共混，材料性能不稳定，制备工艺误差较大。还有一种是用丙烯酸消耗环氧树脂中的部分环氧基团来合成即含有双键又含有环氧基团的树脂，再添加相应的引发剂和环氧基团固化剂。但这种方法使用的原材料丙烯酸是易挥发的致癌物，不发满足现在的绿色生产工艺要求，且材料性能较脆，适用范围较窄。本专利用生物基的衣康酸来引入双键，并且合成的树脂分子上既有环氧基团又有双键。制备的材料性能稳定可靠，适用于大规模的生产。
如专利CN 110791196 A使用环氧树脂E51、端羟丙基聚二甲基硅氧烷合成主链带多羟基的甲组分基体树脂，采用异弗尔酮二异氰酸酯、三羟甲基丙烷、丙烯酸羟乙酯、六亚甲基二异氰酸酯三聚体合成乙组分固化剂然后配制成光热双重固化体系，反应过程复杂、原料较贵、材料性能不稳定。且异佛尔酮二异氰酸酯以及合成过程中应用的有机锡类催化剂均是有毒物质。
如专利CN 110643318 A使用几种丙烯酸酯类活性稀释剂，然后在配方中添加热引发剂以及光引发剂的方法无法控制体系中多少比例基团进行光固化和热固化，预固化后的材料性能无法精确控制，制成的材料模量低，适用范围狭窄。
发明内容
基于上述问题，本发明的目的在于提供一种光热双重固化环氧树脂，所述树脂结构如下：
Figure PCTCN2021074149-appb-000001
其中，M代表
Figure PCTCN2021074149-appb-000002
Figure PCTCN2021074149-appb-000003
其中一种，其中R1、R2表示氢原子或甲基，R3表示氢原子或缩水甘油基，R4代表苯环或环己烷结构，*号为基团连接点位置。
在一种实施方式中，所述树脂结构如下：
Figure PCTCN2021074149-appb-000004
本发明的第二个目的在于，提供一种光热双重固化环氧树脂的制备方法，所述方法为：将二官环氧低聚物或环氧树脂、衣康酸、催化剂、阻聚剂充分混合，在高温反应下得到所述光热双重固化环氧树脂；
在一种实施方式中，所述环氧树脂包括具有以下结构的物质
Figure PCTCN2021074149-appb-000005
其中R1代表苯环或环己烷结构，R2表示氢原子或甲基，n代表1～3的整数。
在一种实施方式中，所述环氧树脂包括双酚A型环氧树脂、双酚F型环氧树脂、二官酚醛环氧树脂、二官缩水甘油醚或二官环氧低聚物；所述二官环氧低聚物包括二缩水甘油醚、双酚A二缩水甘油醚、新戊二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、聚(丙二醇)二缩水甘油醚、聚二缩水甘油醚。
所述二官环氧低聚物或环氧树脂的环氧基团会与衣康酸的羧基反应生成光热双重固化环氧树脂。
在一种实施方式中，
二官环氧低聚物或环氧树脂40—99重量份；
衣康酸0.2—30重量份；
催化剂0.5—1.5重量份；
阻聚剂0.05—0.2重量份。
在一种实施方式中，具体方法为：将二官环氧低聚物或环氧树脂、衣康酸、催化剂、阻聚剂充分混合，反应起始温度为95～105℃，反应0.5小时后，升温至105～120℃，间隔半个小时滴定酸值，直到酸值小于1mgKOH/g后终止反应，得到所述光热双重固化环氧树脂。
在一种实施方式中，所述催化剂包括三苯基膦、三乙胺、四丁基溴化胺、乙酰丙酮基金属络合物、五氧化二磷、三氧化二铝、膦类以及胺类催化剂等；所述阻聚剂包括对甲氧基酚、对苯二酚、苯酚类。
本发明的第三个目的在于，提供一种光热双重固化环氧树脂的应用，所述应用为：作为光热双重固化涂料组合物，所述组合物包括：光热双重固化环氧树脂、光固化活性稀释剂、环氧树脂固化剂、热固化引发剂、光固化引发剂。
在一种实施方式中，所述光固化活性稀释剂包括三丙二醇二丙烯酸酯(TPGDA)、二丙二醇二丙烯酸酯(DPGDA)、1,6-己二醇二丙烯酸酯(HDDA)；环氧树脂固化剂包括甲基六氢苯酐(MHHPA)、聚醚胺(D230)、聚醚胺(D400)；热固化反应的催化剂包括1,8-二氮杂二环十一碳-7-烯(DBU)、1,5-二氮杂双环[4.3.0]壬-5-烯(DBN)；光固化引发剂包括1173、819、TPO、184等。
在一种实施方式中，将涂料组合物涂覆在钢板上，先在紫外灯下固化成部分交联反应的涂膜，然后放入130～150℃烘箱内固化4～6小时得到完全固化的涂膜。
在一种实施方式中，辐照波长范围为250nm～600nm、光强为400～1200mJ/cm 2。
有益效果：
本发明利用生物基衣康酸与环氧树脂一步反应制备了光热双重固化环氧树脂，该树脂两端具有环氧基团，中间主链上具有可光固化的双键，然后用丁二酸与环氧树脂一步反应制备的改性环氧树脂进行对比说明双键基团的引入可以提高材料的交联密度，从而提升材料的模量、玻璃化转变温度以及涂膜的硬度等。所述合成反应简单高效，原料绿色环保，合成的树脂固化后的材料玻璃化转变温度高，储能模量高，性能优异。本专利用衣康酸合成的环氧树脂分子上既有环氧基团又有双键，避免了由于原材料简单共混导致的材料性能不稳定的缺陷。本专利的双键引用使用的是生物基的衣康酸，没有毒性和挥发性，生成的树脂分子上既有双键又有环氧基团，制备的配方均一稳定，从而使得制得的材料性能均一稳定，适用于大规模工业生产。
附图说明
说明各附图所表示的含义
图1：实施例1-3中E51-Ita的合成路线图
图2：实施例1-3中E51-Sua的合成路线图
图3：用衣康酸和丁二酸改性环氧树脂后合成的树脂分别为E51-Ita-3、E51-Sua-3，对其进行红外谱图的表征，与原料E51进行对比来说明树脂的成功合成。
图4：用衣康酸和丁二酸改性环氧树脂后合成的树脂分别为E51-Ita-3、E51-Sua-3，对其进行核磁谱图的表征，与原料E51进行对比来说明树脂的成功合成。
图5：实施例2所合成的树脂按照表4的配方固化的样条进行的DMA相位角的表征。
图6：实施例2所合成的树脂按照表4的配方固化的样条进行的DMA储能模量的表征。
具体实施方式
根据权利要求所包含的内容举例说明
实施例1：
称取环氧树脂E51：26g、衣康酸(Ita)：1g、三苯基膦(TPP)：0.2g、对甲氧基酚(MEHQ)：0.03g加入到三口烧瓶中，另安装上机械搅拌桨以及空心玻璃塞，将三口烧瓶固定于油浴锅内，起始温度为95℃， 反应半小时后升温至105℃，间隔半小时滴定酸值，直到酸值小于1mgKOH/g后终止反应，合成的树脂为E51-Ita-1，合成路线见图1。
Figure PCTCN2021074149-appb-000006
另外用于对比，用不含双键的丁二酸合成了不含双键的改性环氧树脂，合成过程如下：称取环氧树脂E51：26g、丁二酸(Sua)：1g、三苯基膦(TPP)：0.2g加入到三口烧瓶中，另安装上机械搅拌桨以及空心玻璃塞，将三口烧瓶固定于油浴锅内，起始温度为95℃，反应半小时后升温至105℃，间隔半小时滴定酸值，直到酸值小于1mgKOH/g后终止反应，合成的树脂为E51-Sua-1，合成路线见图2。
Figure PCTCN2021074149-appb-000007
合成后的树脂按照下表配制成配方
表1：实施例1配方比例单位：g
Figure PCTCN2021074149-appb-000008
将上述两个配方在F300UVA紫外灯下固化(总光强为1600mJ/cm 2)，紫外曝光机的履带速度为4.5m min -1，固化的样品命名为E51-Sua-1-F-UV和E51-Ita-1-F-UV。同样，上述配方在经过紫外曝光后再加热4.5小时，温度为130℃。固化的样品命名为E51-Sua-1-F-UV-Heat和E51-Ita-1-F-UV-Heat。
进行的表征：
1.拉伸测试
表2：实施例1样品的拉伸性能
Figure PCTCN2021074149-appb-000009
从上述结果可以得出，用衣康酸(Ita)改性的环氧树脂相比较丁二酸(Sua)改性的环氧树脂来说， 由于提高了树脂材料的交联密度，所以拉伸强度、以及杨氏模量大幅度提升，只进行光固化的衣康酸组断裂伸长率比丁二酸组高，但进行热固化后的衣康酸组比丁二酸组低。
2.涂膜性能
上述样品制备成涂膜后测试涂膜的基本性能，涂层厚度采用涂层厚度测量仪进行测量。涂层的附着力采用ASTM D3359标准通过交叉缝附着力进行测量。用ASTM D4366和ASTM D3363标准测量了摆杆硬度和铅笔硬度。耐冲击性用ASTM D2794标准进行了表征。
表3：实施例1样品的涂膜性能
Figure PCTCN2021074149-appb-000010
从表3可知，用衣康酸改性的环氧树脂相比较丁二酸改性的环氧树脂具有更优异的涂膜性能，原因是衣康酸的引入提供了更多的交联位点，从而提升交联密度。
实施例2：
称取环氧树脂E51：26g、衣康酸(Ita)：3g、三苯基膦(TPP)：0.2g、对甲氧基酚(MEHQ)0.03g加入到三口烧瓶中，另安装上机械搅拌桨以及空心玻璃塞，将三口烧瓶固定于油浴锅内，起始温度为95℃，反应半小时后升温至105℃，间隔半小时滴定酸值，直到酸值小于1mgKOH/g后终止反应，合成的树脂为E51-Ita-3，合成路线见图1。
Figure PCTCN2021074149-appb-000011
另外用于对比，用丁二酸合成了不含双键的改性环氧树脂，合成过程如下：称取环氧树脂E51：26g、丁二酸(Sua)：3g、三苯基膦(TPP)：0.2g加入到三口烧瓶中，另安装上机械搅拌桨以及空心玻璃塞，将三口烧瓶固定于油浴锅内，起始温度为95℃，反应半小时后升温至105℃，间隔半小时滴定酸值，直到酸值小于1mgKOH/g后终止反应，合成的树脂为E51-Sua-3。
Figure PCTCN2021074149-appb-000012
用衣康酸和丁二酸改性环氧树脂后合成的树脂分别为E51-Ita-3、E51-Sua-3，对其进行红外谱图的表征，与原料E51进行对比来说明树脂的成功合成，见图3。
用衣康酸和丁二酸改性环氧树脂后合成的树脂分别为E51-Ita-3、E51-Sua-3，对其进行核磁谱图的表征，与原料E51进行对比来说明树脂的成功合成，见图4。
合成后的树脂按照下表配制成配方
表4：实施例2配方比例单位：g
Figure PCTCN2021074149-appb-000013
将上述两个配方在F300UVA紫外灯下固化(总光强为1600mJ/cm 2)，紫外曝光机的履带速度为4.5m min -1，固化的样品命名为E51-Sua-3-F-UV和E51-Ita-3-F-UV。同样，上述配方在经过紫外曝光后再加热4.5小时，温度为130℃。固化的样品命名为E51-Sua-3-F-UV-Heat和E51-Ita-3-F-UV-Heat。
进行的表征：
1.拉伸测试
表5：实施例2样品的拉伸性能
Figure PCTCN2021074149-appb-000014
从上述结果可以得出，用衣康酸(Ita)改性的环氧树脂相比较丁二酸(Sua)改性的环氧树脂来说，由于提高了树脂材料的交联密度，所以拉伸强度、以及杨氏模量大幅度提升，只进行光固化的衣康酸组断裂伸长率有所提升，但进行热固化后的断裂伸长率有所下降。
2.涂膜性能
上述样品制备成涂膜后测试涂膜的基本性能，涂层厚度采用涂层厚度测量仪进行测量。涂层的附着力采用ASTM D3359标准通过交叉缝附着力进行测量。用ASTM D4366和ASTM D3363标准测量了摆硬度和铅笔硬度。耐冲击性用ASTM D2794标准进行了表征。
表6：实施例2样品的涂膜性能
Figure PCTCN2021074149-appb-000015
从表7可知，用衣康酸改性的环氧树脂相比较丁二酸改性的环氧树脂具有更优异的涂膜性能，原因是因为衣康酸的引入提供了更多的交联位点，从而提升交联密度。
3.DMA表征
将上述样品进行DMA表征测试玻璃化转变温度以及储能模量。结果见附图5和附图6
结果表明，只进行光固化时，衣康酸改性的环氧树脂E51-Ita-3-F-UV的玻璃化转变温度以及储能模量均高于丁二酸改性的环氧树脂E51-Sua-3-F-UV。光固化然后热固化后E51-Ita-3-F-UV-Heat的玻璃化转变温度以及储能模量均高于E51-Sua-3-F-UV-Heat，结果也说明衣康酸能够提高交联密度。
实施例3：
称取环氧树脂E51：26g、衣康酸(Ita)：5g、三苯基膦(TPP)：0.2g、对甲氧基酚(MEHQ)0.03g加入到三口烧瓶中，另安装上机械搅拌桨以及空心玻璃塞，将三口烧瓶固定于油浴锅内，起始温度为95℃，反应半小时后升温至105℃，间隔半小时滴定酸值，直到酸值小于1mgKOH/g后终止反应，合成的树脂为E51-Ita-5，合成路线见图1。
Figure PCTCN2021074149-appb-000016
另外用于对比，用丁二酸合成了不含双键的改性环氧树脂，合成过程如下：称取环氧树脂E51：26g、丁二酸(Sua)：5g、三苯基膦(TPP)：0.2g加入到三口烧瓶中，另安装上机械搅拌桨以及空心玻璃塞，将三口烧瓶固定于油浴锅内，起始温度为95℃，反应半小时后升温至105℃，间隔半小时滴定酸值，直到酸值小于1mgKOH/g后终止反应，合成的树脂为E51-Sua-5。
Figure PCTCN2021074149-appb-000017
合成后的树脂按照下表配制成配方
表7：实施例3配方比例单位：g
Figure PCTCN2021074149-appb-000018
进行的表征：
1.拉伸测试
表8：实施例3样品的拉伸性能
Figure PCTCN2021074149-appb-000019
从上述结果可以得出，用衣康酸(Ita)改性的环氧树脂相比较丁二酸(Sua)改性的环氧树脂来说，由于提高了树脂材料的交联密度，所以拉伸强度、以及杨氏模量大幅度提升，只进行光固化的衣康酸组断裂伸长率高于丁二酸组，但进行热固化后的断裂伸长率低于丁二酸组。
2.涂膜性能
上述样品制备成涂膜后测试涂膜的基本性能，涂层厚度采用涂层厚度测量仪进行测量。涂层的附着力采用ASTM D3359标准通过交叉缝附着力进行测量。用ASTM D4366和ASTM D3363标准测量了摆硬度和铅笔硬度。耐冲击性用ASTM D2794标准进行了表征。
表9：实施例3样品的涂膜性能
Figure PCTCN2021074149-appb-000020
从表9可知，用衣康酸性的环氧树脂相比较丁二酸改性的环氧树脂具有更优异的涂膜性能，原因是因为衣康酸的引入提供了更多的交联位点，从而提升交联密度。
实施例4：
称取1,4-丁二醇二缩水甘油醚(DDE)：26g、衣康酸(Ita)：5g、三苯基膦(TPP)：0.2g、对甲氧基酚(MEHQ)0.03g加入到三口烧瓶中，另安装上机械搅拌桨以及空心玻璃塞，将三口烧瓶固定于油浴锅内，起始温度为95℃，反应半小时后升温至105℃，间隔半小时滴定酸值，直到酸值小于1mgKOH/g后终止反应，合成的树脂为DDE-Ita-7。
Figure PCTCN2021074149-appb-000021
另外用于对比，用1,4-丁二醇二缩水甘油醚(DDE)合成了改性环氧树脂，合成过程如下：称取二缩水甘油醚(DDE)：12g、丁儿酸(Sua)：5g、三苯基膦(TPP)：0.2g加入到三口烧瓶中，另安装上机械搅拌桨以及空心玻璃塞，将三口烧瓶固定于油浴锅内，起始温度为95℃，反应半小时后升温至105℃，间隔半小时滴定酸值，直到酸值小于1mgKOH/g后终止反应，合成的树脂为DDE-Sua-7。
Figure PCTCN2021074149-appb-000022
合成后的树脂按照下表配制成配方
表10：实施例4配方比例单位：g
Figure PCTCN2021074149-appb-000023
Figure PCTCN2021074149-appb-000024
进行的表征：
1.拉伸测试
表11：实施例3样品的拉伸性能
Figure PCTCN2021074149-appb-000025
从上述结果可以得出，用1,4-丁二醇二缩水甘油醚(DDE)与衣康酸改性的环氧树脂相比较二缩水甘油醚(DDE)与丁二酸改性的环氧树脂来说，由于提高了材料的交联密度，所以材料的拉伸断裂伸长率大，具有优异的柔韧性。
2.涂膜性能
上述样品制备成涂膜后测试涂膜的基本性能，涂层厚度采用涂层厚度测量仪进行测量。涂层的附着力采用ASTM D3359标准通过交叉缝附着力进行测量。用ASTM D4366和ASTM D3363标准测量了摆硬度和铅笔硬度。耐冲击性用ASTM D2794标准进行了表征。
表12：实施例3样品的涂膜性能
Figure PCTCN2021074149-appb-000026
从表12可知，用衣康酸与1,4-丁二醇二缩水甘油醚(DDE)改性的环氧树脂相比较用丁二酸与二缩水甘油醚(DDE)改性的环氧树脂来说材料的柔韧性优异，涂膜的附着力达到5B，抗冲击性能佳。

Claims (10)

  1. 一种光热双重固化环氧树脂，其特征在于，所述树脂结构如下：
    Figure PCTCN2021074149-appb-100001
    其中，M代表
    Figure PCTCN2021074149-appb-100002
    Figure PCTCN2021074149-appb-100003
    其中一种，其中R1、R2表示氢原子或甲基，R3表示氢原子或缩水甘油基，R4代表苯环或环己烷结构，*号为基团连接点位置。
  2. 如权利要求1所述的一种光热双重固化环氧树脂，其特征在于，所述树脂结构如下：
    Figure PCTCN2021074149-appb-100004
  3. 如权利要求1所述的一种光热双重固化环氧树脂的制备方法，其特征在于，将二官环氧低聚物或环氧树脂与衣康酸、催化剂、阻聚剂充分混合，在高温反应下得到所述光热双重固化环氧树脂。
  4. 如权利要求3所述的一种光热双重固化环氧树脂的制备方法，其特征在于，所述环氧树脂包括具有以下结构的物质
    Figure PCTCN2021074149-appb-100005
    其中R1代表苯环或环己烷结构，R2表示氢原子或甲基，n表示0～3的整数。
  5. 如权利要求3所述的一种光热双重固化环氧树脂的制备方法，其特征在于，所述环氧树脂包括双酚A型环氧树脂、双酚F型环氧树脂、二官酚醛环氧树脂、二官缩水甘油醚或二官环氧低聚物；所述二官环氧低聚物包括二缩水甘油醚、双酚A二缩水甘油醚、新戊二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、聚(丙二醇)二缩水甘油醚、聚二缩水甘油醚。
  6. 根据权利要求3所述的一种光热双重固化环氧树脂的制备方法，其特征在于，
    二官环氧低聚物或环氧树脂40—99重量份；
    衣康酸0.2—30重量份；
    催化剂0.5—1.5重量份；
    阻聚剂0.05—0.2重量份。
  7. 根据权利要求3所述的一种光热双重固化环氧树脂的制备方法，其特征在于，具体方法为：将二官环氧低聚物或环氧树脂、衣康酸、催化剂、阻聚剂充分混合，反应起始温度为95～105℃，反应0.5小时后，升温至105～120℃，间隔半个小时滴定酸值，直到酸值小于1mgKOH/g后终止反应，得到所述光热双重固化环氧树脂。
  8. 根据权利要求3-7任一所述的一种光热双重固化环氧树脂的制备方法，其特征在于，所述催化剂包括三苯基膦、三乙胺、四丁基溴化胺、乙酰丙酮基金属络合物、五氧化二磷、三氧化二铝、膦类以及胺类催化剂等；所述阻聚剂包括对甲氧基酚、对苯二酚、苯酚类。
  9. 根据权利要求1或2所述的或权利要求3-7任一所述方法制备的光热双重固化环氧树脂的应用，其特征在于，作为光热双重固化涂料组合物，所述组合物包括：光热双重固化环氧树脂、光固化活性稀释剂、环氧树脂固化剂、热固化引发剂、光固化引发剂。
  10. 根据权利要求9所述的光热双重固化环氧树脂的应用，其特征在于，将涂料组合物涂覆在钢板上，先在紫外灯下固化成部分交联反应的涂膜，然后放入130～150℃烘箱内固化4～6小时得到完全固化的涂膜。
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