WO2019206200A1 - 一种含硫可降解超支化环氧树脂及其制备方法 - Google Patents

一种含硫可降解超支化环氧树脂及其制备方法 Download PDF

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WO2019206200A1
WO2019206200A1 PCT/CN2019/084160 CN2019084160W WO2019206200A1 WO 2019206200 A1 WO2019206200 A1 WO 2019206200A1 CN 2019084160 W CN2019084160 W CN 2019084160W WO 2019206200 A1 WO2019206200 A1 WO 2019206200A1
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epoxy resin
compound
organic solvent
preparation
hyperbranched
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PCT/CN2019/084160
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English (en)
French (fr)
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张道洪
郭文强
张俊珩
程娟
张爱清
李金林
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中南民族大学
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Priority to US16/568,831 priority Critical patent/US10808071B2/en
Publication of WO2019206200A1 publication Critical patent/WO2019206200A1/zh

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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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/022—Polycondensates containing more than one epoxy group per molecule characterised by the preparation process or apparatus used
    • 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
    • C08G59/1483—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing sulfur
    • 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
    • C08G59/3263—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing sulfur
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • 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
    • C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules
    • 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
    • C08G85/00—General processes for preparing compounds provided for in this subclass
    • C08G85/004—Modification of polymers by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation

Definitions

  • the invention relates to the technical field of hyperbranched epoxy resin and a preparation method thereof, in particular to a sulfur-containing degradable hyperbranched epoxy resin and a preparation method thereof.
  • the synthesis of the sulfur-containing epoxy resin is mainly obtained by (1) the mercapto compound and the epichlorohydrin are obtained by ring-opening or ring-closing reaction or (2) by using an epoxy resin and a thiourea.
  • the sulfur-containing epoxy resin prepared by the two methods has a hydrogen bond effect due to the hydroxyl group, so that the molecular chain of the sulfur-containing epoxy resin is easily entangled, resulting in a high viscosity of the product, which is usually required to be diluted by an organic solvent when applied; Existence, when applied to an acid anhydride curing system, it is easy to cause the acid anhydride to be opened and unstable, which eventually leads to a shortened storage period of the product.
  • the conventional process for preparing sulfur-containing epoxy resin usually requires adding a large amount of organic solvent, and most processes require a water washing step after the reaction is completed, which has certain pollution to the environment.
  • An epoxy resin or a sulfur-containing epoxy resin having a low viscosity and a low hydroxyl group can be prepared by a hydrosilylation reaction, but the product cost of the silicone is high, the efficiency is low, the yield is not high, the reaction time is long, and the energy consumption is large. It is difficult to scale up applications.
  • the inventors of the present application have prepared a sulfur-containing epoxy resin (ZL201310091452.0, ZL201210566173.0) by a reaction of a mercapto compound-olefin click reaction technique in a solution, which has high efficiency and high yield, and is the simplest method at that time.
  • all epoxy resin and hyperbranched epoxy resin prepared by the process technology are three-dimensional network structure after curing, and internal chemical bonds (carbon-carbon bonds, carbon-oxygen bonds) are difficult to be degraded, recycled and reused, and waste epoxy resin.
  • the product is highly polluting to the environment and restricts the sustainable development of the epoxy resin industry. Therefore, the preparation technology is simple, the reaction time is short, and the preparation technology of the sulfur-containing degradable hyperbranched epoxy resin is the fundamental way to solve the problems existing in the field.
  • the object of the present invention is to provide a novel sulfur-containing degradable hyperbranched epoxy resin according to the deficiencies in the prior art, and the structural formula is as follows:
  • R 7 is:
  • R 8 is:
  • Another object of the present invention is to provide a method for preparing a sulfur-containing degradable hyperbranched epoxy resin of the foregoing structural formula, the reaction formula of which is as follows:
  • n 6, 12, 24 or 48.
  • the thiol-olefin click reaction is carried out by ultraviolet light at room temperature for 10 to 30 minutes, and the power of the ultraviolet light is 800 ⁇ . 3000W, vacuum extraction of the organic solvent and excess epoxy compound to obtain a sulfur-containing degradable hyperbranched epoxy resin having a molecular weight of about 3000-35400 g/mol.
  • the epoxy compound is glycidyl methacrylate (GMA) or allyl glycidyl ether (AGE).
  • the molar ratio of the tridecylcyclotriazine compound and the diolefin compound A2 in the step (a) is (1 to 1.5):1.
  • the molar ratio of the thiol group of the terminal fluorenyl hyperbranched polymer described in the step (b) to glycidyl methacrylate (GMA) or allyl glycidyl ether (AGE) is 1: (1 to 2.5).
  • the photoinitiator described in the step (a) is benzophenone, p-aminopropiophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl).
  • One or two or more of 1-acetone, the photoinitiator of the step (a) is used in an amount of from 0.5 to 3% by mass based on the mass of the tridecylcyclotriazine compound.
  • the photoinitiator described in the step (b) is benzophenone, p-aminopropiophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl).
  • One or more of 1-acetone, the photoinitiator of the step (b) is used in an amount of 0.5 to 3% by mass of the terminal fluorenyl hyperbranched polymer.
  • the organic solvent described in the step (a) is one or more selected from the group consisting of methanol, ethanol, tetrahydrofuran, dioxane, ethyl acetate and butyl acetate.
  • the organic solvent used in the step (a) is a trimethyl fluorene ring.
  • the triazine compound is 0.5 to 3.0 times the mass.
  • the organic solvent described in the step (b) is one or more of methanol, ethanol, tetrahydrofuran, dioxane, ethyl acetate and butyl acetate, and the organic solvent used in the step (b) is an end group.
  • the mass of the hyperbranched polymer is 0.5 to 3.0 times.
  • the sulfur-containing degradable hyperbranched epoxy resin prepared by the invention has the advantages of high reaction speed, high yield, low viscosity, and degradable (the triazine ring can be degraded under high temperature under acidic conditions), and is expected to be applied to environmental protection. Adhesives, environmentally friendly low-volatile coatings, low-volatility resins, and enhanced toughening of epoxy resins.
  • the present invention introduces a cyclic triazine structure into the structure of a hyperbranched epoxy resin, which can realize a degradable function after curing of the epoxy resin, and an amino compound is produced after degradation of the cyclic triazine structure, and the amino compound can be used as an epoxy resin.
  • the curing agent and the raw material for the synthesis of the cyclic triazine realize the recycling of the epoxy resin;
  • the sulfur-containing degradable hyperbranched epoxy resin of the invention has rapid degradation ability after curing, and degrades in a phosphoric acid solution at 80 ° C for 1.5 hours, and the degradation rate can reach 99.5% or more;
  • the sulfur-containing degradable hyperbranched epoxy resin of the invention has the advantages of hyperbranched polymer, has reinforcing and toughening function for ordinary epoxy resin, and is expected to be widely used in the field of strengthening and toughening of epoxy resin;
  • the sulfur-containing epoxy resin of the present invention is prepared by a mercapto compound-olefin click ultraviolet photoreaction technique, and has a simple preparation process, high yield, short reaction time, low pollution, and low cost.
  • the preparation method of the sulfur-containing hyperbranched epoxy resin of the invention has the characteristics of low raw material cost, low reaction temperature, high efficiency, high yield, short reaction time, and is a new suitable for industrial production of hyperbranched epoxy.
  • the energy-saving process of the resin, the process does not need water washing and the like in the process of preparing the sulfur-containing hyperbranched epoxy resin, and avoids environmental pollution caused by the conventional water washing preparation of the sulfur-containing hyperbranched epoxy resin.
  • the sulfur-containing degradable hyperbranched epoxy resin of the invention has low viscosity, and is added to the bisphenol A type epoxy resin (viscosity of 15600 cp) to significantly reduce the viscosity, act as a reactive diluent, and simultaneously contain sulfur.
  • the structure can promote the curing of epoxy resin, improve crosslink density and heat resistance, and is expected to be applied in the fields of solventless coatings, electronic packaging and the like.
  • the molecular weight of the product was determined by GPC of British PL Company.
  • the epoxy value was determined by the national standard hydrochloric acid acetone method, and the viscosity was measured by a Brookfield viscometer at 25 °C.
  • Example 1 A sulfur-containing degradable hyperbranched epoxy resin prepared by the following method:
  • Example 2 A sulfur-containing degradable hyperbranched epoxy resin prepared by the following method:
  • Example 3 A sulfur-containing degradable hyperbranched epoxy resin prepared by the following method:
  • Example 4 A sulfur-containing degradable hyperbranched epoxy resin prepared by the following method:
  • the organic solvent methanol was extracted in vacuo to obtain a terminal mercapto hyperbranched polymer (THHBP-24, containing 24 mol of mercapto groups per mol of THHBP-24) having a number average molecular weight of about 11,500 g/mol.
  • Example 5 A sulfur-containing degradable hyperbranched epoxy resin prepared by the following method:
  • Example 6 A sulfur-containing degradable hyperbranched epoxy resin prepared by the following method:
  • the sulfuric acid obtained in the curing agent 4,4-diaminodiphenylmethane and the respective examples 1 to 6 were respectively subjected to the same method under the conditions of an equimolar ratio of the hydrogen equivalent of the curing agent to the epoxy value of the hyperbranched epoxy resin.
  • Degradable hyperbranched epoxy resin, bisphenol A epoxy resin (E51, epoxy value 0.51mol/100g) uniformly mixed, and then solidified into a film, curing conditions are cured at 80-90 ° C for 6 hours, and then heated Curing to 150-160 ° C for 4 hours.
  • the pencil hardness and wear resistance of the film were tested according to the national standards GB/T6739-1996 and GB/T1768-2006, and the properties are shown in Table 1.
  • Degradation rate (%) (1 - mass after drying of filter cake / quality of solidified powder) * 100%;

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)

Abstract

本发明属环氧树脂技术领域，具体公开了一种含硫可降解超支化环氧树脂及其制备方法：将巯基环三嗪化合物、二元烯烃经紫外光引发反应制备巯基超支化聚合物；再与甲基丙烯酸缩水甘油酯反应即可得到可降解含硫超支化环氧树脂，其分子量约为3000-35400g/mol。可降解含硫超支化环氧树脂固化后在磷酸溶液、80℃的条件下，1.5小时即可实现环三嗪结构的完全降解，实现环氧树脂的可循环利用。本发明工艺简单，反应温度低，反应快速，产量高，且含硫结构具有降低固化温度和快速固化，含环三嗪结构具有降解功能，可望用于环氧树脂的增强增韧，无溶剂涂料，电子封装等领域。

Description

一种含硫可降解超支化环氧树脂及其制备方法 技术领域
本发明涉及超支化环氧树脂及其制备方法技术领域，具体涉及一种含硫可降解超支化环氧树脂及其制备方法。
背景技术
含硫环氧树脂的合成主要利用(1)巯基化合物与环氧氯丙烷经开环、关环反应而获得或者(2)利用环氧树脂与硫脲反应而获得。这两种方法制备的含硫环氧树脂，由于含有羟基而具有氢键作用使含硫环氧树脂分子链容易缠结，导致产物粘度大，应用时通常需要加入有机溶剂稀释；另外由于羟基的存在，应用于酸酐固化体系时容易引发酸酐开环而使其不稳定，最终导致产品的储存期变短。而且传统制备含硫环氧树脂的工艺通常需要加入大量的有机溶剂，反应完成后大多工艺都需要水洗步骤，对环境有一定污染。利用硅氢加成反应可以制备粘度低、羟基少的环氧树脂或含硫环氧树脂，但是有机硅的产品成本高、效率偏低、产率不高、反应时间长、能耗大，而难于大规模化应用。
本申请发明人曾以巯基化合物-烯烃点击反应技术在溶液中反应制备含硫环氧树脂(ZL201310091452.0、ZL201210566173.0)，效率高、产率高，是当时工艺最简单的方法。目前所有工艺技术制备的环氧树脂、超支化环氧树脂，经固化后都是三维网状结构，内部的化学键(碳碳键、碳氧键)难于降解、回收循环再利用，废旧环氧树脂产物对环境污染严重且制约环氧树脂行业的可持续性发展技术。因此开发工艺简单、反应时间短、含硫可降解超支化环氧树脂的制备技术是解决目前该领域存在的问题的根本途径。
发明内容
本发明的目的在于针对现有技术中存在的不足，提供了一种新的含硫可降解超支化环氧树脂，其结构式如下：
Figure PCTCN2019084160-appb-000001
其中：R 7的结构为：
Figure PCTCN2019084160-appb-000002
R 8的结构为：
Figure PCTCN2019084160-appb-000003
式中，R 4为-H或-CH 3，当R 4为-H时，R 5＝-OCH 2-；当R 4为-CH 3时，R 5＝-O-CO-；R 1为-C 6H 4(CH 2) r-或者-CH 2(CH 2) k-，其中r＝1、2、3或4，k＝2、3、4或5，所述-C 6H 4(CH 2) r-中苯环为对位、间位或邻位取代，且为氨基取代苯环结构；R 3为-H或-CH 3，当R 3为-H时，R 2＝-CH 2O(CH 2) mOCH 2-或者-COO(CH 2) mOOC-，m＝2、3、4、5或6；当R 3为-CH 3时，R 2＝-COO(CH 2) mOOC-，m＝2、3、4、5或6；
Figure PCTCN2019084160-appb-000004
本发明的另一个目的在于提供了一种前述结构式的含硫可降解超支化环氧树脂的制备方法，其全过程的反应式如下所示：
Figure PCTCN2019084160-appb-000005
n＝6、12、24或48。
为了对上述全过程的反应式做进一步的阐述，该制备方法的具体步骤如下：
(a)将三巯基环三嗪化合物B3、二烯烃化合物A2、光引发剂和有机溶剂混合均匀后，在室温条件下紫外光照反应10～30分钟，紫外光的功率为800～3000W，真空抽出有机溶剂，即可得到端巯基超支化聚合物；
所述三巯基环三嗪化合物B3的结构为
Figure PCTCN2019084160-appb-000006
其中，R 1为-C 6H 4(CH 2) r-或者-CH 2(CH 2) k-，其中r＝1、2、3或4，k＝2、3、4或5，所述-C 6H 4(CH 2) r-中苯环为对位、间位或邻位取代，且为氨基取代苯环结构；
所述二烯烃化合物A2的结构为CH 2＝C(R 3)R 2(R 3)C＝CH 2，其中，R 3为-H或-CH 3，当R 3为-H时，R 2＝-CH 2O(CH 2) mOCH 2-或者-COO(CH 2) mOOC-，其中m＝2、3、4、5或6；当R 3为-CH 3时，R 2＝-COO(CH 2) mOOC-，m＝2、3、4、5或6。
(b)将端巯基超支化聚合物、环氧化合物、光引发剂和有机溶剂混合均匀后，在室温条件下紫外光照进行硫醇-烯烃点击反应10～30分钟，紫外光的功率为800～3000W，真空抽出有机溶剂和过量的环氧化合物，得到含硫可降解超支化环氧树脂，其分子量约为3000-35400g/mol。
所述环氧化合物为甲基丙烯酸缩水甘油酯(GMA)或烯丙基缩水甘油醚(AGE)。
步骤(a)中所述三巯基环三嗪化合物、二烯烃化合物A2的摩尔比为(1～1.5)：1。
步骤(b)中所述的端巯基超支化聚合物的巯基与甲基丙烯酸缩水甘油酯(GMA)或烯丙基缩水甘油醚(AGE)的摩尔比为1：(1～2.5)。
步骤(a)所述的光引发剂为二苯甲酮、对氨基苯丙酮、2-甲基-1-[4-(甲基硫代)苯基]-2-(4-吗啉基)-1-丙酮中一种或两种以上，步骤(a)所述光引发剂的用量为三巯基环三嗪化合物质量的0.5～3％。
步骤(b)所述的光引发剂为二苯甲酮、对氨基苯丙酮、2-甲基-1-[4-(甲基硫代)苯基]-2-(4-吗啉基)-1-丙酮中一种或两种以上，步骤(b)所述光引发剂的用量为端巯基超支化聚合物质量的0.5～3％。
步骤(a)所述的有机溶剂为甲醇、乙醇、四氢呋喃、二氧六环、乙酸乙酯、乙酸丁酯中一种或两种以上，步骤(a)所述有机溶剂的用量为三巯基环三嗪化合物质量的0.5～3.0倍。
步骤(b)所述的有机溶剂均为甲醇、乙醇、四氢呋喃、二氧六环、乙酸乙酯、乙酸丁酯中一种或两种以上，步骤(b)所述有机溶剂的用量为端巯基超支化聚合物质量的0.5～3.0倍。
本发明所制备的含硫可降解超支化环氧树脂具有反应速度快、产率高、较低的粘度、可降解(三嗪环在酸性条件下高温可降解)等优点，可望应用于环保胶粘剂、环保低挥发涂料、低挥发树脂、环氧树脂的增强增韧等领域。
本发明的技术方案与现有技术相比具有如下优点和有益效果：
1、本发明将环三嗪结构引入到超支化环氧树脂的结构中，可实现环氧树脂固化后的可降解功能，环三嗪结构降解后产生氨基化合物，氨基化合物可作为环氧树脂的固化剂和作为环三嗪合成的原料，实现环氧树脂的循环利用；
2、本发明的含硫可降解超支化环氧树脂固化后具有快速降解能力，在磷酸溶液中，80℃降解1.5小时，降解率可达99.5％以上；
3、本发明的含硫可降解超支化环氧树脂具有超支化聚合物的优点，对普通环氧树脂具有增强增韧功能，可望广泛应用于环氧树脂的 增强增韧领域；
4、本发明的含硫环氧树脂是通过巯基化合物-烯烃点击紫外光反应技术来制备的，其制备工艺简单，产率高、反应时间短、污染小，成本低。
5、本发明的含硫超支化环氧树脂的制备方法，具有原料成本低、反应温度低、效率高、产率高等特点，反应时间短，是一种新的适于工业化生产超支化环氧树脂的节能工艺，该工艺在制备含硫超支化环氧树脂过程中无需水洗等工艺，避免了传统水洗制备含硫超支化环氧树脂对环境的污染。
6、本发明的含硫可降解超支化环氧树脂粘度低，添加到双酚A型环氧树脂(粘度为15600cp)中可显著减低其粘度，起到活性稀释剂的作用，同时含硫的结构可促进环氧树脂的固化，提高交联密度和耐热性，可望应用于无溶剂涂料、电子封装等领域。
具体实施方式
下面结合具体的实施例对本发明进行详细说明，但这些实施例不应以任何方式限制本发明的保护范围。
产物的分子量测定采用的是英国PL公司的GPC，环氧值采用国家标准的盐酸丙酮法测定，粘度采用Brookfield粘度计在25℃条件下测定。
以下诸实施例中的环三嗪化合物B3(即
Figure PCTCN2019084160-appb-000007
)为本申请的发明人自制，具体制备过程如下：
化合物B3的制备：
巯基环三嗪化合物B3的制备参考文献(Science 2014,344,(6185),732-735)的反应原理，具体的工艺步骤如下：取0.1mol对氨基苯甲基硫醇H 2N-C 6H 4CH 2-SH(R 1＝-C 6H 4CH 2-)、0.20mol三聚甲醛、60mL蒸馏水添加到带冷凝管、温度计和搅拌器的三口烧瓶中，在温度为30℃左右搅拌反应8小时，停止反应。在真空度为2-3mmHg、60℃ 左右条件下旋转蒸发除去水和未反应的甲醛等，得到三(4-巯基甲基-苯基)环三嗪化合物记为B3-01，产率约为85％。其余B3化合物用类似的方法可以获得，产率在70-90％之间，相应的化合物记为B3-02(R 1＝-C 6H 4(CH 2) 2-)，B3-03(R 1＝-C 6H 4(CH 2) 4-)，B3-04(R 1＝-CH 2(CH 2) 2-)，B3-05(R 1＝-CH 2(CH 2) 3-)，B3-06(R 1＝-CH 2(CH 2) 5-)。
实施例1 一种含硫可降解超支化环氧树脂，由以下方法制备而成：
将0.4mol(181.2g)三巯基环三嗪化合物B3-01、0.3mol(42.6g)二烯烃化合物CH 2＝CHCH 2O(CH 2) 2OCH 2CH＝CH 2、112.0g甲醇和1.12g二苯甲酮光引发剂混合均匀后，在室温条件下用800W的紫外光照反应30分钟，真空抽出有机溶剂甲醇，即可得到端巯基超支化聚合物(THHBP-a6，每摩尔THHBP-a6含6mol巯基)，数均分子量约为2200g/mol。
(b)将0.1mol(220g)端巯基超支化聚合物THHBP-a6、0.63mol甲基丙烯酸缩水甘油酯(GMA)、110.0g四氢呋喃和2.0g二苯甲酮光引发剂混合均匀后，在室温条件下用1500W的紫外光照进行硫醇-烯烃点击反应20分钟，真空抽出有机溶剂和过量的GMA，得到含硫可降解超支化环氧树脂，其数均分子量约为3000g/mol，25℃的粘度为1300cp，环氧值为0.20mol/100g，产率为99.2％。
实施例2 一种含硫可降解超支化环氧树脂，由以下方法制备而成：
(a)将0.23mol(113.9g)环三嗪化合物B3-02、0.225mol(38.25g)二烯烃化合物CH 2＝CHCH 2O(CH 2) 4OCH 2CH＝CH 2、152.0g乙醇和4.5g光引发剂2-甲基-1-[4-(甲基硫代)苯基]-2-(4-吗啉基)-1-丙酮混合均匀后，在室温条件下用3000W的紫外光照反应10分钟，真空抽出有机溶剂乙醇，即可得到端巯基超支化聚合物(THHBP-48，每摩尔THHBP-48含48mol巯基)，数均分子量约为30000g/mol。
(b)将0.01mol(300g)端巯基超支化聚合物THHBP-48、1.05mol(119.7g)烯丙基缩水甘油醚(AGE)、300g乙酸乙酯和3.0g光引发剂对氨基苯丙酮混合均匀后，在室温条件下用3000W的紫外 光照进行硫醇-烯烃点击反应10分钟，真空抽出有机溶剂和过量的AGE，得到含硫可降解超支化环氧树脂，其数均分子量约为35400g/mol，25℃的粘度为3200cp，环氧值为0.13mol/100g，产率为99.5％。
实施例3 一种含硫可降解超支化环氧树脂，由以下方法制备而成：
(a)将0.05mol(28.95g)环三嗪化合物B3-03、0.045mol(7.65g)二烯烃化合物CH 2＝CHCOO(CH 2) 2OOCCH＝CH 2、109.8g乙酸丁酯和1.1g光引发剂对氨基苯丙酮混合均匀后，在室温条件下用2000W的紫外光照反应15分钟，真空抽出有机溶剂乙酸丁酯，即可得到端巯基超支化聚合物(THHBP-a12，每摩尔THHBP-a12含12mol巯基)，数均分子量约为7300g/mol。
(b)将0.01mol(73g)端巯基超支化聚合物THHBP-a12、0.24mol(27.4g)烯丙基缩水甘油醚(AGE)、219g乙酸乙酯和2.19g光引发剂对氨基苯丙酮混合均匀后，在室温条件下用2000W的紫外光照进行硫醇-烯烃点击反应15分钟，真空抽出有机溶剂和过量的AGE，得到含硫可降解超支化环氧树脂，其数均分子量约为8600g/mol，25℃的粘度为1900cp，环氧值为0.14mol/100g，产率为99.3％。
实施例4 一种含硫可降解超支化环氧树脂，由以下方法制备而成：
(a)将0.11mol(34.0g)环三嗪化合物B3-04、0.105mol(23.73g)二烯烃化合物CH 2＝CHCOO(CH 2) 6OOCCH＝CH 2、34.0g甲醇和0.68g光引发剂2-甲基-1-[4-(甲基硫代)苯基]-2-(4-吗啉基)-1-丙酮混合均匀后，在室温条件下用1000W的紫外光照反应20分钟，真空抽出有机溶剂甲醇，即可得到端巯基超支化聚合物(THHBP-24，每摩尔THHBP-24含24mol巯基)，数均分子量约为11500g/mol。
(b)将0.01mol(115g)端巯基超支化聚合物THHBP-24、0.36mol(41.04g)烯丙基缩水甘油醚(AGE)、200g二氧六环和2.0g光引发剂对氨基苯丙酮混合均匀后，在室温条件下用2000W的紫外光照进行硫醇-烯烃点击反应12分钟，真空抽出有机溶剂和过量的 AGE，得到含硫可降解超支化环氧树脂，其数均分子量约为14200g/mol，25℃的粘度为2100cp，环氧值为0.16mol/100g，产率为99.6％。
实施例5 一种含硫可降解超支化环氧树脂，由以下方法制备而成：
(a)将0.10mol(35.1g)环三嗪化合物B3-05、0.09mol(17.82g)二烯烃化合物CH 2＝C(CH 3)COO(CH 2) 2OOC(CH 3)C＝CH 2、17.5g二氧六环和0.3g光引发剂二苯甲酮混合均匀后，在室温条件下用2000W的紫外光照反应10分钟，真空抽出有机溶剂，即可得到端巯基超支化聚合物(THHBP-b12，每摩尔THHBP-b12含12mol巯基)，数均分子量约为5200g/mol。
(b)将0.01mol(52g)端巯基超支化聚合物THHBP-b12、0.24mol(34.08g)甲基丙烯酸缩水甘油酯(GMA)、100g二氧六环和1.0g光引发剂对氨基苯丙酮混合均匀后，在室温条件下用1500W的紫外光照进行硫醇-烯烃点击反应20分钟，真空抽出有机溶剂和过量的GMA，得到含硫可降解超支化环氧树脂，其数均分子量约为6900g/mol，25℃的粘度为1700cp，环氧值为0.17mol/100g，产率为99.5％。
实施例6 一种含硫可降解超支化环氧树脂，由以下方法制备而成：
(a)将0.2mol(87.0g)环三嗪化合物B3-06、0.15mol(33.9g)二烯烃化合物CH 2＝C(CH 3)COO(CH 2) 4OOC(CH 3)C＝CH 2、100.0g甲醇和0.44g光引发剂2-甲基-1-[4-(甲基硫代)苯基]-2-(4-吗啉基)-1-丙酮混合均匀后，在室温条件下用1000W的紫外光照反应20分钟，真空抽出有机溶剂甲醇，即可得到端巯基超支化聚合物(THHBP-b6，每摩尔THHBP-b6含6mol巯基)，数均分子量约为2400g/mol。
(b)将0.01mol(24g)端巯基超支化聚合物THHBP-b6、0.132mol(15.05g)烯丙基缩水甘油醚(AGE)、60g二氧六环和0.6g光引发剂对氨基苯丙酮混合均匀后，在室温条件下用2000W的紫外光照进行硫醇-烯烃点击反应15分钟，真空抽出有机溶剂和过量的AGE，得到含硫可降解超支化环氧树脂，其数均分子量约为 3000g/mol，25℃的粘度为1100cp，环氧值为0.20mol/100g，产率为99.8％。
在固化剂的氢当量与超支化环氧树脂的环氧值等摩尔比的条件下，利用同样的方法将固化剂4,4-二氨基二苯甲烷分别与实施例1～6得到的含硫可降解超支化环氧树脂、双酚A型环氧树脂(E51，环氧值0.51mol/100g)进行混合均匀，然后固化成膜，固化条件为在80-90℃下固化6小时，再升温至150-160℃下固化4小时。分别依据国家标准GB/T6739-1996和GB/T1768-2006测试薄膜的铅笔硬度和耐磨性，性能如表1所示。分别取0.5克上述固化的薄膜研磨成粉，然后放入12mL、0.5mol/L的磷酸水溶液进行降解反应，在80℃的条件下搅拌1.5小时后对溶液进行过滤，将滤饼在120℃干燥2小时，从而分析固化粉末降解率，数据如表1所示。
降解率(％)＝(1-滤饼干燥后的质量/固化粉末的质量)*100％；
表1 实施例1-6所制得可降解超支化环氧树脂产品的性能
树脂种类 铅笔硬度 耐磨性(mg/1000转) 降解率(％)
环氧树脂E51 4H 17.36 9.2
实施例1 4H 13.20 99.6
实施例2 4H 10.52 99.7
实施例3 4H 12.36 99.5
实施例4 4H 10.87 99.7
实施例5 4H 11.34 99.6
实施例6 3H 14.05 99.6

Claims (10)

  1. 一种含硫可降解超支化环氧树脂，其结构式如下：
    Figure PCTCN2019084160-appb-100001
    式中，其中：R 7的结构为：
    Figure PCTCN2019084160-appb-100002
    R 8的结构为：
    Figure PCTCN2019084160-appb-100003
    R 1为-C 6H 4(CH 2) r-或者-CH 2(CH 2) k-，其中r＝1、2、3或4，k＝2、3、4或5，所述-C 6H 4(CH 2) r-中苯环为对位、间位或邻位取代，且为氨基取代苯环结构；R 3为-H或-CH 3，当R 3为-H时，R 2＝-CH 2O(CH 2) mOCH 2-或者-COO(CH 2) mOOC-，m＝2、3、4、5或6；当R 3为-CH 3时，R 2＝-COO(CH 2) mOOC-，m＝2、3、4、5或6；R 4为-H或-CH 3，当R 4为-H时，R 5＝-OCH 2-；当R 4为-CH 3时，R 5＝-O-CO-；
    Figure PCTCN2019084160-appb-100004
  2. 一种权利要求1所述含硫可降解超支化环氧树脂的制备方法，其步骤如下：
    (a)将三巯基环三嗪化合物B3、二烯烃化合物A2、光引发剂 和有机溶剂混合均匀后，在室温条件下紫外光照反应10～30分钟，紫外光的功率为800～3000W，真空抽出有机溶剂，即得到端巯基超支化聚合物；
    所述三巯基环三嗪化合物B3的结构为
    Figure PCTCN2019084160-appb-100005
    其中，R 1为-C 6H 4(CH 2) r-或者-CH 2(CH 2) k-，其中r＝1、2、3或4，k＝2、3、4或5，所述-C 6H 4(CH 2) r-中苯环为对位、间位或邻位取代，且为氨基取代苯环结构；
    所述的二烯烃化合物A2的结构为
    Figure PCTCN2019084160-appb-100006
    其中，R 3为-H或-CH 3，当R 3为-H时，R 2＝-CH 2O(CH 2) mOCH 2-或者-COO(CH 2) mOOC-，m＝2、3、4、5或6；当R 3为-CH 3时，R 2＝-COO(CH 2) mOOC-，m＝2、3、4、5或6。
    (b)将端巯基超支化聚合物、环氧化合物、光引发剂和有机溶剂混合均匀后，在室温条件下紫外光照进行硫醇-烯烃点击反应10～30分钟，紫外光的功率为800～3000W，真空抽出有机溶剂和过量的环氧化合物，得到含硫可降解超支化环氧树脂。
  3. 根据权利要求2所述的制备方法，其特征在于：步骤(b)中所述的环氧化合物为甲基丙烯酸缩水甘油酯或烯丙基缩水甘油醚。
  4. 根据权利要求3所述的制备方法，其特征在于：步骤(a)中所述三巯基环三嗪化合物B3与二烯烃化合物A2的摩尔比为(1～1.5)：1。
  5. 根据权利要求3所述的制备方法，其特征在于：步骤(b)中所述的端巯基超支化聚合物中巯基与环氧化合物的摩尔比为1：(1～2.5)。
  6. 根据权利要求3所述的制备方法，其特征在于：步骤(a)所述的光引发剂为二苯甲酮、对氨基苯丙酮、2-甲基-1-[4-(甲基硫代)苯基]-2-(4-吗啉基)-1-丙酮中一种或两种以上，光引发剂的用量为三巯基环三嗪化合物质量的0.5～3％。
  7. 根据权利要求3所述的制备方法，其特征在于：步骤(b)中所述的光引发剂为二苯甲酮、对氨基苯丙酮、2-甲基-1-[4-(甲基硫代)苯基]-2-(4-吗啉基)-1- 丙酮中一种或两种以上，光引发剂的用量为端巯基超支化聚合物质量的0.5～3％。
  8. 根据权利要求3所述的制备方法，其特征在于：步骤(a)中所述的有机溶剂为甲醇、乙醇、四氢呋喃、二氧六环、乙酸乙酯、乙酸丁酯中一种或两种以上，所述有机溶剂的用量为三巯基环三嗪化合物质量的0.5～3.0倍。
  9. 根据权利要求3所述的制备方法，其特征在于：步骤(b)中所述的有机溶剂为甲醇、乙醇、四氢呋喃、二氧六环、乙酸乙酯、乙酸丁酯中一种或两种以上，所述有机溶剂的用量为端巯基超支化聚合物质量的0.5～3.0倍。
  10. 根据权利要求2所述的制备方法，其特征在于：所述含硫可降解超支化环氧树脂的分子量为3000-35400g/mol。
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