CN112608452B - High-performance recyclable and easily-repaired epoxy resin and preparation method thereof - Google Patents
High-performance recyclable and easily-repaired epoxy resin and preparation method thereof Download PDFInfo
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 63
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical group OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 10
- 150000002009 diols Chemical class 0.000 claims abstract description 8
- 239000012634 fragment Substances 0.000 claims abstract description 8
- 229920000768 polyamine Polymers 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 15
- 125000000524 functional group Chemical group 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- -1 tertiary amine small molecules Chemical class 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000002274 desiccant Substances 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 150000003335 secondary amines Chemical group 0.000 claims description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 13
- 239000011347 resin Substances 0.000 abstract description 13
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000008439 repair process Effects 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000009849 vacuum degassing Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 238000005649 metathesis reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- NAIUYXOLMQYLIG-UHFFFAOYSA-N (3,5-diboronophenyl)boronic acid Chemical compound OB(O)C1=CC(B(O)O)=CC(B(O)O)=C1 NAIUYXOLMQYLIG-UHFFFAOYSA-N 0.000 description 2
- BODYVHJTUHHINQ-UHFFFAOYSA-N (4-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)C=C1 BODYVHJTUHHINQ-UHFFFAOYSA-N 0.000 description 2
- KQIGMPWTAHJUMN-UHFFFAOYSA-N 3-aminopropane-1,2-diol Chemical compound NCC(O)CO KQIGMPWTAHJUMN-UHFFFAOYSA-N 0.000 description 2
- ARZSRJNMSIMAKS-UHFFFAOYSA-N 4-aminobutane-1,2-diol Chemical compound NCCC(O)CO ARZSRJNMSIMAKS-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 2
- 125000005621 boronate group Chemical group 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- JMZFEHDNIAQMNB-UHFFFAOYSA-N m-aminophenylboronic acid Chemical compound NC1=CC=CC(B(O)O)=C1 JMZFEHDNIAQMNB-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C08G59/18—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
- C08G59/40—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 curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
本发明涉及一种高性能可回收、易修复环氧树脂及制备方法。该可回收、易修复环氧树脂由环氧树脂、固化剂及促进剂经固化反应制得，所述固化剂为动态硼酸酯键桥联的改性多胺固化剂，其每一个重复单元中至少含有如下片段：
Description
技术领域technical field
本发明具体涉及一种高性能可回收、易修复环氧树脂及制备方法，属于高性能树脂领域。The invention specifically relates to a high-performance recyclable and easy-to-repair epoxy resin and a preparation method, and belongs to the field of high-performance resins.
背景技术Background technique
环氧树脂因其优异的性能在众多领域均得到广泛应用，每年均有大量的环氧废弃物迫切需要回收再利用。然而热固性的环氧树脂由于其不可逆的化学交联结构，一方面导致材料在使用过程中发生损伤时，很难进行原位本体修复，极大增加了维护成本；另一方面，热固性树脂一旦固化成型后就不溶不熔，大量废弃的树脂及复合材料无法进行有效的再加工及回收利用，由此产生的环境污染及能源浪费将成为阻碍树脂基复合材料应用和发展的突出问题。Epoxy resin is widely used in many fields because of its excellent properties, and a large amount of epoxy waste is urgently needed to be recycled and reused every year. However, due to its irreversible chemical cross-linking structure of thermosetting epoxy resin, on the one hand, when the material is damaged during use, it is difficult to carry out in-situ body repair, which greatly increases the maintenance cost; on the other hand, once the thermosetting resin is cured After molding, it is insoluble and infusible, and a large number of discarded resins and composite materials cannot be effectively reprocessed and recycled. The resulting environmental pollution and energy waste will become prominent problems hindering the application and development of resin-based composite materials.
2011年，Leibler等在《Science》上报道了一种基于动态酯交换反应的环氧树脂材料，研究发现这种环氧树脂材料可以像玻璃一样在高温条件下熔融加工，实现真正意义上的可回收利用。这一工作发表后，通过在聚合物网络中引入基于动态共价键的可逆交联网络受到广泛关注，成为解决热固性聚合物回收再加工问题的重要方法之一。目前，研究较多的动态共价键体系有酯交换反应、双硫键交换反应、烯烃复分解反应等，然而这些反应均存在着在热氧环境下不稳定或高温下产生副交联反应等问题，严重影响了树脂在修复或回收后的利用效率及性能。In 2011, Leibler et al. reported an epoxy resin material based on dynamic transesterification in "Science", and the study found that this epoxy resin material can be melted and processed at high temperature like glass, realizing the true sense of plasticity. recycle and re-use. After the publication of this work, the introduction of reversible cross-linking networks based on dynamic covalent bonds in the polymer network has received extensive attention and has become one of the important methods to solve the problem of recycling and reprocessing of thermosetting polymers. At present, the most studied dynamic covalent bond systems include transesterification reaction, disulfide bond exchange reaction, olefin metathesis reaction, etc. However, these reactions all have problems such as instability in thermal oxygen environment or secondary crosslinking reaction at high temperature. , which seriously affects the utilization efficiency and performance of the resin after repair or recycling.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服现有技术的不足，提供一种可回收、易修复环氧树脂，所述环氧树脂具有优异的可回收、易修复、耐热氧及抗水解性能。The purpose of the present invention is to overcome the deficiencies of the prior art and provide a recyclable and easy-to-repair epoxy resin, the epoxy resin has excellent recyclability, easy-to-repair, heat-resistant oxygen and hydrolysis resistance.
本发明的技术解决方案：Technical solution of the present invention:
一种可回收、易修复环氧树脂，由环氧树脂、固化剂及促进剂经固化反应制得，所述固化剂为动态硼酸酯键桥联的改性多元胺分子，其每一个重复单元里面至少含有如下片段：A recyclable and easy-to-repair epoxy resin is prepared by curing an epoxy resin, a curing agent and an accelerator, wherein the curing agent is a modified polyamine molecule bridged by dynamic borate bonds, and each repeating The unit contains at least the following fragments:
所述固化剂为动态硼酸酯键桥联的多胺类固化剂，所述硼酸酯键由苯硼酸基团与二元醇基团通过酯化脱水缩合反应得到，具有以下结构式特征：The curing agent is a polyamine curing agent bridged by dynamic boronic ester bonds, and the boronic ester bonds are obtained by esterification dehydration condensation reaction between phenylboronic acid groups and dihydric alcohol groups, and have the following structural formula characteristics:
其中R1为任意官能团，R2为
所述固化剂可由一端带有苯硼酸基团的有机胺分子A1与多元二醇分子B1，或一端带有单二醇基团的有机胺分子A2与多元苯硼酸分子B2反应制得。The curing agent can be prepared by reacting an organic amine molecule A1 with a phenylboronic acid group at one end and a polyvalent diol molecule B1, or an organic amine molecule A2 with a monodiol group at one end and a polybasic phenylboronic acid molecule B2.
所述一端带有苯硼酸基团的有机胺分子A1具有以下结构式特征：The organic amine molecule A1 with a phenylboronic acid group at one end has the following structural formula characteristics:
其中R1可为任意官能团，如间位或对位官能团。Wherein R 1 can be any functional group, such as meta or para functional group.
所述有机胺分子A1可优选为但不局限于下列结构式中的一种：The organic amine molecule A1 can be preferably, but not limited to, one of the following structural formulas:
所述多元二醇分子B1具有以下结构式特征：The polyol molecule B1 has the following structural formula features:
其中R1可为任意官能团。wherein R 1 can be any functional group.
所述多元二醇分子B1可优选为但不局限于下列结构式中的一种：The polyol molecule B1 can be preferably, but not limited to, one of the following structural formulas:
所述一端带有单二醇基团的有机胺分子A2具有以下结构式特征：The organic amine molecule A2 with a monodiol group at one end has the following structural formula characteristics:
其中R1可为任意官能团。wherein R 1 can be any functional group.
所述有机胺分子A2可优选为但不局限于下列结构式中的一种：The organic amine molecule A2 can be preferably, but not limited to, one of the following structural formulas:
所述多元苯硼酸分子B2具有以下结构式特征：Described polybasic phenylboronic acid molecule B2 has following structural formula characteristic:
其中，连接官能团可为间位或对位，n≥2。R1可为任意官能团。Wherein, the linking functional group can be meta-position or para-position, and n≥2. R 1 can be any functional group.
所述多元苯硼酸分子B2可优选为但不局限于下列结构式中的一种：Described polybasic phenylboronic acid molecule B2 can be preferably but not limited to one of the following structural formulas:
本发明还提供一种制备上述高性能可回收、易修复环氧树脂的方法，通过以下步骤实现：The present invention also provides a method for preparing the above-mentioned high-performance recyclable and easy-to-repair epoxy resin, which is achieved by the following steps:
1)将一定比例的有机分子A1和分子B1或A2和B2混合溶解在有机溶剂中，加入分子筛或干燥剂，在室温下充分反应，过滤后真空浓缩，得到动态硼酸酯键桥联的改性多胺固化剂；所述条件选择目的在于确保脱水缩合反应充分进行；1) Mix and dissolve a certain proportion of organic molecules A1 and B1 or A2 and B2 in an organic solvent, add molecular sieves or a desiccant, fully react at room temperature, filter and concentrate in vacuo to obtain a modified version of the dynamic boronic ester bond bridge. The purpose of selecting the conditions is to ensure that the dehydration condensation reaction is fully carried out;
2)将环氧树脂和步骤1)制备的固化剂、促进剂混合均匀，固化反应完全后即得环氧树脂材料。2) Mix the epoxy resin with the curing agent and accelerator prepared in step 1) evenly, and obtain the epoxy resin material after the curing reaction is complete.
所述有机胺分子和多元苯硼酸或多元二醇分子按照摩尔比例f：1(即A1与B1的比例，或A2与B2的比例)加入，其中f为多元苯硼酸或多元二醇单体的官能团数量，f≧2。Described organic amine molecule and polybasic benzene boronic acid or polyvalent diol molecule are added according to the mole ratio f: 1 (that is, the ratio of A1 and B1, or the ratio of A2 and B2), wherein f is polybasic benzene boronic acid or polyvalent diol monomer. Number of functional groups, f≧2.
所述促进剂为含有N原子的二级或三级胺小分子，可优选为叔胺或吡啶。The accelerator is a secondary or tertiary amine small molecule containing N atom, and may preferably be a tertiary amine or pyridine.
所述环氧树脂优选缩水甘油基环氧树脂体系，可以为缩水甘油醚型环氧树脂、缩水甘油酯型环氧树脂、缩水甘油氨型环氧树脂中的任意一种或者几种的混合物，更有选为双酚A型环氧树脂或双酚F型环氧树脂。The epoxy resin is preferably a glycidyl epoxy resin system, which can be any one or a mixture of a glycidyl ether epoxy resin, a glycidyl ester epoxy resin, and a glycidyl amine epoxy resin, More preferably, it is bisphenol A epoxy resin or bisphenol F epoxy resin.
所述有机溶剂可为任意常用有机溶剂，优选四氢呋喃、乙酸乙酯、二氯甲烷、甲苯中的任意一种或几种的混合物。The organic solvent can be any common organic solvent, preferably any one or a mixture of tetrahydrofuran, ethyl acetate, dichloromethane and toluene.
所述步骤2)中，所述固化反应条件可采用常规的环氧树脂固化条件，可以为：将混合均匀的环氧树脂和固化剂的混合物放入真空烘箱中抽真空脱泡30-50min，将脱好泡的溶液倒入预热的不锈钢模具中进行加热固化，冷却脱模即可。In the step 2), the curing reaction conditions can be conventional epoxy resin curing conditions, which can be: putting the uniformly mixed mixture of epoxy resin and curing agent into a vacuum oven for vacuum degassing for 30-50min, Pour the defoamed solution into a preheated stainless steel mold for heating and solidification, and then cool and demould.
本发明的设计原理在于：The design principle of the present invention is:
本发明通过合成带有硼酸酯桥联基团的改性多元胺类固化剂，利用胺类固化剂和促进剂的引入构筑含N→B配位键的硼酸酯交联点，制备基于硼酸酯复分解反应的环氧树脂。在一定条件下，环氧树脂碎片或损伤界面可通过硼酸酯复分解反应引发高分子链运动和重排进行融合，实现树脂的再次成型及损伤界面修复。本发明构筑的硼酸酯交联点具有较高的键能，热氧稳定性好，且N→B配位键的引入又极大改善了传统硼酸酯键的不耐水解问题，克服了传统动态键交联聚合物存在的热氧不稳定、不耐水解、力学性能差等缺陷。In the present invention, a modified polyamine curing agent with a boronic ester bridging group is synthesized, and a boronic ester cross-linking point containing N→B coordination bond is constructed by the introduction of an amine curing agent and an accelerator, and the preparation based on Epoxy resins for boronate metathesis. Under certain conditions, epoxy resin fragments or damaged interfaces can be fused through the boron ester metathesis reaction to trigger polymer chain movement and rearrangement to achieve resin re-molding and damaged interface repair. The boronic ester cross-linking point constructed by the invention has high bond energy, good thermal-oxygen stability, and the introduction of N→B coordination bond greatly improves the hydrolysis resistance problem of traditional boronic ester bonds, and overcomes the problem of hydrolysis resistance. The traditional dynamic bond cross-linked polymers have the defects of thermal-oxygen instability, hydrolysis resistance, and poor mechanical properties.
本发明的有益效果在于：The beneficial effects of the present invention are:
本发明通过在树脂固化交联网络中构筑含N→B配位键的动态硼酸酯交联点，得到具有可回收、易修复性能的环氧树脂。本发明制备的固化剂对于不同种类环氧树脂具有普适性，通用性高，反应条件温和，制备工艺简单，回收或修复时无需其它催化剂，基于硼酸酯的复分解反应，树脂在一定的加热条件下即可实现较好的回收及修复性能。此外，和其它动态键体系交联的聚合物相比，本发明制备的环氧树脂兼具优异的力学性能、热氧稳定性及抗水解性能，对于推进该类树脂材料在工程中的实际应用具有重要意义。The present invention obtains the epoxy resin with recyclable and easy-to-repair properties by constructing dynamic boronic ester cross-linking points containing N→B coordination bonds in the resin-cured cross-linking network. The curing agent prepared by the invention has universality for different types of epoxy resins, high versatility, mild reaction conditions, simple preparation process, no other catalysts needed for recovery or repair, and based on metathesis reaction of borate esters, the resin can be heated at a certain temperature. Under these conditions, better recovery and repair performance can be achieved. In addition, compared with other polymers cross-linked by dynamic bond systems, the epoxy resin prepared by the present invention has both excellent mechanical properties, thermo-oxidative stability and hydrolysis resistance, which is very useful for promoting the practical application of such resin materials in engineering. significant.
具体实施方式Detailed ways
下面以实施例进一步详细说明本发明，但并不限制本发明。The present invention is further described in detail below with examples, but does not limit the present invention.
本发明所提供的环氧树脂回收方法为将本发明方法制备的环氧树脂进行破坏细碎，在空气气氛下，100～160℃、5～10MPa下模压6～12h。The epoxy resin recovery method provided by the present invention is to destroy and finely crush the epoxy resin prepared by the method of the present invention, and press the epoxy resin for 6 to 12 hours at 100-160° C. and 5-10 MPa in an air atmosphere.
实施例1：本实施例的固化剂由一端带有单二醇基团的有机胺分子A2与多元苯硼酸分子B2反应制得，其中A2采用3-氨基-1.2-丙二醇，B2采用1,4-苯二硼酸。Example 1: The curing agent of this example is prepared by reacting an organic amine molecule A2 with a monodiol group at one end and a polyphenylboronic acid molecule B2, wherein A2 adopts 3-amino-1.2-propanediol, and B2 adopts 1,4 - Phenyldiboronic acid.
步骤1：氮气保护下，将1,4-苯二硼酸(16.5g)溶解在150mL的四氢呋喃中，超声、搅拌至其完全溶解，然后加入3-氨基-1.2-丙二醇(18.2g)、20mL的去离子水充分溶解，搅拌2h，再加入硫酸镁(20g)，加热回流反应2h，反应结束后过滤，滤液旋蒸浓缩得白色固体，得到含有硼酸酯桥联基团的固化剂，结构式为：Step 1: Under nitrogen protection, dissolve 1,4-benzenediboronic acid (16.5 g) in 150 mL of tetrahydrofuran, sonicate and stir until it is completely dissolved, then add 3-amino-1.2-propanediol (18.2 g), 20 mL of Fully dissolved in deionized water, stirred for 2h, then added magnesium sulfate (20g), heated and refluxed for 2h, filtered after the reaction, and the filtrate was concentrated by rotary evaporation to obtain a white solid, to obtain a solidifying agent containing a borate bridging group, the structural formula is :
步骤2：将50g双酚A环氧树脂溶液E51、17.5g上述所制备的固化剂及叔胺促进剂0.6g(1wt％质量比)混合均匀，放入真空烘箱中抽真空脱泡30-50min，将脱好泡的溶液倒入预热的不锈钢模具中，室温固化8h，冷却脱模后即得所述环氧树脂。Step 2: Mix 50g of bisphenol A epoxy resin solution E51, 17.5g of the above-prepared curing agent and 0.6g (1wt% mass ratio) of tertiary amine accelerator, and put them into a vacuum oven for vacuum degassing for 30-50min , pouring the defoamed solution into a preheated stainless steel mold, curing at room temperature for 8 hours, and cooling and demoulding to obtain the epoxy resin.
将所制备环氧树脂破坏细碎，树脂碎片在110℃、8MPa压力下模压6h，对回收后的样品进行拉伸性能测试，回收后环氧树脂的回收效率见表1。The prepared epoxy resin was broken into pieces, and the resin fragments were molded at 110 °C and 8 MPa pressure for 6 h. The tensile properties of the recovered samples were tested. The recovery efficiency of the recovered epoxy resin is shown in Table 1.
实施例2：本实施例的固化剂由一端带有苯硼酸基团的有机胺分子A1与多元二醇分子B1反应制得，其中A1采用3-氨基苯硼酸，B1采用季戊四醇。Embodiment 2: The curing agent of this embodiment is prepared by reacting an organic amine molecule A1 with a phenylboronic acid group at one end and a polyvalent diol molecule B1, wherein A1 adopts 3-aminophenylboronic acid, and B1 adopts pentaerythritol.
步骤1：称取季戊四醇(13.6g)和3-氨基苯硼酸(27.4g)溶解在150ml四氢呋喃中，超声、搅拌至其完全溶解。加入硫酸镁15g，在室温下充分反应24h后，反应结束后过滤，滤液旋蒸浓缩得白色固体，得到含有硼酸酯桥联基团的固化剂，结构式为：Step 1: Weigh pentaerythritol (13.6 g) and 3-aminophenylboronic acid (27.4 g) and dissolve them in 150 ml of tetrahydrofuran, sonicate and stir until they are completely dissolved. Add 15 g of magnesium sulfate, fully react at room temperature for 24 h, filter after the reaction, and concentrate the filtrate by rotary evaporation to obtain a white solid, to obtain a curing agent containing a boronate bridging group, the structural formula is:
步骤2：将50g双酚A环氧树脂溶液E51、21.5g上述所制备的固化剂及吡啶促进剂0.7g(1wt％质量比)混合均匀，放入真空烘箱中抽真空脱泡30-50min，将脱好泡的溶液倒入预热的不锈钢模具中，90℃固化1h，130℃后固化6h，冷却脱模后即得所述环氧树脂。Step 2: Mix 50g of bisphenol A epoxy resin solution E51, 21.5g of the above-prepared curing agent and 0.7g (1wt% mass ratio) of pyridine accelerator evenly, put it into a vacuum oven for vacuum degassing for 30-50min, The defoamed solution was poured into a preheated stainless steel mold, cured at 90° C. for 1 hour, and then cured at 130° C. for 6 hours. After cooling and demoulding, the epoxy resin was obtained.
将所制备环氧树脂破坏细碎，树脂碎片在140℃、10MPa压力下模压6h，对回收后的样品进行拉伸性能测试，回收后环氧树脂的回收效率见表1。The prepared epoxy resin was broken into pieces, and the resin fragments were molded at 140 °C and 10 MPa pressure for 6 h. The tensile properties of the recovered samples were tested. The recovery efficiency of the recovered epoxy resin is shown in Table 1.
实施例3：本实施例的固化剂由一端带有单二醇基团的有机胺分子A2与多元苯硼酸分子B2反应制得，其中A2采用4-氨基-1.2-丁二醇，B2采用1,3,5-苯三硼酸。Embodiment 3: The curing agent of this embodiment is prepared by reacting an organic amine molecule A2 with a monodiol group at one end and a polyphenylboronic acid molecule B2, wherein A2 adopts 4-amino-1.2-butanediol, and B2 adopts 1 ,3,5-benzenetriboronic acid.
步骤1：氮气保护下，将1,3,5-苯三硼酸(20.9g)溶解在300mL的甲苯中，超声、搅拌至其完全溶解，然后加入4-氨基-1.2-丁二醇(31.5g)，搅拌2h，使其充分溶解混合，再加入4A分子筛(20g)，加热回流反应2h，反应结束后过滤，滤液旋蒸浓缩得白色固体，得到含有硼酸酯桥联基团的固化剂，结构式为：Step 1: Under nitrogen protection, dissolve 1,3,5-benzenetriboronic acid (20.9 g) in 300 mL of toluene, sonicate and stir until it is completely dissolved, then add 4-amino-1.2-butanediol (31.5 g) ), stirred for 2h to make it fully dissolved and mixed, then added 4A molecular sieve (20g), heated and refluxed for 2h, filtered after the reaction, and the filtrate was concentrated by rotary evaporation to obtain a white solid, to obtain a solidifying agent containing a boronate bridging group, The structural formula is:
步骤2：将51g双酚F环氧树脂CYDF-170、20.8g上述所制备的固化剂及叔胺促进剂0.7g(1wt％质量比)混合均匀，放入真空烘箱中抽真空脱泡30-50min，将脱好泡的溶液倒入预热的不锈钢模具中，60℃固化3h，130℃后固化1h，冷却脱模后即得所述环氧树脂，冷却脱模后即得所述环氧树脂。Step 2: Mix 51g of bisphenol F epoxy resin CYDF-170, 20.8g of the above-prepared curing agent and 0.7g (1wt% mass ratio) of tertiary amine accelerator, and put them into a vacuum oven for vacuum degassing for 30- 50min, pour the defoamed solution into a preheated stainless steel mold, cure at 60°C for 3 hours, and cure at 130°C for 1 hour. After cooling and demoulding, the epoxy resin is obtained, and the epoxy resin is obtained after cooling and demoulding. resin.
将所制备环氧树脂破坏细碎，树脂碎片在130℃、8MPa压力下模压6h，对回收后的样品进行拉伸性能测试，回收后环氧树脂的回收效率见表1。The prepared epoxy resin was broken into pieces, and the resin fragments were molded at 130 °C and 8 MPa pressure for 6 hours. The tensile properties of the recovered samples were tested. The recovery efficiency of the recovered epoxy resin is shown in Table 1.
对比例1：Comparative Example 1:
步骤1：将100g双酚A环氧树脂溶液E51与固化剂二氨基二苯甲烷(DDM)混合均匀，放入真空烘箱中抽真空脱泡30-50min，将脱好泡的溶液倒入预热的不锈钢模具中，60℃固化4h，100℃后固化4h，冷却脱模后即得所述环氧树脂。Step 1: Mix 100g of bisphenol A epoxy resin solution E51 with the curing agent diaminodiphenylmethane (DDM) evenly, put it in a vacuum oven to vacuumize for 30-50min, and pour the defoamed solution into the preheated solution In the stainless steel mold, the epoxy resin is obtained after curing at 60°C for 4 hours, after curing at 100°C for 4 hours, and cooling and demoulding.
步骤2：将所制备环氧树脂破坏细碎，树脂碎片在140℃、10MPa压力下模压6h，对回收后的样品进行拉伸性能测试，回收后环氧树脂的回收效率见表1。Step 2: Destroy the prepared epoxy resin into fine pieces, and mold the resin fragments at 140° C. and 10 MPa pressure for 6 hours. The recovered samples are tested for tensile properties. The recovery efficiency of the recovered epoxy resin is shown in Table 1.
表1本发明提供的环氧树脂和对比材料的性能及回收效率比较Table 1 Comparison of performance and recovery efficiency of epoxy resins provided by the present invention and comparative materials
本发明未详细说明部分为本领域技术人员公知技术。The parts of the present invention that are not described in detail are well known to those skilled in the art.
以上公开的本发明的具体实施例，其目的在于帮助理解本发明的内容并据以实施，本领域的普通技术人员可以理解，在不脱离本发明的精神和范围内，各种替换、变化和修改都是可能的。本发明不应局限于本说明书的实施例所公开的内容，本发明的保护范围以权利要求书界定的范围为准。The specific embodiments of the present invention disclosed above are intended to help understand the content of the present invention and implement them accordingly. Those skilled in the art can understand that various substitutions, changes and modifications can be made without departing from the spirit and scope of the present invention. Modifications are possible. The present invention should not be limited to the contents disclosed in the embodiments of this specification, and the protection scope of the present invention shall be subject to the scope defined by the claims.
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