用含螺环原碳酸酯的预聚物改性环氧树脂的研究

合成了一个新的螺环原碳酸酯单体，３，９ 二羟甲基 ３’，９’ 二苯基 １，５，７，１１ 四氧杂螺环［５，５］十一烷，它与二苯甲烷二异氰酸酯（ＭＤＩ）反应生成了低分子量预聚物，用该预聚物对环氧树脂进行改性，可以减少残留在树脂基体中的环氧基团，这说明该预聚物与环氧树脂之间发生了共聚固化反应．基体的Ｔｇ和热稳定性随预聚物加入量的增加而降低，但改性环氧树脂的粘接强度则随预聚物的加入量的增加而增加，螺环基团上的取代基对改性环氧树脂基体也有一定的影响，作者对上述试验观察到的现象进行了讨论．     

用含螺环原碳酸酯的预聚物改性环氧树脂的粘接性能

用含螺环原碳酸酯的预聚物改性环氧树脂的粘接性能白如科，王长松，齐龙武，潘才元（中国科学技术大学材料科学与工程系，合肥，２３００２６）关键词螺环原碳酸酯，齐聚物，改性环氧树脂，粘接性能Ｂａｉｌｅｙ［１］发现双螺环化合物在双开环聚合反应时，伴随着体积膨胀...     

含螺环原碳酸酯的预聚物对环氧树脂的改性研究

Bailey发现螺环原酸酯和螺环原碳酸酯等单体在阳离子引发剂作用下进行双开环聚合反应时，伴随着体积膨胀［‘j．这一现象引起了高分子材料学家的极大兴趣，因为树脂固化时产生体积收缩，会使树脂材料内部产生收缩应力，是导致材料力学性能下降，使用寿命降低的主要原因之一．例如，用不饱和螺环原碳酸酯改性的某种补牙材料与牙的粘接力比不含螺环原碳酸酯的大一倍，并且改善了冲击强度而不改变模量．更为重要的是，由于体积稍微膨胀，补牙材料与牙齿间无缝隙，从而消除了在缝隙中繁殖细菌的可能性，达到既结实又卫生的目的【‘］．利用螺环…     

螺环原酸酯类膨胀化合物研究进展

膨胀单体的特点是在聚合过程中没有体积收缩,甚至会产生体积膨胀,这种特殊的性能使其具有广阔的应用前景。目前可用作膨胀单体的螺环化合物主要有螺环原碳酸酯(SOC)、螺环原酸酯(SOE)和双环原酸酯(BOE)。螺环原酸酯(SOE)是最早发现能进行膨胀聚合反应的一类化合物。本文介绍了螺环原酸酯类化合物的发现、合成方法、聚合反应及应用的研究进展,并提出未来的发展前景。     

含螺环原碳酸酯齐聚物的合成表征及与环氧树脂的固化反应

合成了一种新的带羟基的螺环原碳酸酯，根据它与ＭＤＩ或ＨＤＩ的不同配比，制备了分子量不同的预聚物，其结构得到了核磁和红外数据的证实。用示差扫描量热仪和红外跟踪环氧树脂及其与预聚物混合后的固化反应过程。     

螺环单体的合成、聚合及与环氧树脂的固化反应

合成了新螺环原碳酸酯单体：３，９－二（对甲氧基苄基）－１，５，７，１１－四氧杂螺环［５，５］十一烷．以ＢＦ３·ＯＥｔ２为催化剂，实现了其阳离子聚合．聚合产物的１ＨＮＭＲ、１３ＣＮＭＲ、ＩＲ及元素分析均表明发生了双开环聚合反应．探讨了其聚合历程．用ＤＳＣ和ＩＲ跟踪环氧树脂及其与螺环单体混合后的固化反应过程，研究了固化剂、反应条件对固化反应的影响     

含氧螺环侧基线型共聚物的光交联和应用

研究了乙烯基螺环原酯和马来酸酐共聚物的光交联反应 ,使用碘金翁盐作为阳离子光引发剂 ,在UV光作用下 ,通过乙烯基螺环原酯单元上的螺环开环聚合反应产生交联 ,产物的体积发生膨胀 ,膨胀率为 2 %左右。由于乙烯基螺环原酯单元生成的长侧链的作用 ,增进了高分子链的活动性 ,使得在固体膜中螺环开环反应转化率达到 80 %以上 ,同时光交联产物不产生脆性。进一步研究了光引发剂碘金翁盐 (PhI+Ph·R)X-的浓度和结构对乙烯基螺环原酯 /马来酸酐共聚物光交联反应的影响 ,发现螺环开环反应转化率随金翁盐浓度增大而增加 ,并于 2wt%出现最高点 ,而其取代基的碳链长度对交联速度的效果是C4>C8>C12 ,其对离子X-的影响则和它们的离子强度相关。应用乙烯基螺环原酯 /马来酸酐共聚物与改性环氧丙烯酸酯和季戊四醇三丙烯酸酯组成感光树脂 ,经曝光和碱水显影加工可获得清晰的图像。     

3，9－二羟乙基－3＇，9＇－二苯甲基－1，5，7，11－四氧杂螺环［5，5］十一烷的合成和聚合反应

从两二酸二乙酯、氯乙酸乙酯和氯苄出发，经ＬｉＡｌＨ４还原，合成新的二元醇，进而合成新的螺环化合物：３，９－二羟乙基－３＇，９＇－二苯甲基－１，５，７，１１－四氧杂螺［５，５］十一烷．该化合物的结构由它的氢和碳－１３核磁共振谱、红外光谱和元素分析得到证明．该单体在三氟化硼乙醚络合物的作用下进行开环聚合反应．由于环上四个取代基的稳定作用，聚合物的收率比较低（产率１０％左右）．通过对聚合物的结构分析，提出了这一单体的阳离子开环聚合反应机理．对随聚合温度升高，聚合物中酯基／苯基的克分子比降低，以及本体聚合时得到交联聚合物等一系列现象作了探讨．     

螺环原碳酸酯的单体合成及阳离子聚合

螺环原碳酸酯的单体合成及阳离子聚合袁金颖（合肥工业大学化工学院，合肥２３０００９）潘才元白如科（中国科学技术大学材料科学与工程系，合肥２３００２６）关键词合成螺环原碳酸酯阳离子聚合双开环聚合反应中图分类号Ｏ５２３．６２４Ｂａｉｌｅｙ于１９７２年发现，...     

环单体的合成,聚合及与环氧树脂的固化反应

合成了新螺环原碳酸酯单体：３，９－二（对甲氧基苄基）－１，５，７，１１－四氧杂螺环［５，５］十一烷。以ＢＦ３·ＯＥｔ２为催化剂，实现了其阳离子聚合。聚合产物的＾１Ｈ ＮＭＲ、＾１３Ｃ ＮＭＲ、ＩＲ及元素分析均表明发生了双开环聚合反应。探讨了其聚合历程。用ＤＳＣ和ＩＲ跟踪环氧树脂及其与螺环单体混合后的固化反应过程，研究了固化剂、反应条件对固化反应的影响。     

Study on curing reaction of epoxy resin modified with prepolymers containing spiro orthocarbonate

Prepolymers were prepared by the reaction of 3,9-dihydroxyethyl-3′9′-dibenzyl-1,5,7,11-tetraoxaspiro(5,5)undecane with 4,4′-diphenylmethane diisocyanate (MDI) and 1,6-hexa-methylene diisocyanate (HDI). The number-average molecular weights of the prepolymers can be controlled by changing the mole ratios of spiro compound and diisocyanates. Kinetic studies of the cure reaction for the epoxy resin system modified with or without prepolymers were followed by a HLX-1 dynamic torsional vibration apparatus. The results indicated that gel time (t_g) and activation energy (E_a) increased as the content of prepolymers in the epoxy resin system increased. A difference with the cure reaction of the pure epoxy resin, the second-order reaction for the epoxy resin modified with the prepolymers, was obtained. Rate constants (k) of the cure reaction are 0.231 min^?1 for the epoxy resin, and 0.312 min^?1 for the modified epoxy resin. The mechanism of the cure reaction was discussed. © 1995 John Wiley & Sons, Inc.     

Studies on thermal and morphological properties of 1,1-bis(3-methyl-4-cyanatophenyl)cyclohexane-epoxy-bismaleimide matrices

A new cyanate ester monomer, 1,1-bis(3-methyl-4-cyanatophenyl)cyclohexane has been synthesized and characterized. Epoxy modified with 4, 8 and 12% (by weight) of cyanate ester were made using epoxy resin and 1,1-bis(3-methyl-4-cyanatophenyl)cyclohexane and cured by using diaminodiphenylmethane. The cyanate ester modified epoxy matrix systems were further modified with 4, 8 and 12% (by weight) of bismaleimide (N,N′-bismaleimido-4,4′-diphenylmethane). The formation of oxazolidinone and isocyanurate during cure reaction of epoxy and cyanate ester blend was confirmed by IR spectral studies. Bismaleimide-cyanate ester-epoxy matrices were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and heat deflection temperature (HDT) analysis. Thermal studies indicate that the introduction of cyanate ester into epoxy resin improves the thermal degradation studies at the expense of glass transition temperature. Whereas the incorporation of bismaleimide into epoxy resin enhances the thermal properties according to its percentage content. However, the introduction of both cyanate ester and bismaleimide influences the thermal properties according to their percentage content. DSC thermogram of cyanate ester modified epoxy and bismaleimide modified epoxy show unimodel reaction exotherms. The thermal degradation temperature and heat distortion temperature of the cured bismaleimide modified epoxy and cyanate ester-epoxy systems increased with increasing bismaleimide content. The morphology of the bismaleimide modified epoxy and cyanate ester-epoxy systems were also studied by scanning electron microscopy. Copyright © 2003 John Wiley & Sons, Ltd.     

一种液晶环氧增韧环氧树脂的研究

环氧树脂具有优异的机械性能 ,耐高温以及良好的加工工艺性 .被广泛用于机械、航天、船舶等领域 .由于环氧树脂固化后断裂延伸率小 ,脆性大 ,使其应用受到了一定的限制 .为此 ,国内外学者对环氧树脂进行了大量的改性研究工作 .用含有“柔性链段”的固化剂固化环氧 ,在交联网络中引入柔性链段[1] ;在环氧基体中加入橡胶弹性体[2 ] 、热塑性树脂[3 ,4] 、液晶聚合物[5,6] 等分散相或用热固性树脂连续贯穿于环氧树脂网络中形成互穿、半互穿网络结构[7] ,以改善环氧树脂的韧性 .本文采用液晶环氧化合物原位复合增韧环氧树脂 ,考察了液晶环氧对环…     

Properties of Aqueous Polyurethane Dispersion Modified by Epoxide Resin and Their Use as Adhesive

The aqueous polyurethane hybrid dispersion modified by the epoxy resin were synthesized using 1,4-butanediol ( BDO ) and dimethylolpropionic(DMPA) as chain extenders. A kind of automobile interior decoration adhesive was made by the modified hybrid dispersions. Effects of the content and the kinds of epoxide resin on the properties of dispersions and dispersion-cast films such as appearance, pot life, viscosity, particle size, molecular mass, hardness, swelling in water, contact angle, strength of stress, elongation at break, and other mechanical properties were studied. At the same time the effect of the E20 content on the peel strength of the adhesive for several automobile interior decoration substrates such as rubber/wood, poly(vinyl chloride)/wood; leather/wood, sponge/wood was investigated. The experimental results show that when the epoxy resin E20 content was 8%, the modified polyurethane hybrid dispersions possess better properties and the adhesive made by the modified dispersions posses better adhesion for automobile interior decoration substrates. The stress-strain curve of the modified aqueous polyurethane hybrid dispersions films shows the modified aqueous cast films possess better rigidity and toughness.     

新型耐腐蚀含氟环氧乙烯基酯树脂的合成与性能

以含氟环氧树脂（F-EP）、丙烯酸（AA）和甲基丙烯酸（MAA）为单体,用顺丁烯二酸（MA）进行改性,合成了含氟环氧乙烯基酯树脂（F-EVER）。用傅里叶红外光谱、热重分析、力学性能分析等手段对产物进行表征,研究了树脂的耐腐蚀性能。结果表明：当以N,N-二甲基甲酰胺（DMF）为催化剂,羧基与环氧基摩尔比为0.9,MA与...     

Microencapsulation of hydrophilic solid powder as a flame retardant with epoxy resin by using interfacial reaction method

Microencapsulation of Bistetrazol · diammonium (BHT · 2NH₃) as a hydrophilic powdery flame retardant was tried by the interfacial reaction method in reverse emulsion. In this microencapsulation method, water droplets containing BHT · 2NH₃ and hydrazine as gelation agent for epoxy resin were dispersed in the continuous phase of corn oil. When epoxy resin was added to the continuous phase, BHT · 2NH₃ as a core material was microencapsulated by the reaction of epoxy resin with hydrazine on the interface between the surface of water droplet and the continuous phase. The content of the core material from 70 to 85%, and the microencapsulation efficiency from 89 to ca 100% were able to be attained under the experimental conditions adopted here. Copyright © 2009 John Wiley & Sons, Ltd.