含羧基丙烯酸酯低聚物改性环氧树脂胶黏剂的研究

采用溶液聚合法合成了以BA、AN为主链结构的液态含羧基丙烯酸酯低聚物,并用其对双酚A型环氧树脂胶黏剂进行增韧改性。讨论了丙烯酸、丙烯腈以及低聚物用量对改性环氧树脂体系粘接性能的影响;通过SEM观察了改性体系微观形态,讨论了结构与增韧性能的关系。结果表明,BA/AN/AA为75/20/5的低聚物,其用量为10%时,改性体系的25℃、80℃和150℃剪切强度比纯环氧树脂分别提高94.1%、28.6%和27.8%;用量为20%时,改性体系的150℃剪切强度下降幅度不大,25℃剥离强度从纯环氧树脂的0.8 kN/m增大到7.0 kN/m;从SEM可以看出,改性体系呈两相结构。     

聚丙烯酸酯液体橡胶增韧环氧树脂体系研究

采用溶液聚合法合成了以丙烯酸丁酯、丙烯酸乙酯、丙烯酸缩水甘油酯为主链的液体橡胶,将其用于增韧改性环氧树脂/间苯二甲胺(EP 828/mXDA)体系,研究了聚丙烯酸酯液体橡胶用量对共混体系的微观形态、力学性能和玻璃化温度的影响。电镜观察显示液体橡胶改性EP828/mXDA的共混物呈海岛结构,连续相为环氧树脂,分散相为液体橡胶。随着丙烯酸酯液体橡胶用量增加,海岛相区的粒径和数量均呈增长趋势。当丙烯酸酯液体橡胶质量分数为15%时,共混物中海岛相区的尺寸为1μm左右,共混体系的冲击强度增加151.8%,玻璃化温度下降11.3℃。以丙烯酸液体橡胶改性EP828/mXDA环氧树脂体系,可以较大程度提高其韧性,同时其耐热性基本保持不变。     

聚丙烯酸酯增韧改性环氧树脂的研究

以丙烯酸正丁酯(BA)、甲基丙烯酸甲酯(MMA)及甲基丙烯酸缩水甘油酯(GMA)为单体通过悬浮聚合反应合成了共聚物P(MMA-BA-GMA)简称(PMBG),采用傅里叶红外光谱仪、核磁共振波谱仪、凝胶渗透色谱仪对PMBG的结构与组成进行了表征。采用合成的PMBG对环氧树脂(DER663)/固化剂(HTP-305)体系进行增韧改性,研究了PMBG含量对体系力学性能和热性能的影响,并通过扫描电镜(SEM)对固化物断面的微观结构进行了分析。结果表明:PMBG改性后的环氧树脂冲击强度及断裂伸长率提高,当PMBG的质量分数为5%时,冲击强度显著提高,增韧改性效果最好,并且对体系的玻璃化转变温度(Tg)影响不大;共聚物在体系固化时发生微相分离,因而提高了环氧树脂的韧性。     

含环氧基团硅氧烷低聚物的制备与研究

将环氧基团引入到硅氧烷低聚物结构中,采用"溶胶-凝胶"法研究制备了一种含有环氧基团的硅氧烷低聚物EES。利用合成低聚物增韧环氧树脂,考察了改性后混合树脂的外观状态、黏度、机械性能、玻璃化转变温度和热稳定性。结果表明:环氧基团的存在增加了硅氧烷低聚物的反应性,且具有良好的环氧树脂相容性,能够有效地增韧环氧树脂。EES的添加量为25份时,混合树脂固化样的拉伸强度高达21.027MPa,剪切强度与纯环氧树脂固化相比增长约140%,并表现出优异的热机械性能和热稳定性。     

树脂传递模塑工艺用改性氰酸酯树脂体系研究

由自制改性剂苯乙烯和丙烯酸正丁酯低聚物及TDE-85环氧树脂协同改性氰酸酯树脂,采用示差扫描量热仪,动态热机械分析仪,力学性能和粘度测试研究了改性后的氰酸酯树脂的性能。结果表明,改性氰酸酯树脂浇铸体玻璃化转变温度高于215℃,TDE-85环氧树脂质量分数为15%时,改性氰酸酯树脂浇铸体的综合性能最佳,拉伸强度为45 MPa,弯曲强度为86 MPa,冲击韧性为17 k J/m~2。改性树脂体系室温下6 h内粘度保持在1 000 m Pa·s以下,满足树脂传递模塑成型工艺的要求。     

丙烯酸酯低聚物改性环氧树脂的研究

以2-甲基-2-丙烯酸-2-异氰酸基乙酯(2-IEMA)和环氧树脂(E-03)生成物作为官能单体,同丙烯酸酯软硬单体在引发剂的作用下,以环氧树脂为分散介质,合成了丙烯酸酯低聚物。讨论了2-IEMA/E-03(质量比)及不同软单体对体系粘接性能的影响。结果表明:在2-IEMA/E-03为5.0/95.0,选BA作为软单体时,改性体系的综合性能较好。改性体系的剥离强度为9k N/m,常温剪切强度达到36.1MPa,断裂伸长率为8.7%。通过对体系DMA分析可以看出,BA改性体系的玻璃化转变温度最高为116.2℃。     

环氧树脂/环氧液晶/蒙脱土纳米复合材料研究

采用液晶环氧预聚物(PHQEP)与有机蒙脱土(OMMT)共混改性环氧树脂制备三元共混体系的环氧基复合材料。用X射线衍射法(XRD)测试了有机化蒙脱土在被插层前后片层间距的变化,通过DSC、TGA及SEM等对PHQEP/OMMT增韧改性环氧树脂固化体系的力学性能,热性能及微观相态结构进行了研究。结果表明:当PHQEP质量分数为5%,添加1.5%的有机蒙脱土可以使环氧树脂的冲击强度达到最大值23.43 kJ/m2,比纯环氧树脂提高2倍左右,玻璃化转变温度及5%热分解温度比纯环氧树脂分别高出15℃和27℃。PHQEP与OMMT的加入使纳米复合材料的力学性能和热性能得到明显提高。     

固态环氧树脂的一步密炼增韧

以乙烯-丙烯酸-甲基丙烯酸缩水甘油酯共聚物（EGMA）为增韧相，通过一步密炼共混的方式对固态环氧树脂进行增韧。通过力学测试、扫描电镜、动态热机械分析及热重分析研究了EGMA的加入对固态环氧树脂的力学性能、断面形貌、玻璃化转变温度及热稳定性的影响。结果表明：EGMA的加入显著提高了固态环氧树脂的韧性，对玻璃化转变温度无影响，热稳定性略有下降。添加质量分数4%的EGAM，环氧树脂复合材料的拉伸和弯曲韧性较纯EP分别提高了209%和157%，冲击强度、拉伸强度、弯曲强度分别提升了55%,22%以及25%。     

不同丙烯腈含量的NBR增容SBR/PVC弹性体

通过加入不同丙烯腈含量的丁腈橡胶(NBR)增容改性丁苯橡胶(SBR)/聚氯乙烯(PVC)弹性体合金,采用扫描电子显微镜(SEM)、动态热机械分析仪(DMA)以及力学性能测试等方法,研究了不同丙烯腈质量分数的NBR对SBR/PVC合金的物理力学性能、动态力学性能和微观形态结构等的影响。结果表明,丙烯腈含量越高,对SBR/PVC的增容改性效果越好,当丙烯腈质量分数为40%时,SBR/PVC合金的拉伸强度达到了18.9 MPa, 300%定伸应力达到了16.8 MPa,断裂伸长率达到了356.1%;DMA数据表明,当丙烯腈质量分数为40%时,低温区域玻璃化转变温度为-38.04℃,高温区域玻璃化转变温度为46.13℃,呈现出了明显的玻璃化转变温度相互靠近的现象;SEM分析结果也表明,当丙烯腈质量分数为40%时,试样的拉伸断面比较平整光滑,两相界面过渡平滑,无明显相分离状态。     

纳米SiO_2/聚氨酯弹性体协同增韧增强环氧树脂的研究

采用力学性能测试,扫描电子显微镜(SEM),透射电子显微(TEM)及动态力学性能分析(DMA)研究了纳米SiO2以及聚氨酯弹性体(PUR)对环氧树脂(EP)的改性效果。结果表明,纳米SiO2质量分数0.3%时可同时增韧、增强EP。纳米SiO2与PUR有协同增韧增强EP的作用,纳米SiO2质量分数0.3%,PUR质量分数20%时,纳米SiO2/PUR/EP三元复合材料的冲击强度比纯EP,纳米SiO2/EP及PUR/EP体系分别提高110%,11%和7%;弯曲强度分别相应提高21%,5%和15%。改性体系的断口形貌呈现明显的韧性断裂,表明纳米SiO2颗粒较均匀分布在基体中。三元复合材料的储能模量和玻璃化转变温度(T g)高于PUR/EP二元体系,损耗峰明显宽化。     

环氧改性醇溶性丙烯酸酯干式复膜胶的研制

介绍了一种新型环氧改性醇溶性丙烯酸酯干式复膜胶的制备方法和性能。首先以环氧树脂E-44和丙烯酸(AA)为原料,合成了一种丙烯酸环氧单酯(EA);再以乙醇为溶剂,采用半连续加料法合成了醋酸乙烯酯(VAc)、丙烯酸丁酯(BA)、丙烯酸2-乙基己酯(2-EHA)和EA四元共聚物。该复膜胶合成的适宜条件为:m(VAc)∶m(BA)∶m(2-EHA)∶m(EA)=40∶25∶20∶15,w(引发剂)=1.0%,反应温度为73℃,反应时间为7h。实验结果表明,该复膜胶可用于制备塑料复合薄膜,具有环保、无毒、剥离强度高和快速固化等特点,适用于快速干式复合薄膜的生产线。     

Synthesis and characterization of UV-curable dual hybrid oligomers based on epoxy acrylate containing pendant alkoxysilane groups

This work involves the synthesis of novel hybrid oligomers based on a UV-curable epoxy acrylate resin (EA). The EA resin was modified with various amount of 3-isocyanatopropyl trimethoxysilane (IPTMS) coupling agent. The modification percentage of the hybrid oligomer was varied from 0 to 50 wt.%. UV-curable, hard and transparent organic–inorganic hybrid coatings were prepared on Plexiglas substrates and their characterization was performed by the analyses of various properties such as hardness, gloss, tape adhesion test and stress–strain test. Results from the mechanical measurements show that the properties of hybrid coatings improve with the increase in modification ratio. The thermal behavior of coatings was also evaluated. It is observed that the thermal stability of epoxy acrylate coatings is enhanced with incorporation of siloxane. Gas chromatography/mass spectrometry analyses showed that the initial weight loss obtained in thermogravimetric analysis is due to the degradation products of the photoinitator and the acrylic acid moiety of acrylic monomers.     

耐候性AAS树脂的制备及对PVC的改性

采用乳液聚合接枝法,以丙烯酸丁酯橡胶为核,以苯乙烯丙烯腈共聚物为壳,制备了AAS树脂。并用AAS树脂对硬质聚氯乙烯(PVC)进行了改性。同时考察了复合稳定剂对PVC加工性能的影响。实验结果发现:当AAS树脂质量分数由10%提高到30%时,材料的冲击强度由200 J/m提高到了1 000 J/m,复合稳定剂的加入明显提高了PVC树脂的挤出性能。     

Controlled preparation and properties of acrylic acid epoxy-acrylate composite emulsion for self-crosslinking coatings

A stable epoxy-acrylate composite latex was successfully prepared through emulsion polymerization of modified epoxy acrylic (EPAC) oligomer with acrylate monomer. The EPAC oligomer was obtained using active acrylic acid (AA) to react with epoxy resin. And by regulating the reaction degree of the active hydrogen of AA and epoxide group, there is the acquisition of terminal double bond that gives EPAC reactivity, together with the partial retention of the epoxide group that enables self-crosslinking during film formation. The structural conformation of the oligomer was ascertained by Fourier transform infrared (FTIR) spectroscopy. The factors influencing the stability of the epoxy-acrylate composite latex were investigated. The epoxy-acrylate composite latex was the most stable when methyl acrylic acid was 1.5 wt% and modified EPAC oligomer was 15 wt% of the total monomer weight. The morphology and property of the composite latex films were characterized by scanning electron microscopy, transmission electron microscopy (TEM), and temperature-modulated differential scanning calorimetry (TOPEM-DSC). The results confirm that there is successful emulsion copolymerization between modified EPAC oligomer and acrylate monomer. TEM show that the particles of epoxy-acrylate composite have a core-shell structure, and there is no free epoxy resin. The FTIR and TOPEM-DSC results reveal that the copolymer emulsion possesses self-crosslinking ability. During film formation, self-crosslinking reaction occurs between epoxide groups with carboxyl groups, giving exothermal phenomena. The thermal stability as well as the corrosion resistance of the films was analyzed. The results show outstanding thermal stability as well as corrosion resistance attributable to the crosslinking reticulation structure. It is envisaged that the epoxy-acrylate composite latex has great potential in the development of high-performance aqueous coatings.     

树状大分子聚酰胺-胺固化环氧树脂性能研究

采用发散法由乙二胺和丙烯酸甲酯合成了树状聚酰胺-胺(PAMAM).以PAMAM作为环氧树脂(EP)的固化剂,用差示扫描量热法确定其固化工艺及固化物的玻璃化转变温度(T_g),探讨了树状PAMAM用量对固化物力学性能的影响.结果表明,PAMAM与EP的质量比为0.26时,固化物的力学性能最佳,其冲击强度为166.43 kJ/m~2,拉伸强度为43.54 Mpa;明显高于低分子量聚酰胺/EP固化物的冲击强度和拉伸强度.     

甲基丙烯酸改性环氧树脂改进环氧胶膜性能研究

甲基丙烯酸(MAA)和环氧树脂(EP)进行反应后,添加偶氮二异丁腈(AIBN)和丙烯酸异辛酯,合成的含有丙烯酸树脂链段的环氧树脂作为增韧剂,制备成环氧胶膜。改性后的环氧树脂胶膜剪切强度及剥离强度明显提高,DSC测试显示体系的耐热性能损失不大,用红外光谱分析了固化过程及其改性过程中的反应情况。结果表明,改性后的EP制备出的树脂固化物具有良好的力学及耐热性能。     

水性羟基丙烯酸树脂的制备与研究

以甲基丙烯酸甲酯(MMA)、苯乙烯(St)和丙烯酸丁酯(BA)等为主要单体,引入丙烯酸(AA)、丙烯酸羟基乙酯(HEA)与甲基丙烯酸异冰片酯(IBOMA)等作为功能单体,通过半连续溶液聚合工艺,最后加水分散制得水性羟基丙烯酸树脂。利用FT-IR、透光度、粘度分析研究了单体配比、引发剂(BPO)用量、温度、链转移剂(DDM)用量、功能单体用量等因素对树脂性能的影响。结果表明,当AA、HEA、IBOMA、BPO和DDM的质量分数分别为3%、12%、10%、3%和2%,聚合反应温度100℃时可获得粘度为5 Pa.s,固含量约45%的水性羟基丙烯酸树脂。     

Modification of epoxy resins with acrylic rubbers containing a pendant epoxy group

New acrylic rubbers with a pendant epoxy group were prepared by copolymerization of butyl acrylate (BA) with vinylbenzyl glycidyl ether (VBGE). The modification of an epoxy system (bisphenol-A diglycidyl ether/p,p′-diaminodiphenyl sulfone) with the acrylic rubbers was carried out in order to increase the toughness of the cured epoxy resin. The addition of 20 wt.-% of the copolymer containing 74% of BA and 26% of VBGE units resulted in a 30% increase in the fracture toughness (K_IC) of the cured resin at minimal expenses of strength and modulus of the resin. The modified epoxy resin had two-phase morphology in which the rubber particles with average diameter of 2 μm are dispersed in the epoxy matrix. The copolymer without the pendant epoxy group, prepared from BA and vinylbenzyl methoxyethyl ether, was ineffective as a modifier, indicating that the reaction of the pendant epoxide with the epoxy matrix resulted in good interfacial adhesion between the rubber particles and the matrix, and in the increased toughness. The epoxide-containing copolymers with 55 or 86% of BA units were also insufficient modifiers. The addition of the former yielded cured resins with homogeneous structure, whereas that of the latter resulted in macroscopic phase separation between the rubber and the epoxy resin.     

水基改性环氧树脂涂料的合成研究

研究了以环氧树脂Ｅ－ ４４（ 简称为环氧树脂） 为主要原料, 对水基改性环氧树脂涂料———环氧磷酸酯 丙烯酸接枝共聚物的合成反应, 探讨了丙烯酸及其酯, 苯乙烯和引发剂的用量,接枝反应温度, 接枝反应时间等因素对该接枝共聚物水分散稳定性的影响, 确定了较佳的工艺条件。并对该接枝共聚物进行了有关的产品性能和应用性能检测。     

水性环氧改性丙烯酸防火磁漆的制备

以丙烯酸、丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸2,4,6-三溴苯酯和环氧树脂（E-44）等为原料合成了水性环氧改性丙烯酸树脂,讨论了丙烯酸2,4,6-三溴苯酯的含量对涂层阻燃性能的影响,E-44、丙烯酸的含量以及中和度对水性环氧改性丙烯酸树脂性能的影响。讨论了阻燃助剂等对涂层阻燃性能的影响。