环氧丙烯酸酯/乙烯基醚光聚合反应动力学研究

以二缩乙二醇二乙烯基醚 (DVE -3 )为活性稀释剂 ,研究其与环氧丙烯酸酯 (EOA)所组成的光聚合体系在自由基型光引发剂下引发的光聚合反应动力学及其影响因素。DVE -3含量越大 ,EOA/DVE -3体系的转化率越低。体系粘度的提高有利于提高其反应速率。若在环氧丙烯酸酯中引入马来酸酯结构 ,则马来酸酯的含量越大 ,体系的转化率越高 ,马来酸酯结构的引进 ,可以降低体系聚合后残余的双键含量。     

2-(4-甲氧基苯基)-4,6-双(三氯甲基)-S-三嗪光引发剂的合成及其光聚合动力学性能研究

以对甲氧基苯甲腈和三氯乙腈为原料合成了光引发剂2-(4-甲氧基苯基)-4,6-双(三氯甲基)-S-三嗪(MBTT),通过傅里叶红外光谱仪、核磁共振仪和紫外吸收光谱对所合成的产物结构进行了表征.并利用实时红外(RT-IR)对该引发剂进行了光聚合反应动力学研究,考察了单体、引发剂浓度和光强对引发速率及单体转化率的影响.结果表明,MBTT是一种高效的紫外光引发剂,在引发剂用量为0.1%时光聚合的单体转化率就能达到90%;随着光强的增大,单体的双键转化率和最大反应速率都增大,诱导期缩短;双丙烯酸酯类单体的双键转化率比三丙烯酸酯类单体的双键转化率要高.     

二苯甲酮环缩醛单组分光引发剂的合成与光聚合性能的研究

本文合成了一种新型二苯甲酮基复合光引发剂5-(4'-苯甲酰基苯甲氧基)-1,3-二氧苯并环戊烷(BPCH2BDO),利用FIR、1HNMR对其结构进行表征。并采用实时红外光谱研究了BPCH2BDO光引发剂引发丙烯酸酯类单体的光聚合行为。结果表明,该引发剂的最大吸收光谱在258 nm,随着紫外光照的进行,BPCH2BDO的最大吸收峰258 nm逐渐减少。当引发剂的浓度不断增大时,单体的反应速率和该体系的反应程度先增大后减小;随着光照强度增大,单体转化率和最大聚合速率都增大。BPCH2BDO与传统的光引发剂二苯甲酮/4-二甲基氨基苯甲酸乙酯(BP/EDAB)引发效率相当。     

适用于纸制餐具柔性印刷的环保UV光油的研制

利用正交实验设计方法,研制出一种新型的环保UV光油。将预聚物种类和比例、活性单体种类和比例、光引发剂种类以及比例和固化时间作为考察因素,以UV光油在纸制餐具基材上的附着力和耐摩擦性能作为因变量,得到最优的UV光油配方。选择聚氨酯丙烯酸酯(PUA)与环氧丙烯酸酯(EPA)作为预聚物,其比例为1∶1;选择活性单体TMPTA和NPGDA作为活性稀释剂,其比例为1∶2;选择自由基光引发剂和阳离子光引发剂作为混杂引发剂,其比例为1∶1。该配方为混杂光固化体系,兼具自由基光固化和阳离子光固化特点,固化程度高,活性单体和光引发剂残余少,有优良的附着力和耐摩擦性。     

环氧丙烯酸酯的光固化动力学研究

采用光差扫描量热法考察了环氧丙烯酸酯的光固化动力学行为。实验结果表明，增加光引发剂和活性单体的浓度的都可以使反应的转化率有明显的提升，当光引发剂的质量分数从2％增加到5％，转化率由76．2％上升至88.3％；当活性单体质量分数从15％增加到25％，转化率由73．8％上升至95．3％，但单体质量分数的提高对反应速率的变化不是很明显。此外，光固化反应速率对光强非常敏感，而氧气对丙烯酸酯光固化体系的阻聚作用较弱。     

邻羟基环己基丙烯酸酯光聚合动力学研究

采用实时红外光谱技术(RTIR)研究了邻羟基环己基丙烯酸酯(HCA)光聚合反应动力学,探讨了光照强度、光引发剂种类和浓度对其光聚合动力学的影响,并与脂肪族羟基丙烯酸酯单体丙烯酸羟乙酯(HEA)进行了对比。结果表明,最终双键转化率和相对反应速率随光强增大而增加;光引发剂浓度对最终双键转化率和反应速率的影响随引发剂不同呈现不同规律;与HEA相比,HCA具有更高的反应活性,但最终双键转化率较低。     

新型杂化单体4-(1-丙烯基)氧丁基缩水甘油醚的合成及光聚合性能研究

通过3步反应合成了一种新型杂化单体4-(1-丙烯基)氧丁基缩水甘油醚(POBGE)。使用傅立叶红外光谱和核磁共振仪对相应产物结构进行了表征。同时使用傅立叶实时红外(FT-RTIR)对该杂化单体的光聚合性能进行了研究。考察了引发剂种类,不同浓度光引发剂,不同光照强度对杂化单体的光聚合性能的影响。结果表明,光引发剂硫鎓盐的引发性能要优于碘鎓盐,随着光引发剂浓度以及光照强度的增大杂化单体双键及环氧基团的转化率都相应提高。     

环氧–丙烯酸酯混杂体系光聚合动力学及其力学性能的研究

研究了阳离子和自由基引发剂对混杂体系动力学以及丙烯酸酯种类和含量对混杂体系光固化膜力学性能的影响.结果表明,在阳离子聚合体系中,引发剂6976具有较高的引发活性,双键的转化率随其质量分数的增加而提高,而环氧转化率在其质量分数为3%时存在一个最优值;混杂体系自由基引发剂以651的增感作用最为明显,随着651质量分数的增加,环氧的转化平衡时间减少,当其质量分数为0.5%时,环氧转化平衡时间为8 min,双键转化率达到100%,双键的最大转化速率达到11.5 min-1.动态力学热分析和静态力学性能测试表明,改变丙烯酸酯单体的含量和官能度,可有效改善固化膜的力学性能,当,m(CER-170):m(TPGDA)为2:1～1:4时,混杂体系玻璃化温度为34～44℃,固化膜拉伸模量为25～90 MPa,柔韧性为7,硬度为3H～6H.     

不同链长杂化单体合成及光聚合性能研究

通过三步反应合成了三种不同链长的新型杂化单体。使用傅里叶红外光谱和核磁共振仪对相应产物进行了表征。同时使用傅里叶实时红外(FT-RTIR)对三种杂化单体的光聚合性能进行了研究。考察了引发剂种类、不同浓度光引发剂以及链长对杂化单体的光聚合性能的影响。结果表明,光引发剂硫钅翁盐的引发性能要优于碘钅翁盐,随着光引发剂浓度的增大,杂化单体双键及环氧基团的转化率都相应提高,随着链长的增长,相应单体中的双键的转化率降低,但是相应单体中环氧基团的转化率随之升高。     

二苯甲酮LED光引发剂的合成及性能研究

为了延长二苯甲酮光引发剂的吸收波长,使其与LED光源更好的匹配,本研究将苄氨基基团引入二苯甲酮结构,合成了3种4-双苄胺基二苯甲酮衍生物,其吸收波长延长至400 nm,与不同波长（365～405 nm）的LED光源能较好的匹配。利用实时红外对其光聚合动力学进行测试,通过电化学测试以及光降解测试等对其作用机理进行研究。结果表明：双苄胺基二苯甲酮衍生物是一类高效的LED光引发剂,其可作为单组分光引发剂引发1,6-己二醇二丙烯酸酯发生自由基聚合,双键转化率可达80%～83%。与碘鎓盐复配,引发阳离子聚合时环氧单体转化率可达45%,引发自由基-阳离子混杂光固化时双键转化率为69%～71%,环氧单体转化率为58%～61%,在自由基聚合及互穿网络聚合物结构光固化材料制备方面存在潜在应用价值。     

The effect of interpenetrating polymer network formation on polymerization kinetics in an epoxy‐acrylate system

The kinetics of thermally initiated cationic epoxy polymerization and free radical acrylate photopolymerization were studied using photo-differential scanning calorimetry. The reactions of the neat monomers and diluted monomers as well as interpenetrating polymer networks (IPNs) were studied as a function of dilution by the other monomer and temperature. The reaction sequence was also varied to study its effect on the kinetics of formation of the simultaneous IPN's. Both reactions quickly become diffusion controlled. The effects of increasing temperature and dilution on the acrylate polymerization rate profiles are similar, leading to reduced polymerization rate and longer polymerization times. The dilution effect on the epoxy polymerization is similar to that of the acrylate. However, unlike the acrylate reaction the epoxy polymerization rate increases strongly with temperature. The preexistence of one polymer has a significant effect on the polymerization of the second monomer. This effect is larger for the acrylate than for the epoxy polymerization. New kinetic models are needed to capture these complex behaviors.     

环氧树脂对环氧树脂/丙烯酸酯复合乳液聚合速度的影响

将环氧树脂溶于丙烯酸酯混合单体中，采用环氧树脂／聚乙二醇嵌段共聚物、十二烷基磺酸钠和壬基酚聚氧乙烯醚的混合物作乳化剂，制备了环氧树脂／丙烯酸酯共聚物复合乳液。研究了乳液聚合过程中，环氧树脂对聚合速度的影响。结果表明，环氧树脂的存在，延长了引发剂的引发诱导期，单体的转化速率减慢。     

密封胶用环氧改性丙烯酸树脂生产工艺的研究

以甲基丙烯酸甲酯为硬单体,丙烯酸丁酯为软单体,丙烯酸为功能单体,环氧树脂为改性剂制备了密封胶用环氧改性丙烯酸树脂。讨论了环氧树脂的类型及用量,溶剂的种类,反应的温度,溶剂和相对分子质量调节剂的选择,确定了适宜于制备密封胶用环氧改性丙烯酸树脂的反应条件及最佳的配方。     

水性环氧丙烯酸乳液的合成研究

以甲基丙烯酸甲酯、苯乙烯为硬单体,丙烯酸丁酯为软单体,甲基丙烯酸、丙烯酸羟乙酯和双丙酮丙烯酰胺为功能单体,环氧树脂为改性剂,水为分散介质,通过乳液共聚合制备环氧-丙烯酸乳液,讨论了聚合工艺、引发剂用量、反应温度、环氧树脂种类和用量以及软硬单体配比对乳液聚合反应及涂膜性能的影响。     

一种丙烯酸改性乳化环氧树脂的制备与研究

提供了一种制备改性环氧树脂乳液的新方法,以丙烯酸酯类为聚合性单体,加入环氧树脂,利用乳液聚合方法制成了环氧树脂含量达50％的丙烯酸酯改性环氧树脂乳液。通过测试交联度,证明环氧树脂确实参与了聚合反应。同时,还对乳化剂、功能性单体以及环氧树脂含量对乳液稳定性、产品收率、吸水性以及各项力学性能的影响问题进行了研究,得出：丙烯酸对环氧树脂的聚合交联起到了决定性的作用,丙烯酰胺的引入大大提高了乳液的稳定性和力学性能,环氧树脂含量越多产品性能越接近纯环氧树脂,聚合应采用阴、非离子复合乳化剂。     

Dispersed acrylate rubber-modified epoxy resins for electronic encapsulation

A process was developed to incorporate stable dispersed acrylate rubber particles in an epoxy resin matrix which greatly reduces the stress of cured epoxy resins for electronic encapsulation application. The effect of the alkyl group of the acrylate monomer on the phase separation of resultant elastomers from epoxy resin was investigated. The dispersed acrylate rubbers effectively reduce the stress of cured epoxy resins by reducing the flexural modulus, while the glass transition temperature (T_g) was hardly depressed. Electronic devices encapsulated with the dispersed acrylate rubber-modified epoxy molding compounds have exhibited excellent resistance to the thermal shock cycling test and resulted in an extended device use life.     

新型UV固化P／Si协同阻燃EA涂层的制备与性能研究

为了提高uv固化环氧丙烯酸酯（EA）涂层的阻燃性能,并保持其良好的力学及光学性能,将丙烯酸羟乙酯（HEA）分别与KH-5707LPzOs反应合成新型含Si／P功能单体,并将其掺杂于EA中,制备了uV固化新型含P／Si协同阻燃EA透明涂层。利用红外光谱仪、紫外／可见光谱仪、热重及涂层力学测试仪等研究了涂层的性能。     

耐高温丙烯酸酯压敏胶的研制

以丙烯酸丁酯(BA)和丙烯酸-2-乙基己酯(2-EHA)为软单体、甲基丙烯酸甲酯(MMA)为硬单体、环氧树脂(EP)为改性单体、丙烯酰胺(AM)为内交联剂、过氧化苯甲酰(BPO)为引发剂以及乙酸乙酯/乙醇为混合溶剂,采用溶液聚合法制备出一种耐高温溶剂型丙烯酸酯PSA(压敏胶)。研究了单体、引发剂和交联剂等对PSA性能的影响。结果表明:当w(2-EHA)=20%、w(MMA)=13%、w(BPO)=0.5%和w(AM)=0.6%时,PSA的综合性能相对最好;当w(EP)=5%时,PSA的耐高温性能显著提高。     

Preparation and properties of UV-curable di-functional sulfur-containing thioacrylate and thiourethane acrylate monomers with high refractive indices

We synthesized UV-curable di-functional sulfur-containing thioacrylate and thiourethane acrylate with high refractive indices. The structures of monomers were confirmed by nuclear magnetic resonance spectroscopy (NMR) and Fourier transform infrared spectroscopy (FT-IR). The formulation of UV-curable coating film was prepared by thioacrylate monomer, thiourethane acrylate monomer, α-hydroxy-α-methylpropiophenone as the photoinitiator, and bisphenol A epoxy acrylate as the oligomer. The cured coating films were investigated using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), Taber abraser tests, transmittance, and refractive index. The value of refractive index for all coating films increased after UV-curing. Transparent, photocurable coating films with high abrasion resistance were prepared. The monomers showed high refractive index. The refractive indices of synthesized monomers (thioacrylate and thiourethane acrylate monomer) are 1.623 and 1.577, respectively.     

Preparation of waterborne phosphated acrylate–epoxy hybrid dispersions and their application as coil coating primer

In this paper, a series of waterborne acrylic-modified epoxy hybrid dispersions were synthesized and successfully used as primers for coil coatings. Epoxy was phosphated to improve its adhesion to the metal substrate. The grafting reaction of acrylate monomers onto the high molecular weight epoxy resins was studied with infrared spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance. The structure and resin molecules were found to be as expected and the film had the best performance when the acrylate monomer made up less than 40 wt% of the epoxy resin. Modification of the epoxy with phosphoric acid could increase the adhesion to the metal substrate. Better adhesion was achieved with greater amounts of phosphoric acid. R578 urea resin was found to be the most suitable for crosslinking of the resin in this system, and a paint film based on the resulting resin had excellent overall performance.