氨基甲酸酯基丙烯酸酯的合成及其光固化性能

利用碳酸亚乙酯与1,6-己二胺、异佛尔酮二胺反应,制备出两种含氨基甲酸酯基的二元醇,基于氨基甲酸酯二元醇与1,6-己二醇二丙烯酸酯（HDDA）、新戊二醇二丙烯酸酯（NPGDA）及三羟甲基丙烷三丙烯酸酯（TMPTA）本体条件下的Oxa-Michael加成反应及酯交换反应,合成出6种含氨基甲酸酯基的丙烯酸酯混合物。利用FTIR及高分辨质谱分析了产物结构,用FTIR考察了所合成氨基甲酸酯基丙烯酸酯光固化过程的动力学,测定了光固化膜的性能。结果表明,在含占总质量分数3% 的2-羟基-2-甲基-1-苯基-1-丙酮（1173）光引发剂的引发下,氨基甲酸酯基丙烯酸酯能在30s内固化形成表面平整、柔韧性（0.5~2.5mm）良好、透明或半透明的膜;固化膜的凝胶率及铅笔硬度分别为92%~96%、4~5H,对玻璃的附着力为0~1级。     

光固化聚氨酯丙烯酸酯涂料的合成及其性能研究

采用异佛尔酮二异氰酸酯(1PDl)制备了可光固化的聚氨酯丙烯酸酯预聚体,研究了制备过程的条件,选择了活性稀释单体配制成涂膜固化,对其一些物理性能进行了测试研究。结果表明,和常用的2,4-甲苯二异氰酸酯(TDl)制备的可光固化的聚氨酯丙烯酸酯预聚体相比,该预聚体具有更加优良的力学性能和抗老化性能。     

聚氨酯丙烯酸酯的合成及光固化胶性能研究

以聚四氢呋喃醚二醇、甲苯-2,4-二异氰酸酯和丙烯酸羟乙酯为原料合成了稳定的聚氨酯丙烯酸酯,并利用傅立叶变挟红外光谱（FTIR）对其进行表征．考察了反应的主要影响因素。确定适宜的聚氨酯丙烯酸酯合成条件为：反应温度60-65℃、催化剂二月桂酸二丁基锡用量1．0％、反应时间5h,在此条件下,-NCO含量接近0．1％。将合成的聚氨酯丙烯酸酯制成光固化胶,对玻璃和金属有良好的粘接作用,综合性能优良。     

叔胺型聚氨酯丙烯酸酯的合成及其光固化性能研究

合成了一种可紫外光聚合的助引发剂——叔胺型聚氨酯丙烯酸酯,对中间体及产物进行了表征。研究了将叔胺型聚氨酯丙烯酸酯和二苯甲酮配合用于紫外光固化体系的光引发,结果表明叔胺型聚氨酯丙烯酸酯参与了光固化过程,与单独采用二苯甲酮光引发剂相比,它可提高体系的C=C双键速率和转化率,且随着添加量的增大,C=C双键转化速率加快,在相同的光照条件下,C=C双键转化率升高。     

含硅丙烯酸酯化合物光固化性能的研究

本文主要研究含硅丙烯酸酯预聚物ANS的感光性能及光敏剂种类、活性稀释剂丙烯酸β-羟乙酯(HEA)用量、预聚体ANS本身结构对ANS感光体系感光性能的影响．发现ANS具有很高光敏性,其紫外响应峰在334mm处．安息香双甲醚(651)作为ANS的光引发剂,引发效果最好．活性稀释剂HEA可以降低体系的粘度,提高光固化膜透光率,调解光固化物的性能．预聚体结构不同,其感光性能有着很大差别。     

UV固化丙烯酸酯改性硅油的合成及性能

以甲基丙烯酸烯丙酯和含氢硅油为原料,通过硅氢加成反应制得丙烯酸酯改性硅油。采用FT—IR表征了产物结构;研究了反应温度、含氢量、催化剂用量对合成反应的影响,以及紫外光（UV）固化性能。结果表明,最佳反应条件为：含氢硅油的活性氢质量分数0．3％、反应温度85℃、铂催化剂质量分数为3×10^-6。产物具有UV固化活性,指干法测定固化时间45s。     

有机硅改性丙烯酸酯树脂的合成及其光固化动力学研究

以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(n-BA)、二缩三丙二醇二丙烯酸酯(TPGDA)、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(KH-570)为单体,正十二烷基硫醇(NDM)为链转移剂,偶氮二异丁腈(AIBN)为引发剂,合成了一种可紫外光固化的丙烯酸酯树脂(UV-WZF)。通过FT-IR、DSC、TGA对其结构和性能进行了研究。讨论了KH-570的含量和TPGDA的含量对光固化膜的附着力、光固化速率的影响。结果表明:当硅烷偶联剂KH-570的用量为6%时,涂膜附着力良好;当TPGDA的用量为26%时,固化漆膜的光固化时间最短。采用实时红外光谱原位跟踪监测了该树脂的光固化动力学行为,结果表明:当光引发剂Darocur1173含量为树脂质量的5%时,体系的光固化速率最优,增大光强利于光固化。     

多官能度类哑铃形光固化树脂合成及性能

以甲基丙烯酸-β-羟乙酯、异佛尔酮二异氰酸酯、六乙氧基双季戊四醇为主要原料,利用羟基与异氰酸酯的反应,合成出类哑铃型多官能度聚氨酯丙烯酸酯预聚物PUA1~PUA8,用FTIR及1HNMR确证了预聚物结构,用原位红外光谱考察了不同预聚物的光固化动力学。探讨了预聚物结构、体系双键密度对双键转化率、光固化速率及光固化后膜的铅笔硬度、附着力、柔韧性、凝胶率的影响。结果表明,延长丙烯酸酯间的距离,双键的转化率升高,PAU5及PAU1光照20 min后,丙烯酸酯双键的转化率分别为56%及36%。在同样的丙烯酸酯浓度下,适当增加丙烯酸酯官能团间距,可以在保持光固化速率及膜铅笔硬度的同时,提高固化膜的附着力及韧性。PAU5与1,6-己二醇二丙烯酸酯(HDDA)的复配体系光固化后的凝胶率达到99%,固化膜铅笔硬度为6 H,柔韧性可以保持为1.0 mm。     

Novel reactive diluents for UV/moisture dual‐curable coatings

The novel silicone‐modified polyacrylate reactive diluents for UV/moisture dual‐curable coatings were synthesized from N,N‐bis[3‐(trimethoxysilyl)propyl]amine and multifunctional acrylates such as ethoxylated trimethylolpropane triacrylate and polyethyleneglycol diacrylate through Michael addition reaction. Their structures were characterized by NMR and FTIR and their average molecular weights were determined by vapor pressure osmometry. With FTIR, it was found that the obtained diluents could be cured both by UV radiation and moisture mode. The ²⁹Si‐NMR showed that dimer was the main condensation product at the initial stage of moisture curing. The rheological behavior of the diluents investigated by rotary viscometer indicated they were very close to Newtonian fluid, and the viscosity of coatings decreased evenly with increasing concentration of reactive diluents in the coatings. In particular, they were found to be highly efficient in diluency and reactivity for UV polymerization. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1500–1504, 2005     

Asymmetric Synthesis of Dihydrocoumarins Containing Contiguous Quaternary and Tertiary Stereogenic Centers Catalyzed by a Cinchona‐Alkaloid‐Based Bifunctional Thiourea Derivative

A series of enantiomerically enriched 3,4‐dihydrocoumarins containing contiguous quaternary and tertiary stereogenic centers has been efficiently constructed via domino asymmetric Michael addition/transesterification reactions of azlactones with o‐hydroxychalcones using a quinine‐derived thiourea as bifunctional organocatalyst. Under mild reaction conditions, the optically active 3,4‐dihydrocoumarins were generally obtained in 63–96% yields with >20:1 dr and 81–96% ee.

     

环氧丙烯酸光敏树脂的研制及应用

以环氧树脂和丙烯酸为原料,合成了紫外光固化环氧丙烯酸树脂,研究了投料比、反应时间、引发剂、阻聚剂的加入量与加料方式对反应程度的影响。用IR对环氧树脂与环氧丙烯酸树脂的结构进行了表征,并制备了紫外光固化胶。     

Multifunctional Luminescent Organic/Inorganic Hybrid Films

Transparent light‐emitting hybrid materials are produced by UV curing of acrylic resins containing silica precursors and photoluminescent [Cu₄I₄L₄] clusters. Acrylic double‐bond conversion is followed by means of FT‐IR spectroscopy, and optical measurements are performed on cured films showing a high transparency of the films up to a content of 30 wt% TEOS and a bright luminescence with a maximum of emission centered at 565 nm (yellow‐orange). This study shows the possibility to obtain new advanced materials in which functional properties such as photoluminescence and scratch resistance are successfully conjugated in a hybrid film that maintains high transparency.

     

丙烯酸聚氨酯的结构和相对分子质量对紫外光固化反应的影响

合成了一系列不同结构的丙烯酸聚氨预聚物，重点讨论预聚物的分子结构及相对分子质量对紫外光固化反应的影响。     

An advanced multipurpose dental adhesive system

An advanced dental adhesive system, composed of acrylic monomers and coupling agents, characterized by high tensile bond strength, enhanced durability, and biocompatibility was developed. The adhesive composition is curable chemically (self curing) or by visible light. This adhesive composition can be used for bonding to various substrates such as dentin, enamel, precious and nonprecious alloys, 'fresh' and 'set' amalgam, porcelain, and dental composite. Thus, the developed liquid adhesive composition could be considered as a universal dental adhesive.     

氟硅烷改性水性丙烯酸二级分散体的制备与涂层性能

将1,1,3,3-四甲基-1,3-二乙烯硅氮烷(DVDZ)和甲基丙烯酸六氟丁酯(EINECS)进行Micheal加成反应,合成2,2,3,4,4,4-六氟丁基-3-(二(二甲基(乙烯基)硅基)氨基)-2-甲基丙酸酯(DVE)功能有机氟硅单体,与甲基丙烯酸甲酯(MMA)、甲基丙烯酸羟乙酯(HEMA)等单体混合,以偶氮二异丁腈(AIBN)为引发剂,异丙醇(IPA)为溶剂,合成氟硅烷改性水性丙烯酸二级分散体。然后,将其与异氰酸酯固化剂混合,制备了双组分水性聚氨酯(2K-WPU)涂膜。通过FTIR、1HNMR、TG、SEM、XPS对DVE和2K-WPU进行表征和检测,结果表明:随着DVE质量分数的增加,丙烯酸二级分散体的粒径增大,黏度降低,涂膜的耐水性增强,铅笔硬度和附着力减弱。当DVE质量分数为6%时,吸水率为8.2%,接触角为91.5?,热失重10%和50%时的温度分别为220.9和438.5℃,涂膜耐热、耐水和耐酸碱等性能均有提升。