前端聚合法合成聚氨酯的研究

使用甲苯二异氰酸酯（TDI）和聚丙二醇（PPG）通过前端聚合,制备出聚氨酯预聚体。研究了前端聚合反应速率与PPG分子质量以及催化剂DBTDL与TDI比例之间的关系。傅立叶红外光谱（FT—IR）分析表明,前端聚合法合成的聚氨酯与传统聚合法合成的聚氨酯具有相同的特征吸收峰,运用扫描电镜（SEM）可以看出前端聚合法合成的聚氨酯具有良好的分散性。     

环氧丙烯酸酯改性光固化水性聚氨酯的合成及性能研究

采用环氧丙烯酸酯（PPG-EA）、甲苯-2,4-二异氰酸酯（TDI）、聚丙二醇（PPG）、二羟甲基丙酸（DM-PA）和丙烯酸羟乙酯（HEA）等制备了环氧丙烯酸酯改性光固化水性聚氨酯乳液（WPU）;研究了改性环氧丙烯酸酯用量、DMPA用量、n（—NCO）∶n（—OH）对乳液及涂膜性能的影响。结果表明：通过环氧丙烯酸酯改性的水性聚氨酯涂膜具有硬度高、耐水性和力学性能好的特点,并且克服了环氧树脂直接用于水性聚氨酯改性制备的乳液贮存稳定性差的不足。当改性环氧丙烯酸酯用量为6%-10%、DMPA用量为5.5%-7.5%、n（—NCO）∶n（—OH）为1.3-1.4时,UV固化水性聚氨酯乳液的综合性能较好。     

聚氨酯-丙烯酸酯树脂颗粒的研究

制备了丙烯酸羟乙酯（HEA）封端的聚氨酯大分子单体（PUA）,并采用悬浮聚合法合成了一系列聚氨酯-丙烯酸酯树脂颗粒,分析了分散剂用量及种类对颗粒大小的影响;热重分析表明聚氨酯-聚甲基丙烯酸乙酯（PUA-PEMA）树脂的起始分解温度为230.5℃;采用SEM表征了树脂的表面形貌;溶胀性能测试表明PUA-PEMA和聚氨酯-苯乙烯（PUA/PSt）2种树脂对甲苯均有良好的吸附性能,在5 min时的吸附率分别达到了3.38 g/g和4.28 g/g,PUA-PSt树脂对有毒单体甲苯和氯仿的溶胀率为255%和330%。     

新型紫外线固化环氧树脂/丙烯酸酯改性水性聚氨酯的合成与性能

合成了一种新型的具有高交联密度和优异涂膜性能的环氧树脂和丙烯酸酯同时改性的紫外线（UV）固化水性聚氨酯（UV-EP-AC-WPUD）。通过环氧基团与以异氰酸酯基团（-N=C=O）封端的聚氨酯预聚体之间的反应引入质量分数为4%的环氧树脂E-20。同时,通过聚氨酯链的-N=C=O与二元丙烯酸酯（PEDA）以及季戊四醇三丙烯酸酯（PETA）的羟基之间的反应引入碳碳双键（C=C）,C=C的含量达到4.65 meq·g-1。 质量分数为3%的光引发剂Irgacure 2959被用于引发涂膜中C=C的聚合,涂膜的凝胶含量在12 s UV辐射之后达到91%,意味着C=C的聚合和交联速度快,同时所得到的涂膜的交联度非常高,不溶于溶剂丙酮,测试表明环氧树脂和两种丙烯酸酯单体已经成功嵌入聚氨酯链中,涂膜具有优异的力学性能和化学性能。     

铝箔用丙烯酸酯接枝环氧树脂防腐涂料的合成研究

文章通过丙烯酸酯类单体和环氧树脂（E-44）接枝聚合,制备环氧-丙烯酸酯树脂涂料作为铝箔的防腐涂层。同时研究了接枝温度,环氧树脂用量对环氧-丙烯酸酯树脂的透明性的影响;引发剂用量对环氧-丙烯酸酯树脂的玻璃化转变温度（Tg）和分子量（Mn）的影响;环氧树脂用量对环氧-丙烯酸酯树脂涂膜性能的影响。     

聚氨酯-丙烯酸酯复合乳液成功合成

聚氨酯-丙烯酸酯复合乳液虽然较单一乳液的性能有很大改善,但是其涂膜的硬度、耐水性、耐化学品性还难以满足高档水性木器涂料的要求。最近,湖南大学化学化工学院在聚氨酯-丙烯酸酯复合乳液中,以不同方式加入环氧树脂,分别制备了物理共混和化学共聚的聚氨酯-丙烯酸酯-环氧树脂复合乳液（PUEA）,着重研究了环氧树脂加入方式、用量等对乳液及涂膜性能的影响。发现环氧树脂对于涂膜的硬度、耐水性、耐化学品性等有明显改进．研究还表明,环氧树脂的质量分数在3％～4％为宜。近年许多研究者利用PU乳液和PA乳液性能上具有的良好互补作用,共聚制备聚氨酯-丙烯酸酯（PUA）复合乳液;在先前的PUA复合乳液研究基础上,加入环氧树脂,合成环氧树脂改性的聚氨酯-丙烯酸酯（PUEA）复合乳液,可使其涂膜的吸水率显著降低,硬度与其他有关性能也有一定提高。     

紫外光固化聚氨酯丙烯酸酯研究进展

综述丁紫外光（UV）固化聚氨酯丙烯酸酯的研究进展,主要包括：UV固化的聚氨酯丙烯酸酯预聚物;光固化有机／无机复合材料;水性UV固化聚氨酯丙烯酸酯和UV固化超支化聚氨酯丙烯酸酯。     

甲苯二异氰酸酯交联阳离子型丙烯酸酯树脂的制备及性能

用自由基聚合法制备了阳离子型羟基丙烯酸酯树脂,以甲苯-2,4-二异氰酸酯(TDI)和丁酮肟合成出半封端型TDI,将两种产物混合反应,制备出系列聚氨酯改性的丙烯酸酯树脂分散液.分散液成膜后,在高温(140 ℃)下解封的异氰酸酯官能团与丙烯酸酯树脂上的羟基反应得到异氰酸酯交联丙烯酸酯树脂膜.结果表明,随着交联度的提高,丙烯酸酯树脂的玻璃化转变温度升高,凝胶含量增加,拉伸性能、邵尔A硬度、耐腐蚀性及耐水性得以提高.     

丙烯酸酯在建筑涂料开发中的应用

简述了近年来丙烯酸酯在建筑涂料开发中的应用进展情况，并对纯丙烯酸酯、苯乙烯-丙烯酸（酯）、醋酸乙烯-丙烯酸（酯）、有机硅-丙烯酸酯、聚氨酯-丙烯酸酯等多类含丙烯酸酯建筑涂料产品的开发进行介绍。结合国内丙烯酸化工及应用的进展和城乡建筑业的迅猛发展的态势，对今后丙烯酸酯类建筑涂料的开发生产提出建议。     

制备聚氨酯-丙烯酸酯分散体的物料体系及工艺

介绍了制备聚氨酯-丙烯酸酯（PUA）分散体用的原料及其作用。以及典型的制备工艺及其特点，指出了开发新的功能性原料，完善原位聚合法和溶液聚合法，以及探索新的合成工艺将是今后研制高性能PUA分散体的重要领域。     

Frontal copolymerization of 2‐hydroxyethyl methacrylate and ethylene glycol dimethacrylate without porogen: comparison with suspension polymerization

Networked, crosslinked poly[(2‐hydroxyethyl methacrylate)‐co‐(ethylene glycol dimethacrylate)] (HEMA‐EGDM) was synthesized by frontal polymerization (FP) using azobisisobutyronitrile as initiator. HEMA‐EGDM copolymers of similar composition were also synthesized by suspension polymerization. The two sets of copolymers were characterized for functional groups (IR), pore volume (mercury intrusion porosimetry), surface area (nitrogen adsorption) and morphology (scanning electron microscopy). FP‐generated polymeric network structures had higher internal pore volumes and surface areas but their surface morphologies were inferior to those of copolymers synthesized by suspension polymerization. Copyright © 2004 Society of Chemical Industry     

波聚合及其在功能高分子材料合成中的应用

介绍了波聚合的原理，分析了引发剂、单体和其他因素对波聚合的影响。综述了波聚合在功能高分子材料合成中的应用。     

Preparation of porous polyacrylamide hydrogels by frontal polymerization

Polyacrylamide hydrogels with defined porous structure were synthesized through frontal polymerization (FP) in the presence of NaHCO₃ as a foaming agent. Pore properties were analyzed using scanning electron microscopy and mercury intrusion porosimetry. The as‐prepared hydrogels displayed a small cell diameter of ca 2 µm. The dissolved foaming agent dispersing at the level of molecules and the polymerization front propagating step by step should be responsible for the small uniform cell structure. The pore volume varied from 0.63 to 3.65 cm³ g^?1 and the bulk density changed from 0.48 to 0.28 g cm^?3 for a foaming agent content from 0 to 18%. The hydrogels synthesized by FP exhibited higher swelling rate and swelling ratio with respect to conventional batch polymerization. The highest swelling ratio and rate were obtained at a foaming agent concentration of 12% based on monomer. Copyright © 2007 Society of Chemical Industry     

Frontal polymerization of superabsorbent polymers based on vermiculite with slow release of urea

Poly(acrylic acid‐co‐acrylamide)/sodium carboxymethyl cellulose/vermiculite (VMT) superabsorbent polymers (SAPs) were prepared by frontal polymerization (FP), a kind of polymerization model characterized by short reaction times and low‐energy consumption. The effects of VMT content and monomer ratios on frontal parameters and water absorbency were investigated. Due to the good heat insulation property of VMT, the propagating front still sustained at high VMT concentrations (over 30%). The preparation of SAPs with high VMT‐loading via FP has advantages of low energy consumption and low materials prices, decreasing the cost of SAPs effectively. SAPs with slow‐release fertilizer (SSRF) were obtained by embedding urea into their networks during the FP process. The addition of urea not only endows SAPs with slow release function of urea (more than 30 days in soil), but also increases their water absorbency (by 17.4%). The effects of obtained SSRF on tall fescue seeds germination and growth were studied. Compared with the control group, the germination rate and vigor index of tall fescue seeds applied SSRF with 10% urea increased by 17.5 and 80.2%, respectively. POLYM. ENG. SCI., 57:69–77, 2017. © 2016 Society of Plastics Engineers     

Synthesis of polymer materials by low energy electron beam. III. Effects of polymerization temperature in EB solid-state polymerization of semicrystalline urethane-acrylate film

In an electron beam (EB) polymerization of a urethane-acrylate prepolymer, the polymerization temperature greatly affected the structure and properties of the resulting gel film. Urethaneacrylate, which was synthesized by the reaction of poly(butylene adipate)diol, 4,4′-diphenylmethane diisocyanate, and 2-hydroxyethyl acrylate, was used as a prepolymer. The prepolymer was semicrystalline and showed a melting point in the region of 50–60°C. The maximum polymerization rate of the prepolymer was obtained when the prepolymer film was irradiated in the temperature range of 25–40°C. EB polymerization below the melting point (T_m) of the prepolymer produced semicrystalline polyurethane-acrylate gel films with a spherulitic texture. On the other hand, EB polymerization above the T_m destroyed the crystalline phase of the prepolymer to give transparent gel films. The gel film cured below the T_m had higher stress at yield, Young's modulus, and tensile strength than those cured above the T_m. Such temperature effects are attributed to whether or not the EB polymerization proceeds with retention of crystalline structure of the prepolymer.     

Three component terpolymer and IPN hydrogels with response to stimuli

Two different types of multi-stimuli-shrinking hydrogels were synthesized (IPNs and terpolymeric hydrogels) by properly polymerizing N-isopropylacrylamide, 2-hydroxyethyl methacrylate and 2-acrylamido-2-methylpropanesulfonic acid in various mutual ratios and different synthetic orders. Both classical (CP) and frontal (FP) polymerizations were used and the resulting material properties compared. The best compositions and synthetic routes were found and the swelling, morphological and thermal material properties were studied. The results show that some IPNs exhibit marked stimuli-shrinking properties while some terpolymers present an opposite behavior. IPNs swell more than terpolymers and show a sharper stimuli-response, with a larger swelling ratio variation. In addition, FP allowed obtaining samples with the same characteristic of CP materials, but with significant preparation advantages. It has been demonstrated that by varying monomer mutual ratio, synthetic technique (FP or CP) and structural architecture (terpolymers or IPNs), different materials having peculiar properties and characteristics can be obtained.     

Novel sulfur—containing benzophenone derivative as radical photoinitiator for photopolymerization

A novel, highly efficient, polymerizable sulfur‐containing photoinitiator for free radical polymerization, benzophenone thio‐acetic acid (BP‐S‐CH₂‐COOH) was synthesized, characterized, and compared to photoinitiator parameters of the benzophenone (BP) and benzophenone/(phenylthio)acetic acid couple. The photoinitiator possesses a greatly redshifted UV maximal absorption in comparison to BP. Laser flash photolysis studies suggest that photoinitiator radicals are generated by photocleavage of C? S bond. Photopolymerization of 2‐ethyl‐2‐(hydroxymethyl)‐1,3‐propanediol triacrylate (TMPTA) demonstrated that one‐component system BP? S? CH₂? COOH is more efficient for polymerization than two‐component system. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Investigation of redox initiators for free radical frontal polymerization

BACKGROUND: The reaction temperature for frontal polymerization (FP) initiated by redox initiators can be greatly decreased compared with FP initiated by peroxide initiator and disulfide initiator. We report the synthesis of poly(hydroxyethyl acrylate)s via free radical FP using benzoyl peroxide (BPO)/N,N‐dimethylaniline (DMA) and ammonium persulfate (APS)/N,N,N′,N′‐tetramethylethylenediamine (TMEDA) couples as redox initiators at ambient pressure. RESULTS: The results show that unlike the phenomenon of bubbles and ‘fingers’ when using BPO alone, a self‐sustaining and stable front can be obtained when the [DMA]/[BPO] ratio is higher than 1 (mol/mol). A slight increase of the DMA (or TMEDA) reductant concentration causes a marked decrease of front temperature to 53 °C (or 61 °C). CONCLUSION: We investigated the effects of the ratio of the oxidant to the reductant and the initiator and monomer concentrations on certain parameters of FP: formation of bubbles, front velocity and front temperature. This opens the way to the potential development of FP using more appropriate monomers with low boiling points. Copyright © 2009 Society of Chemical Industry     

Frontal polymerization of superabsorbent nanocomposites based on montmorillonite and polyacrylic acid with enhanced soil properties

Polyacrylic acid/montmorillonite(MMT)/carboxymethylcellulose (CMC) superabsorbent nanocomposites were prepared by frontal polymerization (FP), an economic method characterized by low‐energy consumption and short‐reaction time. They were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy. The effects of reaction parameters on the front propagation and the water absorbency of the nanocomposites were investigated. Furthermore, the effects of the obtained products on soil water holding capacity and soil water stable macro‐aggregates were studied. Compared with the control soil, soil mixed with the nanocomposites showed a significant increase (by 52.4%) in field water holding capacity. The incorporation small amounts of MMT effectively promoted the formation of soil water stable macro‐aggregates, which increased by 76% as the addition of the MMT increased to 4 wt %. The samples obtained by FP showed much better performance in the formation of soil water stable macro‐aggregates, salt resistance, and thermal stability than those obtained by conventional batch polymerization. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39825.