乙酰乙酸基聚丙烯酸酯与端烯基聚氨酯交联反应机理

乙酰乙酸基聚丙烯酸酯与端烯基聚氨酯交联反应机理唐黎明＊郭伟刘德山周其庠（清华大学化工系北京１０００８４）关键词乙酰乙酸基，聚丙烯酸酯，聚氨酯，双键，交联机理１９９６－０８－２０收稿，１９９６－１２－０５修回近年来，含有乙酰乙酸基团的聚合物在涂料、粘合...     

聚氨酯脲—丙烯酯酯水分散液的粒径及形态研究

研究了羰基含量、异氰权酯指数（〖－ＮＯＯ〗／〖－ＯＨ〗、聚氨酯脲与聚丙烯酸酯组成比（ＰＵＵ／ＰＡ）以及一系列制备江艺因素对聚氨酯脲－丙烯酸酯（ＰＵＡ）水分散液粒子尺寸及形态的影响。结果表明：羰基含量和ＰＵＵ／ＰＡ组成比增大或异氰酸酯指数减小都会导致分散液粒径减小;ＰＵＡ中ＰＡ含量越大,ＰＵＡ水分散液粒子形态越不规整;工艺因素如搅拌强度、升温速率等对ＰＵＡ水分散液粒子尺寸及形态的影响不符合传统乳液聚     

聚氨酯脲-丙烯酸酯水分散液的粒径及形态研究

研究了羧基含量、异氰酸酯指数（［ － ＮＣＯ］／［ － ＯＨ］） 、聚氨酯脲与聚丙烯酸酯组成比（ＰＵＵ／ＰＡ） 以及一系列制备工艺因素对聚氨酯脲—丙烯酸酯（ＰＵＡ） 水分散液粒子尺寸及形态的影响。结果表明：羧基含量和ＰＵＵ／ＰＡ 组成比增大或异氰酸酯指数减小都会导致分散液粒径减小;ＰＵＡ 中ＰＡ 含量越大,ＰＵＡ 水分散液粒子形态越不规整;工艺因素如搅拌强度、升温速率等对ＰＵＡ 水分散液粒子尺寸及形态的影响不符合传统乳液聚合的规律。     

聚氨酯型互穿网络聚合物的研究

以甲苯二异氰酸酯和蓖麻油反应，合成了一系列室温固化的蓖麻油型聚氨酯。分别研究了蓖麻油聚氨酯（ＣＯＰＵ）／聚苯乙烯（ＰＳｔ）ＩＰＮｓ、ＣＯＰＵ／聚丙烯腈（ＰＡＮ）ＩＰＮｓ的结构和性能。结果表明：ＣＯＰＵ／ＰＡＮ的力学性能较ＣＯＰＵ／ＰＳｔ的力学性能为好。为进一步改善聚合物之间的相容性，在聚苯乙烯网络中引入极性较大的丙烯腈制备了ＣＯＰＵ／Ｐ（Ｓｔ－ＣＯ－ＡＮ）ＩＰＮｓ，并对它的力学性能、热分析、动态力学性能、热稳定性等作了系统的研究。结果表明：当聚氨酯浓度为６０％时，改变Ｓｔ、ＡＮ的比例，随ＡＮ含量的增加，体系的微相分离程度降低。改变ＣＯＰＵ／Ｐ（Ｓｔ－ＣＯ－ＡＮ）的比例，ｔａｎδ－Ｔ曲线上均呈现一个较宽的玻璃化转变温度；热重分析表明，其初始分解温度可达２４４℃。     

核—壳结构聚丙烯酸酯—聚氨酯微乳液膜的相行为

用动态力学、红外光谱和差热分析方法研究了非交联核－壳结构聚丙烯酸酯－聚氨酯（ＰＡＣ－ＰＵ）微乳液膜的相行为．结果表明：核壳间的氢键增强了壳层软硬段间的相分离，同时破坏了硬段相中的短程有序结构，但增强了核壳相容性     

pH敏感性两亲聚合物网络PAA—l—PTHF的研究

以具有良好柔性和生物相容性的聚四氢呋喃（ＰＴＨＦ）为疏水链段,具有ｐＨ敏感性的聚丙烯酸（ＰＡＡ）为亲水链段,通过ＰＴＨＦ双端基大分子单体与丙烯酸自由基共聚,首次合成了聚丙烯酸－ｌ－聚四氢呋喃（ＰＡＡ－ｌ－ＰＴＨＦ）两亲聚合物网络,并对网络的结构、组成以及交联点密度进行了表征。两亲聚合物网络溶胀行为研究表明,ＰＡＡ－ｌ－ＰＴＨＦ既能在水中溶胀又能在有机溶剂中溶胀,在水中的溶胀度随网络亲水链段ＰＡＡ含     

聚碳酸亚丙酯聚氨酯的合成与性能

用ＣＯ２与环氧丙烷共聚产物聚碳酸亚丙酯制备出聚氨酯（ＰＰＣＰＵ）．同时探讨了ＰＰＣＰＵ最佳合成方法,考察了异氰酸酯基与羟基的比值、扩链交联剂用量等因素对其力学性能的影响．研究了ＰＰＣＰＵ的形态结构及其性能对配比的依赖关系．发现聚碳酸亚丙酯的耐热性因聚氨酯的形成而得到较大的改善,并发现该类材料具有优异的耐水性能．     

二胺扩链剂对RIM聚氨酯－脲弹性体的结构与性能的影响

采用实验室小型ＲＩＭ机制备了一组不同芳香二胺扩链的嵌段聚氨酯－脲（ＰＵＵ）弹性体，借助于ＩＲ、ＤＳＣ、ＤＭＴＡ、ＳＥＭ以及拉伸试验等测试手段对其结构与性能进行了研究．通过比较由ＭＤＡ、ＤＥＴＤＡ以及ＣＡＭＤＡ三种不同活性和结构的芳香二胺扩链剂与二异氰酸酯反应形成的硬链段对ＲＩＭＰＵＵ弹性体的结构与性能的影响，表明：ＭＤＡ基ＲＩＭＰＵＵ中软、硬链段微区界面作用指数很小，微相分离程度却很大，其性能最差；ＤＥＴＤＡ基ＲＩＭＰＵＵ弹性体有理想的界面作用指数，以及适当的微相分离程度，其性能位于三者之中最佳．ＤＭＴＡ研究证实在一定的温度范围内ＤＥＴＤＡ基ＲＩＭＰＵＵ的模量稳定性最好．     

氨酯丙烯酸酯树脂的合成及其固化反应动力学研究

用不同分子量的聚氧化丙烯二元醇合成了一系列氨酯丙烯酸酯齐聚物（ＵＡＯ）以及含硬段／软段结构的ＵＡＯ，并用ＦＴ－ＩＲ跟踪了这类ＵＡＯ的合成过程。通过ＵＡＯ的链端双键测定，以及ＧＰＣ、ＶＰＯ测定的分子量，表征了ＵＡＯ的数均官能团度。进一步通过ＦＴ－ＩＲ研究了由ＵＡＯ与甲基丙烯酸甲酯形成的氨酯丙烯酸酯树脂（ＵＡＲ）固化时的共聚反应动力学，发现其共聚反应速率与体系中的扩散效应密切相关。在这类ＵＡＯ中引入硬段后，共聚合体系呈现出反常的动力学行为，与网络结构形成过程中材料的形态发展有关。     

交联密度对聚氨酯／聚苯乙烯互穿聚合物网络动态力学性能的影响

采用同步法合成了聚氨酯／聚苯乙烯（ＰＵ／ＰＳ）互穿聚合物网络（ＩＰＮ）．通过改变ＮＣＯ／ＯＨ比、三元醇／二元醇（３ＯＨ／２ＯＨ）比、异氰酸酯类型、多元醇分子量、二乙烯基苯含量及丙烯酸β－羟乙酯的含量，研究了单网及网间交联密度对ＰＵ／ＰＳＩＰＮ动态力学性能影响的规律．结果表明：对相容性差的ＰＵ／ＰＳＩＰＮ体系，采用增加交联密度、加快网络固化速度导致“强迫互容”，能提高两网的互穿与缠结，增进组份的互容．但单网固化速度过快相容性反而下降．     

Effect of the content of urea groups on the particle size in water-borne polyurethane or polyurethane/polyacrylate dispersions

A series of anionic water-borne polyurethane and polyurethane/polyacrylate dispersions and their paint films was prepared. It was found by using TEM that there were three phases in the polyurethane/polyacrylate film, i.e. the hard segment-rich phase and the soft segment-rich phase of polyurethane, and the polyacrylate phase. By increasing the content of urea groups, the glass transition temperature of the soft segments and the dissociation temperature of the long-distance ordering of the hard segments were raised. This should mean that the motion of macromolecular chains was hindered by increasing the content of urea groups, and the hydrophilic carboxyl groups embedded initially in macromolecular coils could thus not transfer easily to the particle surface, which resulted in a greater average particle size in the dispersion.     

SYNTHESIS, CROSSLINKING MECHANISM AND PROPERTIES OF A POLYACRYLATE/POLYURETHANE COMPOSITE COATING

A polyacrylate/polyurethane (P(A) / P(U)) composite coating has been prepared bycrosslinking an acetoacetylated polyacrylate with a vinylic group terminated polyurethaneat room temperature. A model Michael reaction between ethyl acetoacetate (EAA) andmethyl acrylate (MA) was designed to study the crosslinking mechanism. It was foundthat the two active hydrogen atoms in acetoacetyl group can both add to vinylic groupsand the yield of mono- and bis-adducts are much affected by the molar ratio of acetoacetylto vinylic groups. Higher crosslinking degree and better properties could be obtained withdecreasing the molar ratio of the two active groups from 1/1 to 0.6/1 in the compositecoatings.     

Eco-efficiency analysis of textile coating materials

Eco-efficiency is critical for organisations that seek to be both environmentally conscious and profitable. It helps to “produce more out of less” to avoid wasting natural resources and to reduce emissions and damage to the environment. The textile coating and laminating industry, utilising solvent or water-based polymeric mixtures, is one of the industries coming under extreme environmental pressure to replace traditional procedures and use eco-efficient coating agents. In this study, eco-efficiency analysis was used to compare the eco-effectiveness of two different coating agents, polyacrylate and polyurethane, each in organic solution as well as aqueous dispersion forms. The “ecological fingerprint” and eco-efficiency portfolio were graphically illustrated for these coating agents based on the customer benefit, defined as coating one square meter of a textile fabric in a conventional laminating unit. According to the analysis results, polyacrylate dispersion in water was the most eco-efficient coating agent whilst polyurethane resin dissolved in organic solvent was found as the coating agent with the least acceptability as an eco-efficient product.     

A Polyurethane Coating Based on Hydroxyethylated Diphenylolpropane

To improve the thermal resistance of a coating, a polyurethane binder has been synthesized with the use of hydroxyethylated diphenylolpropane. The influence of the catalyst concentration, solvent nature, and structure and molar ratio of the initial reagents on the properties of the coatings is studied. The composition, corresponding to the polyurethane coating with high physicomechanical properties combined with thermal and chemical resistance, is established.     

Comparative study between core-shell and interpenetrating network structure polyurethane/polyacrylate composite emulsions

Anionic aqueous polyurethane dispersion was prepared by using carboxyl acid group to make the polyurethane dispersible, and then nanograde core-shell and crosslinked IPN structure polyurethane/polyacrylate composite latex (PUA) were synthesized by soap-free emulsion polymerization method with polyurethane dispersion as seed. FTIR, DSC, dynamic light scattering, TEM, ESCA, TGA, electronic tensile machine were employed to investigate the structures and properties of the composite latex and their polymers. Meanwhile the core-shell composite PUA emulsion and the crosslinked IPN composite PUA emulsion were compared. The results showed that the particle morphology of PUA composite emulsion is inverted core-shell structure with polyacrylate as the core and with polyurethane as the shell. The morphology of the crosslinked PUA emulsion was multi-core structure. The surface in core-shell PUA contains rich PU phase. The phase structure of the crosslinked PUA is more uniform. Three transition temperatures are observed for the core-shell composite PUA, two transitions are observed for the film from the crosslinked PUA. The TGA curves of core-shell PUA and crosslinked PUA exhibit two stages, the first stage corresponds to the thermal decomposition of hard segments in seed polyurethane; the second stage corresponds to the decomposition of soft segments in PUA and decomposition of polyacrylate. With the increase of glycidyl methacrylate (GMA) amounts in PUA composite emulsions, the tensile strength of the PUA films as well as the average diameter of the PUA composite emulsion particles increase, the elongation at break of the PUA films decreases.     

聚氨酯/聚丙烯酸酯复合乳液的研制进展

概述聚氨酯－聚丙烯酸酯复合乳液的制备方法。特别对聚氨酯－聚丙烯酸酯复合乳液共聚法作了较为系统的介绍和讨论。     

表面处理剂对聚酯薄膜与紫外光固化光油之间附着力的影响

聚酯薄膜与紫外光(UV)固化光油之间的附着力极差,用胶带拉脱时完全脱落.为此,分别采用AF-201磺化聚酯、YF-40聚丙烯酸树脂、PR-32聚氨酯、EX-40F丙烯酸改性聚氨酯和PX-1010丙烯酸改性聚酯等表面处理剂对聚酯薄膜表面进行涂覆处理,以改善聚酯薄膜的表面性能,提高其与UV光油之间的附着力.附着力测定结果表明,PX-1010丙烯酸改性聚酯可明显提高聚酯薄膜与UV光油的附着力.     

含苯并噻唑偶氮发色侧基的两种非线性光学高分子

含苯并噻唑偶氮发色侧基的两种非线性光学高分子刘志红，过俊石，谢洪泉（华中理工大学化学系武汉４３００７４）关键词苯并噻唑，聚氨酯，聚丙烯酸酯，非线性光学聚合物用于集成光学光波导电光调制器件的非线性光学聚合物要求具有大的电光系数、高透明性、良好的加工性能...     

天然生漆/丙烯酸树脂IPN涂料的制备与性能

研究了直接由天然生漆(raw lacquer,RL)和多羟基丙烯酸树脂(multihydroxyl polyacrylate resin,MPAR)制备IPN(interpenetrating polymer network)涂料的方法,以及生漆的预聚合对涂料成膜的作用,并对共混物涂膜的物理机械性能、抗溶剂性能、抗紫外线性能等进行了测试表征。结果表明,天然生漆/丙烯酸树脂互穿网络共混能使RL与MPAR相互交联、缠结,其涂膜兼具有天然生漆和丙烯酸树脂的优良性能。