聚氨酯改性氟代聚丙烯酸酯易去污整理剂的合成及应用

采用聚氨酯对氟代聚丙烯酸酯进行改性,制备出一种新型的易去污整理剂。利用红外光谱(IR)对其进行了结构表征,用扫描电镜(SEM)对其在纤维上的膜形貌进行观察并结合疏水疏油、易去污等应用性能予以分析。结果表明,在纤维表面,聚合物能形成一层光滑且有优异疏水性的膜,能使整理后棉织物的疏水性达到95分,疏油等级6级,易去污可达到5级。     

乳化剂对丙烯酸酯微乳液聚合的影响

考察了4种不同类型乳化剂及其复配使用对丙烯酸酯三元微乳液聚合的影响,结果表明:反应型乳化剂TS-02与阴离子乳化剂SDS复配为制备聚丙烯酸酯微乳液的较佳乳化体系。乳化剂用量由1%增加到4%,乳胶粒径由208nm降至26nm;微乳液黏度随之升高,凝聚率降低。乳化剂用量过低,则微乳液稳定性降低,转变为水凝胶时间缩短。     

A crosslinked waterborne poly(urethane-urea) oligomer enables mechanically strong waterborne polyacrylate–poly(urethane-urea) hybrid films with superior film-forming ability

In this article, a crosslinked waterborne poly(urethane-urea) (WPUU) is synthesized based on the terminal aromatic amine polyether (DP-1000) and aliphatic isophorone diisocyanate. Then WPUU is compound with acrylate monomer by emulsion polymerization to produce waterborne polyacrylate–poly(urethane-urea) (WPUUA) hybrid emulsions. Compared with waterborne polyacrylate (WPA) film, the film-forming ability of WPUUA film is improved and the surface roughness R_a and R_q of WPUUA film decreases from 47.5 and 36.4 nm to 35.2 and 18.8 nm, respectively. Meanwhile, the mechanical properties of WPUUA films are significantly improved compared to WPA film. In addition, the performances of WPUUA hybrid films can be modified according to requirements by adjusting the molar ratio between DP-1000 and polyisocyanate. As a result, these WPUUA hybrid emulsions have great application potential in waterborne coatings and other fields.     

聚氨酯——聚丙烯酸酯复合聚合物乳液的研究

本文研究了几种聚氨酯——聚丙烯酸酯乳液复合的方法，制备了新单体N-（4’-甲基3’-二正丁脲基）苯基氨基甲酸内烯酰氧-2-丙酯，使其与丙烯酸酯类单体共聚，显著提高了聚合物的抗张强度，简单介绍了聚合物膜接技法，共混复合法和种子聚合法的实施方法，聚合物膜性能及粒子结构等有关研究内容，实验表明，用几种方法都可以获得综合性能好的复合聚合物乳液。     

Transport Studies of Monovalent Ions through Nafion-117 Ion Exchange Membrane in Presence of Polyacrylate

The results of equilibrium distribution and transport kinetics of monovalent (Li⁺, Na⁺, and Cs⁺) ions through Nafion-117 ion exchange membrane in presence of polyacrylate anion have been presented. For Na⁺-Li⁺ system, equilibrium distributions in the presence and absence of polyacrylate have been found to be the same indicating that the Donnan membrane equilibrium is not affected by the presence of polyacrylate. For the Na⁺-Cs⁺ system, a favored transport of Cs⁺ ion to the polyacrylate compartment has been observed, indicating the binding of Cs⁺ ion with polyacrylate is stronger than other monovalent ions. This is due to the lower hydration radius of Cs⁺ ions. The deviation from Donnan membrane equilibrium condition has been used to obtain information about the fraction of counter-ions bound to the polyacrylate. The transport profile in the presence of polyacrylate has also been calculated based on the modified Nernst Planck (NP) approach, taking into account the fraction of counter-ions bound to the polyacrylate ion. The Donnan relation has been used to obtain the concentration of ions at the solution/membrane interface. The self-diffusion coefficients of ions and membrane ion exchange capacity have been given as input parameters in the calculations. The calculated time profile has been found to agree well with the experimental time profile.     

Synthesis and characterization of fluorinated polyacrylate–cellulose acetate butyrate interpenetrating polymer networks

Fluorinated polyacrylates are highly hydrophobic and oleophobic. However, their poor mechanical properties prevent their development in many applications. Combination of a fluorinated polyacrylate network with a rigid cellulose acetate butyrate (CAB) network in an interpenetrating polymer network (IPN) architecture is an effective method for improving the mechanical properties of fluorinated polyacrylates. IPNs combining poly(3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctyl acrylate) (polyAcRf6) with CAB were prepared according to an in situ polymerization/crosslinking synthesis. CAB was crosslinked by addition between unmodified hydroxyl groups and the isocyanate of a pluri‐isocyanate crosslinker. The fluorinated network was obtained through free‐radical copolymerization of 3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctyl acrylate with poly(ethylene glycol dimethacrylate). The rates of formation of both networks were followed using Fourier transform infrared spectroscopy. Differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) of IPNs show a single glass transition temperature and a single mechanical relaxation temperature, which are characteristic of a high degree of interpenetration between the partner networks. The mechanical properties of IPNs are greatly improved compared with those of the single fluorinated network. CAB/polyAcRf6 IPNs were prepared, and characterized using DSC and DMTA as well as contact angle measurements for their surface properties. As hoped, the mechanical properties of such materials are much improved compared with those of the fluorinated partner alone. Copyright © 2010 Society of Chemical Industry     

D4-丙烯酸酯水性胶粘剂的研制

研究了以ＯＰ－１０、十二烷基硫酸钠为乳化剂，以Ｋ２Ｓ２Ｏ８为引发剂，以八甲基环四硅氧烷（Ｄ４）与丙烯酸丁酯为主要单体，进行乳液聚合反应，制取水性胶粘剂。在固含量一定的前提下，通过正交试验确定了最佳粘结强度的条件。     

外交联型聚丙烯酸酯固化行为研究

利用动态力学扭瓣分析研究了聚丙烯酸酯的升温固化过程，提出了一种两步固化机理，并求算得到了体系的固化活化能，发现有机晚催化剂有能有效降低固化活化能并讨论了其催化历程。     

Miscibility and thermal and dynamic mechanical behaviour of semi‐interpenetrating polymer networks based on polyurethane and poly(hydroxyethyl methacrylate)

The thermodynamic miscibility and thermal and dynamic mechanical behaviour of semi‐interpenetrating polymer networks (semi‐IPNs) of crosslinked polyurethane (PU) and linear poly(hydroxyethyl methacrylate) (PHEMA) have been investigated. The free energies of mixing of the semi‐IPN components have been determined by the vapour sorption method and it was established that the parameters are positive and depend on the amount of PHEMA in the semi‐IPN samples. Thermal analyses glass transition temperatures evidenced two in the semi‐IPNs in accordance with the investigation of the thermodynamic miscibility of these systems. Dynamic mechanical analysis revealed a pronounced change in the viscoelastic properties of the PU‐based semi‐IPNs with different amounts of PHEMA in the samples. The semi‐IPNs have two distinct tan δ maxima related to the relaxations of the two polymers in their glass temperature domains. The temperature position of PU relaxation maximum tan δ is invariable but its amplitude decreases in the semi‐IPNs with increasing amount of PHEMA in the systems. The tan δ maximum of PHEMA is shifted to a lower temperature and its amplitude decreases with increasing amount of PU in the semi‐IPNs. The segregation degree of components α was calculated using the viscoelastic properties of semi‐IPNs. It was concluded that the studied semi‐IPNs are two‐phase systems with incomplete phase separation. The different levels of immiscibility lead to the different degree of phase separation in the semi‐IPNs with compositions. Copyright © 2004 Society of Chemical Industry     

室温固化聚丙烯酸酯／聚氨酯复合涂料性能的研究

合成了高固含量乙酰乙酸基聚丙烯酸酯组分和端烯基聚氨酸组分，在碱催化剂作用下，两组分在室温下通过迈克尔加成反应完成交联固化制得了一种新型的复合涂料。研究了催化剂及聚合物组成对漆膜性能的影响。