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     

不饱和聚酯／聚氨酯复合体系的研究

以端羟基不饱和聚酯（ＨＵＰ）与聚氨酯（ＰＵ）浇注型复合网络聚合物（ＣＰＮｓ）为基材，考察了化学动力学及相分离对ＣＰＮ聚合物物理机械性能的影响．数据揭示了不饱和聚酯／聚附聚氨酯（ＨＵＰ／ＰＵ－ｅｓ）ＣＰＮ，当ｒ＝ＮＣＯ／ＯＨ＝０．４时，它的物理力学性能优于不饱和聚酯／聚醚聚氨酯（ＨＵＰ／ＰＵ－ｅｔ）ＣＰＮ或ＨＵＰ／ＰＡＰＩＣＰＮ组成物．最佳ＣＰＮ可通过调整聚氨酯中软段和硬段组分及网络组成而设计与制备．     

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℃。     

四苯氧基酞菁镁、锰、铝和锌的合成和性质

合成了新的酞菁配合物４，４，４，４－四苯氧基酞菁镁［ＴＰｈＯＰｃＭｇ（Ⅱ）］，锰［ＴＰｈＯＰｃＭｎ（Ⅱ）Ａｃ］，铝［ＴＰｈＯＰｃＡｌ（Ⅲ）Ｃｌ］，锌［ＴＰｈＯＰｃＺｎ（Ⅱ）］测定了它们的ＩＲ，ＵＶ－Ｖｉｓ光谱，在ＤＭＦ中的氧化还原半波电势（Ｅ１／２），电子转移速度常数，在乙腈中的荧光性质及锰的配合物在不同电位下的光谱变化情况。     

SYNTHESIS AND CHARACTERIZATION OF NOVEL FUNCTIONAL HOST COMPOUND 2~[1] MONO-

ＳＹＮＴＨＥＳＩＳＡＮＤＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦＮＯＶＥＬＦＵＮＣＴＩＯＮＡＬＨＯＳＴＣＯＭＰＯＵＮＤ２~［１］ＭＯＮＯ－［６－Ｏ－（８－ＱＵＩＮＯＬＹＬ）］－β－ＣＹＣＬＯＤＥＸＴＲＩＮＹｕＬＩＵ；ＹｉＭｉｎＺＨＡＮＧ；ＹｕｎＴｉＣＨＥ?..     

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．     

SYNTHESIS OF A TITANIUM－CONTAINING POLYOXOANION ［ZnW_（11）O_（39）Ti（H_2O）］~（6－）AS CATALYST FOR ALKENE EPOXIDATION

ＳＹＮＴＨＥＳＩＳＯＦＡＴＩＴＡＮＩＵＭ－ＣＯＮＴＡＩＮＩＮＧＰＯＬＹＯＸＯＡＮＩＯＮ［ＺｎＷ_（１１）Ｏ_（３９）Ｔｉ（Ｈ_２Ｏ）］~（６－）ＡＳＣＡＴＡＬＹＳＴＦＯＲＡＬＫＥＮＥＥＰＯＸＩＤＡＴＩＯＮ￥ＭｉｎｇＸｉｕＬＩ；ＪｉｎｇＦｕＬＩＵ；Ｙｉｎｇ...     

RUTHENIUM COORDINATION COMPOUNDS WITH POLYPYRIDINES V．DNA－BINDING STUDIES OF Ru（Ⅱ）COORDINATION COMPOUNDS WITH（2－PHENYL－）IMIDAZO［f］1，10－PHENANTHROLINE

ＲＵＴＨＥＮＩＵＭＣＯＯＲＤＩＮＡＴＩＯＮＣＯＭＰＯＵＮＤＳＷＩＴＨＰＯＬＹＰＹＲＩＤＩＮＥＳＶ．ＤＮＡ－ＢＩＮＤＩＮＧＳＴＵＤＩＥＳＯＦＲｕ（Ⅱ）ＣＯＯＲＤＩＮＡＴＩＯＮＣＯＭＰＯＵＮＤＳＷＩＴＨ（２－ＰＨＥＮＹＬ－）ＩＭＩＤＡＺＯ［ｆ］１，１０－...     

STEREOSTRUCTURE OF POLY［4－（2－METHYLPROPENOYLOXY）－4＇－CYANOBIPHENYL］ BY PHOTOPOLYMERIZATION UNDER AN EXTERNAL ELECTRIC FIELD

ＳＴＥＲＥＯＳＴＲＵＣＴＵＲＥＯＦＰＯＬＹ［４－（２－ＭＥＴＨＹＬＰＲＯＰＥＮＯＹＬＯＸＹ）－４＇－ＣＹＡＮＯＢＩＰＨＥＮＹＬ］ＢＹＰＨＯＴＯＰＯＬＹＭＥＲＩＺＡＴＩＯＮＵＮＤＥＲＡＮＥＸＴＥＲＮＡＬＥＬＥＣＴＲＩＣＦＩＥＬＤ￥ＣｈｏｎｇＷｕＬＩ；Ａ...     

UNUSUAL FORMATION OF ORGANO－NEODYMIUM AND －SAMARIUM CATIOHS AND X－RAY STRUCTURE OF［（MeOCH_2CH_2C_5H_4）_2Sm（thf）］［Co（CO）_4］

ＵＮＵＳＵＡＬ　ＦＯＲＭＡＴＩＯＮ　ＯＦ　ＯＲＧＡＮＯ－ＮＥＯＤＹＭＩＵＭ　ＡＮＤ　－ＳＡＭＡＲＩＵＭ　ＣＡＴＩＯＨＳ　ＡＮＤ　Ｘ－ＲＡＹ　ＳＴＲＵＣＴＵＲＥ　ＯＦ［（ＭｅＯＣＨ_２ＣＨ_２Ｃ_５Ｈ_４）_２Ｓｍ（ｔｈｆ）］［Ｃｏ（ＣＯ）_４］ＵＮＵＳＵＡ...     

Structure and properties of polyurethane/polyacrylate latex interpenetrating networks hybrid emulsions

Some new kinds of novel polyurethane (PU)/polyacrylate (PA) latex interpenetrating networks (LIPNs) were synthesized. Firstly PU dispersions were synthesized by self-emulsification polymerization. Then PU/PA LIPNs using PU dispersion as the seed were prepared by soap free emulsion polymerization. The effects of different PU/PA ratios, the blending method and the NCO/OH molar ratio of PU components on PU/PA LIPNs performance were also investigated. The structure and properties of PU/PA LIPNs such as mechanical properties, particle size, morphology of the surface were characterized by dynamic mechanical analysis, scanning electron microscopy, and dynamic light scattering. It was found that PU/PA LIPNs can markedly improve the water resistance and the mechanical properties of PU latex much more than those of PU/PA physical blends due to a great deal of interpenetrating and entangling between PU and PA latex. Moreover, the particle size of PU/PA LIPNs is related to the PA content and NCO/OH molar ratio of PU components: the higher the NCO/OH molar ratio in PU dispersions, the larger is the particle size of PU/PA LIPNs, and the average particle size of PU/PA LIPNs becomes larger with an increase in PA content.     

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.     

大分子不饱和单体法合成具有核壳结构的丙烯酸酯/聚氨酯乳液及表征

采用丙烯酸酯（AC）对水性聚氨酯（WPU）进行改性,合成了接枝型丙烯酸酯/聚氨酯(PUA)复合乳液。 随着共聚物中丙烯酸酯质量分数的增加,乳液外观由透明变为不透明,乳液粒径随之增大、分布变宽。 TEM显示,PUA乳胶粒子呈现清晰的核壳结构,且形态规整,粒径分布在60~120 nm之间。 FTIR测试表明,随着丙烯酸酯质量分数的增加,聚氨酯(PU)硬段氢键化作用先增强后减弱,硬段的有序度逐渐降低。 DSC分析表明,当AC的质量分数低于75%时,PU、聚丙烯酸酯(PA)两组分相容性较好,只出现一个玻璃化转变温度,并且随着PA质量分数的增加逐渐升高。 PA质量分数的增加,使胶膜的最大热失重速率从363 ℃提高至412 ℃,吸水率从11.3%降低至5.7%,弹性模量从16.4 MPa提高至47.6 MPa,拉伸强度从9.0 MPa提高至23.7 MPa,断裂伸长率从365%提高至408%,同时乳液的粘度下降,干燥时间变短,胶膜的附着力变好。     

Interpenetrating polymer networks from polyurethanes and methacrylate polymers. I. Effect of molecular weight of polyols and NCO/OH ratio of urethane prepolymers on properties and morphology of IPNs

Two types of reinforced elastomeric interpentrating polymer network (IPN) were prepared by simultaneous polymerization and crosslinking in solution. The first type consisted of polyurethane-poly(methyl methacrylate) (PU/PMMA), and the second, of polyurethane-poly(methyl methacrylate-methacrylic acid) PU/P(MMA–MAA) of constant composition (90/10) and (80/20) by weight, respectively. The members of each type differed in the NCO/OH ratio of the PU prepolymer and the molecular weight (MW) of the polyol in the PU component because we wished to investigate systematically the effect of changing the NCO/OH ratio and MW of the polyol on the mechanical properties and morphology of the resulting IPNs. The mechanical properties, particularly the modulus of both tyes of IPN, increased with increasing NCO/OH ratio and decreased with increasing MW of the polyol in the PU. The morphology of the IPNs was studied by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Improved phase compatibility and decreasing extent of phase separation was observed in both types of IPN with increasing NCO/OH ratio and decreasing MW of the polyol used in the PU. These results may imply that improved interpenetration results from increasing the NCO/OH ratio and decreasing the MW of the polyol in the PU component. The fact that the effect is more pronounced with the type of PU-P(MMA–MAA) IPN can be rationalized as due to the additional hydrogen bonding between the carbonyl in the carboxyl groups and the urethane or urea groups in the PU component.     

Synthesis and properties of room temperature curable trimethoxysilane‐terminated polyurethane and their dispersions

The purpose of this research is to study the synthesis and characterization of stable aqueous dispersions of externally chain extended polyurethane/urea compositions terminated by hydrolyzable or hydrolyzed trialkoxysilane groups incorporated through secondary amino groups. These dispersions with excellent storage stability are substantially free from organic solvents which cure to water and solvent resistant, tough, scratch resistant, preferably light stable (non‐yellowing) silylated polyurethane (SPU) films. The films were characterized by FT‐IR, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), tensile strength and water contact angle measurements, nanoindentation, gel content, water and xylene swellability tests. The properties of the films were discussed and correlated in detail by changing length of soft segment, diisocyanates, NCO/OH ratio and chain extender, ethylenediamine (EDA). From the results, it was found that the particle size and viscosity are lower whereas the gel content and thermal stability are higher for SPUs. Modulus, hardness and tensile properties of SPU films are superior compared to EDA‐PU film. Higher water contact angle and residual weight percentage of SPU films confirm silylation of PU by [3‐(phenylamino)propyl]trimethoxysilane (PAPTMS). Increase in NCO/OH ratios consumes more quantity of PAPTMS which makes PU with superior mechanical properties. Higher PAPTMS content in SPU results in effective crosslinking of the functional silanol groups formed by hydrolysis reaction of trimethoxysilane groups. Overall, SPUs synthesized at 1.4 NCO/OH ratio using Poly‐(oxytetramethylene)glycol (PTMG)‐2000 and isophorone diisocyanate (or) toluene‐2,4‐diisocyanate have excellent properties compared to SPUs prepared using PTMG‐1000 and at 1.2 and 1.6 NCO/OH ratios. SPUs prepared at 1.6 NCO/OH ratio are brittle due to higher crosslinking density. In addition, the crosslinking density of the films can be modified through silane end‐group modification to produce SPUs with a wide range of physical properties. Copyright © 2007 John Wiley & Sons, Ltd.     

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。     

水性聚氨酯乳化过程中相转变的研究

本文合成了单官能团小分子物质封端的脂肪族水性聚氨酯预聚物 ,通过考察预聚物加水乳化过程中粘度及电导率的变化 ,研究了其相转变行为 .实验结果表明 ,随着软段分子量升高 ,体系的相转变点后延 ;聚酯体系的相转变比聚醚体系的相转变发生得早 ;[NCO]/ [OH]值越接近 1,体系的粘度就越高 ,相转变发生所需的水含量也越高 ;羧基含量及中和度也会对分散体系的相转变产生影响 .通过选择合适的条件 ,可以实现对乳化过程的优化     

Effect of Molecular Weight of WPU on the Heterogenic PUA Composite Latex Prepared by Soap-Free Emulsion Polymerization

Aqueous acrylic-polyurethane (PUA) composite emulsion was prepared by soap-free seeded emulsion copolymerization. Waterborne polyurethane (WPU) was used as the seeded emulsion and functioned as surfactant. The effect of molecular weight of WPU on the heterogenic was investigated. The molecular weight of WPU was controlled by varying the NCO/OH mole ratio. The GPC results confirmed that the molecular weight of WPU presented double distribution. And the molecular weight of WPU decreased with the increasing NCO/OH mole ratio. Surface tension test indicated that the molecular weight had little influence on the surface activity of WPU. However, after emulsion copolymerization of acrylic monomers, the morphology and properties of the PUA composite were impacted markedly by the molecular weight of WPU. With an increase in the NCO/OH mole ratio, the morphology of PUA composite latex changed from core-shell structures to fish bowl structure, and the mechanical properties of PUA films changed correspondingly.     

Structural parameters of the network formed first in in-situ sequential interpenetrating polymer networks

As part of a study concerning poly(propylene glycol)-based polyurethane / poly(methyl methacrylate) interpenetrating polymer networks, polyurethane networks were synthesized at various dilutions of the reaction medium and at different values of the [NCO]/[OH] ratio. The network defects arising in such materials were evaluated by three independent experimental approaches: solvent extraction, swelling behaviour, and compression measurements. It was found that the networks with the least defects are formed at high precursor concentration, with a [NCO] over [OH] excess of about 7%.     

偶联剂对丙烯酸酯改性聚氨酯聚合物接枝率和乳液性能的影响

合成了含双羟基的甲基丙烯酸甘油酯(GM)并将其作为偶联剂用于聚丙烯酸酯(PAC)对水基聚氨酯(PU)的改性.采用核磁共振、红外光谱和气相色谱等对GM进行了表征.分别以该双羟基GM和单羟基的丙烯酸羟乙酯(HEA)与异氰酸酯基(NCO)封端的PU预聚体进行反应以在PU分子链上引入双键,然后再与丙烯酸酯类单体通过自由基聚合制...