由聚醚合成聚醚酯嵌段共聚物的研究

采用对甲苯磺酸催化剂，以聚醚二元醇（PPG-2000）首先同羧酸反应产生由大部分羧酸基团封端的聚醚酯，随后向该聚醚酯中加入丙二醇继续反应合成由羟基封端的聚醚酯。制得的聚醚酯多元醇应用于微孔聚氨酯弹性体（MPUE）的合成，得到了综合性能均优良的MPUE材料。在相同硬段含量下，聚醚酯型MPUE的力学性能与纯聚酯型MPUE的力学性能接近，而该聚醚酯型MPUE的耐水解性能接近纯聚醚型MPUE。     

水性聚氨酯防水涂膜材料的制备与性能

为了研究多元醇类型对水性聚氨酯防水涂膜材料性能的影响,选用分子量均为1 000的聚酯型、聚醚型多元醇为软段,通过预聚体法制备了一系列水性聚氨酯(WPU)分散体;探讨了WPU的粒径、黏度、结构及结晶性、水抵抗性能。结果表明:制备的WPU分散体粒径较小;聚酯多元醇型[聚己二酸乙二醇酯(PB)、聚碳酸酯(PCL)]WPU膜的拉伸强度、结晶性能高于聚醚多元醇型[聚丙二醇(PPG)、聚四氢呋喃醚二醇(PTMG)]的,但是断裂伸长率低于聚醚多元醇型的WPU膜;其中PTMG型WPU膜的水接触角最大,达到66.5°,吸水率最小(6.2%),防水性最佳,综合性能最好,最适合用作环境友好型纤维织物防水涂膜材料。     

微孔聚氨酯弹性体材料水解稳定性研究

采用相同分子量的聚醚、聚酯和聚醚酯二元醇为原料分别制备密度为0．55g／cm3左右的微孔聚氨酯弹性体（MPUE）材料。并通过一系列测试对这三种微孔聚氨酯弹性体材料进行分析对比。结果发现聚醚型微孔聚氨酯弹性体材料的耐水解性能非常优异,聚酯型微孔聚氨酯弹性体材料的力学性能最好,聚醚酯型微孔聚氨酯弹性体材料的力学性能与聚酯型的力学性能接近,耐水解性能远优于聚酯型,近似于聚醚型。     

铝塑复合用聚氨酯胶粘剂的制备及性能研究

以聚酯、聚醚混合多元醇和异佛尔酮二异氰酸酯为主要原料,制备了一种低粘度无溶剂型聚氨酯覆膜胶粘剂。研究了聚酯、聚醚混合多元醇的配比对胶粘剂合成时间、粘度、抗水性能和粘结强度的影响;同时,探讨了催化剂的添加对胶粘剂综合性能的影响。结果表明:由混合聚酯、聚醚多元醇合成的聚氨酯胶粘剂粘度低、易涂覆且耐水性得以改善,但比例必须适宜,以2种多元醇所含羟基物质的量比为0.3:0.7为佳;催化剂的加入虽能显著提高固化速度,但降低了胶粘剂的剥离强度,不利于胶粘剂综合性能的改善,故应酌情适量添加。     

热塑性聚氨酯弹性体的新进展

一、前言热塑性聚氨酯弹性体(TPU)系由二异氰酸酯、多元醇和短链二元醇所组成。二异氰酸酯及短链二元醇形成TPU的硬段,多元醇形成软段。由于硬、软段互不相容,TPU表现出两相结构。聚氨酯分为聚酯型及聚醚型两类。一般,聚酯型TPU具有更好的物理性质、热氧化稳定性和耐油性。在硬度范围相同的情况下,聚醚型TPU表现     

室温固化聚醚型聚氨酯弹性体的制备及研究

以可再生资源蓖麻油为起始剂环氧丙烷开环聚合的聚醚多元醇、聚丙二醇醚多元醇、TDI、MOCA等为主要原料,采用半预聚物法,室温固化制备双组分浇注型聚氨酯弹性体(CPUE).对该新型聚氨酯弹性体进行了红外光谱测试,结果表明其分子结构中含有氨基甲酸酯基、醚键等基团的特征吸收峰;通过力学性能测试,原料中聚醚多元醇的种类、NCO基质量分数的改变都会引起弹性体性能的差异,这些差异存在一定的规律性;DSC差示扫描结果表明,聚氨酯弹性体分子链中硬段含量升高,玻璃化转变温度(Tg)升高;利用热重分析(TG)研究了其耐高温性能,结果表明硬段含量和扩链剂种类都会影响PUE的热稳定性.     

聚氨酯/无机填料复合弹性体的制备及性能研究

以聚醚多元醇和2,4-二苯基甲烷二异氰酸酯(MDI-50)为原料,二甲硫基甲苯二胺(DMTDA)为扩链剂,采用预聚法分别填充玻璃纤维、石墨片和浮石不同的无机填料制得聚氨酯弹性体(PUE)/玻璃纤维、PUE/石墨片和PUE/浮石3种复合PUE。采用扫描电镜(SEM)、热重分析(TGA)及力学性能测试对3种复合PUE的断面形貌、热稳定性和抗压强度进行了表征。结果表明,添加玻璃纤维、石墨片和浮石后对复合PUE的力学性能和热稳定性均有增强作用。纯PUE抗压强度为3.53MPa,添加质量分数为40%的玻璃纤维、石墨片和浮石制得的3种复合PUE抗压强度分别为3.73、4.30和4.33MPa,比未添加填料的PUE分别提高5.67%、21.81%和22.66%;在失重率为5%时,纯PUE的分解温度为253.70℃,3种复合材料的分解温度分别为277、261和260℃,比未添加无机填料的PUE分别提高9.18%、2.88%和2.48%。     

单组分热固化聚氨酯胶粘剂的研制

以聚醚、聚酯多元醇、TDI和橡胶粒等为原料,制备出粘接橡胶粒的单组分胶粘剂。考察了多元醇种类及配比、异氰酸酯指数等因素对材料性能的影响。     

不同异氰酸酯型聚氨酯弹性体的合成与性能研究

以甲苯二异氰酸酯(TDI)、4,4′-二环己基甲烷二异氰酸酯(HMDI)、异佛尔酮二异氰酸酯(IPDI)、聚醚多元醇和1,4-丁二醇(BDO)等为主要原料制得一系列不同硬度、不同异氰酸酯型聚氨酯弹性体(PUE),研究了异氰酸根指数(R值)、不同多异氰酸酯等对PUE的性能影响。结果表明,随R值增加,3种异氰酸酯型聚氨酯(PU)的硬度、拉伸强度和热性能变化趋势一致,断裂伸长率变化各异。在R值为1.4时,HMDI-PU分子结构最规整,结晶度最高,硬度最大,热性能较优,硬度达到56HA,拉伸强度为2.949MPa,断裂伸长率为390%,起始分解温度为278℃,最大失重温度为321℃,是3种材料中较好的。     

聚酯型聚氨酯油墨连接料的合成及性能研究

指出了聚酯型聚氨酯油墨使用简便、性能稳定、附着力强、光泽度优、耐热性好,能适合各种印刷方式。在制备聚酯多元醇的基础上,通过扩链反应,制备了酯溶性聚氨酯及聚氨酯油墨,并利用红外等对样品的性能进行了表征。     

蓖麻油-聚醚基聚氨酯弹性体的制备和表征

以可再生资源-蓖麻油作为起始荆,环氧丙烷开环聚合制备了不同分子量的蓖麻油-聚醚多元醇,并通过1HNMR 和 FTIR 等手段来分析蓖麻油-聚醚多元醇的结构.以不同分子量的蓖麻油-聚醚多元醇作为原料制备了一系列聚氨酯弹性体,并对其进行物理机械性能和热性能分析.研究结果表明:随着蓖麻油聚醚多元醇分子量的增加,其聚氨酯弹性体的扯断伸长率逐渐增加,拉伸强度、撕裂强度和硬度逐渐降低;同时,热稳定性提高,硬段的结晶熔融温度和结晶度降低.     

封端型水性聚氨酯树脂的结构与性能

以聚酯多元醇、甲苯二异氰酸酯和二羟甲基丙酸为主要原料,丙烯酸单体封端,加入改性剂三羟甲基丙烷脱水蓖麻油酸酯(TMPDCO),制备出稳定的水性聚氨酯分散体。涂膜耐化学品性和凝胶含量测定说明,TMPDCO的加入增加了涂膜的交联度,提高了涂膜的耐化学品性。差示扫描量热法测试表明,加入封端剂增加了涂膜交联度,涂膜玻璃化转变温度明显提高。力学性能测试说明,聚酯作为软段的水性聚氨酯树脂较聚醚型耐水性好。X射线衍射分析说明,随着硬段规整度的增加,衍射峰中心依次向高角度偏移。红外表征说明,不同硬段合成水性聚氨酯的氨基甲酸酯键波数不同。     

苯酐聚酯多元醇在聚氨酯硬泡中的应用

通过选择或合成聚醚多元醇，调整聚氨酯泡沫配方，介绍了苯酐聚酯多元醇在聚氨酯硬泡中的应用。实验证明，泡沫性能良好，泡沫稳定剂使用量减少，泡沫成本大幅度下降。     

基于嵌段聚醚酯多元醇的聚氨酯控释机理研究

针对海洋工程设备中弹性基材的防污特殊需求,合成聚乙二醇(PEG)/聚己内酯(PCL)嵌段共聚物PEG/CLX,并与HDI三聚体固化形成可降解聚氨酯,研究其亲水性能及降解性能,再将PEG/CLX与氧化亚铜等结合,制备成一系列的海洋防污涂层,研究其控释机理.     

Characterization of polyether and polyester polyurethane soft blocks using MALDI mass spectrometry

Selective degradation reactions combined with MALDI analysis have been applied for molecular weight (MW) determination of polyether and polyester polyurethane (PUR) soft blocks. Selective degradation allows recovery of the polyols, and direct observation of the soft block oligomer distribution is possible for the first time by using MALDI. Ethanolamine is applied for polyether PUR degradation. MALDI analysis indicates that the recovered polytetrahydrofuran (pTHF) MW distribution is nearly identical to the unreacted pTHF material. Reduction in the ethanolamine reaction time allows observation of oligomer ions containing the diisocyanate linkage, which provide identification of the diisocyanate. Ethanolamine is not used for polyester PUR's degradation because the ester bonds will be cleaved. Therefore, phenylisocyanate is applied for polyester PUR degradation. Polybutylene adipate (pBA) oligomers were directly observed in the MALDI spectra of the degraded pBA-PUR samples. Comparison of the degraded pBA-PUR oligomer distribution with the unreacted pBA material indicates that low-mass oligomers are less abundant in the degraded pBA-PURs. Oligomer ions containing the diisocyanate linkage are also observed in the spectrum, providing a means for identifying the diisocyanate used for PUR syntheses. Size-exclusion chromatography (SEC) was combined with MALDI to provide accurate MW determination. Narrow MW fractions of the degraded and unreacted polyols were collected and analyzed by MALDI. This method allows precise calibration of the SEC chromatogram. The SEC-MALDI results provide significantly larger Mw and PD values than MALDI alone. Using SEC-MALDI, it was determined that the PD indexes of the pTHF and pBA samples are larger than the assumed values, which are based on the polyol synthesis reactions. The combination of selective degradation with SEC-MALDI, using either ethanolamine or phenylisocyanate, is a viable method for polyurethane polyol characterization.     

Synthesis methods, chemical structures and phase structures of linear polyurethanes. Properties and applications of linear polyurethanes in polyurethane elastomers, copolymers and ionomers

Chemical and supermolecular structures occurring in linear polyurethanes were presented and they were referred to the analysis of the reactions connected with the step-growth polyaddition process of diisocyanates and polyols. Based on the general kinetic model of the step-growth polyaddition process, which is available in papers, inclusive of our own reports published on that subject, and based on experimental verification of that model by GPC chromatography and MALDI-ToF spectrometry, the influence was discussed of reactivity specifications of the diisocyanate and polyol monomers, and of intermediate products (urethane oligomers), on the size of molecules and on molecular weight distribution in linear polyurethane products. The applicability of such research methods as SAXS, SEM, AFM and DSC for the analysis of phase structures and micro-phase separation in the linear polyurethanes was presented. Also, the influence of phase separation on thermal and mechanical properties of the polyurethane products was addressed. Special attention was paid to the influence of polarity of polyurethane chemical structures, dispersion interactions, hydrogen bonding and ionic interactions on the value of free surface energy of polyurethane anionomers and cationomers. The effects on chemical and biological stability of those products were considered, too. Derived from the above analysis, the latest trends were provided for the applications of linear polyurethanes: as liquid crystalline materials, urethane-acrylic and polyurethane-siloxane copolymers in electronics, medicine and civil engineering, and as environmentally friendly elastomers in protective coatings produced from waterborne polyurethane dispersions.     

水性聚氨酯乳液中各组分的定性定量分析方法探讨

采用多种分析仪器和手段包括红外光谱,凝胶色谱,色谱-质谱联用技术,核磁共振波谱等,探讨了水性聚氨酯乳液中的溶剂和树脂成分的定性定量分析方法.对组成水性聚氨酯乳液中的低聚物多元醇种类,异氰酸酯种类,扩链剂,成盐剂,水和有机溶剂,乳化剂等进行了全分析,同时用凝胶色谱对树脂进行分子量及其分布测定.分析结果表明该水性聚氨酯乳液...     

Synthesis of waterborne polyurethane using snow as dispersant: Structures and properties controlled by polyols utilization

Waterborne polyurethane (WPU) dispersions have gained attention towards environmentally-friendly synthesis. In this article, a series of waterborne polyurethane emulsions was successfully synthesized and extensively characterized in terms of thermal, mechanical properties, hydrophilic behavior and morphology. Snow was chosen as dispersant instead of commonly used water. Preparation parameters such as intrinsic properties and molecular weight of polyols were discussed systematically. A chain structure was confirmed by Fourier transform infrared (FT-IR) spectroscopy. When comparing the nature of the polyols (PPG, PEG and PNA, 2000 g/mol) of this study, as-synthesized polyether waterborne polyurethane provided higher solid content, viscosity and water-resistance. However, polyester waterborne polyurethane performed differently and it exhibited higher thermal stability and crystallinity. When comparing the samples (WPU-N210, WPU-N220, WPU-N230 and WPU-N240) with different molecular weight of the same polyol (PPG) used as soft segment, the emulsion WPU-N220 with molecular weight of 2000 g/mol PPG provided the highest solid content and lowest viscosity. It was observed that particle size was uniform and highly dispersed for all samples from TEM images. Thermogravimetric, differential scanning calorimetry (DSC) and X-ray diffraction results demonstrated that the emulsion WPU-N230 with molecular weight of 3000 g/mol PPG possessed higher thermal stability and crystallinity than the other samples. The reason was that the T_g and thermal stability were increased with increasing molecular weight. When molecular weight increased, the arrangement of soft segment became more regular and so did the regularity of the molecular chains. This work demonstrated that different polyols as soft segment applied could lead to great differences in the structure and property of the resulting WPU.