浇注型聚氨酯弹性体的研制

采用2,4-甲苯二异氰酸酯(TDI)、聚醚多元醇或聚酯多元醇、扩链剂等原料通过预聚物法合成了浇注型聚氨酯(PUR)弹性体,分析了柔性链段的分子结构、扩链剂的分子结构及异氰酸酯基的含量等因素对PUR弹性体力学性能的影响。结果表明,以聚己二酸丁二酯为柔性链段、MOCA或TX-2为扩链剂、异氰酸酯基质量分数为5％．5．5％时,所得PUR弹性体具有较好的综合性能。     

E-100扩链的聚氨酯弹性体性能的研究

以不同相对分子质量的聚醚多元醇(PPG)、TDI和3,5-二乙基甲苯二胺(DETDA)为原料,采用溶剂法合成了聚氨酯(PU)弹性体,分别研究了溶剂种类、NCO含量、聚醚多元醇相对分子质量、扩链系数等对PU弹性体力学性能的影响。结果表明,二甲苯对PU弹性体性能影响最小;PU弹性体的硬度、定伸模量、拉伸强度和撕裂强度随聚醚多元醇的相对分子质量的升高而下降,冲击弹性、伸长率和永久变形随聚醚多元醇的相对分子质量的升高而上升;当预聚体NCO质量分数为6.30%、扩链系数为0.95时,PU弹性体的综合力学性能最佳。     

聚氨酯弹性体软段对其力学性能的影响

先用4,4'-二苯基甲烷二异氰酸酯(MDI)与不同相对分子质量不同种类低聚物多元醇合成预聚体,再以1,4-丁二醇(BDO)为扩链剂制备聚氨酯弹性体,考察了软段对聚氨酯弹性体力学性能的影响.结果 表明:当预聚体NCO含量相同时,聚酯型聚氨酯弹性体的力学性能整体优于聚醚型的,随低聚物多元醇相对分子质量的增加,聚氨酯弹性体的...     

聚氨酯弹性体合成工艺研究

对聚氨酯(PUR)弹性体的合成工艺进行详细的研究,重点探讨了4种不同加料方式对PUR弹性体性能的影响。结果表明,将甲苯二异氰酸酯(TDI)溶液滴入已经脱水的聚醚溶液中,待反应完成后滴入扩链剂1,4-丁二醇(BDO)及将已脱水的聚醚溶液滴入TDI溶液中,待反应完成后再滴入扩链剂BDO这两种加料方式合成的PUR弹性体力学性能较好,玻璃化转变温度也较低,微相分离程度最完善。同时通过红外光谱表征了PUR弹性体的分子结构。     

低不饱和度聚醚PU弹性体力学性能的研究

研究了以不同相对分子质量的低不饱和度聚醚多元醇、二异氰酸酯(MDI.TDI)和扩链剂(1．4-BDO．MOCA)为原料制备PU弹性体的力学性能。结果表明：PU弹性体的硬度、拉伸强度和撕裂强度随NCO基含量增加而提高。逐渐提高聚醚的相对分子质量，PU的拉伸强度和撕裂强度下降,冲击弹性提高。相对分子质量为2000的TDB-PU比相同相对分子质量PPG-PU的综合力学性能要好。     

扩链剂与交联剂对NDI型聚氨酯弹性体性能的影响

用1,5-萘二异氰酸酯(NDI)和聚四氢呋喃醚二醇(PTMG)为原料合成了聚氨酯预聚体,以三羟基聚醚多元醇(330N)作为交联剂,1,4-丁二醇(BDO)作为扩链剂制备了NDI型聚氨酯弹性体,讨论了交联剂与扩链剂的不同羟基摩尔比对NDI型聚氨酯弹性体性能的影响。结果表明,随着三羟基聚醚多元醇含量的增加,NDI型聚氨酯弹性体软段玻璃化转变温度有所提高;三羟基聚醚多元醇的加入虽然使得聚氨酯弹性体的滞后损失峰值增加,但对常用温度范围的滞后损失影响不大,0～150℃温度范围内的储能模量降低;聚氨酯弹性体的拉伸强度与断裂伸长率随着三羟基聚醚多元醇含量的增加,呈先增加后下降的趋势变化,硬度则呈下降趋势。     

聚醚型聚氨酯弹性体的合成及其动态力学行为

采用两步合成法,以4,4′-二苯基甲烷二异氰酸酯(MDI)和1,4-丁二醇(BDO)为硬段,相对分子质量分别为1000、2000、4000的聚氧化丙烯二元醇(PPG)为软段,制备了一系列聚醚型聚氨酯(PUR)弹性体,研究了预聚体异氰酸酯指数R及软段相对分子质量对PUR动态力学性能的影响。结果表明,预聚体R值增大,即PUR的硬段含量增加,储能模量G′提高,软段相的玻璃化转变温度(Tg)升高,软硬相区的相容性增大;软段相对分子质量增加,PUR的G′下降,软段相的Tg降低,并出现硬段相的玻璃化转变,软硬相区的相分离程度增大。     

聚醚型高硬度聚氨酯弹性体的研制

采用聚氧化丙烯多元醇、二醇扩链剂和多异氰酸酯为原料，用一步法工艺制得一系列高硬度聚氨酯弹性体。讨论了多元醇组分平均每个羟基所对应的链段的相对分子质量(MOH)、平均官能度以及异氰酸酯种类对高硬度聚氨酯弹性体性能的影响。结果表明，采用液化MDI或粗MDI与聚氧化丙烯醚配合使用可以制得邵D硬度大于65的聚醚型高硬度聚氨酯弹性体。     

高相对分子质量低不饱和度聚醚多元醇技术进展

阐述了传统聚醚多元醇的技术进展、合成高相对分子质量低不饱和度聚醚多元醇的催化体系及研究进展，对高相对分子质量低不饱和度聚醚多元醇在聚氨酯泡沫、弹性体和密封胶中的应用进行概述，并就其未来发展提出建议。     

聚醚型与聚酯型聚氨酯弹性体的性能研究

使用聚乙二醇(PEG)、聚四亚甲基醚二醇(PTMG)、聚己内酯(PCL)和4,4’-二苯基甲烷二异氰酸酯(MDI)合成了聚醚多元醇型和聚酯多元醇型热塑性聚氨酯弹性体(TPU)。研究了各种TPU中异氰酸酯指数(R0)、硬段浓度(Ch)、聚醚和聚酯的种类、摩尔质量及原料用量等对弹性体力学性能的影响;并且使用双酚A型环氧树脂NPEL-127改性了弹性体的耐热性。研究结果表明:TPU的硬度随着R0和Ch的增加而增加;聚醚型TPU中,随着软段中柔性链的增加,TPU的硬度下降而力学性能提高;聚酯型TPU中,随着聚酯和聚酯二元醇摩尔质量的提高,TPU的硬度和力学性能均有提高;聚酯型TPU的力学性能优于聚醚型TPU;环氧树脂改性使得聚醚型TPU耐热性提高。     

Effects of various polyurethanes on the mechanical and structural properties of an epoxy resin

Polyurethanes (PURs) obtained from poly(ethylene glycol)s (PEGs) and polyoxypropylene diols (POPDs) of different molecular weights were used as modifiers of diglycidyl ether of bisphenol A. The impact strength, critical stress intensity factor, stress, and strain during three‐point bending were measured as functions of the PUR type and content. Scanning electron microscopy and infrared spectroscopy were employed for the structure and morphology analysis. The addition of 10 or 15% PUR to the epoxy resin resulted in the most enhanced mechanical properties. However, a modifier loading higher than 15% led to decreases in the impact strength, critical stress intensity factor, and flexural strength. Moreover, shorter flexible segments in PUR obtained from lower molecular weight PEG led to stronger composites, whereas composites containing PUR based on lower molecular weight POPD with long flexible segments exhibited higher toughness and strain at break and lower impact strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Property evaluation and structure analysis of polyurethane/epoxy graft interpenetrating polymer networks

Polyurethanes obtained from 4,4′‐diphenylmethane diisocyanate (MDI) and polydiols with different molecular weights (polyethylene glycol and polyoxypropylene diols) were used as modifiers for diglycidyl ether of bisphenol A. Impact strength (IS), critical stress intensity factor (K_C), flexural strength and flexural strain at break were measured as a function of polyurethane (PUR) type and content. Scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and infrared spectroscopy (FTIR) were employed for the structure and morphology analysis. It was found that the addition of polyurethane with an excess of isocyanate groups to epoxy resin resulted in the formation of a grafted interpenetrating polymer network structure. The mechanical properties of epoxy resin were improved with 5 and 10% PUR. Moreover, it was observed that composites containing PUR based on higher molecular weight (PUR 1002 and PUR 2002) with long flexible segments exhibited higher impact strength while PUR prepared from polyethylene glycol had a higher flexural energy to break and a higher flexural modulus. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal stability of polyurethane elastomers before and after UV irradiation

In this work, we investigated the thermal degradation behavior of segmented polyurethane (PUR) elastomers before and after UV irradiation. The thermal degradation of PUR elastomers was studied over the temperature range of 25–600°C in an atmosphere of nitrogen using thermal gravimetric analysis (TGA). Four series of PUR elastomers derived from poly(oxytetramethylene)glycol (PTMO) of 1000 and 2000 molecular weight and poly(caprolactone glycol) (PCL) of 1250 molecular weight, 4,4′‐diphenylmethane diisocyanate (MDI), and 4,4′‐dicyclohexylmethane diisocyanate (H₁₂MDI) and 1,4‐butanediol as an chain extender were synthesized by the prepolymer method. The derivative thermogravimetric (DTG) peaks observed in the experiments indicated that PUR elastomers degraded through two steps. We attributed the first step to degradation of the hard segment. The second degradation step could be ascribed to degradation of the soft segment. We found that the PUR elastomers based on poly(ester polyol) and aromatic diisocyanate exhibit better thermal stability than that of PUR elastomers based on the poly(ether polyol) soft segment in both steps of degradation. The thermal degradation is more prevalent in PUR elastomers based on cycloaliphatic diisocyanate. The higher values of the temperature of initial decomposition (Tⁱ) indicate a higher thermal stability of UV‐exposed elastomers on the beginning of degradation. This may be due to the formation of a crosslinking structure in the presence of UV irradiation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 864–873, 2001     

PDA型PUR弹性体的制备与性能

以聚己二酸二乙二醇酯二醇(PDA)为软段,4,4′–二苯基甲烷二异氰酸酯(MDI)和1,4–丁二醇(BDO)为硬段,采用预聚体法制备一系列PDA型PUR弹性体。采用力学性能测试、广角X射线衍射(WAXD)、傅立叶变换红外光谱(FTIR)、差示扫描量热(DSC)、热重(TG)分析和维卡软化点温度测定等研究手段,研究硬段含量对其力学性能、微观形态和热性能的影响。结果表明,随着硬段含量的增加,PDA型PUR弹性体的硬度、拉伸强度、300%定伸应力、拉伸永久变形和撕裂强度都增大,当硬段含量为40.1%时,弹性体的综合力学性能最佳,硬度(邵A)为88,拉伸强度为33.9 MPa,300%定伸应力为12.5 MPa,拉伸永久变形为31%,撕裂强度为90.3 k N/m;WAXD分析表明,弹性体为无定型结构;FTIR分析表明,硬段含量的增加使弹性体总的氢键化程度增加,微相分离程度改善;DSC测试表明,硬段含量的增加使弹性体的微相分离程度提高;TG和维卡软化点温度测试表明,弹性体的热性能随着硬段含量的增加而提高,当硬段含量为40.1%时,弹性体的初始分解温度(失重5%的温度)和维卡软化点温度分别达到324.5℃和144.1℃,具有较好的热性能。     

对苯二甲酸改性热塑性聚酰胺弹性体的合成与表征

采用熔融缩聚法,以ε-己内酰胺(CPL),对苯二甲酸(PTA)和聚四氢呋喃醚二醇(PTMG)为原材料合成了一系列具有酰胺结构的PTA改性热塑性聚酰胺(PA)弹性体(TPAE)。其中PTA是用来代替传统己二酸作为分子量控制剂。采用乌氏黏度计测试了PTA改性TPAE的特性黏度,通过傅立叶变换红外光谱(FTIR)、核磁共振氢谱(1H-NMR)确定PTA改性TPAE的分子结构,通过差示扫描量热(DSC)法、热重(TG)分析仪测试分析了PTA改性TPAE的热性能,采用X射线衍射(XRD)仪表征了PTA改性TPAE的结晶性能,同时还测试了PTA改性TPAE纤维的力学性能。通过FTIR和1H-NMR分析表明,成功合成了PTA改性的TPAE。DSC分析结果表明,合成的PTA改性的TPAE最低熔点为96.1℃,而最高可达到193.5℃。TG分析结果表明,当PTA改性TPAE中PA硬链段含量高于35%时,PTA改性TPAE的起始分解温度(失重5%)均高于369℃。XRD分析结果显示,随着PTA改性TPAE中PA硬链段含量的增加,即PTA含量的下降,PTA改性TPAE的结晶性能相应增加。由力学性能数据可知,合成的PTA改性的最大断裂伸长率为1 123.1%,最大断裂强度为0.901 c N/dtex。     

New linear polyurethaneureas based on polyoxytetramethylene,aliphatic diisocyanates,and aromatic diamines

New polyurethaneureas have been synthesized with α-ω hydroxylated polyoxytetramethylene, aliphatic diisocyanates and nonhalogenated aromatic diamines. Four series of PUR have been studied by varying the PTMO molecular weight, the stoichiometry, the nature of the aliphatic diisocyanate, and the steric hindrance of the aromatic diamine. Quantitative evaluation of the degree of phase separation was obtained by DSC. An estimation of the dispersed soft segments outside the soft phase could thus be made. In addition to DSC, dynamic mechanical properties, were obtained for the four series of PUR over a wide temperature range. The hard segments in the PUR chains are amorphous and their high temperature behavior depends only on the strength of interactions in the amorphous state. Finally, stress-strain measurements were carried out on a few samples, and a wide range of tensile properties has been observed.     

PUR／PS间充复合弹性体的制备

本文报道了采用浇铸成型制备ＰＵＲ／ＰＳ间充复合弹性体的方法。考察了不同配方下的多元醇组分中各成分相容性及粘度与所含苯乙烯、预聚物中甘油相对含量的关系；浇铸过程中各类催化剂对工艺及制品性能的影响及ＮＣＯ／ＯＨ、交联密度与制品力学性能的关系。本方法获得的Ａ组分在常温下为稳定的溶体，粘度小，适用于室温下的浇铸成型，简化传统的聚氨酯浇铸成型工艺，并具有优良的脱模性能，所得弹性体的性能基本与市场上现有的中高模量聚氨酯弹性体相当。     

Preparation and Characterization of Thermoplastic Elastomer Based on Amino-terminated Polyamide-6 and Diisocyanate-terminated Polytetramethylene Glycol

Polyamide thermoplastic elastomers are successfully synthesized by adding polycondensation of amino-terminated polyamide-6 (with a molecular weight of 1000 and 2000 g/mol) and diisocyanate-terminated polytetramethylene glycol (with molecular weight of 1500 and2500 g/mol) with dimethylacetamide as solvent at 140°C. The structures of oligomers and polyamide thermoplastic elastomers are characterized by Fourier transform infrared. The thermogravimetry analysis result shows that the product displays good thermostability. Differential scanning calorimetry curves of polyamide thermoplastic elastomers exhibit two melting temperatures indicating phase separation of polyamide thermoplastic elastomers. Besides, the polyamide thermoplastic elastomers display excellent mechanical properties of high tensile strength (33–61 MPa) and high elongation at break (384–1220%).