基于不同软段的聚氨酯弹性体耐热性能研究

分别以聚己内酯二醇(PCL)、聚碳酸酯二醇(PCDL)、聚己二酸-1,4-丁二醇酯二醇(PBA)以及聚四氢呋喃二醇(PTMG)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,采用预聚体法合成4种基于不同软段的聚氨酯弹性体。通过机械性能测试、热失重分析、动态力学性能测试及不同温度下的力学性能分析,研究低聚物二醇种类对聚氨酯弹性体的力学性能和耐热性能的影响。结果表明,以聚酯多元醇作为软段制得的聚氨酯弹性体的耐热性要优于聚醚型;几种聚酯型聚氨酯弹性体中,PCL型聚氨酯弹性体的热稳定性以及不同温度下的力学性能保持率最高,耐热性最好;动态力学性能分析表明,在高弹态平台区PCL型聚氨酯的损耗因子较小,动态内生热较小,且储能模量下降较缓慢,动态力学性能最好。     

不同软链段对水性聚氨酯性能的影响

以低聚物多元醇、IPDI(异佛尔酮二异氰酸酯)、亲水扩链剂DMPA(2,2-二羟甲基丙酸)和成盐剂三乙胺为主要原料,合成一组软段成分不同的水性聚氨酯乳液。通过测定水性聚氨酯乳液的固含、黏度、结构,以及水性聚氨酯胶膜的耐水性、力学性能、T型剥离强度等,对比了不同类型软段对乳液及胶膜性能的影响。研究结果表明:由含6个碳的聚酯多元醇为软段合成的水性聚氨酯的黏度、耐水性、机械强度、T型剥离强度等数据较好。     

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...     

软段含离子的聚氨酯离聚物

概述了一系列新型的软段含离子的聚氨酯离聚物的合成、性能、研究进展,以及这类离聚物对聚氨酯离聚物离子簇解离现象的贡献。     

粒料法合成不同相对分子质量和软段的聚氨酯分散体研究

以异佛尔酮二异氰酸酯(IPDI)为硬段、二羟甲基丙酸(DMPA)为亲水单体,采用粒料法合成了不同Mη(黏均相对分子质量)和不同软段的PU(聚氨酯)离聚物粒料,并制备了固含量约为40%的PUD(PU分散体)。结果表明:PU的Mη随R值[R=n(-NCO)/n(-OH)]增加呈先升后降态势;PU的Mη越高,PUD的平均粒径越小,粒径分布越窄,黏度越大;PUD粒子呈大小不一的球形结构,并且PU的Mη越高,PUD胶膜的拉伸强度越大;聚酯型PUD胶膜的拉伸强度大于聚醚型PUD,并且前者的软段和硬段之间相容性较好,而后者的软段和硬段之间因出现相分离现象而相容性较差;PUD胶膜的吸水率均不超过5.93%,说明其耐水性能优异。     

软段结构对聚氨酯弹性体性能的影响

分别以聚四氢呋喃二醇(PTMG)、聚己内酯二醇(PCL)、高顺式端羟基聚丁二烯(HTPB)和自由基聚合制得的端羟基聚丁二烯(FHTPB)为软段,采用溶液聚合两步法制得了四种聚氨酯弹性体(PUE)。通过拉伸试验、动态力学性能分析(DMA)、差示扫描量热(DSC)和热重分析等手段,考察了软段结构对它们室温及低温下力学性能、热性能等的影响。结果表明,四种PUE低温(-30℃)下的拉伸强度和断裂伸长率均大于室温下的对应值。这不仅与低温下软段诱导结晶所产生的自增强效应有关,也与软、硬两段的微相分离程度增大有关。相较于其他三种PUE,HTPB-PUE软段不仅玻璃化温度(T _g)最低,而且极性也最弱,因而微相分离程度高,具有优异的柔性,-30℃下其断裂伸长率仍达660%以上。PCL-PUE和PTMG-PUE因软段易结晶,且软段与硬段的微相分离程度低,则刚性强。低温循环拉伸试验表明,-30℃下HTPB-PUE和FHTPB-PUE有较强的弹性恢复能力,而PCL-PUE和PTMG-PUE则相对较差。DSC和DMA结果显示HTPB-PUE的T _g远低于其他三种PUE,其T _g(DSC)低至-103℃。此外,四种PUE的初始分解温度十分相近,均在270℃左右。     

复合软段耐热聚氨酯泡沫塑料的制备及表征

选用以丙三醇为起始剂制备的聚醚多元醇N303与聚醚多元醇H303进行复配,采用一步法制备了N303/H303复合软段聚氨酯泡沫塑料（PUF）,研究了N303/H303复合软段配比以及二氧化硅（SiO2）填料对PUF性能的影响。结果表明,N303/H303复合软段PUF压缩模量与冲击强度均高于单一软段PUF; 随软段中H303含量增大,PUF压缩模量与冲击强度呈先上升再下降的趋势,在N303/H303质量比为50/50时达到最大值; 添加5 %~15 %（质量分数,下同）的SiO2能作为成核剂,PUF泡孔均匀性提高且细化泡孔;PUF高温压缩性能保持较好。     

软段结构对聚氨酯酰亚胺结构与性能的影响

分别以聚乙二醇（PEC）,聚己二酸丁二酯二元醇（PBA）及两者的混合物作软段溶液聚合合成了三种类型的聚氨酯酰亚胺（PUI）,红外光谱证实了聚酰亚胺硬段的存在,TG分析表明聚酯型PUI的热稳定性高于聚醚型PUI,DSC及X射线衍射实验表明聚酯PUI及聚酯含量较高的聚醚－酯混合二元醇作软段的PUI中有微晶区存在,研究PUI的应力一应变行为发现,聚酯型PUI具有更高的弹性模量及断裂强度,聚醚一酯混合型PUI随软段中聚酯含量的增加,断裂强度及弹性模量增加。     

软段对水性聚氨酯木器涂料性能的影响

合成了系列水性聚氨酯乳液,研究了低聚物多元醇种类及分子量不同对水性聚氨酯涂料性能的影响。结果表明:聚酯型水性聚氨酯随着软段分子量的增大结晶程度增加,机械强度和硬度较聚醚型高,耐水性较好;结构规整,易结晶的软段合成出的聚氨酯树脂力学性能和耐水性能都较好;而有机硅氧烷改性可以提高聚氨酯材料的耐水性。     

软段含羧基的水性聚氨酯贮存稳定性研究

合成了软段含羟基的水性聚氨酯（WPU），对影响其贮存稳定性的各种因素进行了研究，通过显微镜对PU进行了观察。结果表明：以甲苯二异氰酸酯（TDI）合成，在有性溶剂（如丁酮、丙酮）条件下用三乙胺中和，采用较小相地分子质量的聚酯有利于增强WPU的贮存稳定性，以TDI合成的PU-TDI体系的粒径较PU-IPDI体系的小，稳定性高；以丁酮、丙酮为溶剂的PU-IPDI体系相反转完全。     

Thermoplastic polyurethane elastomers based on polycarbonate diols with different soft segment molecular weight and chemical structure: Mechanical and thermal properties

A series of thermoplastic polyurethane elastomers based on polycarbonate diol, 4,4′‐diphenylmethane diisocyanate and 1,4‐butanediol was synthesized in bulk by two‐step polymerization varying polycarbonate diol soft segment molecular weight and chemical structure, and also hard segment content, and their effects on the thermal and mechanical properties were investigated. Dynamic mechanical analysis termogravimetric analysis, differential scanning calorimetry, Fourier transform infrared‐attenuated total reflection spectroscopy and mechanical tests were employed to characterize the polyurethanes. Thermal and mechanical properties are discussed from the viewpoint of microphase domain separation of hard and soft segments. On one hand, an increase in soft segment length, and on the other hand an increase in the hard segment content, i.e., hard segment molecular weight, was accompanied by an increase in the microphase separation degree, hard domain order and crystallinity, and stiffness. In phase separated systems more developed reinforcing hard domain structure is observed. These hard segment structures, in addition to the elastic nature of soft segment, provide enough physical crosslink sites to have elastomeric behavior. POLYM. ENG. SCI., 2008. © 2007 Society of Plastics Engineers     

Enhancing polyurethane properties via soft segment crystallization

Semi-crystalline polyester diols with relatively high melting points and enthalpies of crystallization are shown to form nearly co-continuous lamellar structures in thermoplastic polyurethanes using polyether soft segments. This high aspect ratio crystalline structure results in materials with exceptional tensile and elastic properties compared to materials made with conventional semi-crystalline soft segments such as polycaprolactone or polybutylene adipate. Additions of semi-crystalline soft segment to foam formulations also result in increased hardness measured by standard foam hardness tests. Halpin-Tsai and percolation model analyses of the results suggest that the crystalline regions exert a global influence on the elastomer structure.     

Characterization of thermoplastic polyurethane adhesives with different hard/soft segment ratios containing rosin as an internal tackifier

Three thermoplastic polyurethanes (TPUs) containing different hard/soft (h/s) segment ratios (1.05-1.4) were prepared using the prepolymer method. MDI (diphenylmethane-4,4′diisocyanate) and polyadipate of 1,4-butanediol (M _w = 2440) were allowed to react to produce the prepolymer. To provide the polyurethanes with high immediate adhesion to different substrates, a rosin + 1,4-butanediol mixture (1 : 1 equivalent%) was used as chain extender (TPU-Rs). These TPU-Rs had two types of hard segments: (i) Urethane hard segments, produced by reaction of the isocyanate and the 1,4-butanediol, and (ii) Urethan-amide hard segments, produced by reaction of the isocyanate and the carboxylic acid functionality of the rosin. The TPUs and TPU-Rs were characterized using FTIR spectroscopy, gel permeation chromatography, differential scanning calorimetry, stress-controlled plate-plate rheology, stress-strain measurements, and Brookfield viscosity. The TPUs and TPU-Rs were used as raw materials to prepare solvent-based polyurethane adhesives, the adhesion properties of which were obtained from T-peel tests on PVC/polyurethane adhesive/PVC joints. The addition of rosin as an internal tackifier increased the average molecular weight, more markedly in the TPU-Rs containing higher hard/soft segment ratios, but the elastic and viscous moduli decreased. An increase in the hard/soft segment ratio of the TPU-Rs retarded the kinetics of crystallization (which was determined by the soft segment content in the polyurethane), and increased the immediate T-peel strength in PVC/polyurethane adhesive/PVC joints (which was determined by the urethan-amide hard segments). Furthermore, addition of rosin to the polyurethanes decreased the final adhesion, although always reasonably high peel strength values were obtained.     

The effect of the soft segment of polyurethane on copolymer-type polyacetal/polyurethane blends

Mechanical blends of copolymer-type polyacetal (POM) with ester-based and ether-based polyurethane (PU) are immiscible over the 0–50% PU compositional range. The PU elastomer was added to the rigid POM matrix to increase its toughness. The mechanical, physical, thermal, dielectric, and dynamic mechanical properties and morphology of POM/PU blends were investigated. The notched Izod-impact strength of blends reaches a maximum at 10 wt % PU. The tensile strength, Young's modulus, volume resistivity, crystallinity, and density decrease with increasing concentration of PU. The elongation of blends reaches a maximum at 20 wt % PU. The dielectric constant and dissipation factor increase with increasing PU content. From dynamic mechanical measurements, as the elastomer content increases, the height of the damping peak also increases, but there is no transition temperature shift. SEM shows that the blends exhibit a continuous morphology with domain size varying from 1 to 10 μm for PU. However, at a concentration of 50 wt % PU, the dispersed PU particles tend to aggregate. Characterization of morphology by a metallurgical microscope has shown that the crystalline materials in the pure POM and the blends exist in a spherulitic superstructure.     

Structural variation in soft segment of waterborne polyurethane acrylate nanoemulsions

High solid content waterborne polyurethane acrylate (WPUA) nanoemulsions are prepared as textile finishes. Two structurally different soft segments, that is, polyether and polyester are used with isophorone diisocyanate, 2‐hydroxyethyl methacrylate, and butyl acrylate. Structural variations are investigated in features of nanoemulsions and their coatings. Physical properties of nanoemulsions, such as average particle size, stability, solid content, and viscosity, are investigated. Nanoemulsions with high solid content, that is, 40–47% are produced without any internal emulsifier. Average nanoparticle size, that is, <100 nm is confirmed by dynamic light scattering and atomic force microscopy (AFM). Fourier transform infrared spectroscopy proved synthesis of proposed WPUA products. Synergistic effect of polyurethane and acrylate is observed in chemical and water resistance of WPUA. Differential scanning calorimetry (DSC) and thermogravimetric analysis indicate stable uniformly cross‐linked network of WPUA. Application of nanoemulsions on 100% cotton fabric shows a significant improvement in tear strength, which is more pronounced for polyester‐based WPUA. Scanning electron microscope images of treated fabric samples show good adhesion of nanoemulsions on cotton surface. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41706.     

软段含磺酸基或羧基的聚己内酯型聚氨酯分散体的结构与性能

采用预聚体直接分散法制备了总固物质量分数为40%的软段含磺酸基和软段含羧基的聚己内酯型聚氨酯分散体(PUD),并对其结构和性能进行了研究.结果表明,软、硬段比例相同的软段含离子PUD和硬段含离子PUD都具有良好的稳定性;与硬段含离子的PUD相比,软段含离子PUD的平均粒径小,粒径分布窄,黏度大,其胶膜的拉伸强度低,邵尔A硬度大,熔点和结晶度低.     

提高聚氨酯材料耐热性能的研究

简述了提高聚氨酯(PU)材料耐热性能的常用方法,包括引入有机杂环、选择耐热聚合物多元醇、引入金属离子、共混和形成互穿聚合物网络(IPN)结构的改性及研究进展,并对耐热PU材料的发展趋势作了展望。     

The effect of mixed soft segment on the microstructure of thermoplastic polyurethane

In this work, we fixed the hard segment content (Ch%) and synthesized thermoplastic polyurethane (TPU) elastomers with one-soft segment (HTPB-PU, PTMG-PU, and PCL-PU) and bi-soft segment (PTMG-HPU and PCL-HPU), using 4,4′-diphenylmethane diisocyanate, 1,4-butanediol, and different oligomer diols as raw materials. This work was used to explore the impact of two polar diols (polytetrahydrofuran diol [PTMG]; polycaprolactone diol [PCL]) of the hydroxy-terminated polybutadiene (HTPB)-based TPU on the microstructure and macroscopic properties. Using Fourier transform infrared spectroscopy, X-ray diffraction, and differential scanning calorimetry to characterize TPU, the results showed that the introduction of PCL was better than PTMG in promoting microphase mixing and crystallization, and reducing microphase separation. This result was closely related because the carbonyl group in PCL was stronger than the ether bond in PTMG in forming hydrogen bonds with ─NH bond. Through mechanical test and isopropyl alcohol (IPA) resistance test, the results showed that HTPB-based TPU with PCL (PCL-HPU) significantly improved tensile strength and elongation at break, and only a small reduction of Young's modulus was observed. PCL-HPU had the best retention of the IPA resistance of HTPB-based TPU.     

The thermal response of the polyether soft segment chain conformation in a polyurethane block copolymer measured by small-angle neutron scattering

The conformation of the soft segment chains in a pair of polyether polyurethanes was studied as a function of temperature using small angle neutron scattering. The samples were synthesized from 3 moles of methylene bis(p-phenyl isocyanate), 2 moles of butanediol, and one mole of a poly(tetramethylene oxide) (PTMO) blend. The PTMO blend was composed of 0.325 moles of deuterated PTMO (d-PTMO) and 0.675 moles of hydrogenous PTMO. This degree of deuterolabelling was chosen so that there would be no interphase scattering in the final sample; only intrachain scattering from the labelled soft segments comprised the coherent part of the total scattering. At room temperature, the average soft segment was found to be in an extended conformation. As the temperature was raised from room temperature, the radius of gyration of the soft segments decreased. This was attributed to the stress exerted by the extended soft segments on the adjoining hard segments increasing as the temperature was increased. The increased stress causes some of the hard segments to pull out of the hard domain into the soft phase, thereby allowing the soft segments adjacent to the extracted hard segment to relax to a more compact conformation. As the temperature was increased above 160°C, the soft segment radius of gyration increased slightly. This behaviour is ascribed to an increased degree of mixing between the phases. The presence of substantial amounts of hard segment material in the soft phase causes the increase in the soft segment R_g due to the greater compatibility between the soft and hard segments in the soft phase at these elevated temperatures. This effect is similar to a homopolymer being swollen by a small amount of a good solvent, where the chain conformation is a random coil, but the radius of gyration is larger than that measured for the pure material.