粒料法合成聚氨酯分散体及性能的研究

以聚四氢呋喃二醇(PTMG)为软段,异氟尔酮二异氰酸酯(IPDI)和1,4-丁二醇(BDO)为硬段,二羟甲基丙酸(DMPA)为亲水单体,采用粒料法合成了聚氨酯离子聚合物粒料,制备了固含量为40%的聚氨酯分散体(PUD),研究了亲水含量和硬段含量对分散体性能及其胶膜性能的影响。PUD的ζ电位处于30~60 mV,黏度小于1100 mPa s。随着亲水含量增加,平均粒径减小,粒径分布变窄,黏度升高;硬段含量增加,平均粒径增大,粒径分布变宽,黏度降低。透射电镜显示,溶胶粒子呈大小不一的球形结构。PUD胶膜吸水率在3.15%~6.67%。力学性能测试表明硬段含量增加,断裂伸长率降低,拉伸强度增强。DMA测试显示胶膜出现相分离,有硬段和软段两个玻璃化转变温度。随着硬段含量增加,相分离程度提高,软段玻璃化温度降低,硬段玻璃化温度升高。     

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。     

软段种类及相对分子质量对阴离子水性聚氨酯性能的影响

采用聚酯多元醇、异佛尔酮二异氰酸酯、二羟甲基丙酸等原料，制备了阴离子型水性聚氨酯乳液，并测试了其性能。结果表明：软段种类及相对分子质量对水性聚氨酯乳液的黏度、粒径和力学性能等均有影响。     

软段对氨基磺酸盐型高固含量聚氨酯分散体性能的影响

以N-(2-氨基乙基)-2-氨基乙烷磺酸钠(AAS-Na)为亲水单体,以不同结构的多元醇、异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)和乙二胺(EDA)等为原料,采用丙酮法合成了固含量为50%的磺酸盐基聚氨酯分散体(PUD)。研究结果表明:PUD的ζ电位均低于-30mV,平均粒径在230～290nm之间,黏度均低于800mPa·s,呈现假塑性流体的特征;PUD胶膜的吸水率均低于10%,具有良好的耐水性能;PUD胶膜的结晶行为和力学性能受软段影响较大,起始分解温度为275℃,具有良好的热稳定性,能满足一般场合的使用要求。     

不同软段类型聚氨酯材料的鉴别及其耐热性

不同原料的聚氨酯材料在红外光谱图上有明显的差异,同时,聚醚型聚氨酯、聚酯型聚氨酯在热重分析图上的分解温度即耐热性有较大的差别。红外光谱法是鉴定聚氨酯类型的有效方法,同时热重分析图表明了聚酯型比聚醚性聚氨酯耐热性好。     

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。     

连续法合成聚氨酯水分散体

根据对有关文献资料的初步分析,推介使用连续法合成聚氨酯水分散体。对比了连续法和间断法制备聚氨酯水分散体的优缺点,介绍了Dow、Bayer、Mobay和BASF等公司专利技术,并初步阐述连续法优越性的理论根据。     

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...     

有机硅改性水性聚氨酯处理剂的合成及性能研究Ⅰ.软段含硅氧烷链段

通过向软段中引入硅氧烷链段合成了一系列改性的水性聚氨酯(WPU)乳液。通过傅里叶变换红外光谱(FTIR)、激光粒度仪、耐湿热老化试验和热重分析(TGA)详细研究了不同n(羟基硅油):n(PCDL-2000)对WPU乳液性能、耐湿热老化性能和胶膜热稳定性的影响。结果表明:当n(羟基硅油):n(PCDL-2000)为10:90时,乳液稳定性、黏结性能较好,耐湿热老化性能得到明显改善;在软段中引入硅氧烷链段使软段的分解速率减缓。     

Inelastic response of copolyurethane elastomers with varying soft segment molecular weights and preparation procedure

A family of thermoplastic polyurethane elastomers (TPUs) based on the soft segment poly(oxytetramethylene) (PTMO₂₀₀₀ and PTMO₁₀₀₀) were synthesized by the one‐shot and prepolymer methods. Two hard segments were chosen, 4,4′‐methylenebis(phenyl isocyanate) (MDI) (non‐crystallizable) and 4,4′‐dibenzyl diisocyanate (DBDI) (crystallizable). Microphase separation and crystallinity were investigated using small‐angle X‐ray scattering and wide‐angle X‐ray scattering, and dynamic viscoelastic properties were also determined. An increased hard phase degree of crystallinity was primarily achieved by use of DBDI instead of MDI, regardless of the preparation procedure and soft segment molecular weight. An increase of the molecular weight leads to an increase in phase separation and to a decrease in hysteresis. For the DBDI based polymers, a lower soft segment molecular weight resulted in an increase in crystallinity. The DBDI series of TPUs obtained by the one‐shot and prepolymer methods showed higher hysteresis and residual elongations compared with the corresponding materials achieved with MDI. Although the materials varied widely in response to first loading, regardless of the preparation procedure, they displayed remarkable reproducibility and commonality in cyclic responses within the maximum strain envelope. The thermomechanical experiments revealed a better thermal behavior with increase of the soft segment molecular weight from PTMO₁₀₀₀ to PTMO₂₀₀₀.© 2013 Society of Chemical Industry     

Thermoplastic polyurethanes from renewable resources: effect of soft segment chemical structure and molecular weight on morphology and final properties

The effect of soft segment molecular weight and chemical structure on the morphology and final properties of segmented thermoplastic polyurethanes containing various hard segment contents has been investigated from the viewpoint of the degree of microphase separation. Vegetable oil‐based polyesters and corn sugar‐based chain extender have been used as renewable resources. The synthesis has been carried out in bulk without catalyst using a two‐step polymerization process. Physicochemical, thermal and mechanical properties, and also morphology, have been studied using Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, atomic force microscopy, X‐ray diffraction and mechanical testing. Chemical structure and molecular weight of polyols strongly affect the properties of the synthesized segmented thermoplastic polyurethanes. An increase in soft segment molecular weight leads to an increase of the degree of soft segment crystallinity and microphase separation, thus giving enhanced mechanical properties and higher thermal stability. Copyright © 2012 Society of Chemical Industry     

Preparation and properties of segmented thermoplastic polyurethane elastomers with two different soft segments

Thermoplastic polyurethane elastomers were prepared from 4,4‐diphenylmethane diisocyanate (MDI)/1,4‐butanediol (BD)/poly(propylene glycol) (PPG) and MDI/BD/poly(oxytetramethylene glycol) (PTMG). The MDI/BD‐based hard‐segment content of polyurethane prepared in this study was of 39–65 wt %. These polyurethane elastomers had a constant soft‐segment molecular weight (M_n , 2000), but a variable hard‐segment block length (n, 3.0–10.1; M_n , 1020–3434). The effects of the hard‐segment content on the thermal properties and elastic behavior were investigated. These properties of the PPG‐based MPP samples and the PTMG‐based MPT samples were compared. The polyurethane prepared in this study had a hard‐segment crystalline melting temperature in the range of 185.5–236.5°C. With increasing hard‐segment content, the dynamic storage modulus and glass transition temperature increased in both the MPP and MPT samples. The permanent set (%) increased with increasing hard‐segment content and successive maximum elongation. The permanent set (%) of the MPP samples was higher than that of MPT samples at the same hard‐segment content. The value of K (area of the hydrogen‐bonded carbonyl group/area of the free carbonyl group) increased with increasing hard‐segment content in both the MPP and MPT samples, and the K value of the MPT samples was higher than that of the MPP samples at the same hard‐segment content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 345–352, 1999     

Comparison of properties of thermoplastic polyurethane elastomers with two different soft segments

Two series of thermoplastic polyurethane elastomers [poly(propylene glycol) (PPG) based PP samples and poly(oxytetramethylene)glycol (PTMG) based PT samples] were synthesized from isophorone diisocyanate (IPDI)/1,4-butanediol (BD)/PPG and IPDI/BD/PTMG. The IPDI/BD based hard segments contents of polyurethane prepared in this study were 40–73 wt %. These polyurethane elastomers had a constant soft segment molecular weight (average M_n, 2000) but a variable hard segment block length (n, 3.5–17.5; average M_n, 1318–5544). Studies were made on the effects of the hard segment content on the dynamic mechanical thermal properties and elastic behaviors of polyurethane elastomers. These properties of PPG based PP and PTMG based PT samples were compared. As the hard segment contents of PP and PT samples increased, dynamic tensile modulus and α-type glass transition temperature (T_g) increased; however, the β-type T_g decreased. The permanent set (%) increased with increasing hard segment content and successive maximum elongation. The permanent set of the PT sample was lower than that of the PP sample at the same hard segment content. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1349–1355, 1998     

Blocking of soft segments with different chain lengths and its impact on the shape memory property of polyurethane copolymer

The arrangements, whether block or random type, of the soft segments of polyurethane block copolymers prepared with MDI and two kinds of poly(tetramethylene glycol) (PTMG; MW of 1000 or 2000) in various ratios were compared for possible effects on the physical properties of the copolymers. A long soft segment, PTMG‐2000, was superior in all mechanical properties (strain, stress, and modulus) because a long chain length could provide more motional freedom than a short one (PTMG‐1000) could and therefore was helpful in forming strong interchain attractions among hard segments. Inclusion of more PTMG‐2000 led to a lower T_g and a peak shift in infrared spectra. The arrangement of two soft segments in a block‐type copolymer, a key finding in this study, was controlled by separately synthesizing two prepolymers, each with a different chain length, and connecting two prepolymers in a second step. Random‐type copolymers prepared for purposes of comparison were allowed to react with two PTMGs in one step. Two types of copolymers were compared, and the reason for the differences in the shape memory property are discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1435–1441, 2007     

Inferential estimation of molecular weights of polybutadiene rubber by neural networks

Molecular weight distribution, which is characterized by its averages like number average (Mn) and weight average (Mw), is one of the important properties of polybutadiene rubber (PBR), and it is difficult to measure. The objective of this work is to develop models to predict Mn and Mw from readily available process variables. Neural networks that are capable of mapping highly complex and non‐linear dependencies have been adapted to develop models for the Mn and Mw of PBR. The molecular weight distribution and its averages of PBR samples collected over a wide range of operating conditions were measured by the conventional Gel Permeable Chromatograph (GPC) method. Neural networks were trained with relevant data to predict Mn and Mw from process variables. The trained networks were found to generalize well when tested with new data. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1611–1618, 2005     

软硬段比对磺酸盐型水性聚氨酯性能的影响

以聚己二酸乙二醇酯二醇(PBA)、异佛尔酮二异氰酸酯(IPDI)和六亚甲基二异氰酸酯(HDI)为主要原料,以乙二胺基乙磺酸钠为亲水性扩链剂,合成了固含量为50%的磺酸盐型水性聚氨酯(WPU)乳液。考察了软硬段比对乳液黏度、粒径及其分布、聚合物重均相对分子质量(Mw)、胶膜结晶性以及力学性能等影响。结果表明:当软硬段比值为2.96时,可以制得固含量为50%的磺酸盐型WPU乳液,其平均粒径为146.0 nm、黏度为143 mPa.s,聚合物Mw为128 488,结晶熔融温度为50℃,结晶性相对最好;此时WPU胶膜的拉伸强度(31.6 MPa)和断裂伸长率(1 702%)相对较大;WPU胶粘剂的初始剥离强度(118.6 N/cm)和最终剥离强度(156.3 N/cm)相对最高。     

Study on high‐solid content Si/PU polyurethane dispersion with PES/PPG composite soft segment

A polyol consists of silicone chains and epoxy acrylate structures, referred to as silicon polyether (PES), was used to prepare crosslinked Si/PU dispersions. Both PES and propylene oxide glycol (PPG) were mixed as soft segments. The effects weight ratios of PES to PPG on properties of the resultant polyurethane dispersions were studied. Morphology and properties of the Si/PU dispersions were characterized by particle size, transmission electron microscopy (TEM), and viscometer. It is shown that the Si/PU dispersions possessed wider particle size distribution and higher average particles diameter because of the use of PES, which contains crosslinked silicone side chains. The Si/PU dispersions have higher solid content as compared to the conventional water‐based polyurethane, because of the volume fraction ratio of bigger particle to small particle from the Si/PU dispersions. As increasing weight ratio of PES to PPG, the solid content of the Si/PU dispersions increased firstly, and then decreased. When the ratio ranges from 4 : 10 to 5 : 10, solid content of the Si/PU dispersions is up to 55%. It was also noticed that apparent viscosity of the Si/PU dispersions decreased with increasing PES to PPG ratio. In the Si/PU dispersions, solid content was increased and viscosity was decreased by the use of PES. Therefore, PES is a potential compound for the application of PU dispersions. In addition, stability of the crosslinked Si/PU dispersions decreases slightly at high‐ and low‐temperature; however, which can meet the basical requirements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

不同分子质量的腐殖酸对溴离子在MIEX树脂上吸附行为的影响

采用静态吸附法研究了不同分子量的腐殖酸对溴离子(Br?)在MIEX树脂上吸附行为的影响. 结果表明,pH为中性时,4种腐殖酸(分子量分别为小于1000, 1000?5000, 5000?10000, 大于10000)使MIEX树脂对Br?的去除率从80.05%分别降至75.39%, 26.32%, 42.67%和49.03%,而酸性(pH<5.0)或碱性(pH>9.0)时,各种腐殖酸则会促进Br?去除,pH为11.0时去除效率增加最明显. 分子量大于10000的腐殖酸可将吸附平衡时间由60 min缩短至20 min,分子质量1000?5000和5000?10000的腐殖酸可将吸附平衡时间缩短至40 min. 但不论有无腐殖酸,MIEX树脂对Br?的吸附过程均符合拟二级反应动力学模型. 不同分子量的腐殖酸均能明显降低Br?在MIEX树脂上的吸附平衡容量,分子量大于10000的腐殖酸影响最大,但均不改变吸附平衡模型类型,吸附平衡规律用Langmuir与Freundlich模型均可很好描述. 不同分子量的腐殖酸对MIEX树脂去除Br?的影响与溶液pH值密切相关,腐殖酸会加速Br?在树脂上的吸附过程,但不改变吸附平衡及动力学模型类型.