高性能透明聚氨酯弹性体的合成研究

以聚氧四亚甲基二醇，异佛尔酮二异氰酸酯，1，4-丁二醇和不同的催化剂合成了透明聚氨酯弹性体，研究了合成方法，催化剂种类，异氰酸酯指数R，固化时间以及固化温度对该弹性体的力学性能，光学透明性，反应程度和热稳定性的影响。结果表明；软段摩尔质量及硬段扩链剂的改变对体系的摩尔质量影响较小，使使力学性能有较大变化。采用复合催化剂，一步法制备的聚氨酯弹性体具有较好的综合力学性能，优良的热稳定性；与基体树脂聚碳酸酯的粘接性好，复合材料的光学透明性优良；助催化剂K的使用可提高聚氨酯弹性体的耐热性和光学透明性。     

软段对IPDI基透明聚氨酯弹性体微相结构与性能的影响

采用不同结构的软段、扩链剂l,4-丁二醇和异佛尔酮二异氰酸酯(IPDI)为主要原料合成了透明聚氨酯弹性体。研究了软段结构变化对聚氨酯弹性体的微相结构、力学性能、热稳定性及光学透明性的影响。结果表明,相对分子质量高的软段比相对分子质量低的软段更易结晶,耐低温性能更好;与聚氧四亚甲基二醇(PTMG)相比,聚酯型聚己二酸丁二醇酯二醇(PBAG)更易结晶。结晶尺寸在纳米级,材料的透明性可达85％以上。软段含量增加对软段区的结晶影响较小,但力学性能下降明显。混合多元醇的加入进一步提高了聚氨酯弹性体的微相分离程度,有利于软段结晶,在宏观上表现为拉伸强度和弹性模量明显增加。     

二醇扩链剂对聚醚聚氨酯弹性体性能的影响

研究了以乙二醇、一缩二乙二醇、1,4-丁二醇和1,6-己二醇作为扩链剂对聚醚聚氨酯弹性体性能的影响。结果表明,扩链剂链长越短,弹性体的微相分离程度和力学性能越好;以BDO扩链为例,随其用量的增加,弹性体的性能提高,达到一定值后再增加用量性能反而下降;混合扩链剂有助于聚氨酯弹性体综合性能的提高。     

聚氨酯微相分离结构对力学性能的影响分析

聚氨酯弹性体(PUE)是目前具有发展潜力的合成材料之一。聚氨酯弹性体具有抗冲击强度高、弹性好、延伸率高、耐磨性好、耐油性和耐溶剂性好、抗撕裂性好等特点,被广泛应用于较多领域。从聚氨酯弹性体的合成原料和工艺角度分析,收集并研究微相分离对聚氨酯弹性体力学性能的影响,总结了聚氨酯弹性体的原料和制备工艺对力学性能的影响;按照原料和工艺进行分类,对近年来不同原料(大分子二元醇、二异氰酸酯和扩链剂)和工艺(共聚方法和退火处理)制备的聚氨酯弹性体进行性能和微相分离进行综述,并且分析不同结构的影响。基于不同微相分离聚氨酯弹性的研究体取得了成果,但是,开发高力学性能的材料仍是一个巨大的挑战。最后,综述了提高聚氨酯弹性体力学性能的方法,为制备高性能的聚氨酯弹性体提供了理论指导。     

浇注型端羟基聚丁二烯聚氨酯弹性体的合成及性能研究

采用不同分子量的端羟基聚丁二烯（ＨＴＰＢ）和甲苯二异氰酸酯为主要原料合成预聚物，以Ｎ，Ｎ－Ｍ（２－羟丙基）苯胺为扩链剂制备了浇注型聚氨酯弹性体，并着重研究了预聚体中游离异氰酸酯基含量、扩链剂用量、ＨＴＰＢ分子量以及不同分子量ＨＴＰＢ并用和扩链剂并用对弹性体力学性能的影响，还对弹性体的结构与形态进行了初步分析和探讨。结果表明，预聚体中游离异氰酸酯基含量为９．０％时，拉伸强度最大，且综合性能最佳；扩链系数为０．８９时，拉伸强度、定伸应力、硬度出现最大值；ＨＴＰＢ分子量增大，弹性体力学性能有下降趋势，不同分子量ＨＴＰＢ并用时分子量大的ＨＴＰＢ增多，力学性能下降；当ＨＴＰＢＭｎ＝３１００，游离异氰酸酯基含量为９．０％，扩链系数为０．８９时，弹性体综合性能最佳。电子显微镜照片显示ＨＴＰＢ型聚氨酯有微相分离，且软硬键段分布不规整。     

聚丁二烯型聚氨酯弹性体的合成及力学性能影响因素

综述了聚丁二烯型聚氨酯弹性体的合成方法及力学性能的影响因素,详尽概述了聚丁二烯型聚氨酯弹性体网络结构、形态结构对力学性能的影响,以及端羟基聚丁二烯、异氰酸酯类型、扩链剂、制备方法等对聚丁二烯型聚氨酯弹性体网络结构、形态结构和力学性能的影响。     

聚氨酯弹性体的力学性能影响因素研究

研究了合成方法,软段及硬段组成结构,熟化条件等因素对聚氨酯弹性和学性能的影响,结果表明,聚氨酯弹性体的结构与组成,以及由此引起微相分离程度的变化,是影响弹性体性能的重要因素,不同的低聚物二醇,二异氰酸酯及扩链剂合成的弹性体性能不同,采用预聚法,以及适当熟化有助于提高弹性体的性能。     

高性能聚氨酯密封材料的微相结构和热性能(Ⅱ)

采用聚碳酸酯二醇(PCDL)、聚四亚甲基醚二醇(PTMG)和4,4′-二苯基甲烷二异氰酸酯通过预聚体法和半预聚体法合成了一系列聚氨酯(PU)弹性体。采用示差热扫描量热,热失重和动态力学性能分析对PU弹性体的性能及多元醇结构和组成,合成方法对PU弹性体微相结构形态的影响进行了研究。结果表明,由预聚体法合成的弹性体的微相分离程度高于半预聚体法,二胺扩链的弹性体的硬段结晶性优于二醇扩链的弹性体,单一二醇合成弹性体的硬段的结晶性优于混合二醇合成的弹性体,几种弹性体的的硬段结晶性依次为PU-LF-950APU-PCDL≈PUPTMGPU-PCDL+PTMG。几种弹性体的热稳定性依次为PU-PCDLPU-PCDL+PTMG≈PU-PTMGPU-LF-950A。PU-LF-950A和PU-PTMG的低温性能优于PU-PCDL和PU-PCDL+PTMG。PU-LF-950A还具有较好的高温动态性能和微相分离程度。     

蓖麻油作交联剂的聚氨酯弹性体的合成及性能

以不同摩尔比的四氢呋喃均聚醚（PTMG）和1,6-亚己基二异氰酸酯（HDI）合成聚氨酯（PU）预聚体,再分别用丁二醇（BD）、蓖麻油（CO）以及BD和CO混合物进行扩链交联,合成了一系列不同CO含量的PU.通过FTIR、AFM、拉伸实验和TGA,对不同硬段含量和CO含量PU的氢键化程度、相形态结构、力学性能和热性能进行了比较。结果表明,二异氰酸酯和扩链剂的种类及用量对PU的性能均有很大的影响。随着PU中二异氰酸酯用量的增加,其力学性能和热稳定性能提高。随着扩链剂中CO用量的增加,PU氨酯键的氢键化程度降低,其软、硬段的微相分离程度降低,导致其力学性能降低。但CO用量的增加会提高PU分子链的交联和支化,因而其热稳定性能得到提高。     

第二十六讲 以聚酯多元醇为基的聚氨酯弹性体的动态力学性能分析

以聚酯多元醇为基,合成了聚氨酯弹性体。研究了聚酯多元醇结构及分子量、扩链剂类型及用量等因素对聚氨酯弹性体的动态力学性能的影响。结果表明：以分子量为2000及3000的聚酯多元醇制得的SPUE中存在明显的相分离;当扩链剂中带有苯环结构时,PUE的玻璃化转变温度升高,储能模量增高,阻尼因子下降;PUE的玻璃化转变温度及储能模量随着扩链剂L-MOCA用量的增加线性升高,阻尼因子线性下降。     

有机硅/丁二醇扩链剂混合比对混合大二醇基聚氨酯弹性体的性能影响

以α,ω-双(γ-羟丙基)聚二甲基硅氧烷(BHPDMS)和聚氧四甲基二醇(PHMO)混合大二醇为软链段;以1,4-丁二醇(BDO)为主要扩链剂,1,3-双(4-羟丁基)-1,1,3,3-四甲基二硅氧烷(BHTD)为次级扩链剂,所有试样中硬链段均由4,4'-二苯基甲烷二异氰酸酯(MDI)和混合扩链剂所构成,且w(硬链段)=40%;采用两步溶液聚合法制备混合大二醇基芳香聚氨酯(PU)弹性体。通过力学性能测试、差示扫描量热法(DSC)和动力学热分析法(DMTA),研究了混合扩链剂中n(BDO)/n(BHTD)比值对该PU弹性体性能的影响。结果表明,当n(BDO):n(BHTD)=3:2时,所得PU弹性体具有优异的综合性能;引入BHTD扩链剂后,破坏了硬链段的有序性。     

Thermal and dynamic mechanical characterization of polyurethane–urea–imide coatings

A series of NCO terminated polyurethane (PU)–imide copolymers were synthesized by a systematic three‐step process and were chain extended with different diol/diamine chain extenders. In the first step, isocyanate terminated PU prepolymers were prepared by reacting soft segments such as polyester (PE) polyols and polyether polyols such as polypropylene glycol (PPG‐1000) with hard segments like 2,4‐tolylene‐diisocyanate (TDI) or isophorone‐diisocyanate (IPDI) with NCO/OH ratio 2:1. In the second step, thermally stable heterocyclic imide ring was incorporated using isocyanate terminated PU prepolymers by reacting with pyromellitic dianhydride (PMDA) in a excess‐NCO:anhydride ratio of 1:0.5. The surplus NCO content after imidization was both moisture cured or partially reacted with chain extender and moisture cured. The films were characterized by thermogravimetric (TG), differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) instruments. The adhesion strength of these coatings on mild steel (MS), copper (Cu), and aluminum (Al) is dependent on the nature of the substrate. The TGA analysis show good thermal stability. The DMTA results show the microphase separation between the different hard and soft segments. Finally, a structure to property correlation was drawn based on the structure of the soft, hard, and chain extender and the observed properties are useful for understanding and design of intelligent coatings. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3158–3167, 2006     

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。     

Effect of the synthesis route on the structure and properties of polyurethane/nitrokonjac glucomannan semi‐interpenetrating polymer networks

With a synthesis route differing from previous methods, novel semi‐interpenetrating polymer networks (semi‐IPNs), coded UNK‐II, were synthesized by the initial mixing of nitrokonjac glucomannan (NKGM) with castor oil in butanone and the subsequent addition of toluene diisocyanate (TDI) to begin the polymerization reaction in the presence of 1,4‐butanediol (BD) as a chain extender at 60°C. The results from dynamic mechanical analysis, differential scanning calorimetry, and ultraviolet spectroscopy indicated that a certain degree of microphase separation occurred between soft and hard segments of polyurethane (PU) in the UNK‐II sheets. The α‐transition temperature, glass‐transition temperature, heating capacity, and tensile strength increased with an increase in the NKGM content, and this suggested an interaction between PU and NKGM in the UNK‐II sheets. In a previous method, semi‐IPN materials (PUNK) were synthesized by the polymerization reaction between castor oil and TDI, and then this PU prepolymer was mixed with NKGM and cured in the presence of BD as a chain extender. The PUNK sheets had relatively good miscibility and mechanical properties. However, for UNK‐II sheets prepared by the method reported in this work, NKGM mainly played a role in reinforcement. When the NKGM content was less than 10%, the UNK‐II sheets exhibited good miscibility, tensile strength (26–28 MPa), and breaking elongation (130–140%), similar to those of PUNK materials. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1948–1954, 2003     

Properties of polyether-polyurethane zwitterionomers

Polyether polyurethanes based on 4,4′-diphenylmethane diisocyanate (MDI), N-methyl diethanolamine (MDEA), and polytetraniethylene oxide (PTMO) were synthesized with varying levels of hard segment content. The tertiary amine of MDEA was sulfonated with γ-propane sultone thereby converting the polyether polyurethane to a polymeric zwitterion. The effect of the chemical composition and the degree of ammonium sulfonation on the extent of phase segregation, and physical properties were studied by differential scanning calorimetry (DSC), dynamic mechanical analysis and tensile testing. It was found that the MDEA chain extender inhibits microphase separation of the polymer in the solid state. As the degree of ammonium sulfonation increases in the zwitterionomers, an improvement of phase separation and domain structure was observed. In addition the tensile properties change dramatically with increasing sulfonate content going from properties characteristic of soft, weak gum rubbers to those of hard, strong thermoplastic elastomers.     

有机硅改性聚氨酯乳液的研制

将甲苯二异氰酸酯加到聚醚二元醇和端羟基有机硅单体的混合物中进行反应,生成端基为异氰酸酯基的聚氨酯预聚体,用1,4-丁二醇进行扩链反应,之后用二羟甲基丙酸进行亲水扩链,然后用三乙胺中和,最后加水乳化,合成了一种有机硅改性聚氨酯乳液。通过傅立叶红外光谱,DSC,TGA,电子拉力试验机,吸水率测试对其进行了研究。结果表明,有机硅改性的聚氨酯材料其耐水性、耐热性和耐低温性有所提高,本体的力学性能也有所提高。     

正交实验优选HTBN/聚氨酯合成的最佳工艺条件

以端羟基聚丁二烯-丙烯腈(HTBN)为软段、甲苯二异氰酸酯(TDI)为硬段和端氨基硅油为改性剂,合成了端氨基硅油改性HTBN型聚氨酯(PU)。以n(-NCO)∶n(HTBN)、n(硅油)∶n(HTBN)、n(扩链剂)∶n(HTBN)和硅油加入方式为主要影响因素,并以断裂伸长率、邵氏硬度、拉伸强度和定伸应力为考核指标,采用L9(34)正交实验方法优选该PU合成的最佳工艺条件。研究结果表明,当n(-NCO)∶n(HTBN)=1.6∶1、n(硅油)∶n(HTBN)=6∶100、n(扩链剂)∶n(HTBN)=5∶100且在后期加入端氨基硅油时,端氨基硅油改性HTBN型PU的综合性能最好。     

Effects of hard-segment compositions on properties of polyurethane–nitrolignin films

Segmented polyurethane (PU) films from castor-oil-based PU prepolymer with different hard-segment compositions and nitrolignin (NL) were synthesized. Diisocyanates (DIs), such as 2,4-tolylene DI (TDI) and 4,4′-diphenylmethane DI (MDI), 1,4-butanediol (BDO) as a chain extender, and trimethanol propane (TMP) as a crosslinker were used to obtain PU films containing NL (UL) which were named as UL–TB for TDI and BDO, UL–TT for TDI and TMP, UL–MB for MDI and BDO, and UL–MT for MDI and TMP, respectively. The mechanical properties and thermal stability of the films were characterized by a tensile test and thermogravimetric analysis, respectively. The MDI-based UL films exhibited a higher tensile strength (σ_b) and thermal stability than TDI-based UL. However, the recoverability of the TDI-based UL films was better than that of others. The UL films with TMP (UL–TT and UL–MT) had higher σ_b and lower breaking elongation (ϵ_b) than the UL films with BDO (UL–TB and UL–MB), caused by enhancement in the crosslinking network of hard segments and microphase separation between soft and hard segments. The values of σ_b and ϵ_b of the UL films that contained NL were much higher than those of the PU films, which indicates that the introduction of NL increased the interaction between hard segments by crosslinking. The hydrogen bonding in the UL films was studied by infrared spectroscopy, which indicated that MDI favored the formation of hydrogen bonds, especially in the ordered domain. Differential scanning calorimetry, dynamic mechanical analysis, and wide-angle X-ray diffraction indicated that the UL films were compatible as a whole, but microphase separation existed between soft and hard segments and significantly affected the mechanical properties. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3251–3259, 2001