嵌段聚醚聚氨酯-酯热塑性弹性体的合成和性质

本文用对苯二甲酸双羟基乙二醇酯及其二聚体作扩链剂,合成了一系列聚醚聚氨酯-酯嵌段共聚物(PEUE),并用热分析法、动态力学分析、应力-应变等方法对所合成的聚氨酯材料进行了形态结构和性能关系的研究,结果表明:这类聚氨酯弹性体由于硬段具有较好的结晶性,致使材料的力学性能得到提高;另外,由于硬段酯基与软段聚醚的相互作用,材料的相容性有所改进.     

接枝环氧树脂/硅溶胶杂化水分散液的制备与表征

利用原位分散法制备了接枝环氧树脂 硅溶胶杂化水分散液 ,并通过红外光谱和 ζ电位测定 ,表征了接枝环氧树脂与硅溶胶之间的杂化作用 .实验结果表明 ,与接枝环氧树脂水分散液相比 ,杂化水分散液的粒径和粘度均减小 .按此探讨了形成杂化水分散液的历程 .初步测定了杂化水分散液成膜后的表面性能 ,发现它们具有更高的硬度和更好的疏水性能 ,与成膜过程中硅溶胶在膜表面的富集效应有关     

扩链剂对脂肪族聚氨酯脲和聚脲弹性体结构与性能的影响

用异佛尔酮二胺(IPDA)、乙二胺(EDA)和己二胺(HDA)三种扩链剂合成了不同结构的脂肪族聚氨酯脲和聚脲, 并考察了扩链剂对聚氨酯脲和聚脲形态结构与性能的影响. 研究结果表明, 与EDA和HDA扩链的聚氨酯脲和聚脲相比, IPDA扩链的聚氨酯脲和聚脲中脲羰基的氢键化程度较低, 软段和硬段间的相混合程度较好; 同时它们具有更好的拉伸强度、硬度和撕裂强度, 但断裂伸长率较低. EDA和HDA扩链的聚氨酯脲和聚脲相比, 两者性能相差不大. 聚氨酯脲的脲羰基较完善氢键化程度以及整个氢键化程度都比聚脲的要低, 同时聚氨酯脲的吸水率也较低.     

嵌段聚醚聚氨酯-酯热塑性弹性体的合成和性质

 本文用对苯二甲酸双羟基乙二醇酯及其二聚体作扩链剂,合成了一系列聚醚聚氨酯-酯嵌段共聚物(PEUE),并用热分析法、动态力学分析、应力-应变等方法对所合成的聚氨酯材料进行了形态结构和性能关系的研究,结果表明:这类聚氨酯弹性体由于硬段具有较好的结晶性,致使材料的力学性能得到提高;另外,由于硬段酯基与软段聚醚的相互作用,材料的相容性有所改进.     

扩链剂对水性聚氨酯脲与聚甲基丙烯酸甲酯复合体系结构和性能的影响

分别用乙二胺 (EDA)和水作为扩链剂制备了聚氨酯脲 聚甲基丙烯酸甲酯 (PUA)水分散液 .借助DSC、DMA、FTIR研究了扩链剂对PUA的结构和性能的影响 .结果表明在EDA扩链体系中 ,虽然聚甲基丙烯酸甲酯 (PMMA)和聚酯软段以及扩链剂与异氰酸酯生成的硬段均有一定程度的相容性 ,但由此合成的PUA仍具有多相结构 ;水扩链体系只有一个较宽的二级转变区 ,各相之间有较大程度的混合 .由EDA扩链合成的PUA在耐溶剂、耐水性及拉伸强度等方面优于水扩链体系 .两种扩链剂体系所得PUA的性能差异 ,主要与二者和异氰酸酯反应生成的脲键密度不同 ,导致不同的微相结构有关     

氨乙基氨丙基聚二甲基硅氧烷改性水性聚酯型聚氨酯的研究

由聚酯二元醇、异佛尔酮二异氰酸酯和二羟甲基丙酸合成聚氨酯预聚体，以氨乙基氨丙基聚二甲基硅氧(AEAPS)为扩链剂，制备了AEAPS改性聚氨酯水分散液。与未改性的聚氨酯水分散液相比，AEAPS改性聚氨酯水分散液的粒径增大，但粒径分布和表面张力基本不变，说明疏水的聚二甲基硅氧烷侧链被包裹于分散颗粒的内部；此外，改性聚氨酯水分散液的冻融稳定性显著增强。AEAPS改性聚氨酯水分散液成膜后，吸水率明显下降，水在膜表面的接触角增加，400℃时热失重下降，具有良好的疏水性和耐热性。     

CAMDA扩链聚氨酯脲的硬段对形态与性能的影响

由红外光谱、核磁共振及质谱分析证实了所合成的3-氯-3’-甲氧基-4,4’-二氨基二苯基甲烷(CAMDA)具有预期的化学结构.用RIM方法制成的CAMDA基聚氨酯脲(PUU)性能接近于DETDA扩链的PUU.用快速手工浇注法制备了一系列由CAMDA扩链的不同硬段含量的PUU样品.采用DSC、SEM观察了硬段含量由10％增加到45％PUU形态的变化,并测量了力学性能.实验结果表明:随着硬段含量增加,PUU的形态由平行间隔的软、硬链段富集区经相互穿叉的软、硬段富集区,进一步聚集成硬链段富集球状超级结构,强度亦相应提高.     

低温等离子体引发聚氨酯脲接枝聚氧乙烯和肝素的研究

合成了以4,4’-二环己基甲烷二异氰酸酯（HMDI）和乙二胺（EDA）为硬段、聚碳酸六亚甲基酯二醇（PHC）为软段的聚酯型聚氨酯脲（PUU）,并用聚氧乙烯和肝素（heparin）对其进行了表面改性。通过红外光谱、X射线光电子能谱、接触角等研究了PUU材料的表面结构和性能。实验结果表明,利用室温等离子体方法,成功在PUU...     

含呱嗪聚硅氧烷聚脲聚氨酸及其离聚物的研究

以氨丙基封端聚二甲基硅氧烷及脲键改性聚硅氧烷低聚体分别与4，4－二异氰酸酯二苯甲烷（MDI)反应，并用1，4二（2－羟乙基）－呱嗪（N）扩链，合成了一系列含氮杂环聚氨酯共聚物。产物为透明热塑性弹性体，具有良好的成膜性能和宽阔的使用温区，通过碘乙烷和γ－丙磺酸内酯对上述样品进行季铵化，合成了阳离子型及双离子型离聚物。用傅里叶红外光谱（FT－IR）、示差量热分析（DSC）、动态力学谱（DMTA）、力学性能等方面对样品进行了表征。结果表明，在聚硅氧烷中引入脲键，提高了软、硬段两相的相容性。体系中既有软段间的氢键作用又有两相间的氢键作用，从而使这类材料的杨氏模量、抗张强度和断裂伸长均明显高于相应的聚二甲基硅氧烷聚脲聚氨酯体系。     

水性聚氨酯甲阶酚醛水分散液微观形态及杂化膜的性能

以自乳化型聚氨酯和甲阶酚醛制备了聚氨酯 酚醛复合水分散液 .pH值与酚醛溶解度的关系表明甲阶酚醛的溶解是酚羟基电离的结果 .聚氨酯 甲阶酚醛水分散液粒子的形态有核壳结构、不完善的核壳结构及纯聚氨酯颗粒三种 ,后者粒径最小 .随着酚醛用量的增大 ,粒子平均粒径增大 .酚醛含量增加使体系热稳定性、机械稳定性、冻融稳定性及临界聚沉值下降 ,pH值稳定范围变窄 .分散液稳定性和电性能考察证明 ,本复合分散液的稳定性主要由分散液的电性能所决定 ,属真溶胶 ,但在一定程度上也具有大分子溶液的特性 .复合液涂膜的性能较纯聚氨酯有所改善 ,尤其在添加了硅溶胶之后     

Preparation and characterization of waterborne poly(urethane urea) with well‐defined hard segments

A series of polyester‐based poly(urethane urea) (PUU) aqueous dispersions with well‐defined hard segments were prepared from polyester polyol, 4,4′‐diphenylmethane diisocyanate, dimethylolpropionic acid, 1,4‐butanediol, isophorone diisocyanate, and ethylenediamine. These anionic‐type aqueous dispersions had good dispersity in water and were stable at the ambient temperature for more than 1 year. For these aqueous dispersions, the particle size decreased as the hard‐segment content increased, and the polydispersity index was very narrow (<1.10). Films prepared with the PUU aqueous dispersions exhibited excellent waterproof performance: the amount of water absorption was as low as 5.0 wt %, and the contact angle of water on the surface of this kind of film was as high as 103° (this led to a hydrophobic surface). The water‐resistant property of these waterborne PUU films could be well correlated with some crystallites and ordered structures of the well‐defined hard segments formed by hydrogen bonding between the urethane/urethane groups and urethane/ester groups, as well as the degree of microphase separation between the hard and soft segments in the PUU systems. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2606–2614, 2005     

Preparation and properties of well‐defined waterborne polyurethaneurea with fluorinated siloxane units in hard or soft segments

Two series of well‐defined polyurethaneurea (PUU) aqueous dispersions consisting of fluorinated siloxane units in the hard and the soft segments, respectively, were prepared from polyester polyol, α,ω‐dihydroxypoly[(3,3,3‐trifluoropropyl) methylsiloxane] (PTFPMS), dimethylolpropionic acid, isophorone diisocyanate, and ethylenediamine. These anionic aqueous dispersions were stable at the ambient temperature for more than 6 months. The experimental results showed that the water‐resistance performance of the PUU films prepared with the insertion of PTFPMS units into the hard segments (HFS series) were better than those prepared with the insertion of PTFPMS units into the soft segments (SFS series). The film prepared from the PUU aqueous dispersion incorporating 5 wt % PTFPMS in the hard segments exhibited the lowest water absorption amount (2.3 wt %) with the contact angle of water on the film surface greater than 90°. In comparison with the PUU film without adding PTFPMS, the waterproof performance and the mechanical properties of both HFS and SFS series were enhanced markedly. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5005–5016, 2007     

Preparation and properties of waterborne polyurethaneurea consisting of fluorinated siloxane units

A series of polyurethaneurea (PUU) aqueous dispersions were prepared via a prepolymer process from polyester polyol, α,ω‐dihydroxypoly[(3,3,3‐trifluoropropyl) methylsiloxane] (PTFPMS), dimethylolpropionic acid, isophorone diisocyanate, and ethylenediamine. These anionic‐type aqueous dispersions were stable at the ambient temperature for more than 6 months, with particle sizes ranging from 69 to 127 nm. For these aqueous dispersions, the surface tension decreased with increasing PTFPMS content, but the particle size increased with a maximum value. The film prepared from the PUU aqueous dispersion consisting of 5 wt % PTFPMS (APU‐FS‐5) exhibited excellent waterproof performance. Furthermore, the tensile strength of the APU‐FS‐5 film increased nearly 3 times compared with that of the PUU film without PTFPMS, whereas the elongation at break only decreased a little; this indicated that the water‐resistant and mechanical properties could be enhanced markedly and simultaneously for the PUU films containing both silicon and fluorine groups. The experimental results showed a high degree of hydrogen bonding for urea groups and an increased microphase‐separation degree between the hard and soft segments in the PTFPMS‐modified system, which resulted in the excellent mechanical properties of these films. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3365–3373, 2006     

Fluorinated siloxane-containing waterborne polyurethaneureas with excellent hemocompatibility, waterproof and mechanical properties

Two series of polyurethaneurea (PUU) aqueous dispersions consisting of fluorinated siloxane segments were prepared from a high-molecular-weight (M_n = 8361) α,ω-dihydroxypoly[(3,3,3-trifluoropropyl)methylsiloxane] (PTFPMS), dimethylolpropionic acid, isophorone diisocyanate and ethylenediamine, with poly (tetramethylene oxide) and polycarbonate polyols as soft segments, respectively. These anionic aqueous dispersions were stable at the ambient temperature for more than 6 months, with particle sizes ranging from 45 to 98 nm. Both series of PUU films showed the excellent waterproof properties, i.e. the decrease in water absorption and surface energy upon the incorporation of PTFPMS segments. The phase mixing increased in the fluorinated siloxane-containing polyether-based PUUs and the phase separation increased first then decreased in the fluorinated siloxane-containing polycarbonate-based PUUs, with increasing PTFPMS content. All the PTFPMS-modified PUU films showed excellent mechanical properties. The polycarbonate-based PUU film consisting of 5 wt.% PTFPMS had a tensile strength of 60.7 MPa and a breaking elongation of 632%, owing to the increase in the ordered hydrogen bonding degree and the microphase-separation degree between the hard and soft segments in the system. In vitro hemolysis and dynamic clotting time measurements indicated that the thromboresistance was enhanced markedly with increasing PTFPMS content for both series of PUUs, which could be ascribed to the synergistic effect between the carboxylate groups and the PTFPMS segments migrating onto the surfaces of the films.     

用可再生原料合成聚氨酯脲水分散液——成膜后的结构与性能研究

以不同组成的蓖麻油和二官能度聚醚多元醇 (GE 2 10 )等原料合成了聚氨酯脲 (PUU)水分散液 ,研究了蓖麻油 GE 2 10的组成对PUU膜结构与性能的影响 .结果表明 ,由GE 2 10合成的PUU虽软硬段间存在一定的相容性 ,但其中脲羰基的氢键化程度高 ,硬段形成较好的有序结构 ,导致PUU膜具有较高的拉伸强度及断裂伸长率 ,但弹性模量和硬度下降 .在蓖麻油合成的PUU中脲羰基的氢键化程度及硬段有序结构均受到化学交联结构的抑制 ,故PUU膜的拉伸强度和断裂伸长率降低 ,但弹性模量及硬度较高 .由蓖麻油与GE 2 10在一定的组成范围内合成的PUU膜 ,具有优良的综合平衡的力学性能 ,后者与材料的结构形态相符     

Poly(urea)urethanes based on amorphous quaternizable hard segments and a crystalline polyol derived from castor oil

A set of poly(urea)urethanes (PUU), with different contents of amorphous hard segment and castor oil-derived crystalline polyol as soft segment, was prepared combining bulk and solution polymerizations. It is shown that both the soft segment crystallinity and hard segment glassy nature control the stiffness of the materials and that phase mixing at intermediate hard segment compositions produces softer materials. Upon yielding, PUU developed large plasticity associated to the nature of soft segments. At longer strains, PUU presented strain-induced crystallization related both to soft segments alignment and crystallization, leading to strong and tough materials, especially with high hard segment content compositions. Despite the hydrophobicity of the soft segments, the PUU with 65 wt% hard segment content was dispersable in water after quaternization with acetic acid. The high amount of urea groups in this quaternized PUU makes one think of these types of polymers as promising water soluble environmentally friendly strong adhesives, coatings, or water soluble polymeric electrolites.     

MODIFIED ULTRAVIOLET-CURABLE WATER DISPERSIBLE POLYURETHANE-ACRYLATES*

Three kinds of UV-curable self-emulsified polyurethane-acrylate (PUA) prepolymer, i.e., conventional, chainextended and grafted PUAs, were prepared. The relatively small particle size of the PUA dispersions indicates that the PUAprepolymers exhibit sufficient aqueous dispersibility. The PUA prepolymers can substantially lower the interfacial tension ofwater. Chain-extended PUA dispersions exhibit pseudoplastic behavior and thixotropy to a greater extent than do theirconventional counterpart. The chain-extended and grafted PUA photocure to higher conversion than do the conventional PUequivalent. The results of DSC measurement suggest that there exists phase mixing between the hard and the soft segmentphases for the PUAs based on PEG 400 that is the comparatively short soft segment in the prepolymer. For the PUAprepolymers based on PEG having higher M_n values, chain-extending and grafting could impede the phase separationbetween the hard and the soft segment domains. The adhesion, impact strength and flexibility of the photocured films were tested.     

UV curable waterborne polyurethane acrylate dispersions based on hyperbranched aliphatic polyester: effect of molecular structure on physical and thermal properties

A novel waterborne hyperbranched polyurethane acrylate for aqueous dispersions (WHPUDs) based on hydroxy‐functionalized hyperbranched aliphatic polyester Boltorn? H20 was investigated. The effects of structural composition and crosslinking density have been studied in terms of swellability by water, thermal degradation, viscosity changes as well as transmission electron microscopy (TEM) morphology. The swell ratio showed an increasing trend with the higher concentration of ionic group, which is due to the increased total surface area of particles. The results of thermogravimetric analysis (TGA) for cured WHPUD films indicated good thermal stability with no appreciable weight loss until 200°C. The activation energies were evaluated and were found in the range 154–186 kJ mol^?1. It was observed that an increase in hard segment content provoked the increases in thermal degradation temperature and activation energy of waterborne dispersions. The transmission electron photographs revealed that the average particle sizes of aqueous dispersions were in the range 30–125 nm. Owing to the enlargement of the stabilization site, the particle size decreased as the content of carboxyl group and degree of neutralization increased. The viscosity of WHPUDs increased rapidly with increasing the degree of neutralization. Moreover, water showed a favorable viscosity reduction effect. Copyright © 2004 John Wiley & Sons, Ltd.     

Photopolymerization of waterborne polyurethane acrylate dispersions based on hyperbranched aliphatic polyester and properties of the cured films

A series of novel waterborne hyperbranched polyurethane acrylates for aqueous dispersions (WHPUD) based on hydroxy-functionalized hyperbranched aliphatic polyester Boltorn H20 were investigated and used as UV curable oligomers. The aqueous dispersions were electrostatically stabilized with carboxyl groups incorporated into their structures, which were neutralized by triethylamine. The photopolymerization kinetics of these WHPUDs was studied with respect to polymerization rates and unsaturation conversions in the presence of a photoinitiator using differential scanning calorimetry. The polymerization rates of the resins under UV irradiation and the gel contents in the cured films showed an increasing trend with higher concentration of acrylate functionality, which is in favor of the theory of radical chain polymerization. The mechanical and thermal behaviors of UV cured films of aqueous dispersions were evaluated by tensile testing and dynamic mechanical thermal analysis (DMTA). The results of DMTA investigations indicated that the glass transition temperature shifted to higher temperature as the content of the hard segment consisting of IPDI-HEA increased. Moreover, the storage modulus and pendulum hardness also increased with increasing the hard segment content. As the degree of neutralization increased, the T_g and tensile strength decreased, whereas, the elongation at break increased.