硬段类型和含量对嵌段聚氨酯脲性能的影响

以聚己二酸乙二醇-丙二醇酯二醇(PEPA)为软段,分别采用4种二胺扩链剂和3种二异氰酸酯为硬段,通过预聚体法合成了一系列不同硬段结构和含量的聚氨酯脲弹性体,并采用红外光谱、热失重分析、差示扫描量热和拉伸测试等手段,研究了硬段类型及含量对聚氨酯脲性能的影响。结果表明,在软段结构一致,硬段含量接近的情况下,兼具柔性和刚性的硬段有助于提升聚氨酯脲的力学性能、热学性能和微相分离程度。几种二胺扩链剂和二异氰酸酯中,由二苯基甲烷二异氰酸酯(MDI)和4,4'-二氨基二苯醚(ODA)构成的硬段性能最佳;在软、硬段结构一致的情况下,硬段含量对聚氨酯脲性能影响明显。随着硬段含量增加,聚氨酯脲的拉伸强度、微相分离程度先增大后减小,5%热失重温度和断裂伸长率逐渐下降。当PEPA/MDI/ODA摩尔比为1∶0.5∶0.5(硬段含量31.7%),聚氨酯脲拉伸强度达51.5 MPa,断裂伸长率为709%,5%热失重温度为282.7℃,性能最佳。     

聚硅氧烷聚脲的结构与性能研究

利用４，４＇－二异氰酸酯二苯醚与胺丙基封端的聚二甲基硅氧烷反应，合成了一类新型聚硅氧烷聚脲嵌段共聚物。结合热分析、动态力学分析以及小角Ｘ光散射的结果对其结构进行了表征。另外还采用紫外吸收、荧光光谱分析、热失重分析和应力－应变分析等手段研究了这一体系的耐热性、抗光老化性及其力学性能。结果表明，将ＭＤＩ中的亚甲基换成醚键后，有利于防止聚脲分子在光作用下形成醌式结构，提高了聚脲的抗光老化性能。醚键的引入     

多交联型聚氨酯材料的制备与性能

以聚酯多元醇(PEA)、2,4-甲苯二异氰酸酯(TDI-100)为原料,采用预聚法制备预聚体,将预聚体分成两部分分别以不同的扩链系数与扩链剂3,5-二甲硫基甲苯二胺(E-300)混合反应,再将两种配料不同的预反应物混合后浇铸成型,即为多交联体系聚氨酯材料。利用差示扫描量热(DSC)、耐溶剂性和力学测试考察其性能并与均一体系聚氨酯(PU)材料的性能进行比较。力学性能测试表明,多交联体系聚氨酯材料的耐撕裂性能明显提高,拉伸性能略微降低;多交联体系聚氨酯材料的耐溶剂性能也明显提高;DSC测定结果表明,多交联体系材料的微相分离更好。     

聚L-乳酸/聚丁二烯基聚氨酯的合成与表征

以乙二醇和L-乳酸熔融直接缩聚制备双端羟基聚L-乳酸预聚物(PLLA),并用1H、13C-NMR、DSC、XRD对PLLA结构和性能分析表征.以液化二苯基甲烷二异氰酸酯(MDI)为偶联剂,端羟基聚L-乳酸和端羟基聚丁二烯(HTPB)偶联反应制备橡胶改性聚乳酸基聚氨酯弹性体,并用FT-IR,1H、13C-NMR对聚合产物进行结构表征确认.DSC测试结果表明聚氨酯有聚丁二烯段和聚乳酸段两个玻璃化转变温度,熔融温度基本在130℃.随着聚丁二烯含量的增加,结晶衍射峰逐渐消失,聚氨酯的拉伸强度降低,断裂伸长率增加.断面扫描电镜结果显示聚氨酯呈微相分离结构和弹性断裂.     

一种含能热塑性聚氨酯弹性体的性能

采用熔融二步法合成了以聚叠氮缩水甘油醚(GAP)为软段、以2,2-二叠氮甲基-1,3-丙二醇和二环已基甲烷二异氰酸酯(HMDI)为硬段的含能热塑性聚氨酯弹性体(ETPUE),通过红外光谱(FT-IR),差示扫描量热(DSC),动态力学性能测试(DMA)及力学性能测试对材料进行了结构和性能的表征.结果表明,所合成的不同硬...     

Effect of glycerol cross-linking and hard segment content on the shape memory property of polyurethane block copolymer

Effect of glycerol cross-linking and hard segment content on the shape memory property of polyurethane block copolymer is comprehensively investigated. Phase separation of hard and soft segment is dependent on glycerol cross-linking and hard segment content as judged from FT-IR and DSC data. Hydrogen bonding and dipole–dipole interaction between hard segments provides strong interaction between copolymer chains in addition to chemical cross-linking by glycerol. As the hard segment content increases, the copolymer shows better tensile mechanical properties and higher melting temperature of soft segment (T _m). Effect of glycerol cross-linking on mechanical properties and T _m of soft segment is low compared to hard segment effect. Although XRD peak at 2θ = 19.5° is observed, clear difference between the copolymers with various hard segment and cross-linking content is not observed. Significant increase in shape recovery rate in the case of 30 wt% hard segment copolymer is observed after glycerol cross-linking. The drastic change of the properties of polyurethane block copolymer is discussed in the point of copolymer chain interaction.     

微相分离结构聚氨酯膜的丁醇/水体系渗透汽化分离

制备了端羟基聚丁二烯-聚氨酯（HTPB-PU）和端羟基聚丁二烯-乙烯基三乙氧基硅烷-聚氨酯（HTPB-VTES-PU）两种聚氨酯膜。采用傅立叶变换红外光谱（FT-IR）、差示扫描量热仪（DSC）和透射电镜（TEM）分析表征了两种膜的结构,结果发现,HTPB-PU有两个玻璃化转变温度,其膜具有一定程度的微相分离结构;HT...     

Effect of the diisocyanate and chain extenders on the properties of the cross-linked polyetherurethane elastomers

Polyurethane elastomers with potential for applications in damping bearings were synthesized with 1,6-hexamethylene diisocyanate, 4,4′-methylenebis-(phenylisocyanate), poly(1,4-butane)diols (Terathane 1400), 1,4-butane diol 1,6-hexane diol and glycerin chain extenders. The glass-transition temperatures of the materials ranged from −42 to −75 °C and were higher for polymers based on 4,4′-methylenebis-(phenylisocyanate) and with higher hard segment (HS) contents. The tensile strengths of the materials were 20–55 MPa and the tensile moduli were 30–134 MPa. These increased with increasing HS content. Interchain cross-linking improves thermal stability, which was measured by thermogravimetric analysis and differential scanning calorimetry. The structure and amount of HS used causes a significant variation in the properties of cross-linked elastomers.     

Polyurethane-maleamides for cardiovascular applications: synthesis and properties

Several polyurethane-maleamides (PUMAs) containing polyether or polycarbonate soft segments, and aromatic or aliphatic hard segments were synthesized by solution or bulk polymerization, using maleic acid (MA) or a mixture of MA and butanediol as chain extenders. Using this process, activated double bonds are introduced into the polymer chains and the base polyurethanes may undergo further modification via specific grafting, thus improving their tissue compatibility. PUMAs chemicophysical properties were evaluated by gel permeation chromatography (GPC), intrinsic viscosity analyses, differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR) and tensile mechanical tests. Polycarbonate diol (PCU)-based PUMAs showed higher molecular weights than polyether diol (PEU)-based ones. The use of butanediol in mixture with maleic acid led to an increase of molecular weights. FT-IR confirmed the presence of the bands related to the amide groups and to the conjugated double bond, yet more evident for the polymer obtained in solution. The higher crystallinity shown by this polymer was also indicative of a better phase separation. All the PCU-PUMAs exhibited similar tensile properties with a higher stiffness than PEU-PUMAs. Among the PEU-PUMAs, the highest tensile properties were shown by the polymer obtained in solution, and by the one derived from a mixture of maleic acid and butanediol.     

Effect of the hard segment chemistry and structure on the thermal and mechanical properties of novel biomedical segmented poly(esterurethanes)

Two series of biomedical segmented polyurethanes (SPU) based on poly(ε-caprolactone) diol (PCL diol), 1,6-hexamethylene diisocyanate (HDI) or l-lysine methyl ester diisocyanate (LDI) and three novel chain extenders, were synthesized and characterized. Chain extenders containing urea groups or an aromatic amino-acid derivative were incorporated in the SPU formulation to strengthen the hard segment interactions through either bidentate hydrogen bonding or π-stacking interactions, respectively. By varying the composition of the hard segment (diisocyanate and chain extender), its structure was varied to investigate the structure-property relationships. The different chemical composition and symmetry of hard segment modulated the phase separation of soft and hard domains, as demonstrated by the thermal behavior. Hard segment association was more enhanced by using a combination of symmetric diisocyanate and urea-diol chain extenders. The hard segment cohesion had an important effect on the observed mechanical behavior. Polyurethanes synthesized using HDI (Series H) were stronger than those obtained using LDI (Series L). The latter SPU exhibited no tendency to undergo cold-drawing and the lowest ultimate properties. Incorporation of the aromatic chain extender produced opposite effects, resulting in polyurethanes with the highest elongation and tearing energy (Series H) and the lowest strain at break (Series L). Since the synthesized biodegradable SPU possess a range of thermal and mechanical properties, these materials may hold potential for use in soft tissue engineering scaffold applications.     

硅胶模具浇注成形用聚氨酯树脂

利用二苯基甲烷二异氰酸酯(MDI)、聚醚多元醇及小分子扩链剂、交联扩链剂合成了一系列适用于快速硅胶模具浇注成形的二组分聚氨酯(PU)树脂.通过粘度测试考察了PU树脂的浇注性能,使用示差扫描量热分析(DSC)和热重分析(TGA)分析了树脂的热性能,并对其相关的力学性能进行了分析测试.结果表明,PU树脂两组分及其混合液的粘度较小,釜内寿命适中,浇注性能优良;通过调节硬段含量及混和扩链交联剂中三羟甲基丙烷(TMP)含量,使得PU树脂具有较高的力学性能和热性能,浇注成形件可在高负荷、高温下的使用.     

聚酯型热塑性聚氨酯弹性体的制备及阻尼性能

以聚酯多元醇、4,4’-二苯基甲烷二异氰酸酯(MDI)和1,4-丁二醇为原料制备了一系列聚酯型热塑性聚氨酯弹性体(TPU),对硬段含量、软段种类和软段的分子量等分子结构参数对其力学性能和阻尼性能的影响进行了研究,探索影响规律性,采用原子力显微镜对其软/硬段微相分离结构进行了研究。     

硬段微区结构与聚氨酯脲弹性体力学性能及耐热性的相关性

以聚四氢呋喃醚二醇(PTMG)为软段,甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、混合异氰酸酯(n(TDI)∶n(MDI)=1∶1)分别为硬段,采用预聚体法合成了一系列不同硬段微区结构的聚氨酯脲弹性体,并通过红外光谱、热重分析、差示扫描量热以及力学表征等方法,研究了不同硬段微区结构与聚氨酯脲(PUU)体系内部微相分离、热稳定性及力学性能的相关性。结果表明,TDI型聚氨酯脲的NH官能团伸缩振动谱带出现在较低位置(3270cm~(-1)),MDI型NH官能团伸缩振动谱带出现在相对较高的位置(3285cm~(-1)),前者的T_g(-57.6℃)低于后者T_g(-49.5℃),而初始降解温度前者(294℃)高于后者(268℃),混合型的均位于两者之间。因此,TDI型PUU表现出较高的微相分离程度和硬段微区有序度,而MDI型微相混合程度较高、且微相混合程度有助于力学性能的改善。随着温度的升高,PUU内部氢键化NH官能团伸缩振动吸收强度逐渐减弱,谱带吸收位置由低波数向高波数移动,力学性能逐渐下降,当温度处于70℃左右时,其波数出现轻微的突越,力学性能也表现出较快的下降趋势。     

Preparation and properties of polyurethane/zeolite 13X composites

The pre-polymerization method was used to prepare polyurethane/zeolite 13X (PU/13X) composites. The effects of zeolite 13X content and its surface organic modification on the mechanical properties of composites were investigated. It was demonstrated that the mechanical properties of PU/13X composites were better than that of pure PU. The surface organic modification of zeolite 13X had no obvious effect on the mechanical properties of PU/13X composites. The optimal tensile strength and tear strength were obtained with 3–5% and 5–7% zeolite 13X loading, respectively. Thermogravimetric analysis (TGA) results showed that the decomposition temperature of PU/13X composites increased in comparison with pure PU. Dynamic mechanical analyzer (DMA) suggested a lower glass transition temperature (T_g) and better micro-phase separation of soft and hard segments in PU/13X composites. Besides, PU/13X composites had excellent solvent resistance performance.     

The waterborne polyurethane dispersions based on polycarbonate diol: Effect of ionic content

Three water-based polyurethane dispersions (PUD) were synthesized by modified dispersing procedure using polycarbonate diol (PCD), isophorone diisocyanate (IPDI), dimethylolpropionic acid (DMPA), triethylamine (TEA) and ethylenediamine (EDA). The ionic group content in the polyurethane-ionomer structure was varied by changing the amount of the internal emulsifier, DMPA (4.5, 7.5 and 10 wt.% to the prepolymer weight). The expected structures of obtained materials were confirmed by FTIR spectroscopy. The effect of the DMPA content on the thermal properties of polyurethane films was measured by TGA, DTA, DSC and DMTA methods. Increased DMPA amounts result in the higher hard segment contents and in the increase of the weight loss corresponding to the degradation of the hard segments. The reduction of hard segment content led to the elevated temperature of decomposition and to the decrease of the glass transition temperature and thermoplasticity. The atomic force microscopy (AFM), results indicated that phase separation between hard and soft segment of PUD with higher DMPA content is more significant than of PUD with lower DMPA content. The physico-mechanical properties, such as hardness, adhesion test and gloss of the dried films were also determined considering the effect of DMPA content on coating properties.     

催化剂对异佛尔酮二异氰酸酯制备的脂肪族聚氨酯弹性体结构和性能的影响

采用一步法通过异佛尔酮二异氰酸酯与聚丙二醇和1,4-丁二醇反应合成了脂肪族聚氨酯（PU）弹性体。考察了催化剂的种类和含量对PU弹性体结构和性能的影响。结果表明,以辛酸亚锡为催化剂时,PU弹性体的软段相和硬段相间的相分离程度最明显且分子量最低,导致其力学性能最差;以辛酸铋为催化剂时,PU弹性体软段相和硬段相的相容性较好且...     

Fluoro-modified elastomeric polyurethanes: effects of synthesis procedure on properties and morphology

Fluorinated polyurethanes characterized by a segmented structure, containing hard segments based on 4,4′-methylenebis (phenylisocyanate) (MDI), chain-extender 1,4 n-butandiol (BDO), and soft blocks like perfluoropolyether (PFPE), and poly-ε-caprolactone (PCL) were synthesized keeping constant the equivalent ratio among reagents, but varying the experimental conditions. Copolymers show a complex micro- and macrostrucrture with different morphology and calorimetry, similar tensile properties and undistinguishable, but strongly upgraded surface properties. The morphology should be governed by the different fluorine content of the polymeric chains along with the hard segment structure; tensile properties are little influenced by the morphology. All these characteristics are interpreted in terms of polymerization procedure which results to be a key parameter for ruling the composition of the different polymeric chains, due to a very limited mutual solubility of the reagents. Surprisingly, a beneficial effect of the catalyst dibutyltindilaurate for the increase of the reaction kinetics among segregated phases in the reaction mass was observed.     

IPDI基和HMDI基热塑性聚氨酯弹性体的合成与性能

采用熔融二步法合成了以环氧乙烷-四氢呋喃无规共聚醚(PET)和聚己二酸乙二醇丙二酯(PEPA)的混合多元醇为软段,1,4-丁二醇(BDO)为扩链剂.不同硬段含量的异佛尔酮二异氰酸酯(IPDI)基和二环已基甲烷二异氰酸酯(HMDI)基热塑性聚氨酯弹性体(TPU).通过红外光谱(FT-IR)对TPU的结构进行了表征,利用差...     

聚甲基乙撑碳酸酯产品中聚醚多元醇的提取及用于聚氨酯的合成

探讨了聚甲基乙撑碳酸酯(PPC)中副产物聚醚的提取方法,对其结构进行了红外光谱(FT-IR),核磁共振谱(1H-NMR)和凝胶渗透色谱(GPC)的表征,并进行了用其合成聚氨酯(PU)的应用研究。通过拉伸测试、邵氏硬度测试和热重分析(TG)考察了不同硬段比例、-NCO与-OH比例对所合成的PU的力学性能及热性能的影响。结果表明,当NCO∶OH略大于1时,随着硬段含量的增加,合成的聚氨酯的力学性能和邵氏硬度随之增加,T-5%、软硬段分解温度及玻璃化转变温度(Tg)无较大变化;当-NCO∶-OH值较低时,聚氨酯的力学性能、硬度及热性能均有降低的趋势。     

不同硬段含量的PU及其纳米复合材料

制备了不同硬段含量的聚氨酯(PU)及其PU/有机蒙脱土(OMMT)纳米复合材料。研究结果表明,随着PU分子链中硬段含量的增加,PU分子链的刚性提高,进入硅酸盐片层间的位阻增大,使插层变得困难,从而导致进入该硅酸盐片层间的PU分子链减少。OMMT对PU有增强增韧作用,但随着PU分子链中的硬段含量增加,OMMT的增强效果下降。PU及其PU/OMMT纳米复合材料的热稳定性均随着PU分子链中的硬段含量增加而下降。