交联对透明聚氨酯弹性体结构与性能的影响

采用一步法以异佛尔酮二异氰酸酯（IPDI）、聚氧四亚甲基二醇（PTMG）、1，4－丁二醇（BD）和聚氧化丙烯三醇（N3010）为原料合成了透明聚氨酯弹性体，通过DSC、FT－IR、TG等方法研究了物理交联和化学交联对聚氨酯弹性体的力学性能、光学透明性和热稳定性的影响。结果表明，尽管聚醚二元醇的分子量增大，但由于硬段间的氢键作用增加，使微相分离程度提高，聚氨酯弹性体的力学强度增加。加入交联剂三元醇N3010，聚氨酯弹性体在硬段间形成化学交联、透度、热稳定性和力学性能与未加交联剂的聚氨酯弹性体相比有明显提高。     

热塑型聚氨酯弹性体的FTIR谱研究

本文以FTIR谱研究了W_h,(?),对热塑性聚氨酯弹性体(TPU)相分离过程及其氢键化程度的影响,并以红外二向色性法研究了软、硬段及界面层的取向机理。     

低分子量HTPB聚氨酯弹性体的制备及其性能

为改善高固含量高聚物黏结炸药(PBX)和丁羟推进剂的工艺性能,以低分子量的端羟基聚丁二烯(HTPB)、异佛尔酮二异氰酸酯(IPDI)为主要原料,选用一缩二乙二醇(DEG)为扩链剂,采用二步法制备了聚氨酯弹性体。研究了催化剂用量对浆料黏度的影响,固化参数R及扩链剂用量对HTPB聚氨酯弹性体力学性能的影响。试验结果表明,当催化剂质量分数为0.004%时,适用期可达5 h;R值为1.1,DEG羟基含量占反应总羟基量的60%时,聚氨酯弹性体力学性能较好,拉伸强度达7.60 MPa,断裂伸长率达540.21%。动态力学分析(DMA)测试结果显示,低分子量HTPB聚氨酯弹性体有两个明显的玻璃化转变温度,说明样品存在明显的微相分离结构。     

聚四氢呋喃醚二醇/聚氧化丙烯二醇共混聚醚聚氨酯弹性体的氢键作用

分别以聚四氢呋喃醚二醇(PTMG)、聚氧化丙烯二醇(PPG)及两者共混物PTMG/PPG作为软段,以2,4-甲苯二异氰酸酯(TDI-100)和扩链剂3,3'-二氯-4,4'-二氨基二苯甲烷(MOCA)作为硬段,采用预聚体法,制备了5种PTMG/PPG不同配比的浇注型聚氨酯弹性体。通过红外分析、差示扫描量热分析、动态力学热分析着重研究了PTMG/PPG不同配比对聚氨酯弹性体氢键的影响。结果表明,随着PPG型预聚体在混合预聚体中的含量增加,聚氨酯中羰基区总氢键度及脲羰基氢键度变化不大,氨酯羰基氢键度呈现先增加后减小的趋势;氨酯羰基氢键解离活化能变大,氢键趋于完善;硬段相长程有序结构熔融焓减小,脲羰基氢键完善程度下降。     

HMDI型透明聚氨酯弹性体合成工艺研究

以氢化二苯基甲烷二异氰酸酯(H12MDI)、多元醇为主要原料,采用半预聚体法合成聚氨酯弹性体。结果表明,合成聚氨酯预聚物较佳的工艺条件为:异氰酸根指数R为4,在50℃的条件下反应1h后,80℃条件下反应2h,预聚物黏度3900mPa·s左右,黏度适中。同时考察了催化剂种类、固化温度、固化时间、多元醇种类和分子量、多元醇交联剂等对聚氨酯力学性能和光学性能的影响,确定合成透明聚氨酯弹性体较好的条件为以TK233为催化剂,以多元醇NJ210、NJ3050为原料,室温固化72h,此种方法合成的聚氨酯具有较好的透光率和力学性能。     

氢键型网络状超分子弹性体的合成与自愈合性能

用脂肪族超支化聚酯和丁二酸酐反应制备端羧基超支化聚酯。端羧基超支化聚酯与叠氮磷酸二苯酯反应引入异氰酸酯基,再与二乙烯三胺反应引入脲基和氨基,制备了具有较多氢键位点的网络状超分子弹性体。实验中发现二乙烯三胺的二甲基亚砜溶液浓度对超分子弹性体的力学、动态力学和自愈合性能有较大影响。浓度低时得到的超分子弹性体的柔顺性较好,具有自愈合性。浓度高时得到的超分子弹性体较硬,具有较高的力学性能。     

自修复聚氨酯弹性体的制备及性能研究

目的对自修复聚氨酯弹性体的制备工艺及性能进行综述,为制备高修复效率的聚合物提供指导,并指出其未来的发展趋势。方法从聚氨酯弹性体的修复机理出发,收集并分析自修复聚氨酯弹性体的最新研究进展,总结典型自修复聚氨酯弹性体的制备工艺和性能指标;根据修复机理进行分类,对近年来本征型(Diels-Alder反应、Disulfide键、氢键等)和外援型(微胶囊化)自修复聚氨酯弹性体的制备和性能进行综述,并讨论自修复聚氨酯弹性体的修复效率。结论虽然基于不同动态键的自修复聚氨酯弹性体取得了一定的发展,但开发高修复效率的材料仍然是一个巨大的挑战。总结了提高自修复聚氨酯弹性体力学性能的途径,为实现修复性能与力学性能的平衡提供了指导。     

用FTIR,ESR研究全热塑性聚氨酯的氢键作用及断裂机理

我们合成了两种氢键强度不同的全热塑性聚氨酯弹性体,凭借FTIR测定了氢键在不同温度时的位移状况,计算了氢键的长度,并用ESR、FTIR测定了两种材料的断裂谱。结果表明,具有强氢键的材料在拉伸断裂时产生了少量主链的断裂,其断裂处在PPG的C—O键上,断键后形成了一个四元环醚结构。     

水用量对全水发泡聚氨酯泡沫形态和力学性能的影响

采用扫描电镜(SEM)和红外光谱(FT-IR)并结合物理力学性能测试,对高水用量(3phr~11phr)所制备的全水发泡低密度聚氨酯泡沫的形态和力学性能进行表征,结果表明,水用量逐渐从3phr增加到11phr,发泡聚氨酯物料的乳白时间、凝胶时间和不粘手时间逐渐延长,泡沫中的取代脲结构含量和氢键化程度逐渐增加,泡沫密度和力学性能逐渐降低,泡孔平均孔径呈先增大、后减小的趋势,然而泡沫的比强度和氨基甲酸酯含量变化不大。     

具有独特性能的超低单醇含量聚醚基聚氨酯弹性体

采用双金属络合催化剂(DMC)制备具有极低的不饱和度、相对分子量高、分子量分布窄、平均官能度高等特点的新型聚醚多元醇。这种超低单醇含量聚醚多元醇及部分该聚醚取代的聚四氢呋喃醚多元醇制备的聚氨酯弹性体与普通聚氧化丙烯醚多元醇(PPG)、聚四氢呋喃醚多元醇(PTMEG)聚氨酯弹性体性能相比,DMC聚醚基聚氨酯弹性体在力学性能(伸长率、拉伸强度、撕裂强度)和加工性能(釜中寿命、脱模时间等)方面获得了明显改善。     

酰亚胺邻接交联型聚氨酯弹性体的制备与性能

以聚醚（PTHF）、端羟基聚丁二烯-丙烯腈（HTBN）甲苯二异氰酸酯为材料,交联剂双二五（B25）和助交联剂N,N-马来酰亚胺间本撑（HAV-2）为添加剂制备出酰亚胺邻接交联型丁腈基聚氨酯弹性体,并研究了其耐热性能。结果表明,邻接交联网络的生成,聚氨酯弹性体的力学性能降低,永久变形下降,耐温性明显提高。随着高温的升高,聚氨酯弹性体的力学性能、硬度和断裂伸长率均表现下降趋势,然而回弹性逐渐升高。     

TDI三聚体的合成及其在弹性体中的应用

以2,4-甲苯二异氰酸酯（TDI）为原料成功合成出了TDI三聚体,并用三聚体合成出了以聚醚二醇（PTHF）为基体的PUU弹性体。结果表明：TDI三聚反应的最佳条件为：反应温度为50℃,催化剂浓度0．05％。在三聚反应进程中,随着反应进度的增加,体系中残余NCO的含量逐渐降低,三聚化程度逐渐提高。用三聚体改性的材料拉伸强度、扯断伸长率和永久变形都有不同程度的下降;在热失重30％时的分解温度提高了约20℃,这对于改善材料在高温下的性能提供了新的思路。     

不饱和烯烃型聚氨酯／蒙脱土复合材料的制备与性能

将丁腈羟液体聚合物多元醇和有机蒙脱土（OMMT）进行预混插层处理,然后与甲苯二异氰酸酯（TDI）进行反应,得到层状硅酸盐复合预聚体。随后预聚体与扩链剂（DMTDA）反应制备出聚氨酯脲（PUU）／有机蒙脱土（OMMT）复合材料。实验结果表明：OMMT含量在3％时,纳米粒子表现出较强的增强作用,材料表现出最高的力学性能。OMMT的加入提高了聚氨酯弹性体第一热失重区和第二热失重区的的热降解温度,同时提高了软段的玻璃化转变温度和材料的内损耗因子tanδ。     

Preparation and properties of adjacency crosslinked polyurethane---urea elastomers

Adjacency crosslinked polyurethane--urea (PUU) elastomers with different crosslinking density were prepared by using hydroxyl-terminated liquid butadiene-nitrile (HTBN), toluene diisocyanate (TDI) and chain extender 3,5-dimethyl thio-toluene diamine (DMTDA) as raw materials, dicumyl peroxide (DCP) as initiator, and N,N'-m-phenylene dimaleimide (HVA-2) as the crosslinking agent. The influences of the crosslinking density and temperature on the structure and properties of such elastomers were investigated. The crosslinking density of PUU elastomer was tested by the NMR method. It is found that when the content of HVA-2 is 1.5%, the mechanical properties of polyurethane elastomer achieve optimal performance. By testing thermal performance of PUU, compared with linear PUU, the thermal stability of the elastomers has a marked improvement. With the addition of HVA-2, the loss factor tanδ decreases. FT-IR spectral studies of PUU elastomer at various temperatures were performed. From this study, heat-resistance polyurethane could be prepared, and the properties of PUU at high temperature could be improved obviously.     

Investigation of effects of dibutyltin dilaurate on reaction injection molding polyurethane-urea kinetics,morphology and mechanical properties by FTIR

The bulk catalyst effect of dibutyltin dilaurate (DBTDL) on the reaction of NCO respectively with OH and NH₂ was investigated in detail. The results showed that DBTDL had specific catalyst effect on the reaction of NCO with OH and no measurable effect on the reaction of NCO with NH₂. In situ Fourier transform infrared spectroscopy (FTIR) used in the reaction injection molding (RIM) process showed that with increasing the concentration of DBTDL, the formation rate of the soft segment became fast, and the order degree of urea carbonyls became worse. Meanwhile, more arrange manners of urea carbonyl were present. The bands at 1653, 1647 and 1637 cm^-1 were able to be detected at the low conversion. No hydrogen-bonded urea carbonyl available in the spectra at the beginning. The tensile-stress behavior showed that, with the increase of the DBTDL content, the interaction between polar groups became weak, while the virtual crosslinks also became weak. Although the break stress (?), 300%? and the hardness of elastomers decreased obviously, however, the tear strength, associated with the morphology of polyurethane-urea (PUU), showed the maximum when the DBTDL content was 2.63‰.     

Investigation of effects of dibutyltin dilaurate on reaction injection molding polyurethane-urea kinetics, morphology and mechanical properties by in situ FTIR

The bulk catalyst effect of dibutyltin dilaurate (DBTDL) on the reaction of NCO respectively with OH and NH₂ was investigated in detail. The results showed that DBTDL had specific catalyst effect on the reaction of NCO with OH and no measurable effect on the reaction of NCO with NH₂. In situ Fourier transform infrared spectroscopy (FTIR) used in the reaction injection molding (RIM) process showed that with increasing the concentration of DBTDL, the formation rate of the soft segment became fast, and the order degree of urea carbonyls became worse. Meanwhile, more arrange manners of urea carbonyl were present. The bands at 1653, 1647 and 1637 cm⁻¹ were able to be detected at the low conversion. No hydrogen-bonded urea carbonyl available in the spectra at the beginning. The tensile-stress behavior showed that, with the increase of the DBTDL content, the interaction between polar groups became weak, while the virtual crosslinks also became weak. Although the break stress (d), 300‰δ and the hardness of elastomers decreased obviously, however, the tear strength, associated with the morphology of polyurethane-urea (PUU), showed the maximum when the DBTDL content was 2.63‰.     

聚碳酸酯型聚氨酯脲弹性体的合成与表征

以聚碳酸酯二醇(PCDL),六亚甲基二异氰酸酯(HDI)为预聚原料,3,3′-二氯-4,4′-二氨基二苯甲烷(MOCA)为扩链剂,两步法合成了一系列不同硬段含量的聚氨酯脲(PUU)弹性体。采用傅里叶变换红外光谱仪(FTIR)、强力拉伸仪等测试手段对其结构特征和材料的力学性能以及耐水性能进行了研究。结果表明,随着硬段含量的增加,材料的拉伸强度先增大后减小最后又增大,而断裂伸长率和吸水率呈现相反的趋势,并以硬段含量47%为分界点。     

Preparation and properties of poly HTBN-based urethane--urea/organo reactive montmorillonite nanocomposites

With ultrasonic assistant mixing way, an intercalated mixture of polyol/organo reactive montmorillonite (ORMMT) was pretreated. The prepolymer composed MMT clay was prepared by reaction of polyol/ORMMT mixture with toluene diisocyanate (TDI). The resultant prepolymer reacted with extender (DMTDA) and then the polyurethane--urea/organo reactive montmorillonite (PUU/ORMMT) nanocomposites were obtained. The structure, morphology and properties of PUU/ORMMT nanocomposites were characterized by FT-IR, TEM, AFM, strain-stress machine, TGA, and dynamic mechanical analysis (DMA). The results showed that when the OMMT content is 3%, the PUU/ORMMT nanocomposities performed super mechanical properties. Because of the presence of ORMMT, both T_g of the soft segment and tanδ of the PUU increased, and the decomposition temperature for the first step and the second step increased respectively. TEM images showed that the organophilic MMT particles in the PUU composite exhibit a high degree of intercalation and exfoliation.     

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...