湿固化聚氨酯热熔胶研究进展

概述了目前反应型湿固化聚氨酯热熔胶的应用和研究方向，介绍了改善热熔胶的初粘强度、韧性、耐热性等性能的方法，以及国内外在聚氨酯预聚体、增韧树脂、增粘树脂、催化剂、添加剂等方面取得的一些研究进展。     

湿固化聚氨酯热熔胶的合成与表征

以多异氰酸醋PAPI和自制多元醇为原料,采用熔融缩聚法合成出了一种具有快速粘接定位功能的新型反应性热熔胶,并利用FTIR、DSC和力学性能测试等手段对产品进行了表征。结果表明,合成产品不仅具有合理的结构特征,而且还具有良好的使用性能和耐热性能。     

单组分湿固化聚氨酯胶粘剂

概述了单组分湿固化聚氨酯胶粘剂在预聚体、改性剂及其它助剂等方面的研究现状,并指出了该类胶粘剂将向环保型胶粘剂发展的趋势。     

单组分湿固化型聚氨酯密封胶催化剂的研究

单组分湿固化型聚氨酯密封胶是一种发展前景很好的密封胶 ,而催化剂是影响其性能的重要因素之一。本文讨论了该类密封胶所用催化剂的种类及其催化效果以及催化剂对材料发泡性的影响     

单组分湿固化聚氨酯胶粘剂的研究进展

介绍了单组分湿固化型PU(聚氨酯)胶粘剂的发展概况,讨论了该类胶粘剂预聚体的合成方法。重点介绍了两种新型单组分湿固化PU胶粘剂(硅氧烷封端湿固化PU胶粘剂和潜性湿固化PU胶粘剂),并展望了其发展前景。     

Self-curing behaviors of single pack aqueous-based polyurethane system

A di- or triaziridinyl compound served as the latent curing agent for the prepared carboxylic groups containing aqueous-based polyurethane (PU) dispersions. It was formulated as a single pack self-curable aqueous-based PU system. This system was stable under an alkaline environment and its curing reaction could be initiated by a pH control. A model reaction between a monoaziridinyl compound and formic acid was demonstrated and identified by infrared spectrophotometry. The stabilities of this convenient one-package PU system with a different dosage of di- or triaziridinyl latent curing agent were monitored by a particle sizer and fluorescence spectroscopy. The PU films were cast and self-cured from these single pack PU dispersions at ambient temperature. The physical and mechanical properties as well as thermal behaviors of each self-cured PU were evaluated. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1609–1623, 1997     

Synthesis of 2‐phenyl‐3‐hydroxyethanyl‐1,3‐oxazolidine and its application as latent curing agents

A kind of new compound of 2‐phenyl‐3‐hydroxyethanyl‐1,3‐oxazolidine was successfully synthesized by addition–condensation reaction of phenyl aldehyde and β‐hydroxylethanolamine and purified by vacuum distillation. Its purity was examined by gas chromatographic analysis. Its structure was confirmed by ¹³C NMR and FTIR. When this compound was added as a latent curing agent in single‐component moisture‐curable polyurethane system (SPU), bubbles of SPU formed during curing was obviously restrained, and the elongation at break of the cured SPU contained a certain content of 2‐phenyl‐3‐hydroxyethanyl‐1,3‐oxazolidine was increased to 16 times when compared with that uncontained this oxazolidine derivative. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

UV固化三官能脂肪族聚氨酯丙烯酸酯的合成

以HDI、三官能团聚酯(PE)、丙烯酸羟乙酯等合成了可以紫外光固化(UV)的脂肪族聚氨酯丙烯酸酯低聚物。研究了反应温度、羟基官能度、加料顺序等对产物合成及性能的影响。结果表明,在合成中,温度控制在第1步是45~50℃,第2步在75℃为好,在第1步中加入丙烯酸羟乙酯便于控制平均分子质量。应用表明该聚合物具有韧性、附着力优、硬度好、耐候性好、耐磨等优点。     

湿固化聚氨酯热熔胶的制备

以聚酯/聚醚多元醇、混合异氰酸酯等为主要原料制备反应型PU-HMA(聚氨酯热熔胶)。考察了R值[R=n(-NCO)/n(-OH)]、多元醇种类及含量、制备工艺、催化剂种类及含量等对湿固化PU-HMA性能的影响。结果表明:当R=1.8~2.4、m(聚酯)∶m(聚醚)=65∶35、w(催化剂T12+催化剂DMDEE)=0.05%~0.2%、70℃加入MDI/TDI(二苯甲基二异氰酸酯/甲苯二异氰酸酯)、反应温度为95~100℃、搅拌速率为400 r/min和反应时间为2 h时,相应的环保型湿固化PU-HMA具有良好的综合性能,可用于织物、PET(涤纶)薄膜等材料的粘接。     

超支化聚氨酯丙烯酸酯的合成及其固化膜性能

以合成的甲苯-2,4-二异氰酸酯.丙烯酸羟丙酯(TDI.HPA)单体对超支化聚酯(HBPE)进行端羟基改性,得到超支化聚氨酯丙烯酸酯(HBPUA)。研究了反应温度、时间对产物游离—NCO含量的影响,通过摆杆硬度、附着力、柔韧性、冲击强度等测试研究了活性单体的种类及用量对固化膜性能的影响,并采用FT-IR及TG对HBPE,HBPUA及其固化膜进行了表征和分析。结果表明,合成HBPUA的最佳条件为:n(2,4-TDI):n(HPA):n(HBPE)=6:6:1,反应温度70℃,反应时间3 h,催化剂二月桂酸丁基锡(DBTDL)用量为总质量的0.6%;TDI.HPA的合成反应温度35℃,反应时间2.5 h,DBTDL用量为总质量的0.4%。采用己二醇二丙烯酸酯为活性单体并控制其质量分数为20%时,超支化聚氨酯丙烯酸酯涂膜的力学性能、热稳定性较好。     

湿固化聚氨酯热熔胶发展近况

简要介绍了湿固化聚氨酯热熔胶的特点、应用和发展近况。并对湿固化聚氨酯热熔胶的制备、主要原料的选择及改性途径进行了详细阐述。     

Highly branched polyurethane acrylates and their waterborne UV curing coating

A series of UV curable highly branched waterborne polyurethane acrylates (BWPUAs) were synthesized using an “oligomeric A₂ + B₃” approach. The thiol-endcapped difunctional oligomeric A₂ was synthesized first by the addition reaction of isophorone diisocyanate, α,α-dimethylol propionic acid and 2-hydroxyethyl acrylate, then further underwent thiol-Michael reaction with 1,6-hexamethylene bis(thioglycolic acetate). Trimethylolpropane triacrylate was used as a B₃ monomer. The molecular structures were characterized with FT-IR and ¹H NMR spectroscopy. 1,6-Hexanediol diacrylate (HDDA) was incorporated into the polymeric chain for preparing the HDDA-modified BWPUAs (BWPUA-Hs). For the comparison, the linear waterborne polyurethane acrylate (LWPUA) was synthesized. The UV curing kinetics study results by using the photo-DSC approach showed that the BWPUAs possessed higher photopolymerization rate and final unsaturation conversion in the UV cured films compared with the LWPUA, which increased with the increase of unsaturation concentration in BWPUA. Moreover, the photopolymerization performance, and water and solvent resistance properties were greatly enhanced by the incorporation of HDDA segment into the BWPUA chain. The dynamic mechanical thermal analysis results showed that the elastic modulus in the rubbery plateau, and the glass transition temperature of UV cured film increased with increasing unsaturation concentration in BWPUA, whereas decreased with the introduction of HDDA flexible segment. The thermogravimetric analysis confirmed the high thermal stability of UV cured BWPUA films. All UV cured BWPUA and BWPUA-H films showed better flexibility and middle refractive indices due to the thioether linkage in the polymer network.     

电子束固化水性聚氨酯丙烯酸酯的制备及性能

研究了一种制备水性聚氨酯丙烯酸酯的新方法,通过在扩链剂分子结构中组装离子基团来改善亲水性,解决了聚氨酯丙烯酸酯与水难相溶的问题。采用这种方法制备了一种聚氨酯丙烯酸酯产物,使用FTIR和1H NMR对产物结构进行了表征。对产物与水的储存稳定性、黏度、电子束固化行为及固化后性能进行了研究。结果表明,分散乳液储存稳定性好,经电子束固化后性能(如硬度、附着力、光泽度、柔韧性、热稳定性)优良。     

湿固化聚氨酯热熔拼板胶的研制

对湿固化聚氨酯热熔拼板胶的合成与配方设计进行了研究。通过考察异氰酸酯指数、萜烯树脂、碳酸钙等三个主要因素对湿固化聚氨酯热熔胶开放时间的影响规律,从而确定了各主要组分的最佳配比。     

水性聚氨酯丙烯酸酯的合成及其应用

带羧基的聚酯多元醇与TD I反应生成APU预聚体,再用聚乙二醇单(甲基)丙烯酸酯封端,制得一种水性聚氨酯丙烯酸酯单体(APU),研究了APU单体对预涂厌氧胶强度及乳液稳定性的影响。结果表明,当APU占胶粘剂总质量的25%时,胶粘剂综合性能最佳,破坏力矩/平均拆卸力矩达到25/28 N.m,贮存期可达6个月。     

用硅烷封端的湿固化聚氨酯热熔胶的研制

通过聚氨酯预聚体法合成出硅烷KH-550封端的聚氨酯热熔胶(SPUR),并制备了一系列不同封端率的硅烷化聚氨酯热熔胶。通过红外光谱、表面接触角等检测了SPUR的结构和性能,研究了硅烷对聚氨酯热熔胶粘接性能的影响。结果表明:硅烷提高了SPUR在粘接面的浸润和对铝片的粘接性能,当KH-550封端率达到15％时,粘接性能最佳。     

交联型水性聚氨酯的合成与研究

采用聚醚多元醇、异佛尔酮二异氰酸酯IPDI、2,2-二羟甲基丙酸(DMPA)、三乙胺为主要原料,采用自乳化法合成一系列的水性聚氨酯乳液。考查了预聚温度和预聚时间、扩链时间和扩链温度对反应的影响;R值(n/n)、DMPA的用量和中和度对乳液性能的影响。结果显示,当预聚温度为60℃、预聚时间为60 min、扩-NCO-OH链温度为75℃、扩链时间为120 min时,可以保证反应的速率和生产周期;选择R=2、DMPA用量为3%、中和度为100%,可以制得稳定的、性能优异的水性聚氨酯乳液,可用于织物的防水透湿整理。()     

低一元醇含量聚醚多元醇及其在PU弹性体中的应用

介绍了新型低一元醇含量聚氧化丙烯多元醇的特点及其在聚氨酯弹性体、密封胶等方面的应用性能,指出该类聚醚具有较好的发展前途。     

聚氨酯改性氟代聚丙烯酸酯的合成及应用

将丙烯酸十二氟庚酯(FA),丙烯酸羟丙酯(HpAA)为单体,偶氮二异丁腈(AIBN)为引发剂在聚氨酯预聚体中进行聚丙烯酸酯自由基聚合,然后用丁酮肟(EtAO)进行完全封端,制得新型易去污整理剂聚氨酯改性氟代聚丙烯酸酯(FPUA).FPUA附着在纤维表面时纤维与空气的界面上富集着疏水的含氟链段,能使整理后棉织物与水的接触角达到146.5°,与油的接触角达到132°;当FPUA用量为1.5 g/100 mL H_2O,使用100℃烘5 min后180℃高温焙烘2 min的工艺时,疏水性达到95分,疏油等级6级,易去污可达到5级.     

抗起毛起球整理用热反应型WPU的合成及应用

以异佛尔酮二异氰酸酯（IPDI）、聚多元醇为主要原料,以异丙醇为溶剂,合成了反应型水性聚氨酯整理剂,既保持了聚氨酯的弹性,又具有极好的反应活性,可以赋予织物各种功能,提高纺织品的附加价值。介绍了该类整理剂在纯棉针织物抗起毛起球整理中的应用。