水性聚氨酯胶粘剂及其在包装领域的应用

分析了反应原料及其用量对水性聚氨酯乳液性能的影响,综述了水性聚氨酯胶粘剂研究进展及其在包装领域的应用,指出初始异氰酸基(NCO)与羟基(OH)摩尔比为3.5,总量的异氰酸基(NCO)与羟基(OH)摩尔比在1.2～1.8之间,中和剂三乙胺(TEA)与二羟甲基丙酸(DMPA)的摩尔比为(0.73～0.78): 1,有机锡类催化剂用量在0.1%～0.2%之间,DMPA含量在3%～8%之间,水性聚氨酯乳液性具有较优异的性能.     

聚氨酯-丙烯酸酯-苯乙烯复合水分散液的粒径及形态

采用原位乳液聚合法制备了水性聚氨酯-丙烯酸酯-苯乙烯(WPUAS)复合水分散液,研究了NCO/OH摩尔比、PU预聚物/MMA/ST质量比、羧基含量及羧基中和度对分散液粒子尺寸及形态的影响。结果表明,NCO/OH摩尔比减小、羧基含量增大及羧基中和度提高,都会导致分散液粒径减小;PU/(MMA+ST)质量比越小,粒径越大,粒子形态越不规整;MMA/ST质量比的变化对粒径影响不明显。     

内交联水性聚氨酯涂膜性能的影响因素

以异氟尔酮二异氰酸酯、1,6-己二异氰酸酯、二羟甲基丙酸、聚氧化丙烯二醇和聚己二酸-1,4丁二醇酯为原料,合成了一系列内交联水性聚氨酯分散体(WPU)。研究了NCO/OH物质的量比和内交联剂三羟甲基丙烷(TMP)用量对水性聚氨酯涂膜性能的影响,并通过红外光谱(FT-IR)、接触角测量、热重分析(TGA)和X射线衍射(XRD)等对涂膜性能进行了表征。实验结果表明,NCO/OH物质的量比和TMP含量的增加均会使涂膜拉伸强度增加。XRD分析表明,软段微区的结晶性能随着二羟甲基丙酸(DMPA)含量的增加而减小,当DMPA的质量分数增加至5.6%时,软段微区表现出非晶态。     

环氧改性水性聚氨酯的合成及因素分析

用异佛尔酮二异氰酸酯(IPDI)、聚丙二醇2000(PPG2000)、2,2-双(羟甲基)丙酸(DMPA)为主要原料合成预聚体,环氧树脂(E44)开环合成环氧改性水性聚氨酯(EWPU),考察了不同影响因素对EWPU乳液及胶膜性能的影响。首先,通过FT-IR证实了环氧改性水性聚氨酯的合成;然后,经过TG测试证明了改性后水性聚氨酯耐热性能优于水性聚氨酯;最后详细探究了DMPA量、—NCO与—OH的摩尔比(R值)、硬单体配比以及环氧量对EWPU乳液粒径、贮存稳定性、涂膜耐水性、涂膜耐磨性和力学性能的影响。结果表明,当DMPA量为5%、R值为1.5、硬单体配比为35%、EP量为8%时,EWPU乳液的综合性能最优。     

正交试验优选水性聚氨酯合成的最佳工艺条件

以聚酯多元醇、甲苯二异氰酸酯TDI、二羟基甲基丙酸DMPA为主要原料合成了水性聚氨酯。以聚酯多元醇的种类、n(NCO):n(OH)和DMPA含量为主要影响因素,并以各因素对BOPP薄膜剥离强度的影响为考核指标,采用L9(33)正交试验优选水性聚氨酯合成的最佳工艺条件。研究结果表明:当树脂为聚己二酸1,4丁二醇酯二醇、n(NCO):n(OH)为1.3,DMPA的添加质量分数为10%时,所制得的水性聚氨酯对BOPP薄膜的黏结性能最好。     

聚己内酯三醇型水性聚氨酯胶黏剂的合成及性能

以三羟甲基丙烷(TMP)引发ε-己内酯(ε-CL)开环聚合,制得支化结构的聚己内酯三醇(PCL),以此为软段,异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)为主要原料,合成了主链为交联结构的水性聚氨酯胶黏剂(WPU)。讨论了R值(NCO/OH)、DMPA含量,聚己内酯三醇相对分子质量对水性聚氨酯乳液及胶膜性能的影响。结果表明,当R值为2.5、二羟甲基丙酸的质量分数为4%~5%、聚己内酯三醇的相对分子质量为1500、中和度为100%时,制得的乳液贮存稳定,粒径较小,胶膜的成膜手感较好,并具有较好的耐水性及力学性能。胶膜在270℃以下具有较好的热稳定性。     

高性能水性聚氨酯弹性体制备及在水性油墨中的应用

以聚四亚甲基醚二醇(PTMEG)、异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)和三羟甲基丙烷(TMP)为主要原料,通过预聚物分散法制备出高性能水性聚氨酯弹性体。研究了R值[n(—NCO)∶n(—OH)]的变化,并着重考察了TMP用量对乳液外观、黏度、抗水性、稳定性和断裂伸长率等影响。结果表明:当R值=1.6、TMP=1.8%(wt,质量分数)时,制得的水性聚氨酯弹性油墨具有最佳的性能。     

MDI-50型水性聚氨酯的合成及应用

以2,4’-二苯基甲烷二异氰酸酯和4,4’-二苯基甲烷二异氰酸酯的混合物(MDI-50)为硬段,二羟甲基丙酸(DMPA)为水性扩链剂,聚碳酸酯二醇(PCDL)和聚丙二醇(PPG)为软段,合成了一系列的单组分水性聚氨酯乳液;研究了-NCO与-OH的摩尔比、DMPA的含量以及PCDL与PPG质量比对固化胶膜力学性能的影响,并将其涂覆在棉织物表面后,对涂层织物进行了扫描电镜观察、表面接触角测试。结果表明,随着-NCO与-OH的摩尔比、DMPA的含量以及PCDL与PPG质量比的增大,胶膜的拉伸强度都随之增大,断裂伸长率都随之减小;而涂覆有水性聚氨酯乳液的织物表面形貌平整,且接触角均大于90°,表现出良好的疏水性。     

木质素改性水性聚氨酯胶膜的制备与性能

以异佛尔酮二异氰酸酯(IPDI)和聚四氢呋喃醚二醇(PTMG)为主要原料,碱木质素(LG)为改性剂,二羟甲基丙酸(DMPA)为亲水扩链剂,合成了一系列木质素改性水性聚氨酯(LWPU)。研究了LG用量、n(NCO)/n(OH)及DMPA用量对LWPU胶膜力学性能和耐水性能的影响。结果表明,当LG质量分数为0.75%,n(NCO)/n(OH)为5∶1,DMPA质量分数为6%时,胶膜的综合性能较好,其吸水率仅为3.24%,耐水性能明显提高。通过红外光谱、热重分析、X射线衍射及原子力显微镜和扫描电镜对LWPU胶膜的结构与性能等进行了表征,热重分析结果表明,LG的加入可提高聚氨酯材料的热稳定性。加入适量的木质素可以改善水性聚氨酯的耐水性及热稳定性。     

高度支化水性聚氨酯的合成及性能EI

以甲苯-2,4-二异氰酸酯(TDI)、聚碳酸酯二醇(PCDL)、二羟甲基丙酸(DMPA)和聚醚胺(ATA)为原料,采用A2+B3法合成了具有高度支化结构的水性聚氨酯(HBAPU)乳液。用红外光谱(FT-IR)对产物结构进行表征;用光子相关光谱(PCS)研究了乳液的稳定性能,NCO/OH=1.3,w(DMPA)=6%时可以得到稳定的HBAPU乳液;采用旋转黏度计、差式扫描量热仪(DSC)、热失重分析仪(TG)、电子拉力机对产物的流变行为和各种性能进行了测试。结果表明,相对于线性水性聚氨酯(LAPU),HBAPU产物具有较低的黏度、良好的热稳定性、较高的Tg和拉伸强度。     

聚氨酯与聚丙烯酸酯混合乳液(PU+PA)共聚氯乙烯复合树脂的性能研究

采用预聚体分散法,以甲苯2,4-二异氰酸酯(TDI)、聚醚(PPG)和二羟甲基丙酸(DMPA)为主要原料,用三乙胺(TEA)为中和剂合成了阴离子水性聚氨酯(PU);以丙烯酸丁酯(BA)为原料,采用乳液聚合的方法制备聚丙烯酸酯乳液(PA),并与PU共混形成(PU+PA)混合乳液。在高压釜中以混合乳液为种子进行氯乙烯(VC)原位共聚,制备了(PU+PA)/PVC复合乳液树脂。通过电子万能试验机、冲击试验机、扫描电子显微镜(SEM)、TA-2000热分析仪和维卡软化点温度测定仪等手段对(PU+PA)/PVC复合树脂进行了测试和表征。结果表明:耐热性较好的PA的加入,不但提高了材料的耐热性能,还能有效地改善复合树脂的抗缺口冲击强度。当PA/PU为4/6,聚醚分子量为3000时,(PU+PA)/PVC复合树脂的缺口冲击强度最大。     

Correlation of Raw Materials and Waterborne Polyurethane Properties by Sequence Similarity Analysis

Anionomer-type waterborne polyurethane dispersions(PUDs) were obtained from poly(propylene glycol)(PPG), isophorone diisocyanate(IPDI) and dimethylolpropionic acid(DMPA) through a modi?ed prepolymer isocyanate process. Two series of polyurethanes were prepared(Groups A and B) and a new prediction model based on grey relational analysis is introduced to predict the impact order of raw materials on several properties, such as solids content, viscosity, acid number and electrolytic stability of polyurethanes. It is found that the model can successfully predict the impact of raw materials on the properties through the designed demonstration experiments. Furthermore, the results of the prediction model show that DMPA plays a key role in viscosity, partial acid values and electrolytic stability.     

超支化水性聚氨酯的合成与表征

以甲苯-2,4-二异氰酸酯(TDI)、聚碳酸酯二醇(PCDL)、二羟甲基丙酸(DMPA)和二乙醇胺(DEOA)为原料合成了一种具有超支化结构的水性聚氨酯,产物具有良好的水溶性。通过红外光谱(FT-IR)和核磁共振(13C-NMR)对产物结构的表征,证实了产物具有超支化结构,其支化度为0.32。用高效液相色谱质谱联用仪(LC-MC)对产物的分子量进行测定,其重均分子量为1.66×104。采用电子拉力机和热失重分析仪(TG)对产物的性能进行测试,结果表明,所制备的水性超支化聚氨酯具有良好的力学性能和热稳定性,并且涂膜具有较好的耐水性。     

交联改性阴离子聚氨酯水分散体的制备与性能研究

由甲苯二异氰酸酯（TDI）、聚己内酯二醇（PCL）和二羟甲基丙酸（DMPA）反应,再与高醚化度甲醇醚化三聚氰胺甲醛树脂（HMMM）反应,制备了一种交联型阴离子水性聚氨酯。采用红外光谱对样品进行表征,并讨论了交联改性对聚氨酯乳液粒径分布、胶膜耐水性、力学性能、热稳定性及结晶度的影响。红外分析证实HMMM与聚氨酯发生了交联反应。当m（HMMM）∶m（—COOH）=2.25时,胶膜拉伸强度达到30.3MPa,吸水率为17.2%,吸乙醇率为10.9%,与水接触角为69.6°,Tmax（最快分解温度）为301.5℃,结晶度为1.10%。     

超支化水性聚氨酯的合成与表征

以异佛尔酮二异氰酸酯(IPDI)、二乙醇胺(DEOA)及二羟甲基丙酸(DMPA)为原料,合成超支化聚氨酯核HBPU-0;以IPDI、聚四氢呋喃(PTMEG)及DMPA等原料合成线性聚氨酯,然后,将线性聚氨酯接枝到HBPU-0上,制备了一种具有超支化结构的水性聚氨酯,产物具有良好的水分散性和耐水性,其中HBPU-6的24h吸水率为6%,48h吸水率为11%,72h吸水率为18%。通过红外光谱对产物结构进行了表征。采用电子万用试验机和热失重分析仪对产物的性能进行测试,结果表明,所制备的水性超支化聚氨酯具有良好的力学性能和热稳定性,HBPU-6的拉伸强度为16.8MPa,热分解温度达到238℃。     

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.     

氧化石墨烯共价杂化水基聚氨酯电沉积树脂的制备及性能

采用超声波辅助反应技术,实现了甲苯二异氰酸酯(TDI)对氧化石墨烯(GO)的改性,成功制备了异氰酸酯共价改性的NCO@GO碳材料。采用原位聚合法制备出GO共价杂化水性聚氨酯,并与交联剂混合后得到聚氨酯(PU)电沉积涂料。利用红外光谱分析了GO改性前后及GO/PU电沉积树脂的特征官能团,用热失重研究了GO/PU电沉积树脂的热稳定性,X射线衍射研究了GO/PU电沉积树脂中GO层间效应,透射电子显微镜表征了GO/PU电沉积树脂的形态,电导率仪测试了漆膜的导电率,研究了氧化石墨烯含量对聚氨酯漆膜外观和性能的影响。结果表明,随着GO含量的增加,水性聚氨酯漆膜的导电性、光泽度、硬度和耐酸性表现出先增大后降低的规律。当石墨烯的质量分数为0.75%时,石墨烯在水性聚氨酯树脂及其乳液中具有较好的分散性,漆膜的导电性、光泽度、硬度和耐酸性等性能达到最佳。     

Crosslinked aqueous dispersion of silylated poly (urethane–urea)/clay nanocomposites

Stable water-borne crosslinked silylated poly (urethane–urea) (CSPU)/clay nanocomposites, reinforced with various amounts of the organically modified clay, were prepared by a polyaddition reaction of toluene diisocyanate (TDI) or isophorone diisocyanate (IPDI), polytetramethylene glycol and dimethylol propionic acid. This was followed by end-capping the free NCO groups of the PU prepolymer with phenylamino propyl trimethoxysilane and self-crosslinking. The particle size, viscosity and storage stability of these nanocomposites were measured. The particle size and viscosity of the IPDI-based nanocomposites were higher than the TDI-based ones. Intercalation of the silicate layer in the CSPU matrix were conformed by X-ray diffraction pattern and transmission electron microscopy studies. The mechanical properties of the SPU/clay nanocomposites were tested by tensile, dynamic mechanical, and nano-indentation measuring techniques and the respective properties were found to be enhanced by the reinforcing effect of organophilic clay. Modulus and hardness increased with an increase in the clay content in the CSPU matrix. Thermal stability, water and xylene resistance of the nanocomposites increased, as compared to pure CSPU and these properties increased with an increase in clay content. The mechanical properties, water and xylene resistance of the TDI-based nanocomposites were higher compared to the IPDI-based nanocomposites. A marginal reduction in transparency was observed with the addition of clay. Storage stability results confirmed that the prepared nanocomposite dispersions were stable.     

水性聚氨酯的硬段结晶与粘接性能

将HDI与IPDI按照不同的摩尔比混合后与PTMG-2000、1,4-BG、DMPA反应,制备了具有不同硬段规整度的系列水性聚氨酯;利用WXRD、DSC、FT-IR等研究了HDI对水性聚氨酯的硬段结晶性能的影响,分析了硬段结晶度与粘接性能之间的关系。结果表明,随着HDI/IPDI摩尔比的增加,水性聚氨酯分子链上氨基甲酸酯键之间氢键密度提高,硬段结晶性能也随之改善;对铝箔的初粘接强度显著增强,最终粘接强度可达8.5 MPa左右。