HMMM树脂改性水性聚氨酯的制备及性能

以聚己二酸丁二醇酯二醇(PBA)、异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)、1,4-丁二醇(BDO)、环氧树脂E51等为原料制备含环氧基团的水性聚氨酯(WPU)乳液。在对甲苯磺酸(PTS)存在下,用六甲氧基亚甲基三聚氰胺树酯(HMMM)对其改性,合成了改性WPU乳液。研究了HMMM用量对WPU乳液和膜性能的影响。结果表明,随着HMMM用量增加,WPU乳液粒径增大,黏度减小; HMMM能明显提高WPU固化膜的性能,HMMM添加量增加,WPU膜的拉伸强度、硬度、耐热性和耐水性能明显提高。当HMMM加入量为WPU固体分的8%时,WPU的综合性能最优。     

水性聚氨酯的环氧共聚改性研究

采用环氧树脂(EP)对水性聚氨酯(WPU)进行改性,通过自乳化法合成了EP改性的WPU.探讨了EP的加入方式、用量以及亲水剂等因素对WPU乳液和涂膜性能的影响.结果表明交联反应显著提高了乳液膜的硬度及其耐水性、力学性能.用二羟甲基丁酸(DMBA)替代二羟甲基丙酸(DMPA)作亲水剂制备的改性WPU乳液,其乳液性能、涂膜的硬度及其耐水性能更佳.     

手套涂饰剂用水性聚氨酯乳液的研制

以聚醚二元醇(N220、N240)、聚醚三元醇(N330)、甲苯二异氰酸酯(TDI)、二羟甲基丙酸(DMPA)、三羟甲基丙烷(TMP)和蓖麻油(C.O)等为原料,采用丙酮法合成出水性聚氨酯(WPU)乳液。着重探讨了R值、C.O和TMP用量等对WPU乳液及成膜性能的影响。研究结果表明,当R值为5、m(N220):m(N240)=1:1、选择8%C.O作为交联剂时,所合成的WPU乳液外观好、拉伸强度大、断裂伸长率适中、附着力优良、胶膜光滑细腻丰满且符合手套涂饰剂的涂层要求;与国外同类产品相比,由该WPU乳液所配制的手套涂饰剂的透气性能和价格更胜一筹,完全可以替代同类进口产品。     

HDI型水性聚氨酯胶粘剂的制备与性能研究

以聚酯二元醇、二异氰酸酯(HDI)与2,2-二羟甲基丙酸(DMPA)为主要原料,采用丙酮法合成了HDI型水性聚氨酯(WPU),探讨了亲水扩链剂DMPA用量对WPU乳液粒径、耐水性、耐热性及剥离强度等性能的影响。结果表明:随着DMPA含量不断增加,WPU乳液粒径减小,WPU膜的吸水强度、耐热性和剥离强度先升高后降低。当R(NCO/OH)值为2.226,扩链剂DMPA的加入量为3.5~4%时,可获得综合性能较好的水性聚氨酯。     

环氧蓖麻油改性水性聚氨酯乳液的制备及其胶膜性能研究

以4,4′-二苯甲烷二异氰酸酯(MDI)、聚乙二醇(PEG)和二羟甲基丙酸(DMPA)等为主要原料,环氧蓖麻油(ECO)为交联改性剂,制备了ECO改性WPU(水性聚氨酯)乳液。研究结果表明:ECO中的羟基和环氧基均参与了WPU的合成反应;随着ECO掺量的不断增加,WPU胶膜的疏水性、拉伸强度及热稳定性提高,WPU乳液的粒径逐渐变大、外观和储存稳定性变差;当w(ECO)=5.5%(相对于预聚体质量而言)时,WPU乳液呈微透明(泛蓝)状,WPU胶膜的综合性能相对最佳。     

羟烷基聚二甲基硅氧烷改性水性聚氨酯的制备及性能研究

以羟烷基封端聚二甲基硅氧烷(PDMS)、聚氧化丙烯二醇N220、异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)和1,4-丁二醇(BDO)为主要原料,制备了改性水性聚氨酯(WPU)乳液,研究了PDMS用量对其乳液性能、固化膜机械性能和表面性能的影响。结果表明,随PDMS用量的增加,WPU乳液粒径先增大后减小,而其粘度先降低后增加。PDMS改性WPU能明显改善固化膜的性能,增加PDMS的用量,固化膜的拉伸强度、硬度和耐水性及光泽度提高,透光度、耐热性和断裂伸长率降低。当软段中PDMS质量分数为20%时,WPU的综合性能最优,在光泽度、耐水、透光率和力学性能方面明显优于羟基硅油改性样品。     

合成革用自消光水性聚氨酯树脂的制备和表征

以聚四氢呋喃二醇(PTMEG)、聚己二酸丁二醇酯二醇(PBA)、异佛尔酮二异氰酸酯(IPDI)为单体,二羟甲基丙酸(DMPA)为亲水扩链剂,三羟甲基丙烷(TMP)为交联单体制备了自消光水性聚氨酯(WPU)树脂乳液。采用傅立叶红外光谱仪、金相显微镜以及粒径分布仪对乳液的结构和形态进行了表征。考察了预聚体R值、DMPA用量对WPU乳液粒径和稳定性的影响,以及TMP用量对自消光WPU树脂消光度和耐热性的影响,并对自消光WPU合成革表面的性能进行了测试。结果表明,预聚体R值为1.9~2.0、DMPA和TMP质量分数分别为1.5%和0.2%~0.4%时,可以得到消光度高、粒径均匀、状态稳定的自消光WPU树脂,用于合成革表面处理具有良好的使用性能。     

油墨用水性聚氨酯乳液的制备及性能研究

以聚醚二元醇、甲苯二异氰酸酯(TDI)和二羟甲基丙酸(DMPA)为原料,制备了聚醚型芳香族水性聚氨酯(WPU)乳液,研究了R值[n(-NCO)∶n(-OH)]、DMPA用量、中和度和温度等对乳液外观、黏度、吸水率和稳定性等影响。结果表明:当R=2.0～2 5、w(DMPA)=5%、预聚温度为80℃和中和温度为40℃时,WPU乳液符合印刷油墨的使用要求。     

环氧树脂改性水性聚氨酯乳液的研究

以甲苯二异氰酸酯(TDI-80)、聚醚二醇(N220)、二羟甲基丙酸(DMPA)、环氧树脂(EP)和1,4-丁二醇(BDO)等为主要原料,合成了EP改性的水性聚氨酯(WPU)乳液。试验结果表明:加入EP后,WPU分散体粒径增大,粒径分布变宽;FT-IR分析验证了EP中的羟基和环氧基完全参与反应,并且生成了EP改性WPU;随着EP用量的增加,胶膜的硬度、耐水性、耐溶剂性及力学性能增强,但乳液外观和稳定性变差,故w(EP)≈4.0%时较适宜;当w(DMPA)=5.0%时,乳液呈微透明状,储存稳定性极佳。     

环氧树脂改性水性聚氨酯乳液的研究

先以异佛尔酮二异氰酸酯(IPDI)、聚氧化丙烯二醇(PPG2000)和二羟甲基丙酸(DMPA)为主要原料合成预聚体,再加入环氧树脂(E44或E51)接枝共聚改性制备了水性聚氨酯(WPU)乳液。探讨了不同环氧树脂及含量对WPU性能的影响,并对乳液稳定性、力学性能、吸水率、接触角和热性能等进行了测试和表征。结果表明,适量的环氧树脂改性的WPU乳液比较稳定;随着环氧树脂含量的增加,乳液粒径和黏度增大,同时涂膜的拉伸强度增大,断裂伸长率下降,吸水率下降,水接触角增大,涂膜的高温分解残余量增加。E44质量分数在6%~8%时,改性WPU乳液综合性能较好。     

新型磺酸盐水性聚氨酯乳液的合成及其性能研究

以聚己二酸乙二醇酯二元醇、甲苯二异氰酸酯、乙二胺基己磺酸钠(N60)等为主要原料,制备了一系列不同N60用量的磺酸盐型水性聚氨酯(WPU)乳液。研究了N60用量对WPU乳液及其胶膜性能的影响,并通过FT-IR、TEM、TGA等方法进行表征。结果表明,磺酸盐型WPU乳液的贮存、冻融、高温稳定性均较好。随N60用量的增加,磺酸盐型WPU乳液粒径先减小后增大,粒径分布变窄,胶膜的拉伸强度、吸水率呈上升趋势、断裂伸长率下降。TEM图显示微粒分散性好,呈球形;相对于羧酸型WPU,磺酸盐型WPU胶膜的拉伸强度提高,热稳定性更好。     

基于羧酸-磺酸盐的聚氨酯乳液的制备及性能研究

以二羟甲基丙酸(DMPA)和1,2-二羟基-3-丙磺酸钠(DHPA)为亲水扩连剂制备含有磺酸基团的水性聚氨酯微乳液。利用傅立叶变换红外光谱(FT-IR)对DHPA和水性聚氨酯的结构进行表征,证实了目标产物DHPA的生成,并作为亲水扩链剂引入PU链上。研究表明,随着DHPA含量增大,乳胶粒平均粒径减小,粒径分布宽度变窄。聚氨酯乳液呈假塑性流体特征。所制得的聚氨酯表面活性剂对丙烯酸单体具有良好的乳化性能,可用于乳液聚合中。     

High-gravity-assisted emulsification for continuous preparation of waterborne polyurethane nanodispersion with high solids content

In this work, we developed a continuous preparation strategy for the production of high-solids-content waterborne polyurethane (WPU) emulsions via high-gravity-assisted emulsification in a rotating packed bed (RPB) reactor. By adjusting the experimental parameters and formula, WPU emulsions with a high solids content of 55% and a low viscosity were prepared. Preliminary applications of the high-solids-content WPU as a thermally insulating material were demonstrated. RPB emulsification is an economical and environmentally friendly production strategy because of the low energy consumption, short emulsification time, and effective devolatilization. This study demonstrated an effective method for preparation of high-solids-content WPU, moving toward commercialization and industrialization.     

Preparation and properties of emulsifier-/solvent-free slightly crosslinked waterborne polyurethane-acrylic hybrid emulsions for footwear adhesives (III)–effect of trimethylol propane (TMP)/ethylene diamine (EDA) content

Stable emulsions of emulsifier-/solvent-free slightly crosslinked waterborne polyurethane-acrylic hybrids (WPU/AC-Ts) with a fixed acrylic monomer content (20 wt.%) and different trimethylol propane (TMP)/ethylene diamine (EDA) (0/0.20, 0.02/0.17, 0.04/0.14, 0.06/0.11, 0.08/0.08, the number indicated the mole% of TMP/EDA) for footwear adhesive materials were successfully prepared in this study. The as-polymerized hybrid emulsion containing 0.10/0.05 mole% of TMP/EDA content was found to be unstable, indicating that near 0.10/0.05 mole% of TMP/EDA content was beyond the limit value of crosslinkable TMP component for self-emulsifing. This study examined the effect of mole% of TMP/EDA on the stability and viscosity of hybrid emulsions, the tensile properties and dynamic mechanical thermal properties of hybrid film samples, and the adhesive strengths of formulated adhesives for footwear at both dry and wet states. As TMP content increased, the tensile strength/modulus/storage modulus/hardness of WPU/AC-Ts film samples increased, however, their elongation at break and water swelling% decreased significantly. The adhesive strength (peel strength) of formulated adhesives was found to be dependent upon the degree of drying, but almost not upon the TMP content in WPU/AC-Ts. The adhesive strength of footwear (EVA/leather) dried at room temperature for 24 h was higher than that of footwear dried for 30 min. However, the adhesive strength at wet state increased significantly with increasing TMP content. The optimum TMP/EDA contents were found to be 0.06/0.11 and 0.08/0.08 mole% to achieve the desired high performance adhesive properties such as high strength in wet state.     

有机氟硅共改性水性聚氨酯乳液的合成及其性能

将异佛尔酮二胺(IPDA)和甲基丙烯酸十二氟庚酯(DFMA)进行Micheal加成反应,合成端仲胺基的有机氟化合物(DFMA-IPDA)。以该化合物为扩链剂、聚醚改性聚二甲基硅氧烷(PDMS)为二元醇,与异佛尔酮二异氰酸酯(IPDI)、聚氧化丙烯二醇(PPG)、二羟甲基丙酸(DMPA)聚合制备了有机氟和硅改性的水性聚氨酯(WPU),研究了有机氟和/或硅用量对WPU乳液性能和胶膜性能的影响。结果表明:用该方法合成的DFMA-IPDA纯度达99.2%,和一定量的PDMS共改性可合成稳定的WPU乳液。随两者用量的增加,WPU乳液的平均粒径增大,胶膜的热稳定性、耐水性提高,表面水接触角增大。PDMS可提高WPU胶膜的柔性,而DFMA-IPDA可提高胶膜的韧性。用PDMS和DFMA-IPDA共改性能获得综合性能优异的WPU,当扩链剂完全采用DFMA-IPDA,PDMS用量为4%时,WPU胶膜的吸水率为4.5%,水接触角达到102.3°。     

Effect of nanosilica content on properties of polyurethane/silica hybrid emulsion and its films

Polyurethane/silica hybrid emulsion (PUSi) was synthesized by the reaction of isophorone isocyanate, polyether polyol, hydrophilic nanosilica (A200), dimethylol propionic acid, trimethylol propane, and 3‐aminopropyltriethoxysilane (KH550). The films of the waterborne polyurethane (WPU) were prepared. The structure of the polyurethane was characterized by Fourier transform infrared spectrometer (FTIR), thermogravimetry (TG), and differential scanning calorimetry (DSC). The particle size distribution and morphology of emulsion were examined. Influence of nanosilica content on the mechanical properties and solvent absorption of the cast films were also measured quantificationally. FTIR indicates that  NH₂ of KH550 reacted with  NCO of polyurethane. TG analysis indicates that nanosilica can improve thermal stability of polyurethane. There is no clear effect of nanosilica on the glass transition of soft segments. It was found that greater mechanical properties of WPU were obtained when chemical networks were formed by sol‐gel process. As the nanosilica content increases, water absorption and ethanol absorption decreased. The particle size increases with increase of A200 content. PUSi hybrid emulsions are endowed with pseudoplasticity. The apparent viscosity of emulsions increased and then decreased with addition of A200. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of Waterborne polyurethane/nanosilica composites: A diol as extender with triethoxysilane group

Waterborne polyurethane (WPU) was prepared from toluene diisocyanate, polypropylene glycol, 2,2‐bis(hydroxymethyl)propionic acid and a diol containing triethoxysilane group as the chain extender which was synthesized via Michael addition between 3‐triethoxysilylpropylamine and 2‐hydroxyethylacrylate. Different amounts of nanosilica were incorporated into the WPU to prepare WPU/nanosilica composites. The results showed that the particle size of the emulsions increased and their viscosity decreased first and then increased with increasing the amount of nanosilica. Incorporation of nanosilica into WPU enhanced the water contact angle and thermal stability of the composites films, meanwhile, their tensile strength and hardness increased first and then decreased. However, increasing the amount of nanosilica resulted in reduction in the elongation at break of the films. It suggested that nanosilca was anchored into the side chain of WPU due to the condensation process between the triethoxysilane group in the side chain of WPU molecular and the silanols group on the surface of nanosilica. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40526.     

无卤阻燃硅溶胶改性水性聚氨酯的研究

以聚醚(N -210)、异佛尔酮二异氰酸酯(IPDI)为基本单体,一缩二乙二醇(EX)为扩链剂,二羟甲基丙酸( DMPA)为亲水扩链剂,制备出固含量为30％的水性聚氨酯(WPU)乳液.采用机械分散的方式将纳米硅溶胶按计量加入到WPU乳液中,得到一系列硅溶胶改性的WPU乳液.研究表明,硅溶胶在WPU中分散得比较均匀,硅溶...     

水性聚氨酯/聚甲基丙烯酸甲酯杂化乳液的合成

用异佛尔酮二异氰酸酯(IPDI)、聚丙二醇(PPG)和二羟甲丙酸(DMPA)合成了水性聚氨酯分散体(WPU),讨论了PPG摩尔质量,NCO/OH及PPG/DMPA比例对WPU乳液和涂膜性能的影响。以WPU为种子与甲基丙烯酸甲酯进行乳液聚合制备杂化乳液,研究了不同PU/PMMA物质的量比例对杂化乳液及涂膜性能的影响,并采用TEM对WPU及杂化乳液粒子进行了表征。结果表明,在以PPG1000为原料,NCO与OH物质的量比为1.4∶1,PPG与DMPA物质的量比为1∶0.8条件下制备的WPU杂化乳液,随着PMMA比例增加,杂化乳液的稳定性和成膜性变差,聚合物膜断裂伸长率降低,但铅笔硬度、耐水性及耐乙醇性均得到了改善。     

纺织整理剂用封端型脂肪族水性聚氨酯的合成与性能研究

以异佛尔酮二异氰酸酯(IPDI)、聚醚多元醇、二羟甲基丙酸(DMPA)为主要原料,采用NaHSO3封端,合成了系列脂肪族水性聚氨酯(WPU)乳液,研究了脂肪族WPU中软段类型、Nnco/Noh、DMPA用量以及NaHSO3用量对乳液及其胶膜相关性能的影响.结果表明,当使用聚醚多元醇GMN3050、Nnco/Noh为1.8、DMPA的质量分数为5.5%、nNaHSO3/Nnco为1.1时,得到的封端型脂肪族水性聚氨酯综合性能最好.