水性聚氨酯印花粘合剂的合成及应用研究

主要研究软段结构、亲水基团含量和n(—NCO)/n(—OH+—NH2)的比值等参数对水性聚氨酯性能的影响。研究表明使用聚酯聚醚共混、亲水基团含量为3%以及n(—NCO)/n(—OH+—NH2)的比值为1.1时,合成的水性聚氨酯用作印花粘合剂性能优异;应用测试表明,合成的水性聚氨酯用作印花粘合剂,总体性能优于市售产品。     

马来酸酐改性蓖麻油制备耐光性聚氨酯复鞣剂——乳液性能研究

用马来酸酐改性蓖麻油(MCO)合成了一系列不同组成的耐光性聚氨酯复鞣剂水乳液(MC-PUR),研究了复鞣剂中—COOH质量分数、n(NCO)/n(OH)、m(MCO)/m(PEG1000)对乳液电导率、黏度、临界聚沉值(CC.C)、耐酸稳定性的影响。结果表明,随—COOH质量分数从3%增大到7%,电导率从1 556μs/cm增大到3 435μs/cm,黏度先从168 mPa.s增大到224 mPa.s,后又降低到85 mPa.s,当w(—COOH)=5%时,黏度达到最大值;随n(NCO)/n(OH)从0.5增大到0.9,电导率从2 943μs/cm降到2 464μs/cm,黏度从428 m Pa.s降到224 mPa.s;随m(MCO)∶m(PEG1000)从1∶1增大到3∶0,黏度从224 mPa.s降到67 mPa.s;CC.C随—COOH质量分数增加和m(MCO)/m(PEG1000)增大而降低;耐酸稳定性结果证明,当w(—COOH)=3%~5%,m(MCO)∶m(PEG1000)=1∶1,n(NCO)/n(OH)=0.5~0.9时,MC-PUR适用于皮革复鞣工序。     

聚酯－ 聚醚复合型水性聚氨酯的制备与性能

以聚碳酸酯二元醇和聚醚二元醇为软段,异佛尔酮二异氰酸酯、扩链剂2,2 － 二羟甲基丙酸( DMPA) 及1,4 －丁二醇为硬段,用预聚法制备了稳定的阴离子型水性聚氨酯乳液及其胶膜,用红外光谱对其结构进行了表征,并研究了DMPA 用量和n( —NCO) /n( —OH) 对聚氨酯乳液稳定性及胶膜性能的影响。结果表明,聚酯－聚醚复合型水性聚氨酯胶膜具有优异的耐水性;在聚酯二元醇与聚醚二元醇的质量比为1 /1 的情况下,当DMPA 质量分数为6%、n( —NCO) /n( —OH) 为1. 3 时水性聚氨酯乳液及其胶膜的综合性能较好。     

聚酯型阴离子水性聚氨酯乳液的合成及性能研究

采用预聚体法,以聚酯多元醇、甲苯二异氰酸酯、二羟甲基丙酸(DMPA)为原料制备了聚酯型阴离子水性聚氨酯乳液,考察了反应温度、反应时间、聚酯多元醇种类、DMPA用量、n(—NCO)/n(—OH)对乳液性能的影响,试验结果表明预聚过程反应温度为75℃,反应时间在120 min;DMPA含量在7%～8%;n(—NCO)/n(—OH)在3.0;采用三乙胺为中和剂,所合成的聚酯型阴离子水性聚氨酯有较好的贮存稳定性,傅里叶红外光谱表征证明了所合成的水性聚氨酯乳液中氨酯基产生明显的氢键行为。     

有机硅环氧树脂对聚氨酯防水涂料结构和耐水性能的影响

以二甲基硅油和环氧树脂对聚氨酯进行复合改性,制备改性聚氨酯防水涂料。通过红外光谱和扫描电镜对改性聚氨酯涂膜进行了表征,研究了n(─NCO)/n(─OH)比值、二甲基硅油和环氧树脂质量分数对涂膜吸水率的影响。结果表明,当n(─NCO)/n(─OH)=2:1、二甲基硅油和环氧树脂含量分别为8%和7%(均为质量分数)时,所制备的有机硅环氧改性聚氨酯涂料的耐水性能最佳,涂膜的拉伸强度为12.02 MPa,抗冲击强度50 kg.cm,吸水率11.37%,附着力1级。     

TDI水性聚氨酯胶粘剂的力学性能研究

以聚已内酯二醇(PCL220N)、甲苯二异氰酸酯(TDI-80)、二羟甲基丙酸(DMPA)为基料,以三羟甲基丙烷(TMP)为交联剂、环氧树脂(E-44)和松香为改性剂,制备出环氧树脂和松香改性的TDI水性聚氨酯胶粘剂。同时考察了环氧树脂(E-44)、松香和三羟甲基丙烷用量以及n(—NCO)/n(—OH)比值对TDI水性聚氨酯胶粘剂力学性能的影响。结果表明,当环氧树脂含量为5.73%,松香含量为8.92%,三羟甲基丙烷含量为2.68%,n(—NCO)/n(—OH)比值为1.23时,TDI水性聚氨酯胶粘剂的拉伸强度达到最大值为4.72 MPa。     

环氧树脂-水性聚氨酯-丙烯酸酯复合乳液的研究

以IPD I、聚醚、BDO、DMPA等为原料合成水性聚氨酯分散体,再加入MMA和引发剂,采用核壳乳液聚合法制备脂肪族水性聚氨酯-丙烯酸酯复合乳液。引入小分子交联剂三羟甲基丙烷(TMP)和环氧树脂E-20进行多重交联改性。用傅立叶红外光谱(FTIR)对树脂结构进行了分析。讨论了n(NCO)/n(OH)比值、环氧树脂E-20、TMP、MMA添加量对乳液性能的影响。研究发现,当n(NCO)/n(OH)=(1.3~1.4)∶1、E-20质量分数为3%~5%、TMP为1%~3%、MMA为20%~30%时,所制备的PUA乳液综合性能较好。     

TDI水性聚氨酯胶粘剂的力学性能研究

以聚已内酯二醇(PCL220N)、甲苯二异氰酸酯(TDI-80)、二羟甲基丙酸(DMPA)为基料,以三羟甲基丙烷(TMP)为交联剂、环氧树脂(E-44)和松香为改性剂,制备出环氧树脂和松香改性的TDI水性聚氨酯胶粘剂。同时考察了环氧树脂(E-44)、松香和三羟甲基丙烷用量以及n(—NCO)/n(—OH)比值对TDI水性聚氨酯胶粘剂力学性能的影响。结果表明,当环氧树脂含量为5.73%,松香含量为8.92%,三羟甲基丙烷含量为2.68%,n(—NCO)/n(—OH)比值为1.23时,TDI水性聚氨酯胶粘剂的拉伸强度达到最大值为4.72 MPa。     

助成膜型PUD的合成及性能影响

采用前中和法合成了助成膜型PUD,取代有机小分子成膜助剂辅助硬树脂乳液成膜,制备超低挥发性有机化合物(VOC)含量的水性木器涂料。考察了助成膜型PUD合成工艺中软段/硬段比例、n(—NCO)/n(—OH)、w(DMPA)%及助成膜PUD用量对复配体系MFT的影响规律。结果表明,当软段/硬段=55/45、n(—NCO)/n(—OH)=1.3、w(DMPA)=5%,按固体分比m(PUD)/m(PA0)=25/75制备的水性木器涂料能够在5℃下不加成膜助剂形成连续透明涂膜,与PA0制备的涂料相比,体系VOC含量降至30 g/L。     

PVC手套涂层用水性聚氨酯的研制

以六次甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)和聚醚PPG等为原料,通过丙酮法合成了PVC手套涂层用高强度、高伸长率水性聚氨酯乳液,探讨了n(NCO)/n(OH)、n(IPDI)/n(HDI)和后扩链剂乙二胺对水性聚氨酯性能的影响,并对水性聚氨酯乳液进行了冻融稳定性测试。结果表明,当n(NCO)/n(OH)=4.5、n(IPDI)/n(HDI)=1.5:1时,后扩链剂用量为0.7 g时,制备的水性聚氨酯具有良好的低温涂层稳定性,胶膜的拉伸强度24.61 MPa,伸长率达到663.5%,且手套在70℃、72 h内壁不粘连。     

高固含量水性聚氨酯分散体的合成

引　言水性聚氨酯是水溶型、水分散型和水乳化型聚氨酯的统称 .水性聚氨酯与溶剂型相比较 ,具有生产、运输和使用安全 ,不污染环境的优点 ,在涂料、黏合剂和皮革涂饰剂等方面的应用备受重视[1] ,成为近 10年来全世界的研究热点 .水性聚氨酯的弱点是其制成的涂料和涂饰剂的机械性能、耐水性不如溶剂型聚氨酯 .克服这些弱点 ,是近年来各国研究者努力的方向[2 ] .在改善水性聚氨酯性能方面有大量研究报道 ,诸如降低亲水基团含量 ,增大乳液粒径 ,采用强力机械分散增加乳液贮存稳定性 ,改善乳液对涂膜基材表面的润湿性、黏附力等等[3] .但很少见…     

软段含羧基的水性聚氨酯贮存稳定性研究

合成了软段含羟基的水性聚氨酯（WPU），对影响其贮存稳定性的各种因素进行了研究，通过显微镜对PU进行了观察。结果表明：以甲苯二异氰酸酯（TDI）合成，在有性溶剂（如丁酮、丙酮）条件下用三乙胺中和，采用较小相地分子质量的聚酯有利于增强WPU的贮存稳定性，以TDI合成的PU-TDI体系的粒径较PU-IPDI体系的小，稳定性高；以丁酮、丙酮为溶剂的PU-IPDI体系相反转完全。     

Structure–properties relationship of starch/waterborne polyurethane composites

The blend materials from waterborne polyurethane (WPU)/starch (ST) with different contents (10–90 wt %) were satisfactorily prepared by using the solution casting method. Their miscibility, structure, and properties were investigated by wide‐angle X‐ray diffraction (WAXD), scanning electron microscope (SEM), different scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and the tensile tests, respectively. The results indicated that tensile strength of composite materials not only depended on the starch content, but also related to the microstructure of WPU. The sample WPU2 (1.75 of NCO/OH molar ratio) exhibited hard‐segment order, but WPU1 (1.25 of NCO/OH molar ratio) had no hard‐segment order. The appropriate starch filled into WPU not only decreased the ordered region of soft‐segment matrix, but also hindered the formation of hard‐segment ordered structure. The blend material from 80 wt % WPU1 and 20 wt % starch exhibited better tensile strength (27 MPa), elongation at break (949%), and toughness than others. With an increase of starch content, the WPU matrix with dispersed starch in the blends transited to dual‐phase continuity and then to starch matrix with dispersed WPU. The results suggested that a certain extent of miscibility existed between WPU and starch in the blend materials on the whole composition ratio. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3325–3332, 2003     

The chain extender content and NCO/OH ratio flexibly tune the properties of natural rubber‐based waterborne polyurethanes

The effects of chain extender content (ethylene diamine, EDA) and NCO/OH ratio on the properties of natural rubber‐based waterborne polyurethanes (WPUs) were investigated experimentally. The particle size of WPU increased significantly with the NCO/OH ratio, in the presence of the EDA chain extender, while it was unaffected by the EDA content. The water uptake of WPU film increased with the EDA content, while the swelling in various solvents decreased. In a thermal analysis, the second decomposition stage of a WPU film increased with the EDA content and with the NCO/OH ratio that also positively affected the dynamic mechanical and mechanical properties. These factors in WPU films had no the effect on the T_g. The stress–strain curves clearly showed the change in WPU films from soft elastomeric materials to ductile and hard plastics. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42505.     

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。     

PCL–PEG–PCL triblock ester–ether copolydiol-based waterborne polyurethane. II. Effect of NCO/OH mole ratio and DMPA content on the physical properties

This article was focused on the effects of the NCO/OH molar ratio and 2,2-bis(hydroxyl methyl) propionic acid (DMPA) content during prepolymerization on the physical properties of synthesized waterborne polyurethane (WBPU) by using the polycaprolactone–poly(ethyl glycol)–polycaprolactone triblock copolydiol (PCL–PEG–PCL) as the soft segment. The results showed that the particle size of the WBPUs' dispersion decreased with a decreasing NCO/OH molar ratio or increasing DMPA content. Regarding thermal and mechanical properties, the WBPUs had a higher T_g's and lower T_m's and a higher breaking stress and a lower breaking strain of film with the NCO/OH molar ratio or DMPA content increase. The increasing NCO/OH molar ratio was advantageous to the water vapor permeability (WVP)-breaking stress balance, but the effect of the DMPA content on the WVP was not significant. The WBPU with PCL–PEG–PCL as the soft segment had a smaller particle size in dispersion and a better WVP-breaking stress balance than those of WBPU with the blending PCL and PEG as the soft segment. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1301–1311, 1998     

蓖麻油改性聚醚型水性聚氨酯乳液的性能

以聚醚、甲苯二异氰酸酯(TDI)、一缩二乙二醇、蓖麻油为主要原料,二羟甲基丙酸(DMPA)为亲水扩链剂,三乙胺为中和剂制备了稳定的阴离子水性聚氨酯乳液(WPU),研究了NCO/OH摩尔比、DMPA及蓖麻油的加入量对WPU的耐水性、稳定性和力学性能的影响,结果表明:改性后的乳液具有较好的稳定性,适量的蓖麻油可提高胶膜的拉伸强度及耐水性。当聚醚与蓖麻油质量比为7︰3、DMPA为5%、NCO与OH摩尔比为1.3时,WPU综合性能最好。     

The influence of the NCO/OH ratio and the 1,6-hexanediol/ dimethylol propionic acid molar ratio on the properties of waterborne polyurethane dispersions based on 1,5-pentamethylene diisocyanate

1,5-Pentamethylene diisocyanate, a novel aliphatic diisocyanate formed from bio-based 1,5-pentamethylenediamine, has been used as a hard segmented material to synthesize polyurethane. In this study, several waterborne polyurethane (WPU) dispersions have been successfully prepared by a prepolymer process from 1,5-pentamethylene diisocyanate poly(polyether) with different NCO/OH ratios and 1,6-hexanediol (HDO)/dimethylol propionic acid (DMPA) molar ratios. The Fourier transfonn infrared (FTIR) spectra, thermogravimetric analysis, differential scanning calorimetry, X-ray diffiraction, and a mechanical tensile test were used to investigate the structures, thermal stability, phase separation, crystallinity, mechanical properties, and adhesive performance of the WPU dispersions. The FTIR results indicate that the degree of hydrogen bonding and the numbers of urea groups increase as the NCO/OH ratio and HDO/DMPA molar ratio increase. Furthermore, the phase separation increases and the thermal stability decreases as the NCO/OH ratio increases or the HDO/DMPA molar ratio decreases. Finally, WPU3.0-2.4 (NCO/OH = 3, HDO/DMPA = 2.4) exhibits a maximum tensile strength and shear strength, pointing to its possible use as an adhesive. These results could provide a very valuable reference for industrial applications of WPU.     

聚碳酸酯型水性聚氨酯乳液的制备与性能

以聚碳酸酯二元醇和异佛尔酮二异氰酸酯为主要原料,采用预聚法合成了聚碳酸酯型水性聚氨酯( WPU) ,用傅里叶变换红外光谱表征了WPU,考察了不同NCO/OH( 摩尔比) 对WPU 乳液粒径及薄膜的耐水性、拉伸性能的影响,并研究了WPU 的热稳定性。结果表明,随着NCO/OH 值的增大,WPU乳液的粒径增大,稳定性降低,薄膜的耐水性和拉伸强度提高,扯断伸长率降低; WPU 薄膜的热分解速率较快,硬段的热分解温度为193 ℃,最大失重温度为287 ℃; 软段的热分解温度为321 ℃,最大失重温度为364 ℃左右。