水性聚氨酯的合成及其改性研究
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摘要
以二羟甲基丙酸(DMPA)为亲水单体，三乙胺(TEA)为中和剂，与甲苯-2，4-二异氰酸酯(TDI)，聚醚二元醇E220(分子量2000)，二甘醇(一缩二乙二醇，DEG)，三羟甲基丙烷(TMP)，制备了水性聚氨酯。研究了各个化学组分对乳液相转变、粘度、稳定性的影响以及对膜机械性能、耐介质性能的影响。结果表明：随着NCO／OH比值的增大，乳化时乳液的粘度升高，相转变点后延，乳液的平均粒径逐渐增大，膜的拉伸强度增加，断裂伸长率降低，耐水性增强，而耐丙酮性下降；随着DMPA用量的增加，体系的粘度升高，相转变点后延，乳液的平均粒径下降，膜的断裂伸长率下降，拉伸强度先增大后减小，当羧基含量大于12％时，强度下降，耐水性下降，而耐丙酮性增强；随着TMP用量的增加，乳液的粘度下降，相转变点前趋，粒径先减小后增大，TMP用量为4％时粒径最小，膜的强度先增加后降低，当交联剂用量约为4％时，拉伸强度达到最大值，膜的耐介质性呈曲线变化，当TMP含量达到4％左右，吸丙酮率及吸水率均低于10％，胶膜具有较好的耐水性；随着DEG用量的增加，乳液的粘度减小，相转变点前趋，乳液粒径下降，膜的强度增大，断裂伸长率增加，耐水性及耐丙酮性均下降。
将聚丙烯酸酯(PA)与制得的水性聚氨酯(PU)乳液进行共混改性，通过透射电镜(TEM)、X射线衍射、红外光谱(FTIR)及热失重法(TGA)研究了共混膜的结构形态，并测定了共混膜的机械性能和耐介质性能。X射线衍射及FTIR光谱的分析结果均表明PU／PA共混膜中，成膜的两种组分间存在某种相互作用，PA的加入促使了聚氨酯结晶结构的形成；热分析结果表明PA的加入提高了聚氨酯的热稳定性；透射电镜结果表明PU与PA之间存在一定的相容性和共混程度；PA的加入有利于提高PU的强度和断裂伸长率，其中当
水性聚氨酷的合成及其改性研究
中文提要
PA的含量为20%时，共混膜的强度和伸长率均达到最大值，耐介质
性能也有较大的提高。
Aqueous polyurethane (PU) dispersions were prepared from toluene-2,4-diisocyanate(TDI), polyols E220, diglycol, trim-ethycolpropane (IMP), and dimethylol propionic acid (DMPA) as anionic center, triethylamine (TEA) as neutralized reagent. The effects of the factors, such as NCO/OH, DMPA, and TMP, on the phase inversion, stability of dispersion and tensile properties, water and acetone absorption of emulsion-cast film were studyied. With increasing NCO/OH ratio, the emulsion viscosity, particle size of the emulsion and tensile strength, acetone absorption of the emulsion-cast film increased, while the phase inversion delayed, elongation at break and water absorption decreased. With more DMPA, the emulsion viscosity and water absorption increased, while the phase inversion delayed, the particle size of the emulsion , elongation at break and acetone absorption of the emulsion-cast film decreased, the tensile strength of the emulsion-cast film was the highest at the DMPA content of 12%. With more TMP, the emulsi
on viscosity decreased, the phase inversion occurred early, the properties was the best at the TMP content of 4%. With more DEG, the tensile strength, elongation at break and water/acetone absorption increased, while the emulsion viscosity increased, the phase inversion occured early.
The blend emulsions of waterborne polyurethane (PU) and polyacrylate (PA) was also prepared in this article, the structure of blend films at different blend ratios were
studied by means of X-ray diffraction, FTIR spectra and thermogravimetry analysis (TGA) . The morphology of PU, PA and the blend emulsions were observed with transmission electronic microphotograph (TEM), and the strength and elongation at break, water/acetone absorption of blend films were determined, too. The results of both X-ray diffraction and FTIR spectra showed that there somehow existed some mutual influence between the two components in PU/PA blend films, which induced the formation of PU in blend films, and the results of thermal analysis indicated that the thermal stability of PU in the blend films was improved, which was attributed to the addition of PA. It was showed in the TEM that there existed some phase blend between in PU/PA emulsions. With increasing PA, the tensile strength and the elongation at break, water/acetone absorption increased, at the PA content of 20%, properties of the blend films were the best.
将聚丙烯酸酯(PA)与制得的水性聚氨酯(PU)乳液进行共混改性，通过透射电镜(TEM)、X射线衍射、红外光谱(FTIR)及热失重法(TGA)研究了共混膜的结构形态，并测定了共混膜的机械性能和耐介质性能。X射线衍射及FTIR光谱的分析结果均表明PU／PA共混膜中，成膜的两种组分间存在某种相互作用，PA的加入促使了聚氨酯结晶结构的形成；热分析结果表明PA的加入提高了聚氨酯的热稳定性；透射电镜结果表明PU与PA之间存在一定的相容性和共混程度；PA的加入有利于提高PU的强度和断裂伸长率，其中当
水性聚氨酷的合成及其改性研究
中文提要
PA的含量为20%时，共混膜的强度和伸长率均达到最大值，耐介质
性能也有较大的提高。
Aqueous polyurethane (PU) dispersions were prepared from toluene-2,4-diisocyanate(TDI), polyols E220, diglycol, trim-ethycolpropane (IMP), and dimethylol propionic acid (DMPA) as anionic center, triethylamine (TEA) as neutralized reagent. The effects of the factors, such as NCO/OH, DMPA, and TMP, on the phase inversion, stability of dispersion and tensile properties, water and acetone absorption of emulsion-cast film were studyied. With increasing NCO/OH ratio, the emulsion viscosity, particle size of the emulsion and tensile strength, acetone absorption of the emulsion-cast film increased, while the phase inversion delayed, elongation at break and water absorption decreased. With more DMPA, the emulsion viscosity and water absorption increased, while the phase inversion delayed, the particle size of the emulsion , elongation at break and acetone absorption of the emulsion-cast film decreased, the tensile strength of the emulsion-cast film was the highest at the DMPA content of 12%. With more TMP, the emulsi
on viscosity decreased, the phase inversion occurred early, the properties was the best at the TMP content of 4%. With more DEG, the tensile strength, elongation at break and water/acetone absorption increased, while the emulsion viscosity increased, the phase inversion occured early.
The blend emulsions of waterborne polyurethane (PU) and polyacrylate (PA) was also prepared in this article, the structure of blend films at different blend ratios were
studied by means of X-ray diffraction, FTIR spectra and thermogravimetry analysis (TGA) . The morphology of PU, PA and the blend emulsions were observed with transmission electronic microphotograph (TEM), and the strength and elongation at break, water/acetone absorption of blend films were determined, too. The results of both X-ray diffraction and FTIR spectra showed that there somehow existed some mutual influence between the two components in PU/PA blend films, which induced the formation of PU in blend films, and the results of thermal analysis indicated that the thermal stability of PU in the blend films was improved, which was attributed to the addition of PA. It was showed in the TEM that there existed some phase blend between in PU/PA emulsions. With increasing PA, the tensile strength and the elongation at break, water/acetone absorption increased, at the PA content of 20%, properties of the blend films were the best.
引文
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6．孙文章，江亦李，蔡再生，周明训，孙铠．水性聚氨酯粘合剂在涂料印花中的应用．印染助剂，2001，18(6)：20
7．朱建平．新型水系聚氨酯抗静电的制备和应用．印染助剂．1998，15(4)：16
8．查刘生，吴明元，杨建军．水性聚氨酯羊毛防缩剂SUW-2的应用．印染助剂1999，16(2)：22
9，于克乾，刘英俊，王仁田，杨东辉，陈建和．水乳型聚氨酯织物涂层剂的生产和应用．聚氨酯工业．1997，12(2)：30
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