水性聚氨酯的合成及其作为纸页增强剂的应用
摘要
由于传统湿强剂存在的局限性,许多新型环保湿强剂被开发出来作为造纸助剂,水性聚氨酯(WPU)作为水性环保型树脂之一,以水为溶剂,具有无污染、无毒、安全可靠、机械性能优良、相容性好、易于改性等优点,被引用到造纸行业成为近期研究的热点。
本文根据异氰酸酯(-NCO)基团与纤维上的羟基(-OH)反应的机理,合成了封闭性的WPU;在应用过程中,由于温度对WPU有很大影响,着重研究了WPU的解封闭温度;并针对漂白针叶木浆,将WPU加入到浆料中,系统地研究了WPU,WPU与阳离子聚丙烯酰胺(CPAM)共用对纸页抗张强度的影响。
合成了水性聚氨酯并对其乳液性能进行了研究。研究结果表明,随着封闭剂用量增加,封闭反应时间相对延长。根据封闭剂用量和溶液的稳定性,确定了亲水扩链剂的用量为甲苯-2,4-二异氰酸酯(2,4-TDI)和聚乙二醇1000(PEG1000)两种单体质量之和的2%。当中和度为0.9-1.1时,WPU乳液的贮存稳定性明显增加。通过搅拌强度、溶剂、温度、加水方式对乳化效果进行了探讨,实验结果显示,在室温下加入适量溶剂,通过强搅拌剪切力先缓慢后快速加入去离子水的方式,有利于乳化成功。
对水性聚氨酯进行了红外表征并对解封温度进行了研究。研究结果表明,封闭后的聚氨酯在2250-2280cm-1附近的-NCO吸收峰明显减弱,说明封闭反应是成功的。扩链之后,3300cm-1附近出现了明显的N-H吸收峰,说明已经引入了亲水基团。对解封温度的研究表明,在100℃、110℃和120℃下,封闭产物都能在2250cm-1附近出现吸收峰,说明在高温下能解封,而且延长加热时间有利于-NCO基团的解封趋于完善。热重分析(TG)曲线进一步证实了红外测试的结果。
研究了水性聚氨酯在纸张中的应用。研究结果表明,将含有不同封闭剂用量的WPU乳液添加到浆料后,发现封闭剂用量为0.1mol的乳液应用性能最佳。通过对WPU乳液应用条件的探讨,确定纸页干燥温度为100℃,高温熟化条件为110℃固化40min,紫外熟化时间为2.5min;通过紫外、紫外+高温和高温三种熟化方式对纸页抗张强度影响的对比,发现适宜的熟化方式为高温熟化。探讨了不同pH值下WPU用量对浆料Zeta电位和纸页抗张强度的影响,表明所制备的WPU是带正电性的,可直接与浆料发生吸附作用;发现自制WPU乳液较适于中性和酸性条件下应用,当WPU乳液用量为3.0%时,在中性条件下湿强保留率达到19.45%;当WPU乳液用量为2.5%时,在酸性条件下湿强保留率达到20.70%。通过对CPAM与WPU共用的探讨,发现CPAM与WPU配合使用能提高纸页的湿强度,添加到浆料中的顺序为先添加WPU后添加CPAM。当添加顺序为2.0% WPU + 0.2% CPAM时,纸页的湿强度比添加单一的WPU提高了16.01%,比空白纸样提高了12.7倍;湿强保留率达到了18.99%,比添加单一的WPU提高了22.52%,比空白纸样提高了9.9倍。当添加顺序为3.0%WPU+0.2%CPAM时,纸页的湿强度比添加单一的WPU提高了12.62%,比空白纸样提高了15倍;湿强保留率达到了21.29%,比空白纸样提高了11倍。
Because of the shortage of traditional wet strength agents, a lot of new environment-friend wet strength agents are developed as paper chemicals. Water-based polyurethane(WPU) as one of environment-friend water-based polyurethane resins with water as solvent, is non-polluting, non-toxic, safe, reliable, excellent mechanical properties, compatibility and easy modification with incomparable advantages that the traditional wet-strength resins are not, is applied in paper industry as a research hotspot recently.
Based on the reaction mechanism of -NCO group and -OH on the fiber, blocked WPU was synthesized on the basis. Because the effect of blocked WPU was affected by temperature in the application, the deblocked temperature was studied. In this paper, according to hand sheets making from bleached softwood pulp, WPU was added to the pulp, the effect on sheet tensile strength of wet strength agents with synthesized WPU and sharing of WPU and CPAM was systematically analyzed. The water-based polyurethane was synthesized. According to the performance of the
synthesized polyurethane, the reaction time became longer relatively with increased blocked agent. In accordance with the dosage of blocked agent and the stability of emulsion, the dosage of the hydrophilic chain extender was 2% of the quality of the two monomers 2,4-TDI and PEG1000. When the degree of neutralization was 0.9-1.1, the storage stability of WPU emulsion increased significantly. Stirring intensity, solvent, temperature and the ways of adding water were discussed on the emulsification effect. Experimental results showed that room temperature, stirred by strong shear stress in a suitable solvent condition, slowly adding water during the final rapid accession to help emulsifying success.
The synthesized products were characterized by IR and the deblocked temperature was studied. The results showed that absorption peak of the -NCO group of the blocked PU products near 2250-2280cm-1 had weakened significantly, indicating that blocked reaction was successful. After chain extender, N-H had a clear absorption peak near 3300cm-1, indicating that introduction of the hydrophilic group was successful. The result of deblocked temperature showed that blocked products at 100℃, 110℃and 120℃heating had absorption peak near 2250cm-1, indicating that the blocked product could be deblocked with high temperature, and the prolonged heated time was in favor of -NCO group deblocked. TG curve confirmed further the results of FTIR test.
The application of the water-based polyurethane in the paper was studied. The synthetic WPU emulsion containing different dosage of blocked agent was added to the pulp, and the results showed that when the dosage of blocked agent was 0.1mol, the application performance of emulsion was the best. According to discussing the application condition of WPU emulsion, drying temperature of the sheets was 100℃; the condition of high temperature curing was 40min at 110℃,the UV curing time was 2.5min. Comparing the methods of UV curing, UV+high temperature curing and high temperature curing, the high temperature curing was the best method. According to discussing the effects of zeta potential of pulp and paper tensile strength were affected by the amount of WPU at different pH, the results showed that the prepared WPU was electropositive which could absorb directly with the pulp; and the synthesized WPU emulsion could be applied better under neutral and acidic conditions. When the amount of emulsion was 3.0%, paper wet-strength retention rate in the neutral condition reached 19.45%; when the amount of emulsion was 2.5%, paper wet-strength retention rate in the acidic condition reached 20.70%. Through CPAM and WPU sharing, the results showed that CPAM and WPU used together and added CPAM after WPU could improve wet strength. When adding the order of 2.0% WPU + 0.2% CPAM, the paper wet strength increased 16.01%, comparing with a single WPU added, increased 12.7 times, and comparing with blank samples, paper wet-strength retention rate reached 18.99%, increased 9.9 times. When adding the order of 3.0% WPU + 0.2% CPAM, the paper wet strength increased 12.62%, comparing with a single WPU added, increased 15 times, comparing with blank samples, paper wet-strength retention rate reached 21.29%, increased 11 times.
本文根据异氰酸酯(-NCO)基团与纤维上的羟基(-OH)反应的机理,合成了封闭性的WPU;在应用过程中,由于温度对WPU有很大影响,着重研究了WPU的解封闭温度;并针对漂白针叶木浆,将WPU加入到浆料中,系统地研究了WPU,WPU与阳离子聚丙烯酰胺(CPAM)共用对纸页抗张强度的影响。
合成了水性聚氨酯并对其乳液性能进行了研究。研究结果表明,随着封闭剂用量增加,封闭反应时间相对延长。根据封闭剂用量和溶液的稳定性,确定了亲水扩链剂的用量为甲苯-2,4-二异氰酸酯(2,4-TDI)和聚乙二醇1000(PEG1000)两种单体质量之和的2%。当中和度为0.9-1.1时,WPU乳液的贮存稳定性明显增加。通过搅拌强度、溶剂、温度、加水方式对乳化效果进行了探讨,实验结果显示,在室温下加入适量溶剂,通过强搅拌剪切力先缓慢后快速加入去离子水的方式,有利于乳化成功。
对水性聚氨酯进行了红外表征并对解封温度进行了研究。研究结果表明,封闭后的聚氨酯在2250-2280cm-1附近的-NCO吸收峰明显减弱,说明封闭反应是成功的。扩链之后,3300cm-1附近出现了明显的N-H吸收峰,说明已经引入了亲水基团。对解封温度的研究表明,在100℃、110℃和120℃下,封闭产物都能在2250cm-1附近出现吸收峰,说明在高温下能解封,而且延长加热时间有利于-NCO基团的解封趋于完善。热重分析(TG)曲线进一步证实了红外测试的结果。
研究了水性聚氨酯在纸张中的应用。研究结果表明,将含有不同封闭剂用量的WPU乳液添加到浆料后,发现封闭剂用量为0.1mol的乳液应用性能最佳。通过对WPU乳液应用条件的探讨,确定纸页干燥温度为100℃,高温熟化条件为110℃固化40min,紫外熟化时间为2.5min;通过紫外、紫外+高温和高温三种熟化方式对纸页抗张强度影响的对比,发现适宜的熟化方式为高温熟化。探讨了不同pH值下WPU用量对浆料Zeta电位和纸页抗张强度的影响,表明所制备的WPU是带正电性的,可直接与浆料发生吸附作用;发现自制WPU乳液较适于中性和酸性条件下应用,当WPU乳液用量为3.0%时,在中性条件下湿强保留率达到19.45%;当WPU乳液用量为2.5%时,在酸性条件下湿强保留率达到20.70%。通过对CPAM与WPU共用的探讨,发现CPAM与WPU配合使用能提高纸页的湿强度,添加到浆料中的顺序为先添加WPU后添加CPAM。当添加顺序为2.0% WPU + 0.2% CPAM时,纸页的湿强度比添加单一的WPU提高了16.01%,比空白纸样提高了12.7倍;湿强保留率达到了18.99%,比添加单一的WPU提高了22.52%,比空白纸样提高了9.9倍。当添加顺序为3.0%WPU+0.2%CPAM时,纸页的湿强度比添加单一的WPU提高了12.62%,比空白纸样提高了15倍;湿强保留率达到了21.29%,比空白纸样提高了11倍。
Because of the shortage of traditional wet strength agents, a lot of new environment-friend wet strength agents are developed as paper chemicals. Water-based polyurethane(WPU) as one of environment-friend water-based polyurethane resins with water as solvent, is non-polluting, non-toxic, safe, reliable, excellent mechanical properties, compatibility and easy modification with incomparable advantages that the traditional wet-strength resins are not, is applied in paper industry as a research hotspot recently.
Based on the reaction mechanism of -NCO group and -OH on the fiber, blocked WPU was synthesized on the basis. Because the effect of blocked WPU was affected by temperature in the application, the deblocked temperature was studied. In this paper, according to hand sheets making from bleached softwood pulp, WPU was added to the pulp, the effect on sheet tensile strength of wet strength agents with synthesized WPU and sharing of WPU and CPAM was systematically analyzed. The water-based polyurethane was synthesized. According to the performance of the
synthesized polyurethane, the reaction time became longer relatively with increased blocked agent. In accordance with the dosage of blocked agent and the stability of emulsion, the dosage of the hydrophilic chain extender was 2% of the quality of the two monomers 2,4-TDI and PEG1000. When the degree of neutralization was 0.9-1.1, the storage stability of WPU emulsion increased significantly. Stirring intensity, solvent, temperature and the ways of adding water were discussed on the emulsification effect. Experimental results showed that room temperature, stirred by strong shear stress in a suitable solvent condition, slowly adding water during the final rapid accession to help emulsifying success.
The synthesized products were characterized by IR and the deblocked temperature was studied. The results showed that absorption peak of the -NCO group of the blocked PU products near 2250-2280cm-1 had weakened significantly, indicating that blocked reaction was successful. After chain extender, N-H had a clear absorption peak near 3300cm-1, indicating that introduction of the hydrophilic group was successful. The result of deblocked temperature showed that blocked products at 100℃, 110℃and 120℃heating had absorption peak near 2250cm-1, indicating that the blocked product could be deblocked with high temperature, and the prolonged heated time was in favor of -NCO group deblocked. TG curve confirmed further the results of FTIR test.
The application of the water-based polyurethane in the paper was studied. The synthetic WPU emulsion containing different dosage of blocked agent was added to the pulp, and the results showed that when the dosage of blocked agent was 0.1mol, the application performance of emulsion was the best. According to discussing the application condition of WPU emulsion, drying temperature of the sheets was 100℃; the condition of high temperature curing was 40min at 110℃,the UV curing time was 2.5min. Comparing the methods of UV curing, UV+high temperature curing and high temperature curing, the high temperature curing was the best method. According to discussing the effects of zeta potential of pulp and paper tensile strength were affected by the amount of WPU at different pH, the results showed that the prepared WPU was electropositive which could absorb directly with the pulp; and the synthesized WPU emulsion could be applied better under neutral and acidic conditions. When the amount of emulsion was 3.0%, paper wet-strength retention rate in the neutral condition reached 19.45%; when the amount of emulsion was 2.5%, paper wet-strength retention rate in the acidic condition reached 20.70%. Through CPAM and WPU sharing, the results showed that CPAM and WPU used together and added CPAM after WPU could improve wet strength. When adding the order of 2.0% WPU + 0.2% CPAM, the paper wet strength increased 16.01%, comparing with a single WPU added, increased 12.7 times, and comparing with blank samples, paper wet-strength retention rate reached 18.99%, increased 9.9 times. When adding the order of 3.0% WPU + 0.2% CPAM, the paper wet strength increased 12.62%, comparing with a single WPU added, increased 15 times, comparing with blank samples, paper wet-strength retention rate reached 21.29%, increased 11 times.
引文
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