水溶性聚氨酯表面施胶剂的合成与应用
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摘要
本论文中采用“自乳化”法合成环氧改性水性聚氨酯表面施胶剂,并在实验设计中使用Minitab软件DOE设计。研究的内容与结果如下:
1.在合成工艺的探索过程中,合成环氧改性阴离子型水性聚氨酯用二羟甲基丙酸(DMPA)作亲水性扩链剂;选择环氧值为0.43的双酚A型E-44环氧树脂改性;环氧树脂E-44加入方式为接枝共聚,先加入DMPA反应一定时间后再加入环氧树脂E-44;选择三乙胺作为成盐剂。
2.采用DOE中2水平因子设计方法,考察主要原料的用量对乳液粒径、Cobb值和印刷表面强度的影响。通过研究发现R值、DMPA的用量和E-44的用量是影响粒径和印刷表面强度的主要因子;R值、DMPA的用量、E-44的用量和中和度是影响Cobb值的主要因子。R值、DMPA的用量、DEG的用量和中和度对粒径的效应符号为正;E-44的用量对粒径的效应符号为负。DMPA的用量对Cobb值的效应符号为正;R值、E-44的用量和中和度对Cobb值的效应符号为负; DEG的用量对Cobb值影响甚微。R值、DMPA的用量、E-44的用量和中和度对印刷表面强度的效应符号为正;DEG的用量对印刷表面强度影响甚微。次要因子的水平设定如下:DEG的用量为4%;中和度为100%。
3.对筛选出的影响主要指标的因子,进行水平确定的优化设计。通过对实验结果的分析得出:主要因子对乳液粒径的影响程度为DMPA的用量>E-44的用量>R值;主要因子对乳液胶膜的吸水率的影响程度为R值>E-44的用量>DMPA的用量;主要因子对乳液应用中Cobb值的影响程度为R值>E-44的用量>DMPA的用量;主要因子对乳液应用中印刷表面强度的影响程度为R值>DMPA的用量>E-44的用量。通过优化实验得出的环氧改性的水性聚氨酯的合成工艺是:R值取2.6、DMPA的用量取8%、E-44的用量取8%、EDG的用量取4%和中和度为100%。同时用红外光谱进行表征证明了产品的结构。
4.合成表面施胶剂的应用中,通过研究分析得出:当合成施胶剂用量为0.9g/m~2、1.2g/m~2、1.5g/m~2时与原纸比较其Cobb值分别降低了24.51%、37.18%、49.56%;印刷表面强度分别提高了37.97%、61.18%、64.97%。氧化淀粉与聚合物表面施胶剂分别以不同比例复配进行表面施胶,最佳比例为氧化淀粉:E-WPU=92:8。因此,以新的聚合方法合成表面施胶剂E-WPU,涂布后不仅高效提高纸张的
抗水性,同时有效改善纸页的表面强度、油墨吸收性等表面性能。
In this paper, use“self-emulsifying”method to Synthesis of epoxy modified polyurethane sizing agent, and this experimental method is designed on the basis of the DOE model of Minitab software. The content and the results of the study are as follows:
1. In the exploration of the synthesis process, the synthesis of epoxy modified anionic polyurethane with dimethylol prop ionic acid (DMPA) for hydrophilic chain extenders; choose a value of 0.43 of biphenyl A epoxy-based E-44 modified epoxy; epoxy resin E-44 joined the manner graft copolymer, the first reaction by adding a certain time and then adding DMPA epoxy resin E-44; choose triethylamine as a salt agent.
2. By DOE in two levels factorial design method to study the affections of the amount of raw materials on the emulsion particle size, Cobb value and strength of the printing paper surface. Through the study found that R value, DMPA usage and E-44 are the main factors which affected the particle size and the strength of the printing paper surface; R value, DMPA usage, E-44 usage and the Neutralization degree of is the main factor affecting Cobb value. Minor factor in the level set as follows: DEG usage amount is 4%, the neutralization degree is 100%.
3. Conduct a level determined optimum design based on the selected main factors which effect key indicators. Obtained by optimizing the experimental water-based epoxy modified polyurethane synthesis is: an R value is 2.6, DMPA using amount is 8%, E-44 using amount is 8%, EDG using amount is 4% and neutralization degree of 100%.
4. In the applications of Synthetic surface sizing, The conclusion of the research is: when the using amount of synthetic sizing agent were 0.9g/m~2, 1.2g/m~2 and1.5g/m~2 ,compared with the base paper, the Cobb values reduced by 24.51%, 37.18% and 49.56% respectively, and the printing paper surface strength increased by 37.97%, 61.18% and 64.97% respectively. Oxidized starch and polymer surface sizing compound in different proportions of each for the surface sizing, the best ratio is: oxidized starch: E-WPU = 92:8.
1.在合成工艺的探索过程中,合成环氧改性阴离子型水性聚氨酯用二羟甲基丙酸(DMPA)作亲水性扩链剂;选择环氧值为0.43的双酚A型E-44环氧树脂改性;环氧树脂E-44加入方式为接枝共聚,先加入DMPA反应一定时间后再加入环氧树脂E-44;选择三乙胺作为成盐剂。
2.采用DOE中2水平因子设计方法,考察主要原料的用量对乳液粒径、Cobb值和印刷表面强度的影响。通过研究发现R值、DMPA的用量和E-44的用量是影响粒径和印刷表面强度的主要因子;R值、DMPA的用量、E-44的用量和中和度是影响Cobb值的主要因子。R值、DMPA的用量、DEG的用量和中和度对粒径的效应符号为正;E-44的用量对粒径的效应符号为负。DMPA的用量对Cobb值的效应符号为正;R值、E-44的用量和中和度对Cobb值的效应符号为负; DEG的用量对Cobb值影响甚微。R值、DMPA的用量、E-44的用量和中和度对印刷表面强度的效应符号为正;DEG的用量对印刷表面强度影响甚微。次要因子的水平设定如下:DEG的用量为4%;中和度为100%。
3.对筛选出的影响主要指标的因子,进行水平确定的优化设计。通过对实验结果的分析得出:主要因子对乳液粒径的影响程度为DMPA的用量>E-44的用量>R值;主要因子对乳液胶膜的吸水率的影响程度为R值>E-44的用量>DMPA的用量;主要因子对乳液应用中Cobb值的影响程度为R值>E-44的用量>DMPA的用量;主要因子对乳液应用中印刷表面强度的影响程度为R值>DMPA的用量>E-44的用量。通过优化实验得出的环氧改性的水性聚氨酯的合成工艺是:R值取2.6、DMPA的用量取8%、E-44的用量取8%、EDG的用量取4%和中和度为100%。同时用红外光谱进行表征证明了产品的结构。
4.合成表面施胶剂的应用中,通过研究分析得出:当合成施胶剂用量为0.9g/m~2、1.2g/m~2、1.5g/m~2时与原纸比较其Cobb值分别降低了24.51%、37.18%、49.56%;印刷表面强度分别提高了37.97%、61.18%、64.97%。氧化淀粉与聚合物表面施胶剂分别以不同比例复配进行表面施胶,最佳比例为氧化淀粉:E-WPU=92:8。因此,以新的聚合方法合成表面施胶剂E-WPU,涂布后不仅高效提高纸张的
抗水性,同时有效改善纸页的表面强度、油墨吸收性等表面性能。
In this paper, use“self-emulsifying”method to Synthesis of epoxy modified polyurethane sizing agent, and this experimental method is designed on the basis of the DOE model of Minitab software. The content and the results of the study are as follows:
1. In the exploration of the synthesis process, the synthesis of epoxy modified anionic polyurethane with dimethylol prop ionic acid (DMPA) for hydrophilic chain extenders; choose a value of 0.43 of biphenyl A epoxy-based E-44 modified epoxy; epoxy resin E-44 joined the manner graft copolymer, the first reaction by adding a certain time and then adding DMPA epoxy resin E-44; choose triethylamine as a salt agent.
2. By DOE in two levels factorial design method to study the affections of the amount of raw materials on the emulsion particle size, Cobb value and strength of the printing paper surface. Through the study found that R value, DMPA usage and E-44 are the main factors which affected the particle size and the strength of the printing paper surface; R value, DMPA usage, E-44 usage and the Neutralization degree of is the main factor affecting Cobb value. Minor factor in the level set as follows: DEG usage amount is 4%, the neutralization degree is 100%.
3. Conduct a level determined optimum design based on the selected main factors which effect key indicators. Obtained by optimizing the experimental water-based epoxy modified polyurethane synthesis is: an R value is 2.6, DMPA using amount is 8%, E-44 using amount is 8%, EDG using amount is 4% and neutralization degree of 100%.
4. In the applications of Synthetic surface sizing, The conclusion of the research is: when the using amount of synthetic sizing agent were 0.9g/m~2, 1.2g/m~2 and1.5g/m~2 ,compared with the base paper, the Cobb values reduced by 24.51%, 37.18% and 49.56% respectively, and the printing paper surface strength increased by 37.97%, 61.18% and 64.97% respectively. Oxidized starch and polymer surface sizing compound in different proportions of each for the surface sizing, the best ratio is: oxidized starch: E-WPU = 92:8.
引文
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[4] Brine W. Ranson. New Surface Size Option Main Tains Performance, Lessens Internal Sizing [J]·Pulp and Paper, American, 2004,(7):50.
[5]张国运.采用新型表面施胶剂降低内部施胶量优化纸页性能[J].造纸化学品,2006,18 (4): 54-56.
[6] Scott WE. The principles of wet end chemistry[D]. Altnata, 1996.
[7]沈一丁.造纸化学品的制备和作用机理[M].北京:中国轻工业出版社,1999:223-224.
[8]腾铭辉,赵传山.表面施胶剂在造纸工业中的应用新进展[J].天津造纸,2008(2):37-41.
[9]许夕峰,勒光秀,梁福根,等.表面施胶剂的发展及其在现代造纸工业中的作用[J].纸和造纸,2007,26 (5): 1-4.
[10]勒光秀,沈一丁.苯乙烯马来酸单酯共聚物乳液表面施胶剂的合成与应用[J].中国造纸,2004,23(3):7
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