阳离子分散松香胶辅助剂
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摘要
本论文是围绕着提高阳离子分散松香胶施胶性能而对松香补充剂及松香施胶媒介物质进行的研究。首先,利用未改性的C5、C9石油树脂及C5/C9石油树脂共混作为松香补充剂分别与固体松香一起熔融乳化,制备阳离子分散松香胶,用于纸张浆内施胶,并初步研究了其施胶特性以及各种因素对施胶效果的影响。结果表明,采用C5、C9石油树脂及C5/C9石油树脂共混做松香补充剂均有助于提高阳离子分散松香胶的施胶效率,且三者分别在其加入量为20%、10%、10%及C5/C9石油树脂共混比例为2:1时所制备的阳离子分散松香胶具有最优施胶性能。虽然添加C5、C9及C5/C9石油树脂混合物后,阳离子分散松香胶的施胶效率仍然随着pH值的提高而降低,但在pH7的中性条件下,添加C5、C9石油树脂及C5/C9石油树脂混合物后的松香胶仍然对纸张具有较好的施胶效果。
其次,选择分别含20%C5石油树脂、10%C9石油树脂的阳离子分散松香胶作为研究对象,利用施胶度测定、红外、扫描电镜、x-射线光电子能谱等手段,对石油树脂的作用机理进行了分析,并与普通阳离子分散松香胶在胶料性质、施胶效果等方面作了综合比较。发现在松香中加入C5或C9石油树脂,混合熔融物中羧基含量及阳离子分散松香胶颗粒表面O与C的比例明显降低,且石油树脂的加入还降低了阳离子分散松香胶中松香的短程有序性,抑制了松香的结晶趋势;松香中的羧基趋于分布在松香胶颗粒的表面,而石油树脂则趋于分布在胶膜表面,且C9石油树脂比C5石油树脂对羧基的屏蔽作用更强,位于外层的石油树脂显著增加了胶膜的疏水性能,从而提高了松香胶的施胶效率。
另外,针对中碱性施胶逐渐替代酸性施胶的趋势,为真正实现松香中碱性施胶,采用碳酸锆铵做松香施胶媒介物质,比较了阳离子分散松香胶分别与碳酸锆铵或硫酸铝联合使用及三者混合使用时对纸张的浸渍施胶效果。结果表明,当碳酸锆铵单独用作松香施胶媒介物时,施胶效果较好,而且在松香胶与碳酸锆铵质量比例为4:1时,纸张获得最高施胶度;但当将硫酸铝与碳酸锆铵混合用作松香施胶媒介物质时,两者之间相互干扰,不利于松香施胶。
最后,为了进一步提高阳离子分散松香胶的施胶效率,采用聚酰胺多胺环-氧氯丙烷树脂(PAE)作阳离子分散松香胶-硫酸铝施胶体系的施胶促进剂,初步探讨了PAE的作用。结果表明,加入PAE可改善阳离子分散松香胶的施胶效果,并在硫酸铝和松香胶加入之前加入PAE效果最好,PAE的加入量以0.1%为宜。
Rosin extenders and mordants were the research highlights of this paper in order to improve the sizing efficiency of cationic rosin size. Unmodified C5 petroleum resin, C9 petroleum resin and their mixtures were used as the extenders and melted together with natural rosin repectively to prepare cationic rosin size emulsions and used as internal sizing agents. The effects of C5 and C9 petroleum resin proportion, the addition levels of alum and cationic rosin sizes, pH value as well as pulps on the sizing degree of hand sheets were investigated. The results show that the cationic rosin sizes with C5 petroleum resin, C9 petroleum resin as well as their mixture as rosin extenders are more effective in internal sizing than the cationic rosin size without extender. When the mass ratios of the C5 petroleum resin, C9 petroleum resin and their mixture to rosin are 1:5, 1:10 and 1:10 repectively while the C5/C9 is 2:1 in the mixture, the obtaind cationic rosin sizes show high sizing efficiency. The cationic rosin sizes with C5 and C9 petroleum resin provide higher sizing degree than usual cationic rosin size even under the neutral condition of pH 7, although the sizing degrees decrease as pH value rises.
The function of the petroleum resins on the stability and sizing performance of the cationic rosin sizes was analyzed by means of the sizing degree measurement of hand sheets, infra-red technology, XRD and XPS. It is found that the addition of C5 and C9 petroleum resins as rosin extenders can significantly lower the content of carboxyl groups in rosin sizes and the ratio of O/C on the surfaces of rosin sizes since both C5 and C9 petroleum resin are hydrocarbon resins. The addition of petroleum resins also reduce the short-range-order domains of cationic rosin sizes, which means that petroleum resins can lower the trend of rosin crystallization. Meanwhile, XPS analysis also confirms that the carboxyl groups tend to distribute on the surfaces of rosin size particles while the petroleum resins tend to locate in the outer surfaces of the rosin sizes. Therefore, the petroleum resins have significantly increased the hydrophobicity of rosin size film, improving the sizing efficiency of cationic rosin sizes.
In view of the develpment towards alkaline sizing, ammonium zirconium carbonate (AZC) was selected as the new mordant of impregnated rosin sizing. The synergistic sizing effects of cationic rosin sizes with AZC, alum and both of them were investigated. The results show that AZC performs very well as the mordant of rosin sizing under neutral conditions. When the mass ratio of rosin to AZC is 4:1, high paper sizing degree was obtained. However, when aluminum sulfate and AZC are used together, they will interfere with each other and the sizing degree of rosin sized paper is lower than the case that they are used separately.
Finally, to further improve the sizing efficiency of the cationic rosin sizes, PAE was employed as accelerant to investigate its function in the rosin sizing. It is discovered that PAE can significantly improve the sizing efficiency of the cationic rosin size/aluminum sulfate system. When it is added before the aluminum sulfate and cationic rosin sizes, it will show the highest promoting effect for sizing. Its suitable addition level is 0.1% based on oven dried pulp.
其次,选择分别含20%C5石油树脂、10%C9石油树脂的阳离子分散松香胶作为研究对象,利用施胶度测定、红外、扫描电镜、x-射线光电子能谱等手段,对石油树脂的作用机理进行了分析,并与普通阳离子分散松香胶在胶料性质、施胶效果等方面作了综合比较。发现在松香中加入C5或C9石油树脂,混合熔融物中羧基含量及阳离子分散松香胶颗粒表面O与C的比例明显降低,且石油树脂的加入还降低了阳离子分散松香胶中松香的短程有序性,抑制了松香的结晶趋势;松香中的羧基趋于分布在松香胶颗粒的表面,而石油树脂则趋于分布在胶膜表面,且C9石油树脂比C5石油树脂对羧基的屏蔽作用更强,位于外层的石油树脂显著增加了胶膜的疏水性能,从而提高了松香胶的施胶效率。
另外,针对中碱性施胶逐渐替代酸性施胶的趋势,为真正实现松香中碱性施胶,采用碳酸锆铵做松香施胶媒介物质,比较了阳离子分散松香胶分别与碳酸锆铵或硫酸铝联合使用及三者混合使用时对纸张的浸渍施胶效果。结果表明,当碳酸锆铵单独用作松香施胶媒介物时,施胶效果较好,而且在松香胶与碳酸锆铵质量比例为4:1时,纸张获得最高施胶度;但当将硫酸铝与碳酸锆铵混合用作松香施胶媒介物质时,两者之间相互干扰,不利于松香施胶。
最后,为了进一步提高阳离子分散松香胶的施胶效率,采用聚酰胺多胺环-氧氯丙烷树脂(PAE)作阳离子分散松香胶-硫酸铝施胶体系的施胶促进剂,初步探讨了PAE的作用。结果表明,加入PAE可改善阳离子分散松香胶的施胶效果,并在硫酸铝和松香胶加入之前加入PAE效果最好,PAE的加入量以0.1%为宜。
Rosin extenders and mordants were the research highlights of this paper in order to improve the sizing efficiency of cationic rosin size. Unmodified C5 petroleum resin, C9 petroleum resin and their mixtures were used as the extenders and melted together with natural rosin repectively to prepare cationic rosin size emulsions and used as internal sizing agents. The effects of C5 and C9 petroleum resin proportion, the addition levels of alum and cationic rosin sizes, pH value as well as pulps on the sizing degree of hand sheets were investigated. The results show that the cationic rosin sizes with C5 petroleum resin, C9 petroleum resin as well as their mixture as rosin extenders are more effective in internal sizing than the cationic rosin size without extender. When the mass ratios of the C5 petroleum resin, C9 petroleum resin and their mixture to rosin are 1:5, 1:10 and 1:10 repectively while the C5/C9 is 2:1 in the mixture, the obtaind cationic rosin sizes show high sizing efficiency. The cationic rosin sizes with C5 and C9 petroleum resin provide higher sizing degree than usual cationic rosin size even under the neutral condition of pH 7, although the sizing degrees decrease as pH value rises.
The function of the petroleum resins on the stability and sizing performance of the cationic rosin sizes was analyzed by means of the sizing degree measurement of hand sheets, infra-red technology, XRD and XPS. It is found that the addition of C5 and C9 petroleum resins as rosin extenders can significantly lower the content of carboxyl groups in rosin sizes and the ratio of O/C on the surfaces of rosin sizes since both C5 and C9 petroleum resin are hydrocarbon resins. The addition of petroleum resins also reduce the short-range-order domains of cationic rosin sizes, which means that petroleum resins can lower the trend of rosin crystallization. Meanwhile, XPS analysis also confirms that the carboxyl groups tend to distribute on the surfaces of rosin size particles while the petroleum resins tend to locate in the outer surfaces of the rosin sizes. Therefore, the petroleum resins have significantly increased the hydrophobicity of rosin size film, improving the sizing efficiency of cationic rosin sizes.
In view of the develpment towards alkaline sizing, ammonium zirconium carbonate (AZC) was selected as the new mordant of impregnated rosin sizing. The synergistic sizing effects of cationic rosin sizes with AZC, alum and both of them were investigated. The results show that AZC performs very well as the mordant of rosin sizing under neutral conditions. When the mass ratio of rosin to AZC is 4:1, high paper sizing degree was obtained. However, when aluminum sulfate and AZC are used together, they will interfere with each other and the sizing degree of rosin sized paper is lower than the case that they are used separately.
Finally, to further improve the sizing efficiency of the cationic rosin sizes, PAE was employed as accelerant to investigate its function in the rosin sizing. It is discovered that PAE can significantly improve the sizing efficiency of the cationic rosin size/aluminum sulfate system. When it is added before the aluminum sulfate and cationic rosin sizes, it will show the highest promoting effect for sizing. Its suitable addition level is 0.1% based on oven dried pulp.
引文
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