CN115044036B - 一种聚酰胺多胺环氧氯丙烷树脂的制备方法 - Google Patents
一种聚酰胺多胺环氧氯丙烷树脂的制备方法 Download PDFInfo
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 6
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Abstract
本发明公开了一种聚酰胺多胺环氧氯丙烷树脂的制备方法。通过将二元胺和二元酸在催化剂的作用下发生缩聚反应,制备得到聚酰胺多胺预聚体;聚酰胺多胺预聚体再进一步与环氧氯丙烷反应,待反应物达到预设的粘度后通过加入强酸弱碱盐水溶液和去离子水终止反应,得到聚酰胺多胺环氧氯丙烷树脂。本发明所制备的聚酰胺多胺环氧氯丙烷树脂具有pH值呈弱酸性,增湿强效果好,且储存三个月后增湿强效果未降低的特点,比传统方法制备的湿强剂应用性能更佳。可应用于造纸领域,作为湿强剂和起皱控制剂使用,也可应用于家居建材领域,作为粘结剂使用。
Description
技术领域
本发明涉及造纸化学品领域,具体涉及一种聚酰胺多胺环氧氯丙烷树脂的制备方法。
背景技术
聚酰胺多胺环氧氯丙烷树脂是一种具有阳电荷的水溶性热固型树脂,在造纸工业中主要作为湿强剂和起皱控制剂中的粘缸剂来使用。作为湿强剂,聚酰胺多胺环氧氯丙烷树脂具有增湿强效果好、无甲醛、用量少、适合中碱性抄纸等优点,已经成为造纸工业中用量最大的湿强剂产品。作为起皱控制剂,聚酰胺多胺环氧氯丙烷树脂具有成膜速度快,成膜性能好的特点,广泛地应用于造纸领域里的起皱过程中。
聚酰胺多胺环氧氯丙烷树脂作为一种水溶性热固性树脂,在碱性条件下或受热过程中其分子链上的阳电荷基团具有快速交联反应的特性,利用这个特性将其应用于造纸系统,可以通过聚酰胺多胺环氧氯丙烷树脂与纤维发生交联反应提高纸张的湿强度,或聚酰胺多胺环氧氯丙烷树脂在高温下自交联反应成膜,用于起皱过程中烘缸表面保护涂层。为了利用聚酰胺多胺环氧氯丙烷树脂的交联反应特性,在制备聚酰胺多胺环氧氯丙烷树脂的过程中,通常在反应溶液达到一定粘度后加入大量的无机酸对聚酰胺多胺环氧氯丙烷树脂的进一步交联反应进行终止,维持聚酰胺多胺环氧氯丙烷树脂产品的储存稳定性。但加入无机酸终止反应具有一系列的问题,首先,加入无机酸后需要将聚酰胺多胺环氧氯丙烷树脂的水溶液pH值调整到2-4,才能满足其稳定储存的要求,目前造纸系统多为中碱性造纸系统,对于一些湿强度要求高的纸种会加入大量的聚酰胺多胺环氧氯丙烷树脂湿强剂,会在造纸系统中引入大量的酸,使系统的pH过低,影响造纸生产的稳定性,也影响其他化学品的使用;其次,硫酸、甲酸等属于强氧化剂,对聚酰胺多胺环氧氯丙烷树脂中阳电荷基团具有水解作用,会导致聚酰胺多胺环氧氯丙烷树脂在存储一段时间后发生性能降低的问题;再次,过低的pH值也会对输送管道造成腐蚀,造成胶黏物的累积,影响生产过程中化学品的稳定添加。
发明内容
为了克服现有技术缺陷,本发明的目的是提供一种聚酰胺多胺环氧氯丙烷树脂的制备方法。
本发明制备聚酰胺多胺环氧氯丙烷树脂的技术方案如下:
一种聚酰胺多胺环氧氯丙烷树脂的制备方法,其特征在于,包括以下步骤:(1)将二元酸和二元胺在催化剂的作用下于120-190℃反应5-10h,加水稀释得到固含量为45%-55%的聚酰胺多胺预聚体水溶液;(2)将固含量为45%-55%的聚酰胺多胺预聚体水溶液、去离子水加入反应釜中,搅拌混合均匀,在10-30℃条件下,向上述溶液中缓慢滴加环氧氯丙烷,滴加完成后保温反应0.5-4小时,然后升温至40-60℃,继续反应,待反应物粘度达到100-200厘泊,加入强酸弱碱盐水溶液和去离子水终止反应,得到聚酰胺多胺环氧氯丙烷树脂水溶液,所述强酸弱碱盐为硫酸铝、硫酸镁、氯化铵、硫酸铵、氯化铁、硫酸铁中一种或几种。
所述步骤(2)中,强酸弱碱盐水溶液的制备方法为,将强酸弱碱盐溶解于水中配成质量浓度为5%-35%的强酸弱碱盐水溶液。
所述步骤(2)中,强酸弱碱盐的加入质量为聚酰胺多胺环氧氯丙烷树脂质量的3%-35%。
所述步骤(2)中,聚酰胺多胺环氧氯丙烷树脂水溶液的固含量为12.5%-20%,pH值为4-6。
所述的一种聚酰胺多胺环氧氯丙烷树脂的应用,作为湿强剂和起皱控制剂用于造纸生产,作为粘结剂用于家居建材领域。
本发明的有益效果包括:
(1)本发明采用强酸弱碱盐水溶液代替无机酸对合成的聚酰胺多胺环氧氯丙烷树脂反应进行终止,得到的聚酰胺多胺环氧氯丙烷树脂水溶液pH值在4-6范围,呈弱酸性,并且增湿强效果好,储存6个月性能稳定未发生凝胶现象,方便了聚酰胺多胺环氧氯丙烷树脂的使用,降低了聚酰胺多胺环氧氯丙烷树脂的强酸性对造纸水系统pH值和输送管路的不利影响。
(2)本发明采用强酸弱碱盐代替酸终止聚酰胺多胺环氧氯丙烷树脂反应,避免了在聚酰胺多胺环氧氯丙烷树脂中引入强氧化性物质,防止聚酰胺多胺环氧氯丙烷树脂上有效基团在储存过程中的氧化水解,得到的聚酰胺多胺环氧氯丙烷树脂增湿强效果好并且性能持久稳定,即使长期储存其增湿强效果也没有降低,方便聚酰胺多胺环氧氯丙烷树脂的储存和运输。
(3)本发明不需要特殊设备、原料易得、成本低廉、制备工艺简单,通过本发明制备的聚酰胺多胺环氧氯丙烷树脂,可应用于造纸领域,作为湿强剂和起皱控制剂使用,也可应用于家居建材领域,作为粘结剂使用。
具体实施方式
以下通过具体实施例进一步说明本发明描述的方法,但是并不意味着本发明局限于这些实施例。
实施例1
将146g己二酸和103g二乙烯三胺加入反应釜中,加入催化剂浓硫酸8g,搅拌均匀后,升温至120℃反应10h,加水稀释得到固含量为50%的聚酰胺多胺预聚体水溶液;取固含量为50%的聚酰胺多胺预聚体水溶液200g,去离子水30g加入反应釜中,搅拌混合均匀,在30℃条件下,向上述溶液中缓慢滴加65g环氧氯丙烷,滴加完成后保温反应0.5h,然后升温至40℃继续反应,待反应物粘度达到200厘泊,加入质量浓度为35%硫酸镁水溶液165g终止反应,加水稀释,得到固含量为20%,pH值为4.2的聚酰胺多胺环氧氯丙烷树脂水溶液。
实施例2
将146g己二酸和113g二乙烯三胺加入反应釜中,加入催化剂浓硫酸6g,搅拌均匀后,升温至190℃反应5h,加水稀释得到固含量为55%的聚酰胺多胺预聚体水溶液;取固含量为55%的聚酰胺多胺预聚体水溶液200g,去离子水35g加入反应釜中,搅拌混合均匀,在20℃条件下,向上述溶液中缓慢滴加62g环氧氯丙烷,滴加完成后保温反应2.5h,然后升温至60℃继续反应,待反应物粘度达到100厘泊,加入质量浓度为5%硫酸铝水溶液700g终止反应,加水稀释,得到固含量为12.5%,pH值为6.0的聚酰胺多胺环氧氯丙烷树脂水溶液。
实施例3
将146g己二酸和113g二乙烯三胺加入反应釜中,加入催化剂浓硫酸6g,搅拌均匀后,升温至150℃反应7h,加水稀释得到固含量为45%的聚酰胺多胺预聚体水溶液;取固含量为45%的聚酰胺多胺预聚体水溶液200g,去离子水20g加入反应釜中,搅拌混合均匀,在10℃条件下,向上述溶液中缓慢滴加55g环氧氯丙烷,滴加完成后保温反应4h,然后升温至50℃继续反应,待反应物粘度达到150厘泊,加入质量浓度为20%硫酸铝水溶液155g终止反应,加水稀释,得到固含量为15%,pH值为5.2的聚酰胺多胺环氧氯丙烷树脂水溶液。
实施例4
将146g己二酸和113g二乙烯三胺加入反应釜中,加入催化剂浓硫酸6g,搅拌均匀后,升温至150℃反应7h,加水稀释得到固含量为45%的聚酰胺多胺预聚体水溶液;取固含量为45%的聚酰胺多胺预聚体水溶液200g,去离子水20g加入反应釜中,搅拌混合均匀,在10℃条件下,向上述溶液中缓慢滴加55g环氧氯丙烷,滴加完成后保温反应4h,然后升温至50℃继续反应,待反应物粘度达到150厘泊,加入质量浓度为20%氯化铵水溶液155g终止反应,加水稀释,得到固含量为15%,pH值为5.5的聚酰胺多胺环氧氯丙烷树脂水溶液。
实施例5
将146g己二酸和113g二乙烯三胺加入反应釜中,加入催化剂浓硫酸6g,搅拌均匀后,升温至150℃反应7h,加水稀释得到固含量为45%的聚酰胺多胺预聚体水溶液;取固含量为45%的聚酰胺多胺预聚体水溶液200g,去离子水20g加入反应釜中,搅拌混合均匀,在10℃条件下,向上述溶液中缓慢滴加55g环氧氯丙烷,滴加完成后保温反应4h,然后升温至50℃继续反应,待反应物粘度达到150厘泊,加入质量浓度为20%氯化铵与硫酸铝混合水溶液(氯化铵与硫酸铝质量比为1∶1)155g终止反应,加水稀释,得到固含量为15%,pH值为4.8的聚酰胺多胺环氧氯丙烷树脂水溶液。
对比例1
将146g己二酸和113g二乙烯三胺加入反应釜中,加入催化剂浓硫酸6g,搅拌均匀后,升温至150℃反应7h,加水稀释得到固含量为45%的聚酰胺多胺预聚体水溶液;取固含量为45%的聚酰胺多胺预聚体水溶液200g,去离子水20g加入反应釜中,搅拌混合均匀,在10℃条件下,向上述溶液中缓慢滴加55g环氧氯丙烷,滴加完成后保温反应4h,然后升温至50℃继续反应,待反应物粘度达到150厘泊,加入浓硫酸终止反应,加水稀释,得到固含量为15%,pH值为3.2的聚酰胺多胺环氧氯丙烷树脂水溶液。
应用实施例
将上述实施例和对比例制备的聚酰胺多胺环氧氯丙烷树脂水溶液稀释至固含量为1%添加使用。将漂白针叶木浆和漂白阔叶木浆按25∶75质量比混合打浆,打浆至30°SR。向打好的混合浆料中加入0.2%(对浆料绝干量)的聚酰胺多胺环氧氯丙烷树脂水溶液,然后在自动纸页成型器上分别抄造定量为60g/m2的纸,湿纸页在300KPa压力下压榨30s,在干燥器上于105℃下干燥15min。干燥后的手抄片于110℃条件下继续熟化20min,平衡水分后,测其熟化后干、湿强度,结果如表1所示。
将上述实施例和对比例制备的聚酰胺多胺环氧氯丙烷树脂水溶液在室温条件下放置一个月,然后采用上述同样方法进行抄纸实验,在相同条件下测试其放置三个月后的增干、湿强性能,评价其增湿强性能稳定性,结果如表2所示。
表1.抄纸性能检测数据
表2.放置3个月后抄纸性能检测数据
表1的数据表明,采用本发明方法制备的聚酰胺多胺环氧氯丙烷树脂增干、湿强效果均较好,比采用酸终止的方法效果更优。表2数据表明,本发明方法制备的聚酰胺多胺环氧氯丙烷树脂在放置三个月后增干、湿强效果并没有降低,并且储存三个月后溶液稳定,未出现凝胶。而对比例制备的树脂放置三个月后增湿强效果有明显降低,这是由于用于终止反应的酸具有强氧化性,破坏了树脂的结构,也表明本发明方法制备的树脂具有更佳的应用性能。
以上所述的具体实施方式,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施方式而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (2)
1.一种聚酰胺多胺环氧氯丙烷树脂的制备方法,其特征在于,包括以下步骤:(1)将二元酸和二元胺在催化剂的作用下于120-190℃反应5-10h,加水稀释得到固含量为45%-55%的聚酰胺多胺预聚体水溶液;(2)将固含量为45%-55%的聚酰胺多胺预聚体水溶液、去离子水加入反应釜中,搅拌混合均匀,在10-30℃条件下,向上述溶液中缓慢滴加环氧氯丙烷,滴加完成后保温反应0.5-4h,然后升温至40-60℃,继续反应,待反应物粘度达到100-200厘泊,加入强酸弱碱盐水溶液和去离子水终止反应,得到聚酰胺多胺环氧氯丙烷树脂水溶液;所述强酸弱碱盐为硫酸铝、硫酸镁、氯化铵、硫酸铵中一种或几种,强酸弱碱盐水溶液的制备方法为,将强酸弱碱盐溶解于水中配成质量浓度为5%-35%的强酸弱碱盐水溶液;所述聚酰胺多胺环氧氯丙烷树脂水溶液的固含量为12.5%-20%,pH值为4-6。
2.如权利要求1所述的制备方法,其特征在于,所述步骤(2)中,强酸弱碱盐的加入质量为聚酰胺多胺环氧氯丙烷树脂质量的3%-35%。
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