CN102702497B - 一种聚酯催化剂的制备方法 - Google Patents
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Abstract
本发明涉及一种聚酯催化剂的制备方法，包括如下步骤：(1)依次将含有钛、硅和锡的化合物溶解于有机溶剂，；(2)将酸性或碱性的水溶液加入步骤(1)的混合物中进行水解，收集沉淀物，离心，洗涤，干燥，得到本发明的催化剂，即TiO2/SiO2/SnO2的共沉淀物。该催化剂不仅对聚酯缩聚反应有效果，且对酯化反应也有明显的催化作用，所得聚酯切片色相也较好。
Description
技术领域
本发明涉及一种聚酯催化剂的制备方法，特别是涉及一种可用作聚酯和共聚酯酯化及缩聚反应的钛/硅/锡复合催化剂的制备方法。
背景技术
聚酯是由二元醇和二元酸缩聚而得的聚合物的总称，是一类性能优异、用途广泛的工程塑料，在薄膜、瓶用包装、片材等领域有重要用途。
聚酯催化剂的研究自聚酯问世以来从未停止过，目前应用于工业生产和研究较多的主要有锑、锗和钛三个系列的催化剂，其中最常用的是锑系催化剂(包括Sb2O3、SbAc3和乙二醇锑等)。当今世界上90％的聚酯是由锑系催化剂生产出来的。锑系催化剂活性适中，副反应少，但是在聚酯合成过程中会还原析出，使聚酯切片成灰色，增加纺丝组件的压力，最另外它是重金属催化剂，会对环境造成污染，不符合可持续发展。锗系催化剂稳定性好，所合成的聚酯产品色相佳，但是锗金属价格昂贵，应用有极大的局限性。钛系催化剂活性高，不含重金属，是目前研究最多的一类催化剂，早期使用的是钛的无机盐或者有机酯类，制得的聚酯产品存在稳定性差和制品泛黄、浑浊，应用受到了限制。
在Acordis公司申请的专利WO95191164.3中提到了出牌号为C-94的无毒高效催化剂，主要组分为TiO2/SiO2和TiO2/ZrO2，适合生产PET、PBT和PTT等；Zimmer公司开发出牌号为EcocatB和Ecocat T两种催化剂，在缩聚反应中，具有催化活性的金属化合物吸附在非均相的载体上；ICI公司下属的Synetix公司推出过以钛为基础的聚酯催化剂，牌号分别为AC400、AC300、AC200和AC240等；CN1138339公开了采用钛酸酯和硅酸酯供水解制得的钛系聚酯催化剂，CN1259969公开了钛酸酯与金属化合物共沉淀制得的钛系聚酯催化剂。
上述专利公开的催化剂制得的聚酯色相仍然不是很好，色相值与采用锑系催化剂相比扔然较高，没有解决钛系催化剂制得的聚酯发黄的问题。目前尚无制得的钛系催化剂对酯化及缩聚都有不错的催化作用，且所得产品的色相很好。
发明内容
本发明的目的是提供一种钛/硅/锡复合催化剂的制备方法，制得的固体催化剂不仅对聚酯缩聚反应有效果，且对酯化作用也有很好的作用，所得聚酯切片色相也较好。
本发明的方法包括如下步骤：
(1)依次将含有钛、硅和锡的化合物溶解于有机溶剂，在搅拌下将酸性或碱性水溶液加入其中进行水解0.5～1h，水解温度为15～30℃；
(2)水解结束后，经离心分离得水解沉淀物，然后用去离子水洗涤该产物，即为本发明目的催化剂TiO2/SiO2/SnO2；
所述的含钛化合物为Ti(OR)4，式中R为具有2～4个碳原子的烷基，可选自钛酸四乙酯、钛酸四丙酯、钛酸四异丙酯、钛酸四丁酯中的一种；
所述的含硅化合物为Si(OR)4，式中R为具有2～4个碳原子的烷基，可选自正硅酸乙酯和正硅酸丁酯中的一种；
所述的含锡化合物为SnCl4；
所述Si(OR)4与SnCl4与Ti(OR)4的摩尔比分别为：
Si(OR)4∶Ti(OR)4＝0.05～0.5∶1，优选为0.06～0.1∶1；
Sn(Cl)4∶Ti(OR)4＝0.1～5∶1，优选为0.5～1∶1。
所选用的有机溶剂优选为1-6个碳原子的一元醇或多元醇，可选自甲醇、乙醇、异丙醇，异丁醇，正己醇，乙二醇、丁二醇、己二醇和丙三醇中的一种，优选为乙醇，所述有机溶剂与钛、硅和锡化合物总量的摩尔比为10～40∶1，优选为15～20∶1。
水解过程中，通过加入适量的酸或者碱来调控金属盐类的水解速度，具体量化到水解液的PH，常用的酸类为各种无机酸或者有机酸，优选的有机酸为磷酸、盐酸、硫酸，优选的无机酸为醋酸。常用的碱类为氨水、氢氧化钠、氢氧化钾。
所述水解液的PH值选自为1～4和11～14中的一种；
本发明所述的聚酯制备方法为两步法，即第一步由二元羧酸和二元醇进行酯化反应，得到预聚物，酯化反应温度在200～240℃进行，压力为常压，第二步在真空下进行缩聚反应，反应温度为240～260℃，压力为60～130Pa，以二元酸和二元醇总重量为基准，催化剂的用量为200～250ppm。
与现有技术相比，本发明的创新点在于：本发明在钛和硅的混合物中加入了SnCl4进行共水解，所得的催化不仅对聚酯缩聚过程有效，对酯化过程同样有效果，且所得聚酯具有良好的色相，取得了良好的技术效果。
具体实施方式
下面通过实施例对本发明进一步阐述，但本发明并非局限于这些实施例。其中各实施例中产品的熔融指数采用国家标准GB/T 3682-2000进行测定，表1中的b值指CIE标准中物质由蓝色至黄色的程度，是评估聚酯色相的重要指标，b值越低，色相越好，采用国家标准GB/T14190-93进行测定。
实施例1
将17g钛酸四丁酯，1.2g正硅酸乙酯和6.5g四氯化锡溶于86ml无水乙醇中得溶液A，再将加有适量磷酸，PH为1的9g去离子水溶于86ml无水乙醇中得溶液B。在搅拌均匀的情况下，将溶液B加入溶液A中，滴加时间为半小时，温度为15℃，产生白色沉淀，再将混合物搅拌1小时，离心分离，将沉淀物水洗3次，最后在70℃下干燥24小时，得催化剂Cat-1。
实施例2
将27.2g钛酸四丁酯，1.5g正硅酸乙酯和15.6g四氯化锡溶于134ml无水乙醇中得溶液A，再将加有适量盐酸，PH为4的20.9g去离子水溶于134ml无水乙醇中得溶液B。在搅拌均匀的情况下，将溶液B加入溶液A中，滴加时间为半小时，温度为20℃，产生白色沉淀，再将混合物搅拌45分钟，离心分离，将沉淀物水洗3次，最后在70℃下干燥24小时，得催化剂Cat-2。
实施例3
将22.7g钛酸四异丙酯，2.2g正硅酸乙酯和20.8g四氯化锡溶于139ml无水乙醇中得溶液A，再将加有适量氨水，PH为11的18.1g去离子水溶于139ml无水乙醇中得溶液B。在搅拌均匀的情况下，将溶液B加入溶液A中，滴加时间为半小时，温度为30℃，产生白色沉淀，再将混合物搅拌1小时，离心分离，将沉淀物水洗3次，最后在70℃下干燥24小时，得催化剂Cat-3。
实施例4
将14.2g钛酸四异丙酯，0.8g正硅酸乙酯和13g四氯化锡溶于230ml无水乙醇中得溶液A，再将加有适量氢氧化钠，PH为14的36g去离子水溶于230ml无水乙醇中得溶液B。在搅拌均匀的情况下，将溶液B加入溶液A中，滴加时间为半小时，温度为25℃，产生白色沉淀，再将混合物搅拌1小时，离心分离，将沉淀物水洗3次，最后在70℃下干燥24小时，得催化剂Cat-4。
实施例5
将1.5mol对苯二甲酸与2.4mol丁二醇投入2L反应釜中，加入催化剂Cat-1 0.11g，即220ppm，进行酯化反应，温度为220℃～240℃，压力为常压，通过精馏装置排除反应生成的水。酯化结束后抽真空减压至体系压力低于130Pa，同时反应温度逐渐升至255℃，当体系反应至所需粘度后停止反应，得聚酯P1供测试使用。测试结果见表1。
实施例6
将1.5mol对苯二甲酸与2.4mol丁二醇投入2L反应釜中，加入催化剂Cat-2 0.12g，即250ppm，进行酯化反应，温度为220℃～240℃，压力为常压，通过精馏装置排除反应生成的水。酯化结束后抽真空减压至体系压力低于130Pa，同时反应温度逐渐升至255℃，当体系反应至所需粘度后停止反应，得聚酯P2供测试使用。测试结果见表1。
实施例7
将1.5mol对苯二甲酸与2.4mol丁二醇投入2L反应釜中，加入催化剂Cat-3 0.12g，即250ppm，进行酯化反应，温度为220℃～240℃，压力为常压，通过精馏装置排除反应生成的水。酯化结束后抽真空减压至体系压力低于130Pa，同时反应温度逐渐升至255℃，当体系反应至所需粘度后停止反应，得聚酯P3供测试使用。测试结果见表1。
实施例8
将1.5mol对苯二甲酸与2.4mol丁二醇投入2L反应釜中，加入催化剂Cat-4 0.09g，即200ppm，进行酯化反应，温度为220℃～240℃，压力为常压，通过精馏装置排除反应生成的水。酯化结束后抽真空减压至体系压力低于130Pa，同时反应温度逐渐升至255℃，当体系反应至所需粘度后停止反应，得聚酯P4供测试使用。测试结果见表1。
实施例9
将1.2mol对苯二甲酸，0.225mol间苯二甲酸，0.075mol己二酸与2.565mol丁二醇，羟乙基化双酚A 0.285mol投入2L反应釜中，加入催化剂Cat-1 0.11g，即220ppm，进行酯化反应，温度为220℃～240℃，压力为常压，通过精馏装置排除反应生成的水。酯化结束后抽真空减压至体系压力低于130Pa，同时反应温度逐渐升至255℃，当体系反应至所需粘度后停止反应，得聚酯P5供测试使用。测试结果见表1。
比较例1，由与实施例五同样的方法制备聚酯，采用钛酸四丁酯作为催化剂加入量为0.12g，得聚酯B1供测试使用。测试结果见表1。
比较例2，由与实施例9同样的方法制备聚酯，采用钛酸四丁酯和丁基锡酸作为催化剂，加入量分别为0.12g，0.36g，得聚酯B2供测试使用。测试结果见表1。
表1聚酯性能与催化剂种类之间的关系
Claims (4)
1.一种聚酯催化剂的制备方法，其特征在于包括如下步骤：
将17g钛酸四丁酯，1.2g正硅酸乙酯和6.5g四氯化锡溶于86ml无水乙醇中得溶液A，再将加有适量磷酸，pH为1的9g去离子水溶于86ml无水乙醇中得溶液B；在搅拌均匀的情况下，将溶液B加入溶液A中，滴加时间为半小时，温度为15℃，产生白色沉淀，再将混合物搅拌1小时，离心分离，将沉淀物水洗3次，最后在70℃下干燥24小时，得催化剂。
2.一种聚酯催化剂的制备方法，其特征在于包括如下步骤：
将27.2g钛酸四丁酯，1.5g正硅酸乙酯和15.6g四氯化锡溶于134ml无水乙醇中得溶液A，再将加有适量盐酸，pH为4的20.9g去离子水溶于134ml无水乙醇中得溶液B；在搅拌均匀的情况下，将溶液B加入溶液A中，滴加时间为半小时，温度为20℃，产生白色沉淀，再将混合物搅拌45分钟，离心分离，将沉淀物水洗3次，最后在70℃下干燥24小时，得催化剂。
3.一种聚酯催化剂的制备方法，其特征在于包括如下步骤：
将22.7g钛酸四异丙酯，2.2g正硅酸乙酯和20.8g四氯化锡溶于139ml无水乙醇中得溶液A，再将加有适量氨水，pH为11的18.1g去离子水溶于139ml无水乙醇中得溶液B；在搅拌均匀的情况下，将溶液B加入溶液A中，滴加时间为半小时，温度为30℃，产生白色沉淀，再将混合物搅拌1小时，离心分离，将沉淀物水洗3次，最后在70℃下干燥24小时，得催化剂。
4.一种聚酯催化剂的制备方法，其特征在于包括如下步骤：
将14.2g钛酸四异丙酯，0.8g正硅酸乙酯和13g四氯化锡溶于230ml无水乙醇中得溶液A，再将加有适量氢氧化钠，pH为14的36g去离子水溶于230ml无水乙醇中得溶液B；在搅拌均匀的情况下，将溶液B加入溶液A中，滴加时间为半小时，温度为25℃，产生白色沉淀，再将混合物搅拌1小时，离心分离，将沉淀物水洗3次，最后在70℃下干燥24小时，得催化剂。
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| PCT/CN2013/076580 WO2013182013A1 (zh) | 2012-06-07 | 2013-05-31 | 一种聚酯合成复合催化剂的制备方法 |
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Address after: 215341 No. 366, Shipu Zhongjie Road, Qiandeng Town, Kunshan City, Suzhou City, Jiangsu Province Patentee after: Kunshan Tianyang New Material Co.,Ltd. Patentee after: EAST CHINA University OF SCIENCE AND TECHNOLOGY Patentee after: Tianyang New Material (Shanghai) Technology Co.,Ltd. Address before: 215341 No. 366, Shipu Zhongjie Road, Qiandeng Town, Kunshan City, Suzhou City, Jiangsu Province Patentee before: Kunshan Tianyang New Material Co.,Ltd. Patentee before: EAST CHINA University OF SCIENCE AND TECHNOLOGY Patentee before: SHANGHAI TIANYANG HOT MELT ADHESIVE Co.,Ltd. |