CN102399420A - 一种聚酯粘土纳米复合材料的制备方法 - Google Patents
一种聚酯粘土纳米复合材料的制备方法 Download PDFInfo
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Abstract
本发明涉及一种聚酯粘土纳米复合材料的制备方法;将粘土分散于溶剂中,与含有Ti离子的溶液进行离子交换,钛离子的用量为0.05~1mmol/g粘土;将粘土悬浮于溶剂中,溶剂用量为粘土重量的1-100倍;有机化处理剂或表面处理剂的用量为0.1-1mmol/克粘土;酯交换聚合以乙二醇与对苯二甲酸二甲酯的质量比为50~100∶100进行聚合反应,催化剂为有机化处理的粘土,加入量为聚酯粘土纳米复合材料质量的0.1-10%;或直接酯化聚合是以乙二醇与对苯二甲酸的质量比为40~80∶100进行聚合反应,催化剂加入量为聚酯粘土纳米复合材料质量的0.1-10%;纳米复合材料粘土分散均匀,材料力学和气体阻隔性能好。
Description
技术领域
本发明涉及一种聚酯粘土纳米复合材料的制备方法。
背景技术
聚酯缩聚催化剂是生产PET必不可少的原料。目前世界上90%以上PET装置都采用锑基催化剂,如三氧化二锑,醋酸锑等。锑基催化剂的优点是催化活性较高,对PET的热降解比较低,综合性能优异。但是锑基催化剂的致命缺点是锑有致癌作用,含锑的乙二醇必须在特殊熔炉中燃烧,或者必须按照危险品来处理,导致生产成本增加。另外锑还会在纤维染色过程中浸出,造成水污染,锑基催化剂在日本和欧洲正在面临日益增加的限制使用重金属法规的压力。国内外有关科技人员为此开发了各种非锑催化剂,目的是要使催化剂活性更高,还能满足安全、环保的要求。荷兰Acordis公司开发的可用于各种聚酯缩聚的C94钛硅催化剂。1997年开始应用,C94为钛-硅制剂,亦称Ti02-Si02复合物。其中Ti/Si含量比约为1∶9。杜邦公司于1998年开发了用于PET缩聚的钛基催化剂,型号为Tyzor,有PC-42和PC-50两个牌号,前者具有较高活性,后者可用来代替锑基催化剂。所产PET可用于制纤维、瓶子和薄膜。所产纤维已在欧洲市场上销售。
近年来,出现一种利用层状硅酸盐制备聚酯纳米复合材料的新方法,中国发明专利CN1272513A,CN1597776A,CN1396204A等均有报道。所取用的层状硅酸盐如蒙脱石、云母、麦加石、白云石、皂石、伊利石、高岭土等,由于层状晶体存在结构缺陷,层间吸附了大量的可以交换的阳离子,如Na+、Ca2+、Mg2+、Al3+等。利用有机铵盐、吡啶鎓盐、咪唑鎓盐、有机磷鎓盐等有机阳离子,可以将粘土层间阳离子交换出来,这些尺寸较大的有机阳离子则进入硅酸盐片层之间,从而扩大层间距。但是,蒙脱土等层状硅酸盐,片层和片层之间存在较强的离子键作用,由于聚酯的极性比较微弱,与粘土的相容性较差,粘土在聚酯中很难实现片层之间的完全剥离,容易形成大尺寸的团聚,导致聚酯/粘土纳米复合材料性能提高的幅度有限。而且,PET的合成与加工要经历近300℃的高温,常常会导致有机阳离子的分解,从而诱导PET分解,降低PET的热稳定性。
发明内容
本发明提供一种聚酯粘土纳米复合材料的制备方法,利用聚合所释放的能量使催化剂中粘土片层剥离,提高粘土在PET基体中的分散性制备聚酯/粘土复合材料,催化剂的添加量为0.10wt%至20wt%(相对于聚酯的理论产量),较佳的添加量为0.10wt%至10wt%(相对于聚酯的理论产量)。
本发明所述粘土矿物为:成分为SiO2和Al2O3、粒度小于200目、结构为层状或纤维状的硅铝酸盐矿物粉末,该粘土矿物在210℃的二元醇(如乙二醇、1,3-丙二醇、1,4-丁二醇或1,4-环己烷二甲醇等)中的溶解量高于0.10wt%(相对于催化剂本身干燥质量)。
具体来说,本发明所述粘土矿物为高岭土、云母、蒙脱土、坡缕石、海泡石、蛭石以及它们任意比例的混合物,优选高岭土、云母、蒙脱土、坡缕石以及它们任意比例的混合物,更优选蒙脱土,最优选钠基蒙脱土、钙基蒙脱土或他们任意比例的混合物。以上所述矿物均可从市售渠道获得。
该催化剂的制备方法包括以下步骤:
1)将粘土分散于溶剂中,与含有Ti离子的溶液进行离子交换,除去溶剂并高温锻烧。
2)将步骤1)得到的粘土进行有机化处理或表面处理。
步骤1)中所用到的溶剂包括水,醇类,苯及其同系物,丙酮等常用溶剂。离子交换的温度为0-100℃,高温锻烧温度为200-700℃。所述钛离子的来源主要包括三氯化钛及其水溶液,四氯化钛及其水溶液,钛酸四异丁酯,钛酸四正丁酯,硫酸钛等。处理过程中钛离子的用量为0.05~1mmol/g粘土。
步骤2)制备有机化粘土时,粘土悬浮于溶剂中,常用溶剂可选自水、乙醇、甲醇、乙二醇和甲苯中的一种或几种,其用量为粘土重量的1-100倍。处理过程中,有机化处理剂或表面处理剂的用量为0.1-1mmol/克粘土;所述有机化处理的温度为0-100℃。常用的有机化处理剂有十六烷基三甲基溴化铵、十六烷基三苯基溴化磷、十六烷基溴化吡啶、聚乙烯醇等。常用的表面处理剂有硅烷偶联剂KH560、KH550、KH570等。(来源:市售)
PET的合成采用酯交换法或直接合成法。
酯交换聚合是以乙二醇与对苯二甲酸二甲酯的质量比为50~100∶100进行聚合反应,催化剂为步骤2)有机化处理的粘土,加入量为最终聚酯粘土纳米复合材料质量的0.1-10%。
或直接酯化聚合是以乙二醇与对苯二甲酸的质量比为40~80∶100进行聚合反应,催化剂加入量为最终聚酯粘土纳米复合材料质量的0.1-10%。
反应在260-290℃,压力低于50Pa的条件下缩聚80-200min。
粘土可以在缩聚反应开始前任何时间内添加。使用时,为保证产品品质,可以添加常用添加剂,如着色剂、消光剂、链支化剂、稳定剂等等,其用量和用法与常规方法相同。
本发明适用的聚酯可包括对苯二甲酸(二甲酯)、2,6-萘二甲酸(二甲酯)与乙二醇、1,3-丙二醇、1,4-丁二醇或1,4-环己烷二甲醇的缩聚产物或共缩聚产物,也可以是这些二元羧酸(二甲酯)和二元醇与其它二元羧酸(二甲酯)或二元醇的共聚物,这些其它二元羧酸(二甲酯)或二元醇有间苯二甲酸(二甲酯)、对羟基苯甲酸、4,4′-联苯基二羧酸、二甘醇、分子量低于2000的聚乙二醇、分子量低于3000聚四氢呋喃醚等,优选的聚酯是聚对苯二甲酸乙二醇酯及其共聚物。
粘土具有不含重金属,对人畜无害的特点,本发明中引入的Ti离子对人体环境也无毒害作用。因此,按本发明制备的聚酯/粘土纳米复合材料在保持其原有特点的同时,还具有以下特点和优点:(1)Ti基粘土催化PET缩聚活性高,可以缩短聚合时间(2)传统的聚酯缩聚催化剂以Sb盐使用最为广泛,Sb是一种有害重金属,在发达国家面临越来越大的环保压力,因此以粘土为缩聚催化剂,还具有环保的优点。(3)所制备PET/粘土纳米复合材料中粘土分散性均匀,材料力学性能和气体阻隔性能较好。
附图说明
图1部分PET/粘土纳米复合材料的XRD衍射图:
具体实施方式
如下实施例说明本发明的实施方案,实施例中的一些参数按以下方法进行测量。
特性粘数(I.V.):0.1250g聚酯溶于25ml苯酚/1,1,2,2-四氯乙烷(1/1wt)混合溶剂中,于25℃测量。
端羧基浓度:少量聚酯溶于苯甲醇中,以苯酚红为指示剂,用0.01N的氢氧化钾乙二醇溶液进行酸碱滴定测得。
一.催化剂的制备
实施例1-2
6g钠基蒙脱土分散于600g水中,搅拌5小时。95.7ml HCL溶液中缓慢滴加6.6mlTiCl4,并搅拌5小时。取5.1ml上述溶液滴加入蒙脱土的悬浮液中,并继续搅拌5小时进行离子交换。离子交换完成以后的蒙脱土反复离心水洗,至离心上层清液pH=7且用一滴AgNO3检测不出Cl-。将得到的钛基蒙脱土于110℃烘干5小时并在250℃煅烧2h,过300目筛,得到PET缩聚催化剂A。取催化剂A1.5g,十六烷基三苯基磷0.94g,水60g,于80℃反应3小时。反应产物反复离心洗涤至上层清液用一滴AgNO3检测不出Br-。将产物于110℃烘干5小时过300目筛,得PET缩聚催化剂B。
实施例3-5
20g钠基蒙脱土分散于300g乙二醇中,搅拌5小时。300ml乙二醇溶液中缓慢滴加2.2mlTiCl4,并搅拌5小时。取30ml上述溶液滴加入蒙脱土的悬浮液中,并继续搅拌5小时进行离子交换。离子交换完成以后的蒙脱土反复离心用乙二醇洗,至离心上层清液pH=7且用一滴AgNO3检测不出C1-。将得到的钛基蒙脱土于110℃烘干5小时,并在250℃煅烧2h,得到PET缩聚催化剂C。取催化剂C1.5g,十六烷基溴化吡啶0.8g,水60g,于80℃反应3小时。反应产物反复离心洗涤至上层清液用一滴AgNO3检测不出Br-。将产物于110℃烘干5小时,得PET缩聚催化剂D。取催化剂C1.5g,在400℃煅烧4h,加十六烷基三苯基磷0.94g,水60g,于80℃反应3小时。反应产物反复离心洗涤至上层清液用一滴AgNO3检测不出Br-。将产物于110℃烘干5小时,得PET缩聚催化剂E。
实施例6-7
6g钠基蒙脱土分散于600g水中,搅拌5小时。300ml乙二醇溶液中缓慢滴加2.2mlTiCl4,并搅拌5小时。取18ml上述溶液滴加入蒙脱土的悬浮液中,并继续搅拌5小时进行离子交换。离子交换完成以后的蒙脱土反复离心水洗,至离心上层清液pH=7且用一滴AgNO3检测不出C1-。将得到的钛基蒙脱土于110℃烘干5小时并在250℃煅烧2h,过300目筛,得到PET缩聚催化剂F。催化剂F1.5g,在400℃煅烧4h,加聚乙烯醇1.2g,水60g,于80℃反应3小时。反应产物反复离心洗涤至上层清液用一滴AgNO3检测不出Br-。将产物于110℃烘干5小时,得PET缩聚催化剂G。
实施例8-14
取BHET131.65g,EG14.9g,催化剂A-G任何一种1.5g,在260-290℃,压力低于50Pa的条件下缩聚80-200min,得到PET/粘土的纳米复合材料H-N。
催化剂活性(聚合时间)PET复合材料熔点(℃)结晶温度(℃)
A 150min H 243.6165.0
B 135min I 253.6172.3
C 90min J 251.5180.6
D 88min K 256.4186.7
E 110min L 255.2181.1
F 130min M 252.5195.3
G 110min N 255.2181.1
部分PET/粘土纳米复合材料的端羧基值:
PET/粘土的纳米复合材料K:约10mol/t
PET/粘土的纳米复合材料N:约20mol/t
图1部分PET/粘土纳米复合材料的XRD衍射图:
从图中可以看出,粘土衍射峰较小,说明粘土分散性得到了提高。
Claims (5)
1.一种聚酯粘土纳米复合材料的制备方法,其特征在于:
1)将粘土分散于溶剂中,与含有Ti离子的溶液进行离子交换,除去溶剂并高温锻烧,离子交换的温度为0-100℃,高温锻烧温度为200-700℃;钛离子的用量为0.05~1mmol/g粘土;
2)将步骤1)得到的粘土进行有机化处理或表面处理;制备有机化粘土时,粘土悬浮于溶剂中,溶剂用量为粘土重量的1-100倍;有机化处理剂或表面处理剂的用量为0.1-1mmol/克粘土;有机化处理的温度为0-100℃;
步骤3)聚酯粘土纳米复合材料的制备
酯交换聚合是以乙二醇与对苯二甲酸二甲酯的质量比为50~100∶100进行聚合反应,催化剂为步骤2)有机化处理的粘土,加入量为最终聚酯粘土纳米复合材料质量的0.1-10%;
或直接酯化聚合是以乙二醇与对苯二甲酸的质量比为40~80∶100进行聚合反应,催化剂加入量为最终聚酯粘土纳米复合材料质量的0.1-10%;
反应在260-290℃,压力低于50Pa的条件下缩聚80-200min。
2.根据权利要求1所述的聚酯粘土纳米复合材料的制备方法,其特征在于:所述的钛离子的来源选自三氯化钛及其水溶液,四氯化钛及其水溶液,钛酸四异丁酯,钛酸四正丁酯,硫酸钛。
3.根据权利要求1所述的聚酯粘土纳米复合材料的制备方法,其特征在于:所述的有机化处理剂选自十六烷基三甲基溴化铵、十六烷基三苯基溴化磷、十六烷基溴化吡啶或聚乙烯醇。
4.根据权利要求1所述的聚酯粘土纳米复合材料的制备方法,其特征在于:步骤2)制备有机化粘土时,溶剂选自水、乙醇、甲醇、乙二醇、甲苯中的一种或几种。
5.根据权利要求1所述的聚酯粘土纳米复合材料的制备方法,其特征在于:所述的粘土选自钠基蒙脱土、钙基蒙脱土或他们任意比例的混合物。
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