CN1169859C - 采用钛氧基草酸盐催化剂和催化剂增强剂的聚酯缩聚 - Google Patents

采用钛氧基草酸盐催化剂和催化剂增强剂的聚酯缩聚 Download PDF

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CN1169859C
CN1169859C CNB011013443A CN01101344A CN1169859C CN 1169859 C CN1169859 C CN 1169859C CN B011013443 A CNB011013443 A CN B011013443A CN 01101344 A CN01101344 A CN 01101344A CN 1169859 C CN1169859 C CN 1169859C
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C·M·道林
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S·R·塞沙德里
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Abstract

本发明提供含有钛氧基草酸盐催化剂和金属草酸盐催化剂增强剂并任选含有金属助催化剂的新型催化剂组合物。发现钛氧基草酸盐催化剂、催化剂增强剂和金属助催化剂之间具有协效关系。本发明还提供在催化有效量的缩聚催化剂存在下由缩聚制备聚酯的改进方法,其中的改进包括将所述新型催化剂组合物用作缩聚催化剂。该改进方法可制成乙醛数量较低和颜色优良的改进的聚酯。

Description

采用钛氧基草酸盐催化剂和催化剂 增强剂的聚酯缩聚
IR 3480A
相关申请的参考
本专利申请要求2000年1月申请的美国临时申请No.60/175,006的优先权。
技术领域
本发明涉及制造聚酯的方法,尤其涉及采用钛氧基草酸盐例如钛氧基草酸锂作为该反应的催化剂,结合采用催化剂增强剂例如金属草酸盐如草酸锂,以在催化剂用量大大降低的情形下提供所形成聚酯的性能改进例如乙醛含量降低和颜色优良的快反应。本发明发现了钛氧基草酸盐催化剂和催化剂增强剂之间的协效关系。本发明也发现了钛氧基草酸盐催化剂、催化剂增强剂和金属助催化剂例如氧化锑或三乙酸锑之间的协效关系。
背景技术
形成聚酯的缩聚反应需要极其长的时间,而这可由合适的催化剂大大缩短。多种类型的催化剂都可用来缩短反应时间。例如三氧化锑、三乙酸锑和三乙二醇化锑通常用作缩聚催化剂。
已有人建议钛氧基草酸盐化合物用作制备聚酯的缩聚反应的催化剂。然而,当用作聚酯缩聚的催化剂时,钛氧基草酸盐催化剂会在制成的聚酯内引起颜色问题。
聚酯由二元酸例如对苯二甲酸和间苯二甲酸或其酯、酰氯的官能衍生物,与二醇例如乙二醇、丁二醇或其氧化物和碳酸衍生物的官能衍生物的酯化、酯交换或缩聚获得。在该情形下,当使用一种二元酸成分和二醇成分时,就获得单一的聚酯。当至少两种或多种二元酸组分与二醇组分混合、酯化或进行酯交换并接着进行缩聚时,就获得混合的共聚酯。当单一聚酯或两种或多种混合的共聚酯的起始缩聚物进行缩聚时,就获得有序的聚酯。在本发明中,聚酯一词指这三种的通称。
现有文献已揭示了用作聚酯缩聚催化剂的钛氧基草酸盐化合物。所揭示的钛氧基草酸盐化合物包括钛氧基草酸钾、钛氧基草酸铵、钛氧基草酸锂、钛氧基草酸钠、钛氧基草酸钙、钛氧基草酸锶、钛氧基草酸钡、钛氧基草酸锌和钛氧基草酸铅。然而,基于这些参考文献中的实施例,实际上仅有钛氧基草酸钾和铵被用来催化形成聚酯的反应。见例如日本公开的专利42-13030,1967年7月25日公开。转让给Hoechst、公开于1996年6月3日、题为“热稳定的中性色无锑聚酯的制备方法及由其制备的聚酯”的欧洲专利申请EP0699700 A2,揭示了使用作缩聚催化剂,然而,仅有钛氧基草酸钾和异丙醇钛用作这种催化剂,同时揭示了颜色改善的无锑聚酯,也使用了钴和光学增亮剂。其他专利揭示了钛氧基草酸钾用作制备聚酯的缩聚催化剂,例如美国专利4,245,086,发明人是Keiichi Uno等人;日本专利JP06128464,发明人是Ishida,M等。Hideo,M等的题为“聚酯树脂的制备方法”的美国专利3,957,886,第3栏第59行至第4栏第10行揭示了包括一系列多种钛氧基草酸盐催化剂的聚酯钛氧基草酸盐催化剂。但是,实施例中仅使用了钛氧基草酸钾和钛氧基草酸铵,而钛氧基草酸锂甚至没有列入其优选的钛氧基草酸盐催化剂中。
发明内容
本发明基于非钛氧基草酸盐能够增强钛氧基草酸盐催化剂的催化功能的发现。本发明提供含有钛氧基草酸盐催化剂和金属草酸盐催化剂增强剂并任选含有金属助催化剂例如锑基催化剂的新型催化剂组合物。发现了钛氧基草酸盐催化剂和催化剂增强剂之间的协效关系。还发现了钛氧基草酸盐催化剂、催化剂增强剂和金属助催化剂例如氧化锑或三乙酸锑之间的协效关系。本发明还提供在催化有效量的缩聚催化剂存在下通过形成聚酯的反应物的缩聚制备聚酯的改进的方法,其中改进之处包括将含有钛氧基草酸盐例如钛氧基草酸锂和催化剂增强剂例如非钛氧基金属草酸盐如草酸锂,并任选含有金属催化剂例如氧化锑或三乙酸锑的新型催化剂组合物,用作缩聚催化剂。该改进的方法可制成乙醛量较低和颜色优良的改进聚酯。钛氧基草酸盐/催化剂增强剂组合物能够与其他催化剂结合起来用作缩聚催化剂,以获得协效催化活性。优选钛氧基草酸锂Li2TiO(C2O4)2、草酸锂Li2(C2O4)2与氧化锑或三乙酸锑的组合物。本发明的催化剂组合物中碱金属非钛氧基草酸盐占组合物重量的1-80份。
由形成聚酯的反应物的缩聚制备聚酯对聚酯行业内的普通技术人员是众所周知的。该反应的常规催化剂是氧化锑。本发明基于这样的发现:钛氧基草酸盐催化剂与金属草酸盐催化剂增强剂(例如草酸锂)之间的协效关系比其他钛氧基草酸盐催化剂在催化制成颜色优秀(白色)的聚酯的缩聚反应的性能方面意外地优异。由此就可以不再需要含锑的催化剂,而且由此就能够用钛氧基草酸锂作为催化剂制成无锑聚酯。使用钛氧基草酸锂所提供的这些优点在钛氧基草酸锂与其他制备聚酯的缩聚催化剂结合使用时仍可保持,只要钛氧基草酸锂在反应混合物中占至少1ppm(优选1-20),以反应混合物中的钛的重量为基准。这里所使用的“钛氧基草酸锂”一词所包含的意思是钛氧基草酸二钾[Li2TiO(C2O4)2]和钛氧基草酸单锂,其中钛氧基草酸二锂中的一个锂用另一个碱金属例如钾(例如LiKTiO(C2O4)2)置换,而且这些化合物可含有或无水合水。当不要求所形成的被催化的产物不含锑时,钛氧基草酸锂催化剂能够与锑催化剂结合,以获得两种催化剂的优点。
除了提高催化缩聚反应的钛氧基草酸盐的催化效果,当以对已知参与酯化或酯交换反应的反应物为催化有效量使用时,金属草酸盐也能够增强催化酯化和酯交换反应的钛氧基草酸盐的催化效力。催化的有效量是适宜的。优选约3ppm的钛氧基草酸盐,以酯化或酯交换反应混合物中的钛的重量为基准。
由缩聚反应形成聚酯的反应物对本行业内的普通技术人员是众所周知的,而且在专利例如发明人为Kyber,M等的美国专利5,198,530、发明人为B.Duh的美国专利4,238,593、发明人为Cholod等的美国专利4,356,299、发明人为Tershasy等的美国专利3,907,754中有揭示,它们在这里引入以供参考。该技术也在1989年由牛津Pergamon出版社出版的G.C.Eastmond等人编辑的“综合聚合物科学”第5卷第275-315页,和R.E.Wilfong发表于《聚合物科学杂志》1961年54卷385-410页的文章中有揭示。这样制成的一个极其重要的聚酯商业品种是对苯二甲酸乙二醇酯(PET)。
钛氧基草酸盐:钛氧基草酸盐包括金属钛氧基草酸盐[M2TiO(C2O4)2(H2O)n],其中M独立地选自钾、锂、钠、铯,例如钛氧基草酸锂或钾,和非金属钛氧基草酸盐例如钛氧基草酸铵。钛氧基草酸盐可以是无水的(n=0),或含有部分水合水,即n表示水合水的数量。
非钛氧基草酸盐:起钛氧基草酸盐催化剂的催化增强剂作用的非钛氧基草酸盐包括草酸锂Li2C2O4、草酸钠Na2C2O4、草酸钾K2C2O4、草酸铷Rb2C2O4、草酸铯Cs2C2O4。优选草酸锂。
助催化剂:与钛氧基草酸盐催化剂和金属草酸盐增强剂结合起作用的助催化剂包括三乙酸锑Sb(CH3COO)3、乙二醇化锑Sb2(OCH2CH2O)3、氧化锑(Sb2O3)。
增强钛氧基草酸盐催化剂的催化活性的有效量为对于每份钛氧基草酸盐催化剂至少约1份的金属草酸盐。优选对于每份催化剂约1-100份的增强剂,以钛氧基草酸盐催化剂和助催化剂(如果有助催化剂的话)的总重量为基准。
将催化有效量的钛氧基草酸盐加入形成聚酯的反应物中。优选约1-40ppm的催化剂,以催化剂中钛的重量和形成聚酯的反应物重量为基准,约与形成的聚酯中的1-40ppm(重量)催化剂相等,以催化剂中钛的重量为基准。
与一种或多种制备PET的缩聚反应催化剂结合的催化剂增强剂的协效性能由下述实施例说明。
具体实施方式
用底部装有挤出螺杆的3/16不锈钢、1.5升反应器评价催化剂。容器装有3个入口,用电动机由安培数监控进行垂直搅拌。实验室试验全都在4.0摩尔规模下进行,使用BHET和常规的瓶用树脂反应釜配方作为形成聚酯的反应物。加入BHET时,加入实验用催化剂。
将对苯二甲酸二(2-羟乙酯)(BHET)和催化剂加入反应器内,并用氮气覆盖内容物。在恒定搅拌下减压加热混合物。移出聚合期间生成的EG并捕获。当搅拌器扭矩达到搅拌马达由安培数所指示的一定数值,一般对于聚合物的特性粘度约达0.6时,停止聚合。
采用上述步骤和催化剂与催化剂增强剂的不同用量进行了完成了17个实施例。
实施例A催化剂-240ppm锑,锑来自于氧化锑(Sb2O3)--反应时间为127分钟。
实施例B催化剂-10ppm来自于草酸锂的钛氧基-反应时间100分钟。
实施例1催化剂-10ppm来自于草酸锂的钛氧基+146ppm草酸锂(或约15当量)-反应时间53分钟。
实施例2催化剂-10ppm来自于钛氧基草酸锂的钛+735ppm草酸锂(或约70当量)-反应时间55分钟。
实施例C催化剂-6ppm来自于钛氧基草酸锂的钛+75ppm来自于氧化锑(Sb2O3)的锑-反应时间105分钟。
实施例D催化剂-6ppm来自于钛氧基草酸锂的钛+150ppm来自于氧化锑的锑-反应时间110分钟。
实施例3催化剂-6ppm来自于钛氧基草酸锂的钛+75ppm来自于氧化锑的锑+367ppm草酸锂(或约15当量)-反应时间65分钟。
实施例4催化剂-3ppm来自于钛氧基草酸锂的钛+38ppm来自于氧化锑的锑+184ppm草酸锂(或约35当量)-反应时间90分钟。
实施例5催化剂-2.6ppm来自于钛氧基草酸锂的钛+33ppm来自于氧化锑的锑+160ppm草酸锂-反应时间110分钟。
实施例6催化剂-3ppm来自于钛氧基草酸锂的钛+38ppm来自于氧化锑的锑+185ppm草酸锂-反应时间95分钟。
实施例7催化剂-3.3ppm来自于钛氧基草酸锂的钛+41ppm来自于氧化锑的锑+146ppm草酸锂-反应时间70分钟。
实施例8催化剂-2.0ppm来自于钛氧基草酸锂的钛+25ppm来自于氧化锑的锑+90ppm草酸锂-反应时间120分钟。
实施例9催化剂-4.7ppm来自于钛氧基草酸锂的钛+59ppm来自于氧化锑的锑+118ppm草酸锂-反应时间100分钟。
实施例10催化剂-2.0ppm来自于钛氧基草酸锂的钛+25ppm来自于氧化锑的锑+50ppm草酸锂-反应时间125分钟。
实施例11催化剂-2.0ppm来自于钛氧基草酸钾的钛+25ppm来自于氧化锑的锑+90ppm草酸钾-反应时间115分钟。
实施例12催化剂-2.0ppm来自于钛氧基草酸钾的钛+25ppm来自于氧化锑的锑+50ppm草酸锂-反应时间165分钟。
实施例E催化剂-240ppm来自于氧化锑的锑,包含商品颜色调节剂-反应时间110分钟。
发现含有增强剂的催化剂可提高生产率,并给出较高的亮度、较高的黄度,而且在多数情形下,降低聚合物内的乙醛(AA)含量。
对比实施例B与实施例1,将草酸锂加入钛氧基草酸锂可提供为单用草酸锂获得的聚合速率的两倍的速率。形成的聚合物具有相似的颜色、乙醛浓度和CEG数量。如实施例2的情形,相对于实施例1,加入额外量的草酸锂不会进一步提高聚合速率。这说明了钛氧基草酸锂与草酸锂之间存在协效关系。对比实施例B、1和2与实施例A,可观察到前者金属加入量比实施例A少的情形下聚合速率较高,聚合物的特性粘度、CEG数量、乙醛浓度相似,而前者的L*和b*值较高。
对比实施例C与实施例3,草酸锂加入到钛氧基草酸锂与氧化锑的混合物中,会大大提高聚合速率。所提供的聚合物具有相似的CEG数量和乙醛浓度。然而,实施例3给出的聚合物的L*和b*值比实施例C制成的聚合物高。
对比实施例C与实施例4,其中钛和锑的含量减半,实施例4中草酸锂的加入(在50%钛/锑加入量时)提供较高的聚合速率,这给出了草酸锂能够增强钛和锑催化剂混合物的催化活性的直接证据。由实施例4制成的聚合物内乙醛浓度也比实施例C低很多。由L*和b*值变化所指示的颜色也有改善。
对比由钛氧基草酸盐、金属草酸盐和氧化锑组成的实施例5-12与加有商品颜色调节剂的氧化锑的实施例E。对所有的实施例都可观察到相似的聚合速率。然而,实施例5-12的3元催化剂混合物都大大减少了金属加入量。由实施例5-12制成的聚合物内乙醛浓度也比所观察到的制成的聚合物颜色优良的对照实施例E低(高达50%)。
将商品颜色调节剂加到实施例E的对照物氧化锑中,具有降低制成的聚合物的L*和b*值两方面的效果(即,亮度和黄度)。如果商品颜色调节剂不加到该对照物中,那么制成的聚合物的L*和b*值就与由实施例5-12获得的值相似。
最优选的催化剂是实施例10的催化剂混合物。它给出了对于对照物的优良颜色(L*和b*)、等效聚合时间,并在低催化剂含量下大大降低PET中的AA含量。
提高聚合产量、降低包装树脂内的乙醛含量并有效降低锑与总催化剂的成本是本发明的部分优点,如实施例所示。
17个实施例的结果如下表所示。值得注意的是所有示出的催化剂(实施例12除外)与实施例A和E的常规锑催化剂相比都在BHET聚合方面提高了生产率。所有制得的较亮但更黄的产物和所有分批料的CEG都落入17±7范围内,这对于我们的实验室反应釜操作来说是典型的。含钛聚合物乙醛值一般比含锑聚合物的高。然而,注意:实施例4-12的催化剂在很低的催化剂含量(与对照物对比时,25%或以下的金属含量)下就可制成乙醛比锑对照物大大降低的聚合物。
实施例为两套。实施例A-D和1-4有关钛氧基草酸锂与草酸锂、钛氧基草酸锂与草酸锂与锑之间的增效,该增效作用可大大提高聚合速率。实施例E和5-12说明,当3元成分的量最佳化时,它们形成的催化剂在金属加入量大大降低情形下,速率与对照物速率等效,制成的聚合物具有优良的颜色和降低的AA含量。
 催化剂 用量(克)  聚合时间(分钟)   特性粘度   CEG    AA(ppm)     L*     b*
    A  0.292     127  0.679     16     99   68.1   7.8
    B  0.063     100  0.674     16     95   78.4   26.1
    1  0.212     53  0.666     18     112   75.9   28.3
    2  0.810     55  0.683     18     136   72.9   31.2
    C  0.128     105  0.644     17     126   75.9   28.1
    D  0.220     110  0.694     18     128   72.8   22.5
    3  0.501     65  0.68     14     106   79.8   21.1
    4  0.250     90  0.628     24     47   80.46   20.1
    5  0.220     110  0.599     11     38   53.7   39.4
    6  0.253     95  0.590     13     37   48.3   39.8
    7  0.220     70  0.576     10     29   54.7   39.8
    8  0.135     120  0.603     13     43   48.4   41.9
    9  0.220     100  0.597     12     41   51.5   43.6
    10  0.094     125  0.602     13     26   48.9   38.3
    11  0.137     115  0.598     13     28   43.4   53.9
    12  0.096     165  0.581     16     19   45.4   49.3
    E  0.292     110  0.599     14     48   29.9   -4.2
L*与亮度有关,越接近100,聚合物越亮。对比3元催化剂(实施例4)的L*值80.5与氧化锑的68.1(实施例A)。
b*测量值与聚合物黄度有关,b*值越小,聚合物的黄色越淡。对比3元催化剂(实施例4)的b*值20.1与氧化锑的7.8(实施例A)。
乙醛浓度:AA是不合要求的聚合副产物。对比3元催化剂(实施例10)的AA值26ppm与所观察到的氧化锑对照物(实施例E)的48ppm。
聚合速率:反应期间特性粘度增高的速率,该情形下以特性粘度约为0.6为量度。对比3元催化剂(实施例4)制成的特性粘度大于0.6的聚合物,反应时间90分钟,与氧化锑(实施例A)制成的特性粘度大于0.6的聚合物,反应时间127分钟。
特性粘度(IV):表示反应期间进行的聚合程度。0.6特性粘度表示数均分子量约为19000。
CEG:羧基末端基团,表示单位重量聚合物的酸末端基团的数量。对比3元催化剂(实施例10)制成的CEG含量为13的聚合物与氧化锑制成的CEG含量为14的聚合物。这说明用这两种体系制成的聚合物结构很相似。
催化剂浓度:实施例10的3元催化剂制成的聚合物,含有34ppm来自催化剂的金属,对比由氧化锑制成的聚合物,含有240ppm来自催化剂的金属。

Claims (18)

1.一种增强的钛氧基草酸盐催化剂组合物,其含有碱金属钛氧基草酸盐和有效量的用来增强碱金属钛氧基草酸盐的催化效力的碱金属非钛氧基草酸盐;其中碱金属非钛氧基草酸盐的含量为1-100份,以每份碱金属钛氧基草酸盐催化剂为基准。
2.如权利要求1所述的组合物,其中所述的碱金属非钛氧基草酸盐选自草酸锂Li2C2O4、草酸钠Na2C2O4、草酸钾K2C2O4、草酸铷Rb2C2O4和草酸铯Cs2C2O4
3.如权利要求1所述的组合物,其中所述的碱金属钛氧基草酸盐选自式M2TiO(C2O4)2(H2O)n的金属钛氧基草酸盐,其中每个M都独立地选自钾、锂、钠、铯。
4.如权利要求1所述的组合物,其中所述的碱金属非钛氧基草酸盐是草酸锂,而碱金属钛氧基草酸盐是钛氧基草酸锂。
5.如权利要求1所述的组合物,其中所述的碱金属非钛氧基草酸盐占组合物重量的1-80份。
6.如权利要求2所述的组合物,其中所述的碱金属非钛氧基草酸盐占组合物重量的1-80份。
7.如权利要求3所述的组合物,其中所述的碱金属非钛氧基草酸盐占组合物重量的1-80份。
8.如权利要求4所述的组合物,其中所述的碱金属非钛氧基草酸盐占组合物重量的1-80份。
9.一种增强的催化剂组合物,其含有碱金属钛氧基草酸盐、含锑的金属催化剂和有效量的用来增强碱金属钛氧基草酸盐的催化效力的碱金属非钛氧基草酸盐;其中碱金属非钛氧基草酸盐的含量为1-100份,以每份碱金属钛氧基草酸盐催化剂和含锑的金属催化剂的总重量为基准。
10.如权利要求9所述的组合物,其中所述的含锑的金属催化剂选自三乙酸锑、三乙二醇化锑、氧化锑。
11.如权利要求9所述的组合物,其中所述的碱金属非钛氧基草酸盐占组合物重量的1-80份。
12.如权利要求10所述的组合物,其中所述的碱金属非钛氧基草酸盐占组合物重量的1-80份。
13.一种在缩聚催化剂存在下通过形成聚酯的反应物被催化缩聚制备聚酯的改进方法,其中所述的改进包括将权利要求1所述的组合物用作催化剂。
14.一种在缩聚催化剂存在下通过形成聚酯的反应物被催化缩聚制备聚酯的改进方法,其中所述的改进包括将权利要求2所述的组合物用作催化剂。
15.一种在缩聚催化剂存在下通过形成聚酯的反应物被催化缩聚制备聚酯的改进方法,其中所述的改进包括将权利要求3所述的组合物用作催化剂。
16.一种在缩聚催化剂存在下通过形成聚酯的反应物被催化缩聚制备聚酯的改进方法,其中所述的改进包括将权利要求4所述的组合物用作催化剂。
17.一种在缩聚催化剂存在下通过形成聚酯的反应物被催化缩聚制备聚酯的改进方法,其中所述的改进包括将权利要求9所述的组合物用作催化剂。
18.一种在缩聚催化剂存在下通过形成聚酯的反应物被催化缩聚制备聚酯的改进方法,其中所述的改进包括将权利要求10所述的组合物用作催化剂。
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CN109794290B (zh) * 2019-01-31 2021-08-27 天津城建大学 一种螺旋型草酸氧钛盐光催化剂及其制备方法

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NO20010055D0 (no) 2001-01-04
CN1359963A (zh) 2002-07-24
KR100758517B1 (ko) 2007-09-14
NZ509185A (en) 2001-11-30
ID28868A (id) 2001-07-12
DE60124599D1 (de) 2007-01-04
CA2330283A1 (en) 2001-07-07
MY124539A (en) 2006-06-30
NO20010055L (no) 2001-07-09
EP1114838A1 (en) 2001-07-11
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JP2001190963A (ja) 2001-07-17
EP1114838B1 (en) 2006-11-22
ES2275625T3 (es) 2007-06-16
PT1114838E (pt) 2007-02-28
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