CN1735645A - 催化酯化和酯交换反应的催化剂配合物和使用它的酯化/酯交换方法 - Google Patents
催化酯化和酯交换反应的催化剂配合物和使用它的酯化/酯交换方法 Download PDFInfo
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Abstract
本发明涉及一种用于催化酯化和酯交换反应的新型催化剂配合物,它包括:i)具有化学式[TiO4 (CH2) 4] n的聚合甘醇酸钛,其中n=1-200,和ii)碱金属的甘醇酸盐,其中聚合甘醇酸钛和碱金属的甘醇酸盐的摩尔比为约1.25∶1到约100∶1,优选约1.25∶1到约10∶1,和涉及酯化二羧酸化合物和二醇化合物,接着缩聚形成聚酯的方法。
Description
本发明涉及催化酯化和酯交换反应的催化剂配合物和使用它的酯化/酯交换方法。
聚酯和共聚酯是已知的,它们代表用于各种应用的重要的聚合物材料。优选在催化剂存在下,通过二羧酸,优选芳族酸如对苯二甲酸,与二羟基化合物,优选脂族二羟基化合物如乙二醇反应而制备它们。
热塑性聚酯是商业上大量生产的非常重要的聚合物材料。线性热塑性聚酯如聚(对苯二甲酸乙二酯)(PET)以各种各样的形式使用。例如,它们可以以合成纤维形式使用,所述合成纤维对大多数无机酸显示出良好的抗性且对清洗溶剂和表面活性剂显示出优良的抗性。热塑性聚酯在很大程度上还用作模塑材料。这种材料的特征在于许多所需的性能,如硬度、强度、韧度、良好的耐化学性和低的吸湿性。
通过缩聚二醇和烷基或芳基二酸生产聚酯例如PET,是本领域众所周知的,正如在Encyclopaedia of Polymer Science andEngineering,2nd ed,第12卷,John Wiley and Sons,New York(1988)中所述。在通常称为第一段催化添加剂的物质存在下,通过转化对苯二甲酸与乙二醇或者通过使对苯二甲酸二甲酯与乙二醇酯交换,从而通常将PET形成为低分子量的预聚物[双(羟烷酯)和低聚物]。随后通过酯化和酯交换反应,使该预聚物进行缩聚,形成高分子量聚酯。由于酯交换是固有地慢的反应,这要求使反应物长时间地保持在高温下且伴随热降解,因此缩聚步骤通常被催化。
然而,高度希望在尽可能高的速度下生产分子量高和黄度低的聚酯。聚酯的黄度通常是在或者聚合或者下游加工过程中发生的聚合物降解和副反应发生的结果。因此,所合成的聚合物的黄度不仅是如此生产的聚合物质量的指标,而且还是在色敏应用中聚合物进一步加工成制造形状如纤维、薄膜和一些模塑部件的指标。尽管生产高分子量聚酯的许多催化剂是已知的,但它们的缺点是或者转化速度、使用容易程度,或者用其形成的产品质量不足。
含锑化合物目前广泛地在商业上用作催化剂,所述催化剂提供高反应速度和低色彩的所需结合。然而,由于成本和难以以环境负责的方式处理有毒的锑,因此存在相当大的动机寻找锑的替代品。
常常使用钛基化合物催化缩聚反应。这些催化剂无毒且其反应性甚至好于锑催化剂之一,但观察到它们引起聚酯非所需的黄化。
一些专利包括其中使用钛化合物和碱金属化合物作为催化剂生产聚酯和共聚酯的方法。WO98/56848公开了共沉淀物作为缩聚催化剂。DE19513056A1公开了基于二氧化钛或钛酸酯化合物作为沉淀的催化剂。另外,在日本专利申请52148593A中,公开了在碱金属化合物存在下,通过使用含钛的特定配合物化合物作为催化剂,制备聚酯。在Textil Praxis International 1,1989,pp.29-33中,公开了等摩尔量的甘醇酸钛和碱金属的甘醇酸盐的催化剂,从而导致分子量不足的聚酯。
因此,本发明的目的是提供催化酯化和酯交换反应的催化剂,该催化剂克服了现有技术中所述的缺点,特别是在短的反应时间内形成具有低催化剂浓度和具有改进的聚酯性能,如黄度下降和分子量增加的聚酯。
本发明另一目的是提供使用该新型催化剂配合物制造聚酯的方法。
藉助用于催化酯化/酯交换反应的催化剂配合物,从而实现第一个目的,所述催化剂配合物包括:
i)具有化学式[TiO4(CH2)4]n的聚合甘醇酸钛,其中n=1-200,和
ii)碱金属的甘醇酸盐,
其中聚合甘醇酸钛和碱金属的甘醇酸盐的摩尔比为约1.25∶1到约100∶1,优选约1.25∶1到约10∶1。
优选地,碱金属是钠和该甘醇酸盐具有化学式Na-O-CH2-CH2-OH。
更优选,在被称为酸酯化组分的各酯化组分的混合物内催化剂中金属的总含量为1-约70ppm,优选约10-约50ppm。
至于第二个目的,即,通常使用催化剂配合物制造聚酯,首先用二醇使二羧酸酯化,接着进行酯交换。该催化剂配合物在这两个反应中是活性的。羧酸化合物是化学式HOOC-R-COOH的二羧酸,其中R是直链或支链的亚烷基、亚芳基和亚烯基或其结合。
优选R具有约2-约30,优选约4-约15个碳原子。
此外,优选羧酸化合物选自对苯二甲酸、间苯二甲酸、萘二甲酸、琥珀酸、己二酸、邻苯二甲酸、戊二酸、草酸、马来酸及其结合。
最优选羧酸化合物是对苯二甲酸。
仍然优选羧酸化合物是具有衍生于羧酸的重复单元的低聚物。
仍然优选醇化合物是化学式HO-R′-OH的二元醇,化学式的HO-[R″-O-]n-H的聚亚烷基二醇,或其结合,其中R′是具有2-约10,优选2-4个碳原子的直链或支链的亚烷基,和其中R″相同或者不同,是具有1-约10,优选1-5个碳原子的亚烷基。
此外,醇化合物可选自乙二醇、丙二醇、异丙二醇、丁二醇、1-甲基丙二醇、戊二醇、新戊二醇及其结合。
此外,在进一步的实施方案中,优选在约150℃-约500℃,优选250℃-300℃的温度下进行该方法。
在另一实施方案中,在约0.001-约10个大气压的压力下进行该方法。
此外,醇化合物对羧酸化合物的摩尔比范围可以是约0.1∶1到约10∶1,优选约1∶1到约3∶1。
优选在被称为酸酯化组分的各酯化组分内存在约1-约70ppm范围的催化剂,优选约10-约50ppm。
有利的是,该方法可用于制备聚(对苯二甲酸乙二酯)。
令人惊奇地发现,本发明的催化剂配合物可在短的反应时间内高产率地形成聚酯。此外,本发明的催化剂配合物防止所形成的聚酯非所需的黄变。所得聚酯的分子量范围甚至高于锑基催化剂配合物,因此高度适于工业应用。此外,本发明比现有技术(TPI 1,1989,pp.29-33)获得高得多的分子量。另外,需要仅仅低的催化剂浓度,因此聚合物内总的金属含量低。
用于本发明催化剂配合物的聚合甘醇酸钛具有以下结构式:
其中n=0-200。
可通过添加碱金属的甘醇酸盐,使在乙二醇中不溶的聚合甘醇酸钛溶解,在甘醇酸钛与碱金属的甘醇酸盐之间形成配合物。可使用溶液或者固体形式的该催化剂配合物以供制备聚酯或共聚酯。
可例如通过用乙二醇转化丁酸钛,从而合成聚合甘醇酸钛。可通过在乙二醇内溶解碱金属元素,从而生产碱金属的甘醇酸盐。作为聚合物化合物的甘醇酸钛不能溶溶乙二醇。通过将碱金属的甘醇酸盐在乙二醇内的溶液添加到甘醇酸钛内,形成可溶解在乙二醇内的配合物,从而获得透明的催化剂溶液。该配合物化合物可通过蒸馏乙二醇而沉淀,并且可以以固体或在乙二醇内的溶液形式使用。
通过下述实施例进一步阐述本发明,所述实施例不要解释为不合理地限制本发明的范围。
实施例1:制备甘醇酸Ti/Na
1.1甘醇酸钛的合成
向配有搅拌器、氮气气体入口和蒸馏连接管的500ml三颈烧瓶填充68.0g(0.2mol)丁酸钛和124.2g(2.0mol)乙二醇。通过搅拌5分钟混合该透明溶液。在缓慢的氮气流下,加热混合物一直到160℃(油浴温度)。在加热的同时,白色固体开始沉淀。蒸馏掉在反应过程中生成的正丁醇。反应时间为约9小时。有时需要增加油浴温度到180℃,以便得到理论量的正丁醇(59.3g,0.8mol)。用塞子密闭烧瓶,和冷却反应混合物过夜。将100ml乙酸乙酯加入到该混合物中并搅拌5分钟。通过G3过滤器板过滤掉固体并用50ml乙酸乙酯洗涤。在干燥器内在氧化磷(V)上干燥该产物,之后在60℃下真空(0.1mbar)干燥3小时。产量为33.5g(0.199mol/99.7%)。
1.2甘醇酸钠的合成
在配有搅拌器、高效冷凝器和氮气气体入口的500ml三颈烧瓶中放置155.18g(2.5mol)乙二醇(MEG),并在N2流入下搅拌15分钟。用刀切割11.5g(0.5mol)元素钠成0.5g(0.02mol)的小片。将它们仔细加入到MEG中。可观察到形成小量的氢气。然后仔细地加热该混合物到80℃,直到全部含量的钠溶解。这可能非常快速地发生。
1.3甘醇酸Ti/Na配合物的合成(此处摩尔比为2∶1)
向配有磨口塞子且放置在磁搅拌器上的100ml Erlenmeyer烧瓶中添加0.2360g(1.4×10-3mol)甘醇酸钛和35g(0.56mol)乙二醇。加热该混合物到120℃,并添加5.9046g 1wt%甘醇酸钠在乙二醇内的溶液(0.0590g=0.7×10-3mol甘醇酸钠)。悬浮液在5分钟内变为透明溶液。
实施例2-聚(对苯二甲酸乙二酯)的合成
将配有搅拌器和扭矩测量单元的2升反应器中引入778.09g(4.68mol)对苯二甲酸、377.90g(6.09mol)乙二醇和特定量的催化剂在乙二醇内的溶液,例如在实施例1.3中所述的催化剂配合物。在60分钟内升高温度到235℃和压力提高约9bar。此外,在1.5小时内压力下降到大气压,和收集在烧瓶内的冷凝液量。在完成预酯化之后,在30分钟内升高温度到260℃。在260℃下维持该温度30分钟和压力下降到7mbar。此外,在10分钟内升高温度到275℃和压力下降到低于10-2mbar。此刻开始缩聚的时间测量。在275℃下维持该温度直到获得所需的扭矩(7.5Nm=约24000g/mol)。在缩聚工艺之后使用冰浴收集冷凝液并粒化。在PET完全结晶之后,通过藉助特性粘数获得的数均分子量和颜色,分析所有产物的转化率。
在下表1中描述了实施例编号,聚合母炼胶所使用的催化剂体系,聚合物产物的L*、a*和b*色数,缩聚时间和数均分子量。
其中在CIE色标下:
L*(亮度)轴-0黑色,100白色
a*(红色-绿色)轴-正值为红色;负值为绿色和0为中性色
b*(蓝色-黄色)轴-正值为黄色;负值为蓝色和0为中性色
实施例 | 催化剂ppm(称为酯化组分/此处对苯二甲酸) | L* | a* | B* | 缩聚时间 | 分子量Mn[g/mol] |
1 | 300ppm Sb2Ac3 | 81.1 | -1.9 | -0.8 | 1小时39分 | 23200 |
2 | 300ppm甘醇酸钛 | 78.4 | -1.3 | 8.7 | 1小时38分 | 23100 |
3 | 300ppm甘醇酸钛150ppm甘醇酸钠 | 81.0 | -1.6 | 4.3 | 1小时56分 | 23900 |
4 | 409ppm甘醇酸钛409ppm甘醇酸钠 | 80.5 | -1.1 | 3.2 | 1小时24分 | 24100 |
5 | 20ppm Sb2Ac3 | 81.7 | -1.7 | -0.2 | 3小时30分 | 20600 |
6 | 20ppm甘醇酸钛 | 83.9 | -2.1 | 2.2 | 2小时26分 | 24000 |
7 | 50ppm甘醇酸钛40ppm甘醇酸钠 | 83.1 | -2.8 | 4.0 | 1小时25分 | 24200 |
8 | 40ppm甘醇酸钛30ppm甘醇酸钠 | 83.7 | -2.2 | 1.2 | 1小时22分 | 23500 |
9 | 30ppm甘醇酸钛20ppm甘醇酸钠 | 82.6 | -2.6 | 1.0 | 1小时27分 | 24400 |
10 | 20ppm甘醇酸钛10ppm甘醇酸钠 | 85.3 | -2.3 | 0.9 | 1小时34分 | 24000 |
发现在各种组合物(实施例3、4和7-10)内通过使用催化剂体系甘醇酸Ti/Na,与300ppm商业上使用的锑催化剂情况下的缩聚时间相比(实施例1),缩聚时间在相同的数量级上(参考对苯二甲酸)。表1公开了对于较低的催化剂浓度来说,用锑催化剂获得的聚酯(实施例5)的分子量为20600g/mol,和缩聚时间为3小时30分,而使用甘醇酸钛催化剂(实施例6)的分子量为24000g/mol和缩聚时间较短(2小时26分)。与使用300ppm的锑催化剂相比,通过使用具有较低浓度的催化剂配合物(实施例7-10),缩聚时间较少和分子量较高。通过使用催化剂体系甘醇酸Ti/Na(实施例3、4和7-10)或降低催化剂浓度(实施例6),在制造PET的情况下的黄变可急剧下降,而使用纯甘醇酸钛时黄变较高(实施例2,b*值为8.7)。
前述说明和权利要求中公开的特征独立地和以任何结合方式可成为以各种形式实现本发明的实质。
Claims (15)
1.催化酯化和酯交换反应的催化剂配合物,它包括:
i)具有化学式[TiO4(CH2)4]n的聚合甘醇酸钛,其中n=1-200,和
ii)碱金属的甘醇酸盐,
其中聚合甘醇酸钛和碱金属的甘醇酸盐的摩尔比为约1.25∶1到约100∶1,优选约1.25∶1到约10∶1。
2.权利要求1的催化剂配合物,其特征在于碱金属是钠和该甘醇酸盐具有化学式Na-O-CH2-CH2-OH。
3.权利要求1或2的催化剂配合物,其特征在于在被称为酸酯化组分的酯化组分的混合物内催化剂配合物中的金属总含量为1-约70ppm,优选约10-约50ppm。
4.使用权利要求1-3任何一项的催化剂配合物酯化羧酸化合物和醇化合物的方法,其特征在于羧酸化合物是化学式HOOC-R-COOH的二羧酸,其中R是直链或支链的亚烷基、亚芳基、亚烯基或其结合。
5.权利要求4的方法,其特征在于R具有约2-约30,优选约4-约15个碳原子。
6.权利要求4或5的方法,其特征在于羧酸化合物选自对苯二甲酸、间苯二甲酸、萘二甲酸、琥珀酸、己二酸、邻苯二甲酸、戊二酸、草酸、马来酸及其结合。
7.权利要求6的方法,其特征在于羧酸化合物是对苯二甲酸。
8.权利要求4或5的方法,其特征在于羧酸化合物是具有衍生于羧酸的重复单元的低聚物。
9.权利要求4-8任何一项的方法,其特征在于醇化合物是化学式HO-R′-OH的二元醇,化学式HO-[R″-O-]n-H的聚亚烷基二醇,或其结合,其中R′是具有2-约10,优选2-4个碳原子的直链或支链的亚烷基,和其中R″相同或者不同,是具有1-约10,优选1-5个碳原子的亚烷基。
10.权利要求9的方法,其特征在于醇化合物选自乙二醇、丙二醇、异丙二醇、丁二醇、1-甲基丙二醇、戊二醇、新戊二醇及其结合。
11.权利要求4-10任何一项的方法,其特征在于在约150℃-约500℃,优选250℃-300℃的温度下进行该方法。
12.权利要求4-11任何一项的方法,其特征在于在约0.001-约10个大气压的压力下进行该方法。
13.权利要求4-12任何一项的方法,其特征在于醇化合物对羧酸化合物的摩尔比范围为约0.1∶1到约10∶1,优选约1∶1到约3∶1。
14.权利要求4-13任何一项的方法,其特征在于在被称为酸酯化组分的酯化组分内存在约1-约70ppm范围的催化剂,优选约10-约50ppm。
15.权利要求4-14任何一项的方法,其特征在于该方法用于制备聚(对苯二甲酸乙二酯)。
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CN111094231A (zh) * | 2017-07-12 | 2020-05-01 | Sabic环球技术有限责任公司 | 生产二羧酸双羟亚烷基酯的方法 |
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US8557950B2 (en) | 2005-06-16 | 2013-10-15 | Grupo Petrotemex, S.A. De C.V. | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
US7838596B2 (en) | 2005-09-16 | 2010-11-23 | Eastman Chemical Company | Late addition to effect compositional modifications in condensation polymers |
US9267007B2 (en) | 2005-09-16 | 2016-02-23 | Grupo Petrotemex, S.A. De C.V. | Method for addition of additives into a polymer melt |
HRP20060287A2 (en) * | 2006-08-30 | 2008-03-31 | Kuftinec Josip | Process for production of fatty acid esthers and fuels comprising fatty acid esthers |
TW201100460A (en) | 2009-03-18 | 2011-01-01 | Saudi Basic Ind Corp | Process for making thermoplastic polyesters |
EP2287225A1 (en) | 2009-08-20 | 2011-02-23 | Saudi Basic Industries Corporation | Process for making polyethylene terephthalate |
DE202010013946U1 (de) | 2010-10-05 | 2012-01-11 | Uhde Inventa-Fischer Gmbh | Katalysatormischung zur Herstellung von hochviskosen Polyestern |
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CN104540837A (zh) * | 2012-06-28 | 2015-04-22 | 沙特基础工业公司 | 新的羟乙酸钛催化剂及其制备方法 |
CN111094231A (zh) * | 2017-07-12 | 2020-05-01 | Sabic环球技术有限责任公司 | 生产二羧酸双羟亚烷基酯的方法 |
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