CN101024686B - 制备聚四氢呋喃或四氢呋喃共聚物的方法 - Google Patents
制备聚四氢呋喃或四氢呋喃共聚物的方法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/20—Tetrahydrofuran
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及一种通过在调聚体和/或共聚单体存在下在酸性催化剂上聚合四氢呋喃而制备聚四氢呋喃或四氢呋喃共聚物的方法,其中所述反应混合物包含0.001-5重量%的至少一种线性脂族醚。
Description
本发明涉及一种通过在调聚体和/或共聚单体存在下在酸性催化剂上聚合四氢呋喃(下文称为THF)而得到官能度降低的聚四氢呋喃或四氢呋喃共聚物的方法,其中将反应混合物中线性脂族醚的含量设定为0.001-5重量%。
也称为聚氧丁二醇的聚四氢呋喃(下文称为PTHF)在塑料和合成纤维工业中用作多功能中间体并且尤其用于聚氨酯、聚酯和聚酰胺弹性体的生产。特别重要的应用领域是生产弹力纤维。此外,象某些其衍生物一样,它在许多应用中为有价值的辅助剂,例如作为分散剂或用于废纸的脱墨。
PTHF在工业上通常通过在合适催化剂上聚合四氢呋喃(下文简称为THF)而制备。加入合适的试剂可以控制聚合物链的链长并因此可以将平均分子量设定为所需值。通过选择调聚体的类型和用量进行控制。该类试剂也称为链终止剂或“调聚体”。合适调聚体的选择额外允许在聚合物链的一端或两端引入官能基团。在工业方法中,通常将乙酸酐或水用作调聚体。
不仅将其他调聚体用作链终止剂,而且也引入到PTHF的增长聚合物链中。它们不仅具有调聚体的功能,而且同时用作共聚单体并因此可以同样好地作为调聚体或共聚单体。该类共聚单体的实例是具有两个羟基的调聚体,例如二醇(二元醇)。这些共聚单体例如可以是乙二醇、1,2-丙二醇、丁二醇、新戊二醇、1,3-丙二醇、2-丁炔-1,4-二醇、1,6-己二醇或低分子量PTHF。其他合适的共聚单体是环状醚如1,2-氧化烯,例如氧化乙烯或氧化丙烯,2-甲基四氢呋喃或3-甲基四氢呋喃。除了水、1,4-丁二醇和低分子量PTHF以外,使用该类共聚单体导致制备出四氢呋喃共聚物,下文称为THF共聚物,并以此方式可以对PTHF进行化学改性。
THF在C2-C12羧酸酐或其与C2-C12羧酸的混合物如乙酸酐或乙酸酐/乙酸的混合物存在下和在酸性催化剂存在下聚合或共聚形成PTHF或THF共聚物的单酯和/或二酯,然后PTHF酯或THF共聚物的酯与甲醇进行碱催化的酯交换得到PTHF或THF共聚物(具有端羟基)是特别有利的,这正如例如DE-A 10245198所述。这里可能的酸聚合催化剂例如为酸性矾土、酸性离子交换剂如酸性金属氧化物或混合氧化物、氟磺酸或杂多酸。
通常而言,人们试图得到非常高官能度的PTHF。对本发明而言,官能度是PTHF的端基官能度。若PTHF中PTHF分子的所有末端带有OH基团,则官能度为2.000。单官能醇如正丁醇的官能度为1.000。在PTHF与二异氰酸酯的反应中,所获得的链长越高,PTHF的官能度越大。然而对于某些应用而言,例如为了改善弹力纤维生产方法中纺丝溶液的可纺丝性的应用,希望在PTHF与二异氰酸酯的反应中保持尽可能低的聚合度。为了达到这一目的,已知可以将单官能醇如正丁醇加入PTHF中,如JP-A 07-278246所述。这也有助于控制(聚氨酯-脲聚合物)纺丝溶液的粘度以生产弹力纤维。将这些单官能醇准确混入高度粘稠聚合物中要求大量的工程支出。为了确保单官能醇在PTHF中的精确浓度,通常需要具有合适计量加料和混合装置的特制罐。由于高的资金和操作成本,希望避免随后加入单官能醇,结果也有利地降低了PTHF中正丁醇含量由于正丁醇的高挥发性所引起的波动危险、正丁醇的不受控挥发以及在使用相应PTHF时所致的工艺波动,并且可以从一开始得到官能度低于2的PTHF。
现有技术中未知有直接测定PTHF官能度的方法。因此,PTHF的官能度经由使用该PTHF制备的纺丝溶液(例如聚氨酯-脲聚合物在二甲基乙酰胺或二甲基甲酰胺中的溶液)的粘度而测定。对于其他方面相同的配制剂、浓度和制备方法以及相同的工艺条件和其他原料,纺丝溶液的粘度越低对应于PTHF的官能度越低。
因此,本发明的目的是提供一种制备PTHF或THF共聚物的方法,借此可以简单经济地制备具有特定官能度的PTHF和THF共聚物。
我们因此发现了一种通过在至少一种调聚体和/或共聚单体存在下在酸性催化剂上聚合四氢呋喃而制备官能度低于2的聚四氢呋喃或四氢呋喃共聚物的方法,其中经由未反应THF的再循环和/或经由新鲜进料将基于反应混合物为0.001-5重量%,优选0.005-1重量%的线性脂族醚加入反应混合物中。
反应器进料包括四氢呋喃和调聚体和/或共聚单体。可以将线性脂族醚加入原料之一中或加入它们的混合物中。THF或THF/共聚单体的混合物优选包含线性醚。原则上可以将该线性醚加入反应器的新鲜进料中或加入在聚合产物的后处理中回收的THF和未反应线性醚的再循环料流(优选将其再循环到聚合中)中。
用于本发明方法中的合适线性醚包括衍生于C1-C10线性醇的线性醚,如二甲基醚、乙醚、甲基乙基醚、二丙基醚、甲基丙基醚、乙基丙基醚、二丁基醚、甲基丁基醚、乙基丁基醚、丙基丁基醚、4-羟基丁基丁基醚、4-羟基丁基甲基醚、4-乙酰氧基丁基丁基醚。特别优选乙醚、甲基丁基醚、4-乙酰氧基丁基丁基醚。
具有所需官能度的高纯度PTHF可以通过本发明方法可靠且可再现地制备。
本发明方法所用的非均相或均相酸性催化剂的实例如下所述:
在制备PTHF和THF共聚物的本发明方法中,在第一步中通过THF优选在乙酸酐和合适的话共聚单体存在下在优选非均相的酸性催化剂上聚合而制备PTHF或THF共聚物的单酯和/或二酯。
合适的催化剂例如为例如描述于DE-A 1226560中的基于漂白土的催化剂。漂白土,尤其是活化的蒙脱土可以作为成型体用于固定床中或悬浮液中。
此外,已知将基于混合金属氧化物,尤其是基于元素周期表第3、4、13和14族金属的催化剂用于聚合THF。因此,JP-A 04-306228描述了在羧酸酐存在下在包含式MxOy的金属氧化物的混合金属氧化物上聚合THF,其中x和y为1-3的整数。所提到的实例是Al2O3-SiO2、SiO2-TiO2、SiO2-ZrO2和TiO2-ZrO2。可以将杂多酸,尤其是H3PW12O40和H3PMo12O40用于载体上,但优选以未负载形式用作催化剂。
US 5,208,385公开了基于无定形硅/铝混合氧化物的催化剂。基于SnO2/SiO2、Ga2O3/SiO2、Fe2O3/SiO2、In2O3/SiO2、Ta2O5/SiO2和HfO2/SiO2的混合氧化物也是已知的。上述催化剂优选通过共沉淀/溶胶-凝胶法生产。载体化催化剂公开于DE-A 4433606中,其中将钨氧化物或钼氧化物例如施加于ZrO2、TiO2、HfO2、Y2O3、Fe2O3、Al2O3、SnO2、SiO2或ZnO上。此外,推荐其中载体的碱金属浓度<5000ppm的ZrO2/SiO2催化剂。
所有所述催化剂原则上可以用作固定床催化剂和悬浮催化剂。
此外,粘土矿物,合适的话活化的粘土矿物也已知为聚合催化剂且例如公开于WO 94/05719、WO 96/23833、WO 98/51729、WO 99/12992和DE-A 19513493中。沸石也适合作为催化剂且例如描述于DE-A 4316138中。最后,硫酸化锆氧化物、硫酸化铝氧化物、载体化杂多酸和载体化氟化氢铵(NH4F*HF)或五氟化锑也已知为合适的聚合催化剂。本发明方法优选使用活化的漂白土进行。
基于碲化合物和BF3或B(C6F5)3配合物的催化剂在European Journalof Inorganic Chemistry,18(2003),3314-3317中提到。此外,单独的BF3或加入水后的BF3在该反应中具有催化活性。其他路易斯酸化合物,即AlCl3、SbCl5或SnCl4同样起反应。具有SbCl6、AsF6、SbF6作为抗衡阴离子的盐同样适合在浓硫酸存在下使用THF。还描述了使用发烟硫酸或SO3。此外,可以将浓硫酸与基于乙酰丙酮铁或有机酸的铁盐的催化剂一起使用。
(CF3SO2)2O、CF3SO3H、氟磺酸、氯磺酸和硫酸的类似衍生物及其盐、氟化氢和高氯酸也适合作为催化剂。
若使用固体催化剂,则该催化剂的可能预处理例如为借助气体如空气或氮气进行干燥,该气体已经加热到80-200℃,优选100-180℃。
聚合通常在0-80℃,优选25℃至THF的沸点的温度下进行。所用压力对于聚合结果通常并不重要,这是为什么聚合通常在大气压力下或在聚合体系的自生压力下进行的原因。
为了避免形成醚过氧化物,聚合有利地在惰性气体气氛下进行。作为惰性气体,可以使用例如氮气、二氧化碳或稀有气体,优选氮气。
该方法可以分批或连续操作,但出于经济原因,优选连续操作。
因为调聚体导致链终止,因此可以经由调聚体的用量控制要制备的聚合物的平均分子量。合适的调聚体是C2-C12羧酸酐和/或质子酸与C2-C12羧酸酐的混合物。质子酸优选可溶于反应体系的有机或无机酸。实例是C2-C12羧酸,例如乙酸或磺酸、硫酸、盐酸、磷酸。优选使用乙酸酐和/或乙酸。因此在第一步(聚合)中形成了PTHF或THF共聚物的单酯和二酯。当将杂多酸用作聚合催化剂时,通常将水用作调聚体,从而形成的聚合物具有羟基。
用作调聚体的乙酸酐在引入聚合反应器中的进料中的浓度基于所用THF为0.03-30mol%,优选0.05-20mol%,特别优选0.1-10mol%。若额外使用乙酸,则进行中的聚合的进料中摩尔比基于所用乙酸酐通常为1∶20-1∶20000。
THF共聚物的单酯和二酯可以通过额外使用能够开环聚合的环状醚,优选3、4和5元环,例如1,2-氧化烯如氧化乙烯或氧化丙烯、氧杂丁环、取代的二氧杂丁环如3,3-二甲基氧杂丁环、THF衍生物如2-甲基四氢呋喃或3-甲基四氢呋喃作为共聚单体而制备。特别优选2-甲基四氢呋喃或3-甲基四氢呋喃。
同样可以将C2-C12二醇用作共聚单体。这些例如可以为乙二醇、丙二醇、丁二醇、新戊二醇、1,3-丙二醇、2-丁炔-1,4-二醇、1,6-己二醇或低分子量PTHF。其他合适的共聚单体为环状醚,例如1,2-氧化烯如氧化乙烯或氧化丙烯、2-甲基四氢呋喃或3-甲基四氢呋喃。
取决于聚合混合物中调聚体的含量,可以通过该方法以目标方式制备平均分子量为250-10000道尔顿的PTHF或THF共聚物的单酯和/或二酯。优选借助本发明方法制备平均分子量为500-5000道尔顿,特别优选650-4000道尔顿的相应PTHF酯。对本专利申请而言,术语“平均分子量”或“平均摩尔质量”指聚合物的数均分子量Mn,其例如可以通过湿法化学测定OH数而测定。
若使用固体聚合催化剂,则过滤聚合阶段的包含THF的输出物以留下痕量聚合催化剂并随后将该输出物通过蒸馏除去THF的。然而,还可以首先分离THF,然后通过过滤除去剩余的PTHF单酯或二酯中的催化剂残留物。优选第二种方法。将工业上常用的床过滤器用作过滤装置。
以此方式得到的聚合物中的酯基必须在第二步中转化。常规方法是由碱性催化剂引发的与低级醇的反应。使用碱性催化剂的酯交换由现有技术已知且例如描述于DE-A 10120801和DE-A 19742342中。优选使用甲醇作为低级醇并将甲醇钠用作活性酯交换催化剂。
所得聚合物可以与有机异氰酸酯以本身已知的方式反应以生产聚氨酯和聚氨酯-脲,尤其是生产热塑性氨酯、弹力纤维、热塑性醚酯或共聚醚酰胺。本发明因此进一步提供了通过本发明方法制备的聚四氢呋喃或四氢呋喃共聚物在制备聚氨酯聚合物或聚氨酯-脲聚合物中的用途,所述聚氨酯聚合物或聚氨酯-脲聚合物为例如用于生产也称为弹力纤维或弹性纤维的弹性纤维、热塑性聚氨酯(TPU)或浇铸聚氨酯弹性体所要求的。
这里首先使PTHF或THF共聚物以本身已知的方式与过量的有机二异氰酸酯反应,然后使产物与有机二胺反应,例如如JP-A 07-278246所述。
下面借助实施例对本发明进行说明。
实施例
实施例1
制备纺丝溶液(聚氨酯聚合物)
将如下面本发明实施例2和3所述或如对比例1所述制备的PTHF与二苯基甲烷-4,4’-二异氰酸酯以1∶1.62的摩尔比混合并在玻璃烧杯中加热到90℃。45分钟之后将所得预聚物冷却到30℃并与其量使得形成浓度为45重量%溶液(溶液A))的N,N-二甲基乙酰胺(DMAC)反应。为了延长链,配制浓度为1.9重量%的乙二胺(EDA)、1,2-丙二胺(PDA)和二乙胺(DEA)的混合物在DMAC中的溶液。EDA∶PDA∶DEA的摩尔比为4∶1∶1(溶液B)。在30℃下将96g溶液A置于反应容器中并在30分钟内在搅拌下加入40g溶液B。所形成的纺丝溶液的粘度在40℃下借助Haake VT550SV 2粘度计测量(毫帕斯卡·秒=mPas)。
实施例2
在40℃下使19.8g/h THF和3.4g/h乙酸酐在固定床反应器中如DE-A10245198的实施例3所述连续通过200ml酸活化的挤出蒙脱土催化剂。将0.2g/h(0.85重量%)正丁基甲基醚加入反应器的进料流中。借助泵将反应混合物连续循环通过反应设备中的反应器,并维持50∶1的恒定再循环∶进料比。将23.4g/h新鲜进料引入反应器中,同时从该回路中取出相同量的反应产物混合物。为了进行分析,在70℃/30毫巴的减压下,然后在于170℃/3毫巴的减压下蒸发反应产物混合物中的挥发性组分,其基本上是THF和乙酸酐以及未反应的线性醚。聚合残余物与甲醇和甲醇钠进行酯交换以形成二醇,并通过用磷酸沉淀和随后过滤而除去钠离子。通过在1毫巴/200℃下在短程蒸馏中蒸馏而从PTHF中除去低聚物。以此方式得到的产物的摩尔质量为2055mol/g。最终由通过如实施例1所述的进一步反应而得到的PTHF所形成的聚合物的DMAC溶液在40℃下的粘度为63900mPas。
实施例3
如实施例2所述在乙酸酐存在下聚合THF,但将4.3重量%乙醚加入反应器的进料流中。通过实施例2所述的程序得到的PTHF的摩尔质量为2036g/mol。在转化为对应于实施例1的纺丝溶液之后,测量到该纺丝溶液的粘度为37500mPas。
对比例1
如实施例2所述,在固定床中在40℃下使20g/h THF和3.4g/h乙酸酐如DE-A 10245198的实施例3所述连续通过200ml酸活化的挤出蒙脱土催化剂。与本发明实施例对比,该反应器的进料不含线性醚。
以对应于实施例2的程序的方式借助泵将反应混合物连续循环通过反应设备中的反应器,并维持50∶1的恒定再循环∶进料比。将另外23.4g/h反应混合物引入反应器中,同时从该回路中取出相同量的反应产物混合物。为了进行分析,首先在70℃/30毫巴的减压下,然后在170℃/0.3毫巴的减压下蒸发反应产物混合物中的挥发性组分,其基本上是未反应的THF和乙酸酐。
聚合残余物与甲醇和甲醇钠进行酯交换以形成二醇,并通过用磷酸沉淀和随后过滤而除去钠离子。通过在1毫巴/200℃下在短程蒸馏中蒸馏而从PTHF中除去低聚物。以此方式得到的产物的摩尔质量为2024mol/g。
如实施例1所述将产物转化为纺丝溶液。该纺丝溶液在40℃下的粘度为90300mPas。
Claims (9)
1.一种通过在调聚体和/或共聚单体存在下在酸性催化剂上聚合四氢呋喃而制备聚四氢呋喃或四氢呋喃共聚物的方法,其中所述反应混合物包含0.001-5重量%的至少一种线性脂族醚。
2.根据权利要求1的方法,其中线性脂族醚的含量为0.005-1%。
3.根据权利要求1的方法,其中用于所述聚合的四氢呋喃或四氢呋喃/共聚单体的混合物包含所述线性脂族醚。
4.根据权利要求2的方法,其中用于所述聚合的四氢呋喃或四氢呋喃/共聚单体的混合物包含所述线性脂族醚。
5.根据权利要求1-4中任一项的方法,其中所述催化剂选自漂白土、元素周期表中第3、4、13和14族的混合金属氧化物、载体化钨氧化物或钼氧化物、杂多酸、酸性离子交换剂、沸石、硫酸化锆氧化物和强无机酸。
6.根据权利要求1-4中任一项的方法,其中所述线性脂族醚为二甲基醚、甲基乙基醚、二丙基醚、甲基丙基醚、乙基丙基醚、二丁基醚、甲基丁基醚、乙基丁基醚、丙基丁基醚、4-羟基丁基丁基醚、4-乙酰氧基丁基丁基醚、4-羟基丁基甲基醚或其混合物。
7.根据权利要求1-4中任一项的方法,其中所述线性脂族醚为乙醚、甲基丁基醚和/或4-乙酰氧基丁基丁基醚。
8.通过根据权利要求1-7中任一项的方法制备的聚四氢呋喃或四氢呋喃共聚物在制备聚氨酯-脲聚合物中的用途。
9.根据权利要求8的用途,其中将根据权利要求1-7中任一项的方法制备的聚四氢呋喃或四氢呋喃共聚物用于制备热塑性聚氨酯、弹力纤维、热塑性醚酯或共聚醚酰胺。
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DE102006009150.7A DE102006009150B4 (de) | 2006-02-24 | 2006-02-24 | Verfahren zur Herstellung von Polytetrahydrofuran oder Tetrahydrofuran-Copolymeren |
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CN102516554A (zh) * | 2011-11-23 | 2012-06-27 | 中北大学 | 端羟基聚四氢呋喃聚环氧丙烷嵌段共聚醚的制备方法 |
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CN101024686A (zh) | 2007-08-29 |
DE102006009150B4 (de) | 2018-07-19 |
KR20070088379A (ko) | 2007-08-29 |
DE102006009150A1 (de) | 2007-09-06 |
KR101358470B1 (ko) | 2014-02-05 |
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