CN116355195A - 一种脂肪族聚碳酸酯多元醇的制备方法 - Google Patents
一种脂肪族聚碳酸酯多元醇的制备方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开了一种脂肪族聚碳酸酯多元醇的制备方法,本发明采用商业化的路易斯酸碱对作催化剂,催化引发环氧丙烷、二氧化碳和链转移剂进行三元共聚反应,通过一锅一步法成功合成脂肪族聚碳酸酯多元醇。其制备的分子量可控(600~6000 g/mol),碳酸酯含量高,避免了金属催化剂残留问题,同时反应条件温和,满足工业化生产的需要。本发明的聚醚碳酸酯多元醇可用于生产的聚氨酯泡沫材料、弹性体、涂料、密封剂和粘合剂。
Description
技术领域
本发明涉及高分子材料合成技术领域,涉及一种合成二氧化碳基脂肪族碳酸酯多元醇低聚物的制备方法。
背景技术
聚氨酯全称为聚氨基甲酸酯,是主链上含有重复氨基甲酸酯基团的大分子化合物的统称。它是一类用途十分广泛的高分子合成材料,其工业化生产主要是由异氰酸酯和含端羟基的多元醇化合物反应而成。由脂肪族聚碳酸酯多元醇制备的聚氨酯弹性体,与传统聚醚和聚酯多元醇醇合成的聚氨酯弹性体相比具有优异的机械性能、耐水解性、耐磨性、耐油性、耐化学性和优异的生物相容性等优点。
在低分子脂肪族聚碳酸酯多元醇的合成方法中,光气法是合成族脂肪族聚碳酸酯多元醇最传统的方法,这种传统方法非常危险而且成本较高,不符合绿色化学的要求。环状碳酸酯开环聚合法中,五元环以上的环状碳酸酯价格昂贵,种类少,成本高。碳酸酯与二醇酯交换法也是比较常用的方法,但是能耗较高且制备过程需脱除副产物,所以对设备要求会很高。
金属催化剂是最早用于二氧化碳合成低分子聚碳酸酯多元醇的体系,Lee(Macromolecules.2010,43,7398-7401)报道了在己二酸作为链转移剂的存在下,由季铵盐功能化Salen-Co催化环氧丙烷和二氧化碳共聚合成的可控分子量低聚物(聚碳酸-醚)二醇。虽然金属配合物催化剂对二氧化碳和环氧化物的交替插入具有突出的活性和,但这些方法仍然存在聚醚含量和金属残留量高的问题。冯小双在专利号113195590报道合成各种羧酸盐以及碳酸盐和烷基(芳基)硼烷,使用它们让环氧丙烷共聚与二氧化碳共聚,来获得聚碳酸酯二醇和多元醇。但是,需要高比例的引发剂和有机硼烷才能获得低分子量,例如以环氧丙烷/引发剂/TEB=10/1/2.8的摩尔比获得分子量为1100g mol-1的低聚物,这在成本上不利于工业化。
发明内容
本发明的目的在于克服现有技术的不足,提供一种适用于工业化生产、反应条件温和、对工业设备要求低、分子量可控的脂肪族聚碳酸酯多元醇的制备方法。
为了实现上述目的,本发明采用“有机硼/有机胺”作为非金属催化剂,在链转移剂条件下,通过环氧化物和和CO2共聚合成分子量可控的二氧化碳基脂肪族聚碳酸酯多元醇。
本发明的具体技术方案如下:
一种脂肪族聚碳酸酯多元醇的制备方法,其特征在于包括以下步骤:将环氧单体、非金属催化剂和链转移剂加到高压反应釜中,并通入二氧化碳,进行开环聚合反应,反应结束后用去离子水洗掉未反应的单体和催化剂,得到脂肪族聚碳酸酯多元醇。反应结构式如下所示:
m=6-60,m为整数
作为优选的,在上述的脂肪族聚碳酸酯多元醇的制备方法中,所述开环共聚反应的二氧化碳压力为0.5-3MPa,反应温度为40~60℃,反应时间为12-48h。
作为优选的,在上述的脂肪族聚碳酸酯多元醇的制备方法中,所述非金属催化剂为路易斯酸碱对复合催化剂;路易斯酸为有机硼化合物;路易斯碱为有机胺(盐),路易斯酸与路易斯碱的摩尔比为5~12:1。
作为优选的,在上述的脂肪族聚碳酸酯多元醇的制备方法中,所述的有机硼化合物为三乙基硼、三苯基硼、三丁基硼烷、三异丁基硼烷或三(五氟苯基)硼;所述的有机胺(盐)为双(三苯基正膦基)氯化铵、四正丁基氯化铵、四正丁基溴化铵或1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)、三乙胺(TEA)。
作为优选的,在上述的脂肪族聚碳酸酯多元醇的制备方法中,所述链转移剂选自醇及其组合的单官能或多官能质子化合物,包括各种单醇、乙二醇、二甘醇、三甘醇、丙二醇、双丙甘醇、三丙二醇、新戊二醇、1,3-丙二醇、1,4-丁二醇、1,2-丁二醇、1,3-丁二醇、2,3-丁二醇、1,6-己二醇、水、丙三醇、三羟甲基丙烷、三羟甲基乙烷、季戊四醇、α-甲基葡糖苷、山梨糖醇、甘露醇、羟甲基葡糖苷、羟丙基葡糖苷、蔗糖、1,4-环己二醇、环己烷二甲醇、氢醌或间苯二酚。
作为优选的,在上述的脂肪族聚碳酸酯多元醇的制备方法中,所述环氧单体与非金属催化剂的摩尔比为2000~4000:1,环氧单体与链转移剂的摩尔比为30~150:1。
与现有技术相比,本发明具有如下有益效果:本发明采用商业化的非金属催化剂“有机硼/有机胺”,在链转移剂存在下,通过环氧化物和和CO2共聚合成分子量可控的二氧化碳基脂肪族聚碳酸酯多元醇,避免金属催化剂的残留问题;反应条件温和,聚合温度低,对工业设备要求不高,有利于工业生产的扩大化;碳酸酯含量高(≥95%),窄分子量分布,可控的分子量(600~6000g/mol)。本发明的聚醚碳酸酯多元醇可用于生产聚氨酯泡沫材料、弹性体、涂料、密封剂和粘合剂。
附图说明
附图是为了进一步清楚地阐述和解释本发明技术方案和发明实施例,并不构成对本发明的限制,在附图中:
图1为本发明实施例1所制备的聚合物的核磁氢谱1H NMR图;
图2为实施例1所制备的聚合物的核磁碳谱13C NMR图。
具体实施方式
实施例1:
在无水无氧环境中,以50mL高压反应釜为反应容器将15g环氧丙烷、17.5mg双(三苯基膦)氯化铵、775μL三乙基硼溶液,343μL 1-4丁二醇依次加入高压反应釜中,充入2MPa二氧化碳,在45℃下反应24h,反应结束后用去离子水洗掉未反应的单体和催化剂,聚合物真空干燥后做分子量测试、核磁分析,羟值和热性能分析,具体数据列于表1。所制备的聚合物的核磁氢谱1H NMR图如图1所示,核磁碳谱13C NMR图如图2所示。
实施例2:
在无水无氧环境中,以50mL高压反应釜为反应容器将15g环氧丙烷、33μL三乙胺、775μL三丁基硼溶液,686μL 1-4丁二醇依次加入高压反应釜中,充入1.0MPa二氧化碳,在45℃下反应36h,反应结束后用去离子水洗掉未反应的单体和催化剂,聚合物真空干燥后做分子量测试、核磁分析、羟值和热性能分析,具体数据列于表1。
实施例3:
在无水无氧环境中,以50mL高压反应釜为反应容器将15g环氧丙烷、9.8mg 1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)、54μL三苯基硼溶液,432μL甘油依次加入高压反应釜中,充入1.0MPa二氧化碳,在50℃下反应48h,反应结束后用去离子水洗掉未反应的单体和催化剂,聚合物真空干燥后做分子量测试、核磁分析、羟值和热性能分析,具体数据列于表1。
表1.脂肪族聚碳酸酯多元醇分子量、组成及玻璃化转变温度
表1中PPC%是环氧丙烷和二氧化碳共聚得到的脂肪族聚碳酸酯单元的摩尔百分比;PPO%为环氧单体自聚得到的聚醚单元的摩尔百分比。
硼烷和有机胺(盐)组成的双组分催化体系可以有效催化环氧单体和二氧化碳在链转移剂的存在下聚合生成的脂肪族聚碳酸酯二元醇。脂肪族聚碳酸酯多元醇的分子量和玻璃化温度可以通过改变环氧单体和链转移剂的投料摩尔比进行调控。
实施例4:
将实施例2中15g所述脂肪族聚碳酸酯二元醇PCDL、2.14g BDO加入到250mL三颈圆底烧瓶中并在120℃下抽真空脱水2h,结束后反应底物在氮气气氛的保护下降温至70℃,缓慢加入4.28g MDI以及10mg的异辛酸锡催化剂,机械搅拌5min后倒入模具中,合模放在160℃平板硫化机上模压30min后取下模具,冷却后开模得到无色透明具有弹性的脂肪族聚碳酸酯型聚氨酯,其硬段含量为29.9%。
对比例1:
将16g的聚氧化丙烯二元醇(羟值:100mg/g)、2.25g BDO加入到250mL三颈圆底烧瓶中并在120℃下抽真空脱水2h,结束后反应底物在氮气气氛的保护下降温至70℃,缓慢加入5.16g MDI以及4.6mg的异辛酸锡催化剂,机械搅拌5min后倒入模具中,合模放在160℃平板硫化机上模压30min后取下模具,冷却后开模得到无色透明具有弹性的聚醚型聚氨酯,其硬段含量为31.6%。
对比例2:
将15g的聚己二酸丁二醇酯二元醇(羟值:100mg/g)、2.24g BDO加入到250mL三颈圆底烧瓶中并在120℃下抽真空脱水2h,结束后反应底物在氮气气氛的保护下降温至70℃,缓慢加入4.47g MDI以及2.5mg的异辛酸锡催化剂,机械搅拌5min后倒入模具中,合模放在160℃平板硫化机上模压30min后取下模具,冷却后开模得到无色透明具有弹性的聚酯型聚氨酯,其硬段含量为30.9%。
将所得到的聚氨酯分别按照GB/T 2410-2008进行透光率测试、按照GB/T 1040.1-2006进行力学性能测试、按照GB/T 6031-1998进行硬度测试、按照GB/T 2790-1995进行撕裂强度测试、按照IEC612152-2:2016进行耐紫外老化测试以及耐水解测试,所得数据列于表2。
表2脂肪族聚碳酸酯型TPU、聚醚TPU、聚酯TPU相关性能的对比
以本发明制备得到的二氧化碳基脂肪族聚碳酸酯多元醇为软段合成的聚氨酯弹性体具有优异的力学性能,相比于以聚氧化丙烯二元醇、聚己二酸丁二醇酯二元醇为软段合成的聚氨酯弹性体具有更出色的耐水解性能和透光性。且本发明采用的原料来源广泛,价格低廉,并且合成工艺较为环保,是最具有发展前景的脂肪族脂肪族聚碳酸酯多元醇的生产工艺。
Claims (6)
1.一种脂肪族聚碳酸酯多元醇的制备方法,其特征在于包括以下步骤:将环氧单体、非金属催化剂和链转移剂加到高压反应釜中,并通入二氧化碳,进行开环聚合反应,反应结束后用去离子水洗掉未反应的单体和催化剂,得到脂肪族聚碳酸酯多元醇。
2.如权利要求1所述的脂肪族聚碳酸酯多元醇的制备方法,其特征在于,所述开环共聚反应的二氧化碳压力为0.5-3MPa,反应温度为40~60℃,反应时间为12-48h。
3.如权利要求1所述的脂肪族聚碳酸酯多元醇的制备方法,其特征在于,所述非金属催化剂为路易斯酸碱对复合催化剂;路易斯酸为有机硼化合物;路易斯碱为有机胺(盐),路易斯酸与路易斯碱的摩尔比为5~12:1。
4.如权利要求3所述的脂肪族聚碳酸酯多元醇的制备方法,其特征在于,所述的有机硼化合物为三乙基硼、三苯基硼、三丁基硼烷、三异丁基硼烷或 三(五氟苯基)硼;所述的有机胺(盐)为双(三苯基正膦基)氯化铵、四正丁基氯化铵、四正丁基溴化铵或1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)、三乙胺(TEA)。
5.如权利要求1所述的脂肪族聚碳酸酯多元醇的制备方法,其特征在于,所述链转移剂选自醇及其组合的单官能或多官能质子化合物,包括各种单醇、乙二醇、二甘醇、三甘醇、丙二醇、双丙甘醇、三丙二醇、新戊二醇、1,3- 丙二醇、1,4- 丁二醇、1,2- 丁二醇、1,3- 丁二醇、2,3- 丁二醇、1,6- 己二醇、水、丙三醇、三羟甲基丙烷、三羟甲基乙烷、季戊四醇、α- 甲基葡糖苷、山梨糖醇、甘露醇、羟甲基葡糖苷、羟丙基葡糖苷、蔗糖、1,4- 环己二醇、环己烷二甲醇、氢醌或间苯二酚。
6.如权利要求1所述的脂肪族聚碳酸酯多元醇的制备方法,其特征在于,所述环氧单体与非金属催化剂的摩尔比为2000~4000:1,环氧单体与链转移剂的摩尔比为30~150:1。
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