CN1032010C - 脂肪族聚碳酸酯多醇的制备 - Google Patents
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Abstract
本发明涉及一类脂肪族聚碳酸酯多醇的制备方法。
在高效双金属催化剂作用下进行二氧化碳和环氧化物的共聚，并用含1～10个活泼氢原子的物质作调节剂，可得到脂肪族聚碳酸酯多醇树脂，其含有端羟基的数目与加入的调节剂相同，其数均分子量可在(2～20)×103的范围内，由调节剂加入量控制，其碳酸酯单元含量大于30%，可满足聚氨酯制备等实际应用的需要。
Description
本发明提供一类可以随意调节分子量和官能量，并含有＞30％(摩尔)的碳酸酯单元的脂肪族聚碳酸酯多醇树脂的制备方法。
从二氯化碳和环氧化物共聚制备脂肪族聚碳酸酯(APC)。是综合利用二氧化碳并获得高聚物材料的一个有效途径。实际应用中需要按各种使用目的将APC的分子量调整至某些特定范围。APC的分子量通常仅取决于合成时采用的催化体系，例如：由二乙基锌和某些助催化剂组成的体系。产生的APC分子量都大于2×104，有时还超过105[W.Kuran et al.，Pol.120，677(1983)]。这种体系活性不够高。主、助催化剂用量须严格搭配，难以加人有分子量调节作用的物质。在卟啉铝催化体系(S.Inouc et al.，Macromol.，1986，19，8)的作用下。产生APC的分子置为数千，但催化剂成本较高。以上情况下仅获得双官能度APC，分子量也不易调整。在用金属醋酸盐作催化剂的情况下(K.Soga et al.，Malkromol.Chcm，1978，179，2837)，可以在反应时加入不同量的醋酸来获得各种分子量的单官能度的APC。但产率很低．用锡酸钠作催化剂(M.Cuscurida et al.，US 4，488，982(1984)，或用某种小分子的双金属氰络合物作催化剂(J.Kuypcr，et al.，EP222，453(1986)。都有可能靠加入某些试剂来控制分子量。但仅得到碳酸酯单元含量很低(往往小于15％)的共聚物。它实际上更接近于聚醚而非聚碳酸酯。
本发明的目的是提供一种二氧化碳和环氧化物共聚的可靠而实用的方法。以便用很低的经济代价来获得含较多碳酸酯单元(＞30％摩尔)。而分子量和羟基官能度都可按需要调整的脂肪族聚碳酸酯多醇。
本发明方法的要素之一为，采用高活性、高稳定性，单组分的双金属配位催化剂来进行上述共聚合，以保证获得高产率和低成本。并保证有足够的二氧化碳进入共聚物中。最适合的催化剂是发明人在另一专利(CN10044663A)中提出的双金属络合物，即
式中，MII为2价金属，如锌、镉、钴、镍、铁、铜；M为3价或变价金属。如铁、钴、铬、铝、锡，MI为1价金属，如钾、钠、锂；X为卤素；L为卤素．拟卤素或类似配位基；
为含有K个配位原子的有机螯合剂。最好是聚合物或齐聚物：a，b，c，d，c，f，g为正数或零，通常ak=1～3，ak＋b＋c＋f=3～7，c＋d=6，b＋3e=2。
本发明方法的要素之二是通过在聚合中投入调节剂来达到控制分子量和官能度的目的。调节剂是含有1～10个活泼氢原子的物质，如水、小分子醇类、酚类、硫醇类、羧酸类、含羟基、硫羟基、羧基的聚合物或齐聚物，以及以上物质的混合物。
本发明使用的环氧化物可以是：环氧乙烷、环氧丙烷、环氧丁烷-1。环氧丁烷-2。氧化异丁烯、氧化苯乙烯、氧化环戊烯、氧化环己烯、环氧氯丙烷。
按本发明方法进行二氧化碳和环氧化物的共聚时。可不用溶剂或采用相当于环氧化物重量0-10倍的卤烃、烷烃，环烷烃、芳烃或它们的混合物，如：二氯甲烷、三氯甲烷、四氯化碳、二氯乙烷、三氯乙烷、戊烷、己烷、庚烷、石油醚、环己烷、甲基环己烷、苯、甲苯、二甲苯。催化剂用量是环氧化物重量的0.02～10％。反应温度为10～90℃。反应时间8～200小时．反应产率(按环氧化物转化率计)为50～100％。
按照本发明方法得到的产物具有以下结构：
其中x＞1，n＞0，F=1～10，RHF为调节剂，R′、R″为氢、烃基或卤烃基。该产物是一种粘性树脂。其数均分子量Mn可在(2～20)×103范围内调节，由投入调节剂的数量决定，可用下式预计：
Mn=WAPCMr/Wr
式中WABC为由共聚得到的聚碳酸酯多醇重量，Mr和Wr为投入调节剂的分子量和重量。
聚碳酸酯多醇包含的羟基位于链末端，每分子所含羟基数(官能度F)等于每分子调节剂中包含活泼氢原子数。可用改变调节剂的方法在1～10范围内调节。因此，用正丁醇、己二醇、三羟甲基丙烷和季戊四醇作调节剂合成的树脂的官能度分别为1，2，3和4。当用两种含不同数目活泼氢的调节剂的混合物时，得到树脂的官能度约为两调节剂官能度按分子数的平均值。官能度为1～2的树脂为线型结构。官能度大于2的树脂星支化结构。
用本发明方法合成的树脂中碳酸酯单元的含量，用1HNMR谱法测定，为分子链中单元总数30～50％(摩尔)，接近于交替共聚物。
因为本发明采用的催化剂价格低廉。聚合工艺简便，转化率高。重复性好。产生树脂的成本远低于国际上报导的同类树脂。而且含较多碳酸酯单元，分子量和官能度可调节。可以满足各种不同的使用要求，包括聚氨酯的制备等等，故是一种实用性很强的新材料。
实施例
催化剂制备：向氯化锌和聚乙二醇的混合水溶液，在搅拌下加入铁氰化钾水溶液(各反应物比例符合锌/铁=3.5，螫合原子/锌=3.5)。离心收集生成的黄色沉淀，并用水洗涤两次。干燥至恒重。
聚合操作：在压力釜中加入催化剂，在氮气保护下加入环氧丙烷(PO)。催化剂重量为PO的2～3％。加入溶剂。调节剂。充入二氧化碳至5.0MPa左右，加热到60℃反应24小时。降温，排出剩余气体。按通常方式作后处理。
若干实施例的投料量和反应结果如下表所示，各例所得树脂的实测分子量都接近计算的分子量，实测官能度都接近所加调节剂的官能度。各树脂都含较多碳酸酯单元。各例的产率都较高，不因调节剂的加入而明显变化。
表 不同情况下的反应产物
实施例 1 2 3 4 5 6
溶剂种类 —— 甲苯 四氯化碳 —— 环己烷 ——
溶剂用量a 0 1 1 0 0.3 0
调节剂种类 正丁醇 苯甲酸 1，6-己二醇 三羟甲基 季戊四醇 混合物f
丙烷
调节剂官能度 1 1 2 3 4 2.33
调节剂用量a 0.020 0.022 0.041 0.019 0.028 0.025
环氧转化率，％ 90 85 80 93 70 80
产物
碳酸酯单元，％b 40 39 38 40 37 40Mn计算，×10-1 5.0 7.0 3.5 10.0 5.0 6.0Mn实测，×10-1c 4.8 7.1 3.7 9.3 4.8 5.6羟基当量重×10-1d 4.0 6.6 1.9 2.8 1.1 2.2
官能度e 1.2 1.1 1.9 3.3 4.3 2.5a、用每克环氧丙烷加入的试剂克数表示。b、用1H NMR测定。c、用粘度法测定。d、用酰化法测定。e、用实测分子量除以羟基当量重计算。f 2∶1(摩尔)的1，6-己二醇＋三羟甲基丙烷。
Claims (7)
1.一种制备脂肪族聚碳酸酯多醇的方法。其特征是采用一类双金属催化剂。以及用含1～10个活泼氢原子的调节剂，进行二氧化碳和环氧化物的共聚合。得到以下结构的共聚物：式中x＞1，n＞0，F=1～10，RHP为调节剂，R为可与F个活泼氢原子联结的基团，R′、R″为氢，烃基或卤烃基，所述的双金属催化剂的组成为：○aMIIXb[MLcXd]x(H2O)f(MIX)g，其用量是环氧化物的(0.02～10)％。其中
M为3价或变价金属。包括铁、钴、络、铝、锡；
MII为2价金属。包括锌、镉、钴、镍、铁、铜；
MI为1价金属，包括钾、钠、锂；
X为卤素；
L为卤素、拟卤素或类似配位体；
a，b，c，d，e，f，g为正数或零，它们满足ak=1～3，ak＋b＋e＋f=3～7，c＋d=6，b＋3c=2。
2.根据权利要求1所述的方法，其特征在于共聚产物的数均分子量Mn可用改变调节剂用量的方法在(2～20)×103的范围内控制，其预计数值等于共聚产物质量(克)除以投入调节剂的量(摩尔)。
3.根据权利要求1所述的方法，其特征在于共聚物的羟基官能度F可用改变调节剂种类的方法在1～10的范围内调节。并等于每分子调节剂含活泼氢原子的个数。
4.根据权利要求1所述的方法，其特征是共聚产物中含有30～50％(摩尔)的碳酸酯单元。
5.根据权利要求l所述的方法。其特征是投入的调节剂可以是水，小分子醇类、酚类、硫醇类、羧酸类、或含羟基、硫羟基的聚合物或齐聚物。也可以是以上物质的混合物。
6.根据权利要求1所述的方法。其特征是采用的环氧化物可以是环氧乙烷、环氧丙烷、环氧丁烷-1、环氧丁烷-2、氧化异丁烯、氧化苯乙烯、氧化环戊烯、氧化环己烯、环氧氯丙烷。
7.根据权利要求1所述的方法。其特征是共聚反应可在没有或有溶剂的条件下进行。所用溶剂可以是卤烃、烷烃、环烷烃、芳烃或它们的混合物，溶剂用量是环氧化物单体重量的0～10倍，聚合温度为10～90℃，聚合时间为8～200小时。
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| CN100381480C (zh) * | 1998-12-24 | 2008-04-16 | 中国科学院长春应用化学研究所 | 高分子量脂肪族聚碳酸酯的制备方法 |
| US7671228B2 (en) * | 2005-03-29 | 2010-03-02 | Basf Corporation | Method of forming a polyethercarbonate polyol using a CO2-philic compound or substituent |
| CN101857670B (zh) | 2009-04-10 | 2013-04-03 | 拜耳材料科技(中国)有限公司 | 聚氨酯微孔弹性体及其制备方法和应用 |
| CN101633731B (zh) * | 2009-08-14 | 2011-08-03 | 广州市达志化工科技有限公司 | 一种脂肪族聚碳酸酯多元醇的制备方法 |
| KR101715657B1 (ko) | 2010-04-06 | 2017-03-14 | 에스케이이노베이션 주식회사 | 이산화탄소／에폭사이드 공중합의 분자량 및 사슬 모양 정밀 제어 및 이를 통한 저분자량의 폴리(알킬렌 카보네이트)의 제조 |
| CN102093811B (zh) * | 2010-12-31 | 2013-03-13 | 广东达志环保科技股份有限公司 | 一种环保型聚碳酸亚丙酯型聚氨酯地坪涂料及其制备方法 |
| CN102093836B (zh) * | 2010-12-31 | 2013-06-05 | 广东达志环保科技股份有限公司 | 一种聚碳酸亚乙酯型聚氨酯水性粘合剂 |
| KR101975036B1 (ko) | 2013-03-21 | 2019-05-03 | 에스케이이노베이션 주식회사 | 신규 착화합물 존재 하에 이산화탄소/에폭사이드 공중합에 의한 폴리(알킬렌 카보네이트)의 제조방법 |
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| CN105504257B (zh) * | 2015-12-28 | 2018-04-06 | 广东工业大学 | 一种侧链含氯的聚碳酸亚丙酯多元醇的制备方法 |
| CN106317397A (zh) * | 2016-08-25 | 2017-01-11 | 广东达志环保科技股份有限公司 | 一种聚碳酸环己酯多元醇及其制备方法 |
| CN110330930A (zh) * | 2019-05-23 | 2019-10-15 | 佳化化学科技发展（上海）有限公司 | 一种聚氨酯喷胶及其制备方法 |
| CN114262430A (zh) * | 2021-11-30 | 2022-04-01 | 山东一诺威新材料有限公司 | 实心轮胎用二氧化碳基聚碳酸酯醚多元醇及其制备方法 |
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