CN102597058B - 制备超支化聚羟基苯甲酸烷氧基化物的方法 - Google Patents
制备超支化聚羟基苯甲酸烷氧基化物的方法 Download PDFInfo
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- 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
- C08G65/26—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 and other compounds
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- 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
- C08G65/26—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 and other compounds
- C08G65/2603—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 and other compounds the other compounds containing oxygen
- C08G65/2615—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 and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
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Abstract
本发明涉及一种制备超支化聚羟基苯甲酸烷氧基化物的方法，包括以下步骤：(a)使至少一种聚羟基苯甲酸酯与一种或多种环氧烷反应，任选地在碱性催化剂的存在下进行，(b)使在步骤(a)中形成的聚羟基苯甲酸酯烷氧基化物进行酯交换反应，形成超支化聚羟基苯甲酸烷氧基化物。
Description
本发明涉及一种制备超支化聚羟基苯甲酸烷氧基化物的方法。
树枝状体、树枝醇(arborol)、星形聚合物或超支化聚合物是具有高度支化结构和高官能度特征的聚合物的名称。树枝状体是分子均匀的大分子，其具有高度对称的结构。树枝状体可以从中心分子开始通过多官能单体与已键接的单体受控逐步地键合来制备。在每个键合步骤中，单体端基(进而键合)的数目按照2或更高的倍数增加，并且获得了像树状结构那样一代一代增长的单分散聚合物，其理想地是球形的，并且它们的支链在每种情况下含有完全相同数目的单体单元。但是，单分散树枝状体的制备工艺的复杂之处在于必须引入保护基团，并且在每个键合步骤中再次除去保护基团，在每个新增长阶段开始之前需要充分的清洁操作，所以树枝状体通常仅仅在实验室规模上制备。
为了获得具有完全规律结构的树枝状体结构，所述的“一代一代增长”是必须的。
相比之下，超支化聚合物在分子上和结构上都是非均匀的。它们不是通过一代一代增长获得的。所以也不是必须分离和提纯中间体。超支化聚合物可以通过简单地将形成这些聚合物所需的组分混合并在所谓的一步反应中反应来获得。超支化聚合物可以具有树枝状子结构。但是，另外，它们也具有线性聚合物链和不相同的聚合物支链。为了合成超支化聚合物，尤其合适的是所谓的ABx单体。这些单体在一个分子中具有两种不同的官能团A和B，它们可以按照分子间方式彼此反应形成键。官能团A仅仅在每个分子中存在一次，官能团B在每个分子中存在两次或更多次。所述ABx单体彼此之间的反应形成了具有按照规律排列的支化点的未交联聚合物。这些聚合物在链末端几乎完全具有B基团。
另外，超支化聚合物可以通过Ax+By合成路线制备。在这种情况下，Ax和By代表两种不同的具有官能团A和B的单体，并且指数x和y表示每个单体中的官能团的数目。在Ax+By合成中，在这里使用A2+B3合成作为例子说明，双官能单体A2与三官能单体B3反应。这先形成A和B的1∶1加合物，其具有平均一个官能团A和两个官能团B，它们可以然后也反应得到超支化聚合物。如此获得的超支化聚合物也具有主要B基团作为端基。
在本发明中，与聚合物一起使用的术语“超支化”表示所述物质的支化度(DB)是10-95％，优选25-90％，更优选30-80％，其中支化度(DB)如下定义：
其中T是封端键合的单体单元的平均数，Z是形成支链的单体单元的平均数，L是线性键合到特定物质的大分子中的单体单元的平均数。
非树枝状的超支化聚合物与树枝状聚合物之间的区别是如此定义的支化度。当这些聚合物的支化度DB＝99-100％时，它们是树枝状的。因此，树枝状体具有最大可能的支化点数目，这仅仅能通过高度对称的增长实现。关于支化度的定义，也可以参见H.Frey等，Acta Polym.1997，48，30。
在本发明中，超支化聚合物理解为表示基本非交联的大分子，其在结构上是非均匀的。它们可以从中心分子开始按照与树枝状体类似的方式形成，但是支链的链长度是不均匀的。但是，它们也可以按线性方式且具有官能侧链形成，或者具有线性和支化的分子结构部分。关于树枝状和超支化的聚合物的定义，也可以参见P.J.Flory，J.Am.Chem.Soc.1952，74，2718和H.Frey等，Chem.Eur.J.2000，6，No.14，2499。关于超支化聚合物及其合成方法的其它信息也可以参见例如J.M.S.-Rev.Macromol.Chem.Phys.，C37(3)，555-579(1997)以及其中引用的文献。
C.J.Hawker等，“超支化聚亚乙基二醇：一类新的离子传导聚合物”(“Hyperbranched Poly(ethylene glycol)s：A New Class of Ion-ConductingPolymers″)，Macromolecules 1996，29，3831-3838描述了制备基于低聚亚乙基二醇和3，5-二羟基苯甲酸甲基酯的超支化聚醚酯的方法。在多阶段合成中，先制备基于3，5-二羟基苯甲酸甲基酯和低聚乙二醇的AB2大单体。从可商购的二甘醇、三甘醇或六亚乙基二醇开始，通过与1当量的叔丁基二苯基氯硅烷在三乙胺存在下反应，制备了在一个链端受保护的低聚乙二醇。在另一个链端，通过用四溴甲烷和三苯基膦溴化，羟基被溴原子代替。最后，如此衍生的低聚乙二醇与3，5-二羟基苯甲酸甲基酯在碳酸钾和18-冠-6的存在下反应。最后，硅烷保护基团再次用氯化氢在甲醇中消除。如此获得的AB2大单体进行分离，然后于160℃在催化量的二乙酸二丁锡的存在下和在不存在溶剂的情况下缩聚，得到超支化聚醚酯。
W.Lange和O.Kordsachia，Darstellung und Eigenschaften von ausVanillin und SyringaaldehydPolyestern[可从香草醛和丁香醛获得的聚酯的制备方法和性质]，Holz als Roh-und Werkstoff39(1981)107-112描述了通过缩合羟基乙基香草酸或羟基乙基丁香酸制备基于香草酸(4-羟基-3-甲氧基苯甲酸)或丁香酸(4-羟基-3，5-二甲氧基苯甲酸)的聚酯的方法，得到线性聚酯。羟基乙基香草酸或羟基乙基丁香酸是在上游合成阶段中通过香草酸或丁香酸的钠盐与1摩尔环氧乙烷反应获得的。羟基乙基醚酸是通过加入稀硫酸从钠盐释放出来的。在一个例子中，将香草酸或丁香酸溶解在氢氧化钠溶液中，并于80℃将环氧乙烷引入此溶液中。羟基乙基醚酸是通过加入稀硫酸沉淀出来，并且过滤出沉淀产物，用水洗涤，干燥，最后通过重复重结晶来提纯。聚酯的形成反应最后作为熔体缩合在减压下进行。
US 2,686,198也描述了通过羟基乙基香草酸在200-300℃温度下和在减压下熔体缩合进行缩聚以制备线性聚酯的方法。
DD 273 841涉及用环氧丙烷、环氧乙烷、表氯醇或四氢呋喃将五倍子酸或五倍子酸衍生物进行烷氧基化的方法。所用的五倍子酸衍生物优选是五倍子酸正丙基酯。在实施例中，五倍子酸在高压釜中与环氧乙烷、环氧丙烷或四氢呋喃反应。在环氧丙烷的情况下在氢氧化钾的存在下和在四氢呋喃的情况下，操作是在作为催化剂的三氟化硼醚合物的存在下进行的。没有描述从五倍子酸烷氧基化物形成聚醚酯。
本发明的一个目的是提供一种非常易于实施的制备超支化聚羟基苯甲酸烷氧基化物的方法。
此目的通过一种制备超支化聚羟基苯甲酸烷氧基化物的方法实现，包括以下步骤：
(a)使至少一种聚羟基苯甲酸酯与一种或多种环氧烷反应，任选地在碱性催化剂的存在下进行，
(b)使在步骤(a)中形成的聚羟基苯甲酸烷氧基化物进行酯交换反应，形成超支化聚羟基苯甲酸烷氧基化物。
本发明方法的特点是其实施惊人地简单。在步骤(a)中形成的聚羟基苯甲酸烷氧基化物直接进一步进行酯交换反应，得到超支化聚羟基苯甲酸烷氧基化物。因此，本发明方法能在一个阶段中进行，即所谓的一步法。不需要分离在步骤(a)中形成的中间体。
一般而言，聚羟基苯甲酸酯与一种或多种环氧烷在压力下在高压釜中反应，这任选地在碱性催化剂的存在下进行。在烷氧基化步骤(a)期间的压力一般是1-15巴，优选3-8巴，温度是60-180℃，优选90-120℃。在这些条件下，形成的聚羟基苯甲酸烷氧基化物在原地进一步进行酯交换反应，得到超支化聚醚酯，使得步骤(a)和(b)部分地平行进行。
一般而言，此反应在不存在溶剂的情况下进行。但是，此反应也可以在溶剂的存在下进行。合适的溶剂是甲苯、二甲苯以及其它惰性芳烃、THF、二烷、其它环状惰性醚、DMSO和NMP。
为了形成超支化结构，所用的至少一些聚羟基苯甲酸酯具有至少两个羟基。一般，所用的聚羟基苯甲酸酯具有2或3个羟基。合适的聚羟基苯甲酸酯的例子是2，3-、2，4-、2，5-和2，6-二羟基苯甲酸的酯，3，4-和3，5-二羟基苯甲酸的酯，3，4，5-三羟基苯甲酸(五倍子酸)的酯，1，3，4，5-四羟基苯甲酸的酯，以及1，2，3，4，5-五羟基苯甲酸的酯。优选五倍子酸的酯。也可以使用所述聚羟基苯甲酸酯的混合物。
一般，聚羟基苯甲酸的烷基酯进行反应，优选C1-C6烷基酯。在甲基酯的情况下，也可以进行羧基甲基的烷氧基化；在这种情况下形成的聚亚烷基二醇醚酯(它们具有-C(O)O-[CH2CHRO]n-H(Me)基团)不能有效地进行酯交换。所以，优选从C2烷基开始的烷基酯。特别优选聚羟基苯甲酸的丙基酯和丁基酯。
聚羟基苯甲酸酯在步骤(a)中与一种或多种环氧烷反应，任选地在碱性催化剂的存在下进行。优选的环氧烷是环氧乙烷、环氧丙烷、环氧丁烷和氧化苯乙烯，特别优选环氧乙烷和环氧丙烷。也可以使环氧烷的混合物反应。合适的碱性催化剂是氢氧化钠、氢氧化钾、氢氧化铯，碱金属醇盐，例如甲醇钾和叔丁醇钾，以及胺催化剂，例如二甲基环己胺、二甲基乙醇胺、咪唑、取代的咪唑和胍衍生物。五倍子酸的乙氧基化反应不需要例如碱性催化剂。
一般，超支化聚羟基苯甲酸烷氧基化物的形成是在环氧烷加成反应结束之后在步骤(b)中通过简单地使反应混合物进一步反应完成的。这种进一步反应的时间可以是数小时，例如1-3小时。环氧烷一般在0.25-8小时的时间内加入，优选0.5-5小时。总反应时间(步骤a)和b))一般是1.5-15小时，优选2-6小时。一般，按每摩尔聚羟基苯甲酸的羟基计，反应1-15摩尔、优选1-10摩尔和更优选1-5摩尔的环氧烷。
在反应结束之后，将高压釜解压，汽提产物混合物以除去残余单体。此操作在80-160℃的温度和5-300毫巴的压力下进行。任选地，环氧烷的除去操作也可以用额外的惰性汽提气体支持，例如水蒸气或氮气。
任选地，破坏性阳离子例如碱金属离子可以通过酸性离子交换剂、通过用吸附剂例如硅酸镁搅拌或通过萃取来除去。
所获得的超支化聚羟基苯甲酸烷氧基化物一般具有在500-7000g/mol范围内的数均分子量和在1-4范围内的多分散指数。
下面通过实施例详细说明本发明。
实施例
产物在电雾化电离质谱(ESI-MS)中和用凝胶渗透色谱-ESI-MS联合来分析，其中使用四氢呋喃作为溶剂。
羟值是按照DIN 53 240方法通过滴定检测的。
实施例1
在300ml高压釜中先加入24.87g(0.135mol)的五倍子酸甲基酯和0.3g(0.0043mol)的甲醇钾。高压釜用氮气惰化。将混合物于130℃在减压(＜15毫巴)下干燥2小时。随后，注入氮气，并将高压釜解压到3.5巴。在130℃的温度下，开始添加环氧乙烷，并且观察到压力显著升高。在一定时间后，温度急剧升高。一旦计量加入全部量的环氧乙烷(72.12g，对应于1.75mol)，就使混合物再反应1小时。获得羟值为236mg KOH/g的产物。
产物用MALDI-ToF分析检测，使用羟基亚苄基丙二腈(HBM)作为基质。检测到具有n＝1、2、3、...11个重复单元的超支化低聚物，主要组分具有n＝8个重复单元。每个重复单元含有平均7-8个环氧乙烷单元。
实施例2
在300ml高压釜中先加入24.88g(0.135mol)的五倍子酸甲基酯和0.98g(0.011mol)的二甲基乙醇胺。高压釜用氮气惰化。在注入氮气后，将高压釜解压到3.5巴。在100℃的温度下，加入总共137.7g(3.13mol)的环氧乙烷。压力快速升高；在短时间后，温度也急剧升高。在添加环氧乙烷结束后，使混合物再反应2小时。获得羟值为264mg KOH/g的产物。
实施例3
在300ml高压釜中先加入62.9g(0.296mol)的五倍子酸丙基酯和0.68g(0.006mol)的叔丁醇钾。高压釜用氮气惰化。将反应混合物于130℃在减压(＜15毫巴)下干燥。在注入氮气后，将高压釜解压到3.5巴。在130℃的温度下，开始添加总共157.14g(2.71mol)的环氧丙烷。在19小时的反应时间后，获得羟值为238mg KOH/g的产物。
实施例4
在300ml高压釜中先加入62.9g(0.296mol)的五倍子酸丙基酯和0.66g(0.006mol)的叔丁醇钾。高压釜用氮气惰化。将反应混合物于110℃在减压(＜15毫巴)下干燥。在注入氮气后，将高压釜解压到3.5巴。在110℃的温度下，开始添加总共157.14g(3.57mol)的环氧乙烷。在加入大约一半量的环氧乙烷后，观察到压力和温度显著升高。在加入全部量的环氧乙烷后，环氧乙烷快速贫化，并且在总共10小时的反应时间后获得羟值为220mg KOH/g的产物。
产物用MALDI-ToF分析检测，使用羟基亚苄基丙二腈(HBM)作为基质。检测到具有n＝1-11个重复单元的低聚物。每个重复单元含有平均约7-8个环氧乙烷单元。没有检测到副产物。
各个低聚物的分布是通过GPC-MS检测的。分布中的最大值是在n＝8时(八聚体)。
Claims (9)
1.一种制备超支化聚羟基苯甲酸烷氧基化物的方法，包括以下步骤：
（a）使至少一种聚羟基苯甲酸酯与一种或多种环氧烷反应，任选地在碱性催化剂的存在下进行，
（b）使在步骤（a）中形成的聚羟基苯甲酸酯烷氧基化物进行酯交换反应，形成超支化聚羟基苯甲酸烷氧基化物，
其中此方法是在一步中在不需要分离在步骤（a）中形成的中间体的情况下进行的。
2.权利要求1的方法，其中聚羟基苯甲酸酯具有2-3个羟基。
3.权利要求2的方法，其中聚羟基苯甲酸酯是五倍子酸酯。
4.权利要求1的方法，其中聚羟基苯甲酸酯是聚羟基苯甲酸C1-C6烷基酯。
5.权利要求1的方法，其中聚羟基苯甲酸酯是聚羟基苯甲酸丙基酯或聚羟基苯甲酸丁基酯。
6.权利要求1的方法，其中环氧烷是选自环氧乙烷、环氧丙烷、环氧丁烷和氧化苯乙烯。
7.权利要求1的方法，其中碱性催化剂是碱金属氢氧化物、碱金属醇盐或胺。
8.权利要求1的方法，其中在步骤（a）中按每摩尔聚羟基苯甲酸的羟基计转化1-15摩尔的环氧烷。
9.一种可通过权利要求1-8中任一项方法获得的超支化聚羟基苯甲酸烷氧基化物。
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2488568B1 (de) | 2013-07-31 |
| US20120197042A1 (en) | 2012-08-02 |
| WO2011045357A1 (de) | 2011-04-21 |
| US8664427B2 (en) | 2014-03-04 |
| ES2425207T3 (es) | 2013-10-14 |
| KR20120085268A (ko) | 2012-07-31 |
| EP2488568A1 (de) | 2012-08-22 |
| CN102597058A (zh) | 2012-07-18 |
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