CN1232541C - 制备马来酸酸酐和c1－4烷基乙烯基醚的共聚物的连续、无溶剂方法 - Google Patents

制备马来酸酸酐和c1－4烷基乙烯基醚的共聚物的连续、无溶剂方法 Download PDF

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CN1232541C
CN1232541C CNB018112056A CN01811205A CN1232541C CN 1232541 C CN1232541 C CN 1232541C CN B018112056 A CNB018112056 A CN B018112056A CN 01811205 A CN01811205 A CN 01811205A CN 1232541 C CN1232541 C CN 1232541C
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vinyl ether
alkyl vinyl
solvent
reactor
maleic anhydride
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CN1443202A (zh
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R·比斯
J·科肯
J·扎默拉
K·普洛乔卡
J·A·赖恩
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ISP Investments LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
    • C08F216/18—Acyclic compounds
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Abstract

一种获得马来酸酐和C1-C4烷基乙烯基醚的高分子量交替共聚物的无溶剂、细白粉末的连续、无溶剂的方法，所述共聚物没有气味或味道，具有分子结构(A-B)n，式中A是马来酸酐，B是烷基乙烯基醚，n为指示共聚物分子量的整数，所述方法包括：以预定的加料速率，连续地将作为单体反应物和溶剂、用量超过共聚物中希望的1∶1摩尔比(A∶B)的烷基乙烯基醚、熔融的马来酸酐和游离基引发剂加入在约50-100℃的反应温度下加热的反应器中；将各反应物保持在反应器中一预定的平均停留时间；以与反应物加入反应器相同的速率，取出反应产物、残留的烷基乙烯基醚和引发剂；从反应产物中汽提残余的烷基乙烯基醚；对残留痕量烷基乙烯基醚的共聚物进行干燥；并将回收的烷基乙烯基醚作为反应剂和溶剂再循环入反应器中。

Description

制备马来酸酸酐和C1-4烷基乙烯基醚的 共聚物的连续、无溶剂方法
                     发明背景
1. 发明领域
本发明涉及马来酸酐和C1-4烷基乙烯基醚的共聚物，更准确地说，涉及制备所述共聚物的无溶剂、细白粉末的连续、无溶剂的方法，所述共聚物具有用于口服组合物的有利性能。
2. 现有技术说明
在US5,959,053和5,939,506中描述了：制备马来酸酐(MAN)和C1-C4烷基乙烯基醚(AVE)高分子量交替共聚物细粉末的间歇、无溶剂方法(即除反应剂以外没有溶剂)，所述聚合物的分子结构为(A-B)n，其中A＝MAN，B＝AVE，而n为表示其分子量的整数。在所述方法中，AVE单体以超过1∶1单体摩尔比的比例提供，以便在该体系中起反应剂和溶剂的作用。在反应器中没有其它的溶剂。因此，在从反应产物中对过量AVE汽提之后，得到了无溶剂的共聚物。然而，间歇法需要延长的时间进行反应，通常需要约9-13小时以完成每一批次的反应。
因此，本发明的目的是提供一种制备MAN和AVE共聚物的、无溶剂、细白粉末的、连续、无溶剂方法，所述共聚物具有用于口服组合物的有利性能。
                       发明概述
本发明描述了一种获得马来酸酐(MAN)和C1-C4烷基乙烯基醚高分子量交替共聚物的无溶剂细白粉末的连续、无溶剂的方法，所述共聚物没有气味或味道，具有(A-B)n的分子结构，其中A为马来酸酐，B为烷基乙烯基醚，而n为指示共聚物分子量的整数。所述方法包括：以预定的加料速率，连续地将作为单体反应物和溶剂的、用量超过共聚物中希望的1∶1摩尔比(A∶B)的烷基乙烯基醚、熔融的马来酸酐和游离基引发剂加入在约50-100℃的反应温度下加热的反应器中；将各反应物保持在反应器中一预定的平均停留时间；以与反应物加入反应器相同的速率，取出反应产物、残留的烷基乙烯基醚和引发剂；从反应产物中汽提残留的烷基乙烯基醚；对残余痕量烷基乙烯基醚的共聚物进行干燥；并将回收的烷基乙烯基醚再循环入反应器中。
在本发明连续、无溶剂方法的优选实施方案中，烷基乙烯基醚是甲基乙烯基醚，甲基乙烯基醚与熔融马来酸酐的摩尔比约为25∶1至5∶1、最优选为12∶1至7∶1。以共聚物重量计，引发剂的浓度为0.01-0.2％，从聚合反应器中取出的共聚物的百分固含量约10-40％。
                         发明详述
现在参考附图，所述附图是通过连续、无溶剂的方法制备马来酸酐(MAN)和C1-C4烷基乙烯基醚(AVE)无溶剂共聚物的流程简图。本发明连续的无溶剂方法由溶剂加料体系100、熔融马来酸酐加料体系200、催化剂或引发剂加料体系300、反应器体系400、产物回收和干燥体系500和600、以及溶剂回收体系700和800组成。
在反应器中的停留时间应足以完成MAN的反应，例如从0.5-5小时。为了保证MAN完成反应，在反应区的最后可以使用更高的温度和引发剂促进剂。通过将链转移剂、优选是乙醛添加至AVE中，和/或通过控制反应温度和/或引发剂用量，而控制共聚物的比粘性(SV)。
在体系100中，对液化的溶剂单体(甲基乙烯基醚)加压并以恒定的流量加入反应器体系400中，所述体系可以由连续搅拌的罐状反应器(CSTR)组成，或由串联的两个或多个CSTR组成，或者由搅拌的逆混反应器、或由平推流式管状反应器组成，所述反应器维持在约40-120℃、优选60-90℃的恒定温度。以恒定的速率将也在200中进行加压的熔融马来酸酐加入反应器中并与溶剂单体充分混合；其中，通过恒定地添加半衰期为2-10小时的引发剂，例如得自300的过氧化月桂酰或癸酰(或任何其它的游离基引发剂)，能够迅速地进行反应，从而形成希望固含量的产物浆液，其中液体溶剂单体过量。在该连续方法中，反应器中AVE/MAN的摩尔比约为25∶1至5∶1，优选约12∶1至7∶1。
通过保持反应器中的体积恒定，连续地取出浆液混合物并输送至低压干燥体系500中；在干燥体系中，通过加热，蒸发掉过量的溶剂单体，并分离和回收固体产物。对回收的单体进行冷却并再在回收体系800中加压。在进行组分调节之后，将单体溶剂返回至溶剂加料体系100中。
通过连续干燥或通过过滤，可以从聚合物中分离AVE，并且例如通过连续的蒸馏、用pH＞9的水进行洗涤和干燥，在连续的提纯之后回用。
尽管已参考一定的实施方案对本发明进行了描述，应当理解的是，本领域熟练技术人员可以进行各种改变和变更。因此，本发明仅由下面的权利要求书限定。

Claims (5)

1.一种获得马来酸酐和C1-C4烷基乙烯基醚的高分子量交替共聚物的无溶剂细白粉末的连续、无溶剂的方法，所述共聚物没有气味或味道，具有分子结构(A-B)n，式中A是马来酸酐，B是烷基乙烯基醚，n为指示共聚物分子量的整数，所述方法包括：以预定的加料速率，连续地将作为单体反应物和溶剂的、用量超过共聚物中A∶B希望的1∶1摩尔比的烷基乙烯基醚、熔融的马来酸酐和游离基引发剂加入在50-100℃的反应温度下加热的反应器中；以与反应物加入反应器相同的速率，同时加入和取出反应产物、残留的烷基乙烯基醚和引发剂，从而在反应器中维持固定的体积；从反应产物中汽提残留的烷基乙烯基醚；对残余痕量烷基乙烯基醚的共聚物进行干燥；并将回收的烷基乙烯基醚作为反应物和溶剂再循环入反应器中，其中烷基乙烯基醚与熔融马来酸酐的摩尔比为25∶1至5∶1，且以共聚物计引发剂的浓度为0.01-0.2％，以及从聚合反应器中取出的共聚物的百分固体含量为10-40％。
2.根据权利要求1的连续、无溶剂的方法，其中所述烷基乙烯基醚是甲基乙烯基醚。
3.根据权利要求3的连续、无溶剂的方法，其中所述烷基乙烯基醚与熔融马来酸酐的摩尔比为12∶1至7∶1。
4.根据权利要求1的连续、无溶剂的方法，其中干燥步骤在真空或大气压下于40-100℃进行。
5.根据权利要求1的连续、无溶剂的方法，其中反应物在反应器中的平均停留时间为0.5-5小时。
CNB018112056A 2000-06-15 2001-05-02 制备马来酸酸酐和c1－4烷基乙烯基醚的共聚物的连续、无溶剂方法 Expired - Fee Related CN1232541C (zh)

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US6365691B1 (en) * 2000-07-06 2002-04-02 Isp Investments Inc. Continuous, solvent-free process for making terpolymers of maleic anhydride, C1-4 alkyl vinyl ether and isobutylene
US6692725B2 (en) * 2001-02-19 2004-02-17 Daicel Chemical Industries, Ltd. Composition for oral care
FR2884253B1 (fr) * 2005-04-08 2007-06-22 Univ Lille Sciences Tech Materiaux monolithiques fonctionnalisables
CN102030856B (zh) * 2009-09-25 2012-05-30 博爱新开源制药股份有限公司 乙烯基甲醚/马来酸酐共聚物的脱挥方法
CN107805290A (zh) * 2017-12-05 2018-03-16 博爱新开源制药股份有限公司 一种叔丁基乙烯基醚/马来酸酐共聚物及其制备方法

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DE3108100A1 (de) * 1981-03-04 1982-09-16 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von copolymerisaten des maleinsaeureanhydrids
DE3712265A1 (de) * 1987-04-10 1988-10-20 Giulini Chemie Verfahren zur herstellung von copolymerisaten mit hohem polymerisationsgrad
US5034488A (en) * 1990-01-11 1991-07-23 Gaf Chemicals Corporation Slurry polymerization of crosslinked maleic anhydride-alkyl vinyl ether copolymers in a solvent system comprising a carboxylic acid ester and a saturated hydrocarbon
US5064897A (en) * 1990-08-30 1991-11-12 Isp Investments Inc. Process for making ethanol solutions of alkyl half-esters of copolymers of maleic anhydride and a C1 -C4 alkyl vinyl ether
US5874510A (en) * 1997-09-18 1999-02-23 Isp Investments Inc. Process for making crosslinked copolymers of maleic anhydride and methyl vinyl ether
US5939506A (en) * 1997-10-02 1999-08-17 Isp Investments Inc. Solvent-free process for making high molecular weight terpolymers of maleic anhydride, C1 -C4 alkyl vinyl ether and isobutylene

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US6451944B2 (en) 2002-09-17
AU2001257480A1 (en) 2001-12-24
EP1299425A1 (en) 2003-04-09
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EP1299425A4 (en) 2004-10-27
US20010053829A1 (en) 2001-12-20
CN1443202A (zh) 2003-09-17
EP1299425B1 (en) 2005-10-12

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