CN1286706A - 制备高分子量马来酸酐、c1－c4烷基乙烯基醚及异丁烯三元共聚物的无溶剂法,及包含该三元共聚物的假牙粘合剂和牙膏组合物 - Google Patents

制备高分子量马来酸酐、c1－c4烷基乙烯基醚及异丁烯三元共聚物的无溶剂法,及包含该三元共聚物的假牙粘合剂和牙膏组合物 Download PDF

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CN1286706A
CN1286706A CN98813807A CN98813807A CN1286706A CN 1286706 A CN1286706 A CN 1286706A CN 98813807 A CN98813807 A CN 98813807A CN 98813807 A CN98813807 A CN 98813807A CN 1286706 A CN1286706 A CN 1286706A
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K·普洛科卡
W·E·普洛西塞
H·张
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Abstract

本发明涉及马来酸酐、C1－C4烷基乙烯基醚及异丁烯的高分子量三元共聚物,并涉及制备这些三元共聚物的无溶剂法,该三元共聚物特别适用于假牙粘合剂和牙膏组合物。

Description

制备高分子量马来酸酐、C1-C4烷基乙烯基醚及 异丁烯三元共聚物的无溶剂法，及包含该三元 共聚物的假牙粘合剂和牙膏组合物
                    发明背景
1．技术领域
本发明涉及制备高分子量马来酸酐(MAN)、C1-C4烷基乙烯基醚(AVE)及异丁烯(IB)三元共聚物的无溶剂法，并涉及包含该无溶剂高分子量三元共聚物的牙膏和假牙粘合剂组合物。
2．现有技术详述
美国专利5，037，924公开了马来酸酐、C1-C4烷基乙烯基醚及异丁烯三元共聚物的制备方法，该共聚物的混合盐可用作假牙粘合剂。这些三元共聚物是在添加的溶剂，例如，乙酸乙烯酯与环己烷的共溶剂存在下，通过沉淀聚合制备的。生成的三元共聚物仅具有约30，000-400，000的低分子量。尽管与本领域已知的其它粘合剂相比，该三元共聚物作为假牙粘合剂的性能相对较好，但该三元共聚物及其盐包含不希望有的痕量乙酸乙烯酯和环己烷。
美国专利5，334，375公开了包含MAN、AVE及IB的交联共聚物，用于控制菌斑(controlling plaque)的牙膏组合物。
因此，本发明的一个目标是提供一种制备MAN、AVE及IB的高分子量三元共聚物的无溶剂法。
本文一个具体的目标是提供这种分子量至少约1，500，000的无溶剂三元共聚物，该共聚物，以其混合盐的形式，以优异的方式用作假牙粘合剂，及用于牙膏组合物。
                    发明概述
本文叙述的是制备高分子量的马来酸酐(MAN)、C1-C4烷基乙烯基醚(AVE)及异丁烯(IB)交替三元共聚物的精细粉末的无溶剂法，该共聚物具有(A-B)n的分子结构，其中A=MAN，B=AVE或IB，并优选包含约5-45摩尔％的异丁烯。
这些三元共聚物的NMR波谱显示交替(A-B)n分子结构，其中n的值为使三元共聚物具有超过约1，500，000的重均分子量(GPC，水，pH9)且比粘度≥6(1％DMF溶液，25℃)。
本发明的无溶剂法按下述进行：将烷基乙烯基醚及异丁烯，以比在三元共聚物中所希望的摩尔比大的异丁烯与烷基乙烯基醚的摩尔比，加入到反应器中，加入自由基引发剂，将混合物加热到约50-100℃的反应温度，在一段时间内将熔融马来酸酐进料到反应器中，其中马来酸酐与烷基乙烯基醚及异丁烯总用量的摩尔比不高于1∶3。这里得到的三元共聚物是无味的且不合其它已知的制备该三元共聚物方法所特有的痕量溶剂。
这些三元共聚物可有利地用于假牙粘合剂及牙膏组合物。
                      发明详述
根据本发明，提供了制备高分子量的马来酸酐，C1-C4烷基乙烯基醚，优选甲基乙烯基醚，及异丁烯的高分子量三元共聚物的无溶剂法，该共聚物具有(A-B)n的交替分子结构，其中A=MAN，B=AVE及/或IB。该三元共聚物的马来酸酐：烷基乙烯基醚：异丁烯的摩尔比为约0.50∶0.45-0.25∶0.05-0.45。优选三元共聚物包含约5-45摩尔％的异丁烯。最优选的组合物具有约10-15％异丁烯，如上面所述。分子量为至少1，500，000(GPC，水，pH9)且比粘度(SV)≥6(1％DMF溶液，25℃)。
所得到的三元共聚物为无溶剂白色精细粉末。
当用作假牙粘合剂时，该三元共聚物的混合盐，如Ca/Na或Ca/Zn混合盐，显示了优异的性能。
未交联的三元共聚物特别适合用作牙膏组合物中控制菌斑的部分。
本发明方法的特征是无溶剂聚合方法，其是使用过量烷基乙烯基醚及异丁烯作为反应介质进行的。因此，聚合反应按下述进行：将具有预定组成的AVE/IB混合物预加入到反应器中，加入自由基引发剂，加热到约50-100℃的反应温度，在一段时间内将熔融马来酸酐进料到反应器中。
MAN与MVE+IB总量的摩尔比不高于1∶3，优选小于1∶5。进一步，在预加料中IB与MVE的摩尔比明显高于三元共聚物中所希望的摩尔比，优选，三元共聚物中含1∶2的IB∶MVE预加入约1∶1的IB∶MVE，三元共聚物中含1∶4的IB∶MVE预加入约1∶2的IB∶MVE。
通常，在聚合反应接近完成时加入附加量的MVE，以便耗尽MAN反应物。
反萃取残留的过量MVE及IB后，所得三元共聚物产物是无味精细粉末，没有任何溶剂，即无溶剂。
参照下述实施例详述本发明。
                    实施例1
将装有搅拌器、加热套及加入试剂用注射泵(syringe pump)的1升帕尔(Parr)不锈钢反应器用氮气喷射，加入175g(3.00摩尔)甲基乙烯基醚(MYE)，175g(3.12摩尔)异丁烯(IB)及0.10g过氧化月桂酰。MVE与IB的摩尔比为0.96。将加料后的反应器加热到63℃，保持温度，同时在2小时期间将39.2g(0.400摩尔)熔融马来酸酐(MAN)进料到反应器中。MVE及IB与MAN的摩尔比是15.3。在65℃下保温3小时后，加入50g(0.86摩尔)的附加的MVE。将温度升至70℃，保温1小时。然后，将反应器冷却至室温，释放压力并将反应器出料。得到的反应产物为白色精细粉末，将该粉末在真空干燥箱中65℃下干燥1小时。产物是均匀、白色精细粉末(62g)，不含任何未反应MAN。在其1％DMF溶液中25℃下测量的比粘度(SV)为6.94。13CNMR波谱显示，三元共聚物中单体MAN∶MVE∶IB的摩尔比=0.50∶0.34∶0.16。粉末的重均分子量为2，170，000(GPC，水，Ph9)。
                        实施例2-5
仿照实施例1的步骤，以制备具有不同MAN∶MVE∶IB比的三元共聚物。结果示于下表1。
                          表1
                                            实施例号聚合物            2             3           4            5MVE，g(摩尔)    100(1.72)    200(344)    167(2.87)    200(3.44)IB，g(摩尔)     150(2.67)    50(0.89)    83(1.49)     25(0.44)MAN，g(摩尔)    41(0.418)    41(0.418)   41(0.418)    41(0.418)反应中MVE/IB    0.39∶0.61   0.79∶0.11  0.66∶0.34   0.89∶0.11摩尔比聚合物中MAN∶MVE：.50∶0.28∶0.21 0.50∶0.46∶0.07 0.50∶0.40∶0.10  0.50∶0.44∶0.05IB比值(根据13CNMR，以摩尔分数表示)SV(1％，DMF)    7.71         11.11        6.96        14.46Mw(GPC，        2,100,000  2,101,000   2,180,000  2,150,000水，pH9)
                        实施例6
                  假牙粘合剂组合物
将实施例1-5的三元共聚物转化为它们的Ca/Na(根据当量7/2)及Ca/Zn(根据当量3/1)混合盐，使70％的羧基中和。将产物与由GantrezAN 169 BF制备的等效参比混合盐比较，即与通常用作假牙粘合剂原料的商售MAN-MVE(1∶1)共聚物比较。
所选择的参比Gantrez AN 169 BF材料分子量为2，450，000(GPC)，该分子量比本发明实施例1-5中三元共聚物任何一个的分子量高。所以，本发明三元共聚物的任何性能优点能够归因于它们的分子结构，而不是它们特殊的分子量。基于根据美国专利5，037，924所详细描述的步骤进行的标准假牙粘合剂测试的结果，包含5-45％IB，优选10-25％IB的本发明的三元共聚物盐与参比材料相比，显示了明显较长和较强的保持性能(hold property)。
相反，根据美国专利5，037，924制备的单体比为0.50∶0.37∶0.13及分子量为223，000的MAN-MVE-IB的共聚物，作为假牙粘合剂，显示了明显比Gantrez AN 169 BF参比材料差的性能。类似地，具有少于5％或高于45％IB的高分子量MAN-MVE-IB三元共聚物与GantrezAN169 BF参照物相比，作为假牙粘合剂没有显示任何明显性能改进。
                        实施例7
                  牙膏组合物的测试方法
采用一种在玻璃器内的试验评价所给出的聚合物用于牙膏的性能。在聚合物施加到羟基磷灰石表面，一种假牙表面后，试验测试triclosan★(2，4，4’-三氯-2’-羟基-二苯基醚)的保持量和吸收量。试验与实际的用牙膏刷牙，随后用水清洗有关。
      ★Triclosan是通常用于减少菌斑形成的抗菌药物。
HAP是牙齿的矿物相，HAP能提供均匀大小的表面且可得到定量及可再现的结果。通过放入直径为13mm的模具中并加压，将HAP材料制成圆片状作为参比物。接着将得到的压片干燥，最后在800℃下烧结4小时。
通过将HAP圆片在人工唾液中37℃下培养过夜，在持续摇动下将HAP圆片在37℃下浸在包含给定聚合物及triclosan的样品牙膏溶液中30分钟测量triclosan的吸收量。接着用蒸馏水清洗圆片，在空气流中干燥。将如此处理后的圆片放入乙氰溶剂中，自圆片中抽提triclosan。随后用HPLC确定溶剂中triclosan的量。
在唾液涂覆的HAP圆片上triclosan的保持量如下测量：将圆片用牙膏溶液处理，用水清洗，并在持续摇动下在人工唾液中重新培养60分钟。从唾液中取出圆片，用水清洗并放入乙氰中。用HPLC测量圆片上保留的triclosan的量。对比例不含任何聚合物。
                    表1
                                            实施例号聚合物             2             3         4              5MVZ，g(摩尔)    100(1.72)    200(344)    167(2.87)    200(3.44)IB，g(摩尔)     150(2.67)    50(0.89)    83(1.49)     25(0.44)MAN，g(摩尔)    41(0.418)    41(0.418)   41(0.418)    41(0.418)反应中MVE/IB    0.39∶0.61    0.79∶0.11  0.66∶0.34  0.89∶0.11摩尔比聚合物中MAN∶MVE：.50∶0.28∶0.21  0.50∶0.45∶0.07 0.50∶0.40∶0.10 0.50∶0.44∶0.05IB比值(根据(NMR，以摩尔分数表示)SV(1％，DMP)    7.71         11.11           6.96           14.46Mw(GPC，      2,100,000    2,101,000       2,180,000       2,150,000水，pH9)结果在下述表3给出：
              表3
实施例中三元共聚物    ％聚合物Triclosan收量/保持量毫克/圆片
          吸收量   保持量1(对比)    -    75       452          2   160      1003         0.6  115       70
这里的结果证明了，与先前用于本领域的其它聚合物相比，新聚合物在牙膏组合物中的有效性。

Claims (7)

1．一种制备高分子量的马来酸酐、C1-C4烷基乙烯基醚及异丁烯交替三元共聚物的无溶剂精细粉末的无溶剂法，该共聚物具有(A-B)n的分子结构，其中A是马来酸酐，B是烷基乙烯基醚或异丁烯，并包含约5-45摩尔％的异丁烯，其具有超过约1，500，000的重均分子量(GPC，水，pH9)且比粘度≥6(1％DMF溶液)，其包括：将烷基乙烯基醚及异丁烯加入到反应器中，异丁烯与烷基乙烯基醚的摩尔比基本上比在三元共聚物中所希望的摩尔比大，加入自由基引发剂，将混合物加热到约50-100℃的反应温度，在一段时间内将熔融马来酸酐进料到已加料的反应器中，加入其中的马来酸酐与烷基乙烯基醚及异丁烯总用量的摩尔比不高于1∶3，任选加入附加量的烷基乙烯基醚以完成反应，随后在聚合反应结束后反萃取过量的异丁烯和烷基乙烯基醚。
2．权利要求1的方法，其中所述的C1-C4烷基乙烯基醚是甲基乙烯基醚。
3．权利要求1的方法，其中三元共聚物中马来酸酐：烷基乙烯基醚：异丁烯的摩尔比为0.50∶0.45-0.25∶0.05-0.45。
4．权利要求1的方法，其中对于具有约1∶2所述单体比的三元共聚物，在投料中异丁烯与烷基乙烯基醚的摩尔比为约1∶1。
5．马来酸酐、C1-C4烷基乙烯基醚及异丁烯的交替三元共聚物的无溶剂白色精细粉末，该共聚物具有(A-B)n的分子结构，其中A是马来酸酐，B是烷基乙烯基醚或异丁烯，并具有马来酸酐：烷基乙烯基醚：异丁烯的摩尔比为0.50∶0.45-0.25∶0.05-0.45及约5-25摩尔％的异丁烯，其具有至少约1，500，000的重均分子量，通过GPC在水(pH9)介质中测量，比粘度≥6，在1％DMF溶液中测量。
6．以其混合盐的形式包含权利要求5的无溶剂高分子量三元共聚物的假牙粘合剂组合物，两种阳离子选自Na+、Ca++、Zn++、Al+++及Mg++，优选Ca++/Na+或Ca++/Zn++混合盐。
7．一种牙膏组合物，其包含提高抗菌性能的权利要求5的无溶剂、高分子量、未交联三元共聚物的量。
CN98813807A 1997-10-02 1998-09-22 制备高分子量马来酸酐、c1—c4烷基乙烯基醚及异丁烯三元共聚物的无溶剂法,及包含该三元共聚物的假牙粘合剂和牙膏组合物 Expired - Fee Related CN1113071C (zh)

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US08/942,830 US5939506A (en) 1997-10-02 1997-10-02 Solvent-free process for making high molecular weight terpolymers of maleic anhydride, C1 -C4 alkyl vinyl ether and isobutylene
US09/097,728 1998-06-16
US09/097,895 1998-06-16
US09/097,728 US5900470A (en) 1997-10-02 1998-06-16 Denture adhesive including a solvent-free, high molecular weight terpolymer of maleic anhydride, a C1 -C4 alkyl vinyl ether and isobutylene
US09/097,895 US6046291A (en) 1997-10-02 1998-06-16 Dentifrice composition including a solvent-free, high molecular weight uncrosslinked terpolymer of maleic anhydride, C1 -C4 alkyl ether and isobutylene

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US6355706B1 (en) * 1999-04-14 2002-03-12 The Procter & Gamble Company Denture adhesives with mixed salt copolymers of terpolymers
US6617374B1 (en) 1999-04-14 2003-09-09 The Procter & Gamble Company Denture adhesives with mixed salts of alkyl vinyl ether-maleic copolymer or terpolymer
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US6475498B1 (en) 1999-12-08 2002-11-05 The Procter & Gamble Company Method to inhibit tartar and stain using denture adhesive compositions
US6475497B1 (en) * 1999-12-08 2002-11-05 The Procter & Gamble Company Tartar control denture adhesive compositions
US6905672B2 (en) 1999-12-08 2005-06-14 The Procter & Gamble Company Compositions and methods to inhibit tartar and microbes using denture adhesive compositions with colorants
US6677391B1 (en) 1999-12-08 2004-01-13 The Procter & Gamble Company Tartar control denture adhesive compositions
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

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