CN1199744A - 嵌段共聚物和其作为聚合表面活性剂的用途 - Google Patents
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Abstract
结构为A－B－A的嵌段共聚物适用于作为聚合表面活性剂,其中A表示聚环氧乙烷嵌段,B表示烯烃不饱和季铵化合物。
Description
本发明涉及结构为A-B-A的新型嵌段共聚物，其中A表示聚环氧乙烷嵌段，而B表示烯烃不饱和季铵化合物的聚合物。本发明还涉及其制备方法和它们作为聚合表面活性剂的用途。
聚合表面活性剂在含水体系中用来稳定乳化液，用作乳化聚合中的表面活性剂组分和难溶于水的加溶物质。根据其化学结构，聚合表面活性剂可分为两亲嵌段共聚物和聚皂。
实际中使用的表面活性剂主要是两亲嵌段共聚物，尤其是聚环氧乙烷和聚环氧丙烷嵌段的嵌段共聚物(L.G.Lundsted，I.R.Schmolka“嵌段和接枝共聚反应”，R.J.Ceresa Wiley编辑，伦敦，1976，第2卷，第113页；I.R.SchmolkaJ.Am.Oil Chem.Soc.54(1977)110；I.Piirma，Macromol Chem.，MacromolSymp.35/36(1990)467)。
这些化合物所具有的优点在于通过改变亲水和疏水嵌段的结构和长度，可将它们的HLB用于所需用途。缺点是两亲嵌段共聚物同低分子量表面活性剂一样形成分子间聚集体，因此，它们的活性与它们的临界胶束浓度有关。因此，稳定性仅对用这些化合物稳定的胶乳和乳化液的稀释有限制。对这种体系的稀释而言，加溶物质变成不加溶的物质。另一个缺点是为了得到两亲共聚物，需要采用类硼酸盐合成法例如活性阴离子聚合或准活性阳离子聚合。按这种方法，不可能进行两亲嵌段共聚物的直接合成，其聚合物所含的嵌段带离子电荷。这种类型的聚合物只能通过其它的工艺步骤获得，所述的工艺步骤通常进行地不完全，即需要嵌段共聚物的后续官能作用(W.J.Choi，Y.B.Kim，S.K.Kwon，K.T.Lim，S.K.Choi，J.Polymer Sci.A，《聚合物化学》，30(1992)2143)。
聚合皂可以通过表面活性剂单体的游离基聚合得到，要么通过用疏水残基改性亲水聚合物得到，反之亦然。
从低浓度开始，它们形成胶束，由此使制备乳化液和胶束成为可能，而这些物质对于稀释是稳定的并减少了表面活性剂的需求量(A.Laschewski；《高级聚合科学》124(1995)1；Y.J.Yang，J.B.F.N.Engberts；Eur.Polym.J.28(1992)881)。但是，缺点是建立亲水特性和疏水特性平衡比率的难度很大。用聚合表面活性剂不可能如两亲嵌段共聚物那样清楚地将亲水部分的分子和疏水部分的分子分离开。
本发明的一个目的是发现具有改进特性的新型聚合表面活性剂。
我们发现这个目的可以通过本文开始定义的嵌段共聚物，其制备方法和用途来实现。
根据本发明的方法，通过在常量引发剂的存在下游离基聚合烯烃不饱和季铵化合物来制备嵌段共聚物。使用水作为溶剂。聚合温度为40-95℃，优选55-80℃。
本发明所使用的常量引发剂是偶氮引发剂和具有平均聚合度m的聚乙二醇的反应产物。偶氮双异丁腈优选用作偶氮引发剂。聚乙二醇组分具有平均聚合度m，其中m是5-100的整数。所制成的常量引发剂优选与式IV对应
用常规方法来合成常量引发剂(R.Walz等人，《大分子化学》，178(1977)2527)。
如通常的偶氮引发剂一样，在聚合条件下用消去氮形成游离基。由此通过引发剂向嵌段聚合物中引入聚环氧乙烷嵌段A，所述嵌段A由环氧乙烷单元链和低分子量键-O-CO-C(CH3)2-组成。
可通过加入适当量的引发剂控制A-B-A嵌段结构的系集。引发剂的合适用量按起始单体溶液计为1×10-2mol/l-2×10-2mol/l。适合于本发明用于系集阳离子皂嵌段B的单体是式I的单体I式中x表示5-18的数，优选8-14，R1和R2彼此独立地表示具有1-5个碳原子，优选1-3个碳原子的烷基，R3表示具有1-5个碳原子，优选1-3个碳原子的烷基或羟烷基，以及X-表示卤化物、乙酸酯或甲硫酸酯(methosulfate)，优选氯化物或溴化物。
其它合适的嵌段B的单体是式II和III中单体II和III的混合物
式中R4表示CnH2n+1基团和n表示5-18，优选8-14的数，和
式中R5和R6表示具有1-3个碳原子的烷基或羟烷基，优选甲基，而单体II和III的X-表示优选氯化物的卤化物，乙酸酯或甲硫酸酯。
这样来选择单体I或单体II和III混合物的用量比例，使得产生的嵌段B由z个单元的单体I系集或由p个单元的单体II和q个单元的单体III系集，其中z表示10-200的数，p和q分别彼此独立地表示5-100的数。单体II与单体III的比例为1∶20-20∶1。
单体I，II和III可按已知方法制备(参见Y.J.Yang，J.B.F.N.Engberts；J.Org.Chem.56，4300(1991)；Houben-Weyl“有机化学方法”GeorgThieme出版社，Stuttgart 1958，第11/2卷，第597页；D.F.Evans，H.Wennerstroem“胶体范畴”，VCH出版物，Inc，；纽约，1994，第6页)。
具有m单元的聚环氧乙烷嵌段与阳离子皂嵌段的比率可以根据需要通过适当地选择起始物质的量来调节。m与z或m与(p+q)的比率优选为2∶1-1∶2。由式V和VI描述嵌段共聚物：
所产生的嵌段共聚物中阳离子聚皂嵌段B具有的分子量为1000-350000g/mol，聚环氧乙烷嵌段具有的分子量为200-30000g/mol。
本发明的嵌段共聚物与上文公开的聚合表面活性剂相比，明显地改进了加溶量特性，同时对相应稳定的胶束、乳化液和加溶物等的稀释具有良好的稳定性。
本发明的方法使得可直接具体地调节嵌段共聚物的表面活性特性。
所述嵌段共聚物适合于作为聚合表面活性剂，用来稳定或加溶在水或含水制剂中难溶或略微溶解的生物活性物质，以及作为固体制剂中的加溶辅剂或湿润剂。在这种情况下，生物活性物质是指药物或兽医医用添加剂、农作物保护剂或化妆品添加剂。相应制剂的实例包括化妆品制剂例如皮肤护理产品或头发护理产品的乳化液或洗剂例如泡沫体。
此外，嵌段共聚物适用于口服，尤其是形成用来提高生物利用率的静脉内给药的液态药物制剂，要么是局部施用的药物制剂特别是乳化液、洗剂或悬浮液。
另外，本发明嵌段共聚物适合于作为生产类胡萝卜素(例如食品工业或家畜营养中使用的β-胡萝卜素或虾青素)的稳定液体制剂的聚合表面活性剂。嵌段共聚物的制备
一般方法
按下列实施例1-3的方法，在一个套层反应器中制备嵌段共聚物，反应器内的温度得到控制，并且反应器配有搅拌器、回流冷凝器、温度传感器和气体输送管。向反应器中输入单体和水的起始混合物，用氮气冲洗1小时，然后加热到65℃的反应温度。达到反应温度后，将常量引发剂溶解在起始混合物的试样中并加入到反应混合物中。反应6小时后，向冰中加入混合物，并采用由Filtron提供的具有排阻限为5000道不顿明渠奥米加型膜进行超滤作用，直到滤液的残余导电率为10μs为止。在实施例1和2中，冻干滞留物，在实施例3中进行浓缩并用过量10倍的丙酮沉淀聚合物。
实施例中具体给出了各种情况下起始物质的用量。实施例1起始混合物：
加水将13.0g单体II(其中R4表示正辛烷和X-表示氯化物)和18.1g67％(重量)二烯丙基甲基氯化铵水溶液(单体III)制成50ml的水溶液。常量引发剂溶液：
将2.08g偶氮双异丁腈和聚乙二醇(m＝45)的反应产物溶解在5ml起始混合物中。
制备8.1g嵌段共聚物，其具有的平均值m＝45，p＝35和q＝55，m∶(p+q)比为1∶2。
正癸醇的嵌段共聚物的加溶量因子要比相应的仅由B组成的纯聚皂的加溶量大5.1。一种类似的仅由单体III组成的具有嵌段B的嵌段共聚物不能稳定癸醇。实施例2起始混合物：
加水将12.4g单体II(其中R4表示正C12H25和X-表示氯化物)和16.2g 67％(重量)二烯丙基甲基氯化铵水溶液(单体III)制成50ml的水溶液。常量引发剂溶液：
如实施例1。
制备6.4g嵌段共聚物，其具有的平均值m＝45，p＝5和q＝23，m∶(p+q)比为1.18∶1。
正癸醇的加溶量因子要比相应的纯聚皂的加溶量大1.8。实施例3起始混合物：
15.8g单体I(其中x＝11和X-表示溴化物)在400ml水中的溶液。常量引发剂溶液：
16.66g实施例1反应产物在30ml水中的溶液。
制备13.8g嵌段共聚物，其具有的平均值m＝45，z＝75，m∶z比为1∶1.7。
正癸醇的加溶量因子要比相应的纯聚皂的加溶量大1.35。
Claims (10)
1.结构为A-B-A的嵌段共聚物，其中A表示聚环氧乙烷嵌段，B表示烯烃不饱和季铵化合物。
2.根据权利要求1的嵌段共聚物，含有平均聚合度m为5-100的嵌段A。
3.根据权利要求1或2的嵌段共聚物，含有式I的季铵化合物(单体I)的聚合物作为嵌段B式中x表示5-18的数，R1和R2彼此独立地表示C1-C5烷基，R3表示C1-C5烷基或羟烷基，以及X-表示卤化物、乙酸酯或甲硫酸酯。
4.根据权利要求1或2的嵌段共聚物，含有式II单体II和式III单体III的混合物的聚合物作为嵌段B式中R4表示CnH2n+1基团和n表示5-18的数，式III中单体III中R5和R6表示C1-C3烷基或C1-C3羟烷基，而单体II和III的X-表示卤化物，优选氯、乙酸酯或甲硫酸酯，其中单体II与单体III的比例为1∶20-20∶1。
5.根据权利要求1-4任一项的嵌段共聚物，含有分子量为1000-350000g/mol的嵌段B。
6.根据权利要求1-5任一项的嵌段共聚物，含有分子量为200-30000g/mol的聚环氧乙烷嵌段A。
7.权利要求1-6任一项的嵌段共聚物的制备方法，包括在常量引发剂的存在下游离基聚合烯烃不饱和季铵化合物的水溶液，所述的常量引发剂通过聚乙二醇与偶氮双异丁腈反应得到。
8.权利要求1-6任一项的嵌段共聚物的用途，用作生产生物活性物质的聚合表面活性剂。
9.根据权利要求8的用途，用于生产药物制剂。
10.根据权利要求8的用途，用于生产化妆品制剂。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19714714.3 | 1997-04-09 | ||
| DE19714714A DE19714714A1 (de) | 1997-04-09 | 1997-04-09 | Blockcopolymere und deren Verwendung als polymere Tenside |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1199744A true CN1199744A (zh) | 1998-11-25 |
Family
ID=7825948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98109416A Pending CN1199744A (zh) | 1997-04-09 | 1998-04-09 | 嵌段共聚物和其作为聚合表面活性剂的用途 |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0870781A1 (zh) |
| JP (1) | JPH10292022A (zh) |
| CN (1) | CN1199744A (zh) |
| DE (1) | DE19714714A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100349939C (zh) * | 2001-12-20 | 2007-11-21 | 荷兰联合利华有限公司 | 洗衣清洁组合物用的聚合物 |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19839054A1 (de) | 1998-08-28 | 2000-03-02 | Forschungszentrum Juelich Gmbh | Verfahren zur Effizienzsteigerung von Tensiden bei simultaner Unterdrückung lamellarer Mesophasen sowie Tenside, welchen ein Additiv beigefügt ist |
| WO2002079282A1 (de) * | 2001-04-02 | 2002-10-10 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Wasserlösliche verzweigte blockcopolymere |
| JP2005511851A (ja) * | 2001-12-12 | 2005-04-28 | ロディア・シミ | 重合体を含む組成物を表面に付着する方法 |
| DE10237286A1 (de) | 2002-08-14 | 2004-02-26 | Degussa Construction Chemicals Gmbh | Verwendung von Blockcopolymeren als Dilpergiermittel für wässrige Feststoff-Suspensionen |
| JP4266926B2 (ja) * | 2002-10-21 | 2009-05-27 | ロレアル | 両親媒性ブロックコポリマーを用いた水溶液に脂質親和性化合物を溶解させる方法、及び化粧品用組成物 |
| FR2845930B1 (fr) * | 2002-10-21 | 2006-05-26 | Oreal | Procede de solubilisation de composes lipophiles en solution aqueuse par des copolymeres blocs amphiphiles et composition cosmetique |
| US7677315B2 (en) | 2005-05-12 | 2010-03-16 | Halliburton Energy Services, Inc. | Degradable surfactants and methods for use |
| WO2006137511A1 (ja) * | 2005-06-23 | 2006-12-28 | Shiseido Co., Ltd. | ポリマー及び化粧料 |
| EP2046850A1 (en) * | 2006-08-03 | 2009-04-15 | Ciba Holding Inc. | Block copolymers of diallyldialkylammonium derivatives |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03177426A (ja) * | 1989-11-22 | 1991-08-01 | Arco Chem Technol Inc | 界面活性剤として有用なオキシアルキレン／ｎ―アシルアルキレンイミンブロック共重合体 |
| DE19521096C2 (de) * | 1995-06-09 | 1998-10-08 | Fraunhofer Ges Forschung | Verfahren zur Herstellung von Dispersionen wasserlöslicher Vinylpolymerer und Stabilisator zur Durchführung des Verfahrens |
-
1997
- 1997-04-09 DE DE19714714A patent/DE19714714A1/de not_active Withdrawn
-
1998
- 1998-03-17 EP EP98104772A patent/EP0870781A1/de not_active Withdrawn
- 1998-04-08 JP JP10096122A patent/JPH10292022A/ja not_active Withdrawn
- 1998-04-09 CN CN98109416A patent/CN1199744A/zh active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100349939C (zh) * | 2001-12-20 | 2007-11-21 | 荷兰联合利华有限公司 | 洗衣清洁组合物用的聚合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10292022A (ja) | 1998-11-04 |
| DE19714714A1 (de) | 1998-10-15 |
| EP0870781A1 (de) | 1998-10-14 |
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