CN1108333C - 含羟基官能团聚合物的高内相比乳液和稳定水分散体 - Google Patents

含羟基官能团聚合物的高内相比乳液和稳定水分散体 Download PDF

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CN1108333C
CN1108333C CN98809762A CN98809762A CN1108333C CN 1108333 C CN1108333 C CN 1108333C CN 98809762 A CN98809762 A CN 98809762A CN 98809762 A CN98809762 A CN 98809762A CN 1108333 C CN1108333 C CN 1108333C
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C·比乔奇
J·E·培特
M·N·芒
D·C·史密德特
J·E·怀特
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Abstract

本发明是一种组合物，它包括以下二者之一：a)水作为连续相和热塑性含羟基官能团聚醚作为分散相的高内相比乳液；或b)热塑性含羟基官能团聚醚的稳定水分散体。本发明的组合物满足了本领域的需要，即提供了对氧和二氧化碳有良好屏障作用的热塑性涂层，而与水接触时对屏障性能没有不利影响。本发明组合物在需要生物降解和防止食物变坏的纸包装工业中特别有用。

Description

含羟基官能团聚合物的高内相比乳液 和稳定水分散体
本发明涉及含羟基官能团聚合物的高内相比(HIPR)乳液和稳定水分散体。
在包装用纸应用中，希望有屏障来阻挡水、氧气和二氧化碳。使用施胶剂可以减小纸表面的可湿性，而用适当材料的连续膜涂布纸张可形成气体屏障。生成这样的屏障膜的实例是石腊、聚乙烯、乙烯-醋酸乙烯酯共聚物以及聚偏二氯乙烯(PVDC)。其中，PVDC具有最好的屏障水、蒸汽和氧气的特性。然而，不同于其它的高氧屏障材料，PVDC几乎对水是不敏感的。而且，因为其高的氯含量，PVDC趋向于腐蚀加工设备，从而增加生产成本。
在本领域中，制备这样的不含氯的乳胶是有利的，它可用于形成涂层，该涂层作为屏障有效的抵挡小分子，但在与水接触时，对屏障的性能不会产生不利影响。如果涂层粘着于基质上而不借助于辅助粘合剂将更有利。对于某些用途还要求此涂层可生物降解，以便该产品使用之后可经堆肥而处置。
本发明是一种组合物，包括以下二者之一：a)水作为连续相以及热塑性含羟基官能团聚醚作为分散相的HIPR乳液；或b)热塑性含羟基官能团聚醚的稳定水分散体，其中含羟基官能团聚醚具有的结构单元可用下列两个分子式之一表示：
Figure C9880976200071
或其中R1主要是亚烃基；R5分别是氢或烷基；n是0或1；R3是或
Figure C9880976200083
和R4是或
Figure C9880976200085
其中的R2主要是亚烃基或其中，R6主要是亚烃基；R7在各自情况下分别是氢或甲基；X是
Figure C9880976200087
或
Figure C9880976200088
或其中的R8在各自情况下分别是C2-C20亚烃基；Z在各自情况下分别是H、烷酰氨基、羟基、烷氧基、烷基羰基、芳氧基、芳基羰基、卤素或氰基；Y主要是亚烃基；m分别是从0到100的整数。
另一方面，本发明是制备含羟基官能团聚醚的稳定水分散体的方法，包括以下步骤：
a)将含羟基官能团聚醚溶解在溶剂中或将聚醚熔化，形成与水充分不相混溶的溶液或熔体，以便可形成在水连续相中的聚醚溶液的高内相比乳液；
b)在乳化和稳定量的表面活性剂存在下，将以r1速率流动的水流和以r2速率流动的含有含羟基官能团聚醚溶液的物流连续引入分散器中；
c)以充分的剪切力混合上述物流，形成高内相比乳液；
d)用水稀释高内相比乳液，形成稳定水分散体；和
e)将溶剂从高内相比乳液中除去；其中含羟基官能团聚醚具有的结构单元可用以下两个化学式之一表示：或
Figure C9880976200093
其中：R1主要是亚烃基；R5在各自情况下分别是氢或烷基；n是0或1；R3是或 并且R4是
Figure C9880976200103
或 其中的R2主要是亚烃基或其中的R6主要是亚烃基；R7在各自情况下分别是氢或甲基；X是
Figure C9880976200106
或或：
Figure C9880976200111
其中的R8在各自情况下分别是C2-C20亚烃基；Z在各自情况下分别是H、烷氨基、羟基、烷氧基、烷基羰基、芳氧基、芳基羰基、卤素或氰基；Y主要是亚烃基；m分别是从0到100的整数；其中流动速率比r2∶r1是这样的范围，使得高内相比乳液的体积平均粒径不大于3微米。
本发明通过提供粘合的热塑性涂层满足了本领域的需求，该涂层展示出对于氧和二氧化碳优异的屏障作用，但与水接触时对屏障性能没有不利影响。在某些实施方案中，组合物可提供在包装用纸方面特别有用的可生物降解涂层，在此应用中阻止食物变坏和可生物降解都是所要求的。
图1是多散性(Dv/Dn)和体积平均粒径(微米)对进料比(聚合物溶 液∶水)的曲线图。
用于制备本发明的HIPR乳液或稳定水分散体的热塑性含羟基官能团聚醚具有的结构单元可用下面两个分子式之一表示：或
Figure C9880976200113
其中：X优选是2-羟乙基亚氨基、2-羟丙基亚氨基、哌嗪基、N，N′-二(2-羟乙基)-1，2-亚乙基二亚胺基；Y优选是亚异丙基二亚苯基、1，3-亚苯基或1，4-亚苯基；R3是或
Figure C9880976200122
以及R4是
Figure C9880976200123
或 或
Figure C9880976200125
其中的R5优选是氢，并且优选m分别是0到10的整数。
术语“主要是亚烃基”是指主要是烃基的二价基因，但也可能含有少量的杂原子，如氧、硫、亚胺基、磺酰基和次磺酰基(sulfoxyl)。
用作R1、R2和R6的代表性的亚烃基包括未取代和羟基取代的亚烃基，包括亚烷基、亚环烷基、亚烷基亚芳基、聚(亚烷基氧亚烷基)、亚烷基硫亚烷基、亚烷基磺酰基-亚烷基、亚芳基、二亚烷基亚芳基、二亚芳基酮、二亚芳基砜、二亚芳基氧和二亚芳基硫。
在进一步优选的含羟基官能团聚醚中，R1、R2和R6分别是亚甲基、亚乙基、亚丙基、亚丁基、五亚甲基、六亚甲基、七亚甲基、八亚甲基、九亚甲基、十亚甲基、十二亚甲基、1，4-亚环己基、1，3-亚环己基、1，2-亚环己基、对亚苯基、间亚苯基、邻亚苯基、2，6-亚萘基、二亚苯基-亚异丙基、磺酰基二亚苯基、羰基二亚苯基、氧二亚苯基或9，9-芴二亚苯基。
分子式I所示的聚(羟基酯醚)可用脂肪族或芳族的二酸(如己二酸或对苯二甲酸)与脂肪族或芳族二酸的二缩水甘油酯(如对苯二甲酸二缩水甘油酯)或二元酚或二元醇的二缩水甘油醚反应来进行制备，如美国专利5,171,820和5,496,910中所述。
分子式II所示的聚(羟基氨基醚)(式中n＝1)可用带有两个胺氢原子的胺与一种或多种二元酚的二缩水甘油醚接触进行制备，反应条件要求足以引起胺基与环氧基反应以形成带有胺键、醚键并且带有侧羟基的聚合物主链。在美国专利5,275,853中对这些聚醚进行了描述。这些聚醚也可用二元胺与二缩水甘油醚或表卤代醇接触进行制备。
分子式II所示的含羟基官能团聚醚(式中n＝0)也可用美国专利5,164,472所述方法，通过用二元酚或二元酚的混合物与二缩水甘油醚或二缩水甘油醚的混合物接触进行制备。另外，含羟基官能团聚醚也可由Reinking，Barnabeo，和Hale在 《应用聚合物科学杂志》 (Journal of Applied Polymer Science)，Vol.7，pg.2135(1963)中描述的方法，用表卤代醇与二元酚或二元酚的混合物反应进行制备。
更进一步优选的含羟基官能团聚醚含有由双酚A的二缩水甘油醚和己二酸反应产物形成的结构单元。
含羟基官能团聚醚的优选重均分子量(由凝胶渗透色谱法测定)不小于约1000道尔顿，进一步优选不小于10,000道尔顿，更进一步优选不小于20,000道尔顿，并且优选不大于250,000道尔顿，进一步优选不大于100,000道尔顿。
含羟基官能团聚醚的稳定水分散体可用包括美国专利3,360,599；3,503,917；4,123,403；5,037,864；和5,539,021中所描述的方法在内的任何适当的方法进行制备。优选地，含羟基官能团聚醚的稳定水分散体通过先制备HIPR乳液，然后用水稀释乳液进行制备。
含羟基官能团聚醚的HIPR乳液也可用任何适当的方法进行制备，如美国专利4,018,426；5,250,576；和5,539,021中所述方法。优选地，HIPR乳液的制备，是在乳化和稳定量的表面活性剂存在下，水流以流速r1流动，含有含羟基官能团聚醚的物流以流速r2流动，连续进入分散器中，然后在足够的剪切力下混合这些物流，以形成HIPR乳液。流动速率比r2∶r1优选是在这样的范围内，即HIPR乳液的多分散性-定义为体积平均粒径与数量平均粒径之比(Dv/Dn)-不大于3，进一步优选不大于2，并且更进一步优选不大于1.3；或体积平均粒径-用Coulter LS 230粒径分析仪(Coulter分析仪器公司)进行测量-不大于3微米，进一步优选不大于1微米，并且更进一步优选不大于0.5微米。
现在参阅图1，多分散性(虚线，实心圆点)和粒径(实线，空心圆点)对进料比(聚合物溶液：水)的曲线图，给出最好结果的进料比的范围是不小于3.5，优选不小于3.8，并且不大于4.5，优选不大于4.4。聚合物溶液是45％重量的聚羟基酯醚(由实施例B部分所述方法制备)在体积比60∶40的甲苯和1-丁醇混合物中的溶液。令人吃惊的发现是，具有小粒径和多分散性的含羟基官能团聚醚的水分散体可在没有诸如含羧酸基团这样的接枝官能团存在情况下进行制备。
含羟基官能团聚醚方便地溶解在有机溶剂或混合溶剂中，以便含有含羟基官能团聚醚的物流有充分低的粘度通过导管泵送。另外，不可泵送的含羟基官能团聚醚可通过充分加热使其可以泵送。优选地，将含羟基官能团聚醚溶在溶剂或混合溶剂中。溶剂或混合溶剂的特征在于提供的聚合物溶液充分地与水不相混溶，以便形成在水连续相中的聚合物溶液的HIPR乳液。优选的溶剂是二醇醚、如丙二醇甲醚的乙酸酯；优选的混合溶剂是非极性溶剂和C1-C5醇的混合物，如甲苯和正丁醇的混合物。
用于稳定HIPR乳液的表面活性剂优选是阴离子或非离子的，或它们的组合。优选的非离子表面活性剂是具有下列结构的聚合物表面活性剂：其中：R6和R3如前面所定义；R0是亚烷基，优选是C2-C12亚烷基，进一步优选是亚乙基、亚丙基或亚丁基，更进一步优选是亚乙基；R9和R10各自分别是H、烷基或烯基，优选是H、C1-C20烷基或C2-C20烯基，进一步优选是H、C1-C12烷基或C2-C12烯基，最优选是H或2-十二碳烯-1-基；并且n′和x′是正整数；以及R5优选是二亚苯基-亚异丙基。
制备聚合物表面活性剂(IV)可通过以下步骤进行：首先用酸酐与聚氧化烯二醇、优选与聚氧乙烯二醇反应，以生成二酸中间体，其中二醇与酸酐的摩尔比是1∶2；然后用中间体与二缩水甘油醚、优选与双酚A的二缩水甘油醚反应，二缩水甘油醚与二酸的摩尔比优选是在1到2的范围。反应流程如下所示：
进一步优选的表面活性剂是聚合物表面活性剂(IV)与阴离子表面活性剂的组合，如乙氧基化苯酚的磺酸盐或硫酸盐，如聚(氧-1，2-亚乙基)α-磺基-ω(壬基苯氧基)铵盐(由Rhone Pulenc以商标RhodapexTM CO 436可得到)；或磺基琥珀酸二烷基酯的钠盐，如磺基琥珀酸二辛基酯的钠盐(由Cytec工业公司美国氰胺分部可以AerosolOT75得到)，优选地，阴离子表面活性剂与聚合物表面活性剂的摩尔比不大于2∶1，进一步优选不大于1∶1。
HIPR乳液可简单地用水稀释，优选在搅拌条件下进行稀释，以形成稳定的水分散体。有机溶剂-如果存在-可用任何适当的方法如真空蒸馏法方便地从稳定的水分散体中除去。
含羟基官能团聚醚的稳定水分散体可用于制备不含氯、粘合的热塑性涂层，该涂层具有低的氧和二氧化碳透过率。由聚(羟基酯醚)的稳定水分散体形成的涂层在需要可生物降的应用中是特别有用的。这样的涂层对于食物包装纸或容器(如牛奶或果汁的纸盒)是有用的，在此应用中希望保持新鲜并且(用完后)将容器丢弃到堆肥箱中。
下面的实施例只是为了说明的目的而不是要限制本发明的范围。
实施例1，通过连续法制备含羟基官能团聚醚的稳定水分散体
A.聚合物表面活性剂的制备
在装配有氮气入管、机械搅拌器和冷凝器的圆底烧瓶中，搅拌下在30分钟内加入聚乙二醇400(分子量400，319.5mmol)、聚乙二醇4500(分子量4500，28.5mml)和琥珀酸酐(696mmol)。反应物在90℃加热2小时，随后在150℃下加入Al催化剂(400ppm的70％的与醋酸配合的乙基三苯基鏻乙酸盐的甲醇溶液)和D.E.R.TM330(Dow化学公司的商标，330.5mmol，环氧当量180)，加料时间为90分钟。在150℃下继续搅拌3.5小时，随后添加对甲苯磺酸甲酯(280ppm)。冷却溶液并分离出黄色腊状的聚合物表面活性剂。
B.用聚合物表面活性剂制备稳定水分散体
由约等当量的双酚A的二缩水甘油醚与己二酸反应制备含羟基官能团聚醚(基本上使用与美国专利5,496,910，第6栏，14-25行所描述的相同方法)。聚合物溶液如下制备：将含羟基官能团聚醚(45g)与步骤A制备的聚合物表面活性剂(4.5g)一起溶入60∶40重量比的甲苯和正丁醇混合物(65g)中。聚合物溶液通过0.5英寸(1.27cm)内径的不锈钢管线(装配于第一T形接头)以35g/min的速率连续泵送。同时，Aerosol OT75通过0.125英寸(0.32cm)聚四氟乙烯管线(装配于第一T形接头)以0.7g/min的速率泵送。水以7.2g/min的速率通过另一0.125英寸(0.32cm)的聚四氟乙烯管线(通过位于第一T形接头下游的第二T形接头装配于所述0.5英寸内径的不锈钢管线)进行泵送。使用4英寸(10cm)离心泵并在1200rpm转速下操作，在剪切条件下将聚合物-Aerosol OT75物流与水流合并并且混合在一起，形成水连续相中的聚合物HIPR乳液。此HIPR乳液与水稀释剂一起通过第二离心泵以形成稳定水分散体(胶乳)。将有机溶剂从胶乳中真空除去，以获取50％固含量的胶乳。胶乳的体积平均粒径用Coulter LS230测量是0.569微米(Dv/Dn＝1.3)。

Claims (13)

1.一种组合物，它包含a)水作为连续相和热塑性含羟基官能团聚醚作为分散相的高内相比乳液；或b)热塑性含羟基官能团聚醚的稳定水分散体，其中含羟基官能团聚醚具有的结构单元可用下面两个分子式之一表示：或
Figure C9880976200022
其中：R1主要是亚烃基；R5在各自情况下分别是氢或烷基；n是0或1；R3是或 R4是
Figure C9880976200025
或
Figure C9880976200026
其中的R2主要是亚烃基或
Figure C9880976200031
其中的R6主要是亚烃基；R7在各自情况下分别是氢或甲基；X是或或
Figure C9880976200034
其中的R8在各自情况下分别是C2-C20亚烃基；Z在各自情况下分别是H、烷酰氨基、羟基、烷氧基、烷基羰基、芳氧基、芳基羰基、卤素或氰基；Y主要是亚烃基；每个m分别是0到100的整数。
2.权利要求1的组合物，它是水作连续相并且热塑性含羟基官能团聚醚作为分散相的高内相比乳液。
3.权利要求2的组合物，其中，R4是其中：m是0；R1是亚乙基、亚丙基、六亚甲基、对亚苯基或间亚苯基；R2是对亚苯基、间亚苯基或二亚苯基-亚异丙基；以及R5是H。
4.权利要求2的组合物，其中含羟基官能团聚醚具有的结构单元用分子式表示为：R1是1，4-亚环己基、1，3-亚环己基或1，2-亚环己基、对亚苯基、间亚苯基、2，6-亚萘基、二亚苯基-亚异丙基、磺酰基二亚苯基、羰基二亚苯基、氧二亚苯基或9，9-芴二亚苯基；以及R6是亚甲基、亚乙基、亚丙基、亚丁基、五亚甲基、六亚甲基、七亚甲基、八亚甲基、九亚甲基、十亚甲基或十二亚甲基。
5.权利要求3的组合物，其中R1是二亚苯基-亚异丙基；R6是四亚甲基；并且含羟基官能团聚醚的重均分子量不小于10,000道尔顿并且不大于250,000道尔顿。
6.权利要求2的组合物，由以下步骤制备：
a)将含羟基官能团聚醚溶解在溶剂中或将聚醚熔化，形成与水充分不相混溶的溶液或熔体，以便可形成在水连续相中的聚醚溶液的高内相比乳液；
b)在乳化和稳定量的表面活性剂存在下，将以速率r1流动的水流和含有聚醚溶液的以速率r2流动的物流连续投入分散器中；并且
c)用足够的剪切力将上述物流混合，以形成高内相比乳液，其中流动速率比r2∶r1使高内相比乳液的粒径不大于3微米。
7.权利要求6的组合物，其中表面活性剂包括阴离子表面活性剂和具有如下分子式的聚合物非离子表面活性剂：
Figure C9880976200051
其中：R6主要是亚烃基；R3是或
Figure C9880976200053
其中的每个R5在各自情况下分别是氢或烷基；R0是C2-C12亚烷基；R9和R10各自独立地是H、烷基或烯基；并且n′和x′是正整数。
8.权利要求7的组合物，其中阴离子表面活性剂是乙氧基化酚的磺酸盐或硫酸盐，或是磺基琥珀酸二烷基酯的钠盐；R6是二亚苯基-亚异丙基；R8是亚乙基、亚丙基或亚丁基；R9是H、C1-C12烷基或C2-C12烯基；其中阴离子表面活性剂与聚合物表面活性剂的摩尔比不大于2∶1。
9.权利要求8的组合物，其中阴离子表面活性剂是磺基琥珀酸二辛基酯的钠盐；R9是2-十二碳烯-1-基或H，并且R8是亚乙基；其中阴离子表面活性剂对聚合物表面活性剂的摩尔比不大于1∶1。
10.权利要求1的组合物，它是热塑性含羟基官能团聚醚的稳定水分散体。
11.权利要求1的组合物，其中含羟基官能团聚醚具有的结构单元用以下分子式表示：其中：X是
Figure C9880976200061
或或以及Y是亚异丙基二亚苯基、1，3-亚苯基或1，4-亚苯基，其中聚合物的重均分子量不小于1000并且不大于100,000道尔顿。
12.权利要求1的组合物，其中含羟基官能团聚醚具有的结构单元用分子式表示为：Y是亚异丙基二亚苯基、1，3-亚苯基或1，4-亚苯基，并且聚合物的重均分子量不小于1000并且不大于100,000道尔顿。
13.权利要求12的组合物，它是由二酚与二缩水甘油醚或表卤代醇反应形成的。
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