CN102558440B - 新颖的聚合物珠组合物 - Google Patents
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Abstract
本发明是聚合物珠组合物。更具体,本发明涉及通过悬浮聚合方法由包含含磷的酸的单体形成的新颖的聚合物珠组合物。
Description
技术领域
本发明是聚合物珠组合物。更具体来说,本发明涉及通过悬浮聚合方法由包含含磷的酸(phosphorous acid)及其盐的单体形成的新聚合物珠组合物。
发明背景
在本领域中已经通过各种单体的聚合来制备聚合物珠。通常,制备这些聚合物珠的方法既费力又需要昂贵的单体材料。而且,当需要官能聚合物时,通常需要额外的官能化步骤来使所得聚合物官能化。这增加了聚合物制造方法的花费,废物产生和效率降低。
为了尝试在单步方法中最大程度地减少废物并解决成本和低效率的问题,在本领域中已经使用一类单体,这类单体因为本身含官能团,因而无需额外的官能化步骤。包含含磷的酸的单体如甲基丙烯酸磷酰烷基酯已经被用于此目的。通常,如US4110285所揭示,这些单体通过乳液聚合方法来聚合。乳液聚合的材料通常具有极低含量的含酸单体和交联单体。该方法的问题在于其产生的聚合物珠的平均粒度小于1微米。一些应用需要使用平均粒度大于30微米的大珠或聚合物。
本发明通过提供一种改进的聚合物珠来解决该问题,所述聚合物珠包含甲基丙烯酸磷酰烷基酯的酸单体,其中所述聚合物珠的平均粒度大于30微米。
发明内容
本发明提供一种聚合物珠组合物,其包含:
i.)至少20-99.9重量%的含磷的酸单体;和
ii.)平均粒度为30-1000微米。
本发明还提供一种上述聚合物珠组合物,其中所述聚合物珠通过以下步骤制备:
i)形成悬浮液,
其中所述悬浮液包含至少一种含磷的酸单体、水性介质、自由基引发剂和悬浮剂;
ii)使单体聚合,直到它们形成非水溶性聚合物珠。
具体实施方式
用于本发明制备改进的聚合物珠的单体是含磷的酸单体,该单体含有至少一个烯健式不饱和键和含磷的酸(phosphorus acid)基团。含磷的酸单体可以是酸形式或含磷的酸基团的盐形式。含磷的酸单体的例子包括:
其中R是包含丙烯酸基、甲基丙烯酸基、苯乙烯基、丙烯酰氧基、甲基丙烯酰氧基、苯乙烯基、芳基或乙烯基的有机基团;R’和R”独立地选自H和第二有机基团。所述第二有机基团可以是饱和的或不饱和的。
合适的含磷的酸单体包括二氢磷酸酯/盐官能单体,例如醇的二氢磷酸酯,其中所述醇还包含可聚合的乙烯基或烯烃基团,例如磷酸烯丙酯;二(羟甲基)富马酸酯或衣康酸酯的单磷酸酯或二磷酸酯;(甲基)丙烯酸酯的衍生物,例如(甲基)丙烯酸羟烷基酯的磷酸酯,所述(甲基)丙烯酸羟烷基酯包括(甲基)丙烯酸-2-羟乙酯,(甲基)丙烯酸-3-羟丙酯等。其它合适的含磷的酸单体包括CH2=C(R)-C(O)-O-(R1O)n-P(O)(OH)2,其中R=H或CH3,R1=烷基,例如可购自罗迪亚公司(Rhodia,Inc.)的SIPOMERTM PAM-100、SIPOMERTMPAM-200、SIPOMERTM PAM-300和SIPOMERTM PAM-4000。PEM是甲基丙烯酸羟乙酯的磷酸酯单体。
其它合适的含磷的酸单体是膦酸官能单体(phosphonate functionalmonomer),例如WO 99/25780A1所述,包括乙烯基膦酸、烯丙基膦酸、2-丙烯酰氨基-2-甲基丙烷膦酸、α-膦酰基苯乙烯、2-甲基丙烯酰氨基-2-甲基丙烷膦酸。其它合适的磷官能单体是Harcross T-Mulz 1228和1,2-烯键式不饱和(羟基)氧膦基烷基(甲基)丙烯酸酯单体,如US 4,733,005中所揭示的,包括甲基丙烯酸(羟基)氧膦基甲酯。优选的含磷的酸单体是二氢磷酸酯/盐单体,包括(甲基)丙烯酸-2-磷酰乙酯、(甲基)丙烯酸-2-磷酰丙酯、(甲基)丙烯酸-3-磷酰丙酯,以及(甲基)丙烯酸-3-磷酰基-2-羟丙酯。优选的是(甲基)丙烯酸-2-磷酰乙酯、(甲基)丙烯酸-2-磷酰丙酯、(甲基)丙烯酸-3-磷酰丙酯、(甲基)丙烯酸-3-磷酰基-2-羟丙酯、SIPOMERTM PAM-100和SIPOMERTMPAM-200。
在本发明中,酸单体可以以其原始形式聚合。优选酸单体为质子化形式。或者,在聚合之前,含磷的酸单体可与金属络合。例如,金属可与酸单体的磷酰基部分络合。本发明的含磷的酸单体可以在聚合之前为质子酸形式,或者含磷的酸单体在聚合之前与金属络合。金属络合的单体使用多价金属离子,该离子与不止一种含磷酸根的单体结合。该含磷的酸单体的含量为单体混合物总重的20-99.9重量%,或者40-99.9重量%,或者70-99.9重量%。在本发明的诸多单体中,一种特别合适的含磷的酸单体是酸单体甲基丙烯酸磷酰乙酯。
可用于本发明的交联单体包括非水溶性多烯健式不饱和单体,包括:芳族交联剂,例如二乙烯基苯、三乙烯基苯、二乙烯基萘、二乙烯基甲苯、二乙烯基氯苯、邻苯二甲酸二烯丙酯、二乙烯基二甲苯、二乙烯基乙基苯、三乙烯基萘和聚乙烯基蒽;非芳族交联剂,例如二甘醇二乙烯基醚、三羟甲基丙烷三甲基丙烯酸酯、二甘醇二乙烯基醚、二甲基丙烯酸二甘醇酯、二丙烯酸乙二醇酯、二甲基丙烯酸新戊二醇酯、四甲基丙烯酸季戊四醇酯、三甲基丙烯酸季戊四醇酯、丙烯酸烯丙酯、二乙烯基酮、N,N′-亚甲基二丙烯酰亚胺、N,N′-亚甲基-二甲基丙烯酰亚胺、N,N′-亚乙基二丙烯酰亚胺、马来酸二烯丙酯、富马酸二烯丙酯、琥珀酸二烯丙酯、碳酸二烯丙酯、丙二酸二烯丙酯、草酸二烯丙酯、己二酸二烯丙酯、癸二酸二烯丙酯、酒石酸二烯丙酯、丙三羧酸二烯丙酯、乌头酸三烯丙酯、柠檬酸三烯丙酯;乙二醇、丙三醇和季戊四醇的聚烯丙基和聚乙烯基醚;芳烷基交联单体,例如双酚A二甲基丙烯酸酯,和间苯二酚的聚烯丙基和聚乙烯基醚;以及它们的混合物。优选的交联单体是二乙烯基苯、三羟甲基丙烷三甲基丙烯酸酯、三羟甲基丙烷三丙烯酸酯、六亚甲基-二-甲基丙烯酰胺和二甘醇二乙烯基醚,以及它们的混合物。本文所述的交联单体特别排除含磷的多烯键式不饱和单体,例如多烯键式不饱和PEM二酯等。交联单体的含量为单体混合物总重的0-30重量%,或者2-20重量%,或者4-10重量%。
其它单烯健式不饱和单体可以少量存在于单体混合物中。可用于本发明的非水溶性单体包括可与酸单体和交联单体的组合共聚的单体。这些单体包括具有单烯健式不饱和键的芳族和脂族单体,包括被烯键以外的官能团取代的那些单体。其它单烯健式不饱和单体可以单独一种或组合的形式存在。
可用于本发明的聚合引发剂包括可溶于单体的引发剂,诸如过氧化物、氢过氧化物和相关的引发剂,例如过氧化苯甲酰,氢过氧化叔丁基,过氧化枯烯,过氧化-1,2,3,4-四氢化萘,过氧化乙酰基,过氧化己酰基,过苯甲酸叔丁酯,二过邻苯二甲酸叔丁酯,以及过氧化甲乙酮。还可以使用二(4-叔丁基-环己基)过氧二碳酸酯和偶氮引发剂,例如偶氮二异丁腈,偶氮二异丁酰胺,2,2′-偶氮-二(2,4-二甲基戊腈),偶氮-二(α-甲基丁腈)以及二甲基-、二乙基-或二丁基偶氮-二(甲基戊酸酯)。优选的引发剂是二(4-叔丁基-环己基)过氧二碳酸酯。基于单体的总重量,引发剂的用量优选为0.01-5重量%,或者为0.01-3重量%,优选为0.01-2重量%。可使用引发剂的组合。
可用于降低水溶性单体在水相中的溶解度的盐是水溶性非活性无机盐,包括单价、二价或铝阳离子与单价或二价阴离子的水溶性非活性无机盐,例如盐酸、氢溴酸、氢碘酸、硫酸、碳酸和硝酸的钠盐、钾盐、锂盐和铵盐,以及盐酸、氢溴酸、氢碘酸和硝酸的镁盐和钙盐。优选的盐是氯化钠、硫酸钠和硝酸钠。基于水相的总重,盐以5重量%的含量溶解于水性介质,使盐在水相中达到饱和。文中用于描述盐的术语″非活性″指该盐不能与水、单体或由单体形成的聚合物发生化学反应。
可用于本发明的分散剂或悬浮剂是非离子表面活性剂。这类合适的非离子表面活性剂的例子包括但不限于部分水解的聚丙烯酰胺、聚乙烯醇、高岭土、磷酸三钙、羟烷基纤维素等,以及它们的混合物。
本发明的方法包括在自由基引发剂如0.1-5重量%的可溶于单体的自由基引发剂和0.01-4重量%的非离子表面活性剂型分散剂存在下,在水性介质中形成单体混合物的悬浮液,所述单体混合物包含酸单体和0-30重量%(基于单体总重)的交联单体以及任选的第二单烯健式不饱和单体,所述水性介质包含5重量%至饱和的水溶性非活性无机盐;在悬浮液中建立聚合条件,使单体聚合,直到它们形成非水溶性颗粒。然后可将非水溶性颗粒从水相中分离。
单体相在水相中形成球形小滴;优选通过搅拌将这些小滴保持在悬浮状态,但是也可以采用本领域技术人员熟知的其它技术来保持悬浮,例如使用静态混合器,或者使小滴悬浮在运动方向与小滴由于其密度而倾向运动的方向相反的液流中。聚合反应在悬浮的单体小滴中进行,通过使小滴中的温度至少与将促使单体聚合发生的聚合引发剂的分解温度一样高来引发该反应。用于聚合的合理的较低温度约为40℃;本领域技术人员将认识到如果选择具有较高分解温度的引发剂,将依据实际使用的引发剂的分解温度来选择最低温度。聚合反应的上限温度是悬浮介质的沸腾温度;文中使用的介质是水性的,因此在大气压下最高温度为100℃,在更高的压力下可以使用更高的温度。出于防止一种或多种单体或分散剂分解或其它对本领域技术人员显而易见的原因,较低的温度是有利的。
本发明的方法可用于制备凝胶和大孔树脂。为了制备大孔树脂,常常使用成孔剂(porogen)。成孔剂是单体可溶于其中但所得聚合物不溶于其中的物质,成孔剂将溶解悬浮小滴中的单体,而不会与聚合混合物中的其它组分反应。因此,对于本方法,在悬浮小滴中必需保持足够的成孔剂以至少部分地溶解单体混合物,在聚合物形成时在颗粒内产生孔隙。可用的成孔剂的例子包括例如C7-C10烃、C3-C10卤代烃、C4-C10酮、C3-C10醇和它们的组合。特别优选的成孔剂包括甲基异丁基酮(MIBK)、二异丁基酮(DIBK)、甲基异丁基甲醇(MIBC)、1,2-二氯丙烷、甲苯(tol)、二甲苯、异辛烷、氯苯和乙酸正丁酯。当本发明的树脂珠是大孔性时,它们的最终平均粒度为30-1000微米,优选300-800微米,更优选为400-700微米。
提供了以下实施方式来说明本发明的代表性实施方式。除非另有说明,文中给出的所有比值和百分数是基于重量,实施例中使用的所有试剂具有良好的商品质量。
实施例:
实施例1-6使用以下进料但改变单体比例:
在2升实验室反应器中,在200rpm的搅拌条件下加入390克去离子水、138克NaCl、2.6克羧甲基纤维素钠。在单体制备罐中,对于不同制剂根据表1加入5.8克二(4-叔丁基-环己基)过氧二碳酸酯和冰甲基丙烯酸(GMAA)、PEM和二乙烯基苯(DVB)。聚合反应器中停止搅拌,向该反应器中加入单体混合物。然后,在运行的过程中在150rpm的转速条件下搅拌反应器。温度设计为在室温保持30分钟,加热到58℃并保持6小时,然后加热到97℃并保持4小时。然后将反应冷却至室温。用过量的水洗涤批料,通过20-50目的筛子湿过筛,用布氏漏斗抽滤干燥和包装。得到390毫升最终产物。
表1.单体进料和性质
(*)加入的PEM与GMAA的百分比
Claims (11)
1.一种聚合物珠组合物,其包含:
i)至少20-99.9重量%的含磷的酸单体,其中所述单体含有至少一个烯键式不饱和,并且所述单体选自二氢磷酸酯/盐单体;和
ii)所述聚合物珠组合物的平均粒度为30-1000微米。
2.如权利要求1所述的聚合物珠组合物,其特征在于,所述含磷的酸单体是
其中R是包含丙烯酰氧基、甲基丙烯酰氧基、芳基或乙烯基的有机基团;R’是H。
3.如权利要求2所述的聚合物珠组合物,其特征在于,R是丙烯酸基、甲基丙烯酸基或苯乙烯基。
4.如权利要求2所述的聚合物珠组合物,其特征在于,R是丙烯酸基或甲基丙烯酸基。
5.如权利要求1所述的聚合物珠组合物,其特征在于,所述含磷的酸单体是质子化形式。
6.如权利要求1所述的聚合物珠组合物,其特征在于,所述聚合物珠通过以下步骤制备:
i)形成悬浮液,
其中所述悬浮液包含至少一种含磷的酸单体、水性介质、自由基引发剂和悬浮剂;
ii)使所述单体聚合,直到它们形成非水溶性聚合物珠。
7.如权利要求6所述的聚合物珠组合物,其特征在于,所述悬浮液还包含0-30重量%的交联单体。
8.如权利要求4所述的聚合物珠组合物,其特征在于,所述含磷的酸单体是质子化形式。
9.如权利要求1所述的聚合物珠组合物,其特征在于,所述含磷的酸单体是(甲基)丙烯酸羟烷基酯的二氢磷酸酯。
10.如权利要求1所述的聚合物珠组合物,其特征在于,所述含磷的酸单体是(甲基)丙烯酸羟乙酯的磷酸酯。
11.一种制备如权利要求1所述的聚合物珠组合物的方法,所述方法包括以下步骤:
i)形成悬浮液,
其中所述悬浮液包含至少一种含磷的酸单体、水性介质、自由基引发剂和悬浮剂;
ii)使所述单体聚合,直到它们形成非水溶性聚合物珠。
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