CN113302212A - 制备超吸收性颗粒的方法 - Google Patents
制备超吸收性颗粒的方法 Download PDFInfo
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- CN113302212A CN113302212A CN202080008387.9A CN202080008387A CN113302212A CN 113302212 A CN113302212 A CN 113302212A CN 202080008387 A CN202080008387 A CN 202080008387A CN 113302212 A CN113302212 A CN 113302212A
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- 229920000247 superabsorbent polymer Polymers 0.000 description 1
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Abstract
本发明涉及一种制备超吸收性颗粒的方法,所述方法包括以下步骤:聚合单体制剂、干燥所获得的水性聚合物凝胶、研磨、分级和热表面后交联,所述单体制剂通过混合单体水溶液和经发泡的表面活性剂水溶液来获得。
Description
本发明涉及一种制备超吸收性颗粒的方法,包括聚合单体制剂、干燥所得水性聚合物凝胶、研磨、分级和热表面后交联,其中所述单体制剂通过混合单体水溶液和经发泡的表面活性剂水溶液来制备。
超吸收剂用于制备尿布、卫生棉条、卫生巾和其他卫生用品,而且也在市场园艺农业中用作保水剂。超吸收剂也称为吸水性聚合物。
超吸收剂的制备记载于专著“Modern Superabsorbent Polymer Technology”,F.L.Buchholz和A.T.Graham,Wiley-VCH,1998,第71页至103页中。
为了改善性能特性,例如渗透性(SFC)和在49.2g/cm2压力下的吸收(AUHL),超吸收性颗粒通常经表面后交联。这增加了颗粒表面的交联水平,这可至少部分地减弱在49.2g/cm2压力下的吸收(AUHL)和离心保留容量(CRC)。这种表面后交联可在水凝胶相中进行。然而,优选地,经干燥、研磨和筛分的聚合物颗粒(基础聚合物)利用表面后交联剂经表面涂覆并经热表面后交联。适用于该目的的交联剂是可与聚合物颗粒的至少两个羧酸酯基团形成共价键的化合物。
EP 2 518 092 A1记载了通过在聚合之前使单体溶液发泡来制备多孔超吸收性颗粒。
本发明的一个目的是提供一种用于制备超吸收性颗粒、尤其是具有较高液体吸收的超吸收性颗粒的改进的方法。
该目的通过一种用于制备超吸收性颗粒的方法实现,所述方法包括聚合单体制剂、干燥所得水性聚合物凝胶、研磨、分级和热表面后交联,所述方法包括通过混合单体水溶液和经发泡的表面活性剂水溶液来制备所述单体制剂,所述单体水溶液包含
a)至少一种带有酸基团且至少部分被中和的烯键式不饱和单体,
b)至少一种交联剂,和
c)至少一种引发剂。
在本发明的一个优选实施方案中,所述单体制剂的聚合在捏合反应器中进行。将所述单体水溶液和经发泡的表面活性剂水溶液在该捏合反应器中混合。该捏合反应器可以连续或分批操作。优选连续捏合反应器。
特别合适的引发剂c)是氧化还原引发剂。氧化还原引发剂由氧化组分(例如过氧二硫酸钠和/或过氧化氢)和还原组分(例如抗坏血酸)组成。优选直至捏合反应器才加入还原组分。
单体水溶液包含优选30重量%至60重量%、更优选35重量%至65重量%且最优选40重量%至50重量%的单体a)。优选所述单体a)已中和至40mol%至90mol%、更优选50mol%至85mol%、最优选60mol%至80mol%的程度。优选的单体a)是部分中和的丙烯酸。
经发泡的表面活性剂水溶液包含优选0.1重量%至10重量%、更优选0.5重量%至重量5%且最优选1重量%至3重量%的至少一种表面活性剂。优选的表面活性剂是非离子表面活性剂,例如乙氧基化的C14-C20醇。
首先使所述表面活性剂溶液发泡,然后才将已经发泡的表面活性剂溶液与所述单体溶液混合。
在单体制剂中经发泡的表面活性剂水溶液与单体水溶液的重量比是优选0.01至0.30、更优选0.02至0.20、最优选0.03至0.10。
本发明基于以下发现:方法步骤的顺序对所获得的超吸收性颗粒的特性具有决定性的影响。本发明方法步骤的顺序,即已经发泡的表面活性剂溶液与单体溶液的混合,导致聚合中更高的最高温度。基础聚合物的离心保留容量(CRC)和可萃取物增加。在热表面后交联后,通过本发明的方法制备的超吸收性颗粒具有明显改善的在0.3psi(2.07kPa)压力下的体积液体吸收(VAUL),略有改善的在49.2g/cm2压力下吸收(AUHL),以及相当的离心保留容量(CRC)。
经发泡的表面活性剂水溶液可另外包含,优选0.5重量%至20重量%、更优选2重量%至15重量%且最优选5重量%至10重量%的水溶性聚合物。优选的水溶性聚合物是聚乙二醇。
下面详细说明超吸收性颗粒的制备:
超吸收性颗粒通过聚合单体溶液来制备并且通常是水不溶性的。
单体a)优选是水溶性的,即其在23℃下在水中的溶解度通常是至少1g/100g水、优选至少5g/100g水、更优选至少25g/100g水且最优选至少35g/100g水。
合适的单体a)是例如烯键式不饱和羧酸,例如丙烯酸、甲基丙烯酸和衣康酸。特别优选的单体是丙烯酸和甲基丙烯酸。非常特别优选丙烯酸。
单体a)通常包含阻聚剂作为储存稳定剂,优选氢醌单醚。
合适的交联剂b)是具有至少两个适合交联的基团的化合物。这样的基团是例如可自由基聚合到聚合物链中的烯键式不饱和基团,以及可与单体a)的酸基团形成共价键的官能团。另外,可与单体a)的至少两个酸基团形成配位键的多价金属盐也适合作为交联剂b)。
交联剂b)优选为具有至少两个可自由基聚合至聚合物网络的可聚合基团的化合物。合适的交联剂b)为例如乙二醇二甲基丙烯酸酯、二乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、甲基丙烯酸烯丙酯、三羟甲基丙烷三丙烯酸酯、三烯丙基胺、四烯丙基氯化铵、四烯丙氧基乙烷,如EP 0 530 438 A1中所记载的;二丙烯酸酯和三丙烯酸酯,如EP 0 547 847A1、EP 0 559 476 A1、EP 0 632 068 A1、WO 93/21237 A1、WO 2003/104299 A1、WO 2003/104300 A1、WO 2003/104301 A1和DE 103 31 450 A1中所记载的;混合的丙烯酸酯,其除了丙烯酸酯基团外,还包含其他烯键式不饱和基团,如DE 103 31 456 A1和DE 103 55 401A1中所记载的;或交联剂混合物,如例如DE 195 43 368 A1、DE 196 46 484 A1、WO 90/15830A1和WO 2002/032962 A2中所记载的。
交联剂b)的量是优选0.05重量%至1.5重量%、更优选0.1重量%至1重量%且最优选0.3重量%至0.6重量%,在每种情况下基于所用单体a)的总量计。随着交联剂含量增加,离心保留容量(CRC)降低,并且在21.0g/cm2压力下的吸收(AUL)经过最大值。
所用的引发剂c)可是在聚合条件下产生自由基的所有化合物,例如热引发剂、氧化还原引发剂或光引发剂。合适的氧化还原引发剂为过氧二硫酸钠/抗坏血酸、过氧化氢/抗坏血酸、过氧二硫酸钠/亚硫酸氢钠以及过氧化氢/亚硫酸氢钠。优选使用热引发剂和氧化还原引发剂的混合物,例如过氧二硫酸钠/过氧化氢/抗坏血酸。所用的还原组分优选是2-羟基-2-磺基乙酸的二钠盐或者2-羟基-2-亚磺基乙酸的钠盐、2-羟基-2-磺基乙酸的二钠盐和亚硫酸氢钠的混合物。这样的混合物可作为FF6和FF7(Brüggemann Chemicals;Heilbronn;Germany)获得。
通常,使用单体水溶液。单体溶液的水含量是优选40重量%至70重量%、更优选45重量%至65重量%且最优选50重量%至60重量%。还可使用单体悬浮液,即具有超过溶解度的单体a)(例如丙烯酸钠)的单体溶液。随着水含量升高,随后干燥中的能量消耗升高,而随着水含量下降,聚合热只能被不充分地移除。
为了最佳作用,优选的阻聚剂需要溶解的氧。因此,单体溶液可在聚合之前通过惰性化,即,使惰性气体、优选氮气或二氧化碳流过,而除去溶解的氧。单体溶液的氧含量在聚合之前降低至优选小于1重量ppm、更优选小于0.5重量ppm、最优选小于0.1重量ppm。
经发泡的表面活性剂溶液包含至少一种表面活性剂。至少一种表面活性剂可是阴离子、阳离子和/或非离子表面活性剂。优选非离子表面活性剂,尤其是HLB值为10至25的非离子表面活性剂。HLB值是主要非离子表面活性剂的水或油溶解度的量度并且可以通过常规方法测定。
表面活性剂由至少一个非极性基团和至少一个极性基团组成。优选的表面活性剂具有大的非极性和/或极性基团。大的基团是具有至少130g/mol、优选至少250g/mol、更优选至少500g/mol的摩尔质量的基团。
合适的表面活性剂是例如脱水山梨糖醇酯(如脱水山梨糖醇单硬脂酸酯、脱水山梨糖醇单油酸酯、脱水山梨糖醇单棕榈酸酯和脱水山梨糖醇单月桂酸酯)及甘油酯,其中酸组分衍生自C14-C20羧酸。
优选的表面活性剂是烷氧基化的、优选乙氧基化的醇,其中醇可以任选地是支化的和/或不饱和的;以及烷氧基化的、优选乙氧基化的脱水山梨糖醇单酯,例如脱水山梨糖醇单硬脂酸酯和脱水山梨糖醇单油酸酯。非常特别优选的表面活性剂是乙氧基化的C14-C20醇。
至少一种表面活性剂优选具有大于20mPas、更优选大于25mPas、最优选大于30mPas的粘度(在23℃下根据EN12092测量)。
经发泡的表面活性剂溶液可另外包含水溶性聚合物。所用的水溶性聚合物可是聚乙烯醇、聚乙烯吡咯烷酮、淀粉、淀粉衍生物、经改性的纤维素(例如甲基纤维素或羟乙基纤维素)、明胶、聚乙二醇或聚丙烯酸,优选聚二醇例如聚乙二醇。
表面活性剂溶液是经发泡的。所有已知的发泡方法均适用于此目的。表面活性剂溶液可例如与惰性气体(如氮气或二氧化碳)剧烈混合。
经发泡的表面活性剂溶液随后与单体溶液混合并聚合。由于已经预先产生泡沫,因此不再需要剧烈混合,例如快速搅拌。
用于聚合的合适反应器是例如捏合反应器或带式反应器。在捏合反应器中,将在水性单体制剂的聚合中形成的聚合物凝胶通过例如反向旋转搅拌器轴连续地粉碎,如WO2001/038402 A1中所记载的。在带上的聚合记载于例如DE 38 25 366 A1和US 6,241,928中。在带式反应器中的聚合形成了聚合物凝胶,其必须在例如挤出机或捏合反应器中粉碎。
为改善干燥特性,可另外地将通过捏合反应器获得的粉碎的聚合物凝胶挤出。
所得聚合物凝胶的酸基团通常已被部分中和。中和优选在单体阶段进行。这通常通过在呈水溶液或优选呈固体的中和剂中混合来完成。中和度是优选40mol%至90mol%、更优选50mol%至85mol%且最优选60mol%至80mol%,为此可使用常规中和剂,优选碱金属氢氧化物、碱金属氧化物、碱金属碳酸盐或碱金属碳酸氢盐以及其混合物。还可使用铵盐来替代碱金属盐。特别优选的碱金属是钠和钾,但非常特别优选氢氧化钠、碳酸钠或碳酸氢钠以及其混合物。本文中,固体碳酸盐和碳酸氢盐也可以以包封的形式引入,优选在聚合之前直接引入单体溶液中,在聚合过程中或聚合之后并且在其干燥之前引入聚合物凝胶中。包封是通过用不溶的或仅逐渐可溶解的材料(例如通过成膜聚合物、惰性无机材料或易熔有机材料)涂覆表面来实施,这会使固体碳酸盐或碳酸氢盐的溶解和反应延迟至直到干燥期间才释放出二氧化碳,并且所形成的超吸收剂具有高的内部孔隙率。
然后通常用空气循环带式干燥机干燥聚合物凝胶,直到残余水分含量是优选0.5重量%至10重量%、更优选1重量%至7重量%且最优选2重量%至5重量%,残余水分含量通过EDANA推荐的测试方法第WSP230.2-05“加热时的质量损失(MassUponFleating)”来测定。在残余水分含量过高的情况下,经干燥的聚合物凝胶具有过低的玻璃化转变温度Tg并且难以进一步处理。在残余水分含量过低的情况下,经干燥的聚合物凝胶太脆,并且在随后的粉碎步骤中,获得不希望的大量具有过低粒径的聚合物颗粒(“细粒”)。聚合物凝胶在干燥前的固含量是优选25重量%至90重量%、更优选35重量%至70重量%、最优选40重量%至60重量%。随后,将经干燥的聚合物凝胶压碎并任选地粗粉碎。
随后,通常将经干燥的聚合物凝胶研磨并分级,且用于研磨的装置通常可以是单级或多级的辊式研磨机(优选二级或三级的辊式研磨机)、销棒式研磨机、锤式研磨机或振动式研磨机。
作为产物级分移除的聚合物颗粒的平均粒径为优选150μm至200μm、更优选250μm至600μm、非常特别地300μm至500μm。产物级分的平均粒径可通过EDANA推荐的测试方法第WSP 220.2(05)“粒径分布(Partikel Size Distribution)”来测定,其中筛分级分的质量比以累积形式作图,并且平均粒径以图表方式测定。本文中的平均粒径是产生累积50重量%的筛孔尺寸的值。
为进一步改善特性,聚合物颗粒经热表面后交联。合适的表面后交联剂是包含可与聚合物颗粒的至少两个羧酸酯基团形成共价键的基团的化合物。合适的化合物是例如多官能胺、多官能酰胺基胺、多官能环氧化物,如EP 0 083 022 A2、EP 0 543 303 A1和EP 0937 736 A2中所记载的;二官能醇或多官能醇,如DE 33 14 019 A1、DE 35 23 617 A1和EP0 450 922 A2中所记载的;或β-羟基烷基酰胺,如DE 102 04 938 A1和US 6,239,230中所记载的。
表面后交联剂的量是优选0.001重量%至2重量%、更优选0.02重量%至1重量%且最优选0.05重量%至0.2重量%,在每种情况下均基于聚合物颗粒计。
在本发明的一个优选的实施方案中,除表面后交联剂以外,还将多价阳离子施用于颗粒表面。
可用于本发明的方法中的多价阳离子是,例如,二价阳离子,例如锌、镁、钙和锶的阳离子;三价阳离子,例如铝、铁、铬、稀土和锰的阳离子;四价阳离子,例如钛和锆的阳离子。可能的抗衡离子是氯离子、溴离子、氢氧根、硫酸根、硫酸氢根、碳酸根、碳酸氢根、硝酸根、磷酸根、磷酸氢根、磷酸二氢根和羧酸根,例如乙酸根和乳酸根。优选氢氧化铝、硫酸铝和乳酸铝。
所用的多价阳离子的量是例如0.001重量%至1.5重量%、优选0.005重量%至1重量%且更优选0.02重量%至0.8重量%,在每种情况下均基于聚合物计。
通常以这样的方式进行表面后交联:将表面后交联剂的溶液喷雾到经干燥的聚合物颗粒上。在喷雾施用之后,使涂覆有表面后交联剂的聚合物颗粒进行表面后交联和干燥,并且表面后交联反应可在干燥之前和干燥期间进行。
表面后交联剂的溶液的喷雾施用优选在具有移动的混合工具的混合器(例如螺杆混合器、盘式混合器和桨式混合器)中进行。特别优选卧式混合器例如桨式混合器,非常特别优选立式混合器。卧式混合器与立式混合器之间的区别在于混合轴的位置,即,卧式混合器具有水平安装的混合轴,而立式混合器具有竖直安装的混合轴。合适的混合器是例如卧式犁铧混合器(Gebr.Maschinenbau GmbH;Paderborn;Germany)、Vrieco-Nauta连续混合器(Hosokawa Micron BV;Doetinchem;the Netherlands)、Processall Mixmill混合器(Processall Incorporated;Cincinnati;USA)和Schugi(Hosokawa Micron BV;Doetinchem;the Netherlands)。然而,还可在流化床中喷雾表面后交联剂溶液。
表面后交联剂通常以水溶液的形式使用。可通过非水性溶剂的含量和溶剂的总量来调节表面后交联剂在聚合物颗粒中的渗透深度。
表面后交联优选在接触式干燥器、更优选铲式干燥器、最优选盘式干燥器中进行。合适的干燥器是例如Hosokawa卧式桨式干燥器(Hosokawa Micron GmbH;Leingarten;Germany)、Hosokawa盘式干燥器(Hosokawa Micron GmbH;Leingarten;Germany)、干燥器(Metso Minerals Industries Inc.;Danville;USA)和Nara桨式干燥器(NARA Machinery Europe;Frechen;Germany)。此外,还可使用流化床干燥器。
表面后交联可在混合器本身中通过加热夹套或吹入暖空气来进行。同样合适的是下游干燥器,例如箱式干燥器、旋转管式炉或可加热的螺杆。特别有利的是在流化床干燥器中进行混合和热表面后交联。
优选的反应温度的范围是100℃至250℃、优选110℃至220℃、更优选120℃至210℃且最优选130℃至200℃。在该温度下的优选停留时间是优选至少10分钟、更优选至少20分钟、最优选至少30分钟且通常至多60分钟。
随后,可将表面后交联的聚合物颗粒再次分级,将过小和/或过大的聚合物颗粒移除并再循环到该方法中。
为进一步改善特性,可将表面后交联的聚合物颗粒涂覆或再润湿。
优选在30℃至80℃、更优选35℃至70℃、最优选40℃至60℃下进行再润湿。在过低的温度下,聚合物颗粒易于形成团块,而在较高的温度下,水已经显著蒸发。用于再润湿的水的量是优选1重量%至10重量%、更优选2重量%至8重量%且最优选3重量%至5重量%。再润湿增加了聚合物颗粒的机械稳定性,并降低了它们带静电的倾向。再润湿有利地在热表面后交联之后在冷却器中进行。
适用于改善自由溶胀率和凝胶床渗透性(GBP)的涂料是,例如无机惰性物质(例如水不溶性金属盐)、有机聚合物、阳离子聚合物和二价或多价金属阳离子。适用于灰尘粘结的涂料是例如多元醇。适用于抵消聚合物颗粒的不期望的结块倾向的涂料是例如气相二氧化硅(例如200)、沉淀二氧化硅(例如D17)和表面活性剂(例如20)。
本发明进一步提供通过本发明的方法制备的超吸收性颗粒。
本发明进一步提供包含通过本发明的方法制备的超吸收性颗粒的卫生制品。
方法:
下文中描述并指定为“WSP”的标准测试方法记载于:“Standard Test Methodsfor the Nonwovens Industry”,2005版,由Worldwide Strategie Partners EDANA(Herrmann-Debrouxlaan 46,1160Oudergem,Belgium,www.edana.org)和INDA(1100Crescent Green,Suite 115,Cary,North Carolina 27518,USA,www.inda.org)联合出版。该出版物由EDANA和INDA均可获得。
除非另有指明,所有测量均应在23±2℃的室温和50±10%的相对空气湿度下进行。吸水性聚合物颗粒在测量前充分混合。
水分含量
离心保留容量
离心保留容量(CRC)通过EDANA推荐的测试方法第WSP 241.2(05)好“离心后,在盐水中的流体保留容量(Fluid Retention Capacity in Saline,After Centrifugation)”来测定。
在21.0g/cm2压力下的吸收(负载下的吸收)
在21.0g/cm2压力下的吸收(AUL)通过EDANA推荐的测试方法第WSP 242.2(05)号“在压力下吸收,重力测定(Absorption Under Pressure,Gravimetrie Determination)”来测定。
在49.2g/cm2压力下的吸收(高负载下的吸收)
在49.2g/cm2压力下的吸收(AUHL)类似于EDANA推荐的测试方法第WSP 242.2(05)号“在压力下吸收,重力测定”,除了设定49.2g/cm2(0.7psi)的压力而非21.0g/cm2(0.3psi)的压力。
可萃取物
超吸收性颗粒中的可萃取物的含量通过EDANA推荐的测试方法第WSP 270.2(05)号“可萃取物(Extractable)”来测定。
水性萃取物的表面张力
为了测定水性萃取物的表面张力(ST),将0.50g超吸收性颗粒称重于小烧杯中,并与40ml 0.9重量%的盐溶液混合。将烧杯中的内容物用磁力搅拌棒在500rpm下搅拌3分钟,然后静置2分钟。最后,使用K10-ST数字张力计(Krüss GmbH;Hamburg,Germany)或具有铂板的类似仪器测量上清液水相的表面张力。测量在23℃的温度下进行。
自由溶胀率
为了测定自由溶胀率(FSR),将1.00g(=W1)超吸收性颗粒称重于25ml烧杯中并均匀分布在其底部上。然后通过分配器将20ml 0.9重量%氯化钠溶液计量加入第二个烧杯中,并将该烧杯中的内容物快速加入到第一个烧杯中,并启动秒表。一旦最后一滴盐溶液被吸收(通过液体表面上反射的消失来识别),就停止秒表。从第二个烧杯中倒出并被第一个烧杯中的聚合物吸收的液体的准确量通过重新称重第二个烧杯(=W2)来准确测定。用秒表测量的吸收所需的时间间隔指定为t。表面上最后一滴液滴的消失确定为时间t。
自由溶胀率(FSR)按如下计算:
FSR[g/gs]=W2/(W1 x t)
然而,如果超吸收性颗粒的水分含量大于3%(重量),则重量W1应考虑该水分含量进行修正。
渗透性(盐水导流性)
溶胀凝胶层在0.3psi(2070Pa)压力下的渗透性(SFC)是如EP 2 535698A1所记载的用重量为1.5g的超吸收性颗粒来测定作为溶胀凝胶层的尿液渗透性测量值(UPM)。流量是自动检测的。
渗透性(SFC)按如下计算
SFC[cm3s/g]=(Fg(t=0)×L0)/(d×A×WP)
其中Fg(t=0)是NaCl溶液的流量(以g/s计),其是使用流量测定的Fg(t)数据的线性回归分析通过外推至t=0来获得,L0是凝胶层的厚度(以cm计),d是NaCl溶液的密度(以g/cm3计),A是凝胶层的面积(以cm2计),且WP是凝胶层上的静水压力(以达因(dyn)/cm2计)。
在0.3psi(2.07kPa)压力下液体的体积吸收(VAUL)
对于在0.3psi(2.07kPa)压力下液体的体积吸收(VAUL),τ值通过WO 2014/079694A1第39和40页中记载的测试方法“负载下的体积吸收(VAUL)(Volumetrie AbsorbencyUnder Load(VAUL))”来测定。τ值在本文中记载为“特征溶胀时间(characteristicswelling time)”。
实施例
基础聚合物的制备
实施例1
通过用氮气吹扫使LUK 8.0K2型双轴捏合反应器(Coperion Werner&PfleidererGmbH&Co.KG,Stuttgart,Germany)惰性化。捏合反应器轴分别在96rpm和48rpm下操作。捏合反应器的壳可通过传热剂加热。
将4901g 37.3重量%的丙烯酸钠水溶液和571.9g丙烯酸混合,通过用氮气吹扫除去氧并引入捏合反应器中。随后,将7.9g三重乙氧基化甘油三丙烯酸酯(约85%浓度以重量计)和100g丙烯酸的混合物、11.89g过氧二硫酸钠水溶液(约15%浓度以重量计)和132g过氧化氢水溶液(约3%浓度以重量计)连续计量加入捏合反应器中。
将250g水、29.6g水性聚乙二醇4000(约50%浓度以重量计)和9.9g80-重乙氧基化C16/C18脂肪醇(AT80)的表面活性剂溶液在静态混合器中用氮气发泡。聚乙二醇-4000是平均摩尔质量为约4000g/mol的聚乙二醇。然后将所得稳定泡沫计量加入捏合反应器中。随后用约200g水清洗导管。
随后,将19.7g抗坏血酸水溶液(约0.5%浓度以重量计)计量加入捏合反应器中,并通过传热剂(80℃)加热捏合反应器的壳。将捏合反应器中的温度从22℃升至102℃。一旦温度升高结束,就关闭加热,将获得的聚合物凝胶再捏合13分钟,冷却至63℃并从捏合反应器中排出。
将所得聚合物凝胶以约1080g的分量均匀分布在金属丝网托盘上,并在空气循环干燥箱中在175℃下干燥90分钟。将所得经干燥的聚合物凝胶用LRC250型辊磨机(Bauermeister Zerkleinerungstechnik GmbH,Norderstedt,Germany)三级(1000μm、60μm和400μm)研磨,并筛选出150μm至710μm的粒径。
分析所获得的超吸收性颗粒。结果整理在表1中。
实施例2
分析所获得的超吸收性颗粒。结果整理在表1中。
实施例3(比较实施例)
程序与实施例1相同,除了没有发泡。
分析所获得的超吸收性颗粒。结果整理在表1中。
实施例4(比较实施例)
程序与实施例1相同,除了使用250g水和29.6g水性聚乙二醇-4000(约50%浓度以重量计)的溶液而非所述的表面活性剂溶液,并且没有进行发泡。
分析所获得的超吸收性颗粒。结果整理在表1中。
实施例5(比较实施例)
分析所获得的超吸收性颗粒。结果整理在表1中。
实施例6(比较实施例)
程序与实施例1相同,除了将表面活性剂溶液计量加入捏合反应器中的单体溶液中,并且仅将捏合反应器中的单体溶液和表面活性剂溶液的混合物用氮气(1巴,1166ml/min)使用SIK-R 15AX型(GKN Sinter Metal Filters GmbH,Radevormwald,Germany)的圆柱形烧结过滤器元件发泡两分钟。
分析所获得的超吸收性颗粒。结果整理在表1中。
表1:基础聚合物的特性
*)比较实施例
表面后交联
实施例7
将1200g来自实施例1的基础聚合物在具有加热夹套的Pflugschar M5犁铧混合器(Gebr.Maschinenbau GmbH;Paderborn,Germany)中,在23℃和200转/分钟的轴速度下通过两相喷嘴用54.4g混合物涂覆,该混合物含有1.5重量%N-羟乙基-2-恶唑烷酮、1.5重量%丙烷-1,3-二醇、26.7重量%异丙醇、11.0重量%乳酸铝和59.3重量%水。
在喷雾施用后,将轴速度降低至50转/分钟,并将产物温度升高至185℃。随后,将反应混合物在该温度和该轴速度下保持40分钟。将所得产物冷却至环境温度并用710μm筛子再次分级。
分析所获得的超吸收性颗粒。结果整理在表2中。
实施例8
程序与实施例7相同,除了使用来自实施例2的基础聚合物。
分析所获得的超吸收性颗粒。结果整理在表2中。
实施例9(比较实施例)
程序与实施例7相同,除了使用来自实施例3的基础聚合物。
分析所获得的超吸收性颗粒。结果整理在表2中。
实施例10(比较实施例)
程序与实施例7相同,除了使用来自实施例4的基础聚合物。
分析所获得的超吸收性颗粒。结果整理在表2中。
实施例11(比较实施例)
程序与实施例7相同,除了使用来自实施例5的基础聚合物。
分析所获得的超吸收性颗粒。结果整理在表2中。
实施例12(比较实施例)
程序与实施例7相同,除了使用来自实施例6的基础聚合物。
分析所获得的超吸收性颗粒。结果整理在表2中。
表2:表面后交联后的特性
*)比较实施例
实施例7和12的比较表明,表面活性剂溶液在不存在单体溶液情况下的发泡(实施例7)与存在单体溶液的情况下的发泡(实施例12)导致明显不同的特性分布。
Claims (15)
1.一种制备超吸收性颗粒的方法,包括聚合单体制剂、干燥所得水性聚合物凝胶、研磨、分级和热表面后交联,所述方法包括通过混合单体水溶液和经发泡的表面活性剂水溶液来制备所述单体制剂,所述单体水溶液包含
a)至少一种烯键式不饱和单体,其带有酸基团且至少部分被中和,
b)至少一种交联剂,和
c)至少一种引发剂。
2.根据权利要求1所述的方法,其中所述单体制剂的聚合是在捏合反应器中进行并且将所述单体水溶液和经发泡的表面活性剂水溶液在捏合反应器中混合。
3.根据权利要求1或2所述的方法,其中所述聚合在连续捏合反应器中进行。
4.根据权利要求1至3中任一项所述的方法,其中所述单体水溶液包含40重量%至50重量%的单体a)。
5.根据权利要求1至4中任一项所述的方法,其中单体a)已中和至60mol%至80mol%的程度。
6.根据权利要求1至5中任一项所述的方法,其中单体a)是部分中和的丙烯酸。
7.根据权利要求1至6中任一项所述的方法,其中所述经发泡的表面活性剂水溶液包含1重量%至3重量%的至少一种表面活性剂。
8.根据权利要求1至7中任一项所述的方法,其中所述经发泡的表面活性剂水溶液包含至少一种非离子表面活性剂。
9.根据权利要求1至8中任一项所述的方法,其中在所述单体制剂中经发泡的表面活性剂水溶液与单体水溶液的重量比为0.03至0.10。
10.根据权利要求1至9中任一项所述的方法,其中所述经发泡的表面活性剂水溶液另外包含水溶性聚合物。
11.根据权利要求10所述的方法,其中所述经发泡的表面活性剂水溶液包含5重量%至10重量%的所述另外的水溶性聚合物。
12.根据权利要求10或11所述的方法,其中所述另外的水溶性聚合物是聚乙二醇。
13.根据权利要求1至12中任一项所述的方法,其中所述至少一种引发剂c)是氧化还原引发剂。
14.超吸收性颗粒,其通过权利要求1至13的方法获得。
15.一种卫生制品,其包含通过权利要求1至13的方法制备的超吸收性颗粒。
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PCT/EP2020/050627 WO2020151970A1 (de) | 2019-01-24 | 2020-01-13 | Verfahren zur herstellung von superabsorberpartikeln |
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EP (1) | EP3914628A1 (zh) |
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