CN112804976A - 制备超吸收剂的方法 - Google Patents
制备超吸收剂的方法 Download PDFInfo
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- CN112804976A CN112804976A CN201980062010.9A CN201980062010A CN112804976A CN 112804976 A CN112804976 A CN 112804976A CN 201980062010 A CN201980062010 A CN 201980062010A CN 112804976 A CN112804976 A CN 112804976A
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Abstract
一种通过使单体溶液或悬浮液聚合来制备超吸收剂颗粒的方法,所述方法包含:将所得的水性聚合物凝胶在循环空气带式干燥机中干燥,研磨、分级以及任选地进行热表面后交联,其中水性聚合物凝胶通过振荡式输送带被引入循环空气带式干燥机中,通过至少一个脱除装置将附着的聚合物凝胶从回转的输送带的底面上清除,并且向回转的输送带的底面上喷洒水。
Description
本发明涉及一种通过使单体溶液或悬浮液聚合来制备超吸收剂颗粒的方法,该方法包括:将所得的水性聚合物凝胶在循环空气带式干燥机中干燥,研磨、分级以及任选地进行热表面后交联,其中水性聚合物凝胶通过振荡式输送带被引入循环空气带式干燥机中,回转的输送带的底面通过至少一个脱除装置(stripper device)将附着的聚合物凝胶除去,并且在回转的输送带的底面上喷洒水。
超吸收剂不仅可用于制备尿布、卫生棉条、卫生巾和其他卫生制品,而且还可在商品果蔬种植业用作保水剂。超吸收剂也称为吸水聚合物。
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至103页中。
超吸收剂的性质可通过例如交联剂的用量来调节。随着交联剂量的增加,离心保留容量(CRC)下降,并且在21.0g/cm2(AUL0.3psi)的压力下的吸收量经过一个最大值。
为了改善性能特性——例如凝胶床渗透性(GBP)和在49.2g/cm2(AUL0.7psi)压力下的吸收量——通常将超吸收剂颗粒进行表面后交联。这增加了颗粒表面的交联水平,其可以至少部分地消除49.2g/cm2(AUL0.7psi)压力下的吸收量和离心保留容量(CRC)间的关联。该表面后交联可在水性凝胶相中进行。然而,优选地,已经被干燥、研磨并过筛的聚合物颗粒(基础聚合物)用表面后交联剂进行表面涂覆且进行热表面后交联。适用于该目的的交联剂为可与聚合物颗粒的至少两个羧基形成共价键的化合物。
WO 2008/087114 A1、WO 2010/139680 A2和EP 2 700 667 A1描述了空气循环带式干燥器的传输带借助振荡式输送带装载聚合物水凝胶。
本发明的目的是提供一种改进的制备超吸收剂的方法,特别是简化对所使用的振荡式输送带的清洁和降低输送带本身的机械应力。
该目的通过一种通过使单体溶液或悬浮液聚合来制备超吸收剂的方法来实现,该单体溶液或悬浮液包含:
a)至少一种带有酸基团并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,
c)至少一种引发剂,
d)任选地,一种或多种可与a)中所述的单体共聚的烯键式不饱和单体,和
e)任选地,一种或多种水溶性聚合物,
该方法包含将所得的水性聚合物凝胶在空气循环带式干燥器中干燥,研磨、分级以及任选地进行热表面后交联,其中水性聚合物凝胶通过振荡式输送带被引入空气循环带式干燥器中,借助于至少一个脱除装置将回转的输送带的底面上附着的聚合物凝胶除去,并且在回转的输送带的底面上喷洒水。
回转的输送带的底面为输送带的外侧,其在偏转之后,再次配送(dose)聚合物凝胶。回转的输送带的顶面为输送带的内侧,其不应与聚合物凝胶接触。
脱除装置与振荡式输送带的卸料端的距离优选地小于振荡式输送带长度的20%,更优选地小于振荡式输送带长度的10%,最优选地小于振荡式输送带长度的5%,其中振荡式输送带的长度为转轴(pivot axis)到卸料端的距离。
脱除装置不受任何限制。合适的实例为横向于运行方向布置的刷子。也可使用刮板。刮板是由非柔性材料制成的脱除装置,其横向于输送方向布置。合适的非柔性材料的实例为聚四氟乙烯。为避免损坏输送带,刮板与输送带的直接接触(如果有)应最小化。刮板应相对于回转的输送带的运行方向倾斜。这促进附着的聚合物凝胶的剥离,并防止输送带和刮板之间的阻塞(backup)。脱除下来的聚合物凝胶通常落到空气循环带式干燥机的输送带上。
刮板以与输送带的运行方向相反的方式、相对于水平方向优选倾斜5°至45°,更优选地10°至35°,非常特别地15°至25°。刮板与回转的输送带的底面的距离优选为0.1至5mm,更优选为0.2至2mm,最优选为0.5至1.5mm。
喷嘴到振荡式输送带的卸料端的距离优选为振荡式输送带长度的1%至50%,更优选为振动式输送带长度的2%至30%,最优选为振荡式输送带长度的3%到10%,其中振荡式输送带的长度为转轴到卸料端的距离。
喷嘴到输送带的距离优选为5至50cm,更优选10至30cm和最优选15至25cm。
优选通过至少一个两相喷嘴、更优选通过至少两个两相喷嘴喷洒液体。
两相喷嘴能雾化成细小液滴或喷雾。所采用的雾化形式为圆形或椭圆形的实心或空心锥状。两相喷嘴可配置外部混合或内部混合。在外部混合两相喷嘴的情况下,液体和雾化器气体会通过单独的孔口离开喷嘴头。它们只有在离开喷嘴后才在喷射流中混合。这能大范围独立调节液滴尺寸分布和产生量。喷嘴的喷雾锥可通过设置空气帽调节。在内部混合两相喷嘴的情况下,液体和雾化器气体在喷嘴内混合,并且两相混合物通过相同的孔(或通过多个平行的孔)离开喷嘴头。在内部混合两相喷嘴的情况下,数量比率和压力条件比在外部混合喷嘴的情况下更紧密地联系起来。因此,流量的微小变化导致液滴尺寸分布的变化。期望的流量的调节受所选择的喷嘴孔口的横截面的影响。
有用的雾化器气体的实例为0.5bar或更高的压缩空气。可通过喷嘴的几何形状、喷嘴的类型、水的质量流速与雾化器气体的质量流速之比以及气体和水的压力来分别调节液滴尺寸。
用于喷洒的水的量优选为2至20kg/h,更优选为6至16kg/h,最优选为8至12kg/h。
雾化器气体与水的重量比优选为2至20,更优选为6至16,最优选为8至12。
当使用的水太少时,输送带只会被不充分地润湿。当使用的水过多时,过量的水会滴到空气循环带式干燥机的多孔板上并导致其导致阻塞。通过阻止较大的液滴形成,两相喷嘴的使用进一步改善了水的分布。
在本发明的一个优选实施方案中,在输送带的运行方向上,除了脱除装置之外,还有至少一个喷嘴。这防止了水从脱除装置滴落到空气循环带式干燥机的输送带上。
在本发明的另一优选实施方案中,在空气循环带式干燥器的输送带的上游有至少一个喷嘴。这也防止了水滴落到空气循环带式干燥器的输送带上。
输送带的长度优选为2至10m,更优选为2.5至8m,最优选为3至6m,其中输送带的长度为转轴到卸料端的距离。
输送带的宽度优选为0.5至1.5m,更优选为0.6至1.2m,最优选为0.7至0.9m。
可使用常规用于该目的的输送带。输送带的表面(即与聚合物凝胶接触的一侧)应具有防水性,并且在23℃下对水的接触角优选至少为60°,更优选至少为80°,最优选至少100°。接触角是润湿性能的量度并且是根据DIN 53900测定。
输送带上的聚合物凝胶的含水量优选为20至80重量%,更优选30至70重量%,最优选40至60重量%。
输送带上的聚合物凝胶的温度优选为60至105℃,更优选为70至100℃,最优选为80至95℃。
本发明基于以下发现:附着在振荡式输送带上的温热聚合物凝胶非常容易变干。干燥的聚合物凝胶只能非常困难地从输送带上除去。已经干燥的聚合物凝胶通常是进一步结块的原因。用水喷洒可保持聚合物凝胶湿润并防止干燥。
超吸收剂的制备在下文中详细描述:
超吸收剂通过使单体溶液或悬浮液聚合来制备,且该超吸收剂通常不溶于水。
单体a)优选为水溶性的,即在23℃的水中其溶解度通常为至少1g/100g水,优选至少5g/100g水,更优选至少25g/100g水,最优选至少35g/100g水。
合适的单体a)为例如烯键式不饱和羧酸,例如丙烯酸、甲基丙烯酸和衣康酸。特别优选的单体为丙烯酸和甲基丙烯酸。非常特别优选丙烯酸。
其他合适的单体a)为例如烯键式不饱和磺酸,例如苯乙烯磺酸和2-丙烯酰胺-2-甲基丙烷磺酸(AMPS)。
杂质可对聚合产生相当大的影响。因此,所使用的原料应具有最大的纯度。因此,特别纯化单体a)通常为有利的。合适的纯化方法记载于例如WO 02/055469 A1、WO 03/078378 A1和WO 2004/035514 A1中。合适的单体a)为例如根据WO 2004/035514 A1纯化的丙烯酸,其含有99.8460重量%的丙烯酸、0.0950重量%的乙酸、0.0332重量%的水、0.0203重量%的丙酸、0.0001重量%的糠醛、0.0001重量%的马来酸酐、0.0003重量%的二丙烯酸和0.0050重量%的氢醌单甲醚。
丙烯酸和/或其盐在单体a)的总量中的比例优选为至少50摩尔%,更优选至少90摩尔%,最优选至少95摩尔%。
单体a)通常包含阻聚剂(优选氢醌单醚)作为储存稳定剂。
单体溶液包含的氢醌单醚优选最高达250重量ppm,优选至多130重量ppm,更优选至多70重量ppm,并且优选至少10重量ppm,更优选至少30重量ppm,尤其为约50重量ppm,在每种情况下都基于未中和的单体a)计。例如,单体溶液可通过使用带有酸基团的烯键式不饱和单体与适当含量的氢醌单醚来制备。
优选的氢醌单醚为氢醌单甲醚(MEHQ)和/或α-生育酚(维生素E)。
合适的交联剂b)为具有至少两个适合交联的基团的化合物。这样的基团为例如可自由基聚合进入聚合物链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。此外,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进入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,在EP 0 530 438 A1中记载的二甲基丙烯酸乙二醇酯、二丙烯酸二乙二醇酯、聚二丙烯酸乙二醇酯、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;如在EP 0 547 847 A1、EP 0 559 476 A1、EP0 632 068 A1、WO 93/21237 A1、WO 03/104299 A1、WO 03/104300 A1、WO 03/104301 A1和DE 10331450 A1中记载的二丙烯酸酯和三丙烯酸酯;如在DE 103 31 456 A1和DE 103 55401 A1中记载的混合的丙烯酸酯,其除包含丙烯酸酯基团外还包含烯键式不饱和基团;或例如在DE 195 43 368 A1、DE 196 46 484 A1、WO 90/15830 A1和WO 02/032962 A2中记载的交联剂混合物。
优选的交联剂b)为季戊四醇三烯丙基醚、四烯丙氧基乙烷,亚甲基双甲基丙烯酰胺、15-重乙氧基化三羟甲基丙烷三丙烯酸酯、聚乙二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯和三烯丙基胺。
非常特别优选的交联剂b)为已经用丙烯酸或甲基丙烯酸酯化以产生二丙烯酸酯或三丙烯酸酯的聚乙氧基化甘油和/或聚丙氧基化甘油,例如在WO 03/104301 A1中所记载的。3-至10-重乙氧基化甘油的二和/或三丙烯酸酯为特别有利的。非常特别优选1-至5-重乙氧基化甘油和/或丙氧基化甘油的二丙烯酸酯或三丙烯酸酯。最优选的为3-至5-重乙氧基化甘油和/或丙氧基化甘油的三丙烯酸酯,特别是3-重乙氧基化甘油的三丙烯酸酯。
交联剂b)的量优选为0.05重量%至1.5重量%,更优选0.1重量%至0.8重量%,最优选0.15重量%至0.5重量%,各种情况下均基于所用单体a)的总量计算。随着交联剂含量的增加,离心保留容量(CRC)下降,并且在21.0g/cm2的压力下吸收经过一个最大值。
所使用的引发剂c)可为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/亚硫酸氢钠和过氧化氢/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为2-羟基-2-磺酸基乙酸的二钠盐,或2-羟基-2-磺酸基乙酸的钠盐、2-羟基-2-磺酸基乙酸的二钠盐和亚硫酸氢钠的混合物。这样的混合物可以FF6和FF7(Brüggemann Chemicals;Heilbronn;Germany)获得。
可与带有酸基团的烯键式不饱和单体a)共聚的烯键式不饱和单体d)为,例如,丙烯酰胺、甲基丙烯酰胺、丙烯酸羟乙酯、甲基丙烯酸羟乙酯、甲基丙烯酸二甲氨基乙酯、丙烯酸二甲氨基乙酯、丙烯酸二甲氨基丙酯、丙烯酸二乙氨基丙酯、甲基丙烯酸二甲氨基乙酯、甲基丙烯酸二乙氨基乙酯。
所使用的水溶性聚合物e)可为聚乙烯醇、聚乙烯吡咯烷酮、淀粉、淀粉衍生物、改性纤维素(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,优选淀粉、淀粉衍生物和改性纤维素。
通常,使用单体水溶液。单体溶液的水含量优选为40重量%至75重量%,更优选为45重量%至70重量%,最优选为50重量%至65重量%。也可以使用单体悬浮液,即,具有超过溶解度的单体a)的单体溶液,例如丙烯酸钠。随着含水量的增加,在后续干燥中的能量消耗增加,并且随着含水量的降低,聚合热只能被不充分地除去。
为了达到最佳效果,优选的阻聚剂需要溶解氧。因此,在聚合之前可通过惰性化使单体溶液中不含溶解氧,即,使惰性气体流过——优选氮气或二氧化碳。单体溶液的氧含量优选在聚合之前降低至小于1重量ppm,更优选小于0.5重量ppm,最优选小于0.1重量ppm。
用于聚合的合适的反应器为,例如,捏合反应器或带式反应器。在捏合机中,在单体水溶液或悬浮液的聚合中形成的聚合物凝胶通过例如反向搅拌轴连续粉碎,如WO 2001/038402 A1中所记载。带上聚合记载于例如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,该聚合物凝胶必须在例如挤出机中或捏合机中粉碎。
为了改善干燥性能,通过捏合机获得的粉碎的聚合物凝胶可再被挤出。
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。这通常是通过将中和剂以水溶液或优选以固体的形式混入来实现的。中和度优选为25至85摩尔%,更优选为30至80摩尔%,最优选为40至75摩尔%,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及其混合物。除碱金属盐外,也可使用铵盐。特别优选的碱金属为钠和钾,但是非常特别优选氢氧化钠、碳酸钠或碳酸氢钠及其混合物。固体碳酸盐和碳酸氢盐在这里也可以经包封的形式引入,优选在聚合之前直接引入单体溶液中、在聚合期间或之后以及在干燥之前引入聚合物凝胶中。包封通过使用不溶的或仅逐渐可溶的材料(例如通过成膜聚合物、惰性无机材料或可熔有机材料)盖覆表面来进行,这将固体碳酸盐或碳酸氢盐的溶解和反应延迟到一定程度,以至于直到干燥期间才释放出二氧化碳,且使所形成的超吸收剂具有高的内部孔隙率。
任选地,可以在聚合之前或期间将表面活性剂添加到单体溶液中,然后可在聚合之前或期间用惰性气体或水蒸汽或通过剧烈搅拌使单体溶液发泡。表面活性剂可为阴离子的、阳离子的、两性离子的亦或非离子的。优选使用对皮肤友好的表面活性剂。
然后通常使用空气循环带式干燥器干燥聚合物凝胶,直到残余水分含量优选为0.5至10重量%,更优选1至6重量%,最优选1.5至4重量%,残余水分含量由EDANA推荐的测试方法No.WSP 230.2-05“Mass Loss Upon Heating”测定。在残余水分含量太高的情况下,干燥的聚合物凝胶的玻璃化转变温度Tg太低,并且仅能困难地进一步加工。在残余水分含量太低的情况下,干燥的聚合物凝胶太脆,并且在随后的粉碎步骤中,获得了不期望的大量的具有过低粒度的聚合物颗粒(“细粉”)。干燥之前聚合物凝胶的固含量优选为25重量%至90重量%,更优选为35重量%至70重量%,最优选为40重量%至60重量%。随后,将干燥的聚合物凝胶压碎并任选地粗粉碎。
此后,通常将干燥的聚合物凝胶研磨并分级,并且用于研磨的设备通常可为单级或多级辊磨机,优选两级或三级辊磨机、针磨机、锤磨机或振动磨机。
作为产物级分被除去的聚合物颗粒的平均粒度优选为150至850μm,更优选250至600μm,非常特别300至500μm。产物级分的平均粒度可通过EDANA推荐的测试方法No.WSP220.2(05)“Particle Size Distribution”来确定,其中筛分级分的质量比例以累积形式绘图,平均粒度由图表确定。此处的平均粒度是累积为50重量%的筛网尺寸的值。
粒径大于150μm的聚合物颗粒的比例优选为至少90重量%,更优选至少95重量%,最优选至少98重量%。
粒度太小的聚合物颗粒会降低凝胶床渗透性(GBP)。因此,过小的聚合物颗粒(“细粉”)的比例应当很小。
因此,通常优选在聚合之前、聚合期间或紧接聚合之后(即在聚合物凝胶的干燥之前),将过小的聚合物颗粒移除并再循环到该过程中。在再循环之前或期间,可用水和/或表面活性剂水溶液润湿过小的聚合物颗粒。
也可在随后的工艺步骤中——例如在表面后交联或另一个包覆步骤之后——除去过小的聚合物颗粒。在这种情况下,将回收的过小的聚合物颗粒进行表面后交联或用另一种方法(例如用气相二氧化硅)进行包覆。
粒度至多为850μm的聚合物颗粒的比例优选为至少90重量%,更优选至少95重量%,最优选至少98重量%。
粒度至多为600μm的聚合物颗粒的比例优选为至少90重量%,更优选至少95重量%,最优选至少98重量%。
过大粒度的聚合物颗粒降低自由溶胀速率。因此,过大的聚合物颗粒的比例同样应该低。因此,通常将过大的聚合物颗粒移除并再循环至研磨中。
为了进一步改善性能,可使聚合物颗粒进行热表面后交联。合适的表面后交联剂为包含可与聚合物颗粒的至少两个羧酸酯基形成共价键的基团的化合物。合适的化合物为例如多官能胺、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 0 937 736 A2中所记载;双官能醇或多官能醇,如DE 33 14 019 A1、DE 35 23 617A1和EP 0 450 922 A2中所记载;或β-羟烷基酰胺,如DE 102 04 938 A1和US 6,239,230中所记载。
此外被记载为合适的表面后交联剂的有:DE 40 20 780 C1中的环状碳酸酯;DE198 07 502 A1中的2-噁唑烷酮及其衍生物,例如2-羟乙基-2-噁唑烷酮;DE 198 07 992C1中的双-2-噁唑烷酮和聚-2-噁唑烷酮;DE 198 54 573 A1中的2-氧代四氢-1,3-噁嗪及其衍生物;DE 198 54 574 A1中的N-酰基-2-噁唑烷酮;DE 102 04 937 A1中的环状脲;DE103 34 584 A1中的双环酰胺缩醛;EP 1 199 327 A2中的氧杂环丁烷和环状脲;以及WO03/031482 A1中的吗啉-2,3-二酮及其衍生物。
优选的表面后交联剂为碳酸亚乙酯、乙二醇二缩水甘油醚、聚酰胺与表氯醇的反应产物以及丙二醇和1,4-丁二醇的混合物。
非常特别优选的表面后交联剂为2-羟乙基-2-噁唑烷酮、2-噁唑烷酮和1,3-丙二醇。
此外,还可以使用包含其他可聚合的烯键式不饱和基团的表面后交联剂,如DE 3713 601 A1中所记载。
表面后交联剂的量优选为0.001重量%至3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%,在每种情况下基于聚合物颗粒计。
表面后交联通常以将表面后交联剂的溶液喷洒到干燥的聚合物颗粒上的方式进行。喷涂后,将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在干燥之前和干燥期间均可进行。
表面后交联剂溶液的喷涂优选在具有移动混合工具的混合器中进行,所述混合器为例如螺杆混合器、盘式混合器和桨式混合器。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。卧式混合器和立式混合器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,而立式混合器具有垂直安装的混合轴。合适的混合器为例如卧式犁式混合器(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,还可以在流化床中喷洒表面后交联剂溶液。
表面后交联剂通常以水溶液的形式使用。表面后交联剂渗入聚合物颗粒的深度可通过非水溶剂的含量和溶剂的总量来调节。
当仅使用水作为溶剂时,有利地添加表面活性剂。这改善了润湿特性并降低了形成团块的倾向。然而,优选使用溶剂混合物,例如异丙醇/水、1,3-丙二醇/水和丙二醇/水,其中按质量计的混合比优选为20:80至40:60。
表面后交联优选在接触式干燥器、更优选桨式干燥器、最优选盘式干燥器中进行。合适的干燥器为例如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,还可以使用流化床干燥器。
表面后交联可通过加热夹套或吹入暖空气在混合器自身中进行。同样合适的为下游干燥器,例如托盘式干燥器、旋转管式烘箱或可加热螺杆。特别有利的为在流化床干燥器中进行混合和热表面后交联。
优选的反应温度为100℃至250℃,优选110℃至220℃,更优选120℃至210℃,最优选130℃至200℃。在该温度下优选的停留时间优选为至少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。
在本发明的一个优选的实施方案中,在表面后交联之后将聚合物颗粒冷却。冷却优选在接触式冷却器、更优选桨式冷却器且最优选盘式冷却器中进行。合适的冷却器为例如Hosokawa卧式桨式冷却器(Hosokawa Micron GmbH;Leingarten;Germany)、Hosokawa盘式冷却器(Hosokawa Micron GmbH;Leingarten;Germany)、冷却器(Metso Minerals Industries Inc.;Danville;USA)和Nara桨式冷却器(NARA Machinery Europe;Frechen;Germany)。此外,还可以使用流化床冷却器。
在冷却器中,将聚合物颗粒冷却至优选40℃至90℃,更优选45℃至80℃,最优选50℃至70℃。
随后,可将表面后交联的聚合物颗粒再次分级,其中将过小和/或过大的聚合物颗粒移除并再循环至工艺中。
为了进一步改善性能,可将表面后交联的聚合物颗粒进行包覆或再润湿。
再润湿优选在40℃至120℃、更优选在50℃至110℃、最优选在60℃至100℃下进行。在过低温度下,聚合物颗粒倾向于形成团块,而在较高温度下,水已蒸发到显著程度。用于再润湿的水的量优选为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%。再润湿提高了聚合物颗粒的机械稳定性,并降低了其带静电的趋势。再润湿有利地在热表面后交联之后于冷却器中进行。
用于提高溶胀速率和凝胶床渗透性(GBP)的合适的覆层为例如无机惰性物质,例如水不溶性金属盐、有机聚合物、阳离子聚合物和二价金属阳离子或多价金属阳离子。用于粉尘粘结的合适的覆层为例如多元醇。用于抵消聚合物颗粒不希望的结块倾向的合适的覆层为例如气相二氧化硅(例如200)和表面活性剂(例如20)。用于粉尘粘结、用于降低结块倾向和用于提高机械稳定性的合适的覆层为如EP 0 703 265 B1中所述的聚合物分散体和US 5 840 321中所述的蜡。
随后,可将经包覆和/或再润湿的聚合物颗粒再次分级,其中将过小和/或过大的聚合物颗粒移除并再循环至工艺中。
本发明还提供包含通过本发明的方法制备的超吸收剂的卫生制品。
方法:
下文所描述的且称为“WSP”的标准测试方法记载于:由the Worldwide StrategicPartners EDANA(Avenue Eugène Plasky,157,1030Brussels,Belgium,www.edana.org)和INDA(1100Crescent Green,Suite 115,Cary,North Carolina 27518,U.S.A.,www.inda.org)共同出版的“Standard Test Methods for the Nonwovens Industry”,2005版。该出版物可从EDANA和INDA获得。
除非另有说明,否则测量应在23±2℃的环境温度和50±10%的相对空气湿度下进行。在测量之前,将吸水性聚合物颗粒充分混合。
离心机保留容量
离心保留容量(CRC)由EDANA推荐的测试方法No.WSP 241.2(05)“FluidRetention Capacity in Saline,After Centrifugation”测定。
可提取物
吸水性聚合物颗粒中可提组分的含量通过EDANA推荐的测试方法No.WSP 270.2(05)“Extractable”来测定。
实施例
实施例1
通过将去离子水、50重量%的氢氧化钠溶液和丙烯酸连续混合,制备丙烯酸/丙烯酸钠溶液,使得中和度对应于71.3摩尔%。单体溶液的固含量为38.8重量%。
所使用的聚乙烯式不饱和交联剂为二丙烯酸聚乙二醇-400酯(polyethyleneglycol-400diacrylate)(二丙烯酸酯由平均摩尔质量为400g/mol的聚乙二醇制得)。用量为每吨单体溶液2kg交联剂。
为了引发自由基聚合,每吨单体溶液中使用1.03kg的0.25重量%的过氧化氢水溶液、3.10kg的15重量%的过二硫酸钠水溶液和1.05kg的1重量%的抗坏血酸水溶液。
单体溶液的生产量为20t/h。反应溶液的进料温度为23.5℃。
将各组分以以下量连续计量加入到容量为6.3m3的List Contikneter连续捏合反应器(LIST AG,Arisdorf,Switzerland)中:
在交联剂的添加点和引发剂的添加位置之间,单体溶液用氮气惰性化。
在约50%的停留时间之后,向反应器中再计量加入细粉(1000kg/h),这些细粉是在制备过程中通过研磨和筛分获得的。反应混合物在反应器中的停留时间为15分钟。
借助于振荡式输送带将获得的水性聚合物凝胶施加到空气循环带式干燥器的输送带上。
空气循环带式干燥机的长度为48m。空气循环带式干燥机的输送带的有效宽度为4.4m。
振荡式输送带的长度为5m。输送带的宽度为0.8m,有效宽度为0.5m。水性聚合物凝胶在输送带上的休止角为约15°。输送带上的聚合物凝胶床的横截面约为0.04m2。输送带的速度为0.5m/s。
从一个端位置开始,振荡式输送带通过13°的第一摆角(pivot angle)β1加速到33°/s的角速度,通过20°的第二摆角β2减速到17°/s的角速度并通过第三摆角β3减速到另一个端位置。总摆角为50°。一个往返(double pass)(从第一个端位置到另一个端位置,再返回)持续约7s。回转的输送带具有聚四氟乙烯(PTFE)的表面。
振荡式输送带上的水性聚合物凝胶的温度为90℃。
在振荡式输送带的底面上,有脱除装置。脱除装置是纵向刮板,其横向于回转的输送带的运行方向安装。刮板反向于回转输送带的运行方向倾斜20°。脱除装置与卸料端的距离为约5cm,这意味着脱除装置在偏转辊的区域中。脱除装置与回转的输送带的距离为1mm。脱除装置除去附着在回转的输送带外侧的水性聚合物凝胶。
在振荡式输送带的底面上,另外还有3个两相喷嘴。两相喷嘴横向于输送带的运行方向布置。两相喷嘴之间的距离在每种情况下为约20cm。两相喷嘴距卸料端的距离约为20cm。两相喷嘴距回转的输送带的距离约为20cm。总共喷洒了10kg/h的水和100kg/h的空气。
借助于脱除装置可有效地清洁回转的输送带。在六个月的时间内,输送带上完全没有结块。
在空气循环带式干燥机上,空气/气体混合物在水性聚合物凝胶周围连续流动并将其干燥。在空气循环带式干燥机中的停留时间为37分钟。
将干燥的聚合物凝胶研磨并过筛至150至850μm的粒度级分。
所得吸水聚合物颗粒的离心保留容量(CRC)为34.9g/g,可提取物含量为8.5重量%。
实施例2(比较实施例)
步骤与实施例1相同,除了振荡式输送带上的喷嘴被关闭。
借助于脱除装置,仅可困难地清洁回转的输送带。输送带上有明显的结块,特别是在聚合物凝胶已经干燥的地方。连续生产几周后,必须停止生产并清洁输送带,否则由于损坏必须更换输送带。
Claims (15)
1.一种通过使单体溶液或悬浮液聚合来制备超吸收剂颗粒的方法,所述单体溶液或悬浮液包含:
a)至少一种带有酸基团并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,
c)至少一种引发剂,
d)任选地,一种或多种可与a)中所述的单体共聚的烯键式不饱和单体,和
e)任选地,一种或多种水溶性聚合物,
所述方法包含将所得的水性聚合物凝胶在空气循环带式干燥器中干燥,研磨、分级以及任选地进行热表面后交联,其中水性聚合物凝胶通过振荡式输送带被引入空气循环带式干燥器中,借助于至少一个脱除装置将回转的输送带的底面上附着的聚合物凝胶除去,并通过至少一个喷嘴将水喷洒到回转的输送带的底面上。
2.根据权利要求1所述的方法,其中所述脱除装置与所述输送带的卸料端的距离小于所述输送带长度的20%,其中所述输送带的长度为转轴与所述卸料端的距离。
3.根据权利要求1或2所述的方法,其中安装在所述回转的输送带底面上的所述脱除装置为刮板。
4.根据权利要求3所述的方法,其中所述刮板以与输送带的运行方向相反的方式、相对于水平方向倾斜5°至45°。
5.根据权利要求3或4所述的方法,其中所述刮板与所述回转的输送带的底面的距离为0.1至5mm。
6.根据权利要求1至5中任一项所述的方法,其中所述至少一个喷嘴与所述输送带的卸料端的距离为所述输送带长度的1%至50%,其中传送带的长度为转轴与卸料端的距离。
7.根据权利要求1至6中任一项所述的方法,其中所述喷嘴与所述输送带的距离为5至50cm。
8.根据权利要求1至7中任一项所述的方法,其中将2至20kg/h的水喷洒到所述回转的输送带的底面上。
9.根据权利要求1至8中任一项所述的方法,其中借助于至少一个两相喷嘴将水喷洒到所述回转的输送带的底面上。
10.根据权利要求1至9中任一项所述的方法,其中通过至少一个两相喷嘴将水喷洒到所述回转的输送带的底面上,并且所述雾化器气体与水的重量比为2至20。
11.根据权利要求1至10中任一项所述的方法,其中借助于至少两个两相喷嘴将水喷洒到所述回转的输送带的底面上。
12.根据权利要求1至11中任一项所述的方法,其中所述至少一个喷嘴在所述输送带的运行方向上超出所述脱除装置。
13.根据权利要求1至12中任一项所述的方法,其中所述输送带的长度为2至10m,其中所述输送带的长度为转轴到卸料端的距离。
14.根据权利要求1至13中任一项所述的方法,其中所述输送带的表面在23℃对水的接触角为至少60°。
15.一种卫生制品,其包含通过权利要求1至14的方法制备的超吸收剂。
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CN102459368A (zh) * | 2009-06-03 | 2012-05-16 | 巴斯夫欧洲公司 | 制备吸水聚合物颗粒的方法 |
CN102762616A (zh) * | 2010-02-24 | 2012-10-31 | 巴斯夫欧洲公司 | 制备吸水性聚合物颗粒的方法 |
CN104411732A (zh) * | 2012-07-03 | 2015-03-11 | 巴斯夫欧洲公司 | 用于制备具有改进特性的吸水性聚合物颗粒的方法 |
WO2015163517A1 (en) * | 2014-04-25 | 2015-10-29 | Songwon Industrial Co., Ltd. | Release of polymer gel from polymerization belt in production of water-absorbent polymer particles |
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US20210338882A1 (en) | 2021-11-04 |
WO2020064411A1 (de) | 2020-04-02 |
KR20210073516A (ko) | 2021-06-18 |
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