CN101151412A - 调节水分的复合材料 - Google Patents

调节水分的复合材料 Download PDF

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CN101151412A
CN101151412A CNA2006800101398A CN200680010139A CN101151412A CN 101151412 A CN101151412 A CN 101151412A CN A2006800101398 A CNA2006800101398 A CN A2006800101398A CN 200680010139 A CN200680010139 A CN 200680010139A CN 101151412 A CN101151412 A CN 101151412A
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D·勒施
S·布鲁恩斯
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Abstract

本发明涉及包含如下物质的调节水分的复合材料：片状载体材料，水溶性的吸湿性物质以及在吸湿性物质存在下聚合到载体材料上的吸水性聚合物。本发明还涉及一种生产所述材料的方法，以及所述材料在调节水分中的用途。

Description

调节水分的复合材料
本发明涉及调节水分的复合材料、生产它们的方法及其在调节水分中的用途。
本发明的其它实施方案由权利要求、说明书部分和实施例显而易见。应理解的是，在上文所述的以及将在下文更具体描述的本发明主题的特征不仅可以以所述特定的组合使用，还可以以其它不脱离本发明范围的组合使用。
吸水性聚合物尤其为(共)聚合的亲水单体的聚合物，一种或多种亲水单体在合适的接枝基质上的接枝(共)聚合物，交联的纤维素醚，交联的淀粉醚，交联的羧甲基纤维素，部分交联的聚氧化烯或者可在水性流体中溶胀的天然产品如瓜耳胶衍生物。这类聚合物用作可吸收水溶液的产品来制备尿布、棉塞、卫生棉和其它卫生制品，也作为保水剂用于商品蔬菜种植。
吸水性聚合物的生产描述于专论“Modern Superabsorbent PolymerTechnology”，  F.L.Buchholz和A.T.Graham，Wiley-VCH，1998，第69-117页中。
WO-A-01/56625、EP-A-1 178 149和US-5,962,068描述了生产吸水性复合材料的方法，在各个方法中将吸水性聚合物聚合到载体材料上。
WO-A-00/64311公开了其中将吸水性聚合物聚合到载体材料上的复合材料。复合材料用于在座垫中调节水分。
JP-A-05-105705描述了由载体材料和吸湿性盐组成的非溶解性干燥剂，其中借助吸水性聚合物将吸湿性盐固定在载体材料上。
本发明的目的是提供能够可逆地吸收大量水蒸气的调节水分的复合材料。本发明的另一目的是提供具有高机械稳定性的吸收水蒸气的复合材料。
我们发现该目的通过包含如下物质的调节水分的复合材料实现：
a)至少一种片状载体材料，
b)至少一种水溶性的吸湿性物质，和
c)至少一种在所述物质b)存在下聚合到所述载体材料a)上的吸水性聚合物，
其中所述吸湿性物质b)与所述聚合物c)的比例为0.01-1。
吸湿性物质b)与聚合物c)的比例优选小于0.8，更优选小于0.6，甚至更优选小于0.5，最优选小于0.4且至少为0.05，更优选至少0.1，甚至更优选至少0.15。
载体材料a)不受任何限制。优选的载体材料为如WO-A-01/56625第16页第40行至第20页第27行所述的织造织物和/或网状物(web)。
合适的载体材料a)例如为由合成聚合物纤维组成的织造织物或网状物。纤维可由任何可纺丝聚合物材料制成，该聚合物材料的实例为聚烯烃如聚乙烯或聚丙烯，聚酯如聚对苯二甲酸乙二醇酯，聚酰胺如尼龙-6或尼龙-66，聚丙烯酸酯，改性纤维素如乙酸纤维素。也可使用上述聚合物材料的混合物。
织造织物为由交叉线组成的生产制品，尤其是线以直角交叉。
网状物为非织造制品，其由纤维组成并且通常由纤维的内在粘性产生其整体。网状物优选例如通过穿刺、成圈或借助急速的水或空气射流缠绕而机械结合。网状物也可粘合或内聚结合。粘合结合网状物例如可通过用液体粘合剂将纤维相互粘合或通过熔融粘合在生产网状物过程中加入的纤维而得到。内聚结合的网状物例如可通过首先用合适的化学品溶解纤维并施加压力而得到。
载体材料的基重有利地为20-200g/m2，优选30-150g/m2，更优选35-125g/m2。
载体材料的密度通常为0.005-0.2g/cm3，优选0.008-0.16g/cm3，更优选0.01-0.14g/cm3。
吸湿性物质b)能够吸收水蒸气；即从空气中冷凝到吸湿性物质上的水蒸气，并导致吸湿性物质b)的水含量增加。吸湿性物质b)例如为无机盐如氯化钠、硝酸铅、硫酸锌、高氯酸钠、氧化铬或氯化锂，或至少部分结晶的有机化合物如水溶性聚丙烯酸。吸湿性无机盐是优选的吸湿性物质b)。最优选氯化钠。
特别有利的吸湿性物质b)为其中饱和水溶液上的相对湿度在20℃下平衡小于95％，优选小于90％，更优选小于85％，甚至更优选小于80％且至少40％，优选至少45％，更优选至少50％，甚至更优选至少55％，最优选至少60％的化合物。
相对湿度是水蒸气分压与水蒸气压的商乘以100％。
优选吸湿性物质b)在聚合的吸水性聚合物中处于分散态(disbursedstate)。
当本发明的调节水分的复合材料例如用于座垫中时，高于90％的相对湿度在感觉上是不舒服的，因为在高大气湿度下容易形成汗。然而，低于40％的相对湿度也是不利的，因为如此低的相对湿度对进一步提高座位舒适性没有任何作用并且使得之前吸收的水分难以在不使用的阶段解吸出来。
本发明的调节水分的复合材料可通过将包含如下物质的单体溶液施加至载体材料并聚合而得到：
i)至少一种烯属不饱和单体，
ii)至少一种水溶性的吸湿性物质，
iii)至少一种交联剂，
iv)任选一种或多种可与在i)下提及的单体共聚的烯属和/或烯丙基属不饱和单体，和
v)任选一种或多种水溶性聚合物
其中所述吸湿性物质ii)与所述单体i)的比例为0.01-1。
吸湿性物质ii)与单体i)的比例优选小于0.8，更优选小于0.6，甚至更优选小于0.5，最优选小于0.4且至少为0.05，更优选至少0.1，甚至更优选至少0.15。
合适的单体i)例如为烯属不饱和羧酸如丙烯酸、甲基丙烯酸、马来酸、富马酸和衣康酸或其衍生物如丙烯酰胺、甲基丙烯酰胺、丙烯酸酯和甲基丙烯酸酯。优选包含酸性基团的单体i)。丙烯酸和甲基丙烯酸为特别优选的单体。最优选丙烯酸。
单体i)，尤其是丙烯酸优选包含至多0.025重量％氢醌半醚。优选氢醌半醚为氢醌单甲醚(MEHQ)和/或生育酚。
生育酚指下式化合物：
Figure A20068001013900071
其中R1为氢或甲基，R2为氢或甲基，R3为氢或甲基且R4为氢或具有1-20个碳原子的酸性基团。
优选R4基团为乙酰基、抗坏血酰基(ascorbyl)、琥珀酰基、烟酰基以及其它生理上可接受的羧酸。羧酸可为单-、二-或三羧酸。
优选其中R1＝R2＝R3＝甲基的α-生育酚，尤其是外消旋的α-生育酚。R4更优选为氢或乙酰基。尤其优选RRR-α-生育酚。
单体溶液的氢醌半醚含量优选不超过130重量ppm，更优选不超过70重量ppm，优选至少10重量ppm，更优选至少30重量ppm，尤其优选约50重量ppm，所有量均基于丙烯酸，其中丙烯酸盐以丙烯酸计算。例如，单体溶液可使用具有合适氢醌半醚含量的丙烯酸生产。
可用于本发明方法的吸湿性物质ii)已经作为吸湿性物质b)描述。
吸水性聚合物处于交联状态，即聚合在具有至少两个可自由基共聚入聚合物网络的可聚合基团的化合物存在下进行。有用的交联剂iii)例如包括如EP-A-0 530 438所述的乙二醇二甲基丙烯酸酯、二甘醇二丙烯酸酯、甲基丙烯酸烯丙酯、三羟甲基丙烷三丙烯酸酯、三烯丙基胺、四烯丙氧基乙烷，如EP-A-0 547 847、EP-A-0 559 476、EP-A-0 632 068、WO-A-93/21237、WO-A-03/104299、WO-A-03/104300、WO-A-03/104301和DE-A-103 31 450中所述的二丙烯酸酯和三丙烯酸酯，如DE-A-103 31 456和在先德国专利申请103 55 401.7中所述的除丙烯酸酯基团外还包含其它烯属不饱和基团的混合丙烯酸酯，或者例如如DE-A-195 43 368、DE-A-196 46 484、WO-A-90/15830和WO-A-02/32962中所述的交联剂混合物。
有用的交联剂iii)尤其包括N，N’-亚甲基双丙烯酰胺和N，N’-亚甲基双甲基丙烯酰胺，多元醇的不饱和一元羧酸或多元羧酸的酯，例如二丙烯酸酯或三丙烯酸酯如丁二醇二丙烯酸酯、丁二醇二甲基丙烯酸酯、乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯以及三羟甲基丙烷三丙烯酸酯，以及烯丙基化合物如(甲基)丙烯酸烯丙酯、氰脲酸三烯丙酯、马来酸二烯丙酯、聚烯丙基酯、四烯丙氧基乙烷、三烯丙胺、四烯丙基乙二胺、磷酸的烯丙基酯以及例如如EP-A-0 343 427中所述的乙烯基膦酸衍生物。有用的交联剂iii)还包括季戊四醇二烯丙基醚、季戊四醇三烯丙基醚、季戊四醇四烯丙基醚、聚乙二醇二烯丙基醚、乙二醇二烯丙基醚、甘油二烯丙基醚、甘油三烯丙基醚、基于山梨糖醇的聚烯丙基醚及其乙氧基化变体。本发明方法可利用聚乙二醇的二(甲基)丙烯酸酯，其中所用聚乙二醇的分子量为300-1000。
然而，特别有利的交联剂iii)为3-20重乙氧基化的甘油、3-20重乙氧基化的三羟甲基丙烷、3-20重乙氧基化的三羟甲基乙烷的二丙烯酸酯和三丙烯酸酯，尤其是2-6重乙氧基化的甘油或2-6重乙氧基化的三羟甲基丙烷、3重丙氧基化的甘油、3重丙氧基化的三羟甲基丙烷，以及3重混合乙氧基化或丙氧基化的甘油、3重混合乙氧基化或丙氧基化的三羟甲基丙烷、15重乙氧基化的甘油、15重乙氧基化的三羟甲基丙烷、至少40重乙氧基化的甘油、至少40重乙氧基化的三羟甲基乙烷以及至少40重乙氧基化的三羟甲基丙烷的二丙烯酸酯和三丙烯酸酯。
非常特别优选交联剂iii)为二丙烯酸酯化、二甲基丙烯酸酯化、三丙烯酸酯化或三甲基丙烯酸酯化的多重乙氧基化和/或丙氧基化的甘油，例如如WO-A-03/104301中所述。特别有利的是3-10重乙氧基化甘油的二-和/或三丙烯酸酯。非常特别优选1-5重乙氧基化和/或丙氧基化甘油的二-或三丙烯酸酯。最优选3-5重乙氧基化和/或丙氧基化甘油的三丙烯酸酯。这些交联剂的显著之处在于它们在吸水性聚合物中的残留水平特别低(通常低于10重量ppm)，并且与相同温度下的水的表面张力(通常不低于0.068N/m)相比用其生产的吸水性聚合物的水性提取物具有几乎不变的表面张力。
可与单体i)共聚的烯属不饱和单体iv)的实例为丙烯酰胺、甲基丙烯酰胺、巴豆酰胺、甲基丙烯酸二甲基氨基乙酯、丙烯酸二甲基氨基乙酯、丙烯酸二甲基氨基丙酯、丙烯酸二乙基氨基丙酯、丙烯酸二甲基氨基丁酯、甲基丙烯酸二甲基氨基乙酯、甲基丙烯酸二乙基氨基乙酯、丙烯酸二甲基氨基新戊酯和甲基丙烯酸二甲基氨基新戊酯。
有用的水溶性聚合物v)包括聚乙烯醇、聚乙烯吡咯烷酮、淀粉、淀粉衍生物、聚乙二醇或聚丙烯酸，优选聚乙烯醇和淀粉。
吸湿性聚合物如可溶解的聚丙烯酸不仅可用作吸湿性物质ii)而且可用作水溶性聚合物v)。
当将常规接枝聚合催化剂如铁盐加入单体溶液时，则聚合物用作聚合的接枝基质并且待聚合的单体接枝到聚合物上。当不使用接枝聚合催化剂时，则聚合物在聚合中基本不发生变化并且起吸湿性物质的作用。
优选单体i)的酸性基团通常处于部分中和态，它们的中和度优选为25-95mol％，更优选40-90mol％，甚至更优选50-80mol％，最优选60-80mol％，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及其混合物。也可使用铵盐代替碱金属盐。碱金属特别优选为钠和钾，但最优选氢氧化钠、碳酸钠或碳酸氢钠及其混合物。中和通常通过将中和剂以水溶液或者或以熔体或优选以固体混入单体溶液而实现。例如，具有明显小于50重量％水含量的氢氧化钠可以以熔点高于23℃的蜡状物质存在。此时，可在升高温度下以片料或熔体计量加入。
单体水溶液优选通过喷雾施加到载体上。有用的载体材料已经作为载体材料a)描述。
随后，使载体材料上的单体溶液聚合并将复合材料干燥。聚合优选通过UV辐射和/或热引发。
本发明复合材料尤其可用于在床垫以及如汽车座椅中的座垫中调节水分。
包含本发明复合材料的座垫或床垫通过将相对大气湿度调节至令人愉悦的程度并防止过度出汗而提高了坐或躺的舒适性。同时，本发明复合材料又能够在不使用阶段最佳释放所吸收的水分并且它们自身能够快速再生。由于所述平衡的性能特征，本发明复合材料提供了迄今为止未实现的坐和躺的舒适性。
方法：
测量水分吸收
测量在23±2℃的环境温度下进行。
将复合材料在50％的相对湿度下调节30分钟至平衡。然后将相对湿度升高至90％并维持60分钟(吸收段)。然后，再将相对湿度降至50％并维持30分钟(解吸段)。
连续测量由吸收/解吸引起的重量变化并且其为施加的物质(吸水性聚合物和/或盐)的重量增加(g)。重量增加的参比点为平衡30分钟之后的重量。
实施例
实施例1
用单体溶液喷雾基重为70g/m2的聚对苯二甲酸乙二醇酯网状物，随后借助UV辐射固化2分钟。随后在逆流干燥器中在90℃下干燥5分钟。
单体溶液包含33.6重量％丙烯酸钠，8.5重量％丙烯酸，1.51重量％聚乙二醇二丙烯酸酯(平均摩尔质量为400的聚乙二醇的二丙烯酸酯)，0.22重量％2-羟基-1-[4-(羟基乙氧基)苯基]-2-甲基-1-丙酮和水。
选择单体溶液的量，以使聚对苯二甲酸乙二醇酯网状物负载的聚合的吸水性聚合物为160g/m2。
测量水分吸收。测量结果总结在表1中。
实施例2
按照描述于实施例1中的方法步骤。
单体溶液包含22.8重量％丙烯酸钠，16.9重量％丙烯酸，1.51重量％聚乙二醇二丙烯酸酯(平均摩尔质量为400的聚乙二醇的二丙烯酸酯)，0.22重量％2-羟基-1-[4-(羟基乙氧基)苯基]-2-甲基-1-丙酮和水。
选择单体溶液的量，以使聚对苯二甲酸乙二醇酯网状物负载的聚合的吸水性聚合物为160g/m2。
测量结果总结在表1中。
实施例3
按照描述于实施例1中的方法步骤。
单体溶液包含36.2重量％丙烯酸钠，2.0重量％丙烯酸，1.30重量％聚乙二醇二丙烯酸酯(平均摩尔质量为400的聚乙二醇的二丙烯酸酯)，0.19重量％2-羟基-1-[4-(羟基乙氧基)苯基]-2-甲基-1-丙酮和水。
选择单体溶液的量，以使聚对苯二甲酸乙二醇酯网状物负载的聚合的吸水性聚合物为160g/m2。
测量结果总结在表1中。
实施例4
按照描述于实施例1中的方法步骤。在聚合之后，用25重量％氯化钠水溶液以17g/m2喷雾复合材料，随后干燥。
复合材料缺乏机械稳定性。喷雾上的氯化钠易于脱离。
实施例5
按照描述于实施例1中的方法步骤。单体溶液包含23.7重量％丙烯酸钠，6.0重量％丙烯酸，1.06重量％聚乙二醇二丙烯酸酯(平均摩尔质量为400的聚乙二醇的二丙烯酸酯)，0.15重量％2-羟基-1-[4-(羟基乙氧基)苯基]-2-甲基-1-丙酮，7.4重量％氯化钠和水(由按照实施例1的单体溶液和基于按照实施例1的单体溶液为42重量％的浓度为25重量％的氯化钠水溶液制备)。
选择单体溶液的量，以使聚对苯二甲酸乙二醇酯网状物负载的聚合的吸水性聚合物/氯化钠为160g/m2。
测量结果总结在表1中。
实施例6
按照描述于实施例5中的方法步骤。用15重乙氧基化的三羟甲基丙烷三丙烯酸酯代替单体溶液中的聚乙二醇二丙烯酸酯。
选择单体溶液的量，以使聚对苯二甲酸乙二醇酯网状物负载的聚合的吸水性聚合物/氯化钠为160g/m2。
测量结果总结在表1中。
实施例7
按照描述于实施例3中的方法步骤。单体溶液包含27.8重量％丙烯酸钠，1.5重量％丙烯酸，1.00重量％聚乙二醇二丙烯酸酯(平均摩尔质量为400的聚乙二醇的二丙烯酸酯)，0.15重量％2-羟基-1-[4-(羟基乙氧基)苯基]-2-甲基-1-丙酮，5.8重量％氯化钠和水(由按照实施例3的单体溶液和基于按照实施例3的单体溶液为30重量％的浓度为25重量％的氯化钠水溶液制备)。
选择单体溶液的量，以使聚对苯二甲酸乙二醇酯网状物负载的聚合的吸水性聚合物/氯化钠为160g/m2。
测量结果总结在表1中。
表1：水分吸收
  实施例   中和度   盐/聚合物   在90分钟后的重量增加   在120分钟后的重量增加
  1   75mol％   0.45g/g   0.33g/g
  2   50mol％   0.38g/g   0.21g/g
  3   93mol％   0.56g/g   0.38g/g
  5   75mol％   0.24   0.62g/g   0.46g/g
  6   75mol％   0.24   0.75g/g   0.55g/g
  7   93mol％   0.19   0.78g/g   0.64g/g

Claims (14)

1.一种包含如下物质的调节水分的复合材料：
a)至少一种片状载体材料，
b)至少一种水溶性的吸湿性物质，和
c)至少一种在所述物质b)存在下聚合到所述载体材料a)上的吸水性聚合物，
其中所述吸湿性物质b)与所述聚合物c)的比例为0.01-1。
2.根据权利要求1的复合材料，其中所述载体材料a)为织造织物和/或网状物。
3.根据权利要求1或2的复合材料，其中所述吸湿性物质b)的过饱和水溶液上的相对湿度在20℃下的平衡中为至少40％。
4.根据权利要求1-3中任一项的复合材料，其中所述吸湿性物质b)为无机盐。
5.根据权利要求1-4中任一项的复合材料，其中所述聚合物c)包含酸性基团。
6.根据权利要求5的复合材料，其中所述酸性基团至少25mol％被中和。
7.一种生产调节水分的复合材料的方法，其包括将包含如下物质的单体溶液施加至片状载体材料并聚合：
i)至少一种烯属不饱和单体，
ii)至少一种水溶性的吸湿性物质，
iii)至少一种交联剂，
iv)任选一种或多种可与在i)下提及的单体共聚的烯属和/或烯丙基属不饱和单体，和
v)任选一种或多种水溶性聚合物
其中所述吸湿性物质ii)与所述单体i)的比例为0.01-1。
8.根据权利要求7的方法，其中所述单体i)包含酸性基团。
9.根据权利要求8的方法，其中所述酸性基团至少25mol％被中和。
10.根据权利要求7-9中任一项的方法，其中所述吸湿性物质ii)的过饱和水溶液上的相对湿度在20℃下的平衡中为至少40％。
11.根据权利要求7-10中任一项的方法，其中所述吸湿性物质ii)为无机盐。
12.根据权利要求7-11中任一项的方法，其中所述载体材料为织造织物和/或网状物。
13.根据权利要求1-6中任一项的复合材料在调节水分中的用途。
14.包含根据权利要求1-6中任一项的复合材料的座垫或床垫。
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CN101151412B (zh) 2011-03-16

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