CN110551316B - 水溶性高分子的多孔体的制造方法 - Google Patents
水溶性高分子的多孔体的制造方法 Download PDFInfo
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- CN110551316B CN110551316B CN201910456448.7A CN201910456448A CN110551316B CN 110551316 B CN110551316 B CN 110551316B CN 201910456448 A CN201910456448 A CN 201910456448A CN 110551316 B CN110551316 B CN 110551316B
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Abstract
本发明提供简便性优良的水溶性高分子的多孔体的制造方法。此处公开的水溶性高分子的多孔体的制造方法包括:制备乳液的工序,所述乳液包含水溶性高分子、水和分散质,所述水溶性高分子溶解且所述分散质分散在所述乳液中;以及从所述乳液中将水和所述分散质汽化并除去的工序。所述分散质的沸点高于水的沸点。所述水溶性高分子对所述分散质的溶解度低于对水的溶解度。
Description
技术领域
本发明涉及水溶性高分子的多孔体的制造方法。
背景技术
水溶性高分子的多孔体能够表现出轻量性、缓冲性、隔热性、吸音性、分离性、吸附性等各种特性。因此,水溶性高分子的多孔体用于捆包材料、建筑材料、吸音材料、打扫用品、化妆用品、分离膜、吸附材料、纯化用载体、催化剂载体、培养载体等多样化的用途。
从制造成本等观点考虑,期望水溶性高分子的多孔体的制造方法简便。因此,作为能够简便地制造作为水溶性高分子的聚乙烯醇的多孔体的方法,在专利文献1中公开了包括如下工序的制造方法:在加热的同时在聚乙烯醇水溶液中加入水混溶性的第一溶剂而得到聚乙烯醇溶液,冷却所述聚乙烯醇溶液而得到析出的成形体,将所述成形体浸渍到第二溶剂中,使所述成形体中包含的水和/或第一溶剂与所述第二溶剂置换,得到包含聚乙烯醇作为主要成分的多孔体,所述水与第一溶剂的体积比例(第一溶剂/水)为0.5~1.1。
现有技术文献
专利文献
专利文献1:日本特许申请公开第2012-251057号公报
发明内容
本发明人等进行了深入研究,结果发现,在上述现有技术的制造方法中,在简便地制造多孔体方面存在改善的余地。
因此,本发明的目的在于,提供简便性优良的水溶性高分子的多孔体的制造方法。
此处公开的水溶性高分子的多孔体的制造方法包括:制备乳液的工序,所述乳液包含水溶性高分子、水和分散质,所述水溶性高分子溶解且所述分散质分散在所述乳液中;以及从所述乳液中将水和所述分散质汽化并除去的工序。所述分散质的沸点高于水的沸点。所述水溶性高分子对所述分散质的溶解度低于对水的溶解度。
根据这样的构成,通过乳液的制备以及水和分散质的汽化这种简单操作,能够制造水溶性高分子的多孔体。即,根据这样的构成能够提供简便性优良的水溶性高分子的多孔体的制造方法。
附图说明
[图1]图1为实施例1中得到的薄膜的截面的SEM照片。
[图2]图2为实施例5中得到的薄膜的截面的SEM照片。
具体实施方式
本发明的水溶性高分子的多孔体的制造方法包括:制备乳液的工序,所述乳液包含水溶性高分子、水和分散质,所述水溶性高分子溶解且所述分散质分散在所述乳液中(以下,也称为“乳液制备工序”);以及从所述乳液中将水和所述分散质汽化并除去的工序(以下,也称为“分散质除去工序”)。此处,该分散质的沸点高于水的沸点。该水溶性高分子对该分散质的溶解度低于对水的溶解度。
首先,对乳液制备工序进行说明。本发明中使用的水没有特别限制,从防止杂质混入的观点考虑,优选离子交换水、超滤水、反渗透水、蒸馏水或超纯水,更优选离子交换水。通常使用能够完全溶解水溶性高分子并且能够将分散质分散的水量。
在本说明书中,“水溶性高分子”是指,25℃下对水的溶解度为1质量%以上的高分子。本发明中使用的水溶性高分子优选为25℃下对水的溶解度为5质量%以上,更优选为10质量%以上。作为本发明中使用的水溶性高分子的例子,可以列举:聚乙烯醇类聚合物等具有羟基的水溶性高分子;聚乙烯基吡咯烷酮、聚丙烯酰胺、聚(N,N-二甲基丙烯酰胺)、聚(N-乙烯基乙酰胺)、聚-N-异丙基丙烯酰胺、聚唑啉(例如,聚(2-甲基-2-唑啉)、聚(2-乙基-2-唑啉)、聚(2-丙基-2-唑啉))、水溶性聚酰胺、水溶性聚酰胺酰亚胺等具有酰胺基的水溶性高分子;聚乙二醇、聚丙二醇、聚乙烯基甲基醚等具有醚键的水溶性高分子;聚乙烯亚胺、聚乙烯基胺、聚烯丙基胺等具有氨基的水溶性高分子;聚丙烯酸、聚甲基丙烯酸等具有羧基的水溶性高分子等。另外,作为具有羟基的水溶性高分子,也可以使用支链淀粉、直链淀粉、淀粉、淀粉衍生物、纤维素醚(例如,羟丙基纤维素、羟乙基纤维素、羟甲基纤维素、羧甲基纤维素等)、黄原胶、壳聚糖、褐藻酸、透明质酸等水溶性多糖类。需要说明的是,羧甲基纤维素、褐藻酸和透明质酸也是具有羧基的水溶性高分子。壳聚糖也是具有氨基的水溶性高分子。作为水溶性高分子,优选具有羟基的水溶性高分子,更优选聚乙烯醇类聚合物和纤维素醚,进一步优选聚乙烯醇类聚合物。
在本说明书中,“聚乙烯醇类聚合物”是指在全部单体单元中含有50摩尔%以上乙烯醇单元的聚合物。因此,本发明中使用的聚乙烯醇类聚合物可以含有乙烯醇单元以外的单体单元(以下,也称为“其它单体单元”)。作为其它单体单元的例子,可以列举来自制造时的乙烯基酯等的乙酸乙烯基酯单元等乙烯基酯单元。因此,聚乙烯醇类聚合物除了可以为皂化度为100摩尔%的聚乙烯醇以外,也可以为部分皂化聚乙烯醇。作为聚乙烯醇类聚合物的皂化度,优选为60摩尔%以上,更优选为70摩尔%以上,进一步优选为80摩尔%以上。需要说明的是,可以根据例如JIS K6726:1944测定聚乙烯醇类聚合物的皂化度。作为其它单体单元的其它例子,可以列举:乙烯单元、丙烯单元等α-烯烃单元;(甲基)丙烯酸单元;(甲基)丙烯酸酯单元;马来酸单元、衣康酸单元、富马酸单元等不饱和二元羧酸单元;甲基乙烯基醚单元、乙基乙烯基醚单元等乙烯基醚单元;丙烯腈单元、甲基丙烯腈单元等腈单元;氯乙烯单元、氟乙烯单元等卤化乙烯单元等。
水溶性高分子的平均聚合度没有特别限制,优选为80以上且30000以下,更优选为100以上且20000以下。需要说明的是,可以通过例如NMR测定等求出水溶性高分子的平均聚合度。
对水溶性高分子的使用量没有特别限制,优选相对于水100质量份使用水溶性高分子1质量份以上且40质量份以下。通过改变水溶性高分子相对于水的量(即,水溶性高分子在水中的浓度),能够控制所得到的多孔体的孔的状态(例如,孔隙率、孔隙直径等)。特别地,在增加水溶性高分子相对于水的量时,存在孔隙直径变小的倾向。
在本发明中,乳液为O/W型乳液。因此,分散质以液体(特别是液滴)的状态分散在水溶性高分子水溶液中。因此,作为分散质,使用至少在特定的温度(例如25℃)下与水不相容的液体。另外,本发明中使用的分散质的沸点高于水的沸点(100℃),优选比水的沸点高100℃以上(即,分散质的沸点优选为200℃以上)。水溶性高分子对分散质的溶解度低于对水的溶解度。25℃下水溶性高分子对分散质的溶解度优选小于1质量%,更优选为0.5质量%以下,进一步优选为0.2质量%以下。
分散质的溶解度参数(SP值)的值没有特别限制。由于存在乳液进一步稳定化、多孔化更均匀地进行的倾向,因此优选与水的SP值(即,23.4(cal/cm3)1/2)相比小5(cal/cm3)1/2以上。即,分散质的SP值优选为18.4(cal/cm3)1/2以下,更优选为5(cal/cm3)1/2以上且15(cal/cm3)1/2以下。
关于分散质的种类,只要沸点比水高、与水相比更不溶解水溶性高分子、能够以液体的状态分散在水溶性高分子水溶液中,就没有特别限制。作为分散质的优选例,可以列举:癸烷、十一烷、十二烷、十三烷、十四烷、十五烷等烷烃化合物;碳酸亚丙酯(特别是2-氧代-4-甲基-1,3-二氧戊环)、碳酸亚丁酯(特别是4-乙基-1,3-二氧戊环-2-酮)等碳酸酯化合物(特别是环状碳酸酯化合物);十甲基环五硅氧烷等聚硅氧烷化合物等。从容易得到均匀的孔隙考虑,优选碳酸酯化合物(特别是环状碳酸酯化合物)。
分散质的使用量没有特别限制,优选相对于水100质量份使用分散质10质量份以上且400质量份以下。通过改变分散质相对于水的量,能够控制所得到的多孔体的孔的状态(例如,孔隙率、孔隙直径等)。特别是在增加分散质相对于水的量时,存在孔隙率变高的倾向。
在制备乳液时可以添加表面活性剂。因此,乳液可以还包含表面活性剂。通过添加表面活性剂,能够形成更稳定的乳液。另外,通过调节表面活性剂的种类和量,能够控制所得到的多孔体的孔的状态(例如,孔隙率、孔隙直径等)。作为表面活性剂的例子,可以列举:非离子型表面活性剂、阴离子型表面活性剂、阳离子型表面活性剂、两性表面活性剂等。其中,优选非离子型表面活性剂和阴离子型表面活性剂。
作为非离子型表面活性剂,可以列举例如:多元醇脂肪酸酯、聚氧化烯亚烷基二醇、聚氧化烯烷基醚、高级脂肪酸的环氧烷加成物等。作为其具体例,可以列举:脱水山梨糖醇单油酸酯、脱水山梨糖醇单月桂酸酯、脱水山梨糖醇单硬脂酸酯、脱水山梨糖醇单棕榈酸酯、脱水山梨糖醇二硬脂酸酯、脱水山梨糖醇三硬脂酸酯、脱水山梨糖醇三油酸酯、聚甘油月桂酸酯、聚甘油肉豆蔻酸酯、聚甘油油酸酯、聚甘油硬脂酸酯、聚乙二醇、聚丙二醇、聚氧乙烯聚氧丙烯二醇、聚氧乙烯月桂基醚、聚氧乙烯聚氧丙烯月桂基醚、聚氧乙烯十六烷基醚、聚氧乙烯油烯基醚、聚氧乙烯聚氧丙烯油烯基醚、聚氧乙烯月桂酸酯、聚氧乙烯聚氧丙烯月桂酸酯、聚氧乙烯油酸酯、聚氧乙烯聚氧丙烯硬脂酸酯等。
作为阴离子型表面活性剂,可以列举例如:烷基三甲基铵盐、二烷基二甲基铵盐、烷基苄基二甲基铵盐等。作为其具体例,可以列举:十二烷基三甲基氯化铵、辛基十二烷基二甲基氯化铵、二癸基二甲基氯化铵、癸基异壬基二甲基氯化铵等。另外,还可以使用丙烯酸类共聚物的铵盐等具有阴离子基团的聚合物的盐。
作为阳离子型表面活性剂,可以列举例如:脂肪酸盐、烷基硫酸盐、烷基聚氧乙烯硫酸盐、烷基苯磺酸盐、烷基磷酸盐、磺基琥珀酸盐等。作为其具体例,可以列举:亚油酸钠、油酸钠、十二烷基磺酸钠、聚氧乙烯月桂基醚硫酸钠、十二烷基苯磺酸钠、聚氧乙烯烷基醚磷酸钠、乙基己基磺基琥珀酸钠等。
作为两性表面活性剂,可以列举例如烷基二甲基氧化胺、烷基羧基甜菜碱等。作为其具体例,可以列举:十二烷基二甲基氧化胺、月桂基二甲基氧化胺、十二烷基二甲基羧基甜菜碱、十二烷基二甲基酰胺丙基羧基甜菜碱等。
表面活性剂的量没有特别限制,可以根据所使用的水溶性高分子、水、分散质和表面活性剂的种类等适当决定。表面活性剂的量例如相对于水100质量份为0.01质量份以上且30质量份以下。
另外,出于乳液的进一步的稳定化、所得到的多孔体的特性提高等目的,可以添加水、分散质和表面活性剂以外的成分。
乳液的制备方法没有特别限制。优选首先制备水溶性高分子的水溶液。接着,在水溶性高分子的水溶液中添加分散质和表面活性剂等任选成分,然后使分散质分散在该水溶液中。
水溶性高分子的水溶液可以通过将水溶性高分子添加到水中并搅拌来进行制备。此时,可以进行加热。作为加热温度,例如为40℃以上且100℃以下。分散质向水溶性高分子的水溶液的分散可以根据公知方法进行。具体而言,可以列举例如:在常温下,在搅拌分散质和水溶性高分子的水溶液的同时进行混合的方法;将分散质和水溶性高分子的水溶液在加热下进行混合并冷却而进行乳化的方法等。
接着,对分散质除去工序进行说明。在该分散质除去工序中,将水和分散质汽化(特别是挥发)并除去。由于分散质沸点比水高,因此在该工序中,水比分散质优先汽化。随着水减少,水溶性高分子析出。此时,在乳液中分散着的沸点比水高的分散质大量残留,但是在水溶性高分子中分散并残留。由此,形成水溶性高分子的多孔状骨架。并且,高沸点的分散质通过汽化而被除去,从而生成孔隙,得到水溶性高分子的多孔体。
将水和分散质汽化的方法没有特别限制,可以列举例如:利用加热的方法、在减压下放置的方法、在减压下加热的方法、利用风干的方法等。这些方法可以与公知的干燥方法同样地实施。从操作的实施容易性的观点考虑,优选利用加热的方法。加热温度没有特别限制,优选为乳液不沸腾且水溶性高分子和分散质不分解的温度,更优选为50℃以上且150℃以下。在使水和分散质汽化期间,优选将乳液静置。
在要得到期望形状的多孔体的情况下,可以优选使用如下方法:在与该期望形状对应的形状的容器中加入乳液并对其加热。在要得到膜状多孔体的情况下,可以优选使用如下方法:在平板上以薄膜状涂布乳液并对其加热。
以如上的方式能够得到水溶性高分子的多孔体。所得到的水溶性高分子的多孔体可以根据水溶性高分子的种类而用于各种用途。作为用途的例子,可以列举:捆包材料、建筑材料、吸音材料、打扫用品、化妆用品、分离膜、吸附材料、纯化用载体、催化剂载体、培养载体等。
根据本发明,通过乳液的制备以及水和分散质的汽化这种简单操作,能够制造水溶性高分子的多孔体。在本发明中,不需要如现有技术那样进行冷却使成形体析出的操作和置换溶剂的操作。因此,本发明的水溶性高分子多孔体的制造方法在简便性上优良。
[实施例]
以下,对与本发明相关的实施例进行说明,但是并非意在将本发明限定于该实施例所示的方案中。
实施例1
在样品瓶中添加聚乙烯醇2质量份和水10质量份。将样品瓶加热至80℃~90℃,搅拌至聚乙烯醇完全溶解于水中,得到聚乙烯醇水溶液。在搅拌的同时在聚乙烯醇水溶液中添加十四烷5质量份和非离子型表面活性剂(聚氧乙烯十六烷基醚)1.5质量份,冷却至25℃。由此得到乳液。将得到的乳液通过流延涂布在铝板上。将其放入设定为120℃的干燥机中进行加热,将水和十四烷汽化并除去。以这样的方式,在铝板上得到薄膜。利用扫描型电子显微镜(SEM)观察得到的薄膜的截面,结果确认了薄膜为多孔体。作为参考,将实施例1中得到的薄膜的截面SEM照片示于图1。
实施例2
不添加非离子型表面活性剂,将作为分散质的十四烷的量从5质量份变更为10质量份,除此以外,通过与实施例1相同的方法得到薄膜。利用扫描型电子显微镜(SEM)观察得到的薄膜的截面,结果确认了薄膜为多孔体。
实施例3
将作为分散质的十四烷变更为十二烷,除此以外,通过与实施例1相同的方法得到薄膜。利用扫描型电子显微镜(SEM)观察得到的薄膜的截面,结果确认了薄膜为多孔体。
实施例4
不添加非离子型表面活性剂,将作为分散质的十四烷5质量份变更为十二烷10质量份,除此以外,通过与实施例1相同的方法得到薄膜。利用扫描型电子显微镜(SEM)观察得到的薄膜的截面,结果确认了薄膜为多孔体。
实施例5
在样品瓶中添加聚乙烯醇2质量份和水10质量份。将样品瓶加热至80℃~90℃,搅拌至聚乙烯醇完全溶解于水中,得到聚乙烯醇水溶液。在搅拌的同时,在聚乙烯醇水溶液中添加碳酸亚丙酯(2-氧代-4-甲基-1,3-二氧戊环)10质量份,冷却至25℃。由此得到乳液。将得到的乳液通过流延涂布在铝板上。将其放入设定为75℃的干燥机中进行加热,将水和碳酸亚丙酯汽化并除去。以这样的方式,在铝板上得到薄膜。利用扫描型电子显微镜(SEM)观察得到的薄膜的截面,结果确认了薄膜为多孔体。作为参考,将实施例5中得到的薄膜的截面SEM照片示于图2。
实施例6
在聚乙烯醇水溶液中添加阴离子型表面活性剂(丙烯酸类共聚物的铵盐)0.25质量份,将干燥机的温度变更为60℃,除此以外,通过与实施例5相同的方法得到薄膜。利用扫描型电子显微镜(SEM)观察得到的薄膜的截面,结果确认了薄膜为多孔体。
实施例7
将聚乙烯醇2质量份变更为羟乙基纤维素1质量份,将碳酸亚丙酯的量从10质量份变更为2质量份,除此以外,通过与实施例5相同的方法得到薄膜。利用扫描型电子显微镜(SEM)观察得到的薄膜的截面,结果确认了薄膜为多孔体。
实施例8
将聚乙烯醇的量变更为2.5质量份,将碳酸亚丙酯10质量份变更为碳酸亚丁酯(4-乙基-1,3-二氧戊环-2-酮)2.5质量份,除此以外,通过与实施例5相同的方法得到薄膜。利用扫描型电子显微镜(SEM)观察得到的薄膜的截面,结果确认了薄膜为多孔体。
实施例9
将聚乙烯醇的量变更为2.5质量份,将碳酸亚丙酯10质量份变更为十甲基环五硅氧烷7.5质量份,在聚乙烯醇水溶液中添加非离子型表面活性剂(聚甘油肉豆蔻酸酯)2.5质量份,除此以外,通过与实施例5相同的方法得到薄膜。利用扫描型电子显微镜(SEM)观察得到的薄膜的截面,结果确认了薄膜为多孔体。
将以上结果示于表1(需要说明的是,表中的“多孔化”栏的“○”表示已发生多孔化)。由表1的结果能够确认,通过本发明的方法能够制造水溶性高分子的多孔体。
表1
Claims (6)
1.一种水溶性高分子的多孔体的制造方法,所述制造方法包括:
制备乳液的工序,所述乳液包含水溶性高分子、水和分散质,其中所述水溶性高分子溶解且所述分散质分散在所述乳液中;以及
从所述乳液中将水和所述分散质汽化并除去的工序,
所述分散质的沸点高于水的沸点,所述水溶性高分子对所述分散质的溶解度低于对水的溶解度,
其中所述水溶性高分子在25℃下对水的溶解度为1质量%以上,且
其中所述分散质是在25℃下与水不相容的液体。
2.如权利要求1所述的制造方法,其中,
所述乳液还包含表面活性剂。
3.如权利要求1或2所述的制造方法,其中,
所述分散质的沸点与水的沸点之差为100℃以上。
4.如权利要求1或2所述的制造方法,其中,
所述分散质为烷烃化合物、碳酸亚烷基酯化合物或聚硅氧烷化合物。
5.如权利要求1或2所述的制造方法,其中,
所述水溶性高分子为具有羟基的水溶性高分子。
6.如权利要求1或2所述的制造方法,其中,
所述水溶性高分子为聚乙烯醇类聚合物。
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