CN116080220A - 一种三层复合聚乙烯醇缩丁醛海绵清洁滚筒及其制备方法 - Google Patents

一种三层复合聚乙烯醇缩丁醛海绵清洁滚筒及其制备方法 Download PDF

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CN116080220A
CN116080220A CN202211167463.8A CN202211167463A CN116080220A CN 116080220 A CN116080220 A CN 116080220A CN 202211167463 A CN202211167463 A CN 202211167463A CN 116080220 A CN116080220 A CN 116080220A
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徐守萍
吴慧
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Chunyu Technology Guangdong Co ltd
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South China University of Technology SCUT
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Abstract

本发明公开了一种三层复合聚乙烯醇缩丁醛清洁海绵滚筒及其制备方法，该滚筒包括圆管滚轴和三层海绵本体，海绵本体为三层互穿网络结构的聚乙烯醇缩丁醛海绵，且三层海绵一次成型，相互渗透。三层海绵当中，表面层的作用是快速吸水并将水传递到中间层，中间层的作用是锁定水分防止漏水，里层作用是确保海绵可以粘附于各种材质的滚轴表面。本发明的三层复合聚乙烯醇缩丁醛海绵清洁滚筒具有优良的吸水性、保水性能以及优异的粘附性能。此外该三层复合聚乙烯醇缩丁醛海绵清洁滚筒还具有较好的力学性能、快速的干态浸润速率，同时能够高效吸附阳离子型染料，可应用于清洁或染料废水处理等领域。

Description

一种三层复合聚乙烯醇缩丁醛海绵清洁滚筒及其制备方法
技术领域
本发明涉及海绵制品技术领域，具体涉及一种三层复合聚乙烯醇缩丁醛海绵清洁滚筒及其制备方法。
背景技术
聚乙烯醇缩甲醛海绵具有优异的耐化学品性、较强的耐酸碱性和较好的耐热性能，且干态质硬，耐磨性好，力学强度高，不仅避免了挤压变形等问题，还能够在很大程度上延长海绵清洁滚筒的使用寿命。同时聚乙烯醇缩甲醛海绵因其丰富的开孔结构和良好的水亲和力而具有很强的吸水能力，一般吸水量为其质量的6-8倍，湿时质地柔软，有弹性。
但是，甲醛毒性大，对于环境和人体的威胁极大，而且普通的聚乙烯醇缩醛海绵干态浸润速率慢，不能够快速吸水，且保水能力不强。专利TW1520793B《清洗用海绵体以及清洗方法》中提出了一种由一层具有阴离子性官能基的聚乙烯醇缩醛海绵构成的清洗海绵滚轮。但是这种海绵滚轮结构简单，保水能力不强，且需依靠胶水使海绵本体粘附于滚筒表面，不够环保，操作复杂。因此提出一种多层次聚乙烯醇缩丁醛海绵构成的清洗滚筒对于解决现有聚乙烯醇缩甲醛海绵滚筒制备原料毒性大、干态浸润速率慢、保水能力不强以及复杂的胶水粘附的问题具有重要意义。
发明内容
本发明的目的在于提供一种三层复合聚乙烯醇缩丁醛海绵清洁滚筒，以解决上述背景技术中提出的问题。
本发明的目的通过以下技术方案实现。
一种三层复合聚乙烯醇缩丁醛清洁海绵滚筒，包括圆管滚轴和三层海绵本体，所述圆管滚轴的外表面包覆有三层海绵本体，所述三层海绵本体结构均为由聚乙烯醇缩丁醛以及亲水高分子聚合物组成的互穿网络结构。
进一步地，所述圆管滚轴优选为ABS材质，其外壁上间隔1-5毫米处均匀分布着0.01-5mm高的圆型突起，从而提高海绵在材质表面的粘附力。
进一步地，圆管滚轴的外表面包覆的三层海绵由内到外依次为胶粘聚乙烯醇缩丁醛海绵、锁水聚乙烯醇缩丁醛海绵、快速吸水以及透水聚乙烯醇缩丁醛海绵。
进一步地，所述的胶粘聚乙烯醇缩丁醛海绵结构为聚乙烯醇缩丁醛与醋酸乙烯酯聚合物组成的互穿结构，确保海绵可以粘附于各种材质的滚轴表面。
进一步地，所述的锁水聚乙烯醇缩丁醛海绵结构为聚乙烯醇缩丁醛与丙烯酰胺聚合物组成的互穿结构，可以锁定水分防止漏水。
进一步地，所述的快速吸水以及透水聚乙烯醇缩丁醛海绵结构为聚乙烯醇缩丁醛与含磺酸基或羧基的聚合物组成的互穿结构，能够快速吸水并将水传递到中间层。
进一步地，所述三层海绵的厚度均为0.1-100mm，三层海绵一次成型，三层海绵间相互渗透密不可分。
上述一种三层复合聚乙烯醇缩丁醛清洁海绵滚筒的制备方法，包括以下步骤：
(1)向聚合度为1700-2400、醇解度为88mol％-99mol％的聚乙烯醇中加入蒸馏水，升温至95℃水浴加热搅拌1-2小时，得到聚乙烯醇水溶液，并平均分成3份；
(2)分别将3种不饱和烯烃类单体和引发剂溶于蒸馏水中，得到混合物溶液a、b、c；其中混合物溶液a为醋酸乙烯酯或醋酸乙烯酯与丙烯酸丁酯等丙烯酸酯类单体的混合物与引发剂溶于蒸馏水中得到；混合物溶液b为丙烯酰胺类单体和引发剂溶于蒸馏水中得到；混合溶液c为含磺酸基或羧基的烯烃类单体和引发剂溶于蒸馏水中得到；
(3)将步骤(2)中得到的混合物溶液a、b、c分别和步骤(1)中得到的3份聚乙烯醇水溶液混合均匀，得到混合物溶液a1、b1、c1；
(4)在步骤(3)中得到的混合物溶液a1、b1、c1中分别依次加入正丁醛、戊二醛、增塑剂、表面活性剂和稳泡剂，搅拌使其混合均匀，得到反应液a2、b2、c2；
(5)分别将步骤(4)中的反应液a2、b2、c2高速分散，使其发泡，得到混合物泡沫a3、b3、c3；
(6)在步骤(5)得到的混合物泡沫a3、b3、c3中分别加入稀硫酸溶液，混合均匀后从内向外依次注入模具，然后由内向外依次抽出第一层和第二层海绵之间的圆管隔层以及第二层和第三层海绵之间的圆管隔层，烘箱固化3-4小时，结束后将泡沫取出洗净，即得到三层复合聚乙烯醇缩丁醛清洁海绵滚筒。
进一步地，步骤(1)所述的聚乙烯醇水溶液的质量浓度为5％-16.67％，优选为14.28％。
进一步地，步骤(2)所述的引发剂为过硫酸钾、过硫酸铵和偶氮二异丁基脒中的一种或多种。
进一步地，步骤(4)所述的表面活性剂为OP-10、吐温80、司盘80、十二烷基硫酸钠、十二烷基苯磺酸钠中的一种或多种。
进一步地，步骤(4)所述的稳泡剂为十二烷基二甲基氧化铵、烷基醇胺、硅树脂聚醚乳液、硅油、L-580中的一种或多种。
进一步地，上述步骤中，各反应物的配比为：
不饱和烯烃类单体的用量为聚乙烯醇质量的11.11％-55.55％，优选为44.44％；
引发剂的用量为不饱和烯烃单体质量的0.4％-1％，优选为0.6％；
正丁醛的用量为聚乙烯醇质量的45.79％-91.59％，优选为82.43％；
戊二醛的用量为聚乙烯醇质量的1％-5％，优选为2.5％；
增塑剂的用量为聚乙烯醇质量的10％-50％，优选为23.4％；
表面活性剂的用量为聚乙烯醇质量的7％-14％，优选为10.5％；
稳泡剂的用量为聚乙烯醇质量的0.2％-1％，优选为0.2％；
稀硫酸溶液的用量为聚乙烯醇质量的5％-20％，优选为7％。
进一步地，步骤(6)所述固化的温度为50-80℃，优选为55℃。
进一步地，步骤(6)所述圆管隔层优选为PP材质，内外表均光滑，以便于抽出，且由内向外的两层圆管隔层半径依次增大，均大于圆管滚轴的半径。
本发明相对于现有技术具有如下优点和有益效果：
本发明的三层复合聚乙烯醇海绵清洁滚筒，胶粘层、高锁水层以及强吸水层三层海绵一次成型，相互渗透，依次包覆于滚筒表面。该海绵滚筒具有优异的吸水性和保水性以及粘附性能，可依靠海绵本身粘附于滚筒表面而无需使用胶水，绿色环保。而且相较于普通的海绵滚筒，该海绵滚筒还具有较好的力学性能、快速的干态浸润速率，能够快速吸水，同时能够高效吸附亚甲基蓝等阳离子型染料。可应用于清洁或染料废水处理等领域。
附图说明
图1是本发明的三层复合聚乙烯醇缩丁醛海绵清洁滚筒的结构示意图。
图2是本发明的三层复合聚乙烯醇缩丁醛海绵清洁滚筒的主视图。
图3是本发明的三层复合聚乙烯醇缩丁醛海绵成形时的模具示意图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明，但本发明的实施方式不限与此。
如图1和图2所示，一种三层复合聚乙烯醇缩丁醛清洁海绵滚筒，包括圆管滚轴1和海绵本体2、3、4。所述圆管滚轴为ABS材质，其外壁上间隔1-5毫米处均匀分布着0.01-5mm高的圆型突起。所述圆管滚轴1外表面依次包覆有海绵本体2、3、4。所述海绵本体2、3、4分别是胶粘聚乙烯醇缩丁醛海绵2，锁水聚乙烯醇缩丁醛海绵3，快速吸水以及透水聚乙烯醇缩丁醛海绵4。如图3所示，一种三层复合聚乙烯醇缩丁醛海绵成形时的模具，包括圆管隔层5、6，外模具7以及底板8，中心为圆管滚轴，往外依次为第一层海绵区域，第二层海绵区域，第三层海绵区域。所述圆管隔层为PP材质，内外表均光滑，以便于抽出，圆管隔层5、6半径均大于圆管滚轴1的半径，且圆管隔层6的半径大于圆管隔层5的半径。
实施例1
(1)在12g聚合度为2400、醇解度为99％的聚乙烯醇2499中加入228mL蒸馏水，升温至95℃水浴加热搅拌2小时，得到聚乙烯醇水溶液，并平均分成3份；
(2)将0.8888g醋酸乙烯酯和0.0036g过硫酸铵溶解于蒸馏水中，得到混合物溶液a；将0.8888g丙烯酰胺和0.0036g过硫酸铵溶解于蒸馏水中，得到混合物溶液b；将0.8888g2-丙烯酰胺-2-甲基丙磺酸钠和0.0036g过硫酸铵溶解于蒸馏水中，得到混合物溶液c；
(3)将步骤(2)中得到的混合物溶液a、b、c和步骤(1)中得到的3份聚乙烯醇水溶液分别混合均匀，得到混合物溶液a1、b1、c1；
(4)在步骤(3)中得到的混合物溶液a1、b1、c1中均依次加入1.8316g正丁醛、0.04g戊二醛、0.4g增塑剂、0.56g表面活性剂(OP-10、十二烷基硫酸钠和十二烷基苯磺酸钠)、以及0.024g稳泡剂(十二烷基二甲基氧化铵和L-580)，搅拌使其混合均匀，得到混合物溶液a2、b2、c2；
(5)将步骤(4)中得到的混合物溶液a2、b2、c2分别高速分散，使其发泡，得到混合物泡沫a3、b3、c3；
(6)在步骤(5)中得到的混合物泡沫a3、b3、c3中分别加入0.2g稀硫酸溶液混合均匀，由内向外依次注入模具，混合物泡沫a3倒入第一层海绵区域，混合物泡沫b3倒入第二层海绵区域，混合物泡沫c3倒入第三层海绵区域，然后由内向外依次抽出第一层和第二层海绵之间的圆管隔层以及第二层和第三层海绵之间的圆管隔层，烘箱80℃固化3小时，结束后将泡沫取出洗净，得到三层复合聚乙烯醇缩丁醛清洁海绵滚筒。
实施例2
(1)在12g聚合度为1700、醇解度为99％的聚乙烯醇1799中加入72.03mL蒸馏水，升温至95℃水浴加热搅拌2小时，得到聚乙烯醇水溶液，并平均分成3份；
(2)将1.7776g醋酸乙烯酯和丙烯酸丁酯的混合物和0.01067g过硫酸钾溶解于蒸馏水中，得到混合物溶液a；将1.7776g丙烯酰胺和0.01067g过硫酸钾溶解于蒸馏水中，得到混合物溶液b；将1.7776g 2-丙烯酰胺-2-甲基丙磺酸钠和0.01067g过硫酸钾溶解于蒸馏水中，得到混合物溶液c；
(3)将步骤(2)中得到的混合物溶液a、b、c和步骤(1)中得到的3份聚乙烯醇水溶液分别混合均匀，得到混合物溶液a1、b1、c1；
(4)在步骤(3)中得到的混合物溶液a1、b1、c1中均依次加入3.2972g正丁醛、0.1g戊二醛、0.936g增塑剂、0.42g表面活性剂(吐温80、十二烷基硫酸钠和十二烷基苯磺酸钠)、以及0.008g稳泡剂(硅油和L-580)，搅拌使其混合均匀，得到混合物溶液a2、b2、c2；
(5)将步骤(4)中得到的混合物溶液a2、b2、c2分别高速分散，使其发泡，得到混合物泡沫a3、b3、c3；
(6)在步骤(5)中得到的混合物泡沫中分别加入0.28g稀硫酸溶液混合均匀，由内向外依次注入模具，混合物泡沫a3倒入第一层海绵区域，混合物泡沫b3倒入第二层海绵区域，混合物泡沫c3倒入第三层海绵区域，然后由内向外依次抽出第一层和第二层海绵之间的圆管隔层以及第二层和第三层海绵之间的圆管隔层，烘箱55℃固化3小时，结束后将泡沫取出洗净，得到三层复合聚乙烯醇缩丁醛清洁海绵滚筒。
实施例3
(1)在12g聚合度为1700、醇解度为88％的聚乙烯醇1788中加入60mL蒸馏水，升温至95℃水浴加热搅拌2小时，得到聚乙烯醇水溶液，并平均分成3份；
(2)将2.222g醋酸乙烯酯和0.02g过硫酸钾溶解于蒸馏水中，得到混合物溶液a；将2.222丙烯酰胺和0.02g过硫酸钾溶解于蒸馏水中，得到混合物溶液b；将1.111g 2-丙烯酰胺-2-甲基丙磺酸钠和0.02g过硫酸钾溶解于蒸馏水中，得到混合物溶液c；
(3)将步骤(2)中得到的混合物溶液a、b、c和步骤(1)中得到的3份聚乙烯醇水溶液分别混合均匀，得到混合物溶液a1、b1、c1；
(4)在步骤(3)中得到的混合物溶液a1、b1、c1中均依次加入3.6636g正丁醛、0.2g戊二醛、2g增塑剂、0.56g表面活性剂(司盘80、十二烷基硫酸钠和十二烷基苯磺酸钠)、以及0.04g稳泡剂(烷基烯醇、硅树脂聚醚乳液和L-580)，搅拌使其混合均匀，得到混合物溶液a2、b2、c2；
(5)将步骤(4)中得到的混合物溶液a2、b2、c2分别高速分散，使其发泡，得到混合物泡沫a3、b3、c3；
(6)在步骤(5)中得到的混合物泡沫a3、b3、c3中分别加入0.8g稀硫酸溶液混合均匀，由内向外依次注入模具，混合物泡沫a3倒入第一层海绵区域，混合物泡沫b3倒入第二层海绵区域，混合物泡沫c3倒入第三层海绵区域，然后由内向外依次抽出第一层和第二层海绵之间的圆管隔层以及第二层和第三层海绵之间的圆管隔层，烘箱50℃固化4小时，结束后将泡沫取出洗净，得到三层复合聚乙烯醇缩丁醛清洁海绵滚筒。

Claims (10)

1.一种三层复合聚乙烯醇缩丁醛海绵清洁滚筒，其特征在于，包括圆管滚轴和三层海绵本体，所述圆管滚轴外壁上间隔1-5毫米处均匀分布着0.01-5mm高的圆型突起，所述圆管滚轴的外表面包覆有三层海绵本体，所述三层海绵本体结构均为由聚乙烯醇缩丁醛以及亲水高分子聚合物组成的互穿网络结构。
2.根据权利要求1所述的三层复合聚乙烯醇缩丁醛海绵清洁滚筒，其特征在于，圆管滚轴的外表面包覆的三层海绵由内到外依次为胶粘聚乙烯醇缩丁醛海绵、锁水聚乙烯醇缩丁醛海绵、快速吸水以及透水聚乙烯醇缩丁醛海绵。
3.根据权利要求2所述的三层复合聚乙烯醇缩丁醛海绵清洁滚筒，其特征在于，所述的胶粘聚乙烯醇缩丁醛海绵结构为聚乙烯醇缩丁醛与醋酸乙烯酯聚合物组成的互穿结构；所述的锁水聚乙烯醇缩丁醛海绵结构为聚乙烯醇缩丁醛与丙烯酰胺聚合物组成的互穿结构；所述的快速吸水以及透水聚乙烯醇缩丁醛海绵结构为聚乙烯醇缩丁醛与含磺酸基或羧基的聚合物组成的互穿结构。
4.根据权利要求2所述的三层复合聚乙烯醇缩丁醛海绵清洁滚筒，其特征在于，三层海绵的厚度均为0.1-100mm。
5.根据权利要求2所述的三层复合聚乙烯醇缩丁醛海绵清洁滚筒，其特征在于，三层海绵一次成型，三层海绵间相互渗透密不可分。
6.权利要求1-5任一项所述的三层复合聚乙烯醇缩丁醛海绵清洁滚筒的制备方法，其特征在于，包括以下步骤：
(1)向聚合度为1700-2400、醇解度为88mol％-99mol％的聚乙烯醇中加入蒸馏水，升温至95℃水浴加热搅拌1-2小时，得到聚乙烯醇水溶液，并平均分成3份；
(2)分别将3种不饱和烯烃类单体和引发剂溶于蒸馏水中，得到混合物溶液a、b、c；其中混合物溶液a由醋酸乙烯酯或醋酸乙烯酯与丙烯酸酯类单体的混合物与引发剂溶于蒸馏水中得到；混合物溶液b由丙烯酰胺类单体和引发剂溶于蒸馏水中得到；混合溶液c由含磺酸基或羧基的烯烃类单体和引发剂溶于蒸馏水中得到；
(3)将步骤(2)中得到的混合物溶液a、b、c分别和步骤(1)中得到的3份聚乙烯醇水溶液混合均匀，得到混合物溶液a1、b1、c1；
(4)在步骤(3)中得到的混合物溶液a1、b1、c1中分别依次加入正丁醛、戊二醛、增塑剂、表面活性剂和稳泡剂，搅拌使其混合均匀，得到反应液a2、b2、c2；
(5)分别将步骤(4)中的反应液a2、b2、c2高速分散，使其发泡，得到混合物泡沫a3、b3、c3；
(6)在步骤(5)得到的混合物泡沫a3、b3、c3中分别加入稀硫酸溶液，混合均匀后从内向外依次注入模具，然后由内向外依次抽出第一层和第二层海绵之间的圆管隔层以及第二层和第三层海绵之间的圆管隔层，烘箱50-80℃固化3-4小时，结束后将泡沫取出洗净，即得到三层复合聚乙烯醇缩丁醛清洁海绵滚筒。
7.根据权利要求6所述的三层复合聚乙烯醇缩丁醛海绵清洁滚筒的制备方法，其特征在于，步骤(2)所述的引发剂为过硫酸钾、过硫酸铵和偶氮二异丁基脒中的一种或多种。
8.根据权利要求6所述的三层复合聚乙烯醇缩丁醛海绵清洁滚筒的制备方法，其特征在于，步骤(4)所述的表面活性剂为OP-10、吐温80、司盘80、十二烷基硫酸钠、十二烷基苯磺酸钠中的一种或多种；步骤(4)所述的稳泡剂为十二烷基二甲基氧化铵、烷基醇胺、硅树脂聚醚乳液、硅油、L-580中的一种或多种。
9.根据权利要求6所述的三层复合聚乙烯醇缩丁醛海绵清洁滚筒的制备方法，其特征在于，各反应物配比为：
不饱和烯烃单体的用量为聚乙烯醇质量的11.11％-55.55％；
引发剂的用量为不饱和烯烃单体质量的0.4％-1％；
正丁醛的用量为聚乙烯醇质量的45.79％-91.59％；
戊二醛的用量为聚乙烯醇质量的1％-5％；
增塑剂的用量为聚乙烯醇质量的10％-50％；
表面活性剂的用量为聚乙烯醇质量的7％-14％；
稳泡剂的用量为聚乙烯醇质量的0.2％-1％；
稀硫酸溶液的用量为聚乙烯醇质量的5％-20％。
10.根据权利要求6-9任一项所述的三层复合聚乙烯醇缩丁醛海绵清洁滚筒的制备方法，其特征在于，步骤(6)所述圆管隔层内外表均光滑，且由内向外的两层圆管隔层半径依次增大，均大于圆管滚轴的半径。
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