CN107189294A - 一种有机聚合物改性多糖水凝胶保护膜及其制备方法、应用 - Google Patents
一种有机聚合物改性多糖水凝胶保护膜及其制备方法、应用 Download PDFInfo
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- CN107189294A CN107189294A CN201710474461.6A CN201710474461A CN107189294A CN 107189294 A CN107189294 A CN 107189294A CN 201710474461 A CN201710474461 A CN 201710474461A CN 107189294 A CN107189294 A CN 107189294A
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Abstract
本发明公开了一种有机聚合物改性多糖水凝胶保护膜,它为有机聚合物改性多糖水凝胶溶液经溶剂水的蒸发后浓度增加所形成;其中,有机聚合物改性多糖水凝胶溶液包括有机聚合物共混改性多糖水凝胶溶液或者有机聚合物交联改性多糖水凝胶溶液或者有机聚合物接枝共聚改性多糖水凝胶溶液。本发明通过共混、交联、接枝共聚等物理、化学改性方法得到有机聚合物改性多糖水凝胶溶液,克服了现有技术中因多糖浓度过高无法喷涂或过早形成凝胶、材料重复性差、喷涂不美观等缺点,并提高了其作为保护膜的稳定性,保护建筑墙体免受涂鸦等污染物污染,是一种用于保护基底免受污染的水性组合物,常温下稳定美观的且易通过高压冲刷或温水除去。
Description
技术领域
本发明属于建筑领域,具体涉及一种有机聚合物改性多糖水凝胶保护膜及其制备方法、应用。
背景技术
当前,建筑表面经常受到涂鸦、灰尘、动物粪便等污染,需要耗费大量人力物力进行清洁。此外,混凝土材料属多孔物质在自然界中裸露,就会遭受雨水,紫外线,油污等的侵蚀,通常雨水为弱酸性,会使混凝土逐渐失去碱性,强度减弱、逐渐疏松,从而减弱寿命。传统建筑混凝土材料表面的保护方法,仅可保护基板免受雨水等侵蚀,但对涂鸦、鸟粪等污染移除无作用。
在US 5017237中描述了一种包含多糖水凝胶的保护涂层,受到污染后,可以轻易的被除去。但制备该多糖水凝胶水溶液时时,多糖的浓度受到限制,浓度过低不易成膜,浓度过高时粘度过大且容易过早形成凝胶。
在CN201180042866.3中描述了一种包含多糖凝胶颗粒的多糖涂层,由于包含凝胶颗粒,以允许在组合物中更高的多糖浓度,避免反复施涂。但是,由于多糖材料来源不同,材料批次间的差异明显,材料性能重复性差,并且暴露于湿气时膜得稳定性较差,并且由于凝胶中存在多糖颗粒影响成膜外观和透明度,施用在墙体建筑表面影响美观。
发明内容
本发明所要解决的技术问题是针对上述现有技术存在的不足而提供一种有机聚合物改性多糖水凝胶保护膜及其制备方法、应用,常温下稳定美观且易通过高压冲刷或温水除去,保护建筑墙体免受涂鸦等污染物污染。
本发明为解决上述提出的问题所采用的技术方案为:
一种有机聚合物改性多糖水凝胶保护膜,为有机聚合物改性多糖水凝胶溶液经溶剂水的蒸发后浓度增加所形成。其中,有机聚合物改性多糖水凝胶溶液包括有机聚合物共混改性多糖水凝胶溶液或者有机聚合物交联改性多糖水凝胶溶液或者有机聚合物接枝共聚改性多糖水凝胶溶液。
按上述方案,所述有机聚合物共混改性多糖水凝胶溶液为多糖或其衍生物和有机聚合物的混合水溶液。其中,有机聚合物包括聚乙烯吡咯烷酮、聚马来酸酐、聚季胺盐、聚丙烯酰胺、聚丙烯酸、聚乙烯醇、聚乙二醇等等水溶性有机聚合物,并不局限于此范围,水溶性有机聚合物均可应用于本发明。
该类有机物本身具有好的成膜性,可有效解决因多糖浓度过大,导致无法喷涂,同时避免多糖浓度低无法形成凝胶或需要反复喷涂的问题。
优选地,上述有机聚合物共混改性多糖水凝胶溶液的制备方法,主要步骤如下:
1)将多糖配置成多糖或其衍生物的凝胶水溶液,质量分数为0.1-15%;
2)向步骤1)所得水溶液中加入质量分数1%-20%为有机聚合物溶液,使有机聚合物与多糖或其衍生物的质量比为1:1-5:1,然后加热升温至80-90℃共混均匀,降温至40-50℃保温,保温2-4h,得到有机聚合物共混改性多糖水凝胶溶液。
按上述方案,所述有机聚合物交联改性多糖水凝胶溶液,为多糖或其衍生物和醛类有机物缩聚所得缩合物(即第一网络结构)再与亲水性单体丙烯酸及其他可聚合有机单体或其衍生物发生交联反应所得网络互穿结构水溶液。其中,有机醛选自甲醛、丙二醛、戊二醛等的一种或多种;丙烯酸单体及其他可聚合有机单体或其衍生物选自丙烯酸、甲基丙烯酸、丙烯酰胺、N-异丙基丙烯酰胺、丙烯磺酸、β-蒎烯和丙烯氰等中的一种或多种。其中,交联反应中需要引入引发剂和交联剂,在多糖或其衍生物和醛类有机物缩聚所得缩合物(即第一网络结构)的基础上引入引发剂(如过硫酸铵)、交联剂(如N,N’-亚甲基双丙烯酰胺)引发自由基聚合,得到双网络互穿结构的多糖水凝胶。由于丙烯酸或其衍生物与第一网络结构之间存在氢键、静电等作用,可以提高所得到双网络互穿结构的多糖水凝胶的机械强度和稳定性。
优选地,上述有机聚合物交联改性多糖水凝胶溶液的制备方法,主要步骤如下:
1)将多糖或其衍生物与有机醛按质量比1:1-1:10在水溶液中混合,混合物的总浓度1%-10%,然后在50-80℃下进行缩聚反应,反应时间为5-8小时,得多糖与有机醛的第一网络结构水凝胶溶液;
2)将与多糖质量比1:1-1:20的单体丙烯酸加碱中和,中和度为80%,然后加入与多糖质量比1:1-1:20的共聚单体丙烯酸衍生物,再与步骤1)所得溶液混合均匀,然后依次加入单体用量0.1wt%-5wt%的引发剂和单体用量0.05wt%-0.5wt%的交联剂,继而升温至60℃-80℃发生聚合反应,得到具有双网络结构的有机聚合物交联改性多糖水凝胶溶液。
按上述方案,所述有机聚合物接枝共聚改性多糖水凝胶溶液,为多糖或其衍生物和有机物单体聚合所形成的聚合物水溶液。其中,所述有机物单体主要为丙烯酸及其他可聚合有机单体或其衍生物,如丙烯酸、甲基丙烯酸、丙烯酰胺、N-异丙基丙烯酰胺、丙烯磺酸和丙烯氰等中的一种或多种。其中,接枝共聚反应中需要引入引发剂(如过硫酸铵)、交联剂(如N,N’-亚甲基双丙烯酰胺)引发聚合反应。
优选地,上述有机聚合物接枝共聚改性多糖水凝胶溶液的制备方法,主要步骤如下:
1)将多糖配置成多糖或其衍生物的凝胶水溶液,质量分数为0.1-5%;
2)将与多糖质量比1:1-1:20的单体丙烯酸加碱中和,中和度为80%,然后加入与多糖质量比1:1-1:20的共聚单体丙烯酸衍生物,再与步骤1)所得水溶液混合均匀;然后依次加入单体用量0.1wt%-5wt%的引发剂和单体用量0.05wt%-0.5wt%的交联剂,,继而升温至40℃-80℃发生聚合反应,形成有机聚合物接枝共聚改性多糖水凝胶溶液。
本发明水溶液中所选用的多糖或多糖衍生物,包括但不限于植物衍生的多糖、微生物多糖或藻类多糖,如角结冷胶、果胶、阿拉伯胶、黄蓍胶、刺梧桐胶、茄替胶、刺槐豆胶、瓜尔胶、车前籽胶、温柏籽胶、枣胶、松胶等,多糖淀粉如羟甲基淀粉、羟乙基淀粉、纤维素多糖、菊糖、海藻酸、叉菜胶、琼脂等,以及上述多糖或者衍生物中的一种或几种。
本发明所述有机聚合物改性多糖水凝胶溶液通过喷涂、刷涂方法形成保护膜,可以对建筑物等表面形成保护,免受涂鸦等污染物污染。该保护膜的清除方法包括高压冲刷(100巴-200巴)或温水(50-70℃)冲洗,可以将该保护膜和污染物同时除去。
与现有技术相比,本发明的有益效果是:
本发明通过共混、交联、接枝共聚等物理、化学改性方法得到有机聚合物改性多糖水凝胶溶液,克服了现有技术中因多糖浓度过高无法喷涂或过早形成凝胶、材料重复性差、喷涂不美观等缺点,并提高了其作为保护膜的稳定性,保护建筑墙体免受涂鸦等污染物污染,是一种用于保护基底免受污染的水性组合物,常温下稳定美观的且易通过高压冲刷或温水除去。
附图说明
图1为实施例1的所得有机聚合物共混改性多糖水凝胶
图2为实施例1所得有机聚合物共混改性多糖水凝胶喷涂于混凝土表面后的保护膜,白色线条内区域为保护膜区。
图3为实施例1所得保护膜使用20℃的水冲洗后的情况。
图4为实施例1所得保护膜使用60℃的水冲洗后的情况。
具体实施方式
为了更好地理解本发明,下面结合实施例进一步阐明本发明的内容,但本发明不仅仅局限于下面的实施例。
实施例1
一种有机聚合物共混改性多糖水凝胶,为刺槐豆胶与黄原胶和聚乙烯醇(分子量400)的混合水溶液,其中刺槐豆胶与黄原胶质量比3:1,多糖(刺槐豆胶与黄原胶之和)和聚乙烯醇质量比为1:5,混合水溶液中多糖的浓度为0.3%。
上述有机聚合物共混改性多糖水凝胶的制备方法,具体步骤如下:
(1)按质量比3:1选取多糖刺槐豆胶与黄原胶质量比3:1,配制成多糖总浓度为0.3%的100ml水溶液,于90℃机械搅拌均匀;
(2)在85℃下,配制质量分数8%的聚乙烯醇水溶液,然后加入到步骤(1)所得水溶液中(多糖总量和聚乙烯醇质量比为1:5)进行共混,继续加热0.5h,然后降至40℃保温,得有机聚合物共混多糖水凝胶溶液(如图1所示)。
将本实施例所得有机聚合物共混多糖水凝胶溶液采用自动空气喷涂设备喷涂于混凝土表面,在室温下干燥12h形成保护膜(如图2所示)。该保护膜经20℃的水冲洗,保护膜无法去除(如图3所示),同时在湿润情况下,混凝土与保护膜界限较为明显,干燥情况下如图2所示,界限不明显,视觉效果上没有明显区别;经60℃的水冲洗,可以很容易地去除保护膜(如图4所示)。
实施例2
一种有机聚合物共混改性多糖水凝胶,为刺槐豆胶与黄原胶和聚乙烯醇(分子量400)的混合水溶液,其中刺槐豆胶与黄原胶质量比3:1,多糖(刺槐豆胶与黄原胶之和)和聚乙烯醇质量比为1:5,混合水溶液中多糖的浓度为2%。
上述有机聚合物共混改性多糖水凝胶的制备方法,具体步骤如下:
(1)按质量比3:1选取多糖刺槐豆胶与黄原胶质量比3:1,配制成多糖总浓度为2%的100ml水溶液,于90℃机械搅拌均匀;
(2)在85℃下,配制质量分数8%的聚乙烯醇水溶液,然后加入到步骤(1)所得水溶液中(多糖总量和聚乙烯醇质量比为1:5)进行共混,继续加热0.5h,然后降至40℃保温,得有机聚合物共混多糖水凝胶溶液。
将本实施例所得有机聚合物共混多糖水凝胶溶液采用自动空气喷涂设备喷涂于混凝土表面,在室温下干燥12h形成保护膜,然后采用涂鸦喷漆进行喷涂,经60℃的水冲洗,喷涂的涂鸦可以很容易地和保护膜一同去除。
实施例3
一种有机聚合物交联改性多糖水凝胶,具体步骤如下:
(1)按质量比3:1选取多糖刺槐豆胶与黄原胶质量比3:1,配制成多糖总浓度为1%的100ml水溶液,于90℃机械搅拌均匀,缓慢加入丙二醛3g,继续加热3h,得多糖与醛类有机物的第一网络结构水凝胶溶液;
(2)在冰水浴中,将5g丙烯酸单体用25%的NaOH溶液中和,加入5g共聚单体丙烯酰胺,然后与步骤(2)水溶液混合搅拌均匀;
(3)在70℃下,向步骤(2)水溶液中加入两单体总质量1%引发剂过硫酸铵及0.1%交联剂N,N’-亚甲基双丙烯酰胺,反应3h,将所得的溶液在4℃保持18小时,具有双网络结构的有机聚合物交联改性多糖水凝胶溶液。
将本实施例所得有机聚合物交联改性多糖水凝胶溶液采用自动空气喷涂设备喷涂,在室温下干燥18h,采用涂鸦喷漆进行喷涂于铝基表面上,使用60℃的水,施用的涂鸦可以很容易地和涂层一同去除。
实施例4
一种有机聚合物交联改性多糖水凝胶,具体步骤如下:
(1)按质量比3:1选取多糖刺槐豆胶与黄原胶质量比3:1,配制成多糖总浓度为2%的100ml水溶液,于90℃机械搅拌均匀,缓慢加入戊二醛3g,继续加热3h,得多糖与醛类有机物的第一网络结构水凝胶溶液;
(3)在冰水浴中,将5g丙烯酸单体用16g 25%的NaOH溶液中和80%的丙烯酸,然后加入5g共聚单体丙烯酰胺,再与步骤(2)水溶液混合搅拌均匀;
(4)在70℃下,向步骤(2)水溶液中加入两单体总质量的2%引发剂过硫酸铵及0.1%交联剂N,N’-亚甲基双丙烯酰胺,反应3h,将所得的溶液在4℃保持18小时,具有双网络结构的有机聚合物交联改性多糖水凝胶溶液,。
将本实施例所得有机聚合物交联改性多糖水凝胶溶液采用自动空气喷涂设备喷涂,在室温下干燥18h,采用涂鸦喷漆进行喷涂于铝基表面上,使用60℃的水,施用的涂鸦可以很容易地和涂层一同去除。
实施例5
一种有机聚合物接枝改性多糖水凝胶,为刺槐豆胶与黄原胶经丙烯酸、丙烯酰胺接枝改性后的混合水溶液,其中刺槐豆胶与黄原胶质量比3:1,多糖(刺槐豆胶与黄原胶之和)和丙烯酸、丙烯酰胺的质量比为3:5:5,混合水溶液中多糖的浓度为3%。
上述有机聚合物接枝改性多糖水凝胶的制备方法,具体步骤如下:
(1)按质量比3:1选取多糖刺槐豆胶与黄原胶质量比3:1,配制成多糖总浓度为3%的100ml水溶液,于90℃机械搅拌均匀;
(2)在冰水浴中,将5g丙烯酸用25%的NaOH溶液中和,加入5g共聚单体丙烯酰胺,然后与加入步骤(1)水溶液混合搅拌均匀;
(3)在70℃下,向步骤(2)水溶液中加入两单体质量的1%引发剂过硫酸铵及0.1%交联剂N,N’-亚甲基双丙烯酰胺,反应3h,将所得的溶液在4℃保持18小时,得到有机聚合物接枝改性多糖水凝胶溶液。
将本实施例所得有机聚合物共混多糖水凝胶溶液采用自动空气喷涂设备喷涂,在室温下干燥18h,采用涂鸦喷漆进行喷涂于铝基表面上,使用60℃的水,施用的涂鸦可以很容易地和涂层一同去除。
以上所述仅是本发明的优选实施方式,应当指出,对于本领域的普通技术人员来说,在不脱离本发明创造构思的前提下,还可以做出若干改进和变换,这些都属于本发明的保护范围。
Claims (10)
1.一种有机聚合物改性多糖水凝胶保护膜,其特征在于它为有机聚合物改性多糖水凝胶溶液经溶剂水的蒸发后浓度增加所形成;其中,有机聚合物改性多糖水凝胶溶液包括有机聚合物共混改性多糖水凝胶溶液或者有机聚合物交联改性多糖水凝胶溶液或者有机聚合物接枝共聚改性多糖水凝胶溶液。
2.根据权利要求1所述的一种有机聚合物改性多糖水凝胶保护膜,其特征在于所述有机聚合物共混改性多糖水凝胶溶液为多糖或其衍生物和有机聚合物的混合水溶液,有机聚合物包括但不限于聚乙烯吡咯烷酮、聚马来酸酐、聚季胺盐、聚丙烯酰胺、聚丙烯酸、聚乙烯醇、聚乙二醇。
3.根据权利要求2所述的一种有机聚合物改性多糖水凝胶保护膜,其特征在于所述有机聚合物共混改性多糖水凝胶溶液的制备方法,主要步骤如下:
1)将多糖配置成多糖或其衍生物的凝胶水溶液,质量分数为0.1-15%;
2)向步骤1)所得水溶液中加入质量分数1%-20%为有机聚合物溶液,使有机聚合物与多糖或其衍生物的质量比为1:1-5:1,然后加热升温至80-90℃共混均匀,降温至40-50℃保温,保温2-4h,得到有机聚合物共混改性多糖水凝胶溶液。
4.根据权利要求1所述的一种有机聚合物改性多糖水凝胶保护膜,其特征在于所述有机聚合物交联改性多糖水凝胶溶液,为多糖或其衍生物和有机醛缩聚所得缩合物再与亲水性单体丙烯酸及其他可聚合有机单体或其衍生物发生交联反应所得网络互穿结构水溶液。
5.根据权利要求4所述的一种有机聚合物改性多糖水凝胶保护膜,其特征在于有机醛选自甲醛、丙二醛、戊二醛等有机醛中的一种或多种;丙烯酸单体及其他可聚合有机单体或其衍生物选自丙烯酸、甲基丙烯酸、丙烯酰胺、N-异丙基丙烯酰胺、丙烯磺酸、β-蒎烯和丙烯氰中的一种或多种。
6.根据权利要求4所述的一种有机聚合物改性多糖水凝胶保护膜,其特征在于所述有机聚合物交联改性多糖水凝胶溶液的制备方法,主要步骤如下:
1)将多糖或其衍生物与有机醛按质量比1:1-1:10在水溶液中混合,混合物的总浓度1%-10%,然后在50-80℃下进行缩聚反应,反应时间为5-8小时,得多糖与有机醛的第一网络结构水凝胶溶液;
2)将与多糖质量比1:1-1:20的单体丙烯酸加碱中和,中和度为80%,然后加入与多糖质量比1:1-1:20的共聚单体丙烯酸衍生物,再与步骤1)所得溶液混合均匀,然后依次加入单体用量0.1wt%-5wt%的引发剂和单体用量0.05wt%-0.5wt%的交联剂,继而升温至60℃-80℃发生聚合反应,得到具有双网络结构的有机聚合物交联改性多糖水凝胶溶液。
7.根据权利要求1所述的一种有机聚合物改性多糖水凝胶保护膜,其特征在于所述有机聚合物接枝共聚改性多糖水凝胶溶液,为多糖或其衍生物和有机物单体聚合所形成的聚合物水溶液;所述有机物单体主要为丙烯酸及其他可聚合有机单体或其衍生物。
8.根据权利要求7所述的一种有机聚合物改性多糖水凝胶保护膜,其特征在于所述有机聚合物接枝共聚改性多糖水凝胶溶液的制备方法,主要步骤如下:
1)将多糖配置成多糖或其衍生物的凝胶水溶液,质量分数为0.1-5%;
2)将与多糖质量比1:1-1:20的单体丙烯酸加碱中和,中和度为80%,然后加入与多糖质量比1:1-1:20的共聚单体丙烯酸衍生物,再与步骤1)所得水溶液混合均匀;然后依次加入单体用量0.1wt%-5wt%的引发剂和单体用量0.05wt%-0.5wt%的交联剂,,继而升温至40℃-80℃发生聚合反应,形成有机聚合物接枝共聚改性多糖水凝胶溶液。
9.根据权利要求1所述的一种有机聚合物改性多糖水凝胶保护膜,其特征在于所选用的多糖或多糖衍生物,包括但不限于植物衍生的多糖、微生物多糖或藻类多糖,多糖淀粉以及上述多糖或者衍生物中的一种或几种。
10.权利要求1所述的有机聚合物改性多糖水凝胶作为建筑物的反涂鸦膜以及作为各种结构材料的表面防护应用。
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