CN107513116A - 一种聚乙烯醇水凝胶及其制备方法和用途 - Google Patents
一种聚乙烯醇水凝胶及其制备方法和用途 Download PDFInfo
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- C08F118/08—Vinyl acetate
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Abstract
本发明公开一种聚乙烯醇水凝胶及其制备方法和用途,其特点是将去离子水60‑80份,乳化剂0.1‑0.5份,醋酸乙烯20‑40份和引发剂0.2‑1.0份加入到反应釜中,搅拌30min,加入0.1‑1.0份催化剂,于温度5‑30℃,用泵将还原剂加入到上述反应釜中,随着还原剂的加入逐渐进行反应,还原剂在3h之内加完,继续反应3~h,停止搅拌,室温出料;将上述低温聚合得到的聚醋酸乙烯乳液在室温下静置,乳液pH值至酸性,随着时间推移,乳液出现破乳,失去流动性,体系内逐渐由乳白色变为透明凝胶状态;将凝胶取出,在去离子水中充分洗涤,去除其中的酸,盐杂质,得到聚乙烯醇水凝胶,经干燥后测定凝胶的吸水倍率为5‑10倍。它具有很好的力学强度,可作吸水填缝材料,保水材料,污水处理等领域。
Description
技术领域:
本发明涉及一种聚乙烯醇水凝胶及其制备方法和用途,属于功能高分子材料领域。
技术背景:
聚乙烯醇是一种多羟基聚合物,羟基之间容易形成氢键而结晶,同时羟基具有较高的反应活性,易与其他官能团化合物(如酸,醛,异氰酸酯,环氧氯丙烷,等)发生反应,因此通过物理(经典的方法为冻融循环法,通过多次冷冻解冻,聚乙烯醇分子间形成氢键和结晶微区而起到物理交联作用)或者化学方法(即加入各种能与羟基发生反应的而官能团化合物,在一定的催化剂体系中实现聚乙烯醇分子的交联),可以制备得到聚乙烯醇水凝胶。这些方法如中国专利CN103450489公开了一种聚乙烯醇在氧化剂及催化剂存在下的交联而得到一种水凝胶方法。中国专利CN104830001A利用冻融循环方法制备聚乙烯醇复合水凝胶的方法。中国专利CN105885064A一种利用硼化物交联聚乙烯醇制备水凝胶的方法。该类水凝胶具有一定的吸水倍率,较好的保水性,很好的力学强度,在很多方面获得了应用。如医用敷料,保水材料,重金属离子去除。
上述所能看到的聚乙烯醇凝胶一般都是将一定聚合度的聚乙烯醇在其良溶剂水或者DMSO中溶解为20%以下的浓度,然后施以物理或者化学方法获得一定程度交联的聚乙烯醇水凝胶。
发明内容:
本发明的目的是针对现有技术的不足而提供的一种聚乙烯醇水凝胶及其制备方法和用途,其特点是由低温聚合的聚醋酸乙烯乳液自动醇解得到的一种聚乙烯醇水凝胶,它具有方法新颖,路线独特,力学性能好,高透明性和高强度,高吸水倍率的优点。
本发明的目的由以下技术措施实现,其中所述原料份数除特殊说明外,均为重量份数。
一种聚乙烯醇水凝胶的起始原料组成组分以重量份计包括:
所述乳化剂为辛基苯酚聚氧乙烯醚类,烷基硫酸钠类或烷基磺酸钠中的至少一种。
所述催化剂为水溶性二价铁化合物,硫酸亚铁,氯化亚铁,溴化亚铁,碘化亚铁中的任一种。
所述引发剂体系为过硫酸铵和亚硫酸氢钠,过硫酸钾亚硫酸氢钠,双氧水硫酸亚铁等氧化还原引发剂体系中的任一种。
所述聚乙烯醇水凝胶的制备方法包括以下步骤:
(1)醋酸乙烯的低温乳液聚合
将去离子水60-80份加入到带有搅拌器,温度计和回流冷凝器的反应釜中,搅拌状态下加入乳化剂0.1-0.5份,醋酸乙烯单体20-40份和引发剂0.2-1.0份加入到反应釜中,充分搅拌乳化30~50min,加入催化剂0.1-1.0份,于温度5-30℃,用泵将还原剂慢慢加入到上述反应釜中,聚合反应随着还原剂的加入而逐渐进行,还原剂在3h之内加完,然后继续反应3~4h,停止搅拌,室温出料;
(2)聚乙烯醇水凝胶的制备
将上述低温聚合得到的聚醋酸乙烯乳液在室温下放置,静置或者通过添加无机酸调节乳液pH值至酸性,静置,随着时间推移,乳液出现破乳,失去流动性,使体系逐渐由乳白色转变为透明凝胶状态;
(3)将凝胶取出,用去离子水中充分洗涤,去除其中的酸,盐杂质,得到聚乙烯醇水凝胶。
所述无机酸为盐酸,硫酸,硝酸中的任一种。
所述聚乙烯醇水凝胶用于保水材料,种子包覆,农业及园艺;盆栽中水分保持剂,减少浇水次数。
结构表征与性能测试
1、观察乳液放置过程中的变化,详见图1所示,结果表明,图1a,1b中左边塑料瓶为对比乳液,右边为自动醇解乳液随时间的变化情况,明显的看到乳液转变为透明状态的过程,图1c为清洗后的水凝胶照片。
2、采用核磁共振测试聚乙烯醇水凝胶,结果详见图2所示,结果表明,在自动醇解过程中,对凝胶进行取样,洗涤,干燥,溶解在氘代二甲基亚砜中进行核磁氢谱分析,观察到醇解反应逐渐进行,醋酸根脱出,同时聚乙烯醇的羟基特征峰出现。随着醇解程度的加深,凝胶不再能溶解在任何溶剂中,说明交联结构存在。
3、采用吸水称重法测试聚乙烯醇水凝胶的吸水倍率为5-10倍。
本发明与现有技术相比具有如下优点:
(1)本发明不同于一般聚乙烯醇水凝胶的制备方法,不是以聚乙烯醇的溶解为起点,经过物理或者化学交联制备而成得到水凝胶。而是醋酸乙烯乳液聚合得到的乳液经自动醇解得到的聚乙烯醇水凝胶。
(2)为了实现醋酸乙烯的低温聚合,采用氧化还原引发体系,只能在30-50℃聚合,更低的温度条件下不能很好聚合。因此,在本发明引入了二价铁离子催化,成功的实现了5-30℃低温聚合反应。反应完成后,二价铁变成三价铁,在乳液放置过程中,会释放氢离子而催化聚醋酸乙烯水解,脱出醋酸根,在乳液中逐渐累积醋酸,而导致乳液pH值下降,水解速度加快,水解产生的自由基由于相互靠近而形成交联,最终达到一种平衡状态,形成透明的水凝胶。
附图说明
图1乳液放置过程中的外观变化;观察乳液放置过程中的变化,图1a,1b中左边塑料瓶为对比乳液,右边为自动醇解乳液随时间的变化情况,明显的看到乳液转变为透明状态的过程,图1c为清洗后的水凝胶照片;
图2聚乙烯醇凝胶,聚乙烯醇和聚醋酸乙烯核磁谱图;
图3凝胶吸水率测试。
具体实施方式
以下通过实施例对本发明进行具体的描述,有必要在此指出的是本实施例只对于本发明进行进一步说明,不能理解为对本发明保护范围的限制,该领域的技术熟练人员可以根据上述本发明的内容作出一些非本质的改进和调整。
实施例1.
将180g去离子水,1g烷基酚聚氧乙烯醚和0.5g十二烷基硫酸钠,120g醋酸乙烯酯加入到带有搅拌器,温度计和回流冷凝器的反应釜中,设定水浴温度为25℃,待温度稳定后,再加入过硫酸钾水溶液(0.4g过硫酸钾溶于40g去离子水)和氯化亚铁溶液(0.05g氯化亚铁溶于20g去离子水中)。同时控制蠕动泵使亚硫酸氢钠溶液(0.8g亚硫酸氢钠溶于40g去离子水中)在3h滴完。然后再继续反应3h,出料,室温静置。
在放置过程中,可以观察到乳液由可以流动的状态变成一个不具有流动性的乳白色固态,并由最初的乳白色逐渐变为透明。瓶内可检测到明显的醋酸存在。透明凝胶经过洗涤,彻底去除醋酸残留,得到强度良好的聚乙烯醇凝胶。
放置过程中取样分析结果表明,最初的样品可以溶解,表明这时醇解度还不高,而后期的样品已经不能溶解在常用溶剂中,表明随着醇解度的增加,形成了交联结构,最终形成凝胶。测定凝胶的吸水倍率为5倍。
实施例2.
将210g去离子水,0.5g烷基酚聚氧乙烯醚和0.5g十二烷基硫酸钠,120g醋酸乙烯酯加入到带有搅拌器,温度计和回流冷凝器的反应釜中,设定水浴温度为5℃,待温度稳定后,再加入双氧水溶液(0.2g溶于40g去离子水)和硫酸亚铁溶液(0.2g溴化亚铁溶于20g去离子水中)。同时控制蠕动泵使硫酸亚铁溶液(0.5g硫酸亚铁溶于40g去离子水中)在3h滴完。然后再继续反应3h,出料,向瓶内滴加2滴浓盐酸,搅匀,室温静置。
在放置过程中,可以观察到加酸体系的自动醇解速度比不额外加酸的体系快,乳液由可以流动的状态变成一个不具有流动性的乳白色固态,并由最初的乳白色逐渐变为透明。瓶内可检测到明显的醋酸存在。透明凝胶经过洗涤,彻底去除醋酸残留,得到强度良好的聚乙烯醇凝胶。测定凝胶的吸水倍率为8倍。
实施例3
将200g去离子水,0.15g烷基酚聚氧乙烯醚和0.15g十二烷基磺酸钠,100g醋酸乙烯酯加入到带有搅拌器,温度计和回流冷凝器的反应釜中,设定水浴温度为15℃,待温度稳定后,再加入过硫酸胺水溶液(0.3g过硫酸胺溶于40g去离子水)和硫酸亚铁溶液(0.3g硫酸亚铁溶于20g去离子水中)。同时控制蠕动泵使亚硫酸氢钠溶液(0.6g亚硫酸氢钠溶于40g去离子水中)在3h滴完。然后再继续反应3h,出料,向瓶内滴加1毫升1M硫酸溶液,搅匀,40℃放置。
在放置过程中,可以观察到加酸和升高放置温度可以明显加快自动醇解速度,乳液由可以流动的状态变成一个不具有流动性的乳白色固态,并由最初的乳白色逐渐变为透明。瓶内可检测到明显的醋酸存在。透明凝胶经过洗涤,彻底去除醋酸残留,得到强度良好的聚乙烯醇凝胶。测定凝胶的吸水倍率为10倍。
应用实例1
该方法得到的凝胶具有高至10倍的吸水倍率,作为潮湿环境中的填缝剂使用,吸水膨胀后的凝胶具有良好的强度。将粉碎为小颗粒的凝胶,填入3-5毫米,深10毫米的缝隙中,在缝隙中注入适量的水,24h之后,凝胶膨胀,将缝隙完全填满,强度好,不漏水。
应用实例2
该凝胶具有高的吸水倍率,且为多羟基特性,作为保水材料,用于种子包覆,农业及园艺,盆栽中水分保持剂使用,减少浇水次数。将一个直径为10厘米厚度为1厘米的圆盘状凝胶放置在花盆底部,上面盖上泥土,种上花草,浇水次数可以由每天一次减少到3-5天一次。
Claims (7)
1.一种聚乙烯醇水凝胶,其特征在于该水凝胶的起始原料组成组分以重量份计包括:
2.根据权利要求书1所述聚乙烯醇水凝胶,其特征在于乳化剂为辛基苯酚聚氧乙烯醚类,烷基硫酸钠类,烷基磺酸钠类中的至少一种。
3.根据权利要求书1所述聚乙烯醇水凝胶,其特征在于催化剂为水溶性二价铁化合物,硫酸亚铁,氯化亚铁,溴化亚铁,碘化亚铁中的任一种。
4.根据权利要求书1所述聚乙烯醇水凝胶,其特征在于引发剂体系为过硫酸铵和亚硫酸氢钠,过硫酸钾亚硫酸氢钠,双氧水硫酸亚铁等氧化还原引发剂体系中的任一种。
5.根据权利要求1~4之一所述聚乙烯醇水凝胶的制备方法,其特征在于该方法包括以下步骤:
(1)醋酸乙烯的低温乳液聚合
将去离子水60-80份加入到到带有搅拌器,温度计和回流冷凝器的反应釜中,搅拌状态下加入乳化剂0.1-0.5份,醋酸乙烯单体20-40份和引发剂0.2-1.0份加入到反应釜中,充分搅拌乳化30~50min,加入催化剂0.1-1.0份,于温度5-30℃,用泵将还原剂慢慢加入到上述反应釜中,聚合反应随着还原剂的加入而逐渐进行,还原剂在3h之内加完,然后继续反应3~4h,停止搅拌,室温出料;
(2)聚乙烯醇水凝胶的制备
将上述低温聚合得到的聚醋酸乙烯乳液在室温下放置,静置或者通过添加无机酸调节乳液pH值至酸性,静置,随着时间推移,乳液出现破乳,失去流动性,使体系逐渐由乳白色转变为透明凝胶状态;
(3)将凝胶取出,用去离子水中充分洗涤,去除其中的酸,盐杂质,得到聚乙烯醇水凝胶。
6.根据权利要求书5所述聚乙烯醇水凝胶,其特征在于无机酸为盐酸,硫酸,硝酸中的任一种。
7.根据权利要求书1所述聚乙烯醇水凝胶的用途,其特征在于该聚乙烯醇水凝胶用于保水材料,种子包覆,农业及园艺;盆栽中水分保持剂,减少浇水次数。
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