CN113980167A - 一种丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物及其制备方法和应用 - Google Patents
一种丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及水凝胶技术领域，特别涉及丙烯酸‑丙烯酸钠‑磺酸内盐的共聚交联产物及其制备方法和应用，其制备方法为：在一干燥的反应器中加入准确称取的丙烯酸、氢氧化钠和磺酸内盐，用一定量的蒸馏水溶解，均匀搅拌加入交联剂和引发剂，氮封，恒温反应至体系无流动性，得粗产物，再经丙酮浸泡洗涤，抽滤后烘干粉碎过筛，得纯化后的产物；该产物使用价廉易得的丙烯酸为主要原料，辅以适量配比的抗盐敏功能单体磺酸内盐，产生协同效应，同时具备低成本和高抗盐的优点，可应用于水凝胶领域，作为吸水树脂应用在农林保水剂、药物缓释载体、化肥控释控释、高含盐废水中重金属离子吸附等盐环境下，应用前景广泛。
Description
【技术领域】
本发明属于水凝胶技术领域，特别涉及一种丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物及其制备方法和应用。
【背景技术】
吸水树脂是一类重要的功能高分子材料，能够吸收自身质量几十倍到上千倍的水，成为水凝胶，被广泛应用于医药缓释载体、仿生肌肉材料、农林保水剂、缓释控释化肥、生理卫生吸水剂、重金属离子吸附等诸多领域。在世界范围内，商业化的水凝胶中，丙烯酸基水凝胶占产品总量的80％以上。然而，丙烯酸基水凝胶存在严重的盐敏问题，当环境中有盐存在时，凝胶的使用性能急剧降低，限制了应用效果，例如，0.9wt％的NaCl(生理盐水)即可使其吸水率降低至初始值的十分之一以下[朱正，耐盐性丙烯酸系列高吸水树脂的合成与性能研究，中国海洋大学硕士论文，2014]，而环境中的Ca2+、Mg2+等高价态离子还会导致电解质聚沉，使水凝胶完全失去使用性能。
改善水凝胶的抗盐敏性能非常重要，一种方法是使用可聚合的内盐单体为原料，制备聚内盐型(又称为聚两性离子型)的水凝胶[董雯，新型耐温抗盐聚合物增黏剂的合成及性能评价，西安石油大学学报(自然科学版),2014,29(5)，75-79]。此种分子结构在盐环境中，受到盐的阳离子作用，内盐环逐渐打开，使分子链更为伸展，从而在盐水中有较好的溶胀吸水能力。但是，聚内盐型的水凝胶抗盐敏效果良好，却也存在两个缺陷：一是内盐环在淡水中难以扩张，产品吸淡水倍率很低；二是内盐单体成本较高，使得对应产品价格昂贵，商业竞争力有限。
【发明内容】
鉴于上述内容，有必要提供一种丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物，该产物同时具备低成本和高抗盐的优点，应用于水凝胶领域，作为吸水树脂应用在农林保水剂、药物缓释载体、化肥控释控释、高含盐废水中重金属离子吸附等盐环境下。
为达到上述目的，本发明所采用的技术方案是：
一种丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物，所述共聚交联产物的结构式如下：
其中，x+y＝0.5-0.9,x/y＝0.25-4,z＝0.09-0.5,k＝0.0001-0.01,x+y+k+z＝1。
上述比例为质量比。
本发明还提供丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物的制备方法，该方法包括如下步骤:
(1)在一干燥的反应器中加入丙烯酸、氢氧化钠和磺酸内盐，用蒸馏水溶解，均匀搅拌后加入交联剂和引发剂，氮封，恒温反应一段时间至体系无流动性，得粗产物；
(2)将所得粗产物经丙酮浸泡洗涤，抽滤后烘干粉碎过筛，得纯化后的产物，即所述丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物。
本发明中，进一步地，所述磺酸内盐为3-[N,N-二甲基-[2-(2-甲基丙-2-烯酰氧基)乙基]铵]丙烷-1-磺酸内盐；所述交联剂为N,N'-亚甲基双丙烯酰胺；所述引发剂为硝酸铈铵、过硫酸钠和亚硫酸氢钠的复合引发体系，其中，硝酸铈铵、过硫酸钠和亚硫酸氢钠的质量比为1:1-3:0.5-1.5。
反应方程式如下：
本发明中，进一步地，所述丙烯酸、氢氧化钠、磺酸内盐、交联剂和引发剂的质量比为1:0.1-0.4:0.1-1:0.0001-0.01:0.001-0.1。
本发明中，进一步地，所述步骤(1)的反应温度为40-80℃。
本发明中，进一步地，所述步骤(1)的反应时间为3-12h。
本发明还提供上述丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物的应用，具体是作为一种吸水树脂，应用于水凝胶领域。特别是在农林保水剂、药物缓释载体、化肥控释控释、高含盐废水中重金属离子吸附等盐环境下有着广泛的应用前景。
本发明至少具有如下有益效果：
1、本发明的丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物，使用价廉易得的丙烯酸为主要原料，辅以适量配比的抗盐敏功能单体磺酸内盐，该磺酸内盐是改善产物耐盐性的关键因素之一，磺酸内盐的加入量对产物的吸水率和耐盐性有重要影响，经申请人试验发现，若磺酸内盐与丙烯酸的质量比低于0.1，产物几乎无耐盐性，性能接近于常规的丙烯酸水凝胶，而若比例高于1，则因空间位阻效应，聚合反应难以进行，产物吸淡水率低，并且制备成本较高；除此之外，本申请在交联产物的制备过程中还以氢氧化钠作为催化剂，同时控制丙烯酸与氢氧化钠的质量比为1:0.1-0.4，并且在试验中发现，若氢氧化钠与丙烯酸的质量比低于0.1，则产物的羧酸根(-COO-)不足，在淡水中的吸水率低于100g/g，若氢氧化钠与丙烯酸的质量比高于0.4，则羧酸根过量、体系碱性过强、聚合反应难以进行，产物收率低，并且产物耐盐性差。同时加入适量的交联剂和引发剂，在本申请的配比中，原料产生协同效应，所得产物同时具备低成本和高抗盐的优点，反应条件温和，操作简单，收率高于95％。
2、本发明的丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物在淡水中的最大吸水率为186g/g，在盐质量浓度从0.1％到10％的整个区间吸水溶胀性能良好，不产生沉淀。
3、本发明利用丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物赋予水凝胶低成本、高吸水率和高抗盐等优点，在农林保水剂、药物缓释载体、化肥控释控释、高含盐废水中重金属离子吸附等盐环境下有非常广泛的应用前景。
【附图说明】
图1为丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物的FTIR图；
图2为实验例1产物吸淡水率-吸水时间的效果图；
图3为实验例2产物吸盐水率-盐质量浓度的效果图；
图4为实验例3产物与对比物在高浓度盐水中对铜离子的吸附效果对比图；
【具体实施方式】
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似改进，因此本发明不受下面公开的具体实施的限制。
实施例1：
本实施例提供一种丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物，其结构式如下：
使用PerkinElmer公司(USA)的FT-IR/FIR型红外光谱仪对产物分子中的各种官能团进行FTIR分析，结果如图1所示；
对红外谱图(图1)进行分析，可知：
1720cm-1附近是-COOH及-COOR的C＝O振动峰；
1550cm-1是-COO-的-O-C＝O振动特征峰；
1030cm-1附近是C-N振动峰；
1200cm-1是脂肪族磺酸盐的-SO3 -的反对称伸缩振动峰；
3300cm-1是-OH伸缩振动峰；
1450cm-1是甲基伸缩振动峰；
2900cm-1附近是亚甲基伸缩振动峰。
实施例2
本实施例提供一种丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物的制备方法，该制备方法包括如下步骤：
(1)将丙烯酸10g、氢氧化钠4g、磺酸内酯10g装入一干燥的反应器中，用100g蒸馏水溶解，搅拌均匀，再加入交联剂0.005g、硝酸铈铵0.2g、过硫酸钠0.4g、亚硫酸氢钠0.2g，通氮气排空后密封，在40℃恒温反应12小时得粗产物；
(2)将所得粗产物经500mL丙酮浸泡24h，抽滤后在50℃烘干，粉碎过100目筛得纯化产物即丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物，称重计算收率为96.8％。
实施例3
本实施例提供一种丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物的制备方法，该制备方法包括如下步骤：
(1)将丙烯酸10g、氢氧化钠2g、磺酸内酯5g装入反应器中，用80g蒸馏水溶解，搅拌均匀，再加入交联剂0.1g、硝酸铈铵0.1g、过硫酸钠0.3g、亚硫酸氢钠0.1g，通氮气排空后密封，在80℃恒温反应3小时得粗产物；
(2)将所得粗产物经500mL丙酮浸泡24h，抽滤后在50℃烘干，粉碎过100目筛得纯化产物即丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物，称重计算收率为98.9％。
实施例4
本实施例提供一种丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物的制备方法，该制备方法包括如下步骤：
(1)将丙烯酸20g、氢氧化钠6g、磺酸内酯14g装入反应器中，用160g蒸馏水溶解，搅拌均匀，再加入交联剂0.15g、硝酸铈铵0.3g、过硫酸钠0.5g、亚硫酸氢钠0.4g，通氮气排空后密封，在60℃恒温反应8小时得粗产物；
(2)将所得粗产物经1000mL丙酮浸泡24h，抽滤后在50℃烘干，粉碎过100目筛得纯化产物即丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物，称重计算收率为97.7％。
实验例1
产物的吸淡水性能测试：
水凝胶的吸水率是其吸水溶胀性能的重要参数，本实验使用溶胀称重法对产物的吸淡水性能进行测试，具体以实施例2所得的产物为例，称取0.2g样品，浸泡于100mL蒸馏水中一定时间后取出样品，用100目滤网过滤，称重计算吸水率。时间范围从5分钟至1200分钟，记录时间与吸水率的关系，结果见图2。
由图2的结果可知，产物在200分钟内达到吸水饱和，在淡水中的最大吸水率为186g/g，具有良好的吸淡水性能。例如：农林保水剂的行业标准(NY/T 886-2016)规定，水凝胶用做农林保水剂时，吸淡水率不小于100g/g；可见，实施例2所述的产物能够满足水凝胶应用领域的技术要求。
实验例2
产物的吸盐水性能测试：
水凝胶的吸盐水率是其抗盐敏性能的主要参数。本实验使用溶胀称重法对产物的吸盐水性能进行测试，以实施例2所得产物为例，称取0.2g样品，分别浸泡于不同盐浓度的100mL盐水中24h后取出样品，用100目滤网过滤，称重计算吸盐水率，结果见图3。
由图3的结果可知，在盐质量浓度从0.1wt％到10wt％的整个区间，产物的吸盐水率(特别是在高浓度盐水环境中)较高，且远超过NY/T 886-2016的产品要求，此外不会遇盐沉淀，抗盐敏性能良好。
实验例3
测试产物在高浓度盐水环境中，对Cu2+的吸附效果：
以实施例2所得产物为例，称取0.5g样品，浸泡于100mL的盐水溶液中(氯化钠质量浓度10％、铜离子初始浓度1000mg/L的混合溶液)，24h后拍照，并与对比物(对比物为丙烯酸水凝胶：原料中不含磺酸内盐，其余原料及制备过程与实施例2相同)进行比较。结果见图4，图中，左图为本申请实施例2所得产物的吸附效果，右图为对比物的吸附效果。
由图4的结果可知，产物在高浓度盐水环境中具有良好的溶胀和吸附效果，能够保持凝胶状态，而对比物水凝胶发生沉淀，无法保持凝胶状态。
实验例4
对不同原料配比所得产物进行效果对比：
申请人发现，不在本申请的原料配比范围内的产物，其可能出现吸水率低、耐盐性差、收率低、制备成本高等问题，比如：
1、当氢氧化钠与丙烯酸质量比为0.05:1(其他方法与实施例2相同)，所得产物在淡水中的最大吸水率为75g/g，低于农林保水剂的行业标准(NY/T 886-2016)产品要求；经分析，发现是由于产物的羧酸根(-COO-)不足，从而导致吸水率低；
2、当氢氧化钠与丙烯酸质量比为0.5:1(其他方法与实施例2相同)，所得产物的收率为63％，吸生理盐水(0.9wt％氯化钠)率为26g/g，低于农林保水剂的行业标准(NY/T886-2016)产品要求；经分析，发现是由于羧酸根(-COO-)过量、体系碱性过强、聚合反应难以进行，产物收率低，并且产物耐盐性差；
3、当磺酸内盐与丙烯酸的质量比为0.05:1(其他方法与实施例2相同)，所得产物吸生理盐水(0.9wt％氯化钠)率为23g/g，低于农林保水剂的行业标准(NY/T 886-2016)产品要求，吸高浓度盐水(2wt％及以上氯化钠)率接近1g/g；可见该产物几乎无耐盐性；
4、当磺酸内盐与丙烯酸的质量比高于1.2:1，所得产物收率为78％，在淡水中的最大吸水率为90g/g，低于农林保水剂的行业标准(NY/T 886-2016)产品要求；经分析发现是因空间位阻效应，聚合反应难以进行，导致的产物收率低、吸淡水率低，并且制备成本较高。
综合实验例1-3的结果可知，本申请所得丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物收率高于95％，在淡水中的最大吸水率为186g/g，在盐质量浓度从0.1％到10％的整个区间溶胀性能良好，不产生沉淀，该产物同时具备低成本、高收率、制备过程简单易于操作、高吸水率和高抗盐等优点，根据实验例4的结果可知，原料配比对产物的性能有着重要影响，因此，获取合适的原料配比，也是本申请研究的内容之一。
综上，本申请所得产物(丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物)可应用在水凝胶领域中，并赋予水凝胶相应(低成本、高吸水率和高抗盐等)的特性。
以上内容结合具体实施方式对本发明做出进一步详细说明，但本发明的具体实施不局限于这些说明。对于本发明所属技术领域，在不脱离本发明构思之前提下所作的若干简单推演或替换，都应视为属于本发明的保护范围。
Claims (7)
1.种丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物，其特征在于，所述共聚交联产物的结构式如下：
其中，x+y＝0.5-0.9,x/y＝0.25-4,z＝0.09-0.5,k＝0.0001-0.01,x+y+k+z＝1，比例为质量比。
2.一种制备如权利要求1所述的丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物的方法，其特征在于，该方法包括如下步骤:
(1)在一干燥的反应器中加入丙烯酸、氢氧化钠和磺酸内盐，用蒸馏水溶解，均匀搅拌后加入交联剂和引发剂，氮封，恒温反应一段时间，得粗产物；
(2)将所得粗产物经丙酮浸泡洗涤，抽滤后烘干粉碎过筛，得纯化后的产物，即所述丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物。
3.根据权利要求2所述的方法，其特征在于，所述磺酸内盐为3-[N,N-二甲基-[2-(2-甲基丙-2-烯酰氧基)乙基]铵]丙烷-1-磺酸内盐；所述交联剂为N,N'-亚甲基双丙烯酰胺；所述引发剂为硝酸铈铵、过硫酸钠和亚硫酸氢钠的复合引发体系，其中，硝酸铈铵、过硫酸钠和亚硫酸氢钠的质量比为1:1-3:0.5-1.5。
4.根据权利要求2所述的方法，其特征在于，所述丙烯酸、氢氧化钠、磺酸内盐、交联剂和引发剂的质量比为1:0.1-0.4:0.1-1:0.0001-0.01:0.001-0.1。
5.根据权利要求2所述的方法，其特征在于，所述步骤(1)的反应温度为40-80℃。
6.根据权利要求2所述的方法，其特征在于，所述步骤(1)的反应时间为3-12h。
7.如权利要求1所述的丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物和/或权利要求2-6任一项所述方法制备得到的丙烯酸-丙烯酸钠-磺酸内盐的共聚交联产物作为吸水树脂应用在农林保水剂、药物缓释载体、化肥控释控释、高含盐废水中重金属离子吸附等盐环境下。
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