CN112409529B - 基于丙烯酸/二甲基二烯丙基氯化铵制备聚丙烯酸钠的方法及应用 - Google Patents

基于丙烯酸/二甲基二烯丙基氯化铵制备聚丙烯酸钠的方法及应用 Download PDF

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CN112409529B
CN112409529B CN202011260582.9A CN202011260582A CN112409529B CN 112409529 B CN112409529 B CN 112409529B CN 202011260582 A CN202011260582 A CN 202011260582A CN 112409529 B CN112409529 B CN 112409529B
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陈娓
曹广宇
施庆
徐晓峰
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Abstract

本发明公开了基于丙烯酸/二甲基二烯丙基氯化铵制备聚丙烯酸钠的方法及应用,将丙烯酸与二甲基二烯丙基氯化铵的混合物、引发剂溶液、链转移剂溶液同时滴入反应槽中,滴加完成后恒温,然后中和至酸性,得到聚丙烯酸钠。将水、锆珠、碳酸钙与聚丙烯酸钠混合,研磨,实现碳酸钙的分散。实验结果表明,本发明制备的PAANa的分子量在1000~7000范围内,研磨效果好。

Description

基于丙烯酸/二甲基二烯丙基氯化铵制备聚丙烯酸钠的方法 及应用
技术领域
本发明属于分散剂制备技术,具体涉及基于丙烯酸/二甲基二烯丙基氯化铵制备聚丙烯酸钠的方法及应用。
背景技术
在造纸行业中,碳酸钙作为造纸涂料现已广泛应用,然而大理石必须经过机械粉碎、研磨、分级,才可制成细微的颗粒,方可用于纸张涂料的制备。分散剂在碳酸钙中达到的效果是制备高固含、低粘度的碳酸钙浆料。分散剂主要是靠吸附在颜料颗粒表面,产生静电斥力和空间位阻,从而使得颗粒能以悬浮态稳定地存在,研磨效率也得以提高,并能节约研磨所需耗费的能量。现有技术公开了一种利用特种丙烯酸酯废水制备固色剂的工艺方法,将合成特定丙烯酸酯产生的废液作为原料,对废液中的原料丙烯酸和丙烯酸酯进行再利用,将废液、所述二甲基二烯丙基氯化铵、引发剂、链转移剂混合制备得到固色剂,尤其是阳离子聚合物型固色剂,实现了废水的深度资源化利用与近零排放,创造了新的工业产出,且制得的固色剂与市场上其他同类产品进行对比后,经过固色剂处理后织物的色牢度都达到国标的4级以上,使用的效果不输于同类产品,甚至优于同类产品。现有技术涉及一种聚丙烯酸钠的合成方法,属于食品添加剂及其制备方法领域,所述的聚丙烯酸钠的合成方法,包括以下步骤:在丙烯酸中加入氢氧化钠水溶液,调节pH至7-8,在中和液中加入引发剂到薄板反应器中,反复抽真空充氮气三次,于最适温度下聚合得到凝胶状产品,经造粒、干燥、粉碎、包装得产品,合成方法具有工艺简单、可操作性强,适用于工业化生产以及产品质量高等特点,应用实验表明,聚丙烯酸钠具有良好的增稠、增筋、稳定、保鲜等效果,性能达到进口同类产品的先进水平。现有技术公开了一种无色透明聚丙烯酸钠分散剂的制备方法,通过聚合起始阶段光辅助引发聚合,合成低分子量聚合丙烯酸,聚合丙烯酸在用氢氧化钠中和的过程中,持续照射紫外光或可见光,最后,在合成的聚合物中加入一定量的过氧化苯甲酰达到相应的脱色和防腐的效果。现有技术制备出一种聚丙烯酸钠分散剂,该聚丙烯酸钠分散剂呈现无色透明状态,采用分光光度计测试其色度优异,在应用领域中达到了很好的效果,该分散剂制备方法简单,成本低廉,同时具有产品性能稳定,分散性能好的特点。但是现有技术制备的聚丙烯酸钠对无机填料的分散性还需提升。
发明内容
本发明公开了新的制备聚丙烯酸钠的方法,采用如下技术方案:
基于丙烯酸/二甲基二烯丙基氯化铵制备的聚丙烯酸钠,其制备方法包括以下步骤,以丙烯酸、二甲基二烯丙基氯化铵为原料,以过硫酸铵为引发剂、次磷酸钠为链转移剂,制备聚丙烯酸钠。
本发明中,基于丙烯酸/二甲基二烯丙基氯化铵制备聚丙烯酸钠的方法为,将丙烯酸与二甲基二烯丙基氯化铵的混合物、引发剂溶液、链转移剂溶液同时滴入反应槽中,滴加完成后恒温,然后中和至酸性,得到聚丙烯酸钠。
本发明公开了一种研磨分散碳酸钙的方法,包括以下步骤,将丙烯酸与二甲基二烯丙基氯化铵的混合物、引发剂溶液、链转移剂溶液同时滴入反应槽中,滴加完成后恒温,然后中和至酸性,得到聚丙烯酸钠;将水、锆珠、碳酸钙与聚丙烯酸钠混合,研磨,实现碳酸钙的分散。研磨为常规手段,且锆珠及其使用也为常规方法,本发明的创造性在于采用限定制备方法得到新的聚丙烯酸钠,用于分散碳酸钙具有优异的粘度性能。
本发明中,丙烯酸、二甲基二烯丙基氯化铵、过硫酸铵、次磷酸钠的质量比为(200~800)∶(100~400)∶(10~100)∶(10~100);优选为(200~600)∶(100~200)∶(10~60)∶(10~60)。
进一步的,反应槽的温度为80℃,恒温也为80℃,恒温时间为30分钟;利用液碱中和,优选的,酸性的PH值为5~6;本发明中和至酸性,无需提纯步骤,直接得到聚丙烯酸钠水溶液,可以直接作为造纸分散剂使用,也可干燥得到聚丙烯酸钠保存。
本发明首次采用自由基共聚合法,以丙烯酸和二甲基二烯丙基氯化铵为原料,分别选过硫酸铵为引发剂和次磷酸钠为链转移剂,合成聚丙烯酸钠(PAANa);用红外光谱表征了所合成的PAANa的结构,以乌氏粘度计和Mark-HouwinkSakurad方程[η]=K*Mv~α测定了合成产物的粘均分子量,以分散碳酸钙涂料安定性为指标表征其分散能力;结果表明,本发明制备的PAANa的分子量在1000~7000范围内,研磨效果好。
附图说明
图1为得到的产物聚丙烯酸钠的核磁图;
图2为得到的产物聚丙烯酸钠的红外图。
具体实施方式
本发明所有原料为市售常规原料,具体操作方法以及测试方法为本领域常规方法。
实施例一
以丙烯酸和二甲基二烯丙基氯化铵为原料,分别选过硫酸铵为引发剂和次磷酸钠为链转移剂,合成聚丙烯酸钠(PAANa),具体如下:
1、配方如下:
Figure BDA0002774509830000031
2、制备工艺:
(1)将丙烯酸与二甲基二烯丙基氯化铵混合,得到混合物;
(2)主反应槽升温至80℃,常规搅拌下,三项(上述混合物、过硫酸铵水溶液(8wt%)、次磷酸钠水溶液(8wt%))一同滴入主反应槽,8小时滴完,滴定结束恒温半小时;然后自然降温至40℃以下,用液碱中和至酸性(PH值5.5),不需要提纯,得到聚丙烯酸钠水溶液,烘干,得到聚丙烯酸钠;图1为得到的产物聚丙烯酸钠的核磁图,图2为得到的产物聚丙烯酸钠的红外图。
3、产品表征、测试
以乌氏粘度计和Mark-HouwinkSakurad方程[η]=K*Mv~α测定了合成产物的粘均分子量;以分散碳酸钙涂料安定性为指标表征其分散能力,将水、锆珠、碳酸钙与上述制备的聚丙烯酸钠混合,常规研磨,一段时间后检粒径要求占比满足要求后,测浆料黏度,结果见表1编号3,其中碳酸钙与聚丙烯酸钠的重量比为100:1,碳酸钙初始粒径为150μm;研磨要求为碳酸钙粒径<2μm占比99%以上,采用马尔文激光粒度分析仪。
结果表明,本发明制备的PAANa的分子量在1000~7000范围内,研磨效果好,可解决浆料回黏之情况。
对比例
将实施例一的过硫酸铵更换为等量过硫酸钠,其余不变,得到聚丙烯酸钠进行同样的分散碳酸钙测试,结果见表1,为编号1。
将实施例一的次磷酸钠更换为等量焦亚硫酸钠,其余不变,得到聚丙烯酸钠进行同样的分散碳酸钙测试,结果见表1,为编号2。
将实施例一的滴加方式修改为主反应槽升温至80℃,一次加入(常规加入,非滴加方式)过硫酸铵水溶液(8wt%)、次磷酸钠水溶液(8wt%),再滴入混合物,8小时滴完,其余不变,得到聚丙烯酸钠进行同样的分散碳酸钙测试,结果见表1,为编号4。
将实施例一的恒温30分钟更换为恒温50分钟,其余不变,得到聚丙烯酸钠进行同样的分散碳酸钙测试,结果见表1,为编号6。
将实施例一的80℃更换为90℃,其余不变,得到聚丙烯酸钠进行同样的分散碳酸钙测试,结果见表1,为编号7。
表1中编号5为现有市售用于碳酸钙分散的聚丙烯酸钠。
表1不同制备方法得到的聚丙烯酸钠分散碳酸钙测试结果
Figure BDA0002774509830000041
Figure BDA0002774509830000051
备注:TO为研磨后收集的碳酸钙浆料立测黏度;T3为研磨后收集的碳酸钙浆料放置3小时后立测黏度;T3+分散为研磨后收集的碳酸钙浆料放置3小时后再用常规高速分散机8000rpm分散1分钟后所测得黏度;T48为研磨后收集的碳酸钙浆料放置48小时后立测黏度;T48+分散为研磨后收集的碳酸钙浆料放置48小时后再用常规高速分散机8000rpm分散1分钟后所测得黏度。可以看出,本发明限定技术方案制备的产品性能好。

Claims (5)

1.基于丙烯酸/二甲基二烯丙基氯化铵制备的聚丙烯酸钠,其特征在于,所述基于丙烯酸/二甲基二烯丙基氯化铵制备的聚丙烯酸钠的制备方法包括以下步骤,以丙烯酸、二甲基二烯丙基氯化铵为原料,以过硫酸铵为引发剂、次磷酸钠为链转移剂,制备聚丙烯酸钠;丙烯酸、二甲基二烯丙基氯化铵、过硫酸铵、次磷酸钠的质量比为(200~800)∶(100~400)∶(10~100)∶(10~100);将丙烯酸与二甲基二烯丙基氯化铵的混合物、引发剂溶液、链转移剂溶液同时滴入反应槽中,滴加完成后恒温,然后中和至酸性,得到聚丙烯酸钠;反应槽的温度为80℃,恒温为80℃;滴入时间为8小时;恒温时间为30分钟;利用液碱中和。
2.根据权利要求1所述基于丙烯酸/二甲基二烯丙基氯化铵制备的聚丙烯酸钠,其特征在于,丙烯酸、二甲基二烯丙基氯化铵、过硫酸铵、次磷酸钠的质量比为(200~600)∶(100~200)∶(10~60)∶(10~60)。
3.权利要求1所述基于丙烯酸/二甲基二烯丙基氯化铵制备的聚丙烯酸钠在研磨分散碳酸钙中的应用。
4.权利要求1所述基于丙烯酸/二甲基二烯丙基氯化铵制备的聚丙烯酸钠作为造纸分散剂的应用。
5.一种研磨分散碳酸钙的方法,其特征在于,包括以下步骤,将水、锆珠、碳酸钙与权利要求1所述基于丙烯酸/二甲基二烯丙基氯化铵制备的聚丙烯酸钠混合,研磨,实现碳酸钙的分散;丙烯酸、二甲基二烯丙基氯化铵、过硫酸铵、次磷酸钠的质量比为(200~800)∶(100~400)∶(10~100)∶(10~100)。
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