CN114539444A - 一种改性羧甲基壳聚糖季铵盐及其制备方法 - Google Patents
一种改性羧甲基壳聚糖季铵盐及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种改性羧甲基壳聚糖季铵盐及其制备方法,所述改性羧甲基壳聚糖季铵盐以O‑羧甲基壳聚糖、三羟乙基烯丙基季铵盐为原料通过反相乳液聚合法聚合反应,制得三羟乙基烯丙基季铵盐接枝羧甲基壳聚糖。本发明所用的壳聚糖、三羟乙基烯丙基季铵盐易得到、易降解、生物相容性好、成本低。本发明采用的反相乳液聚合法,在水和煤油分别作为水相体系和油相体系的条件下进行反应,相比现有技术的水溶液聚合法、通氮气,反应条件简单,温度低,时间短,能耗少。本发明合成的改性羧甲基壳聚糖季铵盐,可与水中微粒起电中合反应和吸附架桥作用,使体系中的微粒脱稳、絮凝而有助于沉降和脱水,同时具有一定的杀菌抗菌性、保湿性。
Description
技术领域
本发明属于精细化工技术领域,具体涉及一种改性羧甲基壳聚糖季铵盐及其制备方法。
背景技术
水是基础自然资源,也是战略性经济资源,是生态文明建设重要的物质基础。随着工业化的进展,水环境面临的挑战越发严峻,所需要处理的废水更加复杂、难降解。因而研发高效环保的新型絮凝剂材料有着重要的现实意义。
将壳聚糖改性衍生化、引入功能基团不仅能够打破壳聚糖分子链的紧密排列,改善其分子空间结构,削弱分子间作用力,增加其在水中的溶解性。
壳聚糖的季铵化改性,是把一个低分子季铵盐接到壳聚糖主链上,或在壳聚糖的氨基上引入季铵基团,而得到的一类壳聚糖衍生物。季铵基团能使得壳聚糖带上大量正电荷,提高了絮凝时的电荷中和能力。改性后的羧甲基壳聚糖季铵盐不但具有壳聚糖原有的成膜性、生物相容性好和易生物降解等性能,还克服了其溶解性差、絮凝效果差等缺点,并且具有一定典型季铵盐的性质,如高电荷密度、杀菌抑菌。将改性后得到的羧甲基壳聚糖季铵盐作为阳离子絮凝剂应用于工业水处理及生活污水处理过程中预期有良好效果。
田澍等《化工环保》2007第27卷第1期79页,发表的文章公开了:将壳聚糖(CTS)和丙烯酰胺(AM)与二甲基二烯丙基氯化铵(DMDAAC)接枝共聚,以硝酸铈铵为引发剂,得到CTS-AM-DMDAAC三元接枝共聚物。其对高岭土水样具有较强的絮凝能力,可在宽pH范围内使用。用CTS-AM-DMDAAC处理COD为165.5mg/L的啤酒生产废水,COD去除率达90.1%。
杨蔚等《化学世界》2008第11期第667页,发表的文章公开了:以N,O-羧甲基化度为85.6%的羧甲基壳聚糖(CM-CTS)为原料,w=0.40的NaOH水溶液为催化及,3-氯-2-羟丙基三甲氯化铵(CTA)为接枝改性剂,在在异丙醇介质中制备了具有良好水溶性的两性壳聚糖-季铵化N,O-羧甲基壳聚糖。合成产物对Cr(Ⅵ)的最大絮凝去除率为93.16%,对Cd2+的最大絮凝去除率98.52%。
刘剑锋《化学工程与装备》2015第12期第62-64页,发表的文章公开了:以壳聚糖、二甲基二烯丙基氯化铵、二烯丙基胺为原料,以过硫酸铵为引发剂,以乙二胺四乙酸二钠为螯合剂,在水相介质中进行聚合反应,合成了一种季铵盐改性壳聚糖絮凝剂。用于印染废水处理中,CODcr去除率为78.1%,SS去除率为82.8%,色度去除率达80.2%。
刘雪娇等《南京林业大学学报(自然科学版)》2017第41卷第3期,发表的文章公开了:通过在碱性条件下分别以氯乙酸为羧甲基化试剂、CTA 为季铵化试剂,对壳聚糖的改性,结果表明CM-CTS /MMT和 CTA-CTS / MMT复合材料为分散性较好的剥离型插层结构。
综上所述,改性壳聚糖季铵盐,在水处理等领域具有广阔的应用前景。对于羧甲基壳聚糖季铵盐的研究虽然很广泛,但存在接枝效率不合适,接枝位置不确,接枝前后分子量变化不一等缺点。
发明内容
本发明的目的是提供一种通过反相乳液法制备的改性羧甲基壳聚糖季铵盐,该季铵盐作为絮凝剂具有高阳离子度,优良水溶性和絮凝性能。
本发明是通过以下技术方案来实现的:
一种改性羧甲基壳聚糖季铵盐,由如下方法制备获得:
(1)取体积份数为19~21份的煤油,加入质量为煤油质量7~8%的乳化剂,搅拌后得到混合液A,即油相;
(2)取体积份数为10~12份的蒸馏水,加入质量为蒸馏水质量5~15%的O-羧甲基壳聚糖,搅拌后得到混合液B,即水相;
(3)将混合液A与混合液B在常温下搅拌20~30min得到乳化液,向乳化液中加入引发剂,在温度为50~70℃下进行引发反应,反应结束后加入体积份数为8~10份的三羟乙基烯丙基季铵盐水溶液,保持温度50~70℃反应4~5h;
(4)步骤(3)制得乳化物在室温下冷却、静置、纯化、烘干、研磨后得到所述改性羧甲基壳聚糖季铵盐。
本发明将O-羧甲基壳聚糖和三羟乙基烯丙基季铵盐反应得到羧甲基壳聚糖季铵盐,具有O-羧甲基壳聚糖优良的水溶性、生物相容性,并带有季铵盐的高电荷性和良好的杀菌抗菌性,使其表现出优秀的絮凝性能。
本发明还涉及制备所述改性羧甲基壳聚糖季铵盐的方法,所述方法包括:
(1)取体积份数为19~21份的煤油,加入质量为煤油质量7~8%的乳化剂,200~400r/min搅拌后得到混合液A,即油相;
(2)取体积份数为10~12份的蒸馏水,加入质量为蒸馏水质量5%~15%的O-羧甲基壳聚糖,200~400r/min搅拌后得到混合液B,即水相;
(3)将混合液A与混合液B在常温下200~400r/min搅拌20~30min得到乳化液,向乳化液中加入引发剂,在温度为50~70℃下进行引发反应,反应结束后加入体积份数为8~10份的三羟乙基烯丙基季铵盐水溶液,保持温度50~70℃反应4~5h;
(4)步骤(3)制得乳化物在室温下冷却、静置、纯化、烘干、研磨后得到所述改性羧甲基壳聚糖季铵盐。
优选的,步骤(1)中乳化剂为span-80和tween-80的混合物,且HLB值为6~7。
优选的,步骤(3)中三羟乙基烯丙基季铵盐与O-羧甲基壳聚糖质量比为(2~4):1。
优选的,步骤(3)中引发剂为硝酸铈铵,引发剂的量为三羟乙基烯丙基季铵盐的0.14%~0.2%。
优选的,步骤(3)中引发反应时间为20~30min。
优选的,步骤(4)纯化的方法如下:将产物静置分离后加入体积份数为40~80的乙醇和丙酮混合液,快速搅拌破乳,静置20~60min后抽滤,使用乙醇洗涤2~3次,干燥、得到粉末状产物,所述乙醇和丙酮混合液中乙醇和丙酮体积比为1:1~3。
本发明的有益效果主要体现在:
1、本发明所用的壳聚糖、三羟乙基烯丙基季铵盐易得到、易降解、生物相容性好、成本低。本发明采用的反相乳液聚合法,在水和煤油分别作为水相体系和油相体系的条件下进行反应,相比现有技术的水溶液聚合法、通氮气,反应条件简单,温度低,时间短,能耗少。
2、本发明合成的改性羧甲基壳聚糖季铵盐,可与水中微粒起电中合反应和吸附架桥作用,使体系中的微粒脱稳、絮凝而有助于沉降和脱水,同时具有一定的杀菌抗菌性、保湿性。产物的羟基基团和羧基,加宽了混凝剂的溶解范围,通过静电吸引或形成氢键作用吸附水中的胶粒,增加了吸附位点,且使絮凝剂在水溶液中自由地刚性伸展,片状絮体将胶粒和悬浮物网捕、扫卷,促进絮凝剂增长。
附图说明
图1为壳聚糖和本发明制得的改性羧甲基壳聚糖季铵盐的红外谱图。
具体实施方式
下面结合附图及实施例对本发明做进一步详细说明,但本发明保护范围不仅限于此:
本发明中的三羟乙基稀丙基季铵盐通过以下方法制得:
向单口烧瓶中加入三乙醇胺与氯丙烯(三乙醇胺与氯丙烯摩尔比为1:1.1),调节反应体系pH至8~9,放入磁子,用橡胶塞与胶带密封瓶口,40℃水浴加热24h。冷却后得到产物,称取一定量的粗产物,加入乙醇溶液溶解,然后对滤液进行减压蒸馏,除去溶剂。冰水浴后溶液底部有白色针状晶体析出,即为纯化的产物。
本发明中的O-羧甲基壳聚糖通过以下方法制得:
将1.0g壳聚糖溶于1%乙酸中,加入甲醇,在室温下搅拌生成透明质胶体。取含有1.0g苯甲醛的甲醛溶液,逐滴加入,在60℃下搅拌反应4h。加入20mL甲醇和5%的NaOH溶液,搅拌12h,抽滤。依次用95%的乙醇、无水乙醇、丙酮洗涤脱水,除去未反应的苯甲醛,于60℃真空干燥。
取反应后的壳聚糖溶于异丙酮中,搅拌浸渍1h。加入40%NaOH溶液,常温下搅拌碱化2h。取5g氯乙烯溶于异丙酮中,1h内逐滴加入上述碱化后的溶液中,于60℃水浴反应4h。反应结束后用80mL90%乙醇醇洗,抽滤,沉淀加60mL水溶解,再用100mL95%乙醇醇沉,得到大量白色絮状产物,依次用无水乙醇、丙酮脱水,于60℃下烘干,得到O-羧甲基壳聚糖粗产物。
O-羧甲基壳聚糖粗产物用0.5mol·L-1盐酸室温浸泡48h,加入乙醇醇沉,抽滤,洗涤至中性,无水乙醇脱水,于60℃烘干,得到微黄色粉末状的精制O-羧甲基壳聚糖。
O-羧甲基壳聚糖季铵盐的制备方法为:
向三颈烧瓶中加入18~21mL的煤油,搅拌下加入1.4~1.6g span-60和tween-80的混合物(HLB值为6~7),搅拌5~15min,搅拌速率200~400r/min。向烧杯中加入10~12mL水、1.0g O-羧甲基壳聚糖搅拌5~15min,后将溶液加入三颈烧瓶中常温下搅拌30~60min,搅拌速率200~400r/min。加入0.006~0.008g硝酸铈铵,调节温度至50~70℃,进行引发反应20~30min,搅拌速率200~400r/min。引发反应后向三颈烧瓶中加入8~10mL含2~4g三羟乙基稀丙基季铵盐的水溶液,在温度50~70℃下反应4~5h,搅拌速率200~400r/min。反应结束后,加入体积份数为40~80份的混合溶液,混合溶液为体积比为1:(1~3)的乙醇和丙酮混合液,快速搅拌破乳搅拌。静置20~60min后抽滤,并且使用乙醇洗涤3次,经过真空干燥后研磨得到粉末状产物,即为改性O-羧甲基壳聚糖季铵盐。
实施例1:
向三颈烧瓶中加入20mL的煤油,搅拌下加入1.5g的span-60和tween-80的混合物(span-60与tween-80比值为4:1),搅拌15min,搅拌速率400r/min。向烧杯中加入12mL水、1.0g O-羧甲基壳聚糖搅拌10min,后将溶液加入三颈烧瓶中常温下搅拌40min,搅拌速率400r/min。加入0.006g硝酸铈铵,调节温度至70℃,进行引发反应30min,搅拌速率400r/min。引发反应后向三颈烧瓶中加入8mL含3g三羟乙基稀丙基季铵盐的水溶液,在温度70℃下反应4h,搅拌速率400r/min。反应结束后,加入60ml乙醇和丙酮体积比为1:2的混合溶液,快速搅拌破乳搅拌。静置30min后抽滤,并且使用乙醇洗涤3次,经过真空干燥后研磨得到粉末状产物,即为改性O-羧甲基壳聚糖季铵盐。
实施例2:
向三颈烧瓶中加入20mL的煤油,搅拌下加入1.4g的span-60和tween-80的混合物(span-60与tween-80比值为4:1),搅拌12min,搅拌速率400r/min。向烧杯中加入10mL水、1.2gO-羧甲基壳聚糖搅拌10min,后将溶液加入三颈烧瓶中常温下搅拌40min,搅拌速率400r/min。加入0.008g硝酸铈铵,调节温度至70℃,进行引发反应40min,搅拌速率400r/min。引发反应后向三颈烧瓶中加入10mL含4g三羟乙基稀丙基季铵盐的水溶液,在温度70℃下反应4h,搅拌速率400r/min。反应结束后,加入60ml乙醇和丙酮体积比为1:2的混合溶液,快速搅拌破乳搅拌。静置30min后抽滤,并且使用乙醇洗涤3次,经过真空干燥后研磨得到粉末状产物,即为改性O-羧甲基壳聚糖季铵盐。
实施例3:
向三颈烧瓶中加入20mL的煤油,搅拌下加入1.5g的span-60和tween-80的混合物(span-60与tween-80比值为4:1),搅拌15min,搅拌速率400r/min。向烧杯中加入10mL水、1.0gO-羧甲基壳聚糖搅拌10min,后将溶液加入三颈烧瓶中常温下搅拌30min,搅拌速率400r/min。加入0.008g硝酸铈铵,调节温度至70℃,进行引发反应30min,搅拌速率400r/min。引发反应后向三颈烧瓶中加入10mL含4g三羟乙基稀丙基季铵盐的水溶液,在温度70℃下反应5h,搅拌速率400r/min。反应结束后,加入80ml乙醇和丙酮体积比为1:2的混合溶液,快速搅拌破乳搅拌。静置20min后抽滤,并且使用乙醇洗涤3次,经过真空干燥后研磨得到粉末状产物,即为改性O-羧甲基壳聚糖季铵盐。
实施例4:
向三颈烧瓶中加入18mL的煤油,搅拌下加入1.4g的span-60和tween-80的混合物(span-60与tween-80比值为3:1),搅拌12min,搅拌速率300r/min。向烧杯中加入10mL水、1.5gO-羧甲基壳聚糖搅拌10min,后将溶液加入三颈烧瓶中常温下搅拌40min,搅拌速率300r/min。加入0.006g硝酸铈铵,调节温度至60℃,进行引发反应30min,搅拌速率300r/min。引发反应后向三颈烧瓶中加入8mL含3g三羟乙基稀丙基季铵盐的水溶液,在温度60℃下反应4.5h,搅拌速率400r/min。反应结束后,加入50ml乙醇和丙酮体积比为1:2的混合溶液,快速搅拌破乳搅拌。静置25min后抽滤,并且使用乙醇洗涤3次,经过真空干燥后研磨得到粉末状产物,即为改性O-羧甲基壳聚糖季铵盐。
实施例5:
向三颈烧瓶中加入20mL的煤油,搅拌下加入1.5g的span-60和tween-80的混合物(span-60与tween-80比值为4:1),搅拌12min,搅拌速率400r/min。向烧杯中加入10mL水、2.0gO-羧甲基壳聚糖搅拌10min,后将溶液加入三颈烧瓶中常温下搅拌40min,搅拌速率400r/min。加入0.008g硝酸铈铵,调节温度至70℃,进行引发反应30min,搅拌速率400r/min。引发反应后向三颈烧瓶中加入10mL含4g三羟乙基稀丙基季铵盐的水溶液,在温度70℃下反应5h,搅拌速率400r/min。反应结束后,加入80ml乙醇和丙酮体积比为1:2的混合溶液,快速搅拌破乳搅拌。静置30min后抽滤,并且使用乙醇洗涤3次,经过真空干燥后研磨得到粉末状产物,即为改性O-羧甲基壳聚糖季铵盐。
实施例6:
向三颈烧瓶中加入20mL的煤油,搅拌下加入1.5g的span-60和tween-80的混合物(span-60与tween-80比值为3:1),搅拌15min,搅拌速率400r/min。向烧杯中加入12mL水、1.2gO-羧甲基壳聚糖搅拌10min,后将溶液加入三颈烧瓶中常温下搅拌20min,搅拌速率400r/min。加入0.007g硝酸铈铵,调节温度至60℃,进行引发反应30min,搅拌速率300r/min。引发反应后向三颈烧瓶中加入8mL含3g三羟乙基稀丙基季铵盐的水溶液,在温度60℃下反应5h,搅拌速率300r/min。反应结束后,加入40ml乙醇和丙酮体积比为1:2的混合溶液,快速搅拌破乳搅拌。静置30min后抽滤,并且使用乙醇洗涤3次,经过真空干燥后研磨得到粉末状产物,即为改性O-羧甲基壳聚糖季铵盐。
效果验证:
一定条件(温度=25℃)下,将实例1~6制备的改性O-羧甲基壳聚糖季铵盐等量置于预先加入一定量盐酸或氢氧化钠水中,采用磁力搅拌使待测物质充分分散后,观察其溶解性,并测定充分分散后的体系pH值,以壳聚糖为对照,得到待测物质的溶解性对pH的依赖关系。
表1:不同絮凝剂样品在不同pH条件下的溶解性测试结果
注:+可溶;±:部分溶解;-:不溶。
由表1可以看出,使用的壳聚糖仅可溶解于pH<6的水体中,实施例1~6在pH小于下均可溶解;由于羟基和羧基共同作用下,与水分子形成氢键溶解性大大增加。在碱性条件下,引入羧甲基基团以后,羧基以羧酸根离子形式存在,有利于絮凝剂分子的水化和溶解过程;相比壳聚糖基体,样品显示出较优越的溶解性能。
在一定条件(pH=5,温度=25℃)下,取不同投加量的絮凝剂样品对印染废水絮凝性能的测定,采用浊度仪测量絮凝后上清液的浊度(NTU),并根据公式计算残留浊度百分比(Residual Turbidity Percentage,RT,%)。
表2:不同絮凝剂样品对印染废水的絮凝效果
由表2可以看出,实施例1~6制备的改性O-羧甲基壳聚糖季铵盐对以上选取的典型染料废水有明显的絮凝效果,再加入量为3.0mg/L后,浊度去除率能达到80%。
在一定条件(pH=7,温度=25℃)下,将C.I.活性黑5、C.I.活性红195、C.I.活性蓝4、活性黄X-RN用去离子水溶解成均一溶液,用分光光度计测定吸光度值A,取实例1~6絮凝剂样品和壳聚糖20mg/L进行脱色处理,并测得脱色后的吸光度A。
表3:不同絮凝剂样品对模拟废水的脱水性能
由表3可知,实施例1~6制备的改性O-羧甲基壳聚糖季铵盐对以上不同的模拟染料废水有良好的脱色性能,脱色率都可以达到90%以上。
在一定条件,取0.2g/L的壳聚糖和实例1~6中絮凝剂于某电镀废水(pH=5.0),在25℃下搅拌,用原子吸收光度法测定铜、铅、铬。
表4:电镀金属废水中的金属离子去除率
由表4可知,实施例1~6制备的改性O-羧甲基壳聚糖季铵盐对铜、铬的去除率都达到90%以上,对铅的去除率能达到95%以上,处理效果良好。
综上,本发明提供的改性羧甲基壳聚糖季铵盐,在混凝处理过程中只需少量的投加量既能显著去除悬浮物,悬浮物浊度去除率大于90%,色度去除率大于90%,常见金属去除率大于90%,且水溶性良好。
上述实施方式仅为本发明的优选实施方式,不能以此来限定本发明保护的范围,本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
Claims (7)
1.一种改性羧甲基壳聚糖季铵盐,由如下方法制备获得:
(1)取体积份数为19~21份的煤油,加入质量为煤油质量7~8%的乳化剂,搅拌后得到混合液A,即油相;
(2)取体积份数为10~12份的蒸馏水,加入质量为蒸馏水质量5~15%的O-羧甲基壳聚糖,搅拌后得到混合液B,即水相;
(3)将混合液A与混合液B在常温下搅拌20~30min得到乳化液,向乳化液中加入引发剂,在温度为50~70℃下进行引发反应,反应结束后加入体积份数为8~10份的三羟乙基烯丙基季铵盐水溶液,保持温度50~70℃反应4~5h;
(4)步骤(3)制得乳化物在室温下冷却、静置、纯化、烘干、研磨后得到所述改性羧甲基壳聚糖季铵盐。
2.制备权利要求1所述的改性羧甲基壳聚糖季铵盐的方法,所述方法包括:
(1)取体积份数为19~21份的煤油,加入质量为煤油质量7~8%的乳化剂,200~400r/min搅拌后得到混合液A,即油相;
(2)取体积份数为10~12份的蒸馏水,加入质量为蒸馏水质量5%~15%的O-羧甲基壳聚糖,200~400r/min搅拌后得到混合液B,即水相;
(3)将混合液A与混合液B在常温下200~400r/min搅拌20~30min得到乳化液,向乳化液中加入引发剂,在温度为50~70℃下进行引发反应,反应结束后加入体积份数为8~10份的三羟乙基烯丙基季铵盐水溶液,保持温度50~70℃反应4~5h;
(4)步骤(3)制得乳化物在室温下冷却、静置、纯化、烘干、研磨后得到所述改性羧甲基壳聚糖季铵盐。
3.如权利要求2所述的方法, 其特征在于:步骤(1)中乳化剂为span-80和tween-80的混合物,且HLB值为6~7。
4.如权利要求2所述的方法, 其特征在于:步骤(3)中三羟乙基烯丙基季铵盐与O-羧甲基壳聚糖质量比为(2~4):1。
5.如权利要求2所述的方法, 其特征在于:步骤(3)中引发剂为硝酸铈铵,引发剂的量为三羟乙基烯丙基季铵盐的0.14%~0.2%。
6.如权利要求2所述的方法, 其特征在于:步骤(3)中引发反应时间为20~30min。
7.如权利要求2所述的方法, 其特征在于:步骤(4)纯化的方法如下:将产物静置分离后加入体积份数为40~80份的乙醇和丙酮混合液,快速搅拌破乳,静置20~60min后抽滤,使用乙醇洗涤2~3次,干燥、得到粉末状产物,所述乙醇和丙酮混合液中乙醇和丙酮体积比为1:1~3。
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