CN111039889A - 一种含1,3,4-恶二唑荧光基团水溶性聚合物及其合成方法 - Google Patents
一种含1,3,4-恶二唑荧光基团水溶性聚合物及其合成方法 Download PDFInfo
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Abstract
本发明公开一种含1,3,4‑恶二唑荧光基团水溶性聚合物及其合成方法，具体内容包括：（1）将丙烯酸与对甲基苯甲酰肼反应得到单体，结构如：
Description
技术领域
本发明属于循环水处理剂应用技术领域，具体涉及一种荧光聚合物的合成，同时涉及一种含1,3,4-恶二唑基团的不饱和荧光单体的合成方法。
背景技术
为解决长期以来有机膦产品在工业循环水等领域的应用而带来的环境污染问题，水溶性羧酸共聚物成为国内外开发较早的水溶性共聚物类水处理用阻垢剂，该类产品对环境无污染、不产生水体“富营养化”问题以及生产及使用成本低等优势。此外，产品多以丙烯酸等水溶性有机羧酸作为主要单体，对水体中的钙、镁等离子具有较强的螯合分散能力而一直受到人们的重视和青睐。有机膦药剂的使用可以通过在线检测分析水体中磷的含量来判断加药周期和用量，而聚合物的使用，则无法满足这一要求，因此带有荧光示踪基团的聚合物阻垢分散剂的研究及其应用逐渐成为该领域研究的热点问题。荧光示踪剂加入到阻垢分散剂中通常有两种方式，即荧光标记和荧光探针，其工作原理分别为：荧光标记是将荧光发色团用化学键连接到大分子链上；荧光探针是将带荧光发色基团的小分子与高分子体系按照一定的质量比混合。
国内外关于水溶性荧光聚合物的合成报道很多，张跃华及王新刚等分别利用自制的荧光单体与丙烯酸、丙烯酸羟丙酯通过过硫酸铵单引发体系引发聚合合成了一种荧光标记的丙烯酸-丙烯酸羟丙酯，并对其阻垢性能进行研究，但并未对自制荧光单体结构及合成方法进行公开。张宝华等利用自制的二苯乙烯型荧光单体与聚乙二醇在高温（155℃）下发生酯交换反应合成一种可溶于冷水的荧光聚合物。陆均君等利用含芘基团的荧光标记聚合物，并对其性能进行了研究。中国专利CN109824593A介绍了在惰性气体环境下，以4-溴-1,8-萘二甲酸酐和N,N-二甲氨基丙胺为原料、甲醇钠为催化剂合成一种水溶性季铵盐荧光单体；中国专利CN1229091A公开了一种通过荧光有机酸盐与聚合物之间的转酰胺反应合成兼具荧光示踪性和阻垢分散作用的聚合物的方法。美国专利US5128419、US5171450、US5216086、US5260386分别公开了通过反式酰胺化反应制备具有不同悬挂荧光基团的聚合物的合成方法。但是，现有已公开的用于水处理剂聚羧酸阻垢分散剂的荧光示踪剂单体的或存在合成多采用高温、高压或惰性气体环境，反应条件要求严格，或是合成反应步骤繁多、纯化后处理过程复杂等技术问题，不利于安全及环境保护。
发明内容
针对现有技术存在问题，本发明提供一种含1,3,4-恶二唑基团的荧光单体及其聚合物，并提供其制备方法。
一种含1,3,4-恶二唑基团的不饱和荧光单体及其荧光聚合物的合成，具体是通过如下技术方案实现的：
（1）含1,3,4-恶二唑基团的不饱和荧光单体的合成：将丙烯酸与不同分子结构的酰肼按照1:1的摩尔比加入带有干燥装置的反应釜中，-0.02~-0.04MPa负压条件下，加入经蒸馏干燥处理后的三氯氧磷，加热回流反应8~12小时。减压蒸除过量三氯氧磷后，倒入体积为反应产物2~4倍的冰水混合体系中，搅拌条件下滴加氢氧化钠溶液调节体系pH值至中性偏上，慢慢析出浅灰色沉淀固体、经过滤、洗涤、干燥、分离提纯得浅粉或淡黄色产品，产率为65~80%。
（2）水溶性荧光聚合物的合成：将上述步骤（1）合成的荧光单体、异丙醇、去离子水与丙烯酸及其它含不饱和双键的水溶性有机单体依次加入反应釜中，升温至回流状态下，利用过硫酸盐-焦亚硫酸盐氧化-还原体系引发聚合，合成水溶性荧光聚合物。
上述步骤（1）中所述的含1,3,4-恶二唑基团的不饱和荧光单体具有如下结构式（I）：
上述步骤（1）中所述的干燥三氯氧磷在反应过程中既是反应物料同时也充当反应溶剂，其用量可以为丙烯酸与酰肼投料总质量的1~4倍；作为优选地，用量为丙烯酸与酰肼投料总质量的2~3倍。
上述步骤（1）中所述的分离提纯方法为减压柱色谱分离，其具体操作方法为：用体积比V石油醚：V乙酸乙酯=（2~4）：1的溶剂为流动相，经多次减压洗脱下来的物质即为目标产物。
上述步骤（2）中所述的水溶性荧光聚合物具有如下通式（II）：
其中，M可以为H+,NH4 +,Na+,K+中的任一种；R2可以为-H,-CH3；R1可以为
中的任一取代基团。
上述步骤（2）中所述的荧光单体、丙烯酸及其他不饱和双键共聚单体的摩尔比可以为（0.001~0.01）：1：（0~0.75）；其中，作为优选地，荧光单体、丙烯酸及其他不饱和双键共聚单体的摩尔比为（0.005~0.008）：1：（0~0.75）。
上述步骤（2）中所述的氧化-还原体系引发剂分别采用滴加方式入釜，且氧化剂迟于还原剂10~15min后滴加完毕。
上述步骤（2）中所述的水溶性荧光聚合物的平均年均分子量范围为2000~10000。
利用含不饱和双键的羧酸与对甲基苯甲酰肼为原料，在三氯氧磷环境下，经酰胺化、脱水成环一步法合成含1,3,4-恶二唑基团的荧光单体，经柱色谱分离纯化后通过氧化-还原体系引发其与不饱和双键单体发生共聚，合成粘均分子量为2000~1000的水溶性荧光聚合物。该方法合成的荧光单体工艺路线简单，副反应少、易分离纯化；含1,3,4-恶二唑基团的荧光单体的聚合物具有优良的水溶性；与荧光单体相比，聚合物吸收波长发生红移，激发能量降低；产品阻垢分散性能好，不同浓度的产品与其荧光强度之间呈现出良好的线性关系，利于实现药剂的在线监测，便于指导实际应用时及时加药；本发明合成方法简单易操作、安全环保、利于实现溶剂的循环利用。本发明涉及的合成反应机理如下：
本发明的有益作用:
1.与荧光单体相比，荧光聚合物的吸收波长发生明显红移，激发能量降低。同时，荧光聚合物的荧光强度与其在水体中的浓度含量呈现良好的线性关系，利于指导工业应用，实现药剂的在线监测和自动加药；
2. 作为一种新的荧光阻垢聚合物，不影响丙烯酸-羧酸聚合物本身阻垢性能；
3. 丙烯酸进行荧光改性，可一锅法制备最终产物，且以水相为反应介质，产品具有优良的水溶性，合成工艺安全环保，易于实现工业生产。
附图说明
图1.实施例1荧光单体激发光谱及其发射光谱、实施例2荧光聚合物发射光谱对比图；a- 荧光单体激发光谱；b-荧光单体发射光谱；c-实施例2荧光标记型聚合物发射光谱；
图2.实施例2合成荧光聚合物不同浓度对应的荧光强度曲线图。
具体实施例
实施例1（含1,3,4-恶二唑基团的不饱和荧光单体的合成）
（1）室温下，将36.0g质量含量＞99.5%的丙烯酸和75.0g对甲基苯甲酰肼（摩尔比为1:1）加入带有干燥装置的500mL三颈反应釜中；
（2）将反应釜与真空泵建立连接并维持体系-0.04MPa的压力状态，加入225.0g经蒸馏干燥处理后的三氯氧磷，搅拌条件下，75±2℃微回流状态下反应10小时至体系呈黄棕色均一透明状；
（3）维持体系真空在-0.01~-0.02MPa范围内，减压蒸馏至体系无液体馏出，共蒸出回收三氯氧磷140.8g，向釜内快速加入200g冰水混合物并用30%氢氧化钠水溶液调节体系pH值至8~9；
（4）上述步骤（3）所得混合体系室温下静置陈化2~3小时后，经过滤得浅灰色固体65.2g；
（5）将上述步骤（4）所得固体溶于二氯乙烷，用石油醚和乙酸乙酯按照体积比为V石油醚：V乙酸乙酯=3：1的流动相经柱层析分离提纯、旋蒸共收集无色固体56.8g，计算收率为61.07%。结构如下：
。
产品经红外和核磁共振检测分析，结果分别如下：IR（KBr压片，cm-1）:1679cm-1（υ-C=C-），1590cm-1（υ-C=N-），1208cm-1（υ-C-O-C）；1H NMR（CDCl3，δppm）：2.32(s,3H,-CH3)，5.12(s,1H，=C-H)，5.41(s,2H，=C-H)，6.46（s,1H，
），7.09(t,2H,
)，7.24(d,2H,
)。
实施例2（与丙烯酸共聚）
按照n荧光单体：n：AA=0.005:1的比例，分别称取实施例1中荧光单体9.3g、720g丙烯酸及50g异丙醇和1000g去离子水并依次加入5L的三颈玻璃反应釜中；搅拌下升温至85±1℃，控制滴加速度同时将240g质量百分比浓度为5.6%的过硫酸钠溶液和200g质量百分比浓度为4.3%的焦亚硫酸钠溶液滴加入釜，滴加时间为1~1.5h，其中，过硫酸钠溶液较焦亚硫酸钠溶液延后12min滴加完毕；继续保温反应0.5h，负压外蒸出异丙醇循环利用，降温得活性含量为45.72%的浅黄色荧光标记型聚丙烯酸水溶液1725g，经检测，合成聚合物粘均分子量为4281，游离单体含量（以AA计）未检出。荧光标记型聚丙烯酸具有如下结构式：
对比例1
按照n荧光单体：nAA=0:1的比例，即丙烯酸单体均聚，其他工艺参数及操作条件均同实施例2，得活性含量为45.08%的淡黄色聚丙烯酸水溶液1708g，经检测，合成聚合物粘均分子量为4537，游离单体含量（以AA计）未检出。
实施例3（与丙烯酸+丙烯磺酸钠共聚）
按照n荧光单体：nAA：nSAS= 0.008:1:0.10的比例，分别称取实施例1中荧光单体7.5g、360g丙烯酸、90g丙烯磺酸钠及50g异丙醇和500g去离子水并依次加入2L的三颈玻璃反应釜中；搅拌下升温至80±1℃，控制滴加速度同时将120g质量百分比浓度为2.6%的过硫酸钠溶液和100g质量百分比浓度为1.8%的焦亚硫酸钠溶液滴加入釜，滴加时间为0.5~1h，其中，过硫酸钠溶液较焦亚硫酸钠溶液延后15min滴加完毕；继续保温反应0.5h，负压外蒸出异丙醇循环利用，降温得活性含量为44.57%的黄色荧光标记型AA-SAS共聚物水溶液1050g，经检测，合成聚合物粘均分子量为7451，游离单体含量（以AA计）0.003%。荧光标记型聚丙烯酸具有如下结构式：
对比例2
按照n荧光单体：nAA：nSAS=0:1:0.10的比例，即丙烯酸与丙烯磺酸钠单体共聚，其他工艺参数及操作条件均同实施例3，得活性含量为44.68%的淡黄色丙烯酸-丙烯磺酸钠共聚物水溶液1023g，经检测，合成聚合物粘均分子量为7630，游离单体含量（以AA计）0.002%。
实施例4（与丙烯酸+AHA共聚）
按照n荧光单体：nAA：nAHA= 0.006:1:0.4的比例，分别称取实施例1中荧光单体5.6g、360g丙烯酸、260g丙烯酸羟丙酯及100g异丙醇和1000g去离子水并依次加入5L的三颈玻璃反应釜中；搅拌下升温至90±1℃，控制滴加速度同时将250g质量百分比浓度为4.8%的过硫酸钠溶液和180g质量百分比浓度为3.8%的焦亚硫酸钠溶液滴加入釜，滴加时间为1h，其中，过硫酸钠溶液较焦亚硫酸钠溶液延后10min滴加完毕；继续保温反应0.5h，负压外蒸出异丙醇循环利用，降温得活性含量为43.24%的黄色荧光标记型AA-AHA共聚物水溶液1438g，经检测，合成聚合物粘均分子量为2451，游离单体含量（以AA计）0.004%。荧光标记型聚丙烯酸具有如下结构式：
对比例3
按照n荧光单体：nAA：nAHA=0:1:0.4的比例，即丙烯酸与丙烯羟丙酯单体共聚，其他工艺参数及操作条件均同实施例4，得活性含量为44.68%的浅黄色丙烯酸-丙烯羟丙酯共聚物水溶液1389g，经检测，合成聚合物粘均分子量为2840，游离单体含量（以AA计）0.001%。
实施例5
使用Hitachi F-4700型号荧光分光光度计对本发明实施例1制备的荧光单体及实施例2-4合成的荧光聚合物进行荧光扫描：
(1)固定狭缝宽度为5nm，分别扫描实施例1荧光单体激发光谱和发射光谱，得出其最佳激发波长分别为247nm、发射波长为434nm，且具有较强的荧光强度；
(2)固定狭缝宽度为5nm，分别扫描实施例2-4合成的荧光聚合物的激发光谱和发射光谱，得出实施例2-4各荧光聚合物最佳激发波长和发射波长对应数值分别如下表1，且均表现出较强的荧光：
上述荧光单体激发波长及表1数据及检测过程显示：将合成的含有不饱和烯键的荧光单体与不饱和羧酸单体共聚后，在低浓度含量体系中，各物质在相近的波长范围内均表现出较强的荧光强度；且与荧光单体相比，荧光聚合物的激发波长均不同程度的发生了红移，激发能量降低。
实施例6（阻垢分散性能评价对比试验及数据对比列表）
1.阻垢性能测试条件：配制钙离子浓度为240ppm、碳酸氢根浓度为732ppm的溶液，加入20ppm（以干基计）上述各聚合物，调节体系pH值8~9，保持温度80℃，时间10小时；同时做不加药剂的空白试验，通过EDTA滴定法测定反应前后钙离子的浓度变化来计算阻垢率，平行三次试验取平均值；
2.碳酸钙分散力的评价：分别准确称取实施例2-4、对比例1-3样品各1g（以干基计），加入去离子水约80mL，用浓度为80g/L的氢氧化钠溶液调节pH值至6~8，加10mL质量百分比浓度为10%的碳酸钠溶液作为缓冲，然后再用80g/L的氢氧化钠溶液调节pH值至11~11.5，用10g/L的乙酸钙标准溶液滴定至体系明显变浑浊为止，记录消耗的乙酸钙溶液体积。
各实施例合成荧光标记的聚合物及对应不含荧光标记的聚合物阻垢分散性能测试评价数据如表2.所示
从表2.数据比较可知，将一定质量比含有荧光基团的不饱和单体引入水溶性聚合物分子结构中，对原有产品对碳酸钙的阻垢率、分散力等性能均未产生明显的影响，产品质量稳定。
Claims (10)
1.一种含1,3,4-恶二唑基团的荧光单体，其特征在于，为以下结构:
2.一种权利要求1所述的荧光单体的制备方法，其特征在于，包含以下步骤：
（1）将丙烯酸与对甲基苯甲酰肼加入反应釜中，加入三氯氧磷，加热回流反应8~12小时；
（2）减压蒸除过量三氯氧磷后，倒入体积为反应产物2~4倍的冰水混合体系中，搅拌条件下滴加氢氧化钠溶液调节体系pH值至中性偏上，析出浅灰色沉淀固体；
（3）经过滤、洗涤、干燥、分离提纯得最终产品。
3.根据权利要求2所述的制备方法，其特征在于，所述的反应釜为带有干燥装置的反应釜；所述的三氯氧磷加入前经蒸馏干燥处理。
4.根据权利要求2所述的制备方法，其特征在于，所述的步骤（1）在-0.02~-0.04MPa负压条件下进行；所述的步骤（1）在70-90℃下进行。
5.根据权利要求2所述的制备方法，其特征在于，所述的丙烯酸与对甲基苯甲酰肼的摩尔比为1：1-1.2；所述的三氯氧磷在反应过程中既是酰化反应试剂也为反应溶剂，用量为丙烯酸与酰肼投料总质量的1~4倍。
6.一种由权利要求1所述的荧光单体聚合的含1,3,4-恶二唑荧光基团的聚合物，其特征在于，含1,3,4-恶二唑基团的荧光单体和其他一种以上烯类化合物共聚得到。
7.根据权利要求5所述的聚合物，其特征在于，所述的其他一种以上烯类化合物中必须含有丙烯酸。
8.根据权利要求6或7任一所述的聚合物，其特征在于，所述的聚合物，具体结构
所述M可以为NH4 +,Na+,K+,H+中的任一种；R2可以为-H,-CH3；R1可以为
中的任一取代基团；
m∶n：z为0.001~0.01：1：0~0.75；
平均粘分子量范围为2000~10000。
9.根据权利要求6所述的聚合物，其特征在于，所述的聚合物通过氧化-还原引发剂水相引发聚合所得。
10.根据权利要求6所述的聚合物，其特征在于，所述的荧光单体可不经过过滤、洗涤、干燥、分离提纯，直接转料至聚合反应釜，与其他烯类化合物聚合。
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