基于乙二酸封端聚醚无磷水处理剂的合成及性能研究

发布时间：2018-07-11 13:05

本文选题：乙二酸 + 封端聚醚　；参考：《东南大学》2015年博士论文

【摘要】：在工业生产中,为了控制循环冷却水中的结垢、腐蚀等问题,保证工业循环水系统高效、长周期的正常运行,通常采用往循环水系统中添加水处理剂(阻垢剂、缓蚀剂)的方法对循环水进行预处理。随着国家环保法规和人们环保意识的增强,开发无毒、无污染、对环境无害的水处理剂已成为研究的重点。与市场上常用的水处理剂相比,本文研究的水处理剂制备方法简单,具有更加优异的阻垢或分散效果。全文研究内容如下：(1)以烯丙基聚氧乙烯醚(APEG)和乙二酸为原料,通过酯化反应,合成了羧基封端聚醚大分子单体APEM。在APEG末端成功接枝上乙二酸羧基官能团分子,通过傅里叶红外光谱(FT-IR)、核磁共振碳谱和氢谱(13C-NMR和1H-NMR)的验证,可知在羧基化过程中,聚醚单体的双键完好、没有被破坏,合成的APEM热稳定性相对于原料APEG有所提高。以丙烯酸(AA)和APEM为原料,通过水相自由基共聚,制备了不同比例的无磷无氮的水溶性共聚物阻垢剂APEM/AA,通过溴值的测定可以知道反应单体的不饱和双键消失,共聚反应完全,APEM/AA的热稳定性优于APEG和APEM,聚合物分子量数量级为104左右。以丙烯酸(AA)、2-丙烯酰胺-2-甲基丙磺酸AMPS)和APEM为原料,通过水相自由基共聚,制备了不同比例的无磷水溶性共聚物阻垢剂APEM/AMPS/AA,通过FT-IR和1H-NMR的验证,可知反应单体反应完全。(2)乙二酸封端聚醚阻垢剂APEM/AA具有良好的阻碳酸钙、硫酸钙和磷酸钙垢性能,其最佳合成条件为：反应温度80℃℃,滴加时间1.0 h,反应时间2.0 h,引发剂用量为单体总质量的2%,APEM/AA的单体摩尔配比AA:APEM为2：1,环氧乙烯基重复单元数n为9。APEM/AA在最佳合成工艺下,投加至8 mg·L-1的临界值时能达到80%的碳酸钙阻垢率。APEM/AA能在高硬度和高碱度的水质中使用,其性能略接近于市场上最好的碳酸钙阻垢剂2-膦酸基丁烷-1,2,4-三羧酸(PBTC),优于一些常用的无磷阻垢剂。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线粉末衍射(XRD)可知,APEM/AA不仅显著改变碳酸钙晶体的形貌,还改变碳酸钙晶体的晶型。投加至4 mg·L-1的临界值时能达到95%的硫酸钙阻垢率,通过SEM和XRD可知,APEM/AA只改变硫酸钙晶体的形貌,不改变硫酸钙晶体的晶型。投加至5 mg·L-1的临界值时能达到近100%的磷酸钙阻垢率,通过SEM可知,APEM/AA显著改变磷酸钙晶体的形貌。(3) APEM/AA中大量的羧基能螯合溶液中的铁离子,在投加量为6 mg·L-1时,其透光率就可以达到22%,随着阈值效应的出现,继续添加APEM/AA透光率没有明显变化并维持在15%左右。在高钙离子、高铁离子和不同温度下,APEM/AA都有很好的分散氧化铁效果。APEM/AA是阴极抑制型缓蚀剂,具有优异的缓蚀性能：在投加量为60mg·L-‘时有超过70%的缓蚀率。APEM/AA与锌盐、聚膦酸盐缓蚀剂和杀菌剂的二元复配性能优异,最高达到近80%的缓蚀率。(4)通过对APEM/AA/APTA(8-烯丙氧基-1,3,6-芘三磺酸钠)阻垢性能和分散性能的测试,可知荧光标识共聚阻垢剂APEM/AA/APTA具有良好的阻碳酸钙垢和硫酸钙垢性能,APEM/AA/APTA和荧光单体APTA具有相同的激发和发射波长,分别为402nm和430nm。APEM/AA/APTA的荧光强度随着其浓度的增加而增加且呈很好的线性关系,其线性相关系数r为0.99672,样品的检测下限为0.38 mg·L-1。实验还考察了溶液酸度(pH值)、温度、溶剂以及其他水处理剂等因素对APEM/AA/APTA荧光强度的影响,APEM/AA/APTA既是一种无磷无氮的环保水处理剂,同时也满足了在线监测的要求。(5)乙二酸封端聚醚阻垢剂APEM/AMPS/AA具有良好的阻碳酸钙、硫酸钙和磷酸钙垢和分散铁性能,其最佳合成条件为：反应温度80℃C,滴加时间1.5 h,反应时间3.0 h,引发剂用量为单体总质量的6%,APEM/AMPS/AA的单体质量配比/AA:AMPS:APEM 为 4:0.5:0.5。APEM/AMPS/AA在最佳合成工艺下,投加至8 mg·L-1的临界值时能达到75%的碳酸钙阻垢率,通过SEM和TEM可知,APEM/AMPS/AA能显著改变碳酸钙的形貌,通过XRD可知APEM/AMPS/AA改变碳酸钙形貌的同时也改变碳酸钙的晶型；投加至5 mg·L-1的临界值时能达到95%的硫酸钙阻垢率,通过SEM和TEM可知,APEM/AMPS/AA能显著改变硫酸钙的形貌,但通过FT-IR可知/APEM/AMPS/AA并不改变硫酸钙的晶型；投加至3 mg·L-1的临界值时能达到超过85%的磷酸钙阻垢率。在投加量为9 mg-L一时达到阈值效应的临界值,并达到20%左右的透光率。相对于APEM/AA二元聚合物,APEM/AMPS/AA还具有一定的阻硫酸钡效果,当单体的配比为4：0.5：0.5时,当浓度为12 mg·L-1时,阻硫酸钡的效果能达到58%,在临界值16 mg·L-1时阻垢率达到最大值75%,通过SEM可知APEM/AMPS/AA显著改变硫酸钡的形貌,加入APEM/AMPS/AA后的硫酸钡晶体变的细小和圆润。
[Abstract]:In the industrial production, in order to control the scaling and corrosion of the circulating cooling water, to ensure the high efficiency of the industrial circulating water system and the long and normal operation, the circulating water is pretreated by adding water treatment agent (scale inhibitor and corrosion inhibitor) into the circulating water system. With the national environmental protection regulations and people's awareness of environmental protection, The development of non toxic, pollution-free and environmentally friendly water treatment agents has become the focus of research. Compared with common water treatment agents in the market, the preparation method of water treatment agent in this paper is simple and has more excellent scale inhibition or dispersion effect. The content of the full text is as follows: (1) using allyl polyoxyethylene ether (APEG) and ethylene diacid as raw materials, through The carboxyl terminated polyether macromolecule monomer APEM. was successfully grafted on the APEG terminal by carboxyl terminated polyether carboxyl functional group. Through Fourier infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR) and hydrogen spectra (13C-NMR and 1H-NMR), it was found that the double bonds of polyether monomers were intact in the carboxylation process, and the synthesized APEM heat was not destroyed. The stability is improved relative to the raw material APEG. Using acrylic acid (AA) and APEM as raw materials, a water-soluble copolymer scale inhibitor APEM/AA with different proportion of phosphorus free nitrogen free radical is prepared by copolymerization of water phase free radical. Through the determination of bromine value, it is known that the unsaturated double bond of the reaction monomer is disappearing and the copolymerization reaction is complete, and the thermal stability of APEM/AA is better than APEG. And APEM, the molecular weight of the polymer is about 104. With acrylic acid (AA), 2- acrylamide -2- methylpropyl sulfonic acid AMPS) and APEM as raw materials, a different proportion of phosphorus free water-soluble copolymer scale inhibitor APEM/AMPS/AA is prepared by water phase free radical copolymerization. Through the verification of FT-IR and 1H-NMR, it is known that the reaction monomer reaction is complete. (2) the end polymerization of ethylene diacid. The ether scale inhibitor APEM/AA has good properties of calcium carbonate, calcium sulfate and calcium phosphate scale. The optimum synthesis conditions are as follows: the reaction temperature is 80 C, the time is 1 h, the reaction time is 2 h, the dosage of the initiator is 2% of the total mass of the monomer, the AA:APEM of the monomer molar ratio of APEM/AA is 2:1, the number n of the epoxy vinyl repetition unit is 9.APEM/AA in the best way. Under the synthetic process, the critical value of 8 mg. L-1 can reach 80% of calcium carbonate scale inhibition rate.APEM/AA can be used in high hardness and high alkalinity water quality, its performance is close to the best calcium carbonate scale inhibitor 2- phosphonate -1,2,4- three carboxylic acid (PBTC) in the market, which is better than some common phosphorus free scale inhibitor. Through scanning electron microscope (S) EM), transmission electron microscopy (TEM) and X ray powder diffraction (XRD) show that APEM/AA not only significantly changes the morphology of calcium carbonate crystals, but also changes the crystalline form of calcium carbonate crystals. The scaling rate of calcium sulfate can be reached to 95% when the critical value of 4 mg. L-1 is added. Through SEM and XRD, APEM/AA only changes the morphology of calcium sulfate crystals and does not change calcium sulfate crystals. The crystalline form of the body can be added to the critical value of 5 mg. L-1 to reach a nearly 100% calcium phosphate scale inhibition rate. Through SEM, it is known that APEM/AA significantly changes the morphology of calcium phosphate crystals. (3) a large number of carboxyl groups in APEM/AA can chelate the iron ions in the solution. When the dosage is 6 mg L-1, the transmittance can reach 22%. With the emergence of the threshold effect, it continues. The transmittance of APEM/AA has no obvious change and remains around 15%. At high calcium ions, high iron ions and at different temperatures, APEM/AA has a good dispersion of iron oxide,.APEM/AA is a cathodic inhibitor, with excellent corrosion inhibition performance: in the dosage of 60mg. L-, there is more than 70% corrosion inhibition rate,.APEM/AA and zinc salt, Polyphosphonic acid. The two element compound of salt corrosion inhibitor and bactericide has excellent performance, up to up to 80% corrosion inhibition rate. (4) through the test of the scale inhibition and dispersion of APEM/AA/APTA (8- alenoxy -1,3,6- pyrene sodium three sulfonate), it is known that the fluorescent labeling copolymerization scale inhibitor APEM/AA/APTA has good calcium carbonate scale and calcium sulfate scale, APEM/AA/APTA and fluorescein The optical monomer APTA has the same excitation and emission wavelengths. The fluorescence intensity of 402nm and 430nm.APEM/AA/APTA, respectively, increases with the increase of its concentration and has a good linear relationship. The linear correlation coefficient is 0.99672, the lower limit of the sample is 0.38 mg. L-1., and the solution acidity (pH value), temperature, solvent and other water are also investigated. The effect of treatment agent on the fluorescence intensity of APEM/AA/APTA, APEM/AA/APTA is not only a kind of environmental water treatment agent with no phosphorus and nitrogen free, but also meet the requirements of on-line monitoring. (5) the polyether scale polyether scale inhibitor APEM/AMPS/AA has good properties of calcium carbonate, calcium sulfate and calcium phosphate scale and dispersed iron, and the optimum synthesis condition is: inverse The temperature is 80 C C, the drop time is 1.5 h, the reaction time is 3 h, the dosage of the initiator is 6% of the total mass of the monomer, and the /AA:AMPS:APEM of the monomer mass ratio of APEM/AMPS/AA is 4:0.5:0.5.APEM/AMPS/AA in the optimum synthesis process, and the calcium carbonate scale inhibition rate can be reached when the critical value of 8 mg. L-1 is added, and it is known that APEM/AMPS/AA can be significant through SEM and TEM. By changing the morphology of calcium carbonate, it can be found that APEM/AMPS/AA changes the morphology of calcium carbonate and also changes the crystal form of calcium carbonate by XRD. The scaling rate of calcium sulfate can be up to 95% when the critical value of 5 mg. L-1 is added. Through SEM and TEM, it can be found that APEM/AMPS/AA can significantly change the morphology of calcium sulfate, but it can be found that /APEM/AMPS/AA does not change sulphuric acid through FT-IR. The crystalline form of calcium can reach the scale of calcium phosphate scale exceeding 85% when the critical value is added to 3 mg. L-1. The critical value of the threshold effect is reached at the time of adding 9 mg-L, and the transmittance of about 20% is reached. Compared with the APEM/AA two polymer, APEM/AMPS/AA has a certain effect of barium sulfate, when the monomer ratio is 4:0.5:0.5, when the ratio is 4:0.5:0.5. When the concentration is 12 mg. L-1, the effect of barium sulfate can reach 58%. The scale of scale inhibition reaches the maximum value of 75% at the critical value of 16 mg. L-1. Through SEM, it can be found that APEM/AMPS/AA significantly changes the morphology of barium sulfate, and the barium sulfate crystals after APEM/AMPS/AA have become fine and round.
【学位授予单位】：东南大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TQ085.4

【参考文献】