本文選題：乙二酸 + 封端聚醚　； 參考：《東南大學(xué)》2015年博士論文

【摘要】：在工業(yè)生產(chǎn)中,為了控制循環(huán)冷卻水中的結(jié)垢、腐蝕等問題,保證工業(yè)循環(huán)水系統(tǒng)高效、長(zhǎng)周期的正常運(yùn)行,通常采用往循環(huán)水系統(tǒng)中添加水處理劑(阻垢劑、緩蝕劑)的方法對(duì)循環(huán)水進(jìn)行預(yù)處理。隨著國家環(huán)保法規(guī)和人們環(huán)保意識(shí)的增強(qiáng),開發(fā)無毒、無污染、對(duì)環(huán)境無害的水處理劑已成為研究的重點(diǎn)。與市場(chǎng)上常用的水處理劑相比,本文研究的水處理劑制備方法簡(jiǎn)單,具有更加優(yōu)異的阻垢或分散效果。全文研究?jī)?nèi)容如下：(1)以烯丙基聚氧乙烯醚(APEG)和乙二酸為原料,通過酯化反應(yīng),合成了羧基封端聚醚大分子單體APEM。在APEG末端成功接枝上乙二酸羧基官能團(tuán)分子,通過傅里葉紅外光譜(FT-IR)、核磁共振碳譜和氫譜(13C-NMR和1H-NMR)的驗(yàn)證,可知在羧基化過程中,聚醚單體的雙鍵完好、沒有被破壞,合成的APEM熱穩(wěn)定性相對(duì)于原料APEG有所提高。以丙烯酸(AA)和APEM為原料,通過水相自由基共聚,制備了不同比例的無磷無氮的水溶性共聚物阻垢劑APEM/AA,通過溴值的測(cè)定可以知道反應(yīng)單體的不飽和雙鍵消失,共聚反應(yīng)完全,APEM/AA的熱穩(wěn)定性優(yōu)于APEG和APEM,聚合物分子量數(shù)量級(jí)為104左右。以丙烯酸(AA)、2-丙烯酰胺-2-甲基丙磺酸AMPS)和APEM為原料,通過水相自由基共聚,制備了不同比例的無磷水溶性共聚物阻垢劑APEM/AMPS/AA,通過FT-IR和1H-NMR的驗(yàn)證,可知反應(yīng)單體反應(yīng)完全。(2)乙二酸封端聚醚阻垢劑APEM/AA具有良好的阻碳酸鈣、硫酸鈣和磷酸鈣垢性能,其最佳合成條件為：反應(yīng)溫度80℃℃,滴加時(shí)間1.0 h,反應(yīng)時(shí)間2.0 h,引發(fā)劑用量為單體總質(zhì)量的2%,APEM/AA的單體摩爾配比AA:APEM為2：1,環(huán)氧乙烯基重復(fù)單元數(shù)n為9。APEM/AA在最佳合成工藝下,投加至8 mg·L-1的臨界值時(shí)能達(dá)到80%的碳酸鈣阻垢率。APEM/AA能在高硬度和高堿度的水質(zhì)中使用,其性能略接近于市場(chǎng)上最好的碳酸鈣阻垢劑2-膦酸基丁烷-1,2,4-三羧酸(PBTC),優(yōu)于一些常用的無磷阻垢劑。通過掃描電子顯微鏡(SEM)、透射電子顯微鏡(TEM)和X射線粉末衍射(XRD)可知,APEM/AA不僅顯著改變碳酸鈣晶體的形貌,還改變碳酸鈣晶體的晶型。投加至4 mg·L-1的臨界值時(shí)能達(dá)到95%的硫酸鈣阻垢率,通過SEM和XRD可知,APEM/AA只改變硫酸鈣晶體的形貌,不改變硫酸鈣晶體的晶型。投加至5 mg·L-1的臨界值時(shí)能達(dá)到近100%的磷酸鈣阻垢率,通過SEM可知,APEM/AA顯著改變磷酸鈣晶體的形貌。(3) APEM/AA中大量的羧基能螯合溶液中的鐵離子,在投加量為6 mg·L-1時(shí),其透光率就可以達(dá)到22%,隨著閾值效應(yīng)的出現(xiàn),繼續(xù)添加APEM/AA透光率沒有明顯變化并維持在15%左右。在高鈣離子、高鐵離子和不同溫度下,APEM/AA都有很好的分散氧化鐵效果。APEM/AA是陰極抑制型緩蝕劑,具有優(yōu)異的緩蝕性能：在投加量為60mg·L-‘時(shí)有超過70%的緩蝕率。APEM/AA與鋅鹽、聚膦酸鹽緩蝕劑和殺菌劑的二元復(fù)配性能優(yōu)異,最高達(dá)到近80%的緩蝕率。(4)通過對(duì)APEM/AA/APTA(8-烯丙氧基-1,3,6-芘三磺酸鈉)阻垢性能和分散性能的測(cè)試,可知熒光標(biāo)識(shí)共聚阻垢劑APEM/AA/APTA具有良好的阻碳酸鈣垢和硫酸鈣垢性能,APEM/AA/APTA和熒光單體APTA具有相同的激發(fā)和發(fā)射波長(zhǎng),分別為402nm和430nm。APEM/AA/APTA的熒光強(qiáng)度隨著其濃度的增加而增加且呈很好的線性關(guān)系,其線性相關(guān)系數(shù)r為0.99672,樣品的檢測(cè)下限為0.38 mg·L-1。實(shí)驗(yàn)還考察了溶液酸度(pH值)、溫度、溶劑以及其他水處理劑等因素對(duì)APEM/AA/APTA熒光強(qiáng)度的影響,APEM/AA/APTA既是一種無磷無氮的環(huán)保水處理劑,同時(shí)也滿足了在線監(jiān)測(cè)的要求。(5)乙二酸封端聚醚阻垢劑APEM/AMPS/AA具有良好的阻碳酸鈣、硫酸鈣和磷酸鈣垢和分散鐵性能,其最佳合成條件為：反應(yīng)溫度80℃C,滴加時(shí)間1.5 h,反應(yīng)時(shí)間3.0 h,引發(fā)劑用量為單體總質(zhì)量的6%,APEM/AMPS/AA的單體質(zhì)量配比/AA:AMPS:APEM 為 4:0.5:0.5。APEM/AMPS/AA在最佳合成工藝下,投加至8 mg·L-1的臨界值時(shí)能達(dá)到75%的碳酸鈣阻垢率,通過SEM和TEM可知,APEM/AMPS/AA能顯著改變碳酸鈣的形貌,通過XRD可知APEM/AMPS/AA改變碳酸鈣形貌的同時(shí)也改變碳酸鈣的晶型；投加至5 mg·L-1的臨界值時(shí)能達(dá)到95%的硫酸鈣阻垢率,通過SEM和TEM可知,APEM/AMPS/AA能顯著改變硫酸鈣的形貌,但通過FT-IR可知/APEM/AMPS/AA并不改變硫酸鈣的晶型；投加至3 mg·L-1的臨界值時(shí)能達(dá)到超過85%的磷酸鈣阻垢率。在投加量為9 mg-L一時(shí)達(dá)到閾值效應(yīng)的臨界值,并達(dá)到20%左右的透光率。相對(duì)于APEM/AA二元聚合物,APEM/AMPS/AA還具有一定的阻硫酸鋇效果,當(dāng)單體的配比為4：0.5：0.5時(shí),當(dāng)濃度為12 mg·L-1時(shí),阻硫酸鋇的效果能達(dá)到58%,在臨界值16 mg·L-1時(shí)阻垢率達(dá)到最大值75%,通過SEM可知APEM/AMPS/AA顯著改變硫酸鋇的形貌,加入APEM/AMPS/AA后的硫酸鋇晶體變的細(xì)小和圓潤(rùn)。
[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.
【學(xué)位授予單位】：東南大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類號(hào)】：TQ085.4

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