WO2006069504A1 - Procede de purification du monomere cationique de chlorure de dimethyldiallylammonium presentant une grande purete - Google Patents

Procede de purification du monomere cationique de chlorure de dimethyldiallylammonium presentant une grande purete Download PDF

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Publication number
WO2006069504A1
WO2006069504A1 PCT/CN2005/000614 CN2005000614W WO2006069504A1 WO 2006069504 A1 WO2006069504 A1 WO 2006069504A1 CN 2005000614 W CN2005000614 W CN 2005000614W WO 2006069504 A1 WO2006069504 A1 WO 2006069504A1
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solution
cationic monomer
monomer
dmdaac
content
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PCT/CN2005/000614
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English (en)
Chinese (zh)
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Yuejun Zhang
Haiying Wang
Xu Jia
Xiaolei Zhao
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Nanjing University Of Science & Technology
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Publication of WO2006069504A1 publication Critical patent/WO2006069504A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/84—Purification

Definitions

  • the invention relates to a method for purifying a cationic quaternary ammonium salt monomer for polymer synthesis, in particular to a method for purifying a high-purity cationic monomer dimethyl diallyl ammonium chloride.
  • DMDAAC Dimethyldiallylammonium chloride
  • DMDAAC is a quaternary ammonium salt with excellent water solubility and containing two unsaturated double bonds. It is a white needle crystal with a melting point of 146-147 ° C. It is easy to absorb moisture in air as an aqueous solution. Therefore, the compound is mostly stored in the form of an aqueous solution. Due to its high charge density, good water solubility, acid and alkali resistance, non-toxicity, etc., it is itself in the field of petroleum exploitation, paper industry, textile printing and dyeing, sewage treatment, sludge dewatering and household chemicals. There are a wide range of applications. However, whether it is applied directly as a cationic quaternary ammonium salt or as a polymerization monomer, its purity or the content of impurities contained is critical, affecting its application range and application cost.
  • One method is a method for directly preparing DMDAAC by integrating a multi-step reaction in an aqueous solution of dimethylamine, chloropropene and sodium hydroxide.
  • the reaction solution is filtered to remove precipitated sodium chloride, and then purified by distillation to obtain a DMDAAC aqueous solution or a crystal product thereof.
  • the one-step process has the advantages of simple and safe process, high yield, and no need to use organic solvent and less "three wastes" in the production and purification process.
  • the side reaction in the process is increased (formula 2, formula 5 to formula 7), and the amount of impurities in the product is large, so that the reactivity as a polymer monomer is low.
  • the main components of impurities are generally considered to be unreacted starting materials, intermediates and by-products.
  • dimethylamine or a salt thereof
  • a tertiary amine or a salt thereof
  • chloropropene allyl alcohol, allyl aldehyde, sodium chloride or the like.
  • the monomeric DMDAAC aqueous solution treated by the above method 2 has a purity which is significantly higher than that of the original literature 1 method.
  • the monomer product was initiated with tert-butyl peroxide at 40 ° C to give its homopolymerized product.
  • the homopolymerized product was at 20 ° C, the viscosity of the 0.5% aqueous solution reached 180 cps, and its characteristic viscosity was 2.8 dg (30 ° C, measured in a 5% NaCl aqueous solution).
  • Literature 4 Quan Yanmei et al., Synthesis and identification of dimethyldiallylammonium chloride, Xi'an Petroleum Journal, 1992, 7 (1): 58-60 developed a one-step method for one-time feeding.
  • the DMDAAC was prepared by a method of sealing, inert gas protection and pressurization, less than 60 ° C, and reacting for 30 h.
  • the reaction was carried out by alternately adding chloropropene and sodium hydroxide at 65 to 85 ° C under a pressure of 0.2 MPa for 4 to 5 hours.
  • the obtained product was subjected to vacuum distillation under reduced pressure of 0.08 MPa at 55 to 65 ° C to remove NaCl, and a product DMDAAC aqueous solution was obtained.
  • the obtained reaction liquid is separated from NaCl, impurities are removed by distillation under reduced pressure (vacuum), and precipitated NaCl or the like is filtered off, and the obtained DMDAAC product monomer solution is polymerized at 40 ° C with an initiator of 1% by mass of the monomer or
  • the nonionic monomer acrylamide was copolymerized for 8 h to obtain the homopolymer PDMDAAC and the copolymer P (DMDAAC-AM) having a cationic degree of 10%, respectively, and the characteristic viscosity values were 1.96 dL/g (recrystallized with hexanol and acetone). Remove small molecules) and 9.26 dL/g (measured in aqueous solution of lM NaCl at 30 ° C).
  • the cationic monomer DMDAAC prepared by the one-step method impurities such as by-products are formed. Therefore, not only the parameters such as the feed ratio, the feeding mode, the reaction temperature and the pH of the medium are controlled in the preparation process to reduce the formation of by-products, but also the vacuum distillation of the crude cationic monomer solution, decolorization of the activated carbon, or The base is adjusted to pH value and then purified by high-temperature steam to purify the monomer, and the purity of the cationic monomer DMDAAC solution is increased by removing impurities.
  • various refinement methods proposed so far to reduce impurities in the monomeric DMDAAC product are empirical methods, lacking proper theoretical guidance and reasonable analytical methods. Therefore, the main drawbacks of these purification methods are:
  • the object of the present invention is to provide a high-purity cationic monomer dimethyl diallyl ammonium chloride with simple process, low operation cost, basically no "three wastes", high purity of products, clear quality index and stable quality. Refined method.
  • a technical solution for achieving the object of the present invention is: A method for purifying a high-purity cationic monomer dimethyldiallylammonium chloride, characterized in that the process flow and operating conditions are carried out as follows:
  • reaction solution is filtered under reduced pressure or centrifugally to remove precipitated crystal NaCl;
  • the invention has the significant advantages of: 1. Using a chromatographic method, various possible volatile impurities, dimethylamine, tertiary amine, allyl alcohol, chloropropene, in the cationic monomer DMDAAC product solution.
  • the amount of the amine hydrochloride which is obtained by the analysis, the amount of the industrial alkali sodium hydroxide to be added is designed, and the amine hydrochloride is freed from the amine to become a volatile Quality, making it easy to quantitatively remove by vacuum distillation, avoiding the introduction of new impurities and the addition of alkali by the addition of phenolphthalein indicator and pH indicating the end of alkali addition; 3.
  • the filtrate is decolorized by activated carbon to remove the non-volatile impurities which may be formed during the purification process, and further purified; 5.
  • the impurity type and content of the cationic monomer DMDAAC product solution obtained by the purification method of the invention can be characterized by chromatographic analysis results, and can be compared with the pre-refining condition.
  • the polymerization activity of the purified monomer solution can be initiated by the same conditions (mass fraction of 65% monomer solution, initiated by 50% C (NH 4 ) 2 S 2 8 initiator of 0.5% by mass of monomer) Reaction 9h) Comparison of the relative molecular mass (expressed by the intrinsic viscosity value) of the polydimethyldiallylammonium chloride (Poly-DMDAAC, PDMDAAC), a polymerization product of the cationic monomer DMDAAC. See Table 1 for details. Table 1 Impurity content and polymerization activity before and after cationic monomer purification
  • the chromatographic method is used to systematically analyze the cationic monomer to be purified obtained by the one-step process.
  • composition and content of various impurities in the aqueous solution of DMDAAC which contain volatile and hard-to-volatile impurities such as dimethylamine, chloropropene, allyl alcohol, allylaldehyde and sodium chloride, dimethylamine hydrochloride, and uncle
  • volatile and hard-to-volatile impurities such as dimethylamine, chloropropene, allyl alcohol, allylaldehyde and sodium chloride, dimethylamine hydrochloride, and uncle
  • the corresponding content of amine hydrochloride is shown in Table 2.
  • a 50% one-step monomer DMDAAC solution A 50 kg to be purified is added to a 120 L distillation still or a 200 L falling film evaporator, and the amine hydrochloride (dimethylamine hydrochloride) is analyzed according to the chromatographic method.
  • the total amount of salt, tertiary amine hydrochloride) is 0,87 (7.66 tnol), and the ratio of the amount of amine hydrochloride: sodium hydroxide is 1.00: 1.00-0.99, and the content is added under cooling and stirring.
  • a 8.0% aqueous solution of NaOH was 3.79 kg (7.98 mol).
  • the fourth step the monomer solution is subjected to vacuum filtration or centrifugal filtration to remove precipitated crystal NaCl.
  • Step 5 The solution is added with water to adjust the monomer content to (60 ⁇ 5)%, and the activated carbon is less than 1% by mass.
  • the treatment temperature is 45 ⁇ 65°C, and the time is 0.5 ⁇ 1.5h.
  • the activated carbon was removed by filtration under reduced pressure to obtain a high purity cationic monomer DMDAAC product solution, and the impurities contained in Table 2 are shown in Table 2.
  • the chromatographic analysis method is used to systematically analyze various impurity components and contents of the cationic monomer DMDAAC aqueous solution B prepared by the one-step process, and the volatile and hard-to-volatile impurities contained therein are: Dimethylamine, chloropropene, allyl alcohol, allylaldehyde and sodium chloride, dimethylamine hydrochloride, and tertiary amine hydrochloride are shown in Table 3 below.
  • a ruthenium monomer DMDAAC solution B to be purified is added to a 120 L distillation still or a 200 L falling film evaporator, and the hydrochloride salt of the amine (dimethylamine salt) is analyzed according to the chromatographic method.
  • the total amount of the acid salt and the tertiary amine hydrochloride is 1.35 kg (11.81 mol), and the ratio of the amine hydrochloride to sodium hydroxide is 1.00: 1.00. Under cooling, the content is 6.0.
  • the aqueous solution of % NaOH was 7.87 kg (11.81 mol).
  • the third step is to add 12.0kg of water and distill it under reduced pressure of 2.5 ⁇ 5°C and 60 ⁇ 5°C for 2.5 ⁇ 3.5h in two steps at a pressure of 0.099MPa, and distill each step to no significant distillation. Immediately before the liquid, the exhaust gas distilled under reduced pressure is absorbed by water for synthesis reaction.
  • the monomer solution is subjected to vacuum filtration or centrifugal filtration to remove precipitated crystal NaCl.
  • the filtrate is adjusted with water to a monomer content of (60 ⁇ 5)%, and decolorization treatment of activated carbon less than 1% by mass is added, the treatment temperature is 60 ⁇ 5° C., the time is 0.5 to 1.5 h, and the pressure is reduced.
  • the activated carbon was removed by suction filtration or centrifugation to obtain a high-purity cationic monomer DMDAAC product solution, and the impurity content thereof is shown in Table 3. Change of impurity content in monomer DMDAAC solution before and after refining

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de purification du monomère cationique de chlorure de diméthyldiallylammonium présentant une grande pureté comprenant les étapes consistant à : (a) déterminer les composants non-volatiles et volatiles et leurs teneurs dans la solution de monomère cationique à traiter par analyse chromatographique ; (b) charger la solution de monomère cationique dans une cuve et ajouter une solution de NaOH en agitant lors du refroidissement afin d’obtenir des amines libres ; (c) ajouter de l’eau pour ajuster la teneur en monomère de la solution entre 35 et 55 % et soumettre la solution obtenue à une distillation sous vide à deux plages de températures, le distillat est recyclé après adsorption avec de l’eau et le résidu est traité par filtration sous vide ou centrifugation afin de retirer le NaCl précipité ; et (d) ajouter de l’eau au filtrat pour ajuster la teneur en monomère à la plage spécifiée, et incorporer une petite quantité de charbon actif destinée à la décoloration afin d’obtenir le produit souhaité avec un minimum d’impuretés. En raison de la détermination précise des impuretés et de leur teneur, le procédé d’invention peut éliminer l’utilisation des indicateurs de sorte à éviter divers problèmes tels que l’incorporation de nouvelles impuretés et l’ajout en excès de NaOH ce qui rend possible la fabrication d’un produit présentant une grande pureté.
PCT/CN2005/000614 2004-12-31 2005-04-30 Procede de purification du monomere cationique de chlorure de dimethyldiallylammonium presentant une grande purete WO2006069504A1 (fr)

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CNB2004101030782A CN1323064C (zh) 2004-12-31 2004-12-31 高纯度阳离子单体二甲基二烯丙基氯化铵的精制方法
CN200410103078.2 2004-12-31

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Cited By (2)

* Cited by examiner, † Cited by third party
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CN103463956A (zh) * 2013-09-16 2013-12-25 张家港市金源生物化工有限公司 一种正丙胺尾气的回收方法
CN114456075A (zh) * 2022-02-22 2022-05-10 山东蓝湾新材料有限公司 一种工业化二甲基二烯丙基氯化铵合成方法

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CN101993380B (zh) * 2009-08-11 2013-05-01 兆联实业股份有限公司 氢氧化四甲基铵的回收设备及其方法
CN101906050A (zh) * 2010-06-07 2010-12-08 浙江华晟化学制品有限公司 二甲基二烯丙基氯化铵单体的制备方法
CN102628237A (zh) * 2012-04-06 2012-08-08 无锡德冠生物科技有限公司 一种活性染料固色剂及其生产方法
CN102993028B (zh) * 2012-12-26 2014-07-30 四川康庄生物化工有限责任公司 二甲基二烯丙基氯化铵单体的提纯方法
CN106526049A (zh) * 2015-09-09 2017-03-22 南京理工大学 一种二甲基二烯丙基氯化铵单体中有机杂质的精准检测方法
CN106518689B (zh) * 2015-09-09 2019-01-18 南京理工大学 一种高纯度二甲基二烯丙基氯化铵单体的制备方法
CN112266083B (zh) * 2020-10-10 2022-08-19 南京理工大学 工业单体二甲基二烯丙基氯化铵中所含甲醛的减量方法
CN114225864B (zh) * 2021-12-16 2024-04-26 江苏富淼科技股份有限公司 一种用于发绿二甲基二烯丙基氯化铵脱色的方法及装置

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JPS541282B1 (fr) * 1969-08-26 1979-01-23
US4670594A (en) * 1985-08-13 1987-06-02 Hoechst Aktiengesellschaft Continuous process for the preparation of dimethyldiallylammonium chloride
JPH09278721A (ja) * 1996-04-16 1997-10-28 Daiso Co Ltd ジアリルジアルキルアンモニウム化合物の処理方法
CN1243822A (zh) * 1999-04-09 2000-02-09 西南石油学院 一种阳离子聚合物单体的制备方法

Family Cites Families (2)

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Publication number Priority date Publication date Assignee Title
US3461163A (en) * 1967-03-16 1969-08-12 Calgon Corp Synthesis of dimethyl diallyl ammonium chloride
US3472740A (en) * 1967-03-28 1969-10-14 Calgon Corp Process for purifying dialkyl diallyl ammonium chloride and dialkyl dimethallyl ammonium chloride

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JPS541282B1 (fr) * 1969-08-26 1979-01-23
US4670594A (en) * 1985-08-13 1987-06-02 Hoechst Aktiengesellschaft Continuous process for the preparation of dimethyldiallylammonium chloride
JPH09278721A (ja) * 1996-04-16 1997-10-28 Daiso Co Ltd ジアリルジアルキルアンモニウム化合物の処理方法
CN1243822A (zh) * 1999-04-09 2000-02-09 西南石油学院 一种阳离子聚合物单体的制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103463956A (zh) * 2013-09-16 2013-12-25 张家港市金源生物化工有限公司 一种正丙胺尾气的回收方法
CN114456075A (zh) * 2022-02-22 2022-05-10 山东蓝湾新材料有限公司 一种工业化二甲基二烯丙基氯化铵合成方法

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CN1323064C (zh) 2007-06-27

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