CN104788674B - An ionic liquid - Preparation of polyether polyaspartate mixture of catalyst and the reaction medium - Google Patents

An ionic liquid - Preparation of polyether polyaspartate mixture of catalyst and the reaction medium Download PDF

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CN104788674B
CN104788674B CN 201510192601 CN201510192601A CN104788674B CN 104788674 B CN104788674 B CN 104788674B CN 201510192601 CN201510192601 CN 201510192601 CN 201510192601 A CN201510192601 A CN 201510192601A CN 104788674 B CN104788674 B CN 104788674B
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polyether
ionic liquid
liquid
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吴有庭
李强
陈雷
陈永乐
王宏凯
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吴有庭
李强
陈雷
陈永乐
王宏凯
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一种以离子液体‑聚醚混合液为催化剂和反应介质的聚天冬氨酸制备方法。 Polyaspartic acid prepared polyether mixture of a catalyst and medium - An ionic liquid. 它是将L‑天冬氨酸和离子液体‑聚醚混合液,搅拌、升温,在一定真空度下反应得到含聚琥珀亚酰胺、离子液体和聚醚的混合物。 It is the L- aspartic acid and an ionic liquid - polyether mixture, stirring, heating, reaction mixture containing the poly succinimide, the ionic liquid and polyether under a certain vacuum. 然后加入碱的水溶液,进行水解反应。 Then aqueous alkali, hydrolysis reaction. 水解后,体系分为液‑液两相:上相是聚醚水溶液;下相是聚天冬氨酸盐水溶液。 After hydrolysis, the system is divided into liquid - liquid two phases: relative polyether water; lower phase is polyaspartate solution. 液液分相后,下相即为产品,上相经简单再生处理,变成离子液体‑聚醚混合液,重复用于下一批次的聚合反应。 After liquid-liquid phase separation, the lower phase is the product, relative to after simple regeneration process, into the ionic liquid - polyether mixture was reused for the next batch polymerization. 本发明方法以离子液体‑聚醚混合液作为催化剂和溶剂,降低了聚合体系的粘度,改善了聚合反应过程的传质,提高了天冬氨酸的转化率和聚天冬氨酸的聚合度,控制了聚天冬氨酸的分子量及其分子量分布,也降低了过程的能耗和物耗。 The method of the present invention is an ionic liquid - polyether mixture as a catalyst and a solvent, reduces the viscosity of the polymerization system, to improve the mass transfer of the polymerization process, to improve the degree of polymerization conversion of aspartic acid and polyaspartic control the molecular weight and molecular weight distribution of polyaspartic acid, also reduces the energy consumption and material consumption process.

Description

一种离子液体-聚醚混合液为催化剂和反应介质的聚天冬氨酸制备方法 An ionic liquid - polyaspartic acid prepared polyether mixture medium as catalyst and the reaction

技术领域 FIELD

[0001] 本发明涉及一种聚天冬氨酸的制备方法,特别涉及以离子液体-聚醚混合液为催化剂和反应介质的聚天冬氨酸制备方法。 [0001] The present invention relates to a method for producing a polyaspartic acid, in particular, it relates to ionic liquid - polyaspartic acid prepared polyether mixture medium as catalyst and reaction.

背景技术 Background technique

[0002] 离子液体是指全部由阴阳离子组成的液体,由于其具有非挥发性、良好的离子导电性与导热性、高热容及高热稳定性,选择性溶解力等特点,使得离子液体成为目前化学化工领域研究的热点之一。 [0002] The ionic liquid refers to all of the liquid of the anion and cation composition, because of its non-volatile, good ionic conductivity and thermal conductivity, high heat capacity and high thermal stability, selectivity solubility characteristics, so that the ionic liquid becomes currently one of the hotspots of chemistry and chemical engineering fields. 更重要的是离子液体的“可设计”性,通过改变离子液体的阴阳离子来设计不同的离子液体,从而能够更好的适用于目标反应,显示了其更为广阔的应用前景。 More importantly, the ionic liquids "can be designed to" sex, by changing the ionic liquid anions and cations to design different ionic liquids, which can better apply to the target reaction, showing its broader application prospects. 离子液体具有无味、无恶臭、无污染、不易燃、易与产物分离、易回收、可反复多次循环使用、使用方便等优点,是传统挥发性溶剂的理想替代品,它有效地避免了传统有机溶剂的使用所造成严重的环境、健康、安全以及设备腐蚀等问题,为名副其实的、环境友好的绿色溶剂。 Ionic liquids tasteless, non-malodorous, non-polluting, non-flammable and easily separated from the product, easily recycled, can be repeatedly reused, ease of use, is the ideal alternative to traditional volatile solvents, which effectively avoid the traditional serious environmental, health, safety and equipment corrosion problems such as the use of organic solvents caused, is truly environmentally friendly green solvents. 适合于当前所倡导的清洁技术和可持续发展的要求,已经越来越被人们广泛认可和接受。 Suited for clean technology and sustainable development currently advocated, it has been more and more widely recognized and accepted by people.

[0003] 聚天冬氨酸(PolyaspartiCaCid,PASP)是近十几年来在全球销量日增的绿色化学品。 [0003] polyaspartic acid (PolyaspartiCaCid, PASP) is the last decade in global sales growing green chemicals. 聚天冬氨酸通常由天冬氨酸单体的氨基与羧基脱水缩合得到,具有两种不同的结构单元,是一种大分子多肽,通过肽键CO-NH来延长分子链,具有类似蛋白质的分子结构。 Polyaspartic acid is usually obtained from the amino and carboxy dehydration condensation of aspartic acid monomer, having two different structural units, a macromolecular polypeptide to extend molecular chains via a peptide bond CO-NH, with similar protein the molecular structure. 它具有很好的水溶性或亲水性,还对各种阴、阳离子如NH4+、Ca2+、Mg2+、Fe2+、Zn2+、P〇43—、C032—、Cl, 具有络合、活化、传输、运载等作用,可用作亲水剂或保水剂、缓蚀剂、清洗剂、离子缓冲剂、 表面活性剂等等,已在多个行业,如化肥、水处理、医药卫生、染料等中得到了广泛的应用。 It has very good water-soluble or hydrophilic, but also to various anions and cations such as NH4 +, Ca2 +, Mg2 +, Fe2 +, Zn2 +, P〇43-, C032-, Cl, having a complex, activation, transport, carrying, etc. effect, can be used as a hydrophilizing agent or a retaining agent, corrosion inhibitor, detergent, ionic buffers, surfactants and the like, has in many industries, such as fertilizer, water treatment, pharmaceuticals, dyes and the like have been widely Applications. 特别地,在微生物的作用下,聚天冬氨酸可以稳定地分解为氨基酸小分子,并最终降解为水、二氧化碳等对环境无害的物质,是一种可完全生物降解的环境友好型化学品。 In particular, under the action of microorganisms, polyaspartic acid can be stably into amino acids, small molecules, and eventually degrades into water, carbon dioxide and other environmentally harmful substances, a fully biodegradable and environmentally friendly chemical products. 在工业高度发达的今天,环境问题越来越引起人们的重视,聚天冬氨酸的合成与应用已倍受世界各国的关注。 In the industry is highly developed today, environmental issues more and more people's attention, synthesis and application of polyaspartic acid has been closely watched around the world.

[0004] 目前报道的关于聚天冬氨酸的合成方法主要有两种:一种是以马来酸、马来酸酐及其衍生物为原料,通过合成中间产物聚琥珀酰亚胺(PSI),然后将其水解得到聚天冬氨酸(PASP),例如专利0附01768268六、0附108265六、0附02796263六等。 [0004] The synthesis method on polyaspartic acid reported to date there are mainly two: one is maleic acid, maleic anhydride and derivatives thereof as a raw material, polysuccinimide (PSI) by the synthesis of the intermediate , which is then hydrolyzed to polyaspartic acid (PASP), for example, Patent 0 01,768,268 six attachment, attachment 108 265 0 VI 0 02,796,263 six attachment like. 其中专利0价01768268八和CN1108265A所采用的是离心加入磷酸进行催化,高温熔融聚合再水解获得PASP的方法。 Wherein patent 0 monovalent 01768268 VIII and CN1108265A employed centrifugal addition of phosphoric acid catalyst, a high temperature melt polymerization and then hydrolysis to obtain of PASP. 但以酸性很强的磷酸作为催化剂的工艺不仅对设备材料要求高,还会产生大量的废酸液,污染环境。 But the process to highly acidic phosphoric acid as a catalyst, not only the equipment and materials required for high, will produce large amounts of waste acid, pollution of the environment. 而且高温熔融聚合生产PASP的方法易形成半固体状态的聚琥珀亚胺,这会造成传质阻力增大,反应时间加长,PASP的相对分子质量覆盖面(800〜500000)扩大等问题。 The method and the high-temperature melt polymerization production PASP easy to form a semi-solid state polymerization succinimide, which causes the mass transfer resistance is increased, the reaction time becomes longer, the molecular weight of PASP coverage (800~500000) expansion problems. 而专利CN102796263A采用微波加热的方法进行辅助催化,这在工艺工业化中会遇到设备投入成本过高与技术限制的双重难题;另一种合成方法是如CN103724625A、CN102643425A、 CN102250352A等专利中报道的以L-天冬氨酸为原料合成PASP。 And Patent CN102796263A using microwave heating method for assisting catalysis, which encounter excessive equipment investment costs and technical limitations dual problem in the process of industrialization; Another method of synthesis are as CN103724625A, CN102643425A, CN102250352A other patent reported to L- aspartic acid was synthesized PASP. 其中专利CN102643425A和CN102250352A创新性的提出以离子液体为催化剂催化合成PASP,但此二者所用离子液体过于单一,综合效用低,离子液体采用洗涤的方式回收,浓缩过程能耗过高。 Wherein patent CN102643425A and CN102250352A innovative proposed ionic liquid is synthesized PASP catalyzed, but both, the ionic liquid over a single use, low comprehensive utility ionic liquid by way of washing the recovered high concentration process energy.

[0005] 为开发新型绿色的PASP合成工艺,本发明提出一种以离子液体-聚醚混合溶剂作为反应介质和催化剂的聚天冬氨酸合成方法。 [0005] The development of new green PASP synthesis process, the present invention provides an ionic liquid - polyaspartic acid synthesis polyether mixed solvent as a reaction medium and a catalyst. L-天冬氨酸与离子液体-聚醚混合溶剂混合搅拌,加热反应获得聚琥珀亚酰胺(PSI)。 L- aspartic acid and ionic liquid - polyether stirred mixed solvent, the reaction was heated to obtain poly succinimide (PSI). 加入碱,搅拌水解反应,最终获得聚天冬氨酸(PASP)盐溶液。 Base is added, the reaction stirred for hydrolysis, finally obtained polyaspartic acid (PASP) salt solution. 与传统工艺过程相比,新方法在聚合过程中通过添加并在线回收溶剂、反应体系为液体状态,不会损失粉体状态的反应底物。 Compared with the conventional process, a new method in the polymerization process and the online recovery of the solvent by the addition, the reaction system in the liquid state, with no loss of the reaction substrate powder state. 并且选择的新型犁刀式聚合反应器可以取代传统的捏合反应器实现PASP中间体聚马来酰亚胺(PSI)的受控聚合,得到的聚合物分子量比传统方法提高1倍以上,分子量分布也变窄,极大地改善并保证PASP作为化肥增效剂的使用性能。 And new coulter polymerization reactors selected can replace conventional kneading reactor to achieve PASP intermediate polymaleimide (PSI) controlled polymerization, polymer molecular weight obtained increases more times than traditional methods, the molecular weight distribution also narrowed dramatically improve the performance and ensure the PASP as fertilizer synergist.

发明内容 SUMMARY

[0006] 本发明的目的在于提供一种以离子液体-聚醚混合液为催化剂和反应介质的聚天冬氨酸的制备方法。 [0006] The object of the present invention to provide an ionic liquid - polyether polyaspartate mixture preparation for the catalyst and the reaction medium.

[0007] 本发明的技术方案如下: [0007] aspect of the present invention is as follows:

[0008] —种以离子液体-聚醚混合液为催化剂和反应介质的聚天冬氨酸的制备方法,其反应式如下: [0008] - species of ionic liquids - polyether mixture polyaspartic methods of preparation of the catalyst and the reaction medium, the reaction is as follows:

Figure CN104788674BD00041

[0010] 它包括如下步骤: [0010] comprising the steps of:

[0011] 步骤1、离子液体-聚醚混合溶剂的配制:将离子液体与聚醚按照比例进行混合,配制成催化剂-反应介质混合体系,上述的离子液体-聚醚混合液中,离子液体与聚醚的质量之比为1:1 〜1:10 (w/w); [0011] Step 1, an ionic liquid - a mixed solvent of a polyether prepared: ionic liquid were mixed according to the proportion of the polyether to prepare a catalyst - mixed system the reaction medium, the above-described ionic liquid - polyether mixture, and the ionic liquid mass ratio of polyether 1: 1 ~1: 10 (w / w);

[0012] 步骤2、聚琥珀亚酰胺的合成:按照离子液体-聚醚混合液的加入质量为L-天冬氨酸质量的5%_50% (w/w%)分别向反应器中加入L-天冬氨酸和离子液体-聚醚混合溶剂,其中离子液体-聚醚混合溶剂作为反应介质和催化剂,升温至160〜240°C,反应时间为1〜 4.5h,真空度为-90〜-IOkPa,即得到聚琥珀亚酰胺(PSI)-离子液体-聚醚混合溶液; [0012] Step 2 Synthesis of poly succinimide: Following ionic liquid - mass of the polyether mixture were added 5% _50% L- aspartic acid mass (w / w%) were added to the reactor L - aspartic acid and an ionic liquid - polyether mixed solvent, wherein the ionic liquid - polyether mixed solvent as the reaction medium and the catalyst was heated to 160~240 ° C, the reaction time is 1~ 4.5h, the degree of vacuum of -90~ -IOkPa, i.e., to obtain a polylactic succinimide (the PSI) - ionic liquid - polyether mixed solution;

[0013] 步骤3、向混合溶液中加入碱的水溶液,在40〜60°C温度下搅拌水解反应,水解完成后,体系自动分为液-液两相:上相是聚醚水溶液、下相是聚天冬氨酸(PASP)盐水溶液;采用倾析器进行液液分相后,下相即为产品聚天冬氨酸(PASP)盐水溶液,聚天冬氨酸质量含量为40-46 %,上相加入与离子液体-聚醚混合溶剂中离子液体等摩尔的磷酸再生,重新变成离子液体-聚醚混合液,重复用于下一批次的聚合反应。 [0013] Step 3, the mixed solution was added to an aqueous solution of a base, the hydrolysis reaction is stirred at a temperature of 40~60 ° C, after completion of the hydrolysis, the system automatically into liquid - liquid two phases: an aqueous solution relative polyether, the lower phase It is polyaspartic acid (PASP) saline solution; after use decanter liquid-liquid phase separation, the lower phase is the product of polyaspartic acid (PASP) an aqueous solution of a salt of polyaspartic acid content of 40-46% by mass , with the addition of the ionic liquid relative - polyether mole of phosphoric acid mixed solvent regenerated ionic liquid, the ionic liquid back into - polyether mixture, repeated for the next batch polymerization.

[0014] 上述的聚天冬氨酸的制备方法,所述的离子液体-聚醚混合液中,离子液体为烷基咪唑磷酸盐类或N,N-二烷基苯胺磷酸盐类离子液体。 [0014] The preparation of polyaspartic acid, the ionic liquid - polyether mixture, the ionic liquid is an alkyl phosphate imidazole or N, N- dialkylaniline phosphate based ionic liquids.

[0015] 上述的聚天冬氨酸的制备方法,所述的烷基咪唑磷酸盐类离子液体为:1-乙基咪唑磷酸二氢盐([E頂][H2PO4] )、1-丙基咪唑磷酸二氢盐([P頂][H2PO4] )、1-丁基咪唑磷酸二氢盐([BIM] [H2P04])或1-己基咪唑磷酸二氢盐([HM] [H2P04])中的任意一种或几种的组合。 [0015] The preparation of polyaspartic acid, said alkyl imidazole phosphate based ionic liquids are: 1-ethylimidazole dihydrogen phosphate ([E Top] [H2PO4]), 1- propyl imidazole dihydrogen phosphate ([P top] [H2PO4]), 1- butyl imidazole dihydrogen phosphate ([BIM] [H2P04]) or 1-hexyl-imidazole dihydrogen phosphate ([HM] [H2P04]) in the combination of any one or more of.

[0016] 上述的聚天冬氨酸的制备方法,所述的N,N-二烷基苯胺磷酸盐类离子液体为N,N-二甲基苯胺磷酸二氢盐([MMAN] [H2P04])、N,N-二乙基苯胺磷酸二氢盐([EEAN] [H2POJ )中的任意一种或几种的组合。 [0016] The preparation of polyaspartic acid, the N, N- dialkylanilines phosphate ionic liquid is N, N- dimethyl aniline dihydrogen phosphate ([MMAN] [H2P04] ), N, any combination of one or more N- diethylaniline dihydrogen phosphate ([EEAN] [H2POJ) in.

[0017] 上述的聚天冬氨酸的制备方法,所述的离子液体-聚醚混合液中,聚醚为聚乙二醇(PEG)、聚乙二醇单甲醚(MPEG)、聚乙二醇二甲醚(PEG-DM)中的任意一种或它们的混合物, 且聚合物的平均分子量为200〜400。 [0017] The preparation of polyaspartic acid, the ionic liquid - mixture polyether, the polyether is polyethylene glycol (PEG), polyethylene glycol monomethyl ether (the MPEG), polyethylene any glycol dimethyl ether (PEG-DM) or mixtures thereof, and having an average molecular weight of the polymer was 200~400.

[0018] 上述的聚天冬氨酸的制备方法,步骤3所述的水解条件为:碱溶液为氢氧化钾或氢氧化钠水溶液,浓度为1〜6mol/L,水解时间为1〜3小时,碱水溶液在1小时内连续缓慢滴加,水解终点为检测溶液pH值达到10〜12。 [0018] The above method of producing polyaspartic acid, the hydrolysis conditions according to step 3: alkali solution is potassium hydroxide or sodium hydroxide, at a concentration of 1~6mol / L, the hydrolysis time is 1~3 hours , alkaline aqueous solution within one hour of continuous slowly dropped, hydrolysis end point detection solution pH to 10~12.

[0019] 本发明与现有技术相比,其优点是:(1)生产过程成本比现有工艺可以降低20%以上,生产过程无三废排放;(2) PASP产品的重均分子量控制在5000-20000以上,且分子量分散指数在3以内。 [0019] Compared with the prior art, its advantages are: (1) production cost can be reduced more than 20% than the conventional process, the production process without waste discharge; weight (2) PASP average product molecular weight control at 5000 -20000 or more, and a molecular weight dispersion index of less than 3. (3)产品无毒无害,且能在环境中被微生物降解,28天降解率超过50%。 (3) non-toxic products, and that can be microbial degradation in the environment, the degradation rate of more than 28 days 50%.

附图说明 BRIEF DESCRIPTION

[0020] 图1为本发明所述的工艺路线图,其中1为离子液体-聚醚混合液与L-天冬氨酸混合进料,2为碱溶液进料,3为反应完成后混合液出料,4为经分相器分出的下相产品聚天冬氨酸盐溶液出料,5为经分相器分出的上相聚醚回收液出料,6为再生回收的离子液体-聚醚混合液进料。 [0020] FIG. 1 process route according to the present invention, FIG, wherein the ionic liquid is 1 - polyether mixture and mixed feed L- aspartic acid, an alkali solution feed 2, 3 after completion of the reaction mixture the material, via the phase splitter 4 is separated lower phase product polyaspartate solution is discharged, 5 separated by the phase separator relative to the polyether recovered liquid discharge, 6 recuperation ionic liquid - polyether mixture feed. 其中合成与水解步骤均在犁刀式反应器A中进行,反应器B为倾析分相器,C为离子液体-聚醚混合液再生用普通混合搅拌器。 Wherein the hydrolysis and the synthesis steps were carried out in reactor A coulter, the reactor B is a decanter phase splitter, C is an ionic liquid - polyether mixture reproducing ordinary mixing stirrer.

具体实施方式 Detailed ways

[0021] 以下通过实施例进一步说明本发明 [0021] The invention is further illustrated by the following embodiment Examples

[0022] 离子液体-聚醚混合溶剂的配制: [0022] Ionic Liquid - polyether mixed solvent prepared:

[0023] 将离子液体A与聚醚B按一定比例进行混合,搅拌均匀,配制成催化剂-反应介质。 [0023] The ionic liquids A and B in the polyether by mixing uniformly stirred to prepare a catalyst - the reaction medium. 具体配比方案如下: Program specific ratios as follows:

Figure CN104788674BD00051

[0025] [0025]

Figure CN104788674BD00061

[0026] 其中:[EM] [H2PO4]为1-乙基咪唑磷酸二氢盐、[PM] [H2PO4]为1-丙基咪唑磷酸二氢盐、[BIM] [H2PO4]为1-丁基咪唑磷酸二氢盐、[HIM] [H2PO4]为1-己基咪唑磷酸二氢盐、 [MMAN] [H2PO4]为N,N-二甲基苯胺磷酸二氢盐、[EEAN] [H2PO4]为N,N-二乙基苯胺磷酸二氢盐;PEG为聚乙二醇、MPEG为聚乙二醇单甲醚、PEG-DM为聚乙二醇二甲醚。 [0026] wherein: [EM] [H2PO4] imidazol-1-ethyl dihydrogen phosphate, [PM] [H2PO4] imidazol-1-propyl dihydrogen phosphate, [BIM] [H2PO4] 1 -butyl imidazole dihydrogen phosphate, [HIM] [H2PO4] imidazol-1-yl-hexyl dihydrogen phosphate, [MMAN] [H2PO4] is N, N- dimethyl aniline dihydrogen phosphate, [EEAN] [H2PO4] is N , N- diethylaniline dihydrogen phosphate; PEG is a polyethylene glycol, MPEG polyethylene glycol monomethyl ether, PEG-DM is a polyethylene glycol dimethyl ether.

[0027] 实施例11:根据实施例1,300份L-天冬氨酸中加入40份离子液体-聚醚混合溶剂, 采用犁刀式反应器进行搅拌反应。 [0027] Example 11: According to Example 1,300 parts of L- aspartic acid was added 40 parts of an ionic liquid - polyether mixed solvent using coulter reaction was stirred reactor. 反应温度为200°C,真空度为_50kPa,反应4.5h后得到聚琥珀亚酰胺(PSI)-离子液体混合液。 The reaction temperature was 200 ° C, degree of vacuum _50kPa, 4.5h after the reaction to give poly succinimide (PSI) - ionic liquid mixture. 向混合液中滴加3mol/L的氢氧化钾水溶液,50°C水解1.5h,反应结束后体系分为液液双相。 Solution of 3mol / L aqueous potassium hydroxide solution to the mixed solution, 50 ° C hydrolysis 1.5h, after the completion of the reaction system is divided into a liquid-liquid biphase. 其中氢氧化钾水溶液加入量以反应结束后溶液pH在10〜12之间为准。 Wherein the amount of aqueous potassium hydroxide solution was added after the reaction solution pH to between 10~12 prevail. 用倾析器将两相分离,上相混合物加入与离子液体-聚醚混合溶剂中离子液体等摩尔量磷酸使离子液体再生,重新用于下一批次的反应。 The decanter with two phases were separated, and the ionic liquid relative to the mixture was added - a mixed solvent of the ionic liquid polyether equimolar amount of phosphoric acid ionic liquid regeneration, re-used in the next batch reaction. 下相为所获得的聚天冬氨酸(PASP)盐水溶液,质量含量大于等于45%,产品分子量在5000〜8000之间。 The lower phase is obtained polyaspartic acid (PASP) saline solution, greater than or equal to 45% mass content, the product molecular weight between 5000~8000.

[0028] 实施例12:根据实施例4,100份L-天冬氨酸中加入36份离子液体-聚醚混合溶剂, 采用犁刀式反应器进行搅拌反应。 [0028] Example 12: According to Example 4,100 parts of L- aspartic acid was added 36 parts of an ionic liquid - polyether mixed solvent using coulter reaction was stirred reactor. 反应温度为160°C,真空度为-10kPa,反应l.Oh后得到聚琥珀亚酰胺(PSI)-离子液体混合液。 The reaction temperature was 160 ° C, degree of vacuum -10kPa, polysuccinimide obtained after the reaction l.Oh imide (PSI) - ionic liquid mixture. 向混合液中滴加6mol/L的氢氧化钾水溶液,40°C水解I. Oh,反应结束后体系分为液液双相。 Dropwise 6mol / L aqueous potassium hydroxide solution to the mixed solution, 40 ° C hydrolysis I. Oh, after the completion of the reaction system is divided into a liquid-liquid biphase. 其中氢氧化钠水溶液加入量以反应结束后溶液pH在10〜12之间为准。 Wherein the amount of sodium hydroxide aqueous solution was added to the solution after the reaction pH between 10~12 prevail. 用倾析器将混合液分离,上相混合物加入等摩尔量的100份磷酸使离子液体再生,重新用于下一批次的反应。 The mixture was separated by the decanter, the mixture was added relative to 100 parts of an equimolar amount of phosphoric acid ionic liquid regeneration, re-used in the next batch reaction. 下相为所获得的聚天冬氨酸(PASP)盐水溶液,质量含量大于等于40%,产品分子量在15000〜20000之间。 The lower phase is obtained polyaspartic acid (PASP) saline solution, mass content of 40% or more, a molecular weight of between 15000~20000 product.

[0029] 实施例13:根据实施例6,200份L-天冬氨酸中加入90份离子液体-聚醚混合溶剂, 采用普通搅拌式反应器进行搅拌反应。 [0029] Example 13: According to Example 6,200 parts of L- aspartic acid was added 90 parts of an ionic liquid - polyether mixed solvent ordinary stirred reactor the reaction was stirred. 反应温度为200°C,真空度为_70kPa,反应3.Oh后得到聚琥珀亚酰胺(PSI)-离子液体混合液。 The reaction temperature was 200 ° C, degree of vacuum _70kPa, polysuccinimide obtained after the reaction 3.Oh imide (PSI) - ionic liquid mixture. 向混合液中滴加1.5mol/L的氢氧化钠水溶液,40 °C水解1.5h,反应结束后体系分为液液双相。 Solution of 1.5mol / L sodium hydroxide aqueous solution to the mixture, 40 ° C hydrolysis 1.5h, after the completion of the reaction system is divided into a liquid-liquid biphase. 其中氢氧化钾水溶液加入量以反应结束后溶液pH在10〜12之间为准。 Wherein the amount of aqueous potassium hydroxide solution was added after the reaction solution pH to between 10~12 prevail. 用倾析器将两相分离,上相混合物加入等摩尔量的100份磷酸使离子液体再生,重新用于下一批次的反应。 The decanter with two phases were separated, the mixture was added relative to 100 parts of an equimolar amount of phosphoric acid ionic liquid regeneration, re-used in the next batch reaction. 下相为所获得的聚天冬氨酸(PASP)盐水溶液,质量含量大于等于46%,产品分子量在7000〜10000之间。 The lower phase is obtained polyaspartic acid (PASP) saline solution, mass content of not less than 46%, a molecular weight of between 7000~10000 product.

[0030] 实施例14:根据实施例9,400份L-天冬氨酸中加入100份离子液体-聚醚混合溶剂, 采用普通搅拌式反应器进行搅拌反应。 [0030] Example 14: According to Example 9,400 parts of L- aspartic acid was added 100 parts of an ionic liquid - polyether mixed solvent ordinary stirred reactor the reaction was stirred. 反应温度为240Γ,真空度为_90kPa,反应4.5h后得到聚琥珀亚酰胺(PSI)-离子液体混合液。 The reaction temperature is 240Γ, degree of vacuum _90kPa, 4.5h after the reaction to give poly succinimide (PSI) - ionic liquid mixture. 向混合液中滴加lmol/L的氢氧化钾水溶液,60°C 水解3. Oh,反应结束后体系分为液液双相。 To the mixture was added dropwise lmol / L aqueous potassium hydroxide solution, 60 ° C hydrolysis 3. Oh, after the completion of the reaction system is divided into a liquid-liquid biphase. 其中氢氧化钠水溶液加入量以反应结束后溶液pH在10〜12之间为准。 Wherein the amount of sodium hydroxide aqueous solution was added to the solution after the reaction pH between 10~12 prevail. 用倾析器将两相分离,上相混合物加入等摩尔量的100份磷酸使离子液体再生,重新用于下一批次的反应。 The decanter with two phases were separated, the mixture was added relative to 100 parts of an equimolar amount of phosphoric acid ionic liquid regeneration, re-used in the next batch reaction. 下相为所获得的聚天冬氨酸(PASP)盐水溶液,质量含量大于等于41 %,产品分子量在15000〜20000之间。 The lower phase is obtained polyaspartic acid (PASP) saline solution, mass content of not less than 41%, a molecular weight of between 15000~20000 product.

[0031] 实施例15:根据实施例10,500份L-天冬氨酸中加入300份离子液体-聚醚混合溶剂,采用普通搅拌式反应器进行搅拌反应。 [0031] Example 15: According to Example 10,500 parts of L- aspartic acid was added 300 parts of the ionic liquid - polyether mixed solvent ordinary stirred reactor the reaction was stirred. 反应温度为180°C,真空度为-SOkPa,反应4.5h后得到聚琥珀亚酰胺(PSI)-离子液体混合液。 The reaction temperature was 180 ° C, degree of vacuum -SOkPa, 4.5h after the reaction to give poly succinimide (PSI) - ionic liquid mixture. 向混合液中滴加2mol/L的氢氧化钾水溶液,55 °C水解2. Oh,反应结束后体系分为液液双相。 Solution of 2mol / L aqueous potassium hydroxide solution to the mixed solution, 55 ° C hydrolysis 2. Oh, after the completion of the reaction system is divided into a liquid-liquid biphase. 其中氢氧化钾水溶液加入量以反应结束后溶液pH在10〜12之间为准。 Wherein the amount of aqueous potassium hydroxide solution was added after the reaction solution pH to between 10~12 prevail. 用倾析器将两相分离,上相混合物加入等摩尔量的100份磷酸使离子液体再生,重新用于下一批次的反应。 The decanter with two phases were separated, the mixture was added relative to 100 parts of an equimolar amount of phosphoric acid ionic liquid regeneration, re-used in the next batch reaction. 下相为所获得的聚天冬氨酸(PASP)盐水溶液,质量含量大于等于45%,产品分子量在10000〜15000之间。 The lower phase is obtained polyaspartic acid (PASP) saline solution, greater than or equal to 45% mass content, the product molecular weight between 10000~15000.

Claims (7)

  1. 1. 一种以离子液体-聚醚混合液为催化剂和反应介质的聚天冬氨酸的制备方法,其特征是它包括如下步骤: 步骤1、离子液体-聚醚混合溶剂的配制:将离子液体与聚醚按照比例进行混合,配制成催化剂-反应介质混合体系,上述的离子液体-聚醚混合液中,离子液体与聚醚的质量之比为1:1 〜1:10 (w/w); 步骤2、聚琥珀亚酰胺的合成:按照离子液体-聚醚混合液的加入质量为L-天冬氨酸质量的5%-50% (w/w%)分别向反应器中加入L-天冬氨酸和离子液体-聚醚混合溶剂,其中离子液体-聚醚混合溶剂作为反应介质和催化剂,升温至160〜240 °C,反应时间为1〜4.5h,真空度为-90〜-10kPa,即得到聚琥珀亚酰胺(PSI)-离子液体-聚醚混合溶液; 步骤3、向混合溶液中加入碱的水溶液,在40〜60°C温度下搅拌水解反应,水解完成后, 体系自动分为液-液两相:上相是聚醚水溶液、下相是聚 An ionic liquid - polyaspartic preparing the polyether mixture to the catalyst and reaction medium, characterized in that it comprises the following steps: Step 1, an ionic liquid - formulated polyether mixed solvent: ion liquid polyether scale mixed to prepare a catalyst - a reaction medium mixing system, the above-mentioned ionic liquid - polyether mixture, the ionic liquid and polyether mass ratio of 1: 1 ~1: 10 (w / w ); step 2, the synthesis of poly succinimide: Following ionic liquid - polyether mixture added mass of 5% -50% L- aspartic acid mass (w / w%) were added L reactor was - aspartic acid and an ionic liquid - polyether mixed solvent, wherein the ionic liquid - polyether mixed solvent as the reaction medium and the catalyst was heated to 160~240 ° C, the reaction time is 1~4.5h, the degree of vacuum of -90~ -10kPa, to obtain the poly succinimide (PSI) - ionic liquids - polyether mixed solution; step 3, the mixed solution was added an aqueous alkali solution at 40~60 ° C temperature with stirring hydrolysis reaction, the hydrolysis is complete, the system automatic into liquid - liquid two phases: relative polyether aqueous lower phase is polyethylene 冬氨酸(PASP)盐水溶液;采用倾析器进行液液分相后,下相即为产品聚天冬氨酸(PASP)盐水溶液,上相加入与离子液体-聚醚混合溶剂中离子液体等摩尔的磷酸,重新变成离子液体-聚醚混合液,重复用于下一批次的聚合反应。 Aspartate (PASP) saline solution; after use decanter liquid-liquid phase separation, the lower phase is the product of polyaspartic acid (PASP) saline solution, relative to addition of the ionic liquid - polyether mixed solvent of ionic liquid mole of phosphoric acid, back into the ionic liquid - polyether mixture was reused for the next batch polymerization.
  2. 2. 根据权利要求1所述的聚天冬氨酸的制备方法,其特征是:所述的离子液体-聚醚混合液中,离子液体为烷基咪唑磷酸盐类或N,N-二烷基苯胺磷酸盐类离子液体。 2. The polyaspartic acid prepared according to claim 1, wherein: said ionic liquid - polyether mixture, the ionic liquid is an alkyl imidazole phosphates or N, N- dialkyl aniline phosphate based ionic liquids.
  3. 3. 根据权利要求2所述的聚天冬氨酸的制备方法,其特征是:所述的烷基咪唑磷酸盐类离子液体为:1_乙基咪唑磷酸二氢盐、1-丙基咪唑磷酸二氢盐、1-丁基咪唑磷酸二氢盐或1-己基咪唑磷酸二氢盐中的任意一种或几种任意比例的组合物。 The polyaspartic acid prepared according to claim 2, wherein: said alkyl imidazole phosphate based ionic liquids are: 1_ ethyl imidazole dihydrogen phosphate, 1-propyl-imidazole dihydrogen phosphate, 1-butyl imidazole dihydrogen phosphate salt or 1-hexyl-imidazole dihydrogen phosphate salt of any one or more of any proportion of the composition.
  4. 4. 根据权利要求2所述的聚天冬氨酸的制备方法,其特征是:所述的N,N-二烷基苯胺磷酸盐类离子液体为N,N-二甲基苯胺磷酸二氢盐、N, N-二乙基苯胺磷酸二氢盐中的任意一种或两者任意比例的组合物。 Polyaspartic acid preparation according to claim 2, wherein: said N, N- dialkylanilines phosphate based ionic liquid is N, N- dimethyl aniline dihydrogen phosphate salts, N, N- diethyl any one or in any ratio of both compositions aniline dihydrogen phosphate salt.
  5. 5. 根据权利要求1所述的聚天冬氨酸的制备方法,其特征是:所述的离子液体-聚醚混合液中,聚醚为聚乙二醇、聚乙二醇单甲醚或聚乙二醇二甲醚中的任意一种或它们任意比例的混合物,且聚合物的数均分子量为200〜400。 The polyaspartic acid prepared according to claim 1, wherein: said ionic liquid - polyether mixture, the polyether is polyethylene glycol, polyethylene glycol monomethyl ether or a mixture of any one of polyethylene glycol dimethyl ether, or any ratio, and the polymer has a number average molecular weight of 200~400.
  6. 6. 根据权利要求1所述的聚天冬氨酸的制备方法,其特征是:步骤3所述的水解条件为: 碱溶液为氢氧化钾或氢氧化钠水溶液,浓度为1〜6mol/L,水解时间为1〜3小时,碱水溶液在1小时内连续缓慢滴加,水解终点为检测溶液pH值达到10〜12。 6. The polyaspartic acid prepared according to claim 1, wherein: said step 3 hydrolyzing condition: the alkali solution is potassium hydroxide or sodium hydroxide, at a concentration of 1~6mol / L hydrolysis time is 1~3 hours, an aqueous alkali solution continuously slowly added dropwise over 1 hour, the hydrolysis of the end point of the test solution pH to 10~12.
  7. 7. 根据权利要求1所述的一种聚天冬氨酸的制备方法,其特征在于:所述的聚合反应过程通过控制离子液体-聚醚混合液的用量、混合液中离子液体与聚醚的质量之比、及反应过程的真空度几个参数来调控聚合物的分子量及其分布,使得最终聚天冬氨酸产品的平均分子量在5000〜20000之间,分散性指数在3.0以内。 A polyaspartic acid preparation according to claim 1, wherein: the polymerization process by controlling the ionic liquid - polyether mixture the amount of mixture of the ionic liquid with the polyether the mass ratio, and the degree of vacuum of the reaction process several parameters to regulate the molecular weight and its distribution of the polymer, such that the average molecular weight of the final polyaspartate product between 5000~20000, a polydispersity index less than 3.0.
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US5373088A (en) * 1992-09-18 1994-12-13 Donlar Corporation Production of polyaspartic acid from maleic acid and ammonia
CN102250352A (en) * 2011-05-19 2011-11-23 黑龙江大学 Method for catalytic synthesis of polyaspartic acid by using imidazole type ionic liquid
CN102250353A (en) * 2011-05-23 2011-11-23 黑龙江大学 Method for synthesizing polyaspartic acid derivative through multi-component evaporative crystallization copolymerization modification
CN102643425A (en) * 2012-05-16 2012-08-22 黑龙江大学 Method for synthetizing polyaspartic acid by microwaves in ionic liquid
CN103304815A (en) * 2013-06-13 2013-09-18 扬州大学 Preparation method for synthesizing polyaspartic acid by using ionic liquid
CN104327267A (en) * 2014-11-04 2015-02-04 中国林业科学研究院林产化学工业研究所 Preparation method of polyaspartic acid in liquid medium

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5373088A (en) * 1992-09-18 1994-12-13 Donlar Corporation Production of polyaspartic acid from maleic acid and ammonia
CN102250352A (en) * 2011-05-19 2011-11-23 黑龙江大学 Method for catalytic synthesis of polyaspartic acid by using imidazole type ionic liquid
CN102250353A (en) * 2011-05-23 2011-11-23 黑龙江大学 Method for synthesizing polyaspartic acid derivative through multi-component evaporative crystallization copolymerization modification
CN102643425A (en) * 2012-05-16 2012-08-22 黑龙江大学 Method for synthetizing polyaspartic acid by microwaves in ionic liquid
CN103304815A (en) * 2013-06-13 2013-09-18 扬州大学 Preparation method for synthesizing polyaspartic acid by using ionic liquid
CN104327267A (en) * 2014-11-04 2015-02-04 中国林业科学研究院林产化学工业研究所 Preparation method of polyaspartic acid in liquid medium

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