CN102604072B - Preparation method of polyether amine - Google Patents

Preparation method of polyether amine Download PDF

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CN102604072B
CN102604072B CN 201210052388 CN201210052388A CN102604072B CN 102604072 B CN102604072 B CN 102604072B CN 201210052388 CN201210052388 CN 201210052388 CN 201210052388 A CN201210052388 A CN 201210052388A CN 102604072 B CN102604072 B CN 102604072B
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polyether
amine
preparation method
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张文泉
朱学军
尤卫民
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无锡阿科力化工有限公司
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Abstract

本发明涉及一种聚醚胺的制备方法,主链为聚环氧丙烷、聚环氧乙烷、聚四氢呋喃或者三者的共聚物,主链的一端为羟基,主链的另一端为具有H2N-R-OH结构的醇胺类化合物封端。 The present invention relates to a method for preparing a polyether amine, a main chain of polypropylene oxide, polyethylene oxide, polytetrahydrofuran copolymer, or three, one end of the main chain is hydroxy, the other end of the main chain having a H2N alcohol amines -R-OH-terminated structure. 所述的聚醚胺通过下面方法制备得到:(1)利用叔丁氧羰基(BOC)保护醇胺类化合物的胺基,羟基保留,得到BOC-NH-R-OH;(2)BOC-NH-R-OH在强碱或者双金属氰化物催化下,引发环氧乙烷、环氧丙烷、四氢呋喃或者三者的混合物反应,进行开环聚合;(3)在酸性条件下,进行BOC的脱保护反应,得到所述聚醚胺。 The polyetheramine prepared by the following method to give: (1) an amine compound protected amino alcohol using tert-butoxycarbonyl (BOC), hydroxy retained afford BOC-NH-R-OH; (2) BOC-NH -R-OH in the strong base or double metal cyanide catalysis, lead to ethylene oxide, propylene oxide, tetrahydrofuran or all three of the reaction, ring-opening polymerization; (3) under acidic conditions, the removal of BOC 28 gives the polyetheramine. 本发明通过调节聚醚链中环氧丙烷、环氧乙烷与四氢呋喃的比例,可得不同亲水性的聚醚主链,聚醚链的一端含有胺基,酸化之后可提供较强的亲水性,可应用于表面活性剂、絮凝剂、染整助剂以及电泳漆等领域。 The present invention, by adjusting the polyether chain of propylene oxide, the ratio of ethylene oxide and tetrahydrofuran, may be of various hydrophilic polyether backbone, at one end of the polyether chain containing an amine, provides a strong affinity after acidification water, can be applied to the surface-active agent, flocculant, dyeing auxiliaries and other fields electrophoretic paint.

Description

聚醚胺的制备方法 A method of preparing polyetheramine

技术领域 FIELD

[0001] 本发明涉及一种聚醚胺的制备方法,尤其是一种一端含有胺基,另一端为羟基的聚醚胺的制备方法,属于化工技术领域。 [0001] The present invention relates to a method for preparing a polyether amine, in particular a preparation containing an end group, and the other end is hydroxy polyether amines, belonging to the field of chemical technology.

背景技术 Background technique

[0002] 聚醚胺是一类主链含有聚氧化烷基结构,活性官能团为胺基的化合物。 [0002] The polyether amine is a kind of a main chain structure containing a polyoxyalkylene alkyl, amine compound as a reactive functional group. 通过选择不同的聚氧化烷基结构,可调节聚醚胺的韧性、粘度以及亲水性等一系列性能,而胺基提供给聚醚胺与多种化合物反应的可能性。 By selecting different polyoxyalkylene alkyl structure, the adjustable range polyetheramine toughness properties, viscosity, and hydrophilicity, but the possibility of a polyether amine compound with a plurality of amine groups to provide. 因其特殊的结构,聚醚胺在众多应用领域表现出独特的性能,其应用范围也越来越广。 Because of its special structure, polyether amines exhibit unique performance in many applications, its application more widely.

[0003]目前已公开的合成方法,聚醚末端引入胺基的方法主要包括三种:(1)聚醚末端羟基在催化剂作用下利用氨/氢直接胺化;(2)通过引入氰基,催化加氢后得到胺基;(3)通过含胺基的化合物与聚醚反应,引入胺基。 [0003] The synthetic method has been disclosed, a method of introducing amine-terminated polyether include three types: (1) a hydroxyl-terminated polyether with ammonia / hydrogen in the direct amination catalyst; (2) by introducing a cyano group, catalytic hydrogenation of the amine; (3) a compound containing an amine group by reaction with a polyether, amine introduced. 其中前两种方法对设备和工艺要求较高,与之相比,第三种工艺比较容易实现,但是,因为选择的胺类化合物往往同时含有几个胺基,或者含有羟基、羧基等其他含有活性氢原子的基团,因此在与聚醚链连接时很难保证一个胺类化合物只连接一条聚醚主链,因此选择合适的胺类化合物,并有选择性地将之与聚醚链相连,是此类方法的关键。 Wherein the first two methods and apparatus for high process requirements, compared with the third process is easier to achieve, however, because the choice of amine compound contains several amine often simultaneously, or containing a hydroxyl group, a carboxyl group-containing and other groups active hydrogen atoms, and therefore in connection with a polyether chain amine compound only difficult to ensure a polyether backbone connection, thus select the appropriate amine compound, and selectively connect the polyether chains It is the key to such methods.

[0004] CN1546550A公开了在金属催化剂作用下,通过间歇釜式反应,用聚醚多元醇制备胺基聚醚。 [0004] CN1546550A discloses a metal in the catalyst by the batch reactor, a polyether polyol prepared with a polyether amine. CN1803882A公开了一种羟基苄胺封端聚醚多元醇,合成含苯环的聚醚胺的方法。 CN1803882A discloses a hydroxybenzyl amine terminated polyether polyol, aromatic amine-containing polyether is synthesized. CN102212191A公开了一种通过利用二羰基咪唑活化聚醚多元醇羟基,直接与乙二胺反应得到端氨基聚醚的方法。 CN102212191A discloses a method by using two carbonyl imidazole activated hydroxyl groups of polyether polyols, ethylenediamine reacted with a polyether amino terminal directly. CN102086263A公开了一种羟胺基聚醚的合成方法,及工艺路线主要是聚醚多元醇与环氧氯丙烷合成缩水甘油醚,再与单元伯胺反应。 CN102086263A discloses a method for synthesizing hydroxylamine polyether, and the main process route is a polyether polyol synthesis glycidyl ether and epichlorohydrin, and then with a primary amine unit. CN101001902公开了一种利用环氧氯丙烷与聚醚多元·醇反应,然后利用脂肪胺与之反应,将胺基与聚醚链相连。 CN101001902 discloses a method of using a polyether polyol with epichlorohydrin · alcohols, fatty amines and the use of the reaction with the amine group attached to the polyether chain.

[0005] 因为聚醚胺胺基离子化后表现出较强的亲水性,而聚醚结构主链可通过单体选择,控制其表现出亲水性或者疏水性,因此一端为氨基的聚醚胺在表面活性剂、絮凝剂、染整助剂以及电泳漆等领域表现出极佳的性能。 [0005] Because the polyether amine group ionized shows strong hydrophilicity, and the structure of the main chain of a polyether monomer selected by the control which exhibits hydrophilicity or hydrophobicity, to one end of an amino poly ether amines exhibit excellent performance in the surfactant, flocculant, dyeing auxiliaries and other fields electrophoretic paint. 通过结构设计,合成主链结构可控,一端为胺基的聚醚胺,在这些领域有着广泛的应用前景。 By design, the controllable synthesized backbone structure, one end of the group of polyetheramine has wide applications in these fields.

发明内容 SUMMARY

[0006] 本发明的目的是克服现有技术中存在的不足,提供一种聚醚胺的制备方法,可以有效的避免两条或以上聚醚主链连接到同一个醇胺分子之上,可得到结构更加的规整的单端为胺基的聚醚胺结构。 [0006] The object of the present invention is to overcome the disadvantages of the prior art, there is provided a method for preparing a polyether amine, can effectively prevent two or more polyether backbone is connected onto the same molecule olamine, may a more regular structure of the resulting single-ended polyether amine to amine structure.

[0007] 按照本发明提供的技术方案,所述聚醚胺的主链为聚环氧丙烷、聚环氧乙烷、聚四氢呋喃或者三者的共聚物,聚合度为5〜100,主链的一端为羟基,主链的另一端为具有通SH2N-R-OH(I)结构的醇胺类化合物封端; [0007] The present invention provides the technical solution according to the main chain of the polyether amines are polypropylene oxide, polyethylene oxide, polytetrahydrofuran copolymers or three, 5~100 degree of polymerization, backbone a hydroxyl group at one end, the other end of the main chain is an alcohol-based compound having a structure through SH2N-R-OH (I) blocked;

[0008] 其中R为直链或支链的CnH2n, η = 2〜18或CH3 fH3 CH3 [0008] CnH2n wherein R is a linear or branched chain, η = 2~18 or CH3 fH3 CH3

CH-CH2-(>^CH2-CH2-0^^CH-CH2-0^;CH2-1H CH-CH2 - (> ^ CH2-CH2-0 ^^ CH-CH2-0 ^; CH2-1H

CH3 CH3

X = O 〜10, y = O 〜10 或cH2-cH2-0^CH2-CH2-0|^CH-CH2-0^;CH2-CH2 X = O ~10, y = O ~10 or cH2-cH2-0 ^ CH2-CH2-0 | ^ CH-CH2-0 ^; CH2-CH2

X = Q 〜10,y = O 〜10 j|J^CH2-CH2-0Η2.0Η2_0.^.0Η2.0Η2_0Η2.0Η2_0.^.^0Η2_CH2OH2 CH2 X = Q ~10, y = O ~10 j |.... J ^ CH2-CH2-0Η2.0Η2_0 ^ 0Η2.0Η2_0Η2.0Η2_0 ^ ^ 0Η2_CH2OH2 CH2

η = O 〜10。 η = O ~10.

[0009] 本发明还保护一种聚醚胺的制备方法,特征是,采用以下工艺步骤: [0009] The present invention is also a method for preparing protective polyetheramines, characterized in that the following process steps:

[0010] (I)将具有通式H2N-R-OH(I)结构的醇胺类化合物溶于水或者水与有机溶剂的混合溶剂中,浓度为10〜60% ;所述有机溶剂为四氢呋喃或二氧六环,混合溶剂中有机溶剂与水的比例为5: 95〜40: 60 ; [0010] (I) having the general formula H2N-R-OH (I) an alcohol amine compounds dissolved in water or a mixed solvent of water and an organic solvent, at a concentration of 10 to 60%; the organic solvent is tetrahydrofuran or dioxane, a mixed solvent ratio of organic solvent to water is 5: 95~40: 60;

[0011] (2)向步骤(I)得到的化合物中滴加催化剂与二碳酸二叔丁酯,滴加时的温度为-10〜40°C,I〜6小时滴加完成;滴加完成后,在温度为-10〜40°C的条件下反应4〜48小时,反应结束后的pH值为10〜14 ;所述催化剂为Na0H、Na2C03或者三乙胺,催化剂与醇胺类化合物的摩尔比为0.5〜3: 1,二碳酸二叔丁酯与醇胺类化合物的摩尔比为I〜1.1: 1,所述二碳酸二叔丁酯为纯的二碳酸二叔丁酯或二碳酸二叔丁酯与有机溶剂的混合溶液,所述二碳酸二叔丁酯与有机溶剂的混合溶液的浓度为10〜60%,所述有机溶剂为丙酮、四氢呋喃或二氧六环; [0011] (2) The compound obtained in the step (I) catalyst was added dropwise with di-tert-butyl temperature during the dropwise addition of -10~40 ° C, I~6 hours the addition was complete; completion of the dropwise after the reaction at a temperature condition of -10~40 ° C 4~48 hours, pH after the reaction is 10~14; the catalyst is Na0H, Na2C03 or triethylamine, amine catalyst with an alcohol compound molar ratio of 0.5~3: 1 molar ratio of di-tert-butyl alcohol and the amine compound is I~1.1: 1, the di-tert-butyl ester as a pure butyl dicarbonate or di-carbonate a mixed solution of tert-butyl and the organic solvent, the concentration of the mixed solution of di-tertbutyl dicarbonate and 10 to 60% of the organic solvent, the organic solvent is acetone, tetrahydrofuran or dioxane;

[0012] (3)将步骤(2)得到的化合物进行减压蒸馏,以除去化合物中的有机溶剂,真空压力小于500Pa,蒸馏温度`为40〜100°C ; [0012] (3) Step (2) The compound obtained by distillation under reduced pressure to remove the organic solvent compounds, the vacuum pressure is less than 500Pa, `distillation temperature of 40~100 ° C;

[0013] (4)向步骤⑶得到的化合物中加入有机溶剂进行萃取,得到水层和有机层;将水层用有机溶剂再萃取一次后,将得到的有机相与有机层合并;将有机层用饱和食盐水洗涤,加入无水硫酸钠干燥2〜6小时,减压蒸馏除去有机溶剂,得到由叔丁氧羰基(BOC)保护的醇胺类化合物BOC-NH-R-OH ;所述有机溶剂为乙酸乙酯、苯、甲苯、环己烷、二氯甲烷或氯仿; [0013] (4) an organic solvent is added to the compound obtained in step ⑶ extracted aqueous layer and an organic layer was obtained; the organic layer of the organic phase The aqueous layer was extracted once with an organic solvent, and the resulting combined; The organic layer was was washed with saturated brine, dried over anhydrous sodium sulfate was added 2 ~ 6 hours, the organic solvent was distilled off under reduced pressure, to give protected by t-butyloxycarbonyl (BOC) an alcohol amine compound BOC-NH-R-OH; the organic The solvent is ethyl acetate, benzene, toluene, cyclohexane, methylene chloride or chloroform;

[0014] (5)向由叔丁氧羰基(BOC)保护的醇胺类化合物BOC-NH-R-OH中加入碱金属或碱土金属的氧化物或氢氧化物或者双金属氰化物,碱金属或碱土金属的氧化物或氢氧化物或者双金属氰化物的加入量为由叔丁氧羰基(BOC)保护的醇胺类化合物BOC-NH-R-OH的 [0014] (5) an alkali metal or alkaline earth metal is added to a protected by t-butyloxycarbonyl (BOC) an alcohol amine compound BOC-NH-R-OH in the oxide or hydroxide or a double metal cyanide, an alkali metal or an oxide or hydroxide added in an amount of double metal cyanide or alkaline earth metal protected alcohol amine compound by t-butoxycarbonyl (BOC) BOC-NH-R-OH is

0.1〜5% Wt,向反应体系中冲氮气以除去氧气,升温至50〜100°C,抽真空至压力小于500Pa,保持0.5〜2小时,除去反应体系中的水; 0.1~5% Wt, rushed to the reaction system with nitrogen to remove oxygen and heated to 50~100 ° C, evacuated to a pressure less than 500Pa, holding 0.5~2 hours, removing the reaction water in the system;

[0015] (6)向步骤(5)得到的产物中加入单体进行反应,反应温度为80〜120°C,反应压力为0.1〜0.6MPa,每次加入一种单体,待反应压力降至常压后加入下一种单体或反应结束;所述单体的加入量与BOC-NH-R-OH的摩尔比为5〜100: 1,所述单体为环氧乙烷、环氧丙烷或四氢呋喃中的一种或多种; Obtained [0015] (6) of step (5) the reaction product of monomer added, the reaction temperature of 80~120 ° C, a reaction pressure of 0.1~0.6MPa, each one monomer is added until the reactor pressure had dropped was added to the atmospheric pressure at the end of the monomer or reaction; adding an amount of the monomer and the molar ratio of BOC-NH-R-OH is 5~100: 1, the monomer is ethylene oxide, ring one or more propylene oxide or tetrahydrofuran;

[0016] (7)向步骤(6)得到的产物中加入0.5〜5mol/L的盐酸,调节pH值为I〜2,保持温度为50〜80V,反应I〜4小时,以脱去叔丁氧羰基(BOC)基团; The product (6) obtained in [0016] (7) was added to the step 0.5~5mol / L hydrochloric acid, adjusted to pH I~2, maintaining the temperature at 50~80V, I~4 hours the reaction to tert-off butoxycarbonyl (BOC) group;

[0017] (8)保持步骤(7)得到的产物的温度为40〜100°C,抽真空使压力小于500Pa,,至回流管管壁上无水滴形成后,再保持0.5〜I小时;过滤;加入吸附剂进行吸附,吸附过程中保持温度为100〜120°C,吸附时间为I〜3小时;冷却至30〜50°C,过滤,即得到所述的聚醚胺产物。 Temperature of the product (7) obtained in [0017] (8) a step of holding 40~100 ° C, evacuated to a pressure less than 500Pa ,, to reflux pipe wall after no water droplets are formed, maintained 0.5~I h; filter ; adsorbing adsorbent is added, maintaining the temperature during the adsorption is 100~120 ° C, adsorption time I~3 hours; cooled to 30~50 ° C, filtered, to obtain the product of polyetheramine.

[0018] 所述碱金属或碱土金属的氧化物或氢氧化物为氢氧化钠、氢氧化钾、氧化锶、氧化钡、氢氧化锶或氢氧化钡。 [0018] The alkali metal or alkaline earth metal oxide or hydroxide is sodium hydroxide, potassium hydroxide, strontium oxide, barium oxide, strontium hydroxide or barium hydroxide.

[0019] 经步骤(5)处理后,反应体系的含水量小于0.5%。 [0019] (5) by the processing step, the water content of the reaction system is less than 0.5%.

[0020] 所述吸附剂为六硅酸镁或六硅酸铝。 [0020] The adsorbent is six or six magnesium aluminum silicate.

[0021] 所述吸附剂的加入量为步骤(7)得到的产物总量的0.1〜5%。 [0021] The amount of adsorbent is added in step (7) 0.1~5% of the total amount of product obtained.

[0022] 步骤(2)中,催化剂与二碳酸二叔丁酯的加入方式为(I)先加入催化剂,再将二碳酸二叔丁酯溶于有机溶剂后滴加加入;或(2)先加入二碳酸二叔丁酯,再滴加加入催化剂;或(3)同时滴加加入催化剂与二碳酸二叔丁酯。 [0022] Step (2), the catalyst was added di-tert-butyl way (I) catalyst is added first, then tert-butyl dicarbonate was added dropwise dissolved in an organic solvent; or (2) to tert-butyl dicarbonate was added, then dropwise addition of a catalyst; or (3) catalyst was added simultaneously dropwise with di-tert-butyl.

[0023] 与现有的单端为胺基的聚醚胺合成方法比较,本发明在常规条件下实现了目标产物的合成,避免了羟基直接胺化对于反应设备和反应条件的较高要求;同时采用BOC基团对于胺基进行保护,有效减少了胺类化合物与聚醚链相连时的副反应,得到结构规整的聚醚胺产物。 [0023] Compared with the existing single-end is a polyetheramine amine synthesis methods, the present invention achieves the synthesis of the desired product under conventional conditions, avoiding the direct amination of hydroxyl high requirements for the equipment and reaction conditions; while using the BOC group to protect an amine group, effectively reducing the side reaction of the polyether chain linked amine compound to give a polyether amine product regular structure. 产物可应用于表面活性剂、絮凝剂、染整助剂以及电泳漆等领域。 The product may be applied to a surface active agent, a flocculant, dyeing auxiliaries and other fields electrophoretic paint.

具体实施方式 detailed description

[0024] 下面结合具体实施例对本发明作进一步说明。 [0024] The following embodiments in conjunction with specific embodiments of the present invention will be further described.

[0025] 本发明所述的聚醚胺的主链为聚环氧丙烷、聚环氧乙烷、聚四氢呋喃或者三者的共聚物,聚合度为5〜100,主链的一端为羟基,主链的另一端为具有通式H2N-R-OH(I)结构的醇胺类化合物封端; [0025] The main chain of the polyether amines of the present invention is a polyethylene oxide, polypropylene oxide, polytetrahydrofuran copolymers or three degree of polymerization of 5~100, one end of the main chain is a hydroxyl group, primary the other end of the chain having the general formula H2N-R-OH (I) an alcohol amine compound capped structure;

[0026] 其中R为直链或支链的CnH2n, η = 2〜18或 [0026] CnH2n wherein R is a linear or branched chain, η = 2~18 or

Figure CN102604072BD00061

[0027] 本发明所述的聚醚胺通过下面方法制备得到:(I)利用叔丁氧羰基(BOC)保护通式(I)结构的醇胺类化合物的胺基,羟基保留,得到BOC-NH-R-OH ; (2)所得BOC-NH-R-OH,在强碱或者双金属氰化物(DMC)催化下,引发环氧乙烷、环氧丙烷、四氢呋喃或者三者的混合物反应,进行开环聚合;(3)在酸性条件下,进行BOC的脱去保护反应,得到所述聚醚胺。 [0027] polyetheramines prepared according to the present invention obtained by the following method: (I) using t-butyloxycarbonyl (BOC) protected formula (I) an amine compound of amino alcohol, a hydroxyl group reservations, to give BOC- NH-R-OH; (2) the resulting BOC-NH-R-OH, a strong base or a double metal cyanide (DMC) catalysis, lead to ethylene oxide, propylene oxide, tetrahydrofuran or all three of the reaction, ring-opening polymerization; (3) under acidic conditions, removing the BOC protecting reaction, to give the polyetheramine. 采用该方法得到的聚醚胺,通过调节聚醚链中环氧丙烷、环氧乙烷与四氢呋喃的比例,可得不同亲水性的聚醚主链,聚醚链的一端含有胺基,酸化之后可提供较强的亲水性,可应用于表面活性剂、絮凝剂、染整助剂以及电泳漆等领域。 Using the method polyetheramine obtained by adjusting the polyether chain of propylene oxide, the ratio of ethylene oxide and tetrahydrofuran, may be of various hydrophilic polyether backbone, at one end of the polyether chain containing an amine, acidified after strong hydrophilicity can be provided, it can be applied to the surface-active agent, flocculant, dyeing auxiliaries and other fields electrophoretic paint.

[0028] 实施例1:一种聚醚胺的制备方法,采用以下工艺步骤: [0028] Example 1: Preparation of the polyether amines, the following process steps:

[0029] (I)将IOOg 乙醇胺(1.64mol)和13IgNaOH(3.28mol)溶于500ml 水中,冷却至(TC,将375g的二碳酸二叔丁酯(BOC2O)溶于500g丙酮得到二碳酸二叔丁酯的丙酮溶液,将二碳酸二叔丁酯的丙酮溶液缓慢滴加到乙醇胺中,控制滴加温度为0°C,2小时滴加完成,保持温度为0°c,继续反应4小时,反应结束后的pH值约为11 ; [0029] (I) The IOOg ethanolamine (1.64 mol) and 13IgNaOH (3.28mol) was dissolved in 500ml of water, cooled to (the TC, the 375g of butyl dicarbonate (Boc2O) was dissolved in acetone to give di-tert-500g butyl acetone solution, the acetone solution of di-t-butyl dicarbonate was slowly added dropwise ethanolamine, dropwise controlled temperature of 0 ° C, 2 dropped over an hour to complete, maintaining the temperature at 0 ° c, the reaction was continued for 4 hours after completion of the reaction pH of about 11;

[0030] (2)将步骤(I)得到的产物进行减压蒸馏,除去产物中的丙酮,真空压力为500Pa,蒸馏温度为60°C ; [0030] (2) the step (I) the product obtained was distilled under reduced pressure to remove the acetone in the product, the vacuum pressure of 500Pa, a distillation temperature of 60 ° C;

[0031] (3)向步骤(2)得到的产物中加入500ml乙酸乙酯进行萃取,得到水层和有机层;将水层用250ml乙酸乙酯再萃取一次后,将得到的有机相与有机层合并;将有机层用300ml饱和食盐水洗涤两次,加入无水硫酸钠干燥2小时;减压蒸馏,控制压力为500Pa,并缓慢升温至100°C,除去乙酸乙酯,得到由叔丁氧羰基(BOC)保护的乙醇胺B0C-MEA,221.8g ; [0031] (3) step (2) of the product obtained was extracted with ethyl acetate 500ml was added, and the aqueous layer the organic layer obtained; The aqueous layer was extracted once with 250ml of ethyl acetate and the resulting organic phase and organic the combined layers; the organic layer was washed twice with 300ml saturated brine, dried over anhydrous sodium sulfate were added two hours; distillation under reduced pressure, the pressure was 500Pa, and slowly warmed to 100 ° C, ethyl acetate was removed to afford the tert-butyl oxycarbonyl (BOC) protected ethanolamine B0C-MEA, 221.8g;

[0032] (4)将161g的由叔丁氧羰基(BOC)保护的乙醇胺B0C-MEA放入压力釜中,加入3g的Κ0Η,升温至80°C,向反应体系中冲氮气以除去氧气,抽真空至压力为500Pa,保持I小时,除去反应体系中的水,反应后,反应体系的含水量小于0.5% ; [0032] (4) by a tert-butoxycarbonyl group 161g of (BOC) protected ethanolamine B0C-MEA placed in a pressure vessel was charged with 3g of Κ0Η, warmed to 80 ° C, filled with nitrogen to the reaction system to remove oxygen, evacuated to a pressure of 500Pa, I held hours after the reaction water in the system, the reaction was removed, the water content of the reaction system is less than 0.5%;

[0033] (5)关闭真空,向步骤⑷得到的产物中加入440g环氧乙烷进行反应,反应温度为100°C,控制反应压力为0.6MPa,待反应压力降至常压后反应结束; [0033] (5) off in vacuo, the product of Step ⑷ obtained 440g of ethylene oxide was added, the reaction temperature was 100 ° C, the reaction pressure was 0.6MPa control, after the end of the reaction the reaction pressure was lowered to atmospheric pressure;

[0034] (6)向步骤(5)得到的产物中加入0.5mol/L的盐酸,调节pH值为2,保持温度为70°C,反应2小时,以脱去叔丁氧羰基(BOC)基团; [0034] (6) of step (5) was added the product obtained in 0.5mol / L hydrochloric acid to adjust the pH value of 2, maintaining the temperature at 70 ° C, reacted for 2 hours, stripped to t-butoxycarbonyl (BOC) group;

[0035] (7)保持步骤(6)得到的产物的温度为70°C,抽真空使压力为500Pa,,至回流管管壁上无水滴形成后,继续保持0.5小时;过滤;加入Sg六硅酸镁进行吸附,吸附过程中保持温度为105°C,吸附时间为I小时;冷却至30°C,过滤,即得到所述的聚醚胺产物,489g。 Temperature of the product (6) obtained in [0035] (7) a step of maintaining 70 ° C, evacuated to a pressure of 500Pa ,, reflux pipe wall no water droplets are formed after continued for 0.5 hours; filtering; Sg added six magnesium silicate, and the adsorption process to maintain a temperature of 105 ° C, the adsorption time of I hour; cooled to 30 ° C, filtered, to obtain a product of the polyetheramine, 489g.

[0036] 实施例2: —种·聚醚胺的制备方法,采用以下工艺步骤: 2 [0036] Example: - The method of producing polyether-amines, the following process steps:

[0037] (I)将IOOg 乙醇胺(1.64mol)和375g 二碳酸二叔丁酯(1.72mol)溶于IOOOml水中,冷却至_5°C,将131g的Na0H(3.28mol)溶于500ml水中得到NaOH水溶液,将NaOH水溶液在搅拌下缓慢滴加到乙醇胺中,2小时滴加完成,滴加温度为-5°C ;滴加完成后保持-5°C,继续反应6小时,反应结整后,反应体系的pH值为10 ; [0037] (I) The IOOg ethanolamine (1.64 mol) and 375g tert-butyl dicarbonate (1.72 mol) was dissolved in IOOOml water, cooled to _5 ° C, the 131g of Na0H (3.28mol) was dissolved in 500ml of water to give after maintaining -5 ° C after completion of the dropwise addition, reaction was continued for 6 hours, the whole junction; aqueous NaOH, the aqueous solution of NaOH was slowly added dropwise under stirring ethanolamine, dropwise over 2 hours to complete, a solution temperature of -5 ° C , pH value of the reaction system 10;

[0038] (2)向步骤(I)得到的化合物中加入500ml乙酸乙酯进行萃取,得到水层和有机层;将水层用250ml乙酸乙酯再萃取一次后,将得到的有机相与有机层合并;将有机层用300ml饱和食盐水洗涤两次,加入无水硫酸钠干燥3小时,减压蒸馏,控制压力为450Pa,并缓慢升温至100°c,除去乙酸乙酯,得到由叔丁氧羰基(BOC)保护的乙醇胺B0C-MEA,240.3g ; [0038] (2) The compound obtained in the step (I) was added 500ml ethyl acetate was extracted, the aqueous layer and the organic layer obtained; The aqueous layer was re-extracted once with 250ml ethyl acetate and the resulting organic phase and the organic the combined layers; the organic layer was washed twice with 300ml saturated brine, dried over anhydrous sodium sulfate was added for 3 hours and distilled under reduced pressure, the pressure was 450Pa, and slowly warmed to 100 ° c, ethyl acetate was removed to afford the tert-butyl oxycarbonyl (BOC) protected ethanolamine B0C-MEA, 240.3g;

[0039] (3)将161g由叔丁氧羰基(BOC)保护的乙醇胺B0C-MEA放入压力釜中,加入5g的Κ0Η,升温至80°C,抽真空至压力为450Pa,保持I小时,除去反应体系中的水,反应后,反应体系的含水量小于0.5% ; [0039] (3) A 161g protected by t-butyloxycarbonyl (BOC) ethanolamine B0C-MEA placed in a pressure vessel was charged with 5g of Κ0Η, warmed to 80 ° C, evacuated to a pressure of 450Pa, kept I hour, after the reaction water in the system, the reaction was removed, the water content of the reaction system is less than 0.5%;

[0040] (4)关闭真空,向步骤(3)得到的产物中加入300g环氧乙烷,保持反应温度为80°C,反应压力为0.5MPa,待反应压力降至常压后,加入640g环氧丙烷,保持反应温度为100°C,直至反应压力降至常压后反应结束; After [0040] (4) closing the vacuum, the product obtained in step (3) 300g of ethylene oxide was added, keeping the reaction temperature is 80 ° C, the reaction pressure was 0.5MPa, the reaction to be decreased to atmospheric pressure, was added 640g propylene oxide, keeping the reaction temperature is 100 ° C, until the end of the reaction after the reaction pressure was lowered to atmospheric pressure;

[0041] (5)向步骤(4)得到的产物中加入5mol/L的盐酸,调节pH值为1,保持温度为50°C,反应4小时,以脱去叔丁氧羰基(BOC)基团; [0041] The product (4) obtained in (5) was added to the step 5mol / L hydrochloric acid, adjusted to pH 1, maintaining the temperature at 50 ° C, for 4 hours, stripped to t-butoxycarbonyl (BOC) group group;

[0042] (6)保持步骤(5)得到的产物的温度大于70°C,抽真空使压力为450Pa,,至回流管管壁上无水滴形成后,继续保持0.5小时;过滤;加入Sg六硅酸铝,吸附过程中保持温度为105°C,吸附时间为I小时;冷却至30°C,过滤,即得到所述的聚醚胺产物,990g。 Temperature of the product (5) obtained in [0042] (6) the step of retaining greater than 70 ° C, evacuated to a pressure of 450Pa ,, reflux pipe wall no water droplets are formed after continued for 0.5 hours; filtering; Sg added six aluminum silicates, maintaining the temperature during the adsorption is 105 ° C, the adsorption time of I hour; cooled to 30 ° C, filtered, to obtain a product of the polyetheramine, 990g.

[0043] 实施例3: —种聚醚胺的制备方法,采用以下工艺步骤:[0044] (I)将IOOg乙醇胺(1.64mol)溶于IOOOml水中,冷却至5 °C,将131g的NaOH (3.28mol)溶于500ml水中得到NaOH水溶液,将NaOH水溶液和375g 二碳酸二叔丁酯(1.72mol)在搅拌下同时缓慢滴加到乙醇胺中,3小时滴加完成,滴加温度为5°C ;滴加完成后保持5°C,继续反应6小时,反应结整后,反应体系的pH值为11 ; [0043] Example 3: - The method of producing a polyether amines, the following process steps: [0044] (I) The IOOg ethanolamine (1.64 mol) was dissolved in IOOOml water, cooled to 5 ° C, the NaOH 131g of ( 3.28 mol) was dissolved in 500ml of water to obtain an aqueous solution of NaOH, an aqueous solution of NaOH and 375g tert-butyl dicarbonate (1.72 mol) under stirring slowly added dropwise ethanolamine, 3 hours completion of the dropping, a solution temperature of 5 ° C ; after completion of the dropwise maintaining 5 ° C, the reaction was continued for 6 hours. after the reaction the whole, pH value of the reaction system 11;

[0045] (2)向步骤⑴得到的化合物中加入500ml甲苯进行萃取,得到水层和有机层;将水层用250ml甲苯再萃取一次后,将得到的有机相与有机层合并;将有机层用300ml饱和食盐水洗涤两次,加入无水硫酸钠干燥2小时,减压蒸馏,控制压力小于500Pa,并缓慢升温至80°C,除去甲苯,得到由叔丁氧羰基(BOC)保护的乙醇胺B0C-MEA,240.3g ; [0045] (2) To the compound obtained in step ⑴ 500ml of toluene was added for extraction, the aqueous layer and the organic layer obtained; The aqueous layer was extracted once, the organic layer of the organic phase obtained is combined with 250ml toluene; The organic layer was washed twice with 300ml saturated sodium chloride aqueous solution and dried over anhydrous sodium sulfate for 2 hours and distilled under reduced pressure, the control pressure is less than 500Pa, and slowly warmed to 80 ° C, toluene was removed from the ethanolamine to give t-butyloxycarbonyl (BOC) protected B0C-MEA, 240.3g;

[0046] (3)将161g由叔丁氧羰基(BOC)保护的乙醇胺B0C-MEA放入压力釜中,加入4.5g的Κ0Η,升温至80°C,抽真空至压力小于500Pa,保持I小时,除去反应体系中的水,反应后,反应体系的含水量小于0.5% ; [0046] (3) 161g of the t-butyloxycarbonyl (BOC) protected ethanolamine B0C-MEA placed in a pressure vessel, was added Κ0Η 4.5g, the temperature was raised to 80 ° C, evacuated to a pressure less than 500Pa, I held hours after the reaction water in the system, the reaction was removed, the water content of the reaction system is less than 0.5%;

[0047] (4)关闭真空,向步骤(3)得到的产物中加入940g环氧丙烷,保持反应温度为100°c,反应压力小于0.6MPa,直至反应压力降至常压后反应结束; [0047] (4) closing the vacuum, the product obtained in step (3) 940g of propylene oxide was added, keeping the reaction temperature is 100 ° c, the reaction pressure is less than 0.6MPa, until the reaction pressure was reduced to atmospheric pressure after the end of the reaction;

[0048] (5)向步骤(4)得到的产物中加入5mol/L的盐酸,调节pH值为1,保持温度为50°C,反应2小时,以脱去叔丁氧羰基(BOC)基团; [0048] The product (4) obtained in (5) was added to the step 5mol / L hydrochloric acid, adjusted to pH 1, maintaining the temperature at 50 ° C, reacted for 2 hours, stripped to t-butoxycarbonyl (BOC) group group;

[0049] (6)保持步骤(5)得到的产物的温度大于70°C,抽真空使压力小于500Pa,,至回流管管壁上无水滴形成后,继续保持0.5小时;过滤;加入5g六硅酸铝,吸附过程中保持温度为110°C,吸附时间为2小时;冷却至30°C,过滤,即得到所述的聚醚胺产物,992g。 Temperature of the product (5) obtained in [0049] (6) the step of retaining greater than 70 ° C, evacuated to a pressure less than 500Pa ,, to reflux pipe wall no water droplets are formed after continued for 0.5 hours; filtering; 5g of six aluminum silicates, maintaining the temperature during the adsorption is 110 ° C, the adsorption time is 2 hours; cooled to 30 ° C, filtered, to obtain a product of the polyetheramine, 992g.

[0050] 实施例4:一种聚醚胺的制备方法,采用以下工艺步骤: 4 [0050] Example: Preparation of the polyether amines, the following process steps:

[0051] (I)将250g实施例1得到的聚醚胺(0.5mol)和115.5g 二碳酸二叔丁酯(0.53mol)溶于IOOOml水中,冷却至(TC,再将13IgNaOH(3.28mol)溶于500ml水中得到NaOH水溶液,将NaOH水溶液在搅拌下缓慢滴加到聚醚胺中,2小时滴加完成,滴加温度为0°C ;滴加完成后保持0°C,继续反应8小时; [0051] (I) Example 1 The polyetheramine 250g (0.5mol) obtained and 115.5g butyl dicarbonate (0.53mol) IOOOml dissolved in water, cooled to (the TC, then 13IgNaOH (3.28mol) dissolved in 500ml water to obtain an aqueous solution of NaOH, the aqueous NaOH solution was slowly added dropwise with stirring under a polyether amine, dropwise over 2 hours to complete, a solution temperature of 0 ° C; maintaining 0 ° C after the dropwise addition, reaction was continued for 8 hours ;

[0052] (2)向步骤⑴得到的化合物中加入IOOOml乙酸乙酯进行萃取,得到水层和有机层;将水层用500ml乙酸乙酯再萃取一次后,将得到的有机相与有机层合并;将有机层用500ml饱和食盐水洗涤两次,加入无水硫酸钠干燥4小时,减压蒸馏,控制压力小于500Pa,并缓慢升温至100°c,除去乙酸乙酯,得到由叔丁氧羰基(BOC)保护的聚醚胺B0C-PEA,274.4g ; [0052] (2) To the compound obtained in step ⑴ added IOOOml extracted with ethyl acetate, the aqueous layer and the organic layer obtained; The aqueous layer was extracted once, the organic layer was combined organic phase obtained with ethyl acetate 500ml ; the organic layer was washed twice with 500ml saturated brine, dried over anhydrous sodium sulfate was added for 4 hours and evaporated under reduced pressure, the control pressure is less than 500Pa, and slowly warmed to 100 ° c, ethyl acetate was removed to give the tert-butoxycarbonyl group (BOC) protected amine polyether B0C-PEA, 274.4g;

[0053] (3)将由叔丁氧羰基(BOC)保护的聚醚胺BOC-PEA放入压力釜中,加入2gK0H,升温至80°C,向反应体系中冲氮气以除去氧气,抽真空至压力小于500Pa,保持I小时,除去反应体系中的水,反应后反应体系的含水量小于0.5% ; [0053] (3) by the t-butyloxycarbonyl (BOC) protected amine BOC-PEA polyether placed in a pressure vessel, was added 2gK0H, warmed to 80 ° C, the reaction system filled with nitrogen to remove oxygen, evacuated to pressure is less than 500Pa, I kept hours, removing water from the reaction system, the water content of the reaction system after the reaction is less than 0.5%;

[0054] (4)关闭真空,向步骤(3)得到的产物中加入200g环氧丙烷进行反应,反应温度为800C,反应压力小于0.6MPa,待反应压力降至常压后反应结束; [0054] (4) closing the vacuum, the step (3) of the product obtained was added 200g propylene oxide, the reaction temperature was 800C, the reaction pressure is less than 0.6MPa, after the end of the reaction the reaction pressure was lowered to atmospheric pressure;

[0055] (5)向步骤(4)得到的产物中加入2mol/L的盐酸,调节pH值为1,保持温度为70°C,反应2小时,以脱去叔丁氧羰基(BOC)基团; [0055] The product (4) obtained in (5) was added to the step 2mol / L hydrochloric acid, adjusted to pH 1, maintaining the temperature at 70 ° C, reacted for 2 hours, stripped to t-butoxycarbonyl (BOC) group group;

[0056] (8)保持步骤(7)得到的产物的温度大于70°C,抽真空使压力小于500Pa,,至回流管管壁上无水滴形成后,继续保持0.5小时;过滤;加入4g六硅酸镁进行吸附,吸附过程中保持温度为70°C,吸附时间为I小时;冷却至50°C,过滤,即得到所述的聚醚胺产物,396g。 Temperature of the product (7) obtained in [0056] (8) the step of retaining greater than 70 ° C, evacuated to a pressure less than 500Pa ,, to reflux pipe wall no water droplets are formed after continued for 0.5 hours; filtering; 4g of six magnesium silicate, and the adsorption process to maintain a temperature of 70 ° C, the adsorption time of I hour; cooled to 50 ° C, filtered, to obtain a product of the polyetheramine, 396g.

[0057] 实施例5: —种聚醚胺的制备方法,采用以下工艺步骤:[0058] (I)将123g 异丙醇胺(1.64mol)和375g 二碳酸二叔丁酯(1.72mol)溶于IOOOml水中,冷却至(TC,将131g的Na0H(3.28mol)溶于500ml水,搅拌下缓慢滴加到异丙醇胺中,2小时滴加完成,滴加温度2°C ;滴加完成后,保持2°C继续反应4小时,反应结束后反应体系的pH值为10 ; [0057] Example 5: - The method of producing a polyether amines, the following process steps: [0058] (I) The isopropanolamine 123g (1.64 mol) and 375g tert-butyl dicarbonate (1.72 mol) was dissolved IOOOml in water, cooled to (the TC, the 131g of Na0H (3.28mol) was dissolved in 500ml water, was added dropwise slowly with stirring isopropyl amine, dropwise over 2 hours to complete, a solution temperature of 2 ° C; the addition was complete after holding 2 ° C reaction was continued for 4 hours, pH of the reaction system after the reaction is 10;

[0059] (2)向步骤(I)得到的化合物中加入500ml乙酸乙酯进行萃取,得到水层和有机层;将水层用250ml乙酸乙酯再萃取一次后,将得到的有机相与有机层合并;将有机层用300ml饱和食盐水洗涤,加入无水硫酸钠干燥3小时,减压蒸馏控制压力小于500Pa,并缓慢升温至100°c,除去乙酸乙酯,得到由叔丁氧羰基(BOC)保护的异丙醇胺B0C-1PA,272.3g ; [0059] (2) The compound obtained in the step (I) was added 500ml ethyl acetate was extracted, the aqueous layer and the organic layer obtained; The aqueous layer was re-extracted once with 250ml ethyl acetate and the resulting organic phase and the organic the combined layers; 300ml organic layer was washed with saturated brine, dried over anhydrous sodium sulfate was added for 3 hours and distilled under reduced pressure the control pressure is less than 500Pa, and slowly warmed to 100 ° c, ethyl acetate was removed to give a t-butoxycarbonyl ( BOC) protected isopropanolamine B0C-1PA, 272.3g;

[0060] (3)将175g的由叔丁氧羰基(BOC)保护的异丙醇胺B0C-1PA放入压力釜中,加入3g的Κ0Η,升温至80°C,抽真空至压力小于500Pa,保持I小时,除去反应体系中的水,反应后,反应体系的含水量小于0.5% ; [0060] (3) by a tert-butoxycarbonyl group of 175g (BOC) protected amine B0C-1PA isopropanol placed in a pressure vessel was charged with 3g of Κ0Η, warmed to 80 ° C, evacuated to a pressure less than 500Pa, I kept hours, the reaction water in the system is removed, after the reaction, the water content of the reaction system is less than 0.5%;

[0061] (4)关闭真空,向步骤(3)得到的产物中加入440g环氧乙烷进行反应,反应温度为IOO0C,控制反应压力不超过0.6MPa,待反应压力降至常压后反应结束; [0061] (4) closing the vacuum, the product obtained in step (3) 440g of ethylene oxide was added to the reaction, the reaction temperature is IOO0C, control the reaction pressure does not exceed 0.6MPa, after the end of the reaction the reaction pressure was lowered to atmospheric pressure ;

[0062] (5)向步骤(4)得到的产物中加入0.5mol/L的盐酸,调节pH值为2,保持温度为70°C,反应2小时,以脱去叔丁氧羰基(BOC)基团; [0062] The product (4) obtained in (5) was added to the step 0.5mol / L hydrochloric acid to adjust the pH value of 2, maintaining the temperature at 70 ° C, reacted for 2 hours, stripped to t-butoxycarbonyl (BOC) group;

[0063] (6)保持步骤(5)得到的产物的温度大于70°C,抽真空使压力小于500Pa,,至回流管管壁上无水滴形成后,继续保持0.5小时;过滤;加入Sg六硅酸镁进行吸附,吸附过程中保持温度为105°C,吸附时间为I小时;冷却至30°C,过滤,即得到所述的聚醚胺产物,501.5g。 Temperature of the product (5) obtained in [0063] (6) the step of retaining greater than 70 ° C, evacuated to a pressure less than 500Pa ,, to reflux pipe wall no water droplets are formed after continued for 0.5 hours; filtering; Sg added six magnesium silicate, and the adsorption process to maintain a temperature of 105 ° C, the adsorption time of I hour; cooled to 30 ° C, filtered, to obtain a product of the polyetheramine, 501.5g.

[0064] 实施例6: —种聚醚胺的制备方法,采用以下工艺步骤: [0064] Example 6: - The method of producing a polyether amines, the following process steps:

[0065] (I)将146.1g 4-胺基-1- 丁醇(1.64mol)溶于IOOOml 水中,冷却至CTC,将131g的NaOH(3.28mol)溶于500ml水中得到NaOH水溶液,将NaOH水溶液和370.6g 二碳酸二叔丁酯(1.70mol)在搅拌下同时缓慢滴加到乙醇胺中,4小时滴加完成,滴加温度为10〜200C ;滴加完成后保持10〜20°C,继续反应8小时,反应结整后,反应体系的pH值为10〜11 ; [0065] (I) will 146.1g 4- amino-1-butanol (1.64 mol) was dissolved in IOOOml water, cooled to CTCs, the 131g of NaOH (3.28 mol) was dissolved in 500ml of water to obtain an aqueous solution of NaOH, an aqueous solution of NaOH and 370.6g tert-butyl dicarbonate (1.70 mol) under stirring slowly added dropwise to ethanolamine for 4 hours the addition was complete, the temperature of the dropwise addition 10~200C; holding 10~20 ° C after the addition, continue the reaction for 8 hours after the reaction the whole, pH value of the reaction system 10~11;

[0066] (2)向步骤⑴得到的化合物中加入500ml苯进行萃取,得到水层和有机层;将水层用250ml苯再萃取一次后,将得到的有机相与有机层合并;将有机层用300ml饱和食盐水洗涤两次,加入无水硫酸钠干燥4小时,减压蒸馏,控制压力小于500Pa,并缓慢升温至600C,除去苯,得到由叔丁氧羰基(BOC)保护的4-胺基-1- 丁醇B0C-BA,240.3g ; [0066] (2) To the compound obtained in step ⑴ 500ml of benzene was added for extraction, the aqueous layer and the organic layer obtained; the organic phase after the organic layer the aqueous layer was extracted once with 250ml of benzene, and the resulting combined; The organic layer was washed twice with 300ml saturated brine, dried over anhydrous sodium sulfate was added for 4 hours and evaporated under reduced pressure, the control pressure is less than 500Pa, and slowly warmed to 600C, to remove benzene, protected by t-butyloxycarbonyl (BOC) 4- amine -1-butanol B0C-BA, 240.3g;

[0067] (3)将189g由叔丁氧羰基(BOC)保护的4_胺基_1_ 丁醇B0C-BA放入压力釜中,加入4.5g的Κ0Η,升温至70°C,抽真空至压力小于500Pa,保持1.5小时,除去反应体系中的水,反应后,反应体系的含水量小于0.5% ; [0067] (3) 4 _ _1_ 189g from the group tert-butoxycarbonyl group (BOC) protected B0C-BA-butoxide placed in a pressure vessel, was added Κ0Η 4.5g, the temperature was raised to 70 ° C, evacuated to pressure is less than 500Pa, 1.5 hours, removing water from the reaction system after the reaction, the water content of the reaction system is less than 0.5%;

[0068] (4)关闭真空,向步骤(3)得到的产物中加入912g环氧乙烷,保持反应温度为105°C,反应压力小于0.6MPa,直至反应压力降至常压后反应结束; [0068] (4) closing the vacuum, the product obtained in step (3) 912g of ethylene oxide was added, keeping the reaction temperature is 105 ° C, the reaction pressure is less than 0.6MPa, until the reaction pressure was reduced to atmospheric pressure after the end of the reaction;

[0069] (5)向步骤(4)得到的产物中加入3mol/L的盐酸,调节pH值为1.5,保持温度为60°C,反应2小时,以脱去叔丁氧羰基(BOC)基团; [0069] The product (4) obtained in (5) was added to the step 3mol / L hydrochloric acid, adjusted to pH 1.5, maintaining the temperature at 60 ° C, reacted for 2 hours, stripped to t-butoxycarbonyl (BOC) group group;

[0070] (6)保持步骤(5)得到的产物的温度大于70°C,抽真空使压力小于500Pa,,至回流管管壁上无水滴形成后,继续保持I小时;过滤;加入5g六硅酸镁,吸附过程中保持温度为110°C,吸附时间为3小时;冷却至30°C,过滤,即得到所述的聚醚胺产物,993g。 Temperature of the product (5) obtained in [0070] (6) the step of retaining greater than 70 ° C, evacuated to a pressure less than 500Pa ,, to reflux pipe wall after no water droplets are formed, remain I h; filter; 5g of six magnesium silicate, maintaining the temperature during the adsorption is 110 ° C, for 3 hours adsorption; cooled to 30 ° C, filtered, to obtain a product of the polyetheramine, 993g. [0071] 实施例7: —种聚醚胺的制备方法,采用以下工艺步骤: 7 [0071] Example: - The method of producing a polyether amines, the following process steps:

[0072] (I)将200g 异丙醇胺(2.67mol)和610g 二碳酸二叔丁酯(2.80mol)溶于1600ml水中,冷却至(TC,将213g的636g Na2CO3(6.0mol)溶于2000ml水,搅拌下缓慢滴加到异丙醇胺中,3小时滴加完成,滴加温度2 V ;滴加完成后,保持2°C继续反应10小时,反应结束后反应体系的pH值为10 ; [0072] (I) 200g of diisopropanolamine (2.67 mol) and 610g tert-butyl dicarbonate (2.80 mol) was dissolved in 1600ml water, cooled to (the TC, the 213g of 636g Na2CO3 (6.0mol) was dissolved in 2000ml water under stirring slowly added dropwise to the amine in isopropanol for 3 hours completion of the dropping, a solution temperature of 2 V; after the addition was complete, the reaction was continued to maintain 2 ° C for 10 hours after completion of the reaction pH of the reaction system is 10 ;

[0073] (2)向步骤(I)得到的化合物中加入IOOOml乙酸乙酯进行萃取,得到水层和有机层;将水层用500ml乙酸乙酯再萃取一次后,将得到的有机相与有机层合并;将有机层用600ml饱和食盐水洗涤,加入无水硫酸钠干燥3小时,减压蒸馏控制压力小于500Pa,并缓慢升温至100°c,除去乙酸乙酯,得到由叔丁氧羰基(BOC)保护的异丙醇胺B0C-1PA,442.Sg; [0073] (2) The compound obtained in the step (I) was added IOOOml extracted with ethyl acetate, the aqueous layer and the organic layer obtained; the aqueous layer was extracted once with 500ml of ethyl acetate and the resulting organic phase and organic the combined layers; 600ml organic layer was washed with saturated brine, dried over anhydrous sodium sulfate was added for 3 hours and distilled under reduced pressure the control pressure is less than 500Pa, and slowly warmed to 100 ° c, ethyl acetate was removed to give a t-butoxycarbonyl ( BOC) protected isopropanolamine B0C-1PA, 442.Sg;

[0074] (3)将200g的由叔丁氧羰基(BOC)保护的异丙醇胺B0C-1PA放入压力釜中,加入5g的NaOH,升温至100°C,抽真空至压力小于500Pa,保持2小时,除去反应体系中的水,反应后,反应体系的含水量小于0.5% ; [0074] (3) 200g of isopropanol amine B0C-1PA by a tert-butoxycarbonyl group (BOC) protected placed in a pressure vessel was charged with 5g of NaOH, was heated to 100 ° C, evacuated to a pressure less than 500Pa, 2 hours, the reaction water in the system is removed, after the reaction, the water content of the reaction system is less than 0.5%;

[0075] (4)关闭真空,向步骤(3)得到的产物中加入700g环氧乙烷进行反应,反应温度为1200C,控制反应压力不超过0.6MPa,待反应压力降至常压后反应结束; [0075] (4) closing the vacuum, the product obtained in step (3) 700g of ethylene oxide was added, the reaction temperature was 1200C, the reaction pressure does not exceed 0.6MPa control, after the end of the reaction the reaction pressure was lowered to atmospheric pressure ;

[0076] (5)向步骤(4)得到的产物中加入5mol/L的盐酸,调节pH值为1,保持温度为50°C,反应I小时,以脱去叔丁氧羰基(BOC)基团; [0076] The product (4) obtained in (5) was added to the step 5mol / L hydrochloric acid, adjusted to pH 1, maintaining the temperature at 50 ° C, I h the reaction serves to remove t-butoxycarbonyl (BOC) group group;

[0077] (6)保持步骤(5)得到的产物的温度为80°C,抽真空使压力小于500Pa,,至回流管管壁上无水滴形成后,继续保持0.5小时;过滤;加入12g六硅酸镁进行吸附,吸附过程中保持温度为100°C,吸附时间为3小时;冷却至40°C,过滤,即得到所述的聚醚胺产物,815.4g0 Temperature of the product (5) obtained in [0077] (6) a step of maintaining 80 ° C, evacuated to a pressure less than 500Pa ,, to reflux pipe wall no water droplets are formed after continued for 0.5 hours; filtering; 12g was added six magnesium silicate, and the adsorption process to maintain a temperature of 100 ° C, for 3 hours adsorption; cooled to 40 ° C, filtered, to obtain the amine product of a polyether, 815.4g0

Claims (6)

  1. 1.一种聚醚胺的制备方法,其特征是,采用以下工艺步骤: (1)将具有通式H2N-R-OH ( I )结构的醇胺类化合物溶于水或者水与有机溶剂的混合溶剂中,浓度为10〜60% ;所述有机溶剂为四氢呋喃或二氧六环,混合溶剂中有机溶剂与水的比例为5:95〜40:60 ; 其中R为直链或支链的CnH2n, η = 2〜18或 1. A method for preparing a polyether amine, characterized in that the following process steps: (1) an alcohol amine compound having the general formula H2N-R-OH (I) or the structure of water and an organic water soluble solvent a mixed solvent at a concentration of 10 to 60%; the organic solvent is tetrahydrofuran or dioxane, a mixed solvent ratio of organic solvent to water is 5: 95~40: 60; wherein R is a linear or branched, CnH2n, η = 2~18 or
    Figure CN102604072BC00021
    (2)向步骤(I)得到的化合物中滴加催化剂与二碳酸二叔丁酯,滴加时的温度为-10〜400C,I〜6小时滴加完成;滴加完成后,在温度为-10〜40°C的条件下反应4〜48小时,反应结束后的pH值为10〜14 ;所述催化剂为Na0H、Na2C03或者三乙胺,催化剂与醇胺类化合物的摩尔比为0.5〜3:1,二碳酸二叔丁酯与醇胺类化合物的摩尔比为I〜1.1:1,所述二碳酸二叔丁酯为纯的二碳酸二叔丁酯或二碳酸二叔丁酯与有机溶剂的混合溶液,所述二碳酸二叔丁酯与有机溶剂的混合溶液的浓度为10〜60%,所述有机溶剂为丙酮、四氢呋喃或二氧六环; (3)将步骤(2)得到的化合物进行减压蒸馏,以除去化合物中的有机溶剂,真空压力小于500Pa,蒸馏温度为40〜100°C ; (4)向步骤(3)得到的化合物中加入有机溶剂进行萃取,得到水层和有机层;将水层用有机溶剂再萃取一次后,将得到的有机层合并; (2) The compound obtained in the step (I) catalyst was added dropwise with di-tert-butyl temperature during the dropwise addition was -10~400C, I~6 hours the addition was complete; After completion of the dropwise addition, the temperature is -10~40 ° C under conditions of 4~48 hours, pH after the reaction is 10~14; molar ratio of the catalyst Na0H, Na2C03 or triethylamine catalyst with the alcohol amine compound is 0.5~ 3: 1 molar ratio of di-tert-butyl alcohol and the amine compound is I~1.1: 1, the di-tert-butyl ester as a pure butyl dicarbonate or di-tert-butyl dicarbonate and a mixed solution of an organic solvent, the concentration of the mixed solution of di-tertbutyl dicarbonate and 10 to 60% of the organic solvent, the organic solvent is acetone, tetrahydrofuran or dioxane; (3) step (2) compound was subjected to distillation under reduced pressure to remove the organic solvent compounds, the vacuum pressure is less than 500Pa, a distillation temperature of 40~100 ° C; compound (3) obtained in (4) the step of adding an organic solvent for extraction, to obtain an aqueous and organic layers; the combined organic layer the aqueous layer was extracted once with an organic solvent, the resultant; 有机层用饱和食盐水洗涤,加入无水硫酸钠干燥2〜6小时,减压蒸馏除去有机溶剂,得到由叔丁氧羰基(BOC)保护的醇胺类化合物BOC-NH-R-OH ;所述有机溶剂为乙酸乙酯、苯、甲苯、环己烷、二氯甲烷或氯仿; (5)向由叔丁氧羰基(BOC)保护的醇胺类化合物BOC-NH-R-OH中加入碱金属或碱土金属的氧化物或氢氧化物或者双金属氰化物,碱金属或碱土金属的氧化物或氢氧化物或者双金属氰化物的加入量为由叔丁氧羰基(BOC)保护的醇胺类化合物BOC-NH-R-OH的0.1〜5%wt,向反应体系中充氮气以除去氧气,升温至50〜100°C,抽真空至压力小于500Pa,保持.0.5〜2小时,除去反应体系中的水; (6)向步骤(5)得到的产物中加入单体进行反应,反应温度为80〜120°C,反应压力为.0.1〜0.6MPa,每次加入一种单体,待反应压力降至常压后加入下一种单体或反应结束;所述单体的加入量与BOC-NH-R-OH的 The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate was added 2 ~ 6 hours, the organic solvent was distilled off under reduced pressure, to give protected by t-butyloxycarbonyl (BOC) an alcohol amine compound BOC-NH-R-OH; the said organic solvent is ethyl acetate, benzene, toluene, cyclohexane, methylene chloride or chloroform; (5) adding a base to the protected t-butyloxycarbonyl (BOC) an alcohol amine compound BOC-NH-R-OH in amount or alkaline earth metal oxide or hydroxide or a double metal cyanide, an alkali metal or alkaline earth metal oxide or hydroxide or by double metal cyanide t-butyloxycarbonyl (BOC) protected alcohol amine compound BOC-NH-R-OH is 0.1~5% wt, charged to the reaction system with nitrogen to remove oxygen and heated to 50~100 ° C, evacuated to a pressure less than 500Pa, holding .0.5~2 hours, the reaction was removed water in the system; (5) obtained in (6) was added to the monomer product of step a reaction temperature of 80~120 ° C, a reaction pressure of .0.1~0.6MPa, each addition of one monomer to be after the reaction was decreased to atmospheric pressure at the end of the addition of monomer or reaction; adding an amount of the monomer and BOC-NH-R-OH is 尔比为5〜100:1,所述单体为环氧乙烷、环氧丙烷或四氢呋喃中的一种或多种; (7)向步骤(6)得到的产物中加入0.5〜5mol/L的盐酸,调节pH值为I〜2,保持温度为50〜80°C,反应I〜4小时,以脱去叔丁氧羰基(BOC)基团; (8)保持步骤(7)得到的产物的温度为40〜100°C,抽真空使压力小于500Pa,至回流管管壁上无水滴形成后,再保持0.5〜I小时;过滤;加入吸附剂进行吸附,吸附过程中保持温度为100〜120°C,吸附时间为I〜3小时;冷却至30〜50°C,过滤,即得到所述的聚醚胺产物。 Dalby is 5~100: 1, the monomer is ethylene oxide, propylene oxide or tetrahydrofuran, one or more; product (6) obtained in (7) was added to the step 0.5~5mol / L hydrochloric acid, adjusted to pH I~2, maintaining the temperature at 50~80 ° C, the reaction I~4 hours, stripped to t-butoxycarbonyl (BOC) group; (8) holding the step (7) to give the product the temperature of 40~100 ° C, evacuated to a pressure less than 500Pa, no water droplets to reflux pipe wall is formed after maintained 0.5~I hours; filtering; adsorbent was added and the adsorption process to maintain a temperature of 100~ 120 ° C, the adsorption time is I~3 hours; cooled to 30~50 ° C, filtered, to obtain the product of polyetheramine.
  2. 2.如权利要求1所述的聚醚胺的制备方法,其特征是:所述碱金属或碱土金属的氧化物或氢氧化物为氢氧化钠、氢氧化钾、氧化锶、氧化钡、氢氧化锶或氢氧化钡。 2. The method as polyetheramines according to claim 1, wherein: the alkali metal or alkaline earth metal oxide or hydroxide is sodium hydroxide, potassium hydroxide, strontium oxide, barium oxide, magnesium strontium oxide or barium.
  3. 3.如权利要求1所述的聚醚胺的制备方法,其特征是:经步骤(5)处理后,反应体系的含水量小于0.5%。 Polyetheramines prepared according to claim 1, characterized in that: (5) by the processing step, the water content of the reaction system is less than 0.5%.
  4. 4.如权利要求1所述的聚醚胺的制备方法,其特征是:所述吸附剂为六硅酸镁或六硅Ife招。 4. The method of preparing the polyetheramines claim 1, characterized in that: the adsorbent is magnesium or six silicon Ife six strokes.
  5. 5.如权利要求1所述的聚醚胺的制备方法,其特征是:所述吸附剂的加入量为步骤(7)得到的产物总量的0.1〜5%。 5. The method of preparing the polyetheramines claim 1, characterized in that: the adsorbent is added in an amount in step (7) 0.1~5% of the total amount of product obtained.
  6. 6.如权利要求1所述的聚醚胺的制备方法,其特征是:步骤(2)中,催化剂与二碳酸二叔丁酯的加入方式为(I)先加入催化剂,再将二碳酸二叔丁酯溶于有机溶剂后滴加加入;或(2)先加入二碳酸二叔丁酯,再滴加加入催化剂;或(3)同时滴加加入催化剂与二碳酸二叔丁酷。 6. The method as polyetheramines according to claim 1, wherein: step (2), the catalyst was added di-tert-butyl way (I) catalyst is added first, then di after the dropwise addition of tert-butyl in an organic solvent; or (2) was added to tert-butyl dicarbonate, then dropwise addition of a catalyst; or (3) catalyst was added simultaneously dropwise with di-tert-butyl cool.
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