CN101898939B - Method for preparing compound 4-hydroxy butyl vinyl ether - Google Patents

Method for preparing compound 4-hydroxy butyl vinyl ether Download PDF

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CN101898939B
CN101898939B CN 201010247272 CN201010247272A CN101898939B CN 101898939 B CN101898939 B CN 101898939B CN 201010247272 CN201010247272 CN 201010247272 CN 201010247272 A CN201010247272 A CN 201010247272A CN 101898939 B CN101898939 B CN 101898939B
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vinyl ether
reaction
hydroxybutyl vinyl
acetylene
method
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CN101898939A (en )
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方钢
阎璟琪
项雄彪
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安陆新景化工有限公司
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Abstract

The invention belongs to a method for preparing a vinyl ether compound, in particular to the method for preparing 4-hydroxy butyl vinyl ether. In the reaction of 1,4-butanediol and acetylene, dimethyl sulfoxide is added so that beneficial effects are achieved for the reaction, wherein the content of a 4-hydroxy butyl vinyl ether crude product is improved to 81 percent from 72 percent before adding; and a cyclic acetal byproduct is reduced to about 4 percent from 6 percent before adding. The content of the crude product can be further improved by 1 to 2 percent by adding a cationic surface active agent, namely octadecyl trimethyl ammonium chloride.

Description

一种化合物4-羟丁基乙烯基醚的制备方法 A process for producing 4-hydroxybutyl vinyl ether compound

技术领域 FIELD

[0001] 本发明属于乙烯基醚化合物的制备方法,特别是一种4-羟丁基乙烯基醚的制备方法。 [0001] The present invention pertains to preparation of vinyl ether compound, particularly a process for the preparation of 4-hydroxybutyl vinyl ether.

背景技术 Background technique

[0002] 乙烯基醚类化合物是不饱和醚,是一种很重要的有机合成中间体及高聚物的单体,它的均聚物和共聚物被广泛地应用于粘合剂、涂料、润滑剂、增塑剂、杀虫剂,以及表面保护材料等许多领域。 [0002] a vinyl ether compound are unsaturated ethers, it is a very important intermediate in organic synthesis and polymer monomers, homopolymers and copolymers which are widely used in adhesives, coatings, many areas lubricants, plasticizers, insecticides, and a surface protective material. 近年来,发展很快的是作为辐射固化涂料的乙烯基醚类活性稀释剂, 或用乙烯基醚将环氧树脂改性成含有乙烯基醚功能的低聚物,而应用于紫外光固化涂料中。 In recent years, fast development of radiation-curable coating is a vinyl ether reactive diluent, or with a vinyl ether oligomer-modified epoxy resin to contain a vinyl ether functionality, and UV-curable coatings applied in. 为此,乙烯基醚类化合物应用前景极其广阔。 For this purpose, a vinyl ether compound is extremely broad application prospect.

[0003] 4-羟丁基乙烯基醚是乙烯基醚类化合物中重要一种。 [0003] 4-hydroxybutyl vinyl ether, the vinyl ether compound is one kind of important.

[0004] 4-羟丁基乙烯基醚工业化生产主要是乙炔法:在氢氧化钾的存在下,1、4_ 丁二醇与乙炔反应,得到4-羟丁基乙烯基醚。 [0004] 4-hydroxybutyl vinyl ether, acetylene is primarily industrial production: in the presence of potassium hydroxide, 1,4_ butanediol with acetylene to give 4-hydroxybutyl vinyl ether.

[0005] 反应式如下: [0005] The reaction is as follows:

[0006] [0006]

Figure CN101898939BD00031

[0007] 德国专利GB773331,介绍了二羟基醇单乙烯基醚制备方法的改进,与其他乙炔法比较,该专利的优点在于:1.反应中通入了氮气。 [0007] German Patent GB773331, describes an improved method for preparing a dihydric alcohol mono vinyl ether, acetylene compared with other advantages of this patent is: a nitrogen gas into the reaction. 2.反应柱填充陶瓷填料。 2. The reaction column filled with a ceramic filler. 获得含量较高的乙烯基醚。 Obtaining higher levels of vinyl ethers.

[0008] 具体描述如下: [0008] described as follows:

[0009] GB773331有关二羟基醇单乙烯基醚制备方法的改进 [0009] GB773331 For improved method for preparing a dihydric alcohol mono vinyl ether

[0010]实例一 [0010] Examples of a

[0011] 向一个高100cm,直径7cm(容积3. 8L)的铁制反应柱中,加入2000g含7%氢氧化钾的乙二醇,慢慢加热到200°C,用干燥的氮气流带出反应产生的水分,然后,将干燥并预热的乙炔气流,以80-180L/hr的速率通过该反应柱,柱内填充陶瓷填料,填料层高度80cm,反应混合物连续蒸馏出料,乙二醇单乙烯基醚的含量,依据不同的乙炔气流速,在50-70%之间变化,此外,还形成5-20%的环状缩醛副产物,以及未反应的乙二醇,无乙二醇双乙烯基醚生成。 [0011] to a high 100cm, 7cm diameter (volume 3. 8L) the reaction of an iron column, 2000g of ethylene glycol was added with 7% potassium hydroxide was slowly heated to 200 ° C, with a stream of dry nitrogen with out the water generated by the reaction, then dried and preheated acetylene gas flow, at a rate of 80-180L / hr through the reaction column, the column filled with the ceramic filler, the filler height 80cm, the reaction mixture was distilled off continuously feeding, ethylene the content of monovinyl ether of alcohol, depending on the acetylene gas flow rate varied between 50-70%, in addition, 5-20% of cyclic acetal formed by-product, and unreacted ethylene glycol, non-b glycol divinyl ether generated.

[0012] 用微弱的真空可以加强蒸馏速率。 [0012] distilling rate can be enhanced with a weak vacuum.

[0013] 用此过程并连续加入干燥的乙二醇,以维持反应柱内的液位,使反应连续不断的进行,每小时获得60g含乙二醇单乙烯基醚的馏出液。 [0013] This process is continuously added with ethylene glycol dried, to maintain the liquid level in the reaction column, the reaction is carried out continuously, obtained per hour glycol monovinyl ether containing 60g distillate.

[0014] 使用含6. 8%氢氧化钾的乙二醇,反应温度202°C,乙炔气流速130L/hr,每小时获得80g馏出液,其中含66%乙二醇单乙烯基醚、18% 2-甲基-1,3-二氧戊环及16%未反应的原料。 [0014] The use of ethylene glycol containing 6.8% of potassium hydroxide, the reaction temperature of 202 ° C, acetylene gas flow 130L / hr, to obtain 80g of distillate per hour, which contains 66% ethylene glycol monovinyl ether, 18% 2-methyl-1,3-dioxolane and 16% unreacted starting material.

[0015] 使用含4. 9%氢氧化钾的乙二醇,反应温度201°C,乙炔气流速125L/hr,每小时获得93g馏出液,其中含66%乙二醇单乙烯基醚、11% 2-甲基-1,3-二氧戊环。 [0015] The use of ethylene glycol containing 4.9% of potassium hydroxide, the reaction temperature of 201 ° C, acetylene gas flow 125L / hr, to obtain 93g of distillate per hour, which contains 66% ethylene glycol monovinyl ether, 11% 2-methyl-1,3-dioxolane.

[0016] 使用含0.9%氢氧化钾的乙二醇,反应温度196°C,乙炔气流速110L/hr,每小时获得52g馏出液,其中含21%乙二醇单乙烯基醚、2% 2-甲基-1,3-二氧戊环。 [0016] The use of ethylene glycol containing 0.9% of potassium hydroxide, the reaction temperature of 196 ° C, acetylene gas flow 110L / hr, to obtain 52g of distillate per hour, which contains 21% ethylene glycol monovinyl ether, 2% methyl-1,3-dioxolane.

[0017] 实例四 [0017] Four examples of

[0018] 采用与实例一相同的方法,使用比实例一较细一些的反应柱,用含氢氧化钾的二乙二醇,加热至200 V,通入等量的乙炔气及氮气流(200L/hr),可以连续获得含75 %的二乙二醇单乙烯基醚的共沸混合液,其中还含有3-5%的二乙二醇双乙烯基醚及未反应的 [0018] The same method as in Example a, using a smaller number of specific examples of the reaction column with diethylene glycol containing potassium hydroxide and heated to 200 V, into the same amount of acetylene gas and nitrogen gas stream (200L / hr), may be obtained continuously diethylene glycol monovinyl ether azeotropic mixture containing 75%, which also contains 3-5% diethylene glycol divinyl ether and unreacted

二乙二醇。 Diethylene glycol.

[0019] 从以上描述可以看出,德国专利GB773331也有不足之处:反应后乙烯基醚的含量仍不高,环状缩醛副产物较高,这是因为,乙炔法反应是气液相反应,GB773331通过反应柱柱内填充陶瓷填料,以增加乙炔气与二醇类接触的时间(与不填充陶瓷填料比较),但仅靠这种方法是远远不够的。 [0019] As can be seen from the above description, in German Patent GB773331 also has disadvantages: the content of the vinyl ether reaction is still high, higher cyclic acetal by-product, because, acetylene gas-liquid reaction is the reaction , GB773331 reaction columns are filled by the ceramic filler to increase the time (compared with the ceramic filler is not filled) acetylene gas in contact with the glycol, but this method alone is not enough. 增加乙炔气与二醇类接触,使其充分反应,以进一步提高产物的含量,降低环状缩醛副产物产生,是我们急需解决的课题。 Acetylene glycols increased contact with the reaction sufficiently, in order to further improve the content of the product, to reduce the cyclic acetal by-product generation, we need to solve the problem.

发明内容 SUMMARY

[0020] 传统的采用乙炔法得到乙烯基醚的反应是气液相反应,这就是在有机合成中经常会遇到非均相反应,非均相反应的缺点是产率低。 [0020] The traditional method acetylene vinyl ether obtained reaction liquid is the reaction gas, which is often encountered heterogeneous reactions in organic synthesis, heterogeneous reactions disadvantage is the low yield.

[0021] 为了解决这个问题,我们发现,还可以有方法使乙炔气与二醇类充分反应,提高产率。 [0021] In order to solve this problem, we found that the method can also be acetylene gas sufficiently react with the glycol, to improve the yield.

[0022] 我们发现:在氢氧化钾的催化下,1,4- 丁二醇与乙炔反应,制备4-羟丁基乙烯基醚中,反应中加入二甲基亚砜,对该反应产生有益的效果,4-羟丁基乙烯基醚的粗品含量由加入前的72%提高到81 %,环状缩醛副产物由加入前的6%降低到约4%。 [0022] We found: under the catalysis of potassium hydroxide, 1,4-butanediol is reacted with acetylene, 4-hydroxybutyl vinyl ether was prepared in dimethyl sulfoxide was added to the reaction, the reaction beneficial effect, the content of crude 4-hydroxybutyl vinyl ether increased from 72% to 81% before the addition of the cyclic acetal by-product from the reduction of 6% was added prior to about 4%.

[0023] 形成上述有益效果的原因是:二甲基亚砜对乙炔易溶,每升二甲基亚砜能溶解33 升乙炔,二甲基亚砜溶解乙炔后,使乙炔进入液体中,延长与1、4_ 丁二醇接触时间,使反应得以充分进行。 Cause [0023] is formed in the above-described advantageous effects: dimethyl sulfoxide soluble acetylene, 33 liters per liter of dimethyl sulfoxide can dissolve the acetylene, the acetylene dimethyl sulfoxide, acetylene into the liquid, the extended 1,4_ butanediol and contact time, the reaction to proceed sufficiently.

[0024] 我们发现:二甲基亚砜对1、4_ 丁二醇与乙炔反应没有不利的影响,并没有产生新的副产物,并且在精馏中,可以很好地分离和回收。 [0024] We found: DMSO has no adverse effect on the reaction of acetylene with 1,4_ butanediol, no new byproducts, and distillation may be well separated and recovered.

[0025] 我们发现:上述的4-羟丁基乙烯基醚的制备方法中,二甲基亚砜的用量为:1、 4_ 丁二醇:二甲基亚砜=1 : 0. 1-0. 2,w/w。 [0025] We found that: the above-mentioned 4-hydroxybutyl vinyl ether prepared in dimethyl sulfoxide in an amount of: 1, 4_ butanediol: dimethyl sulfoxide = 1: 0. 1-0 . 2, w / w.

[0026] 我们发现:在氢氧化钾的存在下,1、4_ 丁二醇与乙炔制备4-羟丁基乙烯基醚的反应过程中,加入少量十八烷基三甲基氯化铵,可以促进1、4_ 丁二醇转化率的提高,可使4_羟丁基乙烯基醚的含量提高1_2%。 [0026] We found that: in the presence of potassium hydroxide, prepared by reaction with acetylene glycol 1,4_ process 4-hydroxybutyl vinyl ether was added a small amount of stearyl trimethyl ammonium chloride, can be 1,4_ butanediol promote conversion rate, the content can 4_ hydroxybutyl vinyl ether 1_2% increase.

[0027] 乙炔/1、4- 丁二醇/氢氧化钾/ 二甲基亚砜是反应原料,4-羟丁基乙烯基醚是反应产物,他们的溶解性不同,该反应属于相转移催化反应。 [0027] Acetylene / 1,4-butanediol / KOH / DMSO reaction material is, 4-hydroxybutyl vinyl ether is the reaction product of their different solubility, which belongs to the phase transfer catalysis reaction reaction.

[0028] 相转移催化反应属于非均相反应中的两相反应,一相是盐、酸、碱的水溶液或固体,另一相是溶有反应物质的有机介质溶液.通常这种两相反应由于互不相溶,水相(或固相)中的阴离子与有机相中的反应物之间的反应速度甚低,甚至不起反应.而利用相转移催化剂,可将反应物从一相转移到另一相中,随着碰撞几率的增加,反应加速,从而使离子化合物与不溶于水的有机物质在低极性溶剂中顺利地发生了反应。 [0028] belonging to the phase transfer catalysis of heterogeneous two-phase reaction in the reaction, a phase is a salt, an acid, alkali aqueous solution or a solid, the other phase is a solution of an organic solution of the reaction medium substances. Such two phase reaction is usually Since immiscible, reaction rate between the reactants aqueous phase (or solid phase) and the anionic organic phase is very low, or even not react, while using a phase transfer catalyst, the reaction may be transferred from one phase the other phase, with the increase in collision probability, the reaction is accelerated so that the ionic compound with a water-insoluble organic material had reacted smoothly in a low polar solvent. [0029] 我们发现:上述的4-羟丁基乙烯基醚的制备方法中,加入阳离子表面活性剂能使得反应加速。 [0029] We found that: the above-described method for preparing 4-hydroxybutyl vinyl ether, the addition of a cationic surfactant enables to accelerate the reaction.

[0030] 阳离子表面活性剂的亲水基离子中含有氮原子,根据氮原子在分子中的位置不同分为胺盐、季铵盐和杂环型三类。 [0030] The cationic hydrophilic group nonionic surfactants containing a nitrogen atom in accordance with the position of the nitrogen atom in the molecule into different amine salts, quaternary ammonium salts and heterocyclic categories.

[0031] 尤其是加入:阳离子表面活性剂是季铵型表面活性剂。 [0031] especially added: cationic surfactant is a quaternary ammonium surfactant.

[0032] 尤其是加入:季铵型表面活性剂是四丁基溴化铵、三甲基苄基氯化铵、三辛基甲基氯化铵、十六烷基三甲基溴化铵、三乙基苄基氯化铵、四丁基铵硫酸氢盐或三烷基甲基氯化铵、十八烷基三甲基氯化铵。 [0032] Add particular: quaternary ammonium surfactants are tetrabutylammonium bromide, trimethyl benzyl ammonium chloride, trioctyl methyl ammonium chloride, cetyl trimethyl ammonium bromide, triethylbenzylammonium chloride, tetrabutylammonium hydrogen sulfate or trialkyl methyl ammonium chloride, octadecyl trimethyl ammonium chloride.

[0033] 我们发现:上述的4-羟丁基乙烯基醚的制备方法中,十八烷基三甲基氯化铵用量为:1、4_ 丁二醇:十八烷基三甲基氯化铵=1 : 0.003-0. 005,w/w。 [0033] We found that: the above-described method for preparing 4-hydroxybutyl vinyl ethers, octadecyl trimethyl ammonium chloride in an amount of: 1,4_ butanediol: stearyltrimethylammonium chloride ammonium = 1:. 0.003-0 005, w / w.

[0034] 我们发现:乙炔气与氮气混合进入反应器,氮气占混合气的40-45% (V/V),与通常采用的氮气占混合气的50% (V/V)比较,仍能保证4-羟丁基乙烯不被氧化,同时提高单位时间产量5-10%。 [0034] We found: mixing acetylene gas and nitrogen gas into the reactor, the nitrogen gas accounts for 40-45% of the mixture (V / V), generally used with nitrogen gas mixture of 50% (V / V) compared still 4-hydroxybutyl vinyl guaranteed not oxidized, while increasing the yield per unit time is 5-10%.

[0035] 综上所述,由乙炔/1、4-丁二醇为原料,以氢氧化钾/ 二甲基亚砜/阳离子表面活性剂为催化剂,合成得到4-羟丁基乙烯基醚,二甲基亚砜能够使得乙炔/1、4-丁二醇由气液相反应转化为液相反应,阳离子表面活性剂能使得碱溶液一相中所产生的4-羟丁基乙烯基醚更好形成为有机相,提高有机相的产率。 [0035] In summary, the acetylene / 1,4-butanediol as raw materials, KOH / DMSO / cationic surfactant as catalyst to give 4-hydroxybutyl vinyl ether, dimethylsulfoxide enables acetylene / 1,4-butanediol is converted by the gas-liquid phase reaction, a cationic surfactant enables the alkali solution generated hydroxybutyl vinyl ether phase of a more preferably formed into an organic phase, the organic phase to improve the yield.

附图说明 BRIEF DESCRIPTION

[0036] 图14-羟丁基乙烯基醚的合成流程图。 [0036] Figure 14 synthesis scheme hydroxybutyl vinyl ether.

[0037] 1 :填料反应塔 [0037] 1: reaction column packing

[0038] 2:陶瓷环 [0038] 2: a ceramic ring

[0039] 3 :供热控制系统 [0039] 3: Heating control system

[0040] 4:乙炔气阀门 [0040] 4: Acetylene gas valve

[0041] 5:氮气阀门 [0041] 5: nitrogen valve

[0042] 6 :滴加漏斗 [0042] 6: dropping funnel

[0043] 7 :冷凝器 [0043] 7: Condenser

[0044] 8 :接受器 [0044] 8: receptacle

[0045] 9 :导热油 [0045] 9: HTF

具体实施方式 detailed description

[0046] 实施例1 [0046] Example 1

[0047] 将2000gl、4_ 丁二醇,180g氢氧化钾加入到3000ml三口瓶中,启动搅拌,油浴加热至140°C,在0. 05MPa真空下蒸馏,溜出约200g无色透明液体,得到1980g左右棕色粘稠液体,加入400g 二甲基亚砜,搅拌均勻备用。 [0047] The 2000gl, 4_ butanediol, 180g of potassium hydroxide was added to a 3000ml three-necked flask, starting stirring, the oil bath was heated to 140 ° C, distilled under vacuum at 0. 05MPa, slipped about 200g colorless liquid, about 1980g to give brown viscous liquid, was added 400g of dimethyl sulfoxide, stir standby.

[0048] 如图1所示:称取上述原料约400g,加入到填料反应塔1中,填料反应塔高70cm, 直径5cm(容积0. 9L,填装陶瓷环后实际容积为0. 6L),填料为陶瓷环2,开启供热控制系统3,用导热油9油浴供热,至温度达到170°C后,开启乙炔气阀门4及氮气阀门5,通过流量计,乙炔气:氮气=60 : 40 (V/V)的配比通入塔内,混合气体流量为15-20L/H,同时开启滴加漏斗6补加反应原料,使馏出量与补加量平衡,溜出液从塔顶,通过冷凝器7进入接受器8收集溜出液体,得到4-羟丁基乙烯基醚粗品,气相检测4-羟丁基乙烯基醚粗品含量为81.3%,环状缩醛3.8%。 [0048] 1: the raw material weighed about 400g, was added to the filler in the reaction column 1, the reaction tower packing 70cm, diameter 5cm (volume 0. 9L, the ceramic ring after the actual filling volume of 0. 6L) the filler is a ceramic ring (2), the control system 3 is turned on heating, heating with oil bath HTF 9, after the temperature reached to 170 ° C, acetylene gas valves 4 open the valves 5 and nitrogen gas, through a flow meter, acetylene gas: nitrogen = 60: 40 (V / V) ratio into the tower, the mixed gas flow rate of 15-20L / H, while dropping funnel opening 6 additional starting material, so additional amount of the distillate quantity balance, the distillate from the top, through the condenser 7 into the collection receptacle 8 slipped out of the liquid, 4-hydroxybutyl vinyl ether to give a crude product, 4-hydroxybutyl gas detection crude vinyl ether content of 81.3%, 3.8% cyclic acetal .

[0049] 实施例2 [0049] Example 2

[0050] 将2000gl、4-丁二醇,180g氢氧化钾加入到3000ml三口瓶中,启动搅拌,油浴加热至140°C,在0. 05MPa真空下蒸馏,溜出约200g无色透明液体,得到1980g左右棕色粘稠液体,加入400g 二甲基亚砜及IOg十八烷基三甲基氯化铵,搅拌均勻备用。 [0050] The 2000gl, 4- butanediol, 180g of potassium hydroxide was added to a 3000ml three-necked flask, starting stirring, the oil bath was heated to 140 ° C, distilled under vacuum at 0. 05MPa, slipped about 200g colorless liquid , about 1980g to give brown viscous liquid, was added 400g of dimethyl sulfoxide and IOg octadecyl trimethyl ammonium chloride, stir standby.

[0051] 如图1所示:称取上述原料约400g,加入到填料反应塔1中,填料反应塔高70cm, 直径5cm(容积0. 9L,填装陶瓷环后实际容积为0. 6L),填料为陶瓷环2,开启供热控制系统3,用导热油9油浴供热,至温度达到170°C后,开启乙炔气阀门4及氮气阀门5,通过流量计,乙炔气:氮气=60 : 40(V/V)的配比通入塔内,混合气体流量为15-20L/H,同时开启滴加漏斗6补加反应原料,使馏出量与补加量平衡,溜出液从塔顶,通过冷凝器7进入接受器8收集溜出液体,得到4-羟丁基乙烯基醚粗品,气相检测4-羟丁基乙烯基醚粗品含量为83. 4%,环状缩醛2.9%。 [0051] 1: the raw material weighed about 400g, was added to the filler in the reaction column 1, the reaction tower packing 70cm, diameter 5cm (volume 0. 9L, the ceramic ring after the actual filling volume of 0. 6L) the filler is a ceramic ring (2), the control system 3 is turned on heating, heating with oil bath HTF 9, after the temperature reached to 170 ° C, acetylene gas valves 4 open the valves 5 and nitrogen gas, through a flow meter, acetylene gas: nitrogen = 60: 40 (V / V) ratio into the tower, the mixed gas flow rate of 15-20L / H, while dropping funnel opening 6 additional starting material, so additional amount of the distillate quantity balance, the distillate from the top, through the condenser 7 into the collection receptacle 8 slipped out of the liquid, 4-hydroxybutyl vinyl ether to give a crude product, 4-hydroxybutyl gas detection crude vinyl ether content of 83.4%, cyclic acetal 2.9%.

[0052] 实施例3 [0052] Example 3

[0053] 将2000gl、4_ 丁二醇,180g氢氧化钾加入到3000ml三口瓶中,启动搅拌,油浴加热至140°C,在0. 05MPa真空下蒸馏,溜出约200g无色透明液体,得到1980g左右棕色粘稠液体,加入300g 二甲基亚砜及8g十八烷基三甲基氯化铵,搅拌均勻备用。 [0053] The 2000gl, 4_ butanediol, 180g of potassium hydroxide was added to a 3000ml three-necked flask, starting stirring, the oil bath was heated to 140 ° C, distilled under vacuum at 0. 05MPa, slipped about 200g colorless liquid, about 1980g to give brown viscous liquid, was added 300g of dimethyl sulfoxide and 8g octadecyl trimethyl ammonium chloride, stir standby.

[0054] 如图1所示:称取上述原料约400g,加入到填料反应塔1中,填料反应塔高70cm, 直径5cm(容积0. 9L,填装陶瓷环后实际容积为0. 6L),填料为陶瓷环2,开启供热控制系统3,用导热油9油浴供热,至温度达到170°C后,开启乙炔气阀门4及氮气阀门5,通过流量计,乙炔气:氮气=55 : 45 (V/V)的配比通入塔内,混合气体流量为15-20L/H,同时开启滴加漏斗6补加反应原料,使馏出量与补加量平衡,溜出液从塔顶,通过冷凝器7进入接受器8收集溜出液体,得到4-羟丁基乙烯基醚粗品,气相检测4-羟丁基乙烯基醚粗品含量为82.5%,环状缩醛3.0%。 [0054] 1: the raw material weighed about 400g, was added to the filler in the reaction column 1, the reaction tower packing 70cm, diameter 5cm (volume 0. 9L, the ceramic ring after the actual filling volume of 0. 6L) the filler is a ceramic ring (2), the control system 3 is turned on heating, heating with oil bath HTF 9, after the temperature reached to 170 ° C, acetylene gas valves 4 open the valves 5 and nitrogen gas, through a flow meter, acetylene gas: nitrogen = 55: 45 (V / V) ratio into the tower, the mixed gas flow rate of 15-20L / H, while dropping funnel opening 6 additional starting material, so additional amount of the distillate quantity balance, the distillate from the top, through the condenser 7 into the collection receptacle 8 slipped out of the liquid, 4-hydroxybutyl vinyl ether to give a crude product, 4-hydroxybutyl gas detection crude vinyl ether content of 82.5%, 3.0% cyclic acetal .

[0055] 实施例4 [0055] Example 4

[0056] 将2000gl、4_ 丁二醇,180g氢氧化钾加入到3000ml三口瓶中,启动搅拌,油浴加热至140°C,在0. 05MPa真空下蒸馏,溜出约200g无色透明液体,得到1980g左右棕色粘稠液体,加入200g 二甲基亚砜及6g十八烷基三甲基氯化铵,搅拌均勻备用。 [0056] The 2000gl, 4_ butanediol, 180g of potassium hydroxide was added to a 3000ml three-necked flask, starting stirring, the oil bath was heated to 140 ° C, distilled under vacuum at 0. 05MPa, slipped about 200g colorless liquid, about 1980g to give brown viscous liquid, was added 200g of dimethyl sulfoxide and 6g octadecyl trimethyl ammonium chloride, stir standby.

[0057] 如图1所示:称取上述原料约400g,加入到填料反应塔1中,填料反应塔高70cm, 直径5cm(容积0. 9L,填装陶瓷环后实际容积为0. 6L),填料为陶瓷环2,开启供热控制系统3,用导热油9油浴供热,至温度达到170°C后,开启乙炔气阀门4及氮气阀门5,通过流量计,乙炔气:氮气=57 : 43(V/V)的配比通入塔内,混合气体流量为15-20L/H,同时开启滴加漏斗6补加反应原料,使馏出量与补加量平衡,溜出液从塔顶,通过冷凝器7进入接受器8收集溜出液体,得到4-羟丁基乙烯基醚粗品,气相检测4-羟丁基乙烯基醚粗品含量为82. 8%,环状缩醛3.4%。 [0057] 1: the raw material weighed about 400g, was added to the filler in the reaction column 1, the reaction tower packing 70cm, diameter 5cm (volume 0. 9L, the ceramic ring after the actual filling volume of 0. 6L) the filler is a ceramic ring (2), the control system 3 is turned on heating, heating with oil bath HTF 9, after the temperature reached to 170 ° C, acetylene gas valves 4 open the valves 5 and nitrogen gas, through a flow meter, acetylene gas: nitrogen = 57: 43 (V / V) ratio into the tower, the mixed gas flow rate of 15-20L / H, while dropping funnel opening 6 additional starting material, so additional amount of the distillate quantity balance, the distillate from the top, through the condenser 7 into the collection receptacle 8 slipped out of the liquid, 4-hydroxybutyl vinyl ether to give a crude product, 4-hydroxybutyl gas detection crude vinyl ether content of 82.8%, cyclic acetal 3.4%.

[0058] 精馏:将4-羟丁基乙烯基醚粗品液体,加入到填料精馏塔(塔径km/塔高120cm,塔内填充玻璃簧填料)塔釜内,开启真空(0.098MPa),塔釜温度120°C,收集78-820C /0. 098MPa馏分为4-羟丁基乙烯基醚,气相测定含量99. 5%,收集完毕后,塔顶温度上升,回收85-87°C /0. 098MPa组分为二甲基亚砜,回收89_90°C /0. 098MPa未反应完的1、4_ 丁二醇,剩余少量高沸残留液,主要含副产物环状缩醛等。 [0058] Distillation: 4-hydroxybutyl vinyl ether, the crude liquid, the filler is added to the distillation column (column diameter km / 120cm tower, glass-filled spring tower packing) column bottom, turned vacuum (0.098 MPa) tower bottom temperature of 120 ° C, collected 78-820C / 0. 098MPa fraction of 4-hydroxybutyl vinyl ether, 99.5% Determination of vapor, Once gathered, the overhead temperature rises, recovering 85-87 ° C / 0. 098MPa component dimethylsulfoxide, recovering 89_90 ° C / 0. 098MPa End 1,4_ unreacted glycol, a small amount of residual high-boiling liquid residue, mainly comprising cyclic acetal by-product.

[0059] 4-羟丁基乙烯基醚的检测: [0059] 4-hydroxybutyl vinyl ether Detection:

[0060] 仪器:FULI_9790型气相色谱仪 [0060] Instrument: FULI_9790 gas chromatograph

[0061] 色谱柱:DB-FFAP型毛细管柱,规格Φ0. 25mm*30m [0061] Column:. DB-FFAP capillary column, size Φ0 25mm * 30m

[0062] 检测器:氢焰离子检测器 [0062] Detector: hydrogen flame ionization detector

[0063] 检测条件: [0063] Detection condition:

[0064] 气化温度:220°C [0064] The vaporization temperature: 220 ° C

[0065] 检测温度:240°C [0065] The detection temperature: 240 ° C

[0066] 柱室温度(程序升温):初温100°C,升温速率10°C /分钟,终温220°C, [0066] Column compartment temperature (temperature program): initial temperature 100 ° C, heating rate 10 ° C / min, final temperature 220 ° C,

[0067] 保持30分钟。 [0067] 30 minutes.

[0068] 载气表压: [0068] Carrier gas gauge:

[0069] 氮气:0. O8MPa [0069] nitrogen:. 0 O8MPa

[0070] 氢气:0. I5MPa [0070] Hydrogen:. 0 I5MPa

[0071]空气:0.0;35MPa [0071] Air: 0.0; 35MPa

[0072]进样量:0· 4 [0072] Injection volume: 0.4

[0073] 积分方法:面积归一法 [0073] integration method: area normalization method

[0074] 允许误差:两次平行测定结果之差不大于0. 2%。 [0074] tolerance: Results difference between the two replicates is not greater than 0.2%.

7 7

Claims (4)

  1. 1. 一种4-羟丁基乙烯基醚的制备方法:在氢氧化钾的存在下,1、4_ 丁二醇与乙炔反应,得到4-羟丁基乙烯基醚,其特征在于:反应中加入了二甲基亚砜和阳离子表面活性剂;其中1、4_ 丁二醇:二甲基亚砜=1 : 0. 1-0. 2,w/w, 其中阳离子表面活性剂是季铵型表面活性剂,并且季铵型表面活性剂是四丁基溴化铵、三甲基苄基氯化铵、三辛基甲基氯化铵、十六烷基三甲基溴化铵、三乙基苄基氯化铵、四丁基铵硫酸氢盐或十八烷基三甲基氯化铵。 A 4-hydroxybutyl vinyl ether preparation process: in the presence of potassium hydroxide, 1,4_ butanediol with acetylene to give 4-hydroxybutyl vinyl ether, wherein: the reaction DMSO was added and the cationic surfactant; wherein 1,4_ butanediol: dimethyl sulfoxide = 1: 0. 1-0 2, w / w, wherein the cationic surfactant is a quaternary ammonium type. a surfactant, and quaternary ammonium surfactants are tetrabutylammonium bromide, trimethyl benzyl ammonium chloride, trioctyl methyl ammonium chloride, cetyl trimethyl ammonium bromide, triacetyl benzyl chloride, hydrogen sulfate or tetrabutylammonium salt of stearyl trimethyl ammonium chloride.
  2. 2.根据权利要求1所述的4-羟丁基乙烯基醚的制备方法,其特征在于:1、4_ 丁二醇: 十八烷基三甲基氯化铵=1 : 0. 003-0. 005, w/w0 The method of preparation of 4-hydroxybutyl vinyl ether according to claim 1, wherein: 1,4_ butanediol: octadecyl trimethylammonium chloride = 1: 0. 003-0 . 005, w / w0
  3. 3.根据权利要求1或2所述的4-羟丁基乙烯基醚的制备方法,其特征在于:乙炔气与氮气混合进入反应器。 The method of preparation of 4-hydroxybutyl vinyl ether claim 1 or claim 2, wherein: the mixing acetylene gas and nitrogen gas into the reactor.
  4. 4.根据权利要求3所述的4-羟丁基乙烯基醚的制备方法,其特征在于:乙炔气与氮气混合进入反应器,氮气占混合气的40-45%,V/V。 According to claim 3 hydroxybutyl vinyl ether production method as claimed in claim, wherein: the mixing acetylene gas and nitrogen gas into the reactor, the nitrogen gas accounts for 40-45% of the mixture, V / V.
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