CN102585194A - Method for synthesizing allyl fatty alcohol-polyoxyethylene ether or allyl alkylphenol ethoxylate - Google Patents
Method for synthesizing allyl fatty alcohol-polyoxyethylene ether or allyl alkylphenol ethoxylate Download PDFInfo
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229940051841 polyoxyethylene ether Drugs 0.000 title abstract description 73
- 229920000056 polyoxyethylene ether Polymers 0.000 title abstract description 73
- 230000002194 synthesizing effect Effects 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- -1 allyl fatty alcohol Chemical class 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 9
- 239000010935 stainless steel Substances 0.000 claims abstract description 9
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000012047 saturated solution Substances 0.000 claims description 8
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 3
- 150000008045 alkali metal halides Chemical class 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 11
- 239000003513 alkali Substances 0.000 claims 4
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims 2
- 238000010792 warming Methods 0.000 claims 2
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 238000006073 displacement reaction Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 28
- 150000002191 fatty alcohols Chemical class 0.000 abstract description 21
- 238000013517 stratification Methods 0.000 abstract description 7
- 239000012043 crude product Substances 0.000 abstract description 4
- 238000010189 synthetic method Methods 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 7
- 239000003444 phase transfer catalyst Substances 0.000 description 7
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- BVTJGGGYKAMDBN-UHFFFAOYSA-N Dioxetane Chemical compound C1COO1 BVTJGGGYKAMDBN-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006959 Williamson synthesis reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚的合成方法是将脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚与固体碱金属氢氧化物加入不锈钢高压反应釜，保持反应釜真空度为0.085-0.1MPa，反应釜升温至70-200℃，反应时间1-5小时，关闭真空系统，继续向反应釜中滴加烯丙基卤化物，滴加过程持续搅拌物料，反应温度：30-100℃，反应时间：1-8小时，反应压力0.1-0.5MPa，开启真空系统除去产物中剩余的烯丙基卤化物，出料，得到粗产品；向粗产品中加入热水，混合均匀后静置分层得到烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚。本发明具有无污染，成本低，转化率高的优点。A kind of synthetic method of allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether is to add fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether and solid alkali metal hydroxide into stainless steel High-pressure reaction kettle, keep the vacuum degree of the reaction kettle at 0.085-0.1MPa, the temperature of the reaction kettle is raised to 70-200°C, the reaction time is 1-5 hours, close the vacuum system, continue to add allyl halides to the reaction kettle dropwise, drop The process continues to stir the material, the reaction temperature: 30-100 ° C, the reaction time: 1-8 hours, the reaction pressure 0.1-0.5 MPa, open the vacuum system to remove the remaining allyl halide in the product, and discharge the material to obtain the crude product; Hot water is added to the crude product, and after mixing evenly, the mixture is allowed to stand for stratification to obtain allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether. The invention has the advantages of no pollution, low cost and high conversion rate.
Description
技术领域 technical field
本发明涉及一种烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚的合成方法。The invention relates to a method for synthesizing allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether.
背景技术 Background technique
烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚分子结构中含有聚氧乙烯基，端基含有双键，具有活泼的化学性质，可以作为表面活性剂合成的中间体，如醇醚磺酸盐等。其合成采用威廉森反应进行，脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚与碱金属氢氧化物反应，生成相应的醇醚盐，在醇醚盐中加入烯丙基卤化物进行亲核取代反应，生成产物烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚与碱金属卤化物。The molecular structure of allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether contains polyoxyethylene groups, and the end group contains double bonds. It has active chemical properties and can be used as an intermediate in the synthesis of surfactants. , such as alcohol ether sulfonate, etc. Its synthesis is carried out by Williamson reaction. Fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether reacts with alkali metal hydroxide to generate the corresponding alcohol ether salt, and allyl halide is added to the alcohol ether salt for hydrophilic Nucleus substitution reaction to produce allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether and alkali metal halide.
烯丙基醚的制备方法有以下几种：(1)脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚与氢氧化物水溶液，在相转移催化剂存在的条件下进行反应(US4588534、FR2566401)，制备脂肪醇聚氧乙烯醇醚盐或烷基酚聚氧乙烯醚聚氧乙烯醇醚盐，反应完成后加入烯丙基卤化物得到相应的烯丙基醚。(2)脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚与固体氢氧化物、烯丙基卤化物，在有机溶剂存在的条件下进行一步反应制备相应的烯丙基醚(EP265856)。上述两种方法为了提高反应活性，分别在反应体系中加入了水、相转移催化剂以及有机溶剂，在氢氧化物水溶液中进行烯丙基醚合成，体系中的水影响了反应平衡，转化率低；在反应过程中需要加入相转移催化剂，相转移催化剂难以从产物中分离；采用了有机溶剂，反应转化率虽然有所提高，但使用有机溶剂必然带来环境问题，在工程中还需要增加溶剂脱除等设备单元，增加了反应成本。The preparation method of allyl ether has the following several kinds: (1) fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether and hydroxide aqueous solution, carry out reaction under the condition that phase-transfer catalyst exists (US4588534, FR2566401) , to prepare fatty alcohol polyoxyethylene alcohol ether salt or alkylphenol polyoxyethylene ether polyoxyethylene alcohol ether salt, after the reaction is completed, add allyl halide to obtain the corresponding allyl ether. (2) Fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether, solid hydroxide and allyl halide are reacted in one step in the presence of an organic solvent to prepare the corresponding allyl ether (EP265856). In order to improve the reactivity of the above two methods, water, a phase transfer catalyst and an organic solvent were added to the reaction system, and allyl ether was synthesized in an aqueous hydroxide solution. The water in the system affected the reaction balance and the conversion rate was low. ; Need to add phase transfer catalyst in the reaction process, phase transfer catalyst is difficult to separate from the product; adopted organic solvent, although the reaction conversion rate has been improved, but the use of organic solvent will inevitably bring environmental problems, also need to increase the solvent in the project Equipment units such as removal increase the reaction cost.
发明内容 Contents of the invention
本发明的目的是提供一种无污染，成本低，转化率高的一种烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚的合成方法。The purpose of the present invention is to provide a kind of non-polluting, low cost, a kind of synthetic method of allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether with high conversion rate.
本发明采用两步反应法进行了烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚合成，首先，脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚与固体碱在高真空条件下，反应生成脂肪醇聚氧乙烯醇醚盐或烷基酚聚氧乙烯醚聚氧乙烯醇醚盐，采用高真空是为了脱除反应过程中产生的水分，促使反应平衡向生成醇醚盐的方向进行。The present invention adopts two-step reaction method to carry out allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether synthesis, first, fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether and solid base Under high vacuum conditions, the reaction produces fatty alcohol polyoxyethylene alcohol ether salt or alkylphenol polyoxyethylene ether polyoxyethylene alcohol ether salt. The high vacuum is used to remove the moisture generated during the reaction and promote the reaction balance to form Carry out in the direction of alcohol ether salt.
式中：R表示C8-C30的直链烷基、支链烷基、或是C8-C30的酚基；n表示乙氧基加合数，30＞n＞1；M表示I族II族碱金属元素中的一种In the formula: R represents C 8 -C 30 straight chain alkyl, branched chain alkyl, or C 8 -C 30 phenol; n represents the number of ethoxy addition, 30>n>1; M represents I One of the group II alkali metal elements
脂肪醇聚氧乙烯醇醚盐或烷基酚聚氧乙烯醇醚盐再与烯丙基卤化物反应生成烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚。Fatty alcohol polyoxyethylene alcohol ether salt or alkylphenol polyoxyethylene alcohol ether salt reacts with allyl halide to generate allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether.
式中：R表示C8-C30的直链烷基、支链烷基、或是C8-C30的酚基；n表示乙氧基加合数，30＞n＞1；M表示I族II族碱金属元素中的一种；Y表示VII族元素中的一种In the formula: R represents C 8 -C 30 straight chain alkyl, branched chain alkyl, or C 8 -C 30 phenol; n represents the number of ethoxy adducts, 30>n>1; M represents I One of the group II alkali metal elements; Y represents one of the VII group elements
本方法同时解决了烯丙基醚合成过程中转化率低以及相转移催化剂和溶剂的分离问题。The method simultaneously solves the problems of low conversion rate and separation of phase transfer catalyst and solvent in the synthesis process of allyl ether.
本发明的反应步骤包括：Reaction step of the present invention comprises:
(1)、按脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚与固体碱的摩尔比为1∶1-1.5，将脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚与固体碱金属氢氧化物加入不锈钢高压反应釜，加料同时开启搅拌，投料后对反应釜进行封闭，氮气置换反应釜中的空气，置换完成后启动真空系统，保持反应釜真空度为0.085-0.1MPa，在此过程中持继搅拌物料，反应釜升温至70-200℃，优选100-150℃；反应时间1-5小时，优选2-3小时，停止加热，冷却至室温，关闭真空系统；(1), according to the molar ratio of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether and solid base is 1:1-1.5, the fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether and solid base Add the metal hydroxide to the stainless steel high-pressure reactor, start stirring at the same time as feeding, seal the reactor after feeding, replace the air in the reactor with nitrogen, start the vacuum system after the replacement is completed, and keep the vacuum of the reactor at 0.085-0.1MPa. During this process, the materials are continuously stirred, and the temperature of the reactor is raised to 70-200°C, preferably 100-150°C; the reaction time is 1-5 hours, preferably 2-3 hours, stop heating, cool to room temperature, and turn off the vacuum system;
(2)、按脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚与烯丙基卤化物的摩尔比为1∶1-1.5，继续向步骤(1)反应釜中滴加烯丙基卤化物，滴加过程持续搅拌物料，反应温度：30-100℃，优选50-80℃；反应时间：1-8小时，优选2-5小时；反应压力0.1-0.5MPa，开启真空系统除去产物中剩余的烯丙基卤化物，出料，得到粗产品；(2), according to the molar ratio of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether to allyl halide is 1:1-1.5, continue to drop allyl halide into the reaction kettle of step (1) The material is continuously stirred during the dropping process, the reaction temperature: 30-100 ° C, preferably 50-80 ° C; the reaction time: 1-8 hours, preferably 2-5 hours; the reaction pressure is 0.1-0.5 MPa, and the vacuum system is opened to remove the product. Remaining allyl halide, discharging, obtains crude product;
(3)、向粗产品中加入热水，混合均匀后静置分层，下层为碱金属卤化物的饱和溶液，上层为精制产品烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚。(3) Add hot water to the crude product, mix evenly and let it stand for stratification. The lower layer is a saturated solution of alkali metal halide, and the upper layer is the refined product allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether.
如上所述的脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚具有以下通式(1)：Fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether as above has following general formula (1):
式中：R表示C8-C30的直链烷基、支链烷基、或是C8-C30的酚基；n表示乙氧基加合数，30＞n＞1In the formula: R represents C 8 -C 30 straight chain alkyl, branched chain alkyl, or C 8 -C 30 phenol; n represents the number of ethoxy adducts, 30>n>1
如上所述的烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚具有以下通式(2)：Allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether as above has the following general formula (2):
式中：R表示C8-C30的直链烷基、支链烷基、或是C8-C30的酚基；n表示乙氧基加合数，30＞n＞1。In the formula: R represents a C 8 -C 30 linear alkyl group, a branched chain alkyl group, or a C 8 -C 30 phenolic group; n represents the number of adducted ethoxy groups, 30>n>1.
如上所述的固体碱包括I族II族碱金属氢氧化物，如氢氧化钠、氢氧化钾、氢氧化锂、氢氧化镁、氢氧化钙等，优选氢氧化钠、氢氧化钾、氢氧化锂。固体碱的形状包括粒状、片状、块状，粒径为0.01-1mm的固体碱。The solid bases mentioned above include Group I and Group II alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, etc., preferably sodium hydroxide, potassium hydroxide, hydroxide lithium. The shape of the solid base includes granular, flake, block, solid base with a particle size of 0.01-1mm.
如上所述的烯丙基卤化物为烯丙基氯或烯丙基溴。The allyl halide as described above is allyl chloride or allyl bromide.
本发明的优点如下：The advantages of the present invention are as follows:
1、本发明在反应的第一步采用高真空脱除反应过程中生成的水分，促使反应充分向生成中间体脂肪醇聚氧乙烯醇醚盐或烷基酚聚氧乙烯醇醚盐的方向进行，提高了反应转化率。1. In the first step of the reaction, the present invention adopts high vacuum to remove the moisture generated in the reaction process, so that the reaction is fully carried out in the direction of generating intermediate fatty alcohol polyoxyethylene alcohol ether salt or alkylphenol polyoxyethylene alcohol ether salt , which increases the conversion rate of the reaction.
2、本发明所采用的合成方法不使用有机溶剂，减少了溶剂脱除单元，简化了反应工艺。2. The synthetic method adopted in the present invention does not use organic solvents, which reduces the number of solvent removal units and simplifies the reaction process.
3、本发明所采用的合成方法不使用相转移催化剂，解决了传统工艺中相转移催化剂分离困难的问题。3. The synthesis method adopted in the present invention does not use a phase transfer catalyst, which solves the problem of difficult separation of the phase transfer catalyst in the traditional process.
4、本发明所采用的方法无环境污染、成本低、工艺条件温和。4. The method adopted in the present invention has no environmental pollution, low cost and mild process conditions.
具体实施方式 Detailed ways
如下实施例采用的分析为脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚转化率分析采用羟价分析。The analysis used in the following examples is the analysis of the conversion rate of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether using hydroxyl value analysis.
实施例1：Example 1:
第一步反应：向500ml不锈钢高压反应釜中投入脂肪醇聚氧乙烯醚AEO-7(分子量501)200克与固体氢氧化钠22克(粒径1mm)，摩尔比为1∶1，加料同时进行物料搅拌，投料后对反应釜进行封闭，氮气置换反应釜中的空气，置换完成后启动真空系统，保持反应釜真空度为0.085MPa，在此过程中持续搅拌物料，反应釜升温至200℃，反应5小时后，停止加热，冷却至室温，关闭真空系统；The first step reaction: put 200 grams of fatty alcohol polyoxyethylene ether AEO-7 (molecular weight 501) and 22 grams of solid sodium hydroxide (particle size 1mm) into a 500ml stainless steel autoclave, the molar ratio is 1: 1, and feed simultaneously Stir the materials, close the reactor after feeding, replace the air in the reactor with nitrogen, start the vacuum system after the replacement, keep the vacuum of the reactor at 0.085MPa, keep stirring the materials during this process, and raise the temperature of the reactor to 200°C , after reacting for 5 hours, stop heating, cool to room temperature, and close the vacuum system;
第二步反应：向上述反应釜中滴加烯丙基氯39克，脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚与烯丙基氯的摩尔比为1∶1，滴加过程中持续搅拌物料，滴加终了反应放热至30℃，反应釜压力0.1MPa，搅拌1小时后停止反应，开启真空系统除去产物中剩余的烯丙基氯，出料。The second step reaction: add 39 grams of allyl chloride dropwise to the above reaction kettle, the molar ratio of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether to allyl chloride is 1:1, during the dropwise addition process Stir the material continuously, after the dropwise addition, the reaction exotherms to 30°C, the pressure of the reactor is 0.1MPa, the reaction is stopped after stirring for 1 hour, the vacuum system is turned on to remove the remaining allyl chloride in the product, and the material is discharged.
后处理：向产物中加入70克热水，混合均匀后静置分层，下层为氯化钠的饱和溶液，上层为精制产品烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚。产品转化率为82％。Post-processing: Add 70 grams of hot water to the product, mix well and let it stand for stratification. The lower layer is a saturated solution of sodium chloride, and the upper layer is a refined product of allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether. Oxyethylene ether. The product conversion rate was 82%.
实施例2：Example 2:
第一步反应：向500ml不锈钢高压反应釜中投入烷基酚聚氧乙烯醚NP-8(分子量520)200克与固体氢氧化锂12克(粒径0.1mm)，摩尔比为1∶1.3，加料同时进行物料搅拌，投料后对反应釜进行封闭，氮气置换反应釜中的空气，置换完成后启动真空系统，保持反应釜真空度为0.1MPa，在此过程中持续搅拌物料，反应釜升温至140℃，反应3小时后，停止加热，冷却至室温，关闭真空系统；The first step reaction: 200 grams of alkylphenol polyoxyethylene ether NP-8 (molecular weight 520) and 12 grams of solid lithium hydroxide (particle size 0.1mm) were dropped into a 500ml stainless steel autoclave, and the molar ratio was 1: 1.3. Stir the material at the same time as feeding, seal the reactor after feeding, replace the air in the reactor with nitrogen, start the vacuum system after the replacement, keep the vacuum of the reactor at 0.1MPa, keep stirring the materials during this process, and the temperature of the reactor rises to 140°C, after 3 hours of reaction, stop heating, cool to room temperature, and turn off the vacuum system;
第二步反应：向上述反应釜中滴加烯丙基溴60克，脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚与烯丙基溴的摩尔比为1∶1.3，滴加过程中持续搅拌物料，滴加终了反应放热至60℃，反应釜压力0.2MPa，搅拌3小时后停止反应，开启真空系统除去产物中剩余的烯丙基溴，出料。The second step reaction: add 60 grams of allyl bromide dropwise to the above reaction kettle, the molar ratio of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether to allyl bromide is 1: 1.3, during the dropwise addition process Stir the material continuously, after the dropwise addition, the reaction exotherms to 60°C, the pressure of the reactor is 0.2MPa, the reaction is stopped after stirring for 3 hours, the vacuum system is turned on to remove the remaining allyl bromide in the product, and the material is discharged.
后处理：向产物中加入40克热水，混合均匀后静置分层，下层为溴化锂的饱和溶液，上层为精制产品烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚。产品转化率为93％。Post-treatment: Add 40 grams of hot water to the product, mix well and then let it stand for stratification. The lower layer is a saturated solution of lithium bromide, and the upper layer is a refined product of allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether. The product conversion rate was 93%.
实施例3：Example 3:
第一步反应：向500ml不锈钢高压反应釜中投入烷基酚聚氧乙烯醚TX-10(分子量601)200克与固体氢氧化钾28克(粒径0.01mm)，摩尔比为1∶1.5，加料同时进行物料搅拌，投料后对反应釜进行封闭，氮气置换反应釜中的空气，置换完成后启动真空系统，保持反应釜真空度为0.1MPa，在此过程中持续搅拌物料，反应釜升温至70℃，反应1小时后，停止加热，冷却至室温，关闭真空系统；The first step reaction: 200 grams of alkylphenol polyoxyethylene ether TX-10 (molecular weight 601) and 28 grams of solid potassium hydroxide (particle diameter 0.01mm) were dropped into a 500ml stainless steel autoclave, and the molar ratio was 1: 1.5. Stir the material at the same time as feeding, seal the reactor after feeding, replace the air in the reactor with nitrogen, start the vacuum system after the replacement, keep the vacuum of the reactor at 0.1MPa, keep stirring the materials during this process, and the temperature of the reactor rises to 70°C, after reacting for 1 hour, stop heating, cool to room temperature, and turn off the vacuum system;
第二步反应：向上述反应釜中滴加烯丙基氯38克，脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚与烯丙基氯摩尔比为1∶1.5，滴加过程中持续搅拌物料，滴加终了反应放热至100℃，反应釜压力0.5MPa，搅拌5小时后停止反应，开启真空系统除去产物中剩余的烯丙基氯，出料。The second step reaction: add 38 grams of allyl chloride dropwise to the above reaction kettle, the molar ratio of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether to allyl chloride is 1: 1.5, and the dripping process continues Stir the material, drop the reaction heat to 100°C after the dropwise addition, the pressure of the reactor is 0.5MPa, stop the reaction after stirring for 5 hours, turn on the vacuum system to remove the remaining allyl chloride in the product, and discharge the material.
后处理：向产物中加入80克热水，混合均匀后静置分层，下层为氯化钾的饱和溶液，上层为精制产品烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚。产品转化率为94％。Post-treatment: Add 80 grams of hot water to the product, mix well and let it stand for stratification. The lower layer is a saturated solution of potassium chloride, and the upper layer is a refined product of allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether. Oxyethylene ether. The product conversion rate was 94%.
实施例4：Example 4:
第一步反应：向500ml不锈钢高压反应釜中投入烷基酚聚氧乙烯醚AEO-9(分子量590)200克与固体氢氧化镁8克(粒径0.3mm)，摩尔比为1∶1.2，加料同时进行物料搅拌，投料后对反应釜进行封闭，氮气置换反应釜中的空气，置换完成后启动真空系统，保持反应釜真空度为0.1MPa，在此过程中持续搅拌物料，反应釜升温至100℃，反应2小时后，停止加热，冷却至室温，关闭真空系统；The first step reaction: 200 grams of alkylphenol polyoxyethylene ether AEO-9 (molecular weight 590) and 8 grams of solid magnesium hydroxide (particle diameter 0.3mm) were dropped into a 500ml stainless steel autoclave, and the molar ratio was 1: 1.2. Stir the material at the same time as feeding, seal the reactor after feeding, replace the air in the reactor with nitrogen, start the vacuum system after the replacement, keep the vacuum of the reactor at 0.1MPa, keep stirring the materials during this process, and the temperature of the reactor rises to 100°C, after 2 hours of reaction, stop heating, cool to room temperature, and turn off the vacuum system;
第二步反应：向上述反应釜中滴加烯丙基溴49克，脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚与烯丙基卤化物摩尔比为1∶1.2，滴加过程中持续搅拌物料，滴加终了反应放热至70℃，反应釜压力0.2MPa，搅拌2小时后停止反应，开启真空系统除去产物中剩余的烯丙基溴，出料。The second step reaction: add 49 grams of allyl bromide dropwise to the above reaction kettle, the molar ratio of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether to allyl halide is 1: 1.2, during the dropwise addition process Stir the material continuously. After the dropwise addition, the reaction is exothermic to 70°C. The pressure of the reactor is 0.2 MPa. After stirring for 2 hours, the reaction is stopped. The vacuum system is turned on to remove the remaining allyl bromide in the product, and the material is discharged.
后处理：向产物中加入70克热水，混合均匀后静置分层，下层为溴化镁的饱和溶液，上层为精制产品烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚。产品转化率为91％。Post-treatment: Add 70 grams of hot water to the product, mix well and let it stand for stratification. The lower layer is a saturated solution of magnesium bromide, and the upper layer is a refined product of allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether. Oxyethylene ether. The product conversion rate was 91%.
实施例5：Example 5:
第一步反应：向500ml不锈钢高压反应釜中投入烷基酚聚氧乙烯醚NP-30(分子量1480)200克与固体氢氧化钙5克(粒径0.05mm)，摩尔比为1∶1.3，加料同时进行物料搅拌，投料后对反应釜进行封闭，氮气置换反应釜中的空气，置换完成后启动真空系统，保持反应釜真空度为0.1MPa，在此过程中持续搅拌物料，反应釜升温至160℃，反应4小时后，停止加热，冷却至室温，关闭真空系统；The first step reaction: 200 grams of alkylphenol polyoxyethylene ether NP-30 (molecular weight 1480) and 5 grams of solid calcium hydroxide (particle diameter 0.05mm) were dropped into a 500ml stainless steel autoclave, and the molar ratio was 1: 1.3. Stir the material at the same time as feeding, seal the reactor after feeding, replace the air in the reactor with nitrogen, start the vacuum system after the replacement, keep the vacuum of the reactor at 0.1MPa, keep stirring the materials during this process, and the temperature of the reactor rises to 160°C, after 4 hours of reaction, stop heating, cool to room temperature, and turn off the vacuum system;
第二步反应：向上述反应釜中滴加烯丙基氯14克，脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚与烯丙基氯摩尔比为1∶1.3，滴加过程中持续搅拌物料，滴加终了反应放热至60℃，反应釜压力0.2MPa，搅拌4小时后停止反应，开启真空系统除去产物中剩余的烯丙基氯，出料。The second step reaction: 14 grams of allyl chloride is added dropwise to the above reaction kettle, the molar ratio of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether to allyl chloride is 1: 1.3, and the dripping process continues Stir the material, drop the reaction to 60°C after the dropwise addition, the reaction kettle pressure is 0.2MPa, stop the reaction after stirring for 4 hours, open the vacuum system to remove the remaining allyl chloride in the product, and discharge.
后处理：向产物中加入40克热水，混合均匀后静置分层，下层为氯化钙的饱和溶液，上层为精制产品烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚。产品转化率为90％。Post-treatment: Add 40 grams of hot water to the product, mix well and then let it stand for stratification. The lower layer is a saturated solution of calcium chloride, and the upper layer is a refined product of allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether. Oxyethylene ether. The product conversion rate is 90%.
实施例6：Embodiment 6:
第一步反应：向500ml不锈钢高压反应釜中投入烷基酚聚氧乙烯醚AEO-3(分子量325)200克与固体氢氧化钠27克(粒径0.8mm)，摩尔比为1∶1.1，加料同时进行物料搅拌，投料后对反应釜进行封闭，氮气置换反应釜中的空气，置换完成后启动真空系统，保持反应釜真空度为0.1MPa，在此过程中持续搅拌物料，反应釜升温至90℃，反应1小时后，停止加热，冷却至室温，关闭真空系统；The first step reaction: 200 grams of alkylphenol polyoxyethylene ether AEO-3 (molecular weight 325) and 27 grams of solid sodium hydroxide (particle diameter 0.8 mm) were dropped into a 500 ml stainless steel autoclave, and the molar ratio was 1: 1.1. Stir the material at the same time as feeding, seal the reactor after feeding, replace the air in the reactor with nitrogen, start the vacuum system after the replacement, keep the vacuum of the reactor at 0.1MPa, keep stirring the materials during this process, and the temperature of the reactor rises to 90°C, after 1 hour of reaction, stop heating, cool to room temperature, and turn off the vacuum system;
第二步反应：向上述反应釜中滴加烯丙基氯52克，脂肪醇聚氧乙烯醚或烷基酚聚氧乙烯醚与烯丙基卤化物摩尔比为1∶1.1，滴加过程中持续搅拌物料，滴加终了反应放热至50℃，反应釜压力0.2MPa，搅拌5小时后停止反应，开启真空系统除去产物中剩余的烯丙基氯，出料。The second step reaction: add 52 grams of allyl chloride dropwise to the above reaction kettle, the molar ratio of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether to allyl halide is 1: 1.1, during the dropwise addition process Stir the material continuously, and the reaction is exothermic to 50°C after the dropwise addition, the pressure of the reactor is 0.2MPa, the reaction is stopped after stirring for 5 hours, the vacuum system is turned on to remove the remaining allyl chloride in the product, and the material is discharged.
后处理：向产物中加入60克热水，混合均匀后静置分层，下层为氯化钠的饱和溶液，上层为精制产品烯丙基脂肪醇聚氧乙烯醚或烯丙基烷基酚聚氧乙烯醚。产品转化率为89％。Post-processing: Add 60 grams of hot water to the product, mix well and then let stand to separate layers. The lower layer is a saturated solution of sodium chloride, and the upper layer is a refined product of allyl fatty alcohol polyoxyethylene ether or allyl alkylphenol polyoxyethylene ether. Oxyethylene ether. The product conversion rate is 89%.
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Application publication date: 20120718 |