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CN103274973A - Alkyl dinaphthyl ether sulfonate and preparation method thereof - Google Patents

Alkyl dinaphthyl ether sulfonate and preparation method thereof Download PDF

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Publication number
CN103274973A
CN103274973A CN2013102317882A CN201310231788A CN103274973A CN 103274973 A CN103274973 A CN 103274973A CN 2013102317882 A CN2013102317882 A CN 2013102317882A CN 201310231788 A CN201310231788 A CN 201310231788A CN 103274973 A CN103274973 A CN 103274973A
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alkyl
dinaphthyl ether
preparation
dinaphthyl
ether sulfonate
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CN2013102317882A
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杨锌荣
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Abstract

The invention relates to a novel anionic surfactant alkyl dinaphthyl ether sulfonate and a preparation method thereof. The method comprises the steps as follows: halonaphthalenes and alkyl naphthol are taken as main raw materials; with the presence of an acid-binding agent, a catalyst and water absorbent, the main raw materials are subjected to heat preservation for 1-5 hours at the temperature ranging from 80 DEG C to180 DEG C to generate an intermediate product of alkyl dinaphthyl ether and a byproduct of halogen salt; halogen salt and the catalyst are filtered and removed, and alkyl dinaphthyl ether is obtained by rectifying and separating; and a sulfonating agent is added to alkyl dinaphthyl ether step by step, sulfonation is performed at the temperature in a range from 0 to 80 DEG C to generate alkyl dinaphthyl ether sulfoacid, and an antalkali is added to generate alkyl dinaphthyl ether sulfonate.

Description

A kind of alkyl dinaphthyl ether sulfonate and preparation method thereof
Technical field
The invention belongs to tensio-active agent manufacturing technology field, be specifically related to a kind of alkyl dinaphthyl ether sulfonate and preparation method thereof.
Background technology
This product alkyl dinaphthyl ether sulfonate mainly is divided into alkyl dinaphthyl ether monosulfonate, alkyl dinaphthyl ether disulfonate, alkyl dinaphthyl ether trisulfonate, two alkyl dinaphthyl ether disulfonate, products such as two alkyl dinaphthyl ether trisulfonates, and domestic still do not have an example.I to the conditions of demand of high stability, cost performance, the wetting excellent surfactant of emulsification, have developed these series product according to several years of product development and application experience and market.Product can have extensive use at industrial circles such as oil production, textile printing and dyeing, latex processing, metal processing, surface cleaning, and product adopts Williamson's synthesis method to do the etherification reaction of this product, technology theory maturation, easy handling.
Summary of the invention
Goal of the invention: in order to develop a kind of more stable excellent surfactant of performance under different acid, alkali, inorganic salt, the temperature working conditions that has, the invention provides the negatively charged ion novel surfactant of a kind of macromole, many hydrophilic groups;
The present invention specifically realizes with following steps:
(1) 1-10mol naphthalene halide and 1-3mol alkyl naphthol are dropped into etherifying reactor;
(2) drop into acid binding agent and water-retaining agent to etherifying reactor, nitrogen protection simultaneously, stirring reaction is molten entirely to acid binding agent;
(3) drop into catalyzer to etherifying reactor, under 80-180 ℃ of temperature condition, be incubated 1-5 hour, generate intermediates alkyl dinaphthyl ether and by-product halogen;
(4) above-mentioned (3) product is filtered filtering by-product halogen and catalyzer;
(5) above-mentioned (4) product is carried out rectifying, divide and remove naphthalene halide, get the alkyl dinaphthyl ether, send into the sulfonation still;
(6) add inert organic solvents and 1-5mol sulphonating agent 0-80 ℃ of sulfonation to the sulfonation still again, be incubated 1-5 hour, the mixture of generation alkyl dinaphthyl ether sulfonic acid and inert solvent;
(7) add the water of material total amount 10-60% in the still to the sulfonation still, stir the static acid out in back, treat to divide after the layering and go waste water layer, oil reservoir to be alkyl dinaphthyl ether sulfonic acid, during the gained material is sent into and still;
(8) in and still add water and add alkaline neutraliser 1-5mol and be neutralized to neutrality, namely get alkyl dinaphthyl ether sulfonate;
Effect of the present invention and benefit are:
(1) aspect synthetic technology: adopt Williamson's synthesis method etherificate route synthesis of alkyl phenyl ether, technology theory maturation, product yield height;
(2) aspect economic benefit: not only the disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate of alternative import is used for emulsification, dispersed demanding field, reduced the interests loss of national industry, and because the buying of production domesticization back becomes convenient, improved production and operation efficient;
(3) aspect product performance: this excellent product performance, both had anti-strong acid, highly basic, properties such as inorganic salt, surface tension can reach the 29-35 dynes per centimeter when concentration 0.1%, and have remarkable emulsifying property, and cheap, and cost performance is good.Product also alternative commercially available alkylphenol polyoxyethylene, sodium alkyl benzene sulfonate, alkyl sodium sulfonate, fatty alcohol-polyoxyethylene ether in industrial circles such as oil production, textile printing and dyeing, latex processing, metal processing, surface cleaning.Aspect emulsification, dispersing property, acid-and base-resisting, inorganic salt, high-temperature behavior, be that present commercially available alkylphenol polyoxyethylene, sodium alkyl benzene sulfonate, fatty alcohol-polyoxyethylene ether etc. are wetting, the 2-10 of dispersion, emulsification class tensio-active agent doubly.When increasing substantially product stability in use and effect, reduce usage quantity significantly, reduced use cost, reduced the environmental pollution index because using tensio-active agent to cause simultaneously;
Embodiment
Below by embodiment, further illustrate the present invention, this embodiment only is the present invention is described and never limits the present invention:
Embodiment 1
In reactor, add about 650 grams of naphthalene bromide and about 296 grams of dodecyl naphthols, add about 30 grams of solid sodium hydroxide, add about 21 grams of solid potassium hydroxide, the solid alkali that is stirred to adding all dissolves, add dewatering agent anhydrous magnesium sulfate 15, about 15 grams of cuprous chloride, heat up, and unlatching nitrogen protection, under 80-160 ℃ of temperature condition, be incubated 1-5 hour, be entirely reaction end with the dodecyl naphthol reaction, after terminal point arrives, the secondary filter filtration catalizer, by-product Sodium Bromide and Potassium Bromide and water-retaining agent, rectifying separation is fallen the naphthalene bromide of 281-285 ℃ of cut, get the dodecyl dinaphthyl ether, add sherwood oil 200 grams to the dodecyl dinaphthyl ether, under agitation drip 105 oleums, 300 grams, temperature control finishes reaction 1-5 hour at 0-80 ℃, surveys terminal point, after terminal point arrives, add water 500 grams, stir the static acid out in back, divide and go waste water layer, the gained oil reservoir is the mixture of dodecyl dinaphthyl ether disulfonic acid and sherwood oil, sherwood oil is extracted in decompression, adds water and add liquid caustic soda to dodecyl dinaphthyl ether disulfonic acid then to be neutralized to pH value 6.5-7.5 with a small amount of lime, filters, the filtrate moisturizing is to finished product content about 45%, get about 1115 grams of dodecyl dinaphthyl ether sodium disulfonate finished product, in the dodecyl naphthols, yield reaches more than 99%;
Embodiment 2
In reactor, add about 800 grams of naphthalene chloride and about 381 grams of octadecyl naphthols, add about 30 grams of solid sodium hydroxide, add about 21 grams of solid potassium hydroxide, the solid alkali that is stirred to adding all dissolves, add dewatering agent anhydrous magnesium sulfate 15, about 15 grams of cuprous chloride, heat up, and unlatching nitrogen protection, under 80-160 ℃ of temperature condition, be incubated 1-5 hour, be entirely reaction end with the octadecyl naphthol reaction, after terminal point arrives, the secondary filter filtration catalizer, byproduct sodium chloride and Repone K and water-retaining agent, rectifying separation is fallen the naphthalene chloride of 259-263 ℃ of cut, get the octadecyl dinaphthyl ether, add sherwood oil 200 grams to the octadecyl dinaphthyl ether, under agitation drip 105 oleums, 300 grams, temperature control finishes reaction 1-5 hour at 0-80 ℃, surveys terminal point, after terminal point arrives, add water 500 grams, stir the static acid out in back, divide and go waste water layer, the gained oil reservoir is the mixture of octadecyl dinaphthyl ether disulfonic acid and sherwood oil, sherwood oil is extracted in decompression, adds water and add liquid caustic soda to octadecyl dinaphthyl ether disulfonic acid then to be neutralized to pH value 6.5-7.5 with a small amount of lime, filters, the filtrate moisturizing is to finished product content about 45%, get about 1300 grams of octadecyl dinaphthyl ether sodium disulfonate finished product, in the octadecyl naphthols, yield reaches more than 99%;
Embodiment 3
In reactor, add about 1000 grams of naphthalene bromide and about 465 grams of two dodecyl naphthols; add about 30 grams of solid sodium hydroxide; add about 21 grams of solid potassium hydroxide; the solid alkali that is stirred to adding all dissolves; add dewatering agent anhydrous magnesium sulfate 15; about 30 grams of cuprous chloride; heat up; and unlatching nitrogen protection; under 80-160 ℃ of temperature condition; be incubated 1-5 hour; be entirely reaction end with two dodecyl naphthol reactions; after terminal point arrives; the secondary filter filtration catalizer; by-product Sodium Bromide and Potassium Bromide and water-retaining agent; rectifying separation is fallen the naphthalene bromide of 281-285 ℃ of cut; get two dodecyl dinaphthyl ethers, add 1,2-ethylene dichloride, 300 grams to two dodecyl dinaphthyl ethers; under agitation drip chlorsulfonic acid 205 grams; temperature control is at 0-80 ℃, and the hydrogen chloride gas of extraction generation simultaneously, finishes reaction 1-5 hour; survey terminal point; after terminal point arrives, add water 600 grams, stir the static acid out in back; divide and go waste water layer; the gained oil reservoir is the mixture of two dodecyl dinaphthyl ether disulfonic acid and sherwood oil, and sherwood oil is extracted in decompression, adds water and add trolamine to alkyl dinaphthyl ether disulfonic acid then to be neutralized to pH value 6.5-7.5; filter; the filtrate moisturizing is about 45% to finished product content, gets two dodecyl dinaphthyl ether disulfonic acid triethanolamine salts, about 1699 grams of finished product; in two dodecyl naphthols, yield reaches more than 99%.

Claims (11)

1. alkyl dinaphthyl ether sulfonate and preparation method thereof is characterized in that comprising following synthesis step and processing condition:
(1) 1-10mol naphthalene halide and 1-3mol alkyl naphthol are dropped into etherifying reactor;
(2) drop into acid binding agent and water-retaining agent to etherifying reactor, nitrogen protection simultaneously, stirring reaction is molten entirely to acid binding agent;
(3) drop into catalyzer to etherifying reactor, under 80-180 ℃ of temperature condition, be incubated 1-5 hour, generate intermediates alkyl dinaphthyl ether and by-product halogen;
(4) above-mentioned (3) product is filtered filtering by-product halogen and catalyzer;
(5) above-mentioned (4) product is carried out rectifying, divide and remove naphthalene halide, get the alkyl dinaphthyl ether, send into the sulfonation still;
(6) add inert organic solvents and 1-5mol sulphonating agent 0-80 ℃ of sulfonation to the sulfonation still again, be incubated 1-5 hour, the mixture of generation alkyl dinaphthyl ether sulfonic acid and inert solvent;
(7) add the water of material total amount 10-60% in the still to the sulfonation still, stir the static acid out in back, treat to divide after the layering and go waste water layer, oil reservoir to be alkyl dinaphthyl ether sulfonic acid, during the gained material is sent into and still;
(8) in and still add water and add alkaline neutraliser 1-5mol and be neutralized to pH value 6.5-7.5, namely get alkyl dinaphthyl ether sulfonate.
2. a kind of alkyl dinaphthyl ether sulfonate according to claim 1 and preparation method thereof is characterized in that main raw material is: naphthalene halide alkyl naphthol, acid binding agent, sulphonating agent, alkaline neutraliser, water-retaining agent.
3. a kind of alkyl dinaphthyl ether sulfonate according to claim 1 and preparation method thereof is characterized in that: synthesis material naphthalene halide: alkyl naphthol: acid binding agent: sulphonating agent: the molar ratio of alkaline neutraliser is 1-10: 1-3: 1-3:1-5: 1-5.
4. a kind of alkyl dinaphthyl ether sulfonate according to claim 1 and preparation method thereof, it is characterized in that: described alkyl naphthol is that to comprise alkyl C number be 3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18 alkyl naphthol, and the alkyl of alkyl naphthol can be two alkyl or monoalkyl, can be normal chain alkyl or isomery alkyl.
5. a kind of alkyl diphenyl ether sulfonate according to claim 1 and preparation method thereof, it is characterized in that: described naphthalene halide comprises: naphthalene chloride, naphthalene bromide, naphthalene iodide, naphthalene fluoride.
6. a kind of alkyl dinaphthyl ether sulfonate according to claim 1 and preparation method thereof, it is characterized in that: described acid binding agent can be sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate.
7. a kind of alkyl dinaphthyl ether sulfonate according to claim 1 and preparation method thereof, it is characterized in that: described sulphonating agent comprises sulfuric acid, chlorsulfonic acid, thionamic acid, sulphur trioxide.
8. a kind of alkyl dinaphthyl ether sulfonate according to claim 1 and preparation method thereof, it is characterized in that: described alkaline neutraliser can be mineral alkali: sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, lime etc. and organic amine series organic bases: trolamine, diethanolamine, thanomin, ammoniacal liquor, Monomethylamine, dimethylamine, Trimethylamine 99 etc.
9. a kind of alkyl dinaphthyl ether sulfonate according to claim 1 and preparation method thereof, it is characterized in that: the catalyzer in the described alkyl dinaphthyl ether synthesis technique is: benzo pyridine quinoline or three (3,6-dioxo alkyl) catalyzer of amine and mantoquita series, the catalyzer of mantoquita series can be the hydrosulfate of copper, the muriate of copper, the oxide compound of copper, ingredient proportion is the 1-10% of naphthalene halide and alkyl naphthol total amount, described water-retaining agent is the sulfation salt anhydride of magnesium, and dosage is 1-10%.
10. a kind of alkyl dinaphthyl ether sulfonate according to claim 1 and preparation method thereof is characterized in that: sulfonic number can be 1-3 in the finished product structure, and alkyl can be 1-2.
11. a kind of alkyl dinaphthyl ether sulfonate according to claim 1 and preparation method thereof, it is characterized in that: described inert organic solvents can be trichloromethane, methylene dichloride, 1,2-ethylene dichloride, 1,1,2,2 ,-tetrachloroethane, Nitromethane 99Min., trieline, tetracol phenixin, o-nitroethylbenzene, oil of mirbane, nitrotoluene, orthodichlorobenzene, sherwood oil.
CN2013102317882A 2013-06-13 2013-06-13 Alkyl dinaphthyl ether sulfonate and preparation method thereof Pending CN103274973A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108166257A (en) * 2016-12-07 2018-06-15 上海东大化学有限公司 A kind of silkete penetrating agent and preparation method thereof
CN111548781A (en) * 2020-06-05 2020-08-18 赛科思能源技术(重庆)有限责任公司 Hypotonic oil field water injection pressure-reducing injection-increasing agent

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040034131A1 (en) * 2002-08-16 2004-02-19 General Electric Company Antistatic and antidust agents, compositions thereof, and methods of manufacture
CN102452966A (en) * 2010-10-22 2012-05-16 中国石油天然气股份有限公司 Alkyl benzene sulfonate Gemini surfactant and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040034131A1 (en) * 2002-08-16 2004-02-19 General Electric Company Antistatic and antidust agents, compositions thereof, and methods of manufacture
CN102452966A (en) * 2010-10-22 2012-05-16 中国石油天然气股份有限公司 Alkyl benzene sulfonate Gemini surfactant and preparation method thereof

Non-Patent Citations (1)

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Title
张海涛等: "十二烷基二苯醚二磺酸钠的合成新工艺", 《辽宁化工》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108166257A (en) * 2016-12-07 2018-06-15 上海东大化学有限公司 A kind of silkete penetrating agent and preparation method thereof
CN111548781A (en) * 2020-06-05 2020-08-18 赛科思能源技术(重庆)有限责任公司 Hypotonic oil field water injection pressure-reducing injection-increasing agent
CN111548781B (en) * 2020-06-05 2023-03-24 赛科思能源技术(重庆)有限责任公司 Hypotonic oil field water injection pressure-reducing injection-increasing agent

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Application publication date: 20130904