阅读说明：本技术 一种含氟双子表面活性剂及其制备方法 (Fluorine-containing gemini surfactant and preparation method thereof ) 是由 张立亭 于 2019-11-04 设计创作，主要内容包括：本发明涉及含氟新材料制备技术领域,特别涉及一种含氟双子表面活性剂及其制备方法。首先由含4~6全氟链烯烃R<Sub>f</Sub>-A-CH=CH<Sub>2</Sub>与N,N＇-二甲基烷基二胺CH<Sub>3</Sub>NHRNHCH<Sub>3</Sub>反应生成含氟二叔胺,再与双氧水氧化反应、氯乙酸钠(氯烷基磺酸钠)、含卤素烷烃进行季铵化反应,调配后得到产品。本发明产品不含全氟辛基(C8),不会有产生PFOA的风险,属于环保型产品。本发明合成的表面活性剂具有更低的CMC值,表面活性高,在油田采用、消防灭火领域具有广泛用途。(The invention relates to the technical field of preparation of novel fluorine-containing materials, and particularly relates to a fluorine-containing gemini surfactant and a preparation method thereof. First of all from a mixture of a compound containing 4-6 perfluoroalkenes R f ‑A‑CH=CH 2 With N, N' -dimethylalkyldiamine CH 3 NHRNHCH 3 The reaction is carried out to generate fluorine-containing di-tertiary amine, and then the fluorine-containing di-tertiary amine is subjected to oxidation reaction with hydrogen peroxide, quaternization reaction with sodium chloroacetate (sodium chloroalkyl sulfonate) and halogen-containing alkane, and the product is obtained after blending. The product of the invention does not contain perfluorooctyl (C8), does not have the risk of generating PFOA, and belongs to an environment-friendly product. The surfactant synthesized by the invention has lower CMC value and high surface activity, and has wide application in the fields of oil field adoption and fire fighting.)

1. The fluorine-containing gemini surfactant is characterized in that the structural formula of the surfactant is as follows:

wherein R is_fN =4 to 6 perfluoro Chain F (CF)₂)_n；

A is ethoxy, propoxy or none;

r is m = 2-6 (CH)₂)_m；

X is O^—，CH₂COO^—(CH₂CH₂SO₃ ^—)，RY^—Wherein R is methyl or ethyl, Y is chlorine, bromine or iodine.

2. A method for preparing the fluorochemical gemini surfactant according to claim 1, comprising the steps of:

1) the fluorine-containing olefin R_f-A-CH=CH₂Adding a solvent into N, N' -dimethyl diamine to react to generate fluorine-containing dialkyl di-tertiary amine:

after the reaction is finished, evaporating the solvent for recycling to obtain a tan product;

2) adding fluorine-containing di-tertiary amine and hydrogen peroxide, sodium chloroacetate, sodium chloroalkyl sulfonate or haloalkane into a solvent for reaction:

after the reaction is finished, adding a blending agent and deionized water to obtain the fluorine-containing gemini surfactant.

3. The method of claim 2, wherein R is_f-A-CH=CH₂The structural formula of (A) is:

F(CF₂)_nCH₂CH₂OCH=CH₂，F(CF₂)_nCH₂CH₂CH₂OCH=CH₂，F(CF₂)_nCH=CH₂，n=4~6。

4. the preparation method according to claim 2 or 3, wherein in the step (1), the molar ratio of the fluorine-containing olefin to the N, N' -dimethyl diamine is 2.0-3.0: 1; the addition amount of the solvent is 1.5-2.5 times of the mass of the fluorine-containing olefin.

5. The method according to claim 4, wherein in the step (1), the solvent is methanol, ethanol, isopropanol or butanol.

6. The method according to any one of claims 2 to 5, wherein in the step (1), the reaction is carried out at a temperature of 90 to 130 ℃ for 16 to 24 hours.

7. The preparation method according to claim 2, wherein in the step (2), the molar ratio of the fluorine-containing dialkyl di-tertiary amine to hydrogen peroxide, sodium chloroacetate, sodium chloroalkyl sulfonate or haloalkane is 1: 1.00-1.15; the addition amount of the solvent is 0.45-2.5 times of the mass of the fluorine-containing dialkyl di-tertiary amine.

8. The preparation method according to claim 7, wherein in the step (2), the solvent is ethanol or isopropanol solution with a volume concentration of 30-100%.

9. The method according to claim 7 or 5, wherein in the step (2), the reaction is carried out at a temperature of 50 to 90 ℃ for 6 to 12 hours.

10. The preparation method according to claim 2, wherein the addition amount of the blending agent is 20-80% of the mass of the product; the blending agent is ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol or diethylene glycol butyl ether; the deionized water is added in an amount of diluting until the concentration of the product is 20-40%.

Technical Field

The invention belongs to the technical field of preparation of novel fluorine-containing materials, and particularly relates to a fluorine-containing gemini surfactant and a preparation method thereof.

Background

A Gemini surfactant, also called Gemini surfactant, is a surfactant formed by linking two or more same or almost same surfactant monomers together through chemical bonds by using linking groups at or near a hydrophilic head group. The novel water-soluble amphoteric surfactant breaks through an amphiphilic structure of the traditional surfactant, which only contains a single hydrophobic group and a single hydrophilic group, contains two or more hydrophobic groups and hydrophilic groups, has much higher surface activity than the traditional surfactant, and has novel properties which are not possessed by the traditional surfactant and are unexpected.

Compared with the traditional fluorocarbon surfactant, the fluorine-containing gemini surfactant has a lower cmc value, higher surface activity, is easier to adsorb on the surface and easier to aggregate to form micelles, and has wide application in the fields of oilfield adoption and fire fighting.

The document "synthesis of special surfactant and functional surfactant-fluorine-containing gemini surfactant" introduces a synthesis method of fluorine-containing gemini surfactants with various structures:

such as: from perfluorooctyl iodide C₈F₁₇I is an initial raw material, and the gemini fluorine-containing surfactant with the following structural formula is synthesized through six steps:

from perfluoroalkyl propylene oxide C_nF_2n+1CH₂CH(O)CH₂The gemini fluorine-containing surfactant with the following structural formula is synthesized by two steps as an initial raw material:

from perfluorooctanesulfonyl fluoride C₈F₁₇SO₂F is used as an initial raw material, and the gemini fluorine-containing surfactant with the following structural formula is synthesized through two steps:

CN 102389745A fluorine-containing gemini cationic surfactant and a preparation method and application thereof, wherein perfluoroalkyl sulfonyl fluoride and N, N' -dimethyl (ethyl) -1, 3-propane diamine are subjected to amidation reaction to obtain an intermediate 1, and the intermediate 1 is refined and then reacts with 0.5 molar times of dihalogenated alkyl to obtain the fluorine-containing gemini cationic surfactant; or performing amidation reaction on the alkyl sulfonyl fluoride (chlorine) or the alkyl acyl fluoride (chlorine) and N, N' -dimethyl (ethyl) -1, 3-propane diamine to obtain an intermediate 2, and reacting the intermediate 1 and dihalogenated alkyl in an amount which is equal to the molar times of the intermediate 2 to obtain the fluorine-containing double-type cationic surfactant; the surfactant can be used as an emulsifier, a metal surface treatment agent, a fire extinguishing agent additive and a foam flotation agent.

CN102351753A fluorine-containing Gemini anionic surfactant, and its preparation method and application. Carrying out amidation on perfluoroalkyl sulfonyl fluoride and 0.5 molar times of alkyl diamine to obtain an intermediate, refining the intermediate, and reacting the refined intermediate with 2 molar times of halogenated alkyl sodium sulfonate to obtain a fluorine-containing Gemini anionic surfactant; or amidating perfluoroalkyl sulfonyl fluoride and alkyl diamine with equal molar weight, then amidating with alkyl sulfonyl fluoride (chlorine) or alkyl acyl fluoride (chlorine) to obtain an intermediate, refining, and reacting with halogenated alkyl sodium sulfonate with 2 molar times to obtain the fluorine-containing Gemini anionic surfactant. The surfactant can be used as an emulsifier, a metal surface treatment agent, a leveling agent, an electroplating chromium fog inhibitor and a metallurgical foam flotation agent.

At present, the main raw materials for synthesizing the fluorine-containing gemini surfactant are derived from perfluoroalkyl sulfonyl fluoride, the raw materials are generally prepared by a point-decomposition fluorination method, and the method is gradually eliminated. The search for a novel surfactant which is environmentally friendly has become an urgent problem to be solved.

Disclosure of Invention

Aiming at the problems in the prior art and the difficulty of synthesis, the invention provides a fluorine-containing gemini surfactant.

The invention also provides a preparation method of the fluorine-containing gemini surfactant.

The technical scheme adopted by the invention for realizing the purpose is as follows:

the invention provides a fluorine-containing gemini surfactant, which has the following structural formula:

wherein R is_fN =4 to 6 perfluoro Chain F (CF)₂)_n；

A is ethoxy, propoxy or none;

r is m = 2-6 (CH)₂)_m；

X is O^—，CH₂COO^—(CH₂CH₂SO₃ ^—)，RY^—Wherein R is methyl or ethyl, Y is chlorine, bromine or iodine).

The invention also provides a preparation method of the fluorine-containing gemini surfactant, which comprises the following steps:

1) the fluorine-containing olefin R_f-A-CH=CH₂Adding a solvent into N, N' -dimethyl diamine to react to generate fluorine-containing dialkyl di-tertiary amine:

after the reaction is finished, evaporating the solvent for recycling to obtain a tan product;

2) adding fluorine-containing di-tertiary amine and hydrogen peroxide, sodium chloroacetate, sodium chloroalkyl sulfonate or haloalkane into a solvent for reaction:

after the reaction is finished, adding a blending agent and deionized water to obtain the fluorine-containing gemini surfactant.

Further, in the step (1), the R_f-A-CH=CH₂The structural formula of (A) is:

F(CF₂)_nCH₂CH₂OCH=CH₂，F(CF₂)_nCH₂CH₂CH₂OCH=CH₂，F(CF₂)_nCH=CH₂，n=4~6。

in step (1), the molar ratio of the fluorine-containing olefin to the N, N' -dimethyl diamine is 2.0 to 3.0: 1; the addition amount of the solvent is 1.5-2.5 times of the mass of the fluorine-containing olefin.

Further, in the step (1), the solvent is methanol, ethanol, isopropanol or butanol.

The reaction is carried out at a temperature of 90-130 ℃ for 16-24 hours.

Further, in the step (2), the molar ratio of the fluorine-containing dialkyl di-tertiary amine to hydrogen peroxide, sodium chloroacetate, sodium chloroalkyl sulfonate or haloalkane is 1: 1.00-1.15; the addition amount of the solvent is 0.45-2.5 times of the mass of the fluorine-containing dialkyl di-tertiary amine.

Further, in the step (2), the solvent is ethanol or isopropanol solution with the volume concentration of 30-100%.

The reaction is carried out at the temperature of 50-90 ℃ for 6-12 hours.

Further, the adding amount of the blending agent is 20-80% of the mass of the product; the blending agent is ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol or diethylene glycol butyl ether; the deionized water is added in an amount of diluting until the concentration of the product is 20-40%.

The structural formula of the raw material N, N' -dimethyl diamine used in the invention is as follows: CH (CH)₃NH(CH₂)mNHCH₃，m=2~6。

The invention has the beneficial effects that:

(1) the fluorine-containing gemini surfactant product prepared by the method does not contain perfluorooctyl (C8), does not have the risk of generating PFOA, and belongs to an environment-friendly product.

(2) The fluorine-containing gemini surfactant prepared by the method has a lower cmc value and high surface activity, is more easily adsorbed on the surface and aggregated to form micelles, and has wide application in the fields of oilfield adoption and fire fighting.

Detailed Description

The technical solution of the present invention is further explained and illustrated by the following specific examples.