CN112691607B - Gemini type fluorine-containing surfactant and preparation method and application thereof - Google Patents
Gemini type fluorine-containing surfactant and preparation method and application thereof Download PDFInfo
- Publication number
- CN112691607B CN112691607B CN202011570837.1A CN202011570837A CN112691607B CN 112691607 B CN112691607 B CN 112691607B CN 202011570837 A CN202011570837 A CN 202011570837A CN 112691607 B CN112691607 B CN 112691607B
- Authority
- CN
- China
- Prior art keywords
- perfluoropolyether
- reaction
- gemini
- fluorine
- surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/18—Monomers containing fluorine
- C08F114/26—Tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
- Silicon Polymers (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a gemini fluorine-containing surfactant and a preparation method and application thereof, wherein perfluoro polyether alcohol (PFPE-OH) reacts with halogenated allyl to introduce unsaturated double bonds; then carrying out hydrosilylation reaction with methylhydrogen dichlorosilane under the catalysis of platinum; the obtained intermediate product reacts with carbon magnesium polyethylene glycol monomethyl ether to generate perfluoropolyether-polyethylene glycol-methyl chlorosilane (PFPE-SiCl-PEG); further hydrolytic condensation to obtain the Gemini type fluorine-containing surfactant. The hydrophobic group adopted by the surfactant is perfluoropolyether, so that the problems that the common fluorine surfactants such as perfluorooctyl sulfonamide (PFOS), perfluorooctane sulfonic acid (PFOA) and the like are difficult to degrade and accumulate toxicity due to long carbon chain fluoroalkyl groups are avoided, the hydrophobicity of the surfactant is easy to control by controlling the molecular weight of the segment of the perfluoropolyether, and the surfactant has very high hydrophobic efficiency. The gemini fluorine-containing surfactant is simple and convenient in preparation process, mild in reaction condition, only conventional equipment is needed for production, and the gemini fluorine-containing surfactant is suitable for industrial production.
Description
Technical Field
The invention relates to a Gemini type fluorine-containing surfactant, a preparation method and application thereof, belonging to the field of synthesis of fine chemicals and auxiliaries.
Background
Perfluoropolyethers (PFPE) are discovered at the earliest in the 60 th 20 th century, are relatively special perfluoropolymer compounds, have the average molecular weight of 500-15000, and contain no hydrogen elements and only consist of carbon, fluorine and oxygen elements, so that the product has a series of characteristics of heat resistance, oxidation resistance, radiation resistance, corrosion resistance, non-combustion and the like.
The prior art discloses a perfluoropolyether fluorocarbon surfactant, a preparation method and application thereof, belongs to the technical field of high molecular surfactants, can be used as an oil phase component in a PCR method, and can be applied to liquid drop type digital PCR, the stability of liquid drops can be ensured, and the perfluoropolyether fluorocarbon surfactant has excellent surface performance. The prior art discloses a long-chain perfluoropolyether surfactant and a preparation method thereof, wherein the long-chain perfluoropolyether surfactant comprises the following components: firstly, adding perfluoropolyether acyl fluoride ether and a solvent into a reaction kettle, adding a diamine compound while stirring, heating the reaction kettle, and cooling to room temperature after the reaction is finished; and then carrying out reduced pressure treatment and column chromatography purification, finally adding chloroacetate solution and water into the compound, heating and stirring, and obtaining the long-chain perfluoropolyether surfactant after the reaction is finished.
Perfluoropolyethers can be classified into 4-molecular structures of type K, type Y, type Z, type D, depending on the monomers used and the polymerization process: (1) k type structural formula is CF3CF2CF2O[CF(CF3)CF2O]nCF(CF3) COF, which is a series of branched polymers formed by anionic polymerization of hexafluoropropylene oxide (HFPO) under the catalysis of CsF or KF and the like; (2) y-type structural formula is CF3O(C3F6O)m(CF2O)nCF3The ultraviolet light curing agent is a polymer formed by photo-oxidizing Hexafluoropropylene (HFP) under the action of ultraviolet light, and the molecular weight is generally between 1000 and 10000; (3) z-type structural formula is CF3(C2F4O)m(CF2O)nCF3The polymer is a linear chain polymer formed by photo-oxidation of Tetrafluoroethylene (TFE) under ultraviolet irradiation, and the molecular weight is generally between 1000 and 100000; (4) d type structural formula is C3F7O(CF2CF2CF2O)mC2F5It is a polymer obtained by directly fluorinating a polymerization product of tetrafluorooxetane.
The K-type perfluoropolyether belongs to acyl fluoride oligomers, the terminal group of the K-type perfluoropolyether has reactivity, and can be further reacted to generate various derivatives, such as perfluoropolyether carboxylic acid (PFPE-COOH), perfluoropolyether alcohol (PFPE-OH), perfluoropolyether terminal olefin (PFPE-C = C) and the like, and further reacted to synthesize the corresponding fluorocarbon surfactant. In addition, PFOS/PFOA is a new class of organic pollutants of great interest, with high environmental persistence and bioaccumulation. Environmental epidemiological studies have revealed a high degree of correlation between PFOS/PFOA exposure in humans and a variety of adverse health effects. Although the mechanism of action of toxicity of PFOS/PFOA is not clear at present, numerous animal experiments show that PFOS/PFOA has hepatotoxicity, endocrine disrupting action, embryotoxicity, reproductive toxicity, neurotoxicity, potential carcinogenicity and the like.
Disclosure of Invention
The invention aims to provide a Gemini type fluorine-containing surfactant which is formed by coupling a perfluoropolyether chain segment and a polyethylene glycol chain segment, wherein the fluorine-containing chain segment provides strong hydrophobicity, and the fluorine content and the polymerization degree are adjustable; the polyethylene glycol chain segment provides hydrophilicity; the special Gemini structure can provide excellent surface activity, and the preparation process is simple and convenient, the reaction condition is mild, and the method is suitable for industrial production. The fluorine-containing polyether segment is used as a nonpolar group, has hydrophobic property and unique oleophobic property, has extremely high surface activity and stability, can obviously reduce the surface tension of an aqueous solution under extremely low application content, has the characteristics of directional adsorption and micelle formation in the solution, can be used as an emulsifier in emulsion polymerization, and can prevent monomer droplets or polymer particles from being closely associated to generate coagulation when the molecular weight of a polymer is not too high, thereby stabilizing a dispersion system. The surfactant has the advantages of special performance, small dosage, no toxicity and the like, and is a product with high technical content, high added value and environmental friendliness. Therefore, the fluorine-containing surfactant prepared from the perfluoropolyether has wide development and application prospects. Particularly has outstanding advantages and market prospects when replacing long fluorocarbon chain products such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA).
The invention discloses a Gemini type fluorine-containing surfactant, which has the following structure:
wherein m is 1-30; n is 2 to 20.
The fluorine-containing surfactant provided by the invention has high surface activity and strong dispersion effect, and can be used as an emulsifier, a leveling agent, a wetting agent, a defoaming agent and the like. In particular, the method can be applied to fluoroolefin dispersion polymerization, and fluoroolefin monomers such as tetrafluoroethylene, vinylidene fluoride and vinylidene fluoride are dispersed into a water phase by utilizing surface activity to synthesize corresponding fluoropolyolefin.
The invention discloses a preparation method of the gemini fluorinated surfactant, which comprises the steps of coupling reaction of carbon magnesium polyethylene glycol monomethyl ether and silanized perfluoropolyether to obtain a block copolymerization product; hydrolyzing the block copolymerization product and then carrying out condensation reaction to obtain the gemini fluorinated surfactant;
the chemical structural formula of the silanized perfluoropolyether is as follows:
the chemical structural formula of the carbon magnesium polyethylene glycol monomethyl ether is as follows:
the chemical structural formula of the block copolymerization product is as follows:
in the structural formula, m is 1-30; n is 2 to 20.
In the invention, perfluoropolyether alcohol is used as an initial raw material, unsaturated double bonds are introduced through substitution reaction to obtain allylated perfluoropolyether, and hydrosilylation reaction is carried out on the alkenylated perfluoropolyether to obtain silanized perfluoropolyether; reacting halogenated polyethylene glycol monomethyl ether with metal magnesium to prepare the carbon-magnesium polyethylene glycol monomethyl ether. Preferably, the perfluoropolyether alcohol is reacted with a halogenated allyl group to obtain an allylated perfluoropolyether; and (3) carrying out addition reaction on the alkenyl perfluoropolyether and the methylhydrogen dichlorosilane to prepare the silanized perfluoropolyether.
In the invention, the coupling reaction is carried out at room temperature for 0.5-12 hours; the hydrolysis is carried out for 0.5 to 12 hours at room temperature; the condensation reaction temperature is the distillation temperature.
In the present invention, the hydrolysis is carried out in isopropanol in the presence of an aqueous hydrochloric acid solution.
The invention discloses the application of the gemini fluorine-containing surfactant in fluoroolefin dispersion polymerization; such as fluoroolefin dispersion polymerization to give a fluoropolyolefin.
The invention further discloses a preparation method of the Gemini type fluorine-containing surfactant, a segmented copolymer is formed by perfluoropolyether and chlorinated polyethylene glycol monomethyl ether through a coupling method, and the segmented copolymer is further subjected to hydrolytic condensation to obtain the Gemini type surfactant, which specifically comprises the following steps:
(1) perfluoropolyether alkenylation
Adding 50-100 parts by weight of perfluoropolyether alcohol, 0.4-1 part by weight of ammonium salt, 50-3000 parts by weight of fluoroalkyl benzene solvent and 4-50 parts by weight of halogenated allyl into a reactor, controlling the temperature to be 20-85 ℃, and dropwise adding an acid-binding agent for 30 minutes-2 hours; after the addition, the reaction is carried out for 1 to 12 hours in a heat preservation way; after the reaction is finished, standing and layering the reaction solution, wherein the upper layer is a water layer and is discarded; adding 1-10 parts of drying agent into the lower oil layer, drying for 1-24 hours, filtering to remove the drying agent to obtain an alkenyl perfluoropolyether solution, and directly putting the alkenyl perfluoropolyether solution into the next step of perfluoropolyether silylation reaction;
preferably, 4-30 parts by weight of inorganic base is dissolved in 8-300 parts by weight of water to obtain an acid-binding agent;
in the technical scheme, the inorganic base is any one of sodium hydroxide and potassium hydroxide; the halogenated allyl is bromopropylene or chloropropene; the fluoroalkyl benzene is any one of trifluorotoluene or bis (trifluoromethyl) benzene; the ammonium salt is tetrabutylammonium bromide; the drying agent is any one of anhydrous sodium sulfate, anhydrous magnesium sulfate and anhydrous calcium chloride.
(2) Perfluoropolyether silylation
Putting the alkenyl perfluoropolyether solution into a reactor, adding 0.05-0.25 part by weight of platinum catalyst, heating to 60-110 ℃, and then dropwise adding 1-25 parts by weight of methylhydrogen dichlorosilane for 30 minutes-2 hours; after the addition, the reaction is carried out for 0.5 to 12 hours in a heat preservation way; then distilling the reaction liquid under reduced pressure to obtain silanized perfluoropolyether;
in the technical scheme, the platinum catalyst is any one of chloroplatinic acid, Karster catalyst and Piermann catalyst.
(3) Carbon magnesium treatment of chlorinated polyethylene glycol monomethyl ether
Adding 20-120 parts by weight of ether solvent, 1-10 parts by weight of chlorinated polyethylene glycol monomethyl ether and 1-10 parts by weight of magnesium chips into a reactor, heating to reflux, adding 1 particle of iodine to initiate a Grignard reaction, and keeping the temperature for continuous reaction for 30 minutes-2 hours after the initiation of the reaction to obtain a light gray carbon magnesium polyethylene glycol monomethyl ether solution;
in the above technical scheme, the ether solvent is any one of diethyl ether and tetrahydrofuran.
(4) Coupling synthesis of block copolymers
And (3) dropwise adding the carbon-magnesium polyethylene glycol monomethyl ether solution synthesized in the step (3) into the solution of the silanized perfluoropolyether in the step (2), wherein the dropwise adding time is 30 minutes to 2 hours, stirring and reacting at room temperature for 0.5 to 12 hours, filtering to remove the precipitated white solid by-product, and distilling the crude product to remove the solvent to obtain the viscous block copolymerization product.
(5) Hydrolysis-condensation
a. Hydrolysis: dissolving the viscous block copolymerization product in 100-300 parts by weight of isopropanol, adding 0.1-5 parts by weight of dilute hydrochloric acid with the mass concentration of 10% as a catalyst, and carrying out hydrolysis reaction for 0.5-12 hours at room temperature;
b. condensation: after hydrolysis is finished, the hydrolysate is heated while distilling the water/isopropanol azeotrope in the reaction liquid, the distillation time is 30 min-6 h, the temperature of the final reaction liquid is raised to 95-100 ℃, and isopropanol is evaporated to be clean, so that the Gemini type fluorine-containing surfactant prepared by the invention is obtained.
In the preparation method of the Gemini type fluorine-containing surfactant provided by the invention, perfluoropolyether alcohol is used as a starting material, unsaturated double bonds are introduced by substitution reaction with halogenated allyl groups, and allylated perfluoropolyether is obtained, wherein the reaction formula is as follows in the step (1):
wherein m is 1-30; x = Cl or Br.
And (3) carrying out hydrosilylation reaction on the alkenyl perfluoropolyether and methylhydrogen dichlorosilane under the action of a platinum catalyst to prepare the silanized perfluoropolyether, wherein the reaction formula is shown in the step (2) as follows:
reacting chlorinated polyethylene glycol monomethyl ether with magnesium metal in an ether solvent to prepare carbon-magnesium polyethylene glycol monomethyl ether, referring to the step (3), wherein the reaction formula is as follows:
wherein n is 2-20.
And (3) carrying out a coupling method on the carbon magnesium polyethylene glycol monomethyl ether and the silanized perfluoropolyether to prepare the A-B type block copolymer, wherein the reaction formula is shown in the step (4) as follows:
wherein m is 1-30; n is 2 to 20.
The block copolymer contains Si-Cl bonds and is easy to hydrolyze and condense to generate Si-O-Si bonds, so that two block copolymer structures are bonded to generate the Gemini type fluorine-containing surfactant of the invention, which is shown in the step (5) and has the following reaction formula:
wherein m is 1-30; n is 2 to 20.
In the gemini surfactant, the fluoropolyether chain segment is used as a nonpolar group, so that the gemini surfactant has hydrophobic property and unique oleophobic property, has extremely high surface activity and stability, can remarkably reduce the surface tension of an aqueous solution under extremely low application content, has the characteristics of directional adsorption in the solution and micelle formation, can be used as an emulsifier in emulsion polymerization, and can prevent monomer droplets or polymer particles from being closely associated to generate coagulation when the molecular weight of a polymer is not too high, thereby stabilizing a dispersion system. The surfactant has the advantages of special performance, small dosage, no toxicity and the like, is a product with high technical content and high added value, and has wide development and application prospects.
Compared with the prior art, the invention has the advantages that:
1. the gemini fluorinated surfactant synthesized by the invention has very high hydrophobic efficiency because the hydrophobic group adopted by the surfactant is perfluoropolyether, which avoids the difficult degradation and toxicity accumulation of long carbon chains in molecular structures such as common fluorinated surfactants PFOS, PFOA and the like, and is easy to regulate and control the hydrophobicity by controlling the molecular weight of the chain segment of the perfluoropolyether.
2. The Gemini surfactant is formed by directly bonding ether bonds (-O-), and the two hydrophobic chain segments and the two hydrophilic chain segments are tightly coupled to form a compact Gemini surfactant structure, so that the surface activity is very excellent.
3. The gemini fluorine-containing surfactant provided by the invention has the advantages of simple preparation process, mild reaction conditions, production only requiring conventional equipment and suitability for industrial production.
4. The fluorine-containing surfactant provided by the invention is applied to the dispersion polymerization of fluoroolefin, and has the advantages of good dispersion effect of monomer fluoroolefin in a water phase, high solid content in a polymerization single kettle and high productivity.
Drawings
FIG. 1 is an infrared absorption curve of the fluorosurfactants prepared in examples 1 and 2, wherein (a) is the product of example 1 and (b) is the product of example 2.
FIG. 2 is an XPS broad scan spectrum of a fluorosurfactant spin-on film surface prepared in example 1.
FIG. 3 is a surface tension curve of aqueous solutions of fluorosurfactants prepared in example 1 at various concentrations.
Detailed Description
The invention utilizes ether linkage (-O-) to directly bond, so that two hydrophobic chain segments and two hydrophilic chain segments are tightly coupled to form a compact Gemini surfactant structure, thereby providing excellent surface activity. The gemini fluorinated surfactant provided by the invention has the advantages of simple preparation process, mild reaction conditions, and production only requiring conventional equipment, and is suitable for industrial production. The fluorine-containing surfactant provided by the invention is applied to fluoroolefin dispersion polymerization, the monomer fluoroolefin has strong dispersion performance in a water phase, the solid content of a polymerization single kettle can reach 25-32%, and the fluorine-containing surfactant has the advantage of high productivity.
The invention further discloses a preparation method of the Gemini type fluorine-containing surfactant, a segmented copolymer is formed by perfluoropolyether and chlorinated polyethylene glycol monomethyl ether through a coupling method, and the segmented copolymer is further subjected to hydrolytic condensation to obtain the Gemini type surfactant, which specifically comprises the following steps:
(1) perfluoropolyether alkenylation
a. Preparing an acid binding agent: dissolving 4-30 parts by weight of inorganic base in 8-300 parts by weight of water to obtain an acid-binding agent;
b. and (3) substitution reaction: adding 50-100 parts by weight of perfluoropolyether alcohol, 0.4-1 part by weight of tetrabutylammonium bromide, 50-3000 parts by weight of a fluoroalkyl benzene solvent and 4-50 parts by weight of halogenated allyl, controlling the temperature to be 20-85 ℃, and dropwise adding a prepared acid-binding agent for 30 minutes-2 hours; after the addition, the reaction is carried out for 1 to 12 hours in a heat preservation way;
c. separation: after the reaction is finished, standing and layering the reaction solution, wherein the upper layer is a water layer and is discarded; adding 1-10 parts of drying agent into the lower oil layer, drying for 1-24 hours, filtering to remove the drying agent to obtain an alkenyl perfluoropolyether solution, and directly putting the alkenyl perfluoropolyether solution into the next reaction;
in the technical scheme, the inorganic base is any one of sodium hydroxide and potassium hydroxide; the halogenated allyl is bromopropylene or chloropropene; the fluoroalkyl benzene is any one of trifluorotoluene or bis (trifluoromethyl) benzene; the drying agent is any one of anhydrous sodium sulfate, anhydrous magnesium sulfate and anhydrous calcium chloride.
(2) Perfluoropolyether silylation
a. Hydrosilylation: putting the alkenyl perfluoropolyether solution into a reactor, adding 0.05-0.25 part by weight of platinum catalyst, heating to 60-110 ℃, and then dropwise adding 1-25 parts by weight of methylhydrogen dichlorosilane for 30 minutes-2 hours; after the addition, the reaction is carried out for 0.5 to 12 hours in a heat preservation way;
b. and (3) distillation: distilling the reaction liquid under reduced pressure to obtain silanized perfluoropolyether;
in the technical scheme, the platinum catalyst is any one of chloroplatinic acid, Karster catalyst and Piermann catalyst.
(3) Carbon magnesium treatment of chlorinated polyethylene glycol monomethyl ether
Adding 20-120 parts by weight of ether solvent, 1-10 parts by weight of chlorinated polyethylene glycol monomethyl ether and 1-10 parts by weight of magnesium chips into a reactor, heating to reflux, adding 1 particle of iodine to initiate a Grignard reaction, and keeping the temperature for continuous reaction for 30 minutes-2 hours after the initiation of the reaction to obtain a light gray carbon magnesium polyethylene glycol monomethyl ether solution;
in the above technical scheme, the ether solvent is any one of diethyl ether and tetrahydrofuran.
(4) Coupling synthesis of block copolymers
Dissolving the silanized perfluoropolyether in a fluorobenzene solvent to obtain a reaction liquid;
and (3) dropwise adding the reaction liquid synthesized in the step (3) into the reaction liquid obtained in the step (2), stirring and reacting for 0.5-12 hours at room temperature, filtering to remove a precipitated white solid by-product, and distilling a crude product to remove a solvent to obtain a viscous block copolymerization product.
(5) Hydrolysis-condensation
a. Hydrolysis: dissolving the viscous block copolymer product in 100-300 parts by weight of isopropanol, adding 0.1-5 parts by weight of dilute hydrochloric acid with the mass concentration of 10% as a catalyst, and performing hydrolysis reaction at room temperature for 0.5-12 hours;
b. condensation: and (3) slowly distilling the water/isopropanol azeotrope in the reaction liquid while heating the hydrolysis liquid, wherein the distillation time is 30 min-6 h until the final reaction liquid is heated to 95-100 ℃, and steaming to remove the isopropanol to obtain the Gemini fluorine-containing surfactant prepared by the invention.
The raw materials involved in the invention are all commercial products, and the involved specific operation method and test method are conventional technologies; the technical solution of the present invention is further described below with reference to the following examples and accompanying drawings.
Example 1
(1) Synthesis of Chlorosilylated perfluoropolyethers
Dissolving 5.6g of potassium hydroxide in 20g of deionized water to obtain an acid-binding agent for later use;
a 500mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 170g of 1, 3-bistrifluorotoluene, 80g of a number-average perfluoropolyether alcohol (molecular weight 2000, available from east sunlight group), 0.5g of tetrabutylammonium bromide and 5.3g of bromopropene were added; after stirring and completely dissolving, heating to 85 ℃, dropwise adding a prepared acid-binding agent for 30 minutes, and then carrying out heat preservation reaction for 4 hours;
after the reaction is finished, standing and layering, removing an upper water layer, adding 3g of anhydrous magnesium sulfate into a lower oil layer, drying for 12 hours, filtering to remove a drying agent to obtain an alkenyl perfluoropolyether solution, transferring the alkenyl perfluoropolyether solution to a 500mL three-neck flask, configuring a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, adding 0.05g of a Karster catalyst, heating to 85 ℃, dropping 5.5g of methylhydrogen dichlorosilane, reacting to release heat, wherein the dropping time is 45 minutes, preserving the temperature for 2 hours after the dropping is finished, carrying out reduced pressure rotary evaporation on the reaction solution, removing unreacted methylhydrogen dichlorosilane, and obtaining 78.5g of chlorosilane perfluoropolyether, wherein the yield is 90.5%.
(2) Synthesis of perfluoropolyether-polyethylene glycol Block copolymer
A500 mL three-neck flask is provided with a thermometer, a reflux condenser tube and a constant pressure dropping funnel, 60.5g of the chlorosilane perfluoropolyether is added and dissolved in 100g of 1, 3-bis (trifluorotoluene) to prepare the chlorosilane perfluoropolyether solution for later use.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 25g of dry ether was charged into each of the reactor and the dropping funnel. 6.5g of chlorinated polyethylene glycol monomethyl ether (purchased from carbohydrate technology limited, Guangzhou) and 3g of magnesium chips are added into the reactor, the temperature is raised to reflux, 1g of small-particle iodine (0.1 g) is added to initiate reaction, the reaction liquid is quickly converted into gray suspension, the temperature is kept for continuous reaction for 1 hour, and the carbon magnesium polyethylene glycol monomethyl ether solution is obtained. Under the condition of room temperature, dripping the carbon magnesium polyethylene glycol monomethyl ether solution into the prepared chlorine silanization perfluoropolyether solution, finishing the addition for 1 hour, and stirring at room temperature to continue the reaction for 8 hours;
the reaction was stopped, the precipitated salt was removed by filtration, and the solvent was distilled off from the filtrate to obtain 51.2g of a viscous perfluoropolyether-polyethylene glycol block copolymer with a reaction yield of 76.4%.
(3) Hydrolysis-condensation
A250 mL single-neck flask is provided with a straight distillation head, a thermometer, a reflux condenser tube and a liquid receiving tube, 150 mL of isopropanol is added into the flask, 50g of perfluoropolyether-polyethylene glycol block copolymer and 5g of dilute hydrochloric acid aqueous solution with the mass concentration of 10% are added, after hydrolysis reaction is carried out for 2 hours at room temperature, heating is carried out until the mixture is distilled out to obtain an azeotrope, the distillation time lasts for 2 hours, finally, the temperature is raised to 98 ℃, isopropanol is evaporated, 48.2g of fluorine-containing surfactant is obtained, the yield is 97.1%, and the fluorine-containing surfactant is used for the following application experiments. FIG. 1a shows FT-IR (γ, liquid membrane method) as a product: 1125 cm-1，1188 cm-1，1233 cm-1And 1302cm-1Four characteristic absorption peaks are attributed to C-F2And C-F3The stretching vibration of (2). The elemental composition of the product monolayer film was tested using XPS, which identified F1SCorresponding binding energy of 685 eV, O1SCorresponding to binding energy at 532 eV, C1SCorresponding to a binding energy of 290 eV, Si2pThe corresponding binding energy is 99 eV, and the four elements confirm the molecular structural element composition of the perfluoropolyether-block polyethylene glycol.
The molecular structure of the product fluorosurfactant is:
the obtained fluorine-containing surfactant is prepared into aqueous solutions with different concentrations, and the surface tension of the aqueous solutions is tested. Wherein, when the concentration of the surfactant is 1wt%, the surface tension of the aqueous solution is 19.814 mN/m; when the concentration of the surfactant is 10wt%, the surface tension of the aqueous solution is as low as 18.792 mN/m; when the concentration of the surfactant is 85wt%, the surface tension of the aqueous solution is as low as 15.001 mN/m. The surface tension curve of the fluorosurfactant in aqueous solution at different mass concentrations is shown in figure 3.
(4) Application experiments
Adding 980g of deionized water, 4g of ammonium persulfate and 5g of fluorine-containing surfactant into a 2-liter autoclave in sequence at room temperature, stirring uniformly by a conventional method to form a nearly transparent solution, heating to 100 ℃ after 30min, increasing the stirring speed to 60rpm, filling a tetrafluoroethylene/nitrogen mixed gas (volume ratio of 1: 1), slowly increasing the pressure in the autoclave, increasing the pressure in the autoclave to 0.3 MPa after 1 hour, stopping filling the tetrafluoroethylene/nitrogen mixed gas, keeping the temperature and reacting for 3 hours, and stopping the reaction. And (3) cooling the reaction solution to room temperature, discharging gas, opening the reaction kettle after the pressure in the kettle is reduced to normal pressure, pouring out the materials in the kettle, and filtering to obtain 307g of granular polytetrafluoroethylene resin, wherein the solid content of a single polymerization kettle reaches 31.6%, and the particle size of the product is 500-510 nm (D90).
Example 2
(1) Synthesis of Chlorosilylated perfluoropolyethers
Dissolving 5.6g of potassium hydroxide in 20g of deionized water to obtain an acid-binding agent for later use;
a500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 170g of 1, 3-bistrifluorotoluene, 120g of a number-average perfluoropolyether alcohol (molecular weight 3000, available from east sunlight group), 0.5g of tetrabutylammonium bromide and 5.3g of bromopropene were added. After stirring and completely dissolving, heating to 85 ℃, dropwise adding a prepared acid-binding agent for 30 minutes, and then carrying out heat preservation reaction for 4 hours;
after the reaction is finished, standing and layering, removing an upper water layer, adding 3g of anhydrous magnesium sulfate into a lower oil layer, drying for 12 hours, filtering to remove a drying agent to obtain an alkenyl perfluoropolyether solution, transferring the alkenyl perfluoropolyether solution into a 500mL three-neck flask, configuring a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, adding 0.05g of a Karster catalyst, heating to 85 ℃, dropping 5.5g of methylhydrogen dichlorosilane, reacting for heat release, wherein the dropping time is 45 minutes, and preserving the heat for 2 hours after the dropping is finished. And (3) carrying out reduced pressure rotary evaporation on the reaction liquid to remove unreacted methylhydrogen dichlorosilane to obtain 109.5g of chlorosilane perfluoropolyether with the yield of 87.4%.
(2) Synthesis of perfluoropolyether-polyethylene glycol Block copolymer
A500 mL three-neck flask is provided with a thermometer, a reflux condenser tube and a constant pressure dropping funnel, 60.5g of the chlorosilane perfluoropolyether is added and dissolved in 100g of 1, 3-bis (trifluorotoluene) to prepare the chlorosilane perfluoropolyether solution for later use.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 25g of dry ether was charged into each of the reactor and the dropping funnel. 6.5g of chlorinated polyethylene glycol monomethyl ether and 3.1g of magnesium chips are additionally added into the reactor, after the temperature is raised to reflux, 1g of small-particle iodine (0.1 g) is added to initiate the reaction, the reaction liquid is quickly converted into a gray suspension, and the temperature is kept for continuous reaction for 1 hour to obtain the carbon magnesium polyethylene glycol monomethyl ether solution. And (3) dropwise adding the solution into the prepared chlorinated silanization perfluoropolyether solution at room temperature, finishing the addition for 1 hour, and stirring at room temperature after the addition is finished to continue the reaction for 8 hours.
The reaction was stopped, the precipitated salt was removed by filtration, and the solvent was distilled off from the filtrate to obtain 51.5g of a viscous perfluoropolyether-polyethylene glycol block copolymer with a reaction yield of 76.6%.
(3) Hydrolysis-condensation
A 250mL single-neck flask is provided with a straight distillation head, a thermometer, a reflux condenser tube and a liquid receiving tube, 150 mL of isopropanol is added into the flask, 50g of perfluoropolyether-polyethylene glycol block copolymer and 5g of dilute hydrochloric acid aqueous solution with the mass concentration of 10 percent are added, after hydrolysis reaction is carried out for 2 hours at room temperature, the mixture is heated to boil, azeotrope is distilled, and the distillation time lasts for 2 hoursFinally, the temperature is raised to 98 ℃, and isopropanol is evaporated to obtain 45.1g of the fluorine-containing surfactant with the yield of 90.2%. FIG. 1b shows FT-IR (γ, liquid membrane method) as a product: 1125 cm-1，1188 cm-1，1233 cm-1And 1302cm-1Four characteristic absorption peaks are attributed to C-F2And C-F3The stretching vibration of (2). The elemental composition of the product monolayer film was tested using XPS, which identified F1SCorresponding binding energy of 685 eV, O1SCorresponding to binding energy at 532 eV, C1SCorresponding to a binding energy of 290 eV, Si2pThe corresponding binding energy is 99 eV, and the four elements confirm the molecular structural element composition of the perfluoropolyether-block polyethylene glycol.
The molecular structure of the product is as follows:
the surface activity of the surfactant is tested, the obtained fluorine-containing surfactant is prepared into aqueous solutions with different mass concentrations, and the surface tension of the aqueous solutions is tested. Wherein, when the concentration of the surfactant is 1%, the surface tension of the aqueous solution is 19.245 mN/m; when the concentration of the surfactant is 10 percent, the surface tension of the aqueous solution is as low as 18.113 mN/m.
(4) Application experiments
980g of deionized water, 4g of ammonium persulfate and 5g of fluorine-containing surfactant are sequentially added into a 2 liter high-pressure autoclave, and the mixture is uniformly stirred to form a nearly transparent solution. After 30min, the temperature is raised to 90 ℃, the stirring speed is increased to 60rpm, tetrafluoroethylene/nitrogen mixed gas (the volume ratio is 1: 1) is filled, the pressure in the kettle is slowly increased, after 1 hour, the pressure in the kettle is increased to 0.3 MPa, and at the moment, the filling of the tetrafluoroethylene/nitrogen mixed gas is stopped. After the reaction was maintained for 3 hours, the reaction was stopped. And (3) cooling the reaction liquid to room temperature, discharging gas, opening the reaction kettle after the pressure in the kettle is reduced to normal pressure, pouring out the materials in the kettle, and filtering to obtain 288g of granular polytetrafluoroethylene resin with the particle size of 470-480 nm (D90).
Example 3
(1) Synthesis of Chlorosilylated perfluoropolyethers
Dissolving 5.6g of potassium hydroxide in 20g of deionized water in advance to obtain an acid-binding agent, and cooling for later use.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 170g of 1, 3-bistrifluorotoluene, 80g of a number-average perfluoropolyether alcohol (molecular weight 2000, available from east sunlight group), 0.5g of tetrabutylammonium bromide and 5.3g of bromopropene were added. After stirring and dissolving completely, heating to 85 ℃, dripping the prepared acid-binding agent for 30 minutes, and keeping the temperature for reaction for 4 hours after the dripping is finished.
After the reaction is finished, standing and layering, removing an upper water layer, adding 3g of anhydrous magnesium sulfate into a lower oil layer, drying for 12 hours, filtering to remove a drying agent to obtain an alkenyl perfluoropolyether solution, transferring the alkenyl perfluoropolyether solution into a 500mL three-neck flask, configuring a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, adding 0.05g of a Karster catalyst, heating to 85 ℃, dropping 5.5g of methylhydrogen dichlorosilane, reacting for heat release, wherein the dropping time is 45 minutes, and preserving the heat for 2 hours after the dropping is finished. And (3) carrying out reduced pressure rotary evaporation on the reaction liquid to remove unreacted methylhydrogen dichlorosilane to obtain 78.8g of chlorosilane perfluoropolyether with the yield of 90.7%.
(2) Synthesis of perfluoropolyether-polyethylene glycol Block copolymer
A500 mL three-neck flask is provided with a thermometer, a reflux condenser tube and a constant pressure dropping funnel, 60g of chlorosilane perfluoropolyether is added and dissolved in 100g of 1, 3-bis (trifluorotoluene) to prepare a chlorosilane perfluoropolyether solution for later use.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 25g of dry ether was charged into each of the reactor and the dropping funnel. Adding 8.2g of chlorinated polyethylene glycol monomethyl ether (purchased from carbohydrate technology limited, Guangzhou) and 3g of magnesium chips into the reactor, heating to reflux, adding 1g of small-particle iodine (0.1 g) to initiate reaction, quickly converting the reaction liquid into a gray suspension, keeping the temperature, and continuing the reaction for 1 hour to obtain the carbon magnesium polyethylene glycol monomethyl ether solution. And (3) dropwise adding the solution into the prepared chlorinated silanization perfluoropolyether solution at room temperature, finishing the addition for 1 hour, and stirring at room temperature after the addition is finished to continue the reaction for 8 hours.
The reaction was stopped, the precipitated salt was removed by filtration, and the filtrate was distilled to remove the solvent to obtain 55.1g of a viscous perfluoropolyether-polyethylene glycol block copolymer with a reaction yield of 82.2%.
(3) Hydrolysis-condensation
A250 mL single-neck flask is provided with a straight distillation head, a thermometer, a reflux condenser tube and a liquid receiving tube, 150 mL of isopropanol is added into the flask, 50g of perfluoropolyether-polyethylene glycol block copolymer and 5g of dilute hydrochloric acid aqueous solution with the mass concentration of 10% are added, after hydrolysis reaction is carried out for 2 hours at room temperature, heating is carried out until the mixture boils, an azeotrope is distilled out, the distillation time lasts for 2 hours totally, finally, the temperature is raised to 98 ℃, and the isopropanol is evaporated to obtain 48.2g of fluorine-containing surfactant, wherein the yield is 97.1%. Product FT-IR (γ, liquid membrane process): 1125 cm-1，1188 cm-1，1233 cm-1And 1302cm-1Four characteristic absorption peaks are attributed to C-F2And C-F3The stretching vibration of (2). The elemental composition of the product monolayer film was tested using XPS, which identified F1SCorresponding binding energy of 685 eV, O1SCorresponding to binding energy at 532 eV, C1SCorresponding to a binding energy of 290 eV, Si2pThe corresponding binding energy is 99 eV, and the four elements confirm the molecular structural element composition of the perfluoropolyether-block polyethylene glycol.
The molecular structure of the product is as follows:
the surface activity of the surfactant is tested, the obtained fluorine-containing surfactant is prepared into aqueous solutions with different mass concentrations, and the surface tension of the aqueous solutions is tested. Wherein, when the concentration of the surfactant is 1%, the surface tension of the aqueous solution is 19.886 mN/m; when the concentration of the surfactant is 10 percent, the surface tension of the aqueous solution is as low as 19.023 mN/m.
Example 4
(1) Synthesis of Chlorosilylated perfluoropolyethers
Dissolving 5.6g of potassium hydroxide in 20g of deionized water in advance to obtain an acid-binding agent, and cooling for later use.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 170g of 1, 3-bistrifluorotoluene, 80g of a number-average perfluoropolyether alcohol (molecular weight 2000, available from east sunlight group), 0.5g of tetrabutylammonium bromide and 5.3g of bromopropene were added. After stirring and dissolving completely, heating to 85 ℃, dripping the prepared acid-binding agent for 30 minutes, and keeping the temperature for reaction for 4 hours after the dripping is finished.
After the reaction is finished, standing and layering, removing an upper water layer, adding 3g of anhydrous magnesium sulfate into a lower oil layer, drying for 12 hours, filtering to remove a drying agent to obtain an alkenyl perfluoropolyether solution, transferring the alkenyl perfluoropolyether solution into a 500mL three-neck flask, configuring a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, adding 0.05g of a Karster catalyst, heating to 85 ℃, dropping 5.5g of methylhydrogen dichlorosilane, reacting for heat release, wherein the dropping time is 45 minutes, and preserving the heat for 2 hours after the dropping is finished. And (3) carrying out reduced pressure rotary evaporation on the reaction liquid to remove unreacted methylhydrogen dichlorosilane to obtain 78.8g of chlorosilane perfluoropolyether with the yield of 90.7%.
(2) Synthesis of perfluoropolyether-polyethylene glycol Block copolymer
A500 mL three-neck flask is provided with a thermometer, a reflux condenser tube and a constant pressure dropping funnel, 60g of chlorosilane perfluoropolyether is added and dissolved in 100g of 1, 3-bis (trifluorotoluene) to prepare a chlorosilane perfluoropolyether solution for later use.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 25g of dry ether was charged into each of the reactor and the dropping funnel. 4.8g of chlorinated polyethylene glycol monomethyl ether (purchased from carbohydrate technology limited, Guangzhou) and 3g of magnesium chips are added into the reactor, the temperature is raised to reflux, 1g of small-particle iodine (0.1 g) is added to initiate reaction, the reaction liquid is quickly converted into gray suspension, the temperature is kept for continuous reaction for 1 hour, and the carbon magnesium polyethylene glycol monomethyl ether solution is obtained. And (3) dropwise adding the solution into the prepared chlorinated silanization perfluoropolyether solution at room temperature, finishing the addition for 1 hour, and stirring at room temperature after the addition is finished to continue the reaction for 8 hours.
The reaction was stopped, the precipitated salt was removed by filtration, and the filtrate was distilled to remove the solvent to obtain 45.3g of a viscous perfluoropolyether-polyethylene glycol block copolymer with a reaction yield of 76.8%.
(3) Hydrolysis-condensation
A250 mL single-neck flask is provided with a straight distillation head, a thermometer, a reflux condenser tube and a liquid receiving tube, 150 mL of isopropanol is added into the flask, 50g of perfluoropolyether-polyethylene glycol block copolymer and 5g of dilute hydrochloric acid aqueous solution with the mass concentration of 10% are added, after hydrolysis reaction is carried out for 2 hours at room temperature, heating is carried out until the mixture boils, an azeotrope is distilled out, the distillation time lasts for 2 hours totally, finally, the temperature is raised to 98 ℃, and the isopropanol is evaporated to obtain 48.0g of fluorine-containing surfactant, wherein the yield is 96.8%. Product FT-IR (γ, liquid membrane process): 1125 cm-1，1188 cm-1，1233 cm-1And 1302cm-1Four characteristic absorption peaks are attributed to C-F2And C-F3The stretching vibration of (2). The elemental composition of the product monolayer film was tested using XPS, which identified F1SCorresponding binding energy of 685 eV, O1SCorresponding to binding energy at 532 eV, C1SCorresponding to a binding energy of 290 eV, Si2pThe corresponding binding energy is 99 eV, and the four elements confirm the molecular structural element composition of the perfluoropolyether-block polyethylene glycol.
The molecular structure of the product is as follows:
the surface activity of the surfactant is tested, the obtained fluorine-containing surfactant is prepared into aqueous solutions with different mass concentrations, and the surface tension of the aqueous solutions is tested. Wherein, when the concentration of the surfactant is 1%, the surface tension of the aqueous solution is 27.886 mN/m; when the surfactant concentration was 10%, the surface tension of its aqueous solution was 24.623 mN/m.
Comparative example 1
(1) Synthesis of Chlorosilylated perfluoropolyethers
Dissolving 5.6g of potassium hydroxide in 20g of deionized water in advance to obtain an acid-binding agent, and cooling for later use.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 170g of 1, 3-bistrifluorotoluene, 80g of a number-average perfluoropolyether alcohol (molecular weight 2000, available from east sunlight group), 0.5g of tetrabutylammonium bromide and 5.3g of bromopropene were added. After stirring and dissolving completely, heating to 85 ℃, dripping the prepared acid-binding agent for 30 minutes, and keeping the temperature for reaction for 4 hours after the dripping is finished.
After the reaction is finished, standing and layering, removing an upper water layer, adding 3g of anhydrous magnesium sulfate into a lower oil layer, drying for 12 hours, filtering to remove a drying agent to obtain an alkenyl perfluoropolyether solution, transferring the alkenyl perfluoropolyether solution into a 500mL three-neck flask, configuring a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, adding 0.05g of a Karster catalyst, heating to 85 ℃, dropping 5.5g of methylhydrogen dichlorosilane, reacting for heat release, wherein the dropping time is 45 minutes, and preserving the heat for 2 hours after the dropping is finished. And (3) carrying out reduced pressure rotary evaporation on the reaction liquid to remove unreacted methylhydrogen dichlorosilane to obtain 74.1g of chlorosilane perfluoropolyether, wherein the yield is 85.4%.
(2) Synthesis of perfluoropolyether-polyethylene glycol Block copolymer
A500 mL three-neck flask is provided with a thermometer, a reflux condenser tube and a constant pressure dropping funnel, 60.4g of chlorosilane perfluoropolyether is added and dissolved in 100g of 1, 3-bis (trifluorotoluene), and the solution is prepared into perfluoropolyether solution for later use through chlorosilane reaction.
A500 mL three-necked flask was equipped with a thermometer, a reflux condenser and a constant pressure dropping funnel, and 25g of dry ether was charged into each of the reactor and the dropping funnel. 6.5g of chlorinated polyethylene glycol monomethyl ether (purchased from carbohydrate technology limited, Guangzhou) and 3g of magnesium chips are added into the reactor, the temperature is raised to reflux, 1g of small-particle iodine (0.1 g) is added to initiate reaction, the reaction liquid is quickly converted into gray suspension, the temperature is kept for continuous reaction for 1 hour, and the carbon magnesium polyethylene glycol monomethyl ether solution is obtained. And (3) dropwise adding the solution into the prepared chlorinated silanization perfluoropolyether solution at room temperature, finishing the addition for 1 hour, and stirring and reacting at room temperature for 6 hours after the addition is finished.
After the reaction is finished, the ethyl ether solution (the mass concentration is 10%) of the ethyl magnesium bromide Grignard reagent is added dropwise, the reaction is continued for 4 hours after the addition is finished, the reaction is stopped, and insoluble substances are removed by filtration. The filtrate was rotary evaporated to remove the solvent to give 50.1g of the final product in 82.9% yield for the following application experiments. Product FT-IR (γ, liquid membrane process): 1121 cm-1，1189 cm-1，1232 cm-1And 1302cm-1Four characteristic absorption peaks are attributed to C-F2And C-F3The stretching vibration of (2). The elemental composition of the product monolayer film was tested using XPS, which identified F1SCorresponding binding energy of 685 eV, O1SCorresponding to binding energy at 532 eV, C1SCorresponding to a binding energy of 290 eV, Si2pThe corresponding binding energy is 99 eV, and the four elements confirm the molecular structural element composition of the perfluoropolyether-block polyethylene glycol.
The molecular structure of the product is as follows:
the surface activity of the surfactant is tested, the obtained fluorine-containing surfactant is prepared into aqueous solutions with different mass concentrations, and the surface tension of the aqueous solutions is tested. Wherein, when the concentration of the surfactant is 1%, the surface tension of the aqueous solution is 28.432 mN/m; when the surfactant concentration is 10%, the surface tension of the aqueous solution is as low as 25.333mN/m, and the surface activity is inferior to that of gemini type fluorine-containing surfactants.
(3) Application experiments
980g of deionized water, 4g of ammonium persulfate and 5g of fluorine-containing surfactant are sequentially added into a 2 liter autoclave, and the mixture is stirred uniformly by a conventional method to form a nearly transparent solution. After 30min, the temperature is raised to 100 ℃, the stirring speed is increased to 60rpm, tetrafluoroethylene/nitrogen mixed gas (the volume ratio is 1: 1) is filled, the pressure in the kettle is slowly increased, after 1 hour, the pressure in the kettle is increased to 0.3 MPa, and at the moment, the filling of the tetrafluoroethylene/nitrogen mixed gas is stopped. After the reaction was maintained for 3 hours, the reaction was stopped. And (3) cooling the reaction liquid to room temperature, deflating, opening the reaction kettle after the pressure in the kettle is reduced to normal pressure, pouring out the materials in the kettle, and filtering to obtain 211g of polytetrafluoroethylene resin, wherein the resin particles are uneven and have micron-sized particles and blocky materials.
Claims (9)
1. The gemini fluorinated surfactant is characterized by having the following chemical structural formula:
wherein m is 1-30; n is 2 to 20.
2. The preparation method of the gemini type fluorosurfactant of claim 1 is characterized by comprising the following steps: coupling reaction of carbon-magnesium polyethylene glycol monomethyl ether and silanized perfluoropolyether to obtain a block copolymerization product; hydrolyzing the block copolymerization product and then carrying out condensation reaction to obtain the Gemini type fluorine-containing surfactant; the chemical structural formula of the silanized perfluoropolyether is as follows:
the chemical structural formula of the carbon magnesium polyethylene glycol monomethyl ether is as follows:
the chemical structural formula of the block copolymerization product is as follows:
in the structural formula, m is 1-30; n is 2 to 20.
3. The preparation method of the Gemini type fluorinated surfactant according to claim 2, wherein perfluoropolyether alcohol is used as a starting material, unsaturated double bonds are introduced through substitution reaction to obtain allylated perfluoropolyether, and the allylated perfluoropolyether is subjected to hydrosilylation reaction to obtain silanized perfluoropolyether; halogenated polyethylene glycol monomethyl ether is reacted with magnesium metal to prepare the carbon magnesium polyethylene glycol monomethyl ether.
4. The method for preparing gemini fluorinated surfactant according to claim 3, wherein perfluoropolyether alcohol is reacted with halogenated allyl group to obtain allylated perfluoropolyether; and (3) carrying out addition reaction on the alkenyl perfluoropolyether and the methylhydrogen dichlorosilane to prepare the silanized perfluoropolyether.
5. The method for preparing gemini fluorosurfactants according to claim 2, wherein the hydrolysis is performed in the presence of isopropanol and aqueous hydrochloric acid.
6. The use of gemini fluorosurfactants as claimed in claim 1 in fluoroolefin dispersion polymerization.
7. Use according to claim 6, wherein the fluoroolefin is dispersion polymerized to give a fluoropolyolefin.
8. The fluorine-containing block copolymer is characterized in that the chemical structural formula of the fluorine-containing block copolymer is as follows:
wherein m is 1-30; n is 2 to 20.
9. Use of the fluorine-containing block copolymer according to claim 8 for producing a fluorosurfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011570837.1A CN112691607B (en) | 2020-12-26 | 2020-12-26 | Gemini type fluorine-containing surfactant and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011570837.1A CN112691607B (en) | 2020-12-26 | 2020-12-26 | Gemini type fluorine-containing surfactant and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112691607A CN112691607A (en) | 2021-04-23 |
| CN112691607B true CN112691607B (en) | 2022-05-03 |
Family
ID=75511143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011570837.1A Active CN112691607B (en) | 2020-12-26 | 2020-12-26 | Gemini type fluorine-containing surfactant and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112691607B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114213599B (en) * | 2021-12-21 | 2024-07-30 | 华东理工大学 | Fluorine-containing triblock copolymer and preparation method and application thereof |
| CN114349409A (en) * | 2022-01-28 | 2022-04-15 | 湖北淇源新材料科技有限公司 | Composite material for building and preparation method thereof |
| CN115057779B (en) * | 2022-05-23 | 2024-01-05 | 苏州大学 | Y-type fluorine-containing amphiphilic polymer and preparation and application thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3422131A (en) * | 1966-02-10 | 1969-01-14 | Us Agriculture | Fluoroalkoxyalkyl silanes |
| EP0394963A1 (en) * | 1989-04-25 | 1990-10-31 | Shin-Etsu Chemical Co., Ltd. | Fluorine-containing surfactant and process for producing the same |
| WO2015089811A1 (en) * | 2013-12-20 | 2015-06-25 | Givaudan Sa | Fragrance |
| CN104829839A (en) * | 2015-05-12 | 2015-08-12 | 傅筠 | Fluorine-containing organosilicon polymer and preparation method thereof |
| CN106085227A (en) * | 2016-06-21 | 2016-11-09 | 衢州氟硅技术研究院 | A kind of preparation method of high-performance anti-fingerprint agent |
| CN107383361A (en) * | 2017-08-30 | 2017-11-24 | 龙岩思康特种化学品有限公司 | A kind of perfluoropolyether-modified silane compound and its surface treating composition |
| CN108671850A (en) * | 2018-05-11 | 2018-10-19 | 中国石油天然气股份有限公司 | Fluorine-silicon surfactant containing single perfluorooctyl and oil-based foam oil displacement agent |
| CN109897176A (en) * | 2017-12-07 | 2019-06-18 | 乳源东阳光氟有限公司 | A kind of perfluoropolyether silicone compounds and its synthetic method and application |
| CN110156979A (en) * | 2019-06-21 | 2019-08-23 | 东莞东阳光科研发有限公司 | A kind of impurity-removing method and preparation method of perfluoropolyether allyl ether |
| CN110787720A (en) * | 2019-11-04 | 2020-02-14 | 济南齐氟新材料技术有限公司 | Fluorine-containing gemini surfactant and preparation method thereof |
| CN111057231A (en) * | 2019-12-31 | 2020-04-24 | 山东华夏神舟新材料有限公司 | High-wear-resistance perfluoropolyether type fingerprint-resistant agent and preparation method thereof |
| CN111548462A (en) * | 2020-05-18 | 2020-08-18 | 广东健玺表面工程技术有限公司 | Organic fluorine-silicon copolymer and synthesis and application methods thereof |
| CN112047976A (en) * | 2020-09-11 | 2020-12-08 | 苏州东杏表面技术有限公司 | Fluorine-containing organosilicon quaternary ammonium salt and preparation method and application thereof |
| CN113480728A (en) * | 2021-07-01 | 2021-10-08 | 深圳怡钛积科技股份有限公司 | Perfluoropolyether-based silane compound, method for producing same, and intermediate for perfluoropolyether-based silane compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003095083A1 (en) * | 2002-05-10 | 2003-11-20 | Daikin Industries, Ltd. | Surfactant and dispersion aid each comprising graft fluoropolymer |
-
2020
- 2020-12-26 CN CN202011570837.1A patent/CN112691607B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3422131A (en) * | 1966-02-10 | 1969-01-14 | Us Agriculture | Fluoroalkoxyalkyl silanes |
| EP0394963A1 (en) * | 1989-04-25 | 1990-10-31 | Shin-Etsu Chemical Co., Ltd. | Fluorine-containing surfactant and process for producing the same |
| WO2015089811A1 (en) * | 2013-12-20 | 2015-06-25 | Givaudan Sa | Fragrance |
| CN104829839A (en) * | 2015-05-12 | 2015-08-12 | 傅筠 | Fluorine-containing organosilicon polymer and preparation method thereof |
| CN106085227A (en) * | 2016-06-21 | 2016-11-09 | 衢州氟硅技术研究院 | A kind of preparation method of high-performance anti-fingerprint agent |
| CN107383361A (en) * | 2017-08-30 | 2017-11-24 | 龙岩思康特种化学品有限公司 | A kind of perfluoropolyether-modified silane compound and its surface treating composition |
| CN109897176A (en) * | 2017-12-07 | 2019-06-18 | 乳源东阳光氟有限公司 | A kind of perfluoropolyether silicone compounds and its synthetic method and application |
| CN108671850A (en) * | 2018-05-11 | 2018-10-19 | 中国石油天然气股份有限公司 | Fluorine-silicon surfactant containing single perfluorooctyl and oil-based foam oil displacement agent |
| CN110156979A (en) * | 2019-06-21 | 2019-08-23 | 东莞东阳光科研发有限公司 | A kind of impurity-removing method and preparation method of perfluoropolyether allyl ether |
| CN110787720A (en) * | 2019-11-04 | 2020-02-14 | 济南齐氟新材料技术有限公司 | Fluorine-containing gemini surfactant and preparation method thereof |
| CN111057231A (en) * | 2019-12-31 | 2020-04-24 | 山东华夏神舟新材料有限公司 | High-wear-resistance perfluoropolyether type fingerprint-resistant agent and preparation method thereof |
| CN111548462A (en) * | 2020-05-18 | 2020-08-18 | 广东健玺表面工程技术有限公司 | Organic fluorine-silicon copolymer and synthesis and application methods thereof |
| CN112047976A (en) * | 2020-09-11 | 2020-12-08 | 苏州东杏表面技术有限公司 | Fluorine-containing organosilicon quaternary ammonium salt and preparation method and application thereof |
| CN113480728A (en) * | 2021-07-01 | 2021-10-08 | 深圳怡钛积科技股份有限公司 | Perfluoropolyether-based silane compound, method for producing same, and intermediate for perfluoropolyether-based silane compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112691607A (en) | 2021-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112691607B (en) | Gemini type fluorine-containing surfactant and preparation method and application thereof | |
| EP1026152B1 (en) | Process for producing perfluorovinyl ethersulfonic acid derivatives | |
| EP0011853B1 (en) | Vulcanizable fluorinated copolymers | |
| CN1215085C (en) | Process for producing fluoropolymer | |
| CN1206249C (en) | Fluoromonomer polymerization | |
| US5866711A (en) | Fluorocyanate and fluorocarbamate monomers and polymers thereof | |
| EP2058291B1 (en) | Perfluorocarboxylic acid salt and method for producing the same | |
| CN101535352B (en) | Aqueous polymerization of fluorinated monomer using polymerization agent comprising fluoropolyether acid or salt and short chain fluorosurfactant | |
| JP5217090B2 (en) | Tetrafluoroethylene polymer aqueous dispersion, production method thereof, tetrafluoroethylene polymer powder and tetrafluoroethylene polymer molded product | |
| EP0027721A1 (en) | Liquid fluorine-containing polymer and a process for the production thereof | |
| KR100791504B1 (en) | Fluorovinylethers and polymers obtainable therefrom | |
| JPH0216326B2 (en) | ||
| JP3758666B2 (en) | Fluoroalkylcarboxylic acid derivative, method for producing fluoropolymer, and fluoropolymer aqueous dispersion | |
| JPH0764931B2 (en) | Copolymer of difluoromethylene oxide and tetrafluoroethylene oxide | |
| KR100315647B1 (en) | Manufacturing process of perpolo polyethers | |
| KR850000109B1 (en) | Polymerization of acid fluoride monomers | |
| JPH0472850B2 (en) | ||
| JPH10502676A (en) | Carbon-based initiator suitable for use in the polymerization and telomerization of vinyl monomers | |
| JP7287404B2 (en) | Method for producing fluoropolymer containing fluorosulfonyl group, method for producing fluoropolymer containing salt-type sulfonic acid group, and method for producing fluoropolymer containing acid-type sulfonic acid group | |
| CN110770200A (en) | Process for preparing polyfluorinated allyl ethers and compounds related thereto | |
| CN114621427A (en) | Production process for preparing perfluoropolyether with peroxide by photo-oxidative polymerization | |
| CN112457438B (en) | Method for preparing fluorinated polyolefin based on gemini fluorinated surfactant | |
| CN1088071C (en) | Process for preparing perfluoropolyethers with bromo- or iodo-containing end groups | |
| CN1154662C (en) | Aqueous emulsion polymerization process for preparing of fluoropolymers | |
| WO2011129408A1 (en) | Method for reacting ethylene/terafluoroethylene copolymer having functional group |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220818 Address after: 518000 No.57 Zhangqi Road, Daping community, Guanlan street, Longhua District, Shenzhen City, Guangdong Province Patentee after: SHENZHEN TAIKE TECHNOLOGY Co.,Ltd. Address before: Room 503-504, building B, Zhangjiagang Economic and Technological Development Zone, Suzhou City, Jiangsu Province Patentee before: Zhangjiagang Bangli Material Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right |