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CN112079754B - Active group-containing fluorine-containing interface modifier and preparation method and application thereof - Google Patents

Active group-containing fluorine-containing interface modifier and preparation method and application thereof Download PDF

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CN112079754B
CN112079754B CN202011006456.0A CN202011006456A CN112079754B CN 112079754 B CN112079754 B CN 112079754B CN 202011006456 A CN202011006456 A CN 202011006456A CN 112079754 B CN112079754 B CN 112079754B
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fluorine
interface modifier
parts
active
fluororesin
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CN112079754A (en
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张刚
李东升
王晗
杨杰
严光明
陆浩然
吴喆夫
张雨
王孝军
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Sichuan University
Xian Aerospace Propulsion Institute
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Xian Aerospace Propulsion Institute
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Abstract

The invention relates to a fluorine-containing interface modifier containing active groups, a preparation method and application thereof, belonging to the field of high polymer materials. The invention provides a fluorine-containing interface modifier containing active groupsThe structural formula of the fluorine-containing interface modifier is shown as a formula I. Compared with the traditional interface modifier, the interface modifier obtained by the invention greatly improves the stability of the interface modifier, including thermal stability, chemical stability and relevant aging stability, by combining the heat-resistant macromolecular structure main chain; can be used for preparing high-activity reinforced fluororesin.

Description

Active group-containing fluorine-containing interface modifier and preparation method and application thereof
Technical Field
The invention relates to a fluorine-containing interface modifier containing active groups, a preparation method and application thereof, belonging to the field of high polymer materials.
Background
The fluorine-containing interface modifier has high surface activity, high chemical stability, hydrophobicity and oleophobicity, good wetting permeability, foaming stability and excellent compounding performance; these properties of the fluorine-containing interfacial modifier make it have very high added value, wide application and market prospect.
The fluorine-containing interface modifier is widely applied to daily life and production in the form of a surfactant, and comprises the following types according to ionicity: 1) anionic fluorosurfactants including carboxylate, sulfonate, sulfate and phosphate types; it is suitable for detergents, paint pigment additives, emulsifiers, dispersants, wetting agents, foaming agents and the like; 2) cationic fluorosurfactants-including quaternary ammonium salts, amine oxide; is suitable for cleaning agents, emulsifying agents, wetting agents, waterproof and oilproof agents, leather fiber processing additives, releasing agents and the like; 3) amphoteric fluorosurfactants-including betaine and amino acid types; is suitable for fire extinguishing agent, emulsifier, dispersant, wetting agent, petroleum trapping agent, etc.; 4) nonionic fluorine-containing surfactant, polyoxyethylene, polyoxypropylene chain segment polyether type and amide type are more; it is suitable for cleaning agent, emulsifier, wetting agent, antistatic agent or mold release agent, etc.
Although the fluorine-containing interface modifier has wide application, the application and the function of the fluorine-containing interface modifier are mainly embodied in the fields of daily chemicals and general application conditions, and the research and the application of the fluorine-containing interface modifier in the field of polymer composite materials, particularly high-temperature resistant thermoplastic fluororesin composite materials are few, so the manufacturing difficulty is high; meanwhile, the interface compatibility between the fluororesin and the reinforcing filler is poor due to the extremely low surface activity of the fluororesin, so that the strength and the modulus of the material of the common fluororesin reinforced composite material are possibly correspondingly improved, but the impact resistance (toughness) of the composite material is suddenly reduced, so that the composite material is easy to damage and break, and the requirements of use conditions cannot be met.
Disclosure of Invention
Aiming at the defects, the invention provides a novel fluorine-containing interface modifier containing active groups, and the obtained interface modifier can be used for preparing high-activity enhanced fluororesin.
The technical scheme of the invention is as follows:
the first technical problem to be solved by the invention is to provide a fluorine-containing interface modifier containing active groups, wherein the structural formula of the fluorine-containing interface modifier is shown as a formula I:
Figure BDA0002696090180000021
wherein-Ar- ═
Figure BDA0002696090180000022
Figure BDA0002696090180000023
Any one of (a);
x ═ O or NH, -Y ═ OH, -NH2or-COOH;
Figure BDA0002696090180000024
any one of the above.
The second technical problem to be solved by the present invention is to provide a preparation method of the above fluorine-containing interface modifier containing active groups, wherein the preparation method comprises: firstly, reacting methoxyl/carboxyl-containing aromatic diphenol or nitro-containing aromatic diamine and a high fluorine-containing compound for 0.5-6 hours at 0-180 ℃ under the protection of inert gas under the action of an organic solvent, a catalyst and alkali to obtain a high fluorine-containing high-activity functional group interface modifier precursor; then, carrying out carboxylation, hydroxylation or amination treatment on the precursor of the high-fluorine-containing high-activity functional group-containing interface modifier to obtain an active group-containing fluorine-containing interface modifier; wherein the structural formula of the aromatic diphenol containing methoxyl/carboxyl or aromatic diamine containing nitryl is shown as a formula II:
Figure BDA0002696090180000025
wherein-X ═ OH or NH2，-Y＝-COOH，-OCH3or-NO2。
Further, the high fluorine-containing compound is any one of perfluorohexylsulfonic acid, perfluorohexanoic acid, perfluorohexylsulfonyl chloride, perfluorohexanoyl chloride, perfluorooctylsulfonic acid, perfluorooctanoic acid, perfluorooctylsulfonyl chloride, or perfluorooctanoyl chloride.
Further, the mass ratio of the raw materials is as follows: 20-100 parts of methoxyl/carboxyl aromatic diphenol or nitro aromatic diamine, 20-200 parts of high fluorine-containing compound, 100-1000 parts of organic solvent, 0.5-5 parts of catalyst and 20-200 parts of alkali.
Further, the method for preparing the precursor of the interface modifier with high fluorine-containing and high-activity functional groups comprises the following steps: adding 20-100 parts of aromatic diphenol containing methoxyl/carboxyl or aromatic diamine containing nitryl into 100-1000 parts of organic solvent, stirring and dissolving under the protection of inert gas, adding 0.5-5 parts of catalyst and 20-200 parts of alkali, adding 20-200 parts of high-fluorine-containing compound, and reacting at 0-180 ℃ for 0.5-6 hours to obtain the precursor of the high-fluorine-containing high-activity functional group interface modifier.
Further, the carboxylation treatment method comprises the following steps: stirring the precursor solution of the high-fluorine-containing high-activity functional group interface modifier under the protection of inert gas, adding 10-100 parts of a carboxylation reagent, stirring and reacting at 0-60 ℃ for 0.5-1 h, filtering, collecting a filter cake, washing with deionized water, filtering, and drying at 60-100 ℃ and a vacuum degree of 0.07-0.095 MPa for 1-12 h to obtain the active carboxyl-containing fluorine-containing active functional group interface modifier.
Further, the hydroxylation treatment method comprises the following steps: stirring the precursor solution of the high-fluorine-content high-activity functional group-containing interface modifier under the protection of inert gas, adding 30-200 parts of a hydroxylation reagent, stirring and reacting at-5-40 ℃ for 3-24 h, pouring the reaction solution into ice water, filtering, collecting a filter cake, washing the filter cake with deionized water, filtering, and drying at 50-100 ℃ under the vacuum degree of 0.07-0.095 MPa for 1-12 h to obtain the active hydroxyl-containing fluorine-containing active functional group-containing interface modifier.
Further, the amination treatment method comprises the following steps: stirring the precursor solution of the high-fluorine-containing high-activity functional group interface modifier under the protection of nitrogen, adding 30-200 parts of an amination reagent, stirring and reacting at-5-40 ℃ for 3-24 h, pouring the reaction solution into ice water, filtering, collecting a filter cake, washing the filter cake with deionized water, filtering, and drying at 50-100 ℃ under the vacuum degree of 0.07-0.095 MPa for 1-12 h to obtain the active amino group-containing fluorine-containing active functional group interface modifier.
Further, the organic solvent is any one of methanol, ethanol, acetone, butanone, 3-pentanone, cyclopentanone, cyclohexanone, dichloromethane, chloroform, tetrahydrofuran, cyclohexane, n-hexane, petroleum ether, toluene, xylene, diphenyl ether, chlorobenzene, or m-dichlorobenzene.
Further, the catalyst is any one of trimethyl silicon chloride, triethyl silicon chloride, dimethyl ethyl silicon chloride, diethyl methyl silicon chloride, triphenyl phosphite, stannous octoate, 4- (dimethylamino) pyridine, triethylamine, sodium hypophosphite or hypophosphorous acid.
Further, the alkali is any one of sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, or barium bicarbonate.
Further, the carboxylation reagent is any one of glacial acetic acid, formic acid, concentrated hydrochloric acid, phosphoric acid or dilute sulfuric acid.
Further, the hydroxylation reagent is any one of boron tribromide, boron trichloride or aluminum trichloride.
Further, the amination reagent is Pd/C/hydrazine hydrate, reduced iron powder/concentrated hydrochloric acid, reduced octyl powder/concentrated hydrochloric acid, Fe-FeSO4/H2SO4、SnCl2/HCl、H2S/NH4Any one of OH or NaHS.
The third technical problem to be solved by the invention is to point out that the fluorine-containing surfactant is used for preparing a high-activity reinforced fluororesin thermoplastic composite material and a high-temperature-resistant and wear-resistant sealing element, especially in the field of extreme conditions such as bearings, high-speed and ultrahigh-power engine shaft sealing materials, fairing sealing materials and the like.
Further, the method for preparing the high-activity reinforced fluororesin thermoplastic composite material by using the active group-containing fluorine-containing interface modifier comprises the following steps: the fluorine-containing interface modifier containing active groups and the reinforcing filler are added into the fluororesin, and the mass ratio of the raw materials is as follows:
50-90 parts by weight of fluororesin
0.1 to 10 parts by weight of active group-containing fluorine-containing interface modifier
10-70 parts by weight of a reinforcing filler.
Further, the fluororesin is any one of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF), or tetrafluoroethylene-hexafluoropropylene copolymer (FEP).
Further, the reinforcing filler is at least one of glass fiber, quartz fiber, carbon fiber, aramid fiber, basalt fiber, nano calcium carbonate, nano titanium dioxide, nano zinc oxide, nano zirconium oxide, carbon black, graphite, graphene, carbon nanotube, nano diatomite, nano silicon dioxide or montmorillonite.
The fourth technical problem to be solved by the invention is to provide a high-activity reinforced fluororesin thermoplastic composite material, which comprises the following raw materials:
50-90 parts by weight of fluororesin
0.1 to 10 parts by weight of active group-containing fluorine-containing interface modifier
10-70 parts by weight of a reinforcing filler;
the structural formula of the active group-containing fluorine-containing interface modifier is shown as a formula I:
Figure BDA0002696090180000041
wherein-Ar- ═
Figure BDA0002696090180000042
Figure BDA0002696090180000043
Any one of (a);
x ═ O or NH, -Y ═ OH, -NH2or-COOH;
Figure BDA0002696090180000044
any one of the above.
The fifth technical problem to be solved by the invention is to provide a preparation method of a high-activity reinforced fluororesin thermoplastic composite material, which comprises the following steps:
1) firstly, fluororesin is treated by plasma, and the treatment process comprises the following steps: the temperature is between room temperature and 100 ℃; the time is 1-60 min; atmosphere: air, nitrogen or oxygen;
2) uniformly mixing the treated fluororesin and the fluorine-containing interface modifier containing active groups in a high-speed mixer to obtain master batch, and then carrying out melt processing on the master batch and the reinforcing filler to obtain the high-strength high-impact thermoplastic fluororesin composite material; wherein the addition proportion of each raw material is as follows: 50-90 parts of fluororesin, 0.1-10 parts of active group-containing fluorine-containing interface modifier and 10-70 parts of reinforcing filler.
Further, in the above method, the melt processing is performed in one of two ways:
the first method is as follows: melting and blending the master batch and the reinforced filler for 1-6 min through a double-screw extruder, and then extruding, cooling, granulating and drying to obtain the reinforced fluororesin thermoplastic composite material, wherein the rotating speed of a screw is 20-300 rpm, and the temperature of each section of the screw is 100-400 ℃;
the second method comprises the following steps: and (3) carrying out cold pressing on the master batch and the reinforcing filler for 10-300min at room temperature-160 ℃ under 3-40 MPa by a hot press, and carrying out hot-pressing compounding for 10-300min at the temperature of 220-420 ℃ under the pressure of 3-40 MPa to obtain the reinforced fluororesin thermoplastic composite material.
In the present invention, unless otherwise specified, parts are parts by mass.
The invention has the beneficial effects that:
1. compared with the traditional interface modifier, the heat-resistant macromolecular structure main chain is combined, so that the stability of the interface modifier, including thermal stability, chemical stability and related aging stability, is greatly improved.
2. By a molecular construction method, a high fluorine-containing element and a high-activity hydroxyl, carboxyl or amino structure are simultaneously introduced into a molecular chain of an interface compatibilizer, and the interface compatibilizer is applied to a fluororesin-reinforced composite material to greatly improve the interface bonding effect between a reinforced filler and a low-surface-activity fluororesin, so that the strength, the modulus and the frictional wear resistance of the fluororesin are improved, the impact resistance of the composite material is greatly improved, and the running and service stability of a material product is fundamentally improved.
3. The chemical bridging effect of the interface compatibilizer on the reinforced filler and the fluororesin is considered comprehensively, and simultaneously, the resin matrix is subjected to corresponding surface modification through plasma treatment, so that the interface performance of the composite material is further optimized and enhanced, and the whole treatment process is simple and convenient, easy to operate, green and environment-friendly, and low in energy consumption and cost.
Detailed Description
In the invention, the interface modifier with high fluorine-containing and high-activity functional groups can be prepared by the following method:
1) preparing a precursor of the fluorine-containing high-activity functional group interface modifier: adding 20-100 parts of aromatic diphenol containing methoxyl/carboxyl or aromatic diamine containing nitryl into 100-1000 parts of organic solvent, stirring and dissolving under the protection of nitrogen, adding 0.5-5 parts of catalyst and 20-200 parts of alkali, adding 20-200 parts of high-fluorine-containing compound, and reacting at 0-180 ℃ for 0.5-6 hours to obtain a precursor solution of the interface modifier with high-fluorine-containing and high-activity functional groups;
2) activation of active functional group of fluorine-containing high-activity functional group-based interface modifier:
carboxylation: continuously stirring the solution under the protection of nitrogen, adding 10-100 parts of a carboxylation reagent, stirring at 0-60 ℃ for reaction for 0.5-1 h, filtering, collecting a filter cake, washing with deionized water, filtering, and drying at 60-100 ℃ and a vacuum degree of 0.07-0.095 MPa for 1-12 h to obtain an active carboxyl-containing fluorine-containing active functional group interface modifier;
hydroxylation: continuously stirring the solution under the protection of nitrogen, adding 30-200 parts of a hydroxylation reagent, stirring at-5-40 ℃ for reaction for 3-24 hours, pouring the reaction solution into ice water, filtering, collecting a filter cake, washing the filter cake with deionized water, filtering, and drying at 50-100 ℃ and under the vacuum degree of 0.07-0.095 MPa for 1-12 hours to obtain the interface modifier containing active hydroxyl, fluorine and active functional groups;
amination: and continuously stirring the solution under the protection of nitrogen, adding 30-200 parts of amination reagent, stirring and reacting at-5-40 ℃ for 3-24 h, pouring the reaction solution into ice water, filtering, collecting filter cakes, washing the filter cakes with deionized water, filtering, and drying at 50-100 ℃ under the vacuum degree of 0.07-0.095 MPa for 1-12 h to obtain the interface modifier containing active amino, fluorine-containing active functional groups.
The following examples are given to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
1) Preparing a precursor of the fluorine-containing high-activity functional group interface modifier:
adding 20g of methoxy hydroquinone into 100g of dichloromethane, stirring and dissolving under the protection of nitrogen, adding 1g of pyridine and 20g of lithium hydroxide, adding 80g of perfluorohexyl sulfonyl chloride, and reacting at 0 ℃ for 6 hours to obtain a precursor solution of the interface modifier containing methoxy fluorine-containing high-activity functional groups;
2) activation of active functional groups of the interface modifier containing methoxy fluorine-containing high-activity functional groups:
hydroxylation: continuously stirring the solution under the protection of nitrogen, adding 40g of boron tribromide, stirring and reacting at-5 ℃ for 3h, pouring the reaction solution into ice water, filtering, collecting a filter cake, washing the filter cake with deionized water, filtering, and drying at the temperature of 100 ℃ and the vacuum degree of 0.09MPa for 8h to obtain the interface modifier containing active hydroxyl and fluorine-containing active functional groups;
3) pre-treating fluororesin:
treating 700g of polytetrafluoroethylene in an air atmosphere by using plasma at room temperature for 5min, and uniformly mixing the polytetrafluoroethylene and 5g of hydroxyl-containing fluorine-containing interface modifier in a high-speed mixer to obtain master batch;
4) preparing a composite material:
the master batch and 250g of chopped carbon fibers are premixed, then cold pressing is carried out for 1h under 20MPa, then heating is carried out to 300 ℃ for hot pressing for 2h, and the reinforced fluororesin thermoplastic composite material is obtained, wherein the tensile strength, the modulus and the impact strength are shown in table 1, and compared with a blank sample (the blank sample is prepared by premixing only equivalent polytetrafluoroethylene and chopped carbon fibers, then cold pressing is carried out for 1h under 20MPa, then heating is carried out to 300 ℃ for hot pressing for 2h, and then a blank comparison sample is obtained), the tensile strength, the elongation at break, the bending strength and the notch impact strength are respectively increased by 63.9%, 256%, 37.3% and 160%.
Example 2
1) Preparing a precursor of the fluorine-containing high-activity functional group interface modifier:
adding 50g of carboxyl-containing phenolphthalein diphenol into 300g of tetrahydrofuran, stirring and dissolving under the protection of nitrogen, adding 2g of triethyl silicon chloride, 22g of sodium hydroxide, adding 90g of perfluoro caprylic chloride, and reacting at 5 ℃ for 4 hours to obtain a precursor solution of the carboxyl-containing fluorine-containing high-activity functional group interface modifier;
2) activation of the active functional group of the interface modifier containing carboxyl and fluorine-containing high-activity functional group:
carboxylation: continuously stirring the solution under the protection of nitrogen, adding 40g of concentrated hydrochloric acid, stirring at 30 ℃ for reaction for 1h, filtering, collecting a filter cake, washing with deionized water, filtering, and drying at 100 ℃ and the vacuum degree of 0.08MPa for 6h to obtain the interface modifier containing the active carboxyl and the fluorine-containing active functional group;
3) pre-treating fluororesin:
treating 650g of polyvinylidene fluoride at room temperature for 8min by adopting plasma in a nitrogen atmosphere, and uniformly mixing the polyvinylidene fluoride with 8g of carboxyl-containing fluorine-containing interface modifier in a high-speed mixer to obtain a master batch;
4) preparing a composite material:
premixing the master batch and 350g of chopped aramid fiber, melting and blending for 6min by using a double-screw extruder, extruding, cooling, granulating and drying to obtain the reinforced fluororesin thermoplastic composite material, wherein the rotating speed of a screw is 80rpm, the temperature of each section of the screw is 100-300 ℃ from low temperature to high temperature, the reinforced fluororesin thermoplastic composite material is prepared into a standard sample strip by injection molding, the tensile strength, the modulus and the impact strength of the standard sample strip are shown in table 1, and compared with a blank sample without an interface compatibilizer, the tensile strength, the elongation at break, the bending strength and the notch impact strength of the standard sample strip are respectively improved by 64.3%, 203%, 14.2% and 125%.
Example 3
1) Preparing a precursor of the fluorine-containing high-activity functional group interface modifier:
adding 100g of nitro-containing bisphenol S into 400g of cyclohexane, stirring and dissolving under the protection of nitrogen, adding 3g of hypophosphorous acid and 126g of potassium carbonate, adding 150g of perfluoro caprylic acid, and reacting at 165 ℃ for 4 hours to obtain a precursor solution of the nitro-containing fluorine-containing high-activity functional group interface modifier;
2) activation of active functional groups of the nitro-containing fluorine-containing high-activity functional group interface modifier:
amination: continuously stirring the solution under the protection of nitrogen, adding 50g of Pd/C/hydrazine hydrate, stirring and reacting at-5 ℃ for 12h, pouring the reaction solution into ice water, filtering, collecting a filter cake, washing the filter cake with deionized water, filtering, and drying at the temperature of 70 ℃ and the vacuum degree of 0.09MPa for 12h to obtain the interface modifier containing the active amino fluorine-containing active functional groups;
3) pre-treating fluororesin:
treating 800g of polychlorotrifluoroethylene in an air atmosphere by adopting plasma at room temperature for 10min, and then uniformly mixing the treated polychlorotrifluoroethylene with 7g of amino-containing high fluorine-containing interface modifier in a high-speed mixer to obtain a master batch;
4) preparing a composite material:
the master batch and 200g of chopped carbon fibers are premixed, then cold pressing is carried out for 3h under 15MPa, and then the temperature is increased to 260 ℃ for hot pressing for 1h, so that the reinforced fluororesin thermoplastic composite material is obtained, wherein the tensile strength, the modulus and the impact strength are shown in table 1, and compared with a blank sample without the interface compatibilizer, the tensile strength, the elongation at break, the bending strength and the notch impact strength are respectively improved by 40.8%, 351%, 14.6% and 125%.
TABLE 1 mechanical properties of Filler-reinforced fluororesin composites
Figure BDA0002696090180000081

Claims (20)

1. The fluorine-containing interface modifier containing active groups is characterized in that the structural formula of the fluorine-containing interface modifier is shown as a formula I:
Figure FDA0003206387960000011
wherein
Figure FDA0003206387960000012
Figure FDA0003206387960000013
Figure FDA0003206387960000014
Any one of (a);
x ═ O or NH, -Y ═ OH, -NH2or-COOH;
Figure FDA0003206387960000015
any one of the above.
2. The preparation method of the active group-containing fluorine-containing interface modifier according to claim 1, characterized in that the preparation method comprises: firstly, reacting methoxyl/carboxyl-containing aromatic diphenol or nitro-containing aromatic diamine and a high fluorine-containing compound for 0.5-6 hours at 0-180 ℃ under the protection of inert gas under the action of an organic solvent, a catalyst and alkali to obtain a high fluorine-containing high-activity functional group interface modifier precursor; then, carrying out carboxylation, hydroxylation or amination treatment on the precursor of the high-fluorine-containing high-activity functional group-containing interface modifier to obtain an active group-containing fluorine-containing interface modifier; wherein the structural formula of the aromatic diphenol containing methoxyl/carboxyl or aromatic diamine containing nitryl is shown as a formula II:
Figure FDA0003206387960000016
wherein-X ═ OH or NH2，-Y＝-COOH，-OCH3or-NO2。
3. The method of claim 2, wherein the high fluorine-containing compound is any one of perfluorohexylsulfonic acid, perfluorohexanoic acid, perfluorohexylsulfonyl chloride, perfluorohexanoyl chloride, perfluorooctylsulfonic acid, perfluorooctanoic acid, perfluorooctylsulfonyl chloride, or perfluorooctanoyl chloride.
4. The preparation method of the fluorine-containing interface modifier with active groups according to claim 2 or 3, characterized in that the mass ratio of the raw materials is as follows: 20 to 100 parts by weight of methoxy/carboxyl-containing aromatic diphenol or nitro-containing aromatic diamine, 20 to 200 parts by weight of high fluorine-containing compound, 100 to 1000 parts by weight of organic solvent, 0.5 to 5 parts by weight of catalyst and 20 to 200 parts by weight of alkali.
5. The method for preparing the interface modifier containing active groups according to claim 2 or 3, wherein the method for preparing the precursor of the interface modifier containing high-fluorine and high-activity functional groups comprises the following steps: adding 20-100 parts of aromatic diphenol containing methoxyl/carboxyl or aromatic diamine containing nitryl into 100-1000 parts of organic solvent, stirring and dissolving under the protection of inert gas, adding 0.5-5 parts of catalyst and 20-200 parts of alkali, adding 20-200 parts of high-fluorine-containing compound, and reacting at 0-180 ℃ for 0.5-6 hours to obtain the precursor of the high-fluorine-containing high-activity functional group interface modifier.
6. The method for preparing the fluorine-containing interface modifier with active groups according to claim 2 or 3, wherein the carboxylation treatment method comprises the following steps: stirring the precursor solution of the high-fluorine-containing high-activity functional group interface modifier under the protection of inert gas, adding 10-100 parts of a carboxylation reagent, stirring and reacting at 0-60 ℃ for 0.5-1 h, filtering, collecting a filter cake, washing with deionized water, filtering, and drying at 60-100 ℃ and a vacuum degree of 0.07-0.095 MPa for 1-12 h to obtain the active carboxyl-containing fluorine-containing active functional group interface modifier.
7. The method for preparing the fluorine-containing interface modifier with active groups according to claim 2 or 3, wherein the hydroxylation treatment method comprises the following steps: stirring the precursor solution of the high-fluorine-content high-activity functional group-containing interface modifier under the protection of inert gas, adding 30-200 parts of a hydroxylation reagent, stirring and reacting at-5-40 ℃ for 3-24 h, pouring the reaction solution into ice water, filtering, collecting a filter cake, washing the filter cake with deionized water, filtering, and drying at 50-100 ℃ under the vacuum degree of 0.07-0.095 MPa for 1-12 h to obtain the active hydroxyl-containing fluorine-containing active functional group-containing interface modifier.
8. The method for preparing the fluorine-containing interface modifier with active groups according to claim 2 or 3, wherein the amination treatment method comprises the following steps: stirring the precursor solution of the high-fluorine-containing high-activity functional group interface modifier under the protection of nitrogen, adding 30-200 parts of an amination reagent, stirring and reacting at-5-40 ℃ for 3-24 h, pouring the reaction solution into ice water, filtering, collecting a filter cake, washing the filter cake with deionized water, filtering, and drying at 50-100 ℃ under the vacuum degree of 0.07-0.095 MPa for 1-12 h to obtain the active amino group-containing fluorine-containing active functional group interface modifier.
9. The method for preparing fluorine-containing interface modifier with active group according to claim 5, wherein the organic solvent is any one of methanol, ethanol, acetone, butanone, 3-pentanone, cyclopentanone, cyclohexanone, dichloromethane, chloroform, tetrahydrofuran, cyclohexane, n-hexane, petroleum ether, toluene, xylene, diphenyl ether, chlorobenzene, or m-dichlorobenzene.
10. The method for preparing fluorine-containing interface modifier with active group according to claim 5, wherein the catalyst is any one of trimethyl silicon chloride, triethyl silicon chloride, dimethyl ethyl silicon chloride, diethyl methyl silicon chloride, triphenyl phosphite, stannous octoate, 4- (dimethylamino) pyridine, triethylamine, sodium hypophosphite or hypophosphorous acid.
11. The method for preparing fluorine-containing interface modifier with active group according to claim 5, wherein the base is any one of sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate or barium bicarbonate.
12. The method for preparing fluorine-containing interface modifier with active group according to claim 6, wherein the carboxylation reagent is any one of glacial acetic acid, formic acid, concentrated hydrochloric acid, phosphoric acid or dilute sulfuric acid.
13. The method of claim 7, wherein the hydroxylation agent is any one of boron tribromide, boron trichloride, or aluminum trichloride.
14. The method for preparing fluorine-containing interface modifier with active group as claimed in claim 8, wherein the amination reagent is Pd/C/hydrazine hydrate, reduced iron powder/concentrated hydrochloric acid, reduced zinc powder/concentrated hydrochloric acid, Fe-FeSO4/H2SO4、SnCl2/HCl、H2S/NH4Any one of OH or NaHS.
15. Use of a fluorosurfactant for the preparation of a fluororesin thermoplastic composite for the preparation of a seal, characterized in that the fluorosurfactant is the active group-containing fluorochemical interface modifier of claim 1; or the fluorine-containing interface modifier prepared by the preparation method of any one of claims 2 to 14.
16. Use of the fluorosurfactant for the preparation of a fluororesin thermoplastic composite for the preparation of a seal according to claim 15 wherein the process of the reactive group-containing fluorochemical interface modifier for the preparation of a fluororesin thermoplastic composite is: the fluorine-containing interface modifier containing active groups and the reinforcing filler are added into the fluororesin, and the mass ratio of the raw materials is as follows:
50-90 parts by weight of fluororesin
0.1 to 10 parts by weight of active group-containing fluorine-containing interface modifier
10-70 parts by weight of a reinforcing filler.
17. Use of a fluorosurfactant for the preparation of a fluororesin thermoplastic composite material for the preparation of a seal according to claim 16 wherein the fluororesin is any of polytetrafluoroethylene, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polyvinyl fluoride or tetrafluoroethylene-hexafluoropropylene copolymer;
the reinforcing filler is at least one of glass fiber, quartz fiber, carbon fiber, aramid fiber, basalt fiber, nano calcium carbonate, nano titanium dioxide, nano zinc oxide, nano zirconium oxide, carbon black, graphite, graphene, carbon nano tube, nano diatomite, nano silicon dioxide or montmorillonite.
18. The fluororesin thermoplastic composite material is characterized by comprising the following raw materials:
50-90 parts by weight of fluororesin
0.1 to 10 parts by weight of active group-containing fluorine-containing interface modifier
10-70 parts by weight of a reinforcing filler;
the structural formula of the active group-containing fluorine-containing interface modifier is shown as a formula I:
Figure FDA0003206387960000031
Figure FDA0003206387960000041
wherein
Figure FDA0003206387960000042
Figure FDA0003206387960000043
Any one of (a);
x ═ O or NH, -Y ═ OH, -NH2or-COOH;
Figure FDA0003206387960000044
any one of the above.
19. A method of producing a fluororesin thermoplastic composite material according to claim 18, characterized by comprising the steps of:
1) firstly, fluororesin is treated by plasma, and the treatment process comprises the following steps: the temperature is between room temperature and 100 ℃; the time is 1-60 min; atmosphere: air, nitrogen or oxygen;
2) uniformly mixing the treated fluororesin and the fluorine-containing interface modifier containing active groups in a high-speed mixer to obtain master batch, and then carrying out melt processing on the master batch and the reinforcing filler to obtain the fluororesin thermoplastic composite material; wherein the addition proportion of each raw material is as follows: 50-90 parts of fluororesin, 0.1-10 parts of active group-containing fluorine-containing interface modifier and 10-70 parts of reinforcing filler.
20. The method of preparing a fluororesin thermoplastic composite according to claim 19, characterized in that the melt processing is performed in one of two ways:
the first method is as follows: melting and blending the master batch and the reinforcing filler for 1-6 min through a double-screw extruder, and then extruding, cooling, granulating and drying to obtain the fluororesin thermoplastic composite material, wherein the rotating speed of a screw is 20-300 rpm, and the temperature of each section of the screw is 100-400 ℃;
the second method comprises the following steps: and (3) carrying out cold pressing on the master batch and the reinforcing filler for 10-300min at room temperature-160 ℃ under 3-40 MPa by a hot press, and carrying out hot-pressing compounding for 10-300min at the temperature of 220-420 ℃ under the pressure of 3-40 MPa to obtain the fluororesin thermoplastic composite material.
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