CN111363076A - Ternary peroxide fluororubber and preparation method thereof, and intelligent wearing material and preparation method thereof - Google Patents

Ternary peroxide fluororubber and preparation method thereof, and intelligent wearing material and preparation method thereof Download PDF

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CN111363076A
CN111363076A CN202010332924.7A CN202010332924A CN111363076A CN 111363076 A CN111363076 A CN 111363076A CN 202010332924 A CN202010332924 A CN 202010332924A CN 111363076 A CN111363076 A CN 111363076A
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general formula
ternary
monomer
tetrafluoroethylene
hexafluoropropylene
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周武刚
苟文珊
巫文强
郑贤君
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Sichuan Daohong Technology Co ltd
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Sichuan Daohong Technology Co ltd
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    • 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
    • C08F214/00—Copolymers 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
    • C08F214/18—Monomers containing fluorine
    • C08F214/28—Hexyfluoropropene
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C5/00—Bracelets; Wrist-watch straps; Fastenings for bracelets or wrist-watch straps
    • A44C5/0053—Flexible straps
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08F214/00—Copolymers 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
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • 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
    • C08F214/00—Copolymers 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
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The invention provides a ternary peroxide fluororubber, a preparation method thereof, an intelligent wearing material and a preparation method thereof, and solves the technical problems that the wrist strap and the watchstrap materials in the prior art cannot simultaneously and well meet the requirements of swimming pool water resistance, sweat resistance, artificial sebum resistance, oleic acid resistance and dirt resistance required by the intelligent wearing wrist strap and the watchstrap. The preparation of the fluororubber takes iodine as a crosslinking active point, and the iodine as the crosslinking active point is bonded at the tail end of a molecular chain of a fluororubber polymer or the tail end of a side chain of a vulcanization point monomer, so that vulcanization crosslinking is easily carried out by peroxide. The polymer is used for preparing an intelligent wearing material, and the prepared intelligent wearing wrist strap material or watchband material can meet the requirements of swimming pool water resistance, sweat resistance, artificial sebum resistance, oleic acid resistance and dirt resistance.

Description

Ternary peroxide fluororubber and preparation method thereof, and intelligent wearing material and preparation method thereof
Technical Field
The invention relates to the field of fluorine-containing high polymer materials, in particular to ternary peroxide fluororubber and a preparation method thereof, and an intelligent wearable material and a preparation method thereof.
Background
In recent years, with the technological progress and the continuous improvement of the quality of life of people, artificial intelligence and sports are healthy and fast to enter the public life, and intelligent wearable equipment is also promoted. Intelligence wrist-watch and intelligent bracelet have concurrently: traditional watch function, health monitoring, intelligent interaction with smart devices such as smart phones, and the like. Market demand is very big, has driven intelligence and has dressed wrist strap and watchband material explosive growth.
The wrist strap and the watchband material need to be worn to intelligence has characteristics such as safe environmental protection, durable, comfortable and satisfy specific functional requirement, wherein specific functional requirement needs to satisfy: the swimming pool water resistance, sweat resistance, artificial sebum resistance, oleic acid resistance and dirt resistance.
The traditional wrist strap and watch strap materials generally use metal and leather, and in recent years, some high polymer materials such as silica gel, polyurethane, thermoplastic elastomer (TPE), Thermoplastic Polyurethane (TPU), thermoplastic elastomer (TPSiV) and the like also become main materials. The metal material is hard, the comfort is poor, and the oil resistance and the acidity are poor; the leather material has poor environmental protection property, poor swimming pool water resistance and poor sweat resistance; the silica gel material has poor durability and poor dirt resistance; polyurethane, thermoplastic elastomer TPE, TPU, TPSiV etc. have different shortcomings in satisfying intelligence and wearing wrist strap and watchband material requirement.
The fluororubber is a synthetic rubber with fluorine atoms connected to carbon atoms of a main chain or a side chain, and has no double bonds in the molecular chain structure of the fluororubber, and the bond energy of a C-F bond is very high (435-485 KJ/mol), so that the fluororubber has excellent chemical stability, heat resistance, corrosion resistance, weather aging resistance, flame retardance and the like.
Fluororubber can be divided into bisphenol vulcanized fluororubber and peroxide fluororubber according to vulcanization system classification, and peroxide fluororubber is more excellent than bisphenol vulcanized fluororubber in aspects such as resistant swimming pool water, sweat resistance, artificial sebum resistance, oleic acid resistance, dirt resistance, safety, environmental protection, etc., and the wrist strap and the watchband material prepared by taking the peroxide fluororubber as a raw material are easy to match colors, soft in hand feeling and comfortable to wear, and are the best choice as the material of the intelligent wearable wrist strap and the watchband.
The applicant has found that the prior art has at least the following technical problems:
1. the traditional wrist strap and watchband materials cannot simultaneously and well meet the requirements of swimming pool water resistance, sweat resistance, artificial sebum resistance, oleic acid resistance and stain resistance required by the intelligent wearing wrist strap and watchband;
2. the traditional wrist strap and watchband materials can not well meet the requirements on the aspects of safety, environmental protection, durability, body feeling comfort degree and the like.
Disclosure of Invention
The invention aims to provide a ternary oxyfluoride rubber and a preparation method thereof, an intelligent wearing material and a preparation method thereof, and aims to solve the technical problems that the traditional wrist strap and watchstrap materials in the prior art cannot simultaneously and well meet the requirements of swimming pool water resistance, sweat resistance, artificial sebum resistance, oleic acid resistance and dirt resistance required by the intelligent wearing wrist strap and watchstrap, and cannot well meet the requirements in the aspects of safety, environmental protection, durability, body feeling comfort and the like. The technical effects that can be produced by the preferred technical scheme in the technical schemes provided by the invention are described in detail in the following.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a ternary peroxide fluororubber, which has a structure shown as a general formula I, a general formula II or a general formula III; wherein the content of the first and second substances,
the general formula I is as follows:
Figure BDA0002465621430000021
in the general formula I, R is I, CH2I、-CF2I or-CF2(CF2)nI, n is a natural number which is more than or equal to 1 and less than or equal to 11;
the polymer of the general formula I is a fluororubber polymer which takes iodine-containing compounds as chain transfer agents, iodine in the chain transfer agents is bonded with the molecular chain ends of the fluororubber polymer in the polymerization process to form iodine at the molecular chain ends as crosslinking active points;
the general formula II is as follows:
Figure BDA0002465621430000031
in the general formula II, R is I, CH2I、-CF2I or-CF2(CF2)nI, n is a natural number which is more than or equal to 1 and less than or equal to 11; x1Hydrogen atom and fluorine atom; rf 1Is a fluoroalkylene, perfluoroalkylene, fluoropolyoxyalkylene, or perfluoropolyoxyalkylene group; x2Is an iodine atom.
The polymer of the general formula II is a multi-crosslinking-point-structure fluororubber polymer which takes iodine-containing compounds as chain transfer agents, iodine in the chain transfer agents is bonded with the molecular chain ends of the fluororubber polymer in the polymerization process, and simultaneously iodine-containing alkenyl monomers are taken as vulcanization point active monomers to be polymerized on the main chain of the molecular chain to form iodine at the molecular chain ends and iodine on the vulcanization point monomers on the main chain as crosslinking active points;
the general formula III is as follows:
Figure BDA0002465621430000032
in the general formula III, X1Hydrogen atom and fluorine atom; rf 1Is a fluoroalkylene, perfluoroalkylene, fluoropolyoxyalkylene, or perfluoropolyoxyalkylene group; x2Is an iodine atom.
The polymer in the general formula III is polymerized on a molecular chain main chain by taking a non-iodine compound as a chain transfer agent and taking an iodoolefin-based monomer as a vulcanization point active monomer, so that the fluororubber polymer with only the vulcanization point active monomer on the molecular chain main chain and no vulcanization point active monomer at the molecular chain end is formed.
Further, the Mooney viscosity ML (1+10) at 121 ℃ is 15-70, and the fluorine content is 67-70.5%.
The invention provides a preparation method of ternary peroxide fluororubber, which comprises the steps of carrying out polymerization reaction on deionized water, an emulsifier, a pH buffer agent, an initiator, a chain transfer agent and a polymerization monomer in a high-pressure polymerization reaction kettle to prepare the ternary peroxide fluororubber; the polymerization monomers of the general formula I are vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene, and the polymerization monomers of the general formula II and the general formula III are the vinylidene fluoride, the tetrafluoroethylene, the hexafluoropropylene and a vulcanization point active monomer.
Further, in the polymerization reaction, the deionized water, the emulsifier, the pH buffer, the initiator, the chain transfer agent and the polymerization monomer are respectively in parts by weight as follows: 250 parts of deionized water, 0.02-0.75 part of emulsifier, 0.01-0.5 part of pH buffer, 0.02-0.25 part of initiator, 0.1-1.8 part of chain transfer agent and 100 parts of polymerization monomer;
when the polymer of the general formula I is polymerized, the molar ratio of the vinylidene fluoride to the tetrafluoroethylene to the hexafluoropropylene is 45-65: 5-20: 20-45 parts of;
when the polymer of the general formula II is polymerized, the molar ratio of the vinylidene fluoride, the tetrafluoroethylene, the hexafluoropropylene and the vulcanization point active monomer is 45-65: 5-20: 20-45: 0.05-1.8.
When the polymer of the general formula III is polymerized, the molar ratio of the vinylidene fluoride, the tetrafluoroethylene, the hexafluoropropylene and the vulcanization point active monomer is 45-65: 5-20: 20-45: 0.1-2.5.
Further, when the polymer of the general formula I is polymerized, the molar ratio of the vinylidene fluoride to the tetrafluoroethylene to the hexafluoropropylene is 50-65: 5-20: 20-40 parts of;
when the polymer of the general formula II is polymerized, the molar ratio of the vinylidene fluoride, the tetrafluoroethylene, the hexafluoropropylene and the vulcanization point active monomer is 50-65: 5-20: 20-40: 0.1-1.5;
when the polymer of the general formula III is polymerized, the molar ratio of the vinylidene fluoride, the tetrafluoroethylene, the hexafluoropropylene and the vulcanization point active monomer is 50-65: 5-20: 20-40: 0.25-1.8.
Further, the structure of the vulcanization point active monomer is shown as a general formula IV or V:
the general formula IV is as follows: CX1 2＝CX1-Rf 1X2；
The general formula V is: CX1 2＝CX1X2；
In the general formulae IV and V, X1Hydrogen atom and fluorine atom; rf 1Is a fluoroalkylene, perfluoroalkylene, fluoropolyoxyalkylene, or perfluoropolyoxyalkylene group; x2Is an iodine atom.
Further, the vulcanization point active monomer is 2, 2-difluoroiodoethylene, trifluoroiodoethylene, 4-iodo-3, 3, 4, 4-tetrafluorobutene, 4-iodoperfluorobutene or allyl iodide.
Further, the vulcanization point active monomer is 4-iodoperfluorobutene or 2, 2-difluoroiodoethylene.
Further, when the polymers in the general formula I and the general formula II are polymerized, the chain transfer agent is an iodine-containing chain transfer agent;
the iodine-containing chain transfer agent is a monoiodide compound and/or a diiodo compound;
the monoiodine compound is any one or a mixture of any more of methyl iodide, monoiodoperfluoromethane, monoiodoperfluoroethane, monoiodoperfluoropropane, monoiodoperfluorobutane, monoiodoperfluoropentane, monoiodoperfluorohexane, monoiodoperfluoroheptane and monoiodoperfluorooctane;
the diiodo compound is any one or a mixture of any more of diiodomethane, diiododifluoromethane, 1, 2 diiodoperfluoroethane, 1, 3 diiodoperfluoropropane, 1, 4 diiodoperfluorobutane, 1, 6 diiodoperfluorohexane and 1, 8 diiodoperfluorooctane;
when the polymer in the general formula III is polymerized, the chain transfer agent is a non-iodine chain transfer agent;
the non-iodine chain transfer agent is any one or a mixture of any more of vinyl acetate, dimethyl malonate and diethyl malonate.
Further, the iodine-containing chain transfer agent is diiodomethane, 1, 2 diiodoperfluoroethane, 1, 3 diiodoperfluoropropane, 1, 4 diiodoperfluorobutane, 1, 6 diiodoperfluorohexane, monoiodoperfluoromethane, monoiodoperfluoroethane;
the atypical chain transfer agent is vinyl acetate, dimethyl malonate and diethyl malonate.
Further, when the polymer of the general formula I is polymerized, the amount of the chain transfer agent is 0.2-1.8 parts by weight based on 100 parts by weight of the polymerized monomers;
when the polymer of the general formula II is polymerized, the use amount of the chain transfer agent is 0.1-0.9 part in parts by weight based on 100 parts of the polymerized monomer;
when the polymer in the general formula III is polymerized, the amount of the chain transfer agent is 0.2-1.5 parts by weight based on 100 parts of the polymerized monomers.
Further, when the polymer of the general formula I is polymerized, the amount of the chain transfer agent is 0.3-1.2 parts by weight based on 100 parts by weight of the polymerized monomers;
when the polymer of the general formula II is polymerized, the use amount of the chain transfer agent is 0.1-0.7 part in parts by weight based on 100 parts of the polymerized monomer;
when the polymer in the general formula III is polymerized, the amount of the chain transfer agent is 0.25-1.2 parts by weight based on 100 parts by weight of the polymerized monomers.
Further, the emulsifier is ammonium salt of perfluoropolyether carboxylic acid or sodium salt of perfluoropolyether carboxylic acid; the pH buffering agent is dipotassium hydrogen phosphate; the initiator is persulfate or an oxidation-reduction initiation system consisting of persulfate-bisulfite.
Further, the preparation of the ternary peroxide fluororubber comprises the following specific steps:
a1, adding deionized water, an emulsifier and a pH buffer agent into the high-pressure polymerization reaction kettle, introducing nitrogen to discharge oxygen in the high-pressure polymerization reaction kettle, and starting heating;
a2, respectively introducing the initial monomers into a high-pressure polymerization reaction kettle by a compressor to ensure that the pressure in the reaction kettle reaches 1.6-2.7 Mpa, and starting stirring; the initial monomers are vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene;
a3, when the mixture in the high-pressure polymerization reaction kettle is heated to 60-95 ℃, adding an initiator to start polymerization reaction;
a4, adding the initiator 2-5 times in the polymerization process; adding a chain transfer agent for 2-8 times; if the polymerization monomer comprises a vulcanization point monomer, adding the vulcanization point monomer for 2-6 times; replenishing supplementary monomers at intervals, wherein the supplementary monomers are vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene, keeping the pressure at 2.0-3.2 Mpa and the temperature at 75-95 ℃ in the polymerization process, and keeping stirring;
and A5, after the polymerization reaction is finished, removing the emulsion from the high-pressure polymerization reaction kettle, and obtaining the ternary fluorine rubber peroxide after coagulation, washing and drying.
Further, the molar ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene in the initial monomer is 15-25: 35-45: 40-50; the molar ratio of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene in the additional monomer is 50-65: 5-20: 20-40.
The invention provides an intelligent wearing wrist strap material or a watchband material, and the ternary oxyfluoride rubber prepared by the preparation method is applied to the preparation of the intelligent wearing wrist strap material or the watchband material.
The invention provides a preparation method of an intelligent wearable wrist strap material or a watchstrap material, which comprises the following steps:
b1, the ternary perfluoronated rubber prepared by the preparation method of any one of claims 3 to 10;
b2, adding the ternary peroxide fluororubber prepared in the step B1, an acid-absorbing agent, a filling agent, a coloring agent, a processing aid, an auxiliary vulcanizing agent and a vulcanizing agent into an internal mixer for mixing, and then performing back mixing on an open mill to prepare a ternary peroxide fluororubber compound;
when the internal mixer is used for mixing, the temperature is 80-115 ℃, and the mixing time is 180-600 seconds; when the open mill carries out remill, the temperature is 60-95 ℃, and the thin passing is carried out for 3-8 times;
b3, sequentially carrying out first-stage vulcanization, second-stage vulcanization and hand feeling oil spraying on the ternary peroxide fluororubber compound prepared in the step B2 to prepare a fluororubber wristband material or a fluororubber watchband material; in the first-stage vulcanization, the temperature is 170-190 ℃, and the vulcanization time is 120-500 seconds; in the secondary vulcanization, the temperature is 175-230 ℃, and the vulcanization time is 1-4 hours.
Further, in the step B2, the preparation of the ternary peroxide fluororubber compound comprises the following components in parts by weight: 100 parts of ternary fluorine peroxide rubber; 3-10 parts of an acid absorbent; 10-50 parts of a filling agent; 2-10 parts of a coloring agent; 0.3-1.5 parts of processing aid; 1-4 parts of auxiliary vulcanizing agent; 1-4 parts of a vulcanizing agent;
the acid absorbing agent, the filling agent, the coloring agent, the processing aid, the auxiliary vulcanizing agent and the vulcanizing agent are respectively as follows:
the acid absorbent is any one of zinc oxide, hydrotalcite and magnesium oxide;
the filler is any one or a mixture of any more of barium sulfate, calcium silicate, carbon black, diatomite, silica micropowder and white carbon black;
the colorant is any one or a mixture of any more of pigment carbon black, titanium dioxide, halogen-free organic blue pigment, halogen-free organic yellow pigment, halogen-free organic red pigment, iron oxide red, iron oxide yellow and iron oxide green;
the processing aid is any one or a mixture of any several of palm wax, Struktol WS280 and Struktol HT-290;
the co-vulcanizing agent is any one of triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), tri-allyl isocyanate (TMAIC) and Trihydroxy Methyl Propane Trimethacrylate (TMPTMA);
the vulcanizing agent is any one of di-tert-butylperoxyisopropyl benzene (BIBP), 2, 5-di-tert-butylperoxy-2, 5-dimethylethane (bis-dipenta), dicumyl peroxide (DCP) and peroxy-2-ethylhexyl tert-butyl carbonate (TBEC).
Based on the technical scheme, the embodiment of the invention can at least produce the following technical effects:
the ternary peroxide fluororubber wrist strap and watch strap material prepared by the method does not contain halogen bromine, chlorine, perfluorooctanoic acid (PFOA) and salts thereof, meets the requirements of halogen regulations and European Union REACH regulations that the PFOA and the salts thereof are less than 25ppb, and has excellent chemical stability, heat resistance, corrosion resistance, weather resistance and the like. The wrist strap and the watchband prepared by taking the materials as raw materials are easy to match colors, soft in hand feeling and comfortable to wear, have excellent performances of swimming pool water resistance, sweat resistance, artificial sebum resistance, oleic acid resistance, dirt resistance, safety, environmental protection and the like, and are ideal choices for being used as materials of the intelligent wearable wrist strap and the watchband.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Preparation of ternary Peroxyfluorubber
Example 1
The method is carried out in a 10L high-pressure polymerization reaction kettle, the total weight of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment is 2.3Kg, and the specific steps are as follows:
a1, adding 5L of deionized water, 4g of dipotassium phosphate, 4g of diiodomethane and 10g of ammonium salt of perfluoropolyether carboxylic acid (10 wt%) into a high-pressure polymerization reaction kettle, evacuating nitrogen for replacement, reducing the oxygen content in the high-pressure polymerization reaction kettle to be less than 25ppm, and raising the temperature of the reaction kettle to 85 ℃;
a2, adding initial monomers (vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene) into a high-pressure polymerization reaction kettle by a compressor, starting stirring when the pressure in the high-pressure polymerization reaction kettle is 2.0Mpa, and adjusting the rotating speed to 98 rpm;
a3, when the mixture in the high-pressure polymerization kettle is heated to 90 ℃, 4g of initiator ammonium persulfate solution (10 wt%) is added to start the polymerization reaction; the initial monomer composition in mole percent is: 16% vinylidene fluoride, 38% tetrafluoroethylene, 46% hexafluoropropylene;
a4, after the reaction starts, reducing the pressure, and maintaining the reaction rate by periodically and continuously adding additional monomers to maintain the pressure of the reaction kettle at 2.3MPa, controlling the reaction temperature at 90 ℃, and simultaneously keeping the stirring speed at 98rpm unchanged; the mole percentage composition of the supplementary monomers is as follows: 55% of vinylidene fluoride, 15% of tetrafluoroethylene and 30% of hexafluoropropylene; when the monomer amount reaches 1/5, 1/3, 1/2 and 2/3 of the total monomer amount (the total monomer amount is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene added in the embodiment), 1g of ammonium persulfate solution (10 wt%) and 1.5g of diiodomethane are respectively added, and the reaction is stopped after 2.4 hours;
a5, discharging reaction emulsion after the temperature of the high-pressure polymerization reaction kettle is reduced to room temperature, adding 80ml of magnesium sulfate solution (10 percent by weight) while stirring, and coagulating the emulsion into rubber particles; after filtration, the polymer was washed repeatedly with deionized water for 5 times, and finally placed in a vacuum oven to be dried at 120 ℃ for 12 hours to obtain 2.20Kg of the dried polymer.
Example 2
This example was carried out in a 10L autoclave, wherein the total weight of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene added in this example was 2.3Kg, and the specific steps were:
a1, adding 5L of deionized water, 5g of dipotassium phosphate, 6g of diiodomethane and 9g of ammonium perfluoropolyether carboxylate (10 wt%) into a high-pressure polymerization reaction kettle, evacuating nitrogen for replacement, reducing the oxygen content in the high-pressure polymerization reaction kettle to be less than 25ppm, and raising the temperature of the reaction kettle to 83 ℃;
a2, adding initial monomers (vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene) into the high-pressure polymerization reaction kettle by using a compressor, starting stirring when the pressure in the high-pressure polymerization reaction kettle is 2.2Mpa, and adjusting the rotating speed to be 100 rpm;
a3, when the mixture in the high-pressure polymerization kettle is heated to 88 ℃, 2g of initiator ammonium persulfate solution (10 wt%) is added to start the polymerization reaction; the initial monomer composition in mole percent is: 16% vinylidene fluoride, 37% tetrafluoroethylene, 45% hexafluoropropylene;
a4, after the reaction is started, the pressure is reduced, and the reaction rate is kept by periodically and continuously adding additional monomers to maintain the pressure of the high-pressure polymerization reaction kettle at 2.5MPa, controlling the reaction temperature at 88 ℃ and keeping the stirring speed at 100 rpm. The mole percentage composition of the supplementary monomers is as follows: 65% of vinylidene fluoride, 10% of tetrafluoroethylene and 25% of hexafluoropropylene. When the monomer amount reaches 1/5, 1/3, 1/2 and 2/3 of the total monomer amount (the total monomer amount is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene added in the embodiment), 1g of ammonium persulfate solution (10 wt%) and 2g of diiodomethane are respectively added, and the reaction is stopped after 2.3 hours;
a5, discharging the reaction emulsion after the temperature of the high-pressure polymerization reaction kettle is reduced to room temperature, adding 70ml of magnesium sulfate solution (10% wt) while stirring, coagulating the emulsion into rubber particles, filtering, repeatedly washing with deionized water for 5 times, finally dishing up, putting into a vacuum oven, and drying at 120 ℃ for 12h to obtain 2.18Kg of the dried polymer.
Example 3
This example was carried out in a 10L autoclave, wherein the total weight of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene added in this example was 2.3Kg, and the specific steps were:
a1, adding 5L of deionized water, 5g of dipotassium phosphate, 6g of diiodomethane and 11g of ammonium perfluoropolyether carboxylate (10 wt%) into a high-pressure polymerization reaction kettle, evacuating nitrogen for replacement, reducing the oxygen content in the reaction kettle to be less than 25ppm, and raising the temperature of the reaction kettle to 70 ℃;
a2, adding initial monomers (vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene) into the high-pressure polymerization reaction kettle by using a compressor, starting stirring when the pressure in the high-pressure polymerization reaction kettle is 2.7Mpa, and adjusting the rotating speed to 105 rpm;
a3, when the mixture in the high-pressure polymerization reactor was heated to 75 ℃, 2g of an ammonium persulfate solution (10 wt%) and 2g of a sodium hydrogen sulfite solution (10 wt%) were added, respectively, to start the polymerization; the initial monomer composition in mole percent is: 17% vinylidene fluoride, 37% tetrafluoroethylene, 46% hexafluoropropylene;
a4, after the reaction starts, reducing the pressure, and maintaining the reaction rate by periodically and continuously adding additional monomers to maintain the pressure of the reaction kettle at 3.0MPa, controlling the reaction temperature at 75 ℃ and simultaneously keeping the stirring speed at 105rpm unchanged; the mole percentage composition of the supplementary monomers is as follows: 60% of vinylidene fluoride, 10% of tetrafluoroethylene and 30% of hexafluoropropylene; when the monomer amount is added to 1/5, 1/3, 1/2 and 2/3 of the total monomer amount (the total monomer amount is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene added in the embodiment), 1g of ammonium persulfate solution (10 wt%), 1g of sodium bisulfite solution (10 wt%) and 2g of diiodomethane are respectively added, and the reaction is stopped after 3.6 hours;
a5, discharging the reaction emulsion after the temperature of the high-pressure polymerization reaction kettle is reduced to room temperature, adding 80ml of magnesium sulfate solution (10% wt) while stirring, coagulating the emulsion into rubber particles, filtering, repeatedly washing with deionized water for 5 times, finally dishing up, putting into a vacuum oven, and drying at 120 ℃ for 12h to obtain 2.15Kg of the dried polymer.
Example 4
This example was carried out in a 10L autoclave, wherein the total weight of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene added in this example was 2.3Kg, and the specific steps were:
a1, adding 5L of deionized water, 5g of dipotassium phosphate, 4g of diiodomethane and 8g of ammonium salt of perfluoropolyether carboxylic acid (10 wt%) into a high-pressure polymerization reaction kettle, evacuating nitrogen for replacement, reducing the oxygen content in the high-pressure polymerization reaction kettle to be less than 25ppm, and raising the temperature of the high-pressure polymerization reaction kettle to 75 ℃;
a2, adding initial monomers (vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene) into the high-pressure polymerization reaction kettle by using a compressor, starting stirring when the pressure in the high-pressure polymerization reaction kettle is 1.8Mpa, and adjusting the rotating speed to 98 rpm;
a3, when the mixture in the high-pressure polymerization reactor was heated to 80 ℃, 3g of an ammonium persulfate solution (10 wt%) and 3g of a sodium hydrogen sulfite solution (10 wt%) were added, respectively, to start the polymerization; the initial monomer composition in mole percent is: 19% vinylidene fluoride, 36% tetrafluoroethylene, 45% hexafluoropropylene;
a4, after the reaction starts, the pressure is reduced, and the reaction rate is kept by periodically and continuously adding additional monomers to maintain the pressure of the high-pressure polymerization reaction kettle at 2.1MPa, controlling the reaction temperature at 80 ℃ and keeping the stirring speed at 98 rpm. The mole percentage composition of the supplementary monomers is as follows: 65% of vinylidene fluoride, 5% of tetrafluoroethylene and 30% of hexafluoropropylene. When the monomer addition amount reaches 1/5, 1/3, 1/2 and 2/3 of the total monomer amount (the total monomer amount is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene added in the embodiment), 1g of ammonium persulfate solution (10 wt%), 1g of sodium bisulfite solution (10 wt%) and 4g of diiodomethane are respectively added, and the reaction is terminated after 3.2 h; finishing the reaction;
a5, discharging the reaction emulsion after the temperature of the kettle is reduced to room temperature, adding 90ml of magnesium sulfate solution (10 percent by weight) while stirring, coagulating the emulsion into rubber particles, filtering, repeatedly washing with deionized water for 5 times, finally dishing up, putting into a vacuum oven, and drying at 120 ℃ for 12h to obtain 2.17Kg of dried polymer.
Example 5
This example was carried out in a 10L autoclave, wherein the total weight of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene added in this example was 2.3Kg, and the specific steps were:
a1, adding 5L of deionized water, 4g of dipotassium phosphate, 2.5g of 4-iodoperfluorobutene, 2g of diiodomethane and 10g of ammonium salt of perfluoropolyether carboxylic acid (10 wt%) into a high-pressure polymerization reaction kettle, evacuating nitrogen for replacement, reducing the oxygen content in the high-pressure polymerization reaction kettle to be less than 25ppm, and raising the temperature of the high-pressure polymerization reaction kettle to 85 ℃;
a2, adding initial monomers (vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene) into the high-pressure polymerization reaction kettle by using a compressor, starting stirring when the pressure in the high-pressure polymerization reaction kettle is 2.0Mpa, and adjusting the rotating speed to 95 rpm;
a3, adding 2g ammonium persulfate solution (10 wt%) when the mixture in the high-pressure polymerization reaction kettle is heated to 90 ℃ to start the reaction; the initial monomer composition in mole percent is: 20% vinylidene fluoride, 35% tetrafluoroethylene, 45% hexafluoropropylene;
a4, after the reaction starts, the pressure is reduced, and the reaction rate is kept by periodically and continuously adding additional monomers to maintain the pressure of the high-pressure polymerization reaction kettle at 2.3MPa, controlling the reaction temperature at 90 ℃ and keeping the stirring speed at 95 rpm. The mole percentage composition of the supplementary monomers is as follows: 55% of vinylidene fluoride, 15% of tetrafluoroethylene and 30% of hexafluoropropylene. When the amount of the additional monomer reaches 1/5, 1/3, 1/2 and 2/3 of the total amount of the monomer (the total amount of the monomer is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 1g of ammonium persulfate solution (10 wt%) and 2.5g of 4-iodoperfluorobutene are respectively added, when the amount of the additional monomer reaches 1/5, 2/5 and 3/5 of the total amount of the monomer (the total amount of the monomer is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 1g of diiodomethane is respectively added, and the reaction is stopped after 2.2 hours;
a5, discharging the reaction emulsion after the temperature of the kettle is reduced to room temperature, adding 90ml of magnesium sulfate solution (10 percent by weight) while stirring, coagulating the emulsion into rubber particles, filtering, repeatedly washing with deionized water for 5 times, finally dishing up, putting into a vacuum oven, and drying at 120 ℃ for 12h to obtain 2.21Kg of dried polymer.
Example 6
This example was carried out in a 10L autoclave, wherein the total weight of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene added in this example was 2.3Kg, and the specific steps were:
a1, adding 5L of deionized water, 5g of dipotassium phosphate, 4g of diiodomethane, 2.5g of 4-iodoperfluorobutene and 11g of ammonium salt of perfluoropolyether carboxylic acid (10 wt%) into a high-pressure polymerization reaction kettle, evacuating nitrogen for replacement, reducing the oxygen content in the high-pressure polymerization reaction kettle to be less than 25ppm, and raising the temperature of the high-pressure polymerization reaction kettle to 81 ℃;
a2, adding initial monomers (vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene) into the high-pressure polymerization reaction kettle by using a compressor, starting stirring when the pressure in the high-pressure polymerization reaction kettle is 2.0Mpa, and adjusting the rotating speed to 88 rpm;
a3, adding 2g ammonium persulfate solution (10 wt%) to start the polymerization reaction when the mixture in the high-pressure polymerization kettle is heated to 86 ℃; the initial monomer composition in mole percent is: 21% vinylidene fluoride, 35% tetrafluoroethylene, 44% hexafluoropropylene;
a4, after the reaction is started, the pressure is reduced, and the reaction rate is kept by periodically and continuously adding additional monomers to maintain the pressure of the high-pressure polymerization reaction kettle at 2.3MPa, controlling the reaction temperature at 86 ℃ and keeping the stirring speed at 88 rpm. The mole percentage composition of the supplementary monomers is as follows: 51% of vinylidene fluoride, 11% of tetrafluoroethylene and 34% of hexafluoropropylene. When the amount of the additional monomer reaches 1/5, 1/3, 1/2 and 2/3 of the total amount of the monomer (the total amount of the monomer is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 1g of ammonium persulfate solution (10 wt%) and 2.5g of 4-iodoperfluorobutene are respectively added, when the amount of the additional monomer reaches 1/5, 2/5 and 3/5 of the total amount of the monomer (the total amount of the monomer is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 2g of diiodomethane is respectively added, and the reaction is stopped after 3.6 hours;
a5, discharging the reaction emulsion after the temperature of the kettle is reduced to room temperature, adding 70ml of magnesium sulfate solution (10 percent by weight) while stirring, coagulating the emulsion into rubber particles, filtering, repeatedly washing with deionized water for 5 times, finally dishing up, putting into a vacuum oven, and drying at 120 ℃ for 12h to obtain 2.19Kg of dried polymer.
Example 7
This example was carried out in a 10L autoclave, wherein the total weight of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene added in this example was 2.3Kg, and the specific steps were:
a1, adding 5L of deionized water, 4g of dipotassium phosphate, 4g of diiodomethane, 4g of 4-iodoperfluorobutene and 12g of ammonium salt of perfluoropolyether carboxylic acid (10 wt%) into a high-pressure polymerization reaction kettle, evacuating nitrogen for replacement, reducing the oxygen content in the high-pressure polymerization reaction kettle to be less than 25ppm, and raising the temperature of the high-pressure polymerization reaction kettle to 73 ℃;
a2, adding initial monomers (vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene) into the high-pressure polymerization reaction kettle by using a compressor, starting stirring when the pressure in the high-pressure polymerization reaction kettle is 2.5Mpa, and adjusting the rotating speed to 85 rpm;
a3, adding 2g ammonium persulfate solution (10 wt%) and 2g sodium bisulfite solution (10 wt%) when the mixture in the high-pressure polymerization reaction kettle is heated to 78 ℃ respectively to start the reaction; the initial monomer composition in mole percent is: 22% vinylidene fluoride, 37% tetrafluoroethylene, 41% hexafluoropropylene;
a4, after the reaction starts, the pressure is reduced, and the reaction rate is kept by periodically and continuously adding additional monomers to maintain the pressure of the high-pressure polymerization reaction kettle at 2.8MPa, controlling the reaction temperature at 78 ℃ and keeping the stirring speed at 85 rpm. The mole percentage composition of the supplementary monomers is as follows: 58% of vinylidene fluoride, 12% of tetrafluoroethylene and 30% of hexafluoropropylene. When the amount of the additional monomer reaches 1/5, 1/3, 1/2 and 2/3 of the total amount of the monomer (the total amount of the monomer is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 1g of ammonium persulfate solution (10 wt%), 1g of sodium bisulfite solution (10 wt%) and 2g of 4-iodoperfluorobutene are respectively added, when the amount of the additional monomer reaches 1/5, 2/5 and 3/5 of the total amount of the monomer (the total amount of the monomer is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 2g of diiodomethane is respectively added, and the reaction is stopped after 3.3 hours;
a5, discharging the reaction emulsion after the temperature of the kettle is reduced to room temperature, adding 90ml of magnesium sulfate solution (10 percent by weight) while stirring, coagulating the emulsion into rubber particles, filtering, repeatedly washing with deionized water for 5 times, finally dishing up, putting into a vacuum oven, and drying at 120 ℃ for 12h to obtain 2.17Kg of dried polymer.
Example 8
This example was carried out in a 10L autoclave, wherein the total weight of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene added in this example was 2.3Kg, and the specific steps were:
a1, adding 5L of deionized water, 6g of dipotassium phosphate, 3g of diiodomethane, 2g of 4-iodoperfluorobutene and 10g of perfluoropolyether carboxylic acid ammonium salt (10 wt%) into a high-pressure polymerization reaction kettle, evacuating nitrogen for replacement, reducing the oxygen content in the high-pressure polymerization reaction kettle to be less than 25ppm, and raising the temperature of the high-pressure polymerization reaction kettle to 70 ℃;
a2, adding initial monomers (vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene) into the high-pressure polymerization reaction kettle by using a compressor, starting stirring when the pressure in the high-pressure polymerization reaction kettle is 1.8Mpa, and adjusting the rotating speed to 95 rpm;
a3, when the mixture in the high-pressure polymerization kettle is heated to 75 ℃, adding 2g of ammonium persulfate solution (10 weight percent) and 2g of sodium bisulfite solution (10 weight percent) respectively to start the polymerization reaction; the initial monomer composition in mole percent is: 16% vinylidene fluoride, 38% tetrafluoroethylene, 46% hexafluoropropylene;
a4, after the reaction starts, the pressure is reduced, and the reaction rate is kept by periodically and continuously adding additional monomers to maintain the pressure of the high-pressure polymerization reaction kettle at 2.0MPa, controlling the reaction temperature at 75 ℃ and keeping the stirring speed at 95 rpm. The mole percentage composition of the supplementary monomers is as follows: 65% of vinylidene fluoride, 14% of tetrafluoroethylene and 21% of hexafluoropropylene. When the amount of the additional monomer reaches 1/5, 1/3, 1/2 and 2/3 of the total amount of the monomer (the total amount of the monomer is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 1g of ammonium persulfate solution (10 wt%), 1g of sodium bisulfite solution (10 wt%) and 3g of 4-iodoperfluorobutene are respectively added, when the amount of the additional monomer reaches 1/5, 2/5 and 3/5 of the total amount of the monomer (the total amount of the monomer is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 1.5g of diiodomethane is respectively added, and the reaction is stopped after 4 hours;
5. after the temperature of the kettle is reduced to room temperature, discharging the reaction emulsion, adding 80ml of magnesium sulfate solution (10 percent by weight) while stirring, coagulating the emulsion into rubber particles, filtering, repeatedly washing with deionized water for 5 times, finally loading into a tray, and drying in a vacuum oven at 120 ℃ for 12 hours to obtain 2.14Kg of dried polymer.
Example 9
This example was carried out in a 10L autoclave, wherein the total weight of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene added in this example was 2.3Kg, and the specific steps were:
a1, adding 5L of deionized water, 4g of dipotassium phosphate, 4g of diethyl malonate, 9g of 4-iodoperfluorobutene and 10g of ammonium salt of perfluoropolyether carboxylic acid (10 wt%) into a high-pressure polymerization reaction kettle, evacuating nitrogen for replacement, reducing the oxygen content in the high-pressure polymerization reaction kettle to be less than 25ppm, and raising the temperature of the high-pressure polymerization reaction kettle to 85 ℃;
a2, adding initial monomers (vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene) into the high-pressure polymerization reaction kettle by using a compressor, starting stirring when the pressure in the high-pressure polymerization reaction kettle is 2.0Mpa, and adjusting the rotating speed to be 99 rpm;
a3, adding 2g ammonium persulfate solution (10 wt%) when the mixture in the high-pressure polymerization kettle is heated to 90 ℃ to start the polymerization reaction; the initial monomer composition in mole percent is: 18% vinylidene fluoride, 38% tetrafluoroethylene, 44% hexafluoropropylene;
a4, after the reaction starts, the pressure is reduced, and the reaction rate is kept by periodically and continuously adding additional monomers to maintain the pressure of the high-pressure polymerization reaction kettle at 2.3MPa, controlling the reaction temperature at 90 ℃ and keeping the stirring speed at 99 rpm. The mole percentage composition of the supplementary monomers is as follows: 55% of vinylidene fluoride, 15% of tetrafluoroethylene and 30% of hexafluoropropylene. When the amount of the additional monomer reaches 1/5, 1/3, 1/2 and 2/3 of the total amount of the monomer (the total amount of the monomer is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 1g of ammonium persulfate solution (10 wt%) and 6g of 4-iodoperfluorobutene are respectively added, when the amount of the additional monomer reaches 1/5, 2/5 and 3/5 of the total amount of the monomer (the total amount of the monomer is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 2g of diethyl malonate is respectively added, and the reaction is stopped after 2.3 hours;
a5, discharging the reaction emulsion after the temperature of the kettle is reduced to room temperature, adding 80ml of magnesium sulfate solution (10 percent by weight) while stirring, coagulating the emulsion into rubber particles, filtering, repeatedly washing with deionized water for 5 times, finally dishing up, putting into a vacuum oven, and drying at 120 ℃ for 12h to obtain 2.19Kg of dried polymer.
Example 10
This example was carried out in a 10L autoclave, wherein the total weight of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene added in this example was 2.3Kg, and the specific steps were:
a1, adding 5L of deionized water, 4g of dipotassium phosphate, 7g of diethyl malonate, 9g of 4-iodoperfluorobutene and 12g of ammonium salt of perfluoropolyether carboxylic acid (10 wt%) into a high-pressure polymerization reaction kettle, evacuating nitrogen for replacement, reducing the oxygen content in the high-pressure polymerization reaction kettle to be less than 25ppm, and raising the temperature of the high-pressure polymerization reaction kettle to 90 ℃;
a2, adding initial monomers (vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene) into the high-pressure polymerization reaction kettle by using a compressor, starting stirring when the pressure in the high-pressure polymerization reaction kettle is 2.0Mpa, and adjusting the rotating speed to be 102 rpm;
a3, adding 2g ammonium persulfate solution (10 wt%) when the mixture in the high-pressure polymerization reaction kettle is heated to 95 ℃ to start the reaction; the initial monomer composition in mole percent is: 18% vinylidene fluoride, 36% tetrafluoroethylene, 46% hexafluoropropylene;
a4, after the reaction starts, the pressure is reduced, and the reaction rate is kept by periodically and continuously adding additional monomers to maintain the pressure of the high-pressure polymerization reaction kettle at 2.2MPa, controlling the reaction temperature at 95 ℃ and keeping the stirring speed at 102 rpm. The mole percentage composition of the supplementary monomers is as follows: 55% of vinylidene fluoride, 9% of tetrafluoroethylene and 36% of hexafluoropropylene. When the amount of the additional monomer reaches 1/5, 1/3, 1/2 and 2/3 of the total amount of the monomer (the total amount of the monomer, namely, the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 1g of ammonium persulfate solution (10 wt%) and 6g of 4-iodoperfluorobutene are respectively added, when the amount of the additional monomer reaches 1/5, 2/5 and 3/5 of the total amount of the monomer (the total amount of the monomer, namely, the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 3g of diethyl malonate is respectively added, and the reaction is stopped after 1.9 h.
A5, discharging the reaction emulsion after the temperature of the kettle is reduced to room temperature, adding 100ml of magnesium sulfate solution (10 percent by weight) while stirring, coagulating the emulsion into rubber particles, filtering, repeatedly washing with deionized water for 5 times, finally dishing up, putting into a vacuum oven, and drying at 120 ℃ for 12h to obtain 2.24Kg of dried polymer.
Example 11
This example was carried out in a 10L autoclave, wherein the total weight of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene added in this example was 2.3Kg, and the specific steps were:
a1, adding 5L of deionized water, 6g of dipotassium phosphate, 5g of diethyl malonate, 10g of 4-iodoperfluorobutene and 11g of ammonium salt of perfluoropolyether carboxylic acid (10 wt%) into a high-pressure polymerization reaction kettle, evacuating nitrogen for replacement, reducing the oxygen content in the high-pressure polymerization reaction kettle to be less than 25ppm, and raising the temperature of the high-pressure polymerization reaction kettle to 71 ℃;
a2, adding initial monomers (vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene) into the high-pressure polymerization reaction kettle by using a compressor, starting stirring when the pressure in the high-pressure polymerization reaction kettle is 2.3Mpa, and adjusting the rotating speed to 85 rpm;
a3, when the mixture in the high-pressure polymerization kettle is heated to 76 ℃, adding 2g of ammonium persulfate solution (10 weight percent) and 2g of sodium bisulfite solution (10 weight percent) respectively to start the polymerization reaction; the initial monomer composition in mole percent is: 21% vinylidene fluoride, 36% tetrafluoroethylene, 43% hexafluoropropylene;
a4, after the reaction starts, the pressure is reduced, and the reaction rate is kept by periodically and continuously adding additional monomers to maintain the pressure of the high-pressure polymerization reaction kettle at 2.6MPa, controlling the reaction temperature at 76 ℃ and keeping the stirring speed at 85 rpm. The mole percentage composition of the supplementary monomers is as follows: 58% of vinylidene fluoride, 11% of tetrafluoroethylene and 31% of hexafluoropropylene. When the amount of the additional monomer reaches 1/5, 1/3, 1/2 and 2/3 of the total amount of the monomer (the total amount of the monomer is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 1g of ammonium persulfate solution (10 wt%), 1g of sodium bisulfite solution (10 wt%) and 5g of 4-iodoperfluorobutene are respectively additionally added, when the amount of the additional monomer reaches 1/5, 2/5 and 3/5 of the total amount of the monomer (the total amount of the monomer is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 3g of diethyl malonate is respectively additionally added, and the reaction is stopped after 3.8 hours;
a5, discharging the reaction emulsion after the temperature of the kettle is reduced to room temperature, adding 80ml of magnesium sulfate solution (10 percent by weight) while stirring, coagulating the emulsion into rubber particles, filtering, repeatedly washing with deionized water for 5 times, finally dishing up, putting into a vacuum oven, and drying at 120 ℃ for 12h to obtain 2.12Kg of dried polymer.
Example 12
This example was carried out in a 10L autoclave, wherein the total weight of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene added in this example was 2.3Kg, and the specific steps were:
a1, adding 5L of deionized water, 4g of dipotassium phosphate, 2g of diethyl malonate, 8g of 4-iodoperfluorobutene and 12g of ammonium perfluoropolyether carboxylate (10 wt%) into a high-pressure polymerization reaction kettle, evacuating nitrogen for replacement, reducing the oxygen content in the high-pressure polymerization reaction kettle to be less than 25ppm, and raising the temperature of the high-pressure polymerization reaction kettle to 75 ℃;
a2, adding initial monomers (vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene) into the high-pressure polymerization reaction kettle by using a compressor, starting stirring when the pressure in the high-pressure polymerization reaction kettle is 2.5Mpa, and adjusting the rotating speed to 95 rpm;
a3, when the mixture in the high-pressure polymerization kettle is heated to 80 ℃, adding 2g of ammonium persulfate solution (10 weight percent) and 2g of sodium bisulfite solution (10 weight percent) respectively to start the polymerization reaction; the initial monomer composition in mole percent is: 17% vinylidene fluoride, 37% tetrafluoroethylene, 46% hexafluoropropylene;
a4, after the reaction starts, the pressure is reduced, and the reaction rate is kept by periodically and continuously adding additional monomers to maintain the pressure of the high-pressure polymerization reaction kettle at 3.0MPa, controlling the reaction temperature at 80 ℃ and keeping the stirring speed at 95 rpm. The mole percentage composition of the supplementary monomers is as follows: 50% of vinylidene fluoride, 12% of tetrafluoroethylene and 38% of hexafluoropropylene. When the amount of the additional monomer reaches 1/5, 1/3, 1/2 and 2/3 of the total amount of the monomer (the total amount of the monomer is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 1g of ammonium persulfate solution (10 wt%), 1g of sodium bisulfite solution (10 wt%) and 6g of 4-iodoperfluorobutene are respectively additionally added, when the amount of the additional monomer reaches 1/5, 2/5 and 3/5 of the total amount of the monomer (the total amount of the monomer is the total amount of the vinylidene fluoride, the tetrafluoroethylene and the hexafluoropropylene which are added in the embodiment), 2g of diethyl malonate is respectively additionally added, and the reaction is stopped after 3.1 h;
a5, discharging the reaction emulsion after the temperature of the kettle is reduced to room temperature, adding 90ml of magnesium sulfate solution (10 percent by weight) while stirring, coagulating the emulsion into rubber particles, filtering, repeatedly washing with deionized water for 5 times, finally dishing up, putting into a vacuum oven, and drying at 120 ℃ for 12h to obtain 2.18Kg of dried polymer.
Second, comparative example:
comparative example 1
The procedure of example 11 was followed, on the basis of example 11, using 28g of 1, 1-difluoro-2-bromoethylene in place of 30g of 4-iodoperfluorobutene and 9g of ammonium perfluorooctanoate (10 wt%) in place of 11g of ammonium perfluoropolyether carboxylate (10 wt%), to give 2.15Kg of fluororubber polymer designated fluororubber A.
Comparative example 2
A conventional ternary bisphenol fluororubber with Mooney viscosity ML (1+10) at 121 ℃ of 55 and fluorine content of 68.5 percent is taken and is marked as fluororubber B.
Third, Experimental example
1. The ternary peroxy fluororubbers prepared in examples 1 to 12, fluororubbers a and B prepared in comparative example 1 were examined, and the results are shown in table 1 below:
TABLE 1 Properties of the ternary Peroxyfluoroelastomers and fluororubbers A and B prepared in examples 1 to 12
Figure BDA0002465621430000201
2. The ternary peroxide fluororubbers prepared in examples 1 to 12 and the fluororubber a prepared in comparative example 1 were prepared into smart wearing wristband materials or watchband materials respectively, and the preparation method was as follows:
① formula:
100 parts of fluororubber; acid-absorbing agent: 5 parts of zinc oxide; filling agent: 20 parts of calcium silicate; filling agent: 10 parts of barium sulfate; colorant: 5 parts of pigment carbon black; processing aid: struktol HT-2900.5 parts; auxiliary vulcanizing agent: 3 parts of triallyl isocyanurate (TAIC); vulcanizing agent: 2 parts of 2, 5-di-tert-butylperoxy-2, 5-dimethylethane (bis-dipenta);
② the preparation method comprises the following steps:
b1 preparation of the binary Peroxyfluoroelastomers prepared in examples 1 to 12, fluororubber A prepared in comparative example 1;
b2, adding the binary peroxide fluororubber (or fluororubber B) prepared in the step B1, an acid acceptor, a filler, a colorant, a processing aid, an auxiliary vulcanizing agent and a vulcanizing agent into an internal mixer for mixing, and then performing back mixing on an open mill to prepare a binary peroxide fluororubber compound (or fluororubber compound);
when the internal mixer is used for mixing, the mixing is carried out for 480 seconds at the temperature of 95 ℃; when the open mill is used for carrying out the back smelting, the film is thinly passed for 3 times at the temperature of 75 ℃ and is discharged for cooling, and after the film is parked for 24H, the film is thinly passed for 5 times at the temperature of 85 ℃ on the open mill;
b3, sequentially carrying out first-stage vulcanization, second-stage vulcanization and hand feeling oil spraying on the binary peroxide fluororubber mixed rubber (or fluororubber mixed rubber) prepared in the step B2 to prepare a fluororubber wristband material or a fluororubber watchband material;
in the first-stage vulcanization, the vulcanization is carried out for 300 seconds at the temperature of 180 ℃; in the secondary vulcanization, vulcanization is carried out at a temperature of 200 ℃ for 4 hours.
The prepared intelligent wearing materials are respectively marked as material 1, material 2, material 3, material 4, material 5, material 6, material 7, material 8, material 9, material 10, material 11, material 12 and material A.
The composition of 100 parts of polymer B, 2.0 parts of bisphenol AF, 0.7 part of BPP (benzyl triphenyl phosphorus chloride), 3 parts of magnesium oxide, 6 parts of calcium hydroxide, 20 parts of calcium silicate, 10 parts of barium sulfate, 5 parts of pigment carbon black and 1 part of palm wax is mixed in an internal mixer, mixed for 8 minutes at 95 ℃, thinly passed on an open mill at 85 ℃ for 3 times of sheet discharging and cooling, the sheet is thinly passed on the open mill at 85 ℃ for 5 times of sheet discharging after being placed for 24 hours, and is subjected to primary vulcanization at 180 ℃ for 5 minutes and secondary vulcanization at 200 ℃ for 24 hours, and hand feeling oil is sprayed to prepare the vulcanized fluororubber wrist band and watch band material, wherein the material is marked as material B.
The materials 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, a and B were tested for their properties, and the results are shown in table 2 below:
TABLE 2 Intelligent wearing Material Performance Table
Figure BDA0002465621430000221
In table 2, the environmental related test results ND are represented as: the actual content of the substance is less than the detection limit of the method; test results show that the intelligent wearable wrist strap material and the watch strap material prepared from the ternary peroxide fluororubber prepared by the invention have excellent physical and mechanical properties, excellent swimming pool water resistance and medium resistance related to human skin, and the purpose of the invention is completely realized.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention.

Claims (13)

1. A ternary peroxide fluororubber is characterized in that: the structure of the compound is shown as a general formula I, a general formula II or a general formula III; wherein the content of the first and second substances,
the general formula I is as follows:
Figure FDA0002465621420000011
in the general formula I, R is I, CH2I、-CF2I or-CF2(CF2)nI, n is a natural number which is more than or equal to 1 and less than or equal to 11;
the general formula II is as follows:
Figure FDA0002465621420000012
in the general formula II, R is I, CH2I、-CF2I or-CF2(CF2)nI, n is a natural number which is more than or equal to 1 and less than or equal to 11; x1Hydrogen atom and fluorine atom; rf 1Is a fluoroalkylene, perfluoroalkylene, fluoropolyoxyalkylene, or perfluoropolyoxyalkylene group; x2Is an iodine atom;
the general formula III is as follows:
Figure FDA0002465621420000013
in the general formula III, X1Hydrogen atom and fluorine atom; rf 1Is a fluoroalkylene, perfluoroalkylene, fluoropolyoxyalkylene, or perfluoropolyoxyalkylene group; x2Is an iodine atom.
2. The ternary perfluoroelastomer according to claim 1, characterized in that: the Mooney viscosity ML (1+10) is 15-70 at 121 ℃, and the fluorine content is 67-70.5%.
3. The method for producing a ternary perfluoroelastomer according to claim 1 or 2, characterized in that: carrying out polymerization reaction on deionized water, an emulsifier, a pH buffer agent, an initiator, a chain transfer agent and a polymerization monomer in a high-pressure polymerization reaction kettle to prepare ternary perfluoroethylene-propylene-diene monomer; the polymerization monomers of the general formula I are vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene, and the polymerization monomers of the general formula II and the general formula III are the vinylidene fluoride, the tetrafluoroethylene, the hexafluoropropylene and a vulcanization point active monomer.
4. The method for producing a ternary perfluoroelastomer according to claim 3, wherein: in the polymerization reaction, the deionized water, the emulsifier, the pH buffer, the initiator, the chain transfer agent and the polymerization monomer are respectively used in the following parts by weight: 250 parts of deionized water, 0.02-0.75 part of emulsifier, 0.01-0.5 part of pH buffer, 0.02-0.25 part of initiator, 0.1-1.8 part of chain transfer agent and 100 parts of polymerization monomer;
when the polymer of the general formula I is polymerized, the molar ratio of the vinylidene fluoride to the tetrafluoroethylene to the hexafluoropropylene is 45-65: 5-20: 20-45 parts of;
when the polymer of the general formula II is polymerized, the molar ratio of the vinylidene fluoride, the tetrafluoroethylene, the hexafluoropropylene and the vulcanization point active monomer is 45-65: 5-20: 20-45: 0.05-1.8;
when the polymer of the general formula III is polymerized, the molar ratio of the vinylidene fluoride, the tetrafluoroethylene, the hexafluoropropylene and the vulcanization point active monomer is 45-65: 5-20: 20-45: 0.1-2.5.
5. The method for producing a ternary perfluoroelastomer according to claim 4, wherein: when the polymer of the general formula I is polymerized, the molar ratio of the vinylidene fluoride to the tetrafluoroethylene to the hexafluoropropylene is 50-65: 5-20: 20-40 parts of;
when the polymer of the general formula II is polymerized, the molar ratio of the vinylidene fluoride, the tetrafluoroethylene, the hexafluoropropylene and the vulcanization point active monomer is 50-65: 5-20: 20-40: 0.1-1.5;
when the polymer of the general formula III is polymerized, the molar ratio of the vinylidene fluoride, the tetrafluoroethylene, the hexafluoropropylene and the vulcanization point active monomer is 50-65: 5-20: 20-40: 0.25-1.8.
6. The method for producing a ternary perfluoroelastomer according to claim 5, wherein: the structure of the vulcanization point active monomer is shown as a general formula IV or V:
the general formula IV is as follows: CX1 2＝CX1-Rf 1X2；
The general formula V is: CX1 2＝CX1X2；
In the general formulae IV and V, X1Hydrogen atom and fluorine atom; rf 1Is a fluoroalkylene, perfluoroalkylene, fluoropolyoxyalkylene, or perfluoropolyoxyalkylene group; x2Is an iodine atom.
7. The method for producing a ternary perfluoroelastomer according to claim 6, wherein: the active monomer of the vulcanization point is 2, 2-difluoroiodoethylene, trifluoroiodoethylene, 4-iodine-3, 3, 4, 4-tetrafluorobutene, 4-iodoperfluorobutene or allyl iodine.
8. The method for producing a ternary perfluoroelastomer according to claim 7, wherein: when the polymers in the general formula I and the general formula II are polymerized, the chain transfer agent is an iodine-containing chain transfer agent;
the iodine-containing chain transfer agent is a monoiodide compound and/or a diiodo compound;
the monoiodine compound is any one or a mixture of any more of methyl iodide, monoiodoperfluoromethane, monoiodoperfluoroethane, monoiodoperfluoropropane, monoiodoperfluorobutane, monoiodoperfluoropentane, monoiodoperfluorohexane, monoiodoperfluoroheptane and monoiodoperfluorooctane;
the diiodo compound is any one or a mixture of any more of diiodomethane, diiododifluoromethane, 1, 2 diiodoperfluoroethane, 1, 3 diiodoperfluoropropane, 1, 4 diiodoperfluorobutane, 1, 6 diiodoperfluorohexane and 1, 8 diiodoperfluorooctane;
when the polymer in the general formula III is polymerized, the chain transfer agent is a non-iodine chain transfer agent;
the non-iodine chain transfer agent is any one or a mixture of any more of vinyl acetate, dimethyl malonate and diethyl malonate.
9. The process for producing a binary perfluoroelastomer according to claim 8, wherein: the iodine-containing chain transfer agent is diiodomethane, 1, 2 diiodoperfluoroethane, 1, 3 diiodoperfluoropropane, 1, 4 diiodoperfluorobutane, 1, 6 diiodoperfluorohexane, monoiodoperfluoromethane and monoiodoperfluoroethane;
the atypical chain transfer agent is vinyl acetate, dimethyl malonate and diethyl malonate.
10. The method for producing a ternary perfluoroelastomer according to claim 9, wherein: the preparation method of the ternary peroxide fluororubber comprises the following specific steps:
a1, adding deionized water, an emulsifier and a pH buffer agent into the high-pressure polymerization reaction kettle, introducing nitrogen to discharge oxygen in the high-pressure polymerization reaction kettle, and starting heating;
a2, respectively introducing the initial monomers into a high-pressure polymerization reaction kettle by a compressor to ensure that the pressure in the reaction kettle reaches 1.6-2.7 Mpa, and starting stirring; the initial monomer is vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene
A3, when the mixture in the high-pressure polymerization reaction kettle is heated to 60-95 ℃, adding an initiator to start polymerization reaction;
a4, adding the initiator 2-5 times in the polymerization process; adding a chain transfer agent for 2-8 times; if the polymerization monomer comprises a vulcanization point monomer, adding the vulcanization point monomer for 2-6 times; replenishing supplementary monomers at intervals, wherein the supplementary monomers are vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene, keeping the pressure at 2.0-3.2 Mpa and the temperature at 75-95 ℃ in the polymerization process, and keeping stirring;
and A5, after the polymerization reaction is finished, removing the emulsion from the high-pressure polymerization reaction kettle, and obtaining the ternary fluorine rubber peroxide after coagulation, washing and drying.
11. The utility model provides a wrist strap material or watchband material are dressed to intelligence which characterized in that: the ternary peroxide fluororubber prepared by the preparation method of any one of claims 3-10 is used for preparing materials of intelligent wearing wristbands or watchbands.
12. A preparation method of an intelligent wearable wrist strap material or a watchband material is characterized by comprising the following steps: the method comprises the following steps:
b1, the ternary perfluoronated rubber prepared by the preparation method of any one of claims 3 to 10;
b2, adding the ternary peroxide fluororubber prepared in the step B1, an acid-absorbing agent, a filling agent, a coloring agent, a processing aid, an auxiliary vulcanizing agent and a vulcanizing agent into an internal mixer for mixing, and then performing back mixing on an open mill to prepare a ternary peroxide fluororubber compound;
when the internal mixer is used for mixing, the temperature is 80-115 ℃, and the mixing time is 180-600 seconds; when the open mill carries out remill, the temperature is 60-95 ℃, and the thin passing is carried out for 3-8 times;
b3, sequentially carrying out first-stage vulcanization, second-stage vulcanization and hand feeling oil spraying on the ternary peroxide fluororubber compound prepared in the step B2 to prepare a fluororubber wristband material or a fluororubber watchband material; in the first-stage vulcanization, the temperature is 170-190 ℃, and the vulcanization time is 120-500 seconds; in the secondary vulcanization, the temperature is 175-230 ℃, and the vulcanization time is 1-4 hours.
13. The method for preparing a smart wearing wristband material or a wristband material according to claim 12, wherein the method comprises the following steps: in the step B2, the prepared ternary peroxide fluororubber compound comprises the following components in parts by weight: 100 parts of ternary fluorine peroxide rubber; 3-10 parts of an acid absorbent; 10-50 parts of a filling agent; 2-10 parts of a coloring agent; 0.3-1.5 parts of processing aid; 1-4 parts of auxiliary vulcanizing agent; 1-4 parts of a vulcanizing agent;
the acid absorbing agent, the filling agent, the coloring agent, the processing aid, the auxiliary vulcanizing agent and the vulcanizing agent are respectively as follows:
the acid absorbent is any one of zinc oxide, hydrotalcite and magnesium oxide;
the filler is any one or a mixture of any more of barium sulfate, calcium silicate, carbon black, diatomite, silica micropowder and white carbon black;
the colorant is any one or a mixture of any more of pigment carbon black, titanium dioxide, halogen-free organic blue pigment, halogen-free organic yellow pigment, halogen-free organic red pigment, iron oxide red, iron oxide yellow and iron oxide green;
the processing aid is any one or a mixture of any several of palm wax, WS280 and HT-290;
the auxiliary vulcanizing agent is any one of triallyl isocyanurate, triallyl cyanurate, tri-allyl tri-isocyanate and trihydroxy methyl propane tri-methacrylate;
the vulcanizing agent is any one of di-tert-butylperoxyisopropyl benzene, 2, 5-di-tert-butylperoxy-2, 5-dimethyl ethane, dicumyl peroxide and peroxy-2-ethylhexyl tert-butyl carbonate.
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