CN115466344B - Transparent peroxyfluororubber intelligent wearing material and preparation method thereof - Google Patents
Transparent peroxyfluororubber intelligent wearing material and preparation method thereof Download PDFInfo
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- CN115466344B CN115466344B CN202211151267.1A CN202211151267A CN115466344B CN 115466344 B CN115466344 B CN 115466344B CN 202211151267 A CN202211151267 A CN 202211151267A CN 115466344 B CN115466344 B CN 115466344B
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- 239000000463 material Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 81
- 239000000178 monomer Substances 0.000 claims abstract description 60
- 238000004073 vulcanization Methods 0.000 claims abstract description 51
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 34
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920001971 elastomer Polymers 0.000 claims abstract description 32
- 229920001973 fluoroelastomer Polymers 0.000 claims abstract description 32
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 73
- 239000000203 mixture Substances 0.000 claims description 61
- 238000003756 stirring Methods 0.000 claims description 34
- 239000003995 emulsifying agent Substances 0.000 claims description 22
- 239000000839 emulsion Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 18
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000012763 reinforcing filler Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 16
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 14
- JILAKKYYZPDQBE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)I JILAKKYYZPDQBE-UHFFFAOYSA-N 0.000 claims description 12
- 150000007942 carboxylates Chemical class 0.000 claims description 12
- SOEBNUZZZSSRNB-UHFFFAOYSA-N difluoro(diiodo)methane Chemical compound FC(F)(I)I SOEBNUZZZSSRNB-UHFFFAOYSA-N 0.000 claims description 12
- 150000002978 peroxides Chemical class 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 11
- 238000009775 high-speed stirring Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229920002379 silicone rubber Polymers 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000004945 silicone rubber Substances 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000006179 pH buffering agent Substances 0.000 claims description 5
- 239000010702 perfluoropolyether Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 claims description 2
- 239000013638 trimer Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 abstract description 20
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- -1 perfluoroalkyl iodide Chemical compound 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 40
- 230000000052 comparative effect Effects 0.000 description 19
- 238000009472 formulation Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 10
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical group [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 230000001502 supplementing effect Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012780 transparent material Substances 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QZGNGBWAMYFUST-UHFFFAOYSA-N 2-bromo-1,1-difluoroethene Chemical group FC(F)=CBr QZGNGBWAMYFUST-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
Classifications
-
- 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
- C08F214/282—Hexyfluoropropene with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/20—Homopolymers or copolymers of hexafluoropropene
-
- 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
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
-
- 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
- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1408—Monomers containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a transparent intelligent peroxyfluororubber wearing material and a preparation method thereof, belongs to the technical field of fluorine-containing high polymer materials, and solves the technical problem that the color of the peroxyfluororubber in the prior art changes after vulcanization, and the transparent intelligent wearing material cannot be manufactured. The transparent peroxy fluororubber is prepared by taking perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene as main polymerization monomers and perfluoroalkyl iodide as a chain transfer agent. Compared with the traditional peroxyfluororubber, the perfluoromethyl vinyl ether is used for replacing vinylidene fluoride, so that the molecular chain does not contain hydrogen, and the color is not changed after vulcanization. The transparent peroxyfluororubber raw rubber and the formula of the rubber compound meet the preparation requirements of transparent intelligent wearing materials. The transparent intelligent wearing product prepared by the method has the performances of high transparency, safety, environmental protection, comfortable body feeling and the like, and can better meet the increasingly-changing market requirements of intelligent wearing materials.
Description
Technical Field
The invention belongs to the technical field of fluorine-containing high polymer materials, and particularly relates to a transparent peroxy fluororubber intelligent wearing material and a preparation method thereof.
Background
In recent years, following the tide of smartphones, smart wearable devices have become new hotspots. Because excellent intelligent interactive function, intelligent wearing products such as intelligent wrist-watch, intelligent bracelet, AI eyes receive the favor of more and more consumers, have driven the huge market demand of intelligent wearing material. The traditional intelligent wearing materials mainly adopt metal materials, leather materials, silicon rubber, thermoplastic elastomers and the like, and the peroxyfluororubber is gradually becoming a new preference of the intelligent wearing materials in recent years by virtue of excellent physical and chemical properties.
The following are some typical examples of conventional peroxyfluororubber materials and methods for their preparation: patent CN106832691B discloses a method for preparing a binary fluororubber watchband material vulcanized by peroxide, wherein fluororubber takes vinylidene fluoride, hexafluoropropylene and 1, 1-difluoro-2-bromoethylene as comonomers; patent CN103342772B discloses a process for preparing a peroxide curable fluoroelastomer, which is a vinylidene fluoride as a first comonomer and one or more of hexafluoropropylene, tetrafluoroethylene, chlorotrifluoroethylene as a second comonomer; patent CN104558364B discloses a fluoroelastomer and a method for preparing the same, wherein the fluoroelastomer comprises vinylidene fluoride, hexafluoropropylene and perfluoromethyl vinyl ether as comonomers; patent CN111057178B discloses a process for the preparation of low pressure variable fluoroelastomers based on vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoromethyl vinyl ether as comonomer. Although the traditional peroxyfluororubber material and the preparation method thereof meet the requirements of safety, environmental protection, comfort, durability and the like, the traditional peroxyfluororubber can not be used for manufacturing transparent peroxyfluororubber intelligent wearing materials, and can not meet the requirements of continuous change of consumers on colors.
The peroxyfluororubber material and the preparation method thereof in the prior art have at least the following defects:
1. the traditional comonomer of the peroxy fluororubber contains vinylidene fluoride, and the molecular chain of the comonomer contains hydrogen element, so that yellowing can be generated in the vulcanization process, and the comonomer cannot be used for transparent materials; 2. in the traditional formula of the peroxyfluororubber material, the vulcanizing agent TAIC and the vulcanizing accelerator double 2,5 take inorganic filler as a carrier, so that the transparency of the material is affected; 3. white inorganic reinforcing fillers in the traditional peroxyfluororubber material formula, such as: diatomaceous earth, calcium silicate, barium sulfate, etc., cannot be used for transparent materials; 4. processing aids in conventional peroxyfluororubber material formulations, such as: WS280, HT290, octadecylamine, palm wax, etc., cannot be used for transparent materials; 5. in the traditional synthetic process of the raw rubber of the peroxyfluororubber, more than two-order metal salt is needed to be used as a coagulant for emulsion coagulation, and the transparency of the material is affected by the residual metal salt.
In view of this, there is a need for further improvements in the existing peroxyfluororubber smart wear materials and methods for making the same.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a transparent intelligent peroxyfluororubber wearing material and a preparation method thereof, and aims to make the manufactured intelligent peroxyfluororubber wearing material transparent.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a preparation method of a transparent peroxyfluororubber intelligent wearing material comprises the following steps:
(1) Preparing transparent peroxyfluororubber raw rubber:
1-1, adding deionized water, an emulsifying agent, a pH buffering agent and a chain transfer agent into a high-pressure polymerization reaction kettle, and deoxidizing to reduce the oxygen content in the reaction kettle;
1-2, adding an initial mixed monomer into a high-pressure polymerization reaction kettle until the pressure in the high-pressure polymerization reaction kettle is about 2.2Mpa, starting stirring, maintaining the stirring speed of 85-105rpm, starting heating, adding an initiator when the temperature in the reaction kettle is raised to 55-80 ℃, and starting polymerization reaction;
1-3, continuously adding main polymerization monomers in the polymerization reaction process, maintaining the pressure of the reaction kettle at 2.5-4.0MPa, simultaneously adding an initiator and a chain transfer agent at intervals, maintaining the stirring speed at 85-105rpm, and maintaining the temperature of the reaction kettle at 80-95 ℃;
1-4, after the reaction is finished, stirring and condensing the emulsion at a high speed, washing, vacuumizing and drying to obtain transparent peroxy fluororubber raw rubber;
wherein the initial mixed monomer and the main polymerized monomer are the mixture of perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene, and the mole percentages of the components in the initial mixed monomer and the main polymerized monomer are different;
(2) The transparent peroxyfluororubber intelligent wearing material is prepared by the following steps:
adding the transparent peroxide fluororubber raw rubber prepared in the step (1), a reinforcing filler, a processing aid, a vulcanizing agent and a vulcanization accelerator into an internal mixer for mixing, standing for 24 hours at room temperature, then carrying out back mixing on an open mill to prepare transparent peroxide fluororubber compound, and carrying out vulcanization treatment on the transparent peroxide fluororubber compound to prepare the transparent peroxide fluororubber intelligent wearing material.
Preferably, the deoxidizing mode in the step 1-1 is to fill nitrogen to deoxidize or to vacuumize by a vacuum pump to deoxidize.
Preferably, the Mooney viscosity ML121 ℃ 1+10 of the transparent peroxyfluororubber raw rubber prepared in the step (1) is 20-60.
Preferably, the molar ratio of perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene in the initial mixed monomer is 30:5:65, wherein the molar ratio of the perfluoromethyl vinyl ether to the tetrafluoroethylene to the hexafluoropropylene in the main polymerization monomer is 20-40:5-15:75-45, preferably 25:7:68 or 30:10:60 or 40:15: 45.
Preferably, the high-speed stirring in step 1-4 means that the stirring speed is 800-1500rpm, preferably 900-1200 rpm.
Preferably, the components in the step (1) are used in the following amounts in parts by weight: 250 parts of deionized water, 0.03-0.4 part of emulsifying agent, 0.02-0.35 part of pH buffering agent, 0.1-0.35 part of initiator, 0.3-2.5 parts of chain transfer agent and 100 parts of main polymerized monomer of fluororubber. The fluororubber main polymerization monomer includes the initial mixture monomer and the main polymerization monomer.
Further preferred, the emulsifier is an amine perfluoropolyether carboxylate, wherein the ammonium perfluoropolyether carboxylate is made from a trimer of hexafluoropropylene oxide in an amount of 0.03 to 0.4 parts, preferably in an amount of 0.12 to 0.3 parts; the PH buffer is sodium bicarbonate, the dosage is 0.02-0.35 part, and the preferable dosage is 0.08-0.25 part; the initiator is ammonium persulfate, the dosage is 0.1-0.35 part, the preferable dosage is 0.15-0.35 part, the chain transfer agent is perfluoroalkyl iodine chain transfer agent, namely the mixture of diiododifluoromethane and 1,4 diiodoperfluorobutane, and the weight ratio of the diiododifluoromethane to the 1,4 diiodoperfluorobutane in the mixture is 3:1, the perfluoroalkyl iodide chain transfer agent is used in an amount of 0.3 to 2.5 parts, preferably in an amount of 0.8 to 2.0 parts.
Preferably, the amount of each component in the step (2) is as follows: 100 parts of transparent peroxyfluororubber raw rubber, 5-20 parts of reinforcing filler, 0.5-2.0 parts of processing aid, 1.5-3.0 parts of vulcanizing agent and 1.5-3.0 parts of vulcanization accelerator;
further preferably, the reinforcing filler is anhydrous weather white carbon black, the processing aid is a raw silicone rubber (the dosage is 0.5-2.0 parts, preferably 1.0-2.0 parts; in research, we find that the raw silicone rubber can replace the traditional processing aid and can endow transparent peroxyfluororubber with excellent demolding performance and transparency), the vulcanizing agent is a high-purity product (no carrier, 1.5-3.0 parts, preferably 2.0-3.0 parts) of triallyl isocyanurate (TAIC), and the vulcanization accelerator is: high purity 2, 5-di-tert-butylperoxy-2, 5-dimethylethane (bis 2, 5) (no carrier, 1.5-3.0 parts, preferably 1.5-2.5).
Preferably, the vulcanization treatment in the step (2) is a sectional vulcanization treatment, comprising a primary vulcanization and a secondary vulcanization, wherein in the primary vulcanization, the temperature is 160-180 ℃, and the vulcanization time is 180-500 seconds; in the second-stage vulcanization, the temperature is 175-200 ℃, the vulcanization time is 2-4 hours, and the second-stage vulcanization is carried out after the first-stage vulcanization is finished and cooled to room temperature.
Compared with the prior art, the invention has at least the following beneficial effects:
the transparent peroxyfluororubber intelligent wearing material and the preparation method thereof provided by the invention utilize the transparent peroxyfluororubber raw rubber to prepare the intelligent wearing material. The transparent intelligent wearing material of the peroxyfluororubber prepared by the method solves the technical problems that the peroxyfluororubber in the prior art changes color after vulcanization and cannot be manufactured, and adopts specific reinforcing filler, processing aid, vulcanizing agent and the like, thereby realizing high transparency of the material under the condition of ensuring excellent physical and mechanical properties and chemical stability of the material.
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 will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
The invention provides a transparent peroxyfluororubber intelligent wearing material and a preparation method thereof.
1. Preparation of transparent raw peroxyfluororubber
Example 1
The reaction was carried out in a 10L high-pressure polymerization reactor, and the total weight of perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene added in this example was 2.0. 2.0 Kg, which comprises the following steps:
a1, adding 5L of deionized water, 3.0g of sodium bicarbonate, 4g of a chain transfer agent mixture (a mixture of diiododifluoromethane and 1, 4-diiodoperfluorobutane 3:1) and 40g of an emulsifier solution (10 wt% emulsifier solution prepared by ammonium perfluor polyether carboxylate) into a high-pressure polymerization reaction kettle, and filling nitrogen to remove oxygen (or vacuumizing by a vacuum pump) until the oxygen content in the high-pressure polymerization reaction kettle is lower than 30ppm;
a2, adding an initial mixed monomer (the molar percentage of the initial mixed monomer: perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene is 30:5:65) into the high-pressure polymerization reaction kettle by using a compressor until the pressure in the high-pressure polymerization reaction kettle is about 2.2Mpa, starting stirring, and regulating the rotating speed to be 100rpm; starting the mixture in the high-pressure polymerization reaction kettle, adding 20g of initiator ammonium persulfate solution (10 wt%) when the mixture is heated to 70 ℃, and starting the polymerization reaction;
a3, after the reaction starts, the pressure is reduced, the reaction kettle pressure is maintained at 3.7MPa, the reaction temperature is controlled at 88 ℃ by periodically and continuously supplementing main polymerized monomers (the molar percentage of the main polymerized monomers: perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene is 20:5:75), the stirring rotation speed is maintained at 100rpm to maintain the reaction rate, and the reaction is terminated after the ammonium persulfate solution (10 wt%) 6g and the chain transfer agent mixture 4g and 8h are respectively supplemented in the reaction for 1.0h, 2.0h, 3.5h, 4.5h and 6 h;
a4, discharging the reaction emulsion after the kettle temperature of the high-pressure polymerization kettle is reduced to room temperature, and performing high-speed stirring demulsification (stirring speed 1000 rpm) to coagulate the emulsion into rubber particles; and (3) repeatedly washing the polymer with deionized water for 8 times after filtering, finally, dishing the polymer, and putting the polymer into a vacuum oven to dry the polymer for 12 hours at the temperature of 120 ℃ to obtain 1.89Kg of dried polymer.
Example 2
The reaction was carried out in a 10L high-pressure polymerization reactor, and the total weight of perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene added in this example was 2.0. 2.0 Kg, which comprises the following steps:
a1, adding 5L of deionized water, 3.0g of sodium bicarbonate, 4g of a chain transfer agent mixture (a mixture of diiododifluoromethane and 1, 4-diiodoperfluorobutane 3:1) and 40g of an emulsifier solution (10 wt% emulsifier solution prepared by ammonium perfluor polyether carboxylate) into a high-pressure polymerization reaction kettle, and filling nitrogen to remove oxygen (or vacuumizing by a vacuum pump) until the oxygen content in the high-pressure polymerization reaction kettle is lower than 30ppm;
a2, adding an initial mixed monomer (the molar percentage of the initial mixed monomer: perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene is 30:5:65) into the high-pressure polymerization reaction kettle by using a compressor until the pressure in the high-pressure polymerization reaction kettle is about 2.2Mpa, starting stirring, and regulating the rotating speed to be 100rpm; starting the mixture in the high-pressure polymerization reaction kettle, adding 20g of initiator ammonium persulfate solution (10 wt%) when the mixture is heated to 70 ℃, and starting the polymerization reaction;
a3, after the reaction starts, the pressure is reduced, the reaction kettle pressure is maintained at 3.7MPa by periodically and continuously supplementing main polymerized monomers (the molar percentage of the main polymerized monomers: perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene is 25:7:68), the reaction temperature is controlled at 88 ℃, the stirring rotation speed is kept at 100rpm to maintain the reaction rate, and the reaction is terminated after the ammonium persulfate solution (10 wt%) 6g and the chain transfer agent mixture 4g and 8h are respectively supplemented in the reaction for 1.0h, 2.0h, 3.5h, 4.5h and 6 h;
a4, discharging the reaction emulsion after the kettle temperature of the high-pressure polymerization kettle is reduced to room temperature, and performing high-speed stirring demulsification (stirring speed 1000 rpm) to coagulate the emulsion into rubber particles; and (3) repeatedly washing the polymer with deionized water for 8 times after filtering, finally, dishing the polymer, and putting the polymer into a vacuum oven to dry the polymer for 12 hours at the temperature of 120 ℃ to obtain 1.89Kg of dried polymer.
Example 3
The reaction was carried out in a 10L high-pressure polymerization reactor, and the total weight of perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene added in this example was 2.0. 2.0 Kg, which comprises the following steps:
a1, adding 5L of deionized water, 3.0g of sodium bicarbonate, 4g of a chain transfer agent mixture (a mixture of diiododifluoromethane and 1, 4-diiodoperfluorobutane 3:1) and 40g of an emulsifier solution (10 wt% emulsifier solution prepared by ammonium perfluor polyether carboxylate) into a high-pressure polymerization reaction kettle, and filling nitrogen to remove oxygen until the oxygen content in the high-pressure polymerization reaction kettle is lower than 30ppm;
a2, adding an initial mixed monomer (the molar percentage of the initial mixed monomer: perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene is 30:5:65) into the high-pressure polymerization reaction kettle by using a compressor until the pressure in the high-pressure polymerization reaction kettle is about 2.2Mpa, starting stirring, and regulating the rotating speed to be 100rpm; starting the mixture in the high-pressure polymerization reaction kettle, adding 20g of initiator ammonium persulfate solution (10 wt%) when the mixture is heated to 70 ℃, and starting the polymerization reaction;
a3, after the reaction starts, the pressure is reduced, the reaction kettle pressure is maintained at 3.7MPa by periodically and continuously supplementing main polymerized monomers (the molar percentage of the main polymerized monomers: perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene is 30:10:60), the reaction temperature is controlled at 88 ℃, the stirring rotation speed is kept at 100rpm to maintain the reaction rate, and the reaction is terminated after the ammonium persulfate solution (10 wt%) 6g and the chain transfer agent mixture 4g and 8h are respectively supplemented in the reaction for 1.0h, 2.0h, 3.5h, 4.5h and 6 h;
a4, discharging the reaction emulsion after the kettle temperature of the high-pressure polymerization kettle is reduced to room temperature, and performing high-speed stirring demulsification (stirring speed 1000 rpm) to coagulate the emulsion into rubber particles; and (3) repeatedly washing the polymer with deionized water for 8 times after filtering, finally, dishing the polymer, and putting the polymer into a vacuum oven to dry the polymer for 12 hours at the temperature of 120 ℃ to obtain 1.92Kg of dried polymer.
Example 4
The reaction was carried out in a 10L high-pressure polymerization reactor, and the total weight of perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene added in this example was 2.0. 2.0 Kg, which comprises the following steps:
a1, adding 5L of deionized water, 3.0g of sodium bicarbonate, 4g of a chain transfer agent mixture (a mixture of diiododifluoromethane and 1, 4-diiodoperfluorobutane 3:1) and 40g of an emulsifier solution (10 wt% emulsifier solution prepared by ammonium perfluor polyether carboxylate) into a high-pressure polymerization reaction kettle, and filling nitrogen to remove oxygen until the oxygen content in the high-pressure polymerization reaction kettle is lower than 30ppm;
a2, adding an initial mixed monomer (the molar percentage of the initial mixed monomer: perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene is 30:5:65) into the high-pressure polymerization reaction kettle by using a compressor until the pressure in the high-pressure polymerization reaction kettle is about 2.2Mpa, starting stirring, and regulating the rotating speed to be 100rpm; starting the mixture in the high-pressure polymerization reaction kettle, adding 20g of initiator ammonium persulfate solution (10 wt%) when the mixture is heated to 70 ℃, and starting the polymerization reaction;
a3, after the reaction starts, the pressure is reduced, the reaction kettle pressure is maintained at 3.7MPa by periodically and continuously supplementing main polymerized monomers (the molar percentage of the main polymerized monomers: perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene is 35:10:55), the reaction temperature is controlled at 88 ℃, the stirring rotation speed is kept at 100rpm to maintain the reaction rate, and the reaction is terminated after the ammonium persulfate solution (10 wt%) 6g and the chain transfer agent mixture 4g and 8h are respectively supplemented in the reaction for 1.0h, 2.0h, 3.5h, 4.5h and 6 h;
a4, discharging the reaction emulsion after the kettle temperature of the high-pressure polymerization kettle is reduced to room temperature, and performing high-speed stirring demulsification (stirring speed 1000 rpm) to coagulate the emulsion into rubber particles; and (3) repeatedly washing the polymer with deionized water for 8 times after filtering, finally, dishing the polymer, and putting the polymer into a vacuum oven to dry the polymer for 12 hours at the temperature of 120 ℃ to obtain 1.90Kg of dried polymer.
Example 5
The reaction was carried out in a 10L high-pressure polymerization reactor, and the total weight of perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene added in this example was 2.0. 2.0 Kg, which comprises the following steps:
a1, adding 5L of deionized water, 3.0g of sodium bicarbonate, 4g of a chain transfer agent mixture (a mixture of diiododifluoromethane and 1, 4-diiodoperfluorobutane 3:1) and 40g of an emulsifier solution (10 wt% emulsifier solution prepared by ammonium perfluor polyether carboxylate) into a high-pressure polymerization reaction kettle, and filling nitrogen to remove oxygen until the oxygen content in the high-pressure polymerization reaction kettle is lower than 30ppm;
a2, adding an initial mixed monomer (the molar percentage of the initial mixed monomer: perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene is 30:5:65) into the high-pressure polymerization reaction kettle by using a compressor until the pressure in the high-pressure polymerization reaction kettle is about 2.2Mpa, starting stirring, and regulating the rotating speed to be 100rpm; starting the mixture in the high-pressure polymerization reaction kettle, adding 20g of initiator ammonium persulfate solution (10 wt%) when the mixture is heated to 70 ℃, and starting the polymerization reaction;
a3, after the reaction starts, the pressure is reduced, the reaction kettle pressure is maintained at 3.7MPa by periodically and continuously supplementing main polymerized monomers (the molar percentage of the main polymerized monomers: perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene is 40:15:45), the reaction temperature is controlled at 88 ℃, the stirring rotation speed is maintained at 100rpm to maintain the reaction rate, and the reaction is terminated after the ammonium persulfate solution (10 wt%) 6g and the chain transfer agent mixture 4g and 8h are respectively supplemented in the reaction for 1.0h, 2.0h, 3.5h, 4.5h and 6 h;
a4, discharging the reaction emulsion after the kettle temperature of the high-pressure polymerization kettle is reduced to room temperature, and performing high-speed stirring demulsification (stirring speed 1000 rpm) to coagulate the emulsion into rubber particles; and (3) repeatedly washing the polymer with deionized water for 8 times after filtering, finally, dishing the polymer, and putting the polymer into a vacuum oven to dry the polymer for 12 hours at the temperature of 120 ℃ to obtain 1.91Kg of dried polymer.
Comparative example 1
The reaction was carried out in a 10L high-pressure polymerization reactor, and the total weight of perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene added in this comparative example was 2.0. 2.0 Kg, which comprises the following steps:
a1, adding 5L of deionized water, 3.0g of sodium bicarbonate, 4g of a chain transfer agent mixture (a mixture of diiododifluoromethane and 1, 4-diiodoperfluorobutane 3:1) and 40g of an emulsifier solution (10 wt% emulsifier solution prepared by ammonium perfluor polyether carboxylate) into a high-pressure polymerization reaction kettle, and filling nitrogen to remove oxygen until the oxygen content in the high-pressure polymerization reaction kettle is lower than 30ppm;
a2, adding an initial mixed monomer (the molar percentage of the initial mixed monomer: perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene is 30:5:65) into the high-pressure polymerization reaction kettle by using a compressor until the pressure in the high-pressure polymerization reaction kettle is about 2.2Mpa, starting stirring, and regulating the rotating speed to be 100rpm; starting the mixture in the high-pressure polymerization reaction kettle, adding 20g of initiator ammonium persulfate solution (10 wt%) when the mixture is heated to 70 ℃, and starting the polymerization reaction;
a3, after the reaction starts, the pressure is reduced, the reaction kettle pressure is maintained at 3.7MPa by periodically and continuously supplementing main polymerized monomers (the molar percentage of the main polymerized monomers: perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene is 40:15:45), the reaction temperature is controlled at 88 ℃, the stirring rotation speed is maintained at 100rpm to maintain the reaction rate, and the reaction is terminated after the ammonium persulfate solution (10 wt%) 6g and the chain transfer agent mixture 4g and 8h are respectively supplemented in the reaction for 1.0h, 2.0h, 3.5h, 4.5h and 6 h;
a4, discharging the reaction emulsion after the kettle temperature of the high-pressure polymerization kettle is reduced to room temperature, adding 80ml of magnesium sulfate solution (10%wt) while stirring, and agglomerating the emulsion into rubber particles; and (3) repeatedly washing the polymer with deionized water for 8 times after filtering, finally, dishing the polymer, and putting the polymer into a vacuum oven to dry the polymer for 12 hours at the temperature of 120 ℃ to obtain 1.93Kg of dried polymer.
Comparative example 2
The reaction was carried out in a 10L high-pressure polymerization reactor, and the total weight of perfluoromethyl vinyl ether, vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene added in this comparative example was 2.0. 2.0 Kg, which comprises the following steps:
a1, adding 5L of deionized water, 3.0g of sodium bicarbonate, 4g of a chain transfer agent mixture (a mixture of diiododifluoromethane and 1, 4-diiodoperfluorobutane 3:1) and 40g of an emulsifier solution (10 wt% emulsifier solution prepared by ammonium perfluor polyether carboxylate) into a high-pressure polymerization reaction kettle, and filling nitrogen to remove oxygen until the oxygen content in the high-pressure polymerization reaction kettle is lower than 30ppm;
a2, adding an initial mixed monomer (the molar percentage of the initial mixed monomer: perfluoromethyl vinyl ether, vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene is 15:20:10:55) into the high-pressure polymerization reaction kettle by using a compressor until the pressure in the high-pressure polymerization reaction kettle is about 2.2Mpa, starting stirring, and regulating the rotating speed to 100rpm; starting the mixture in the high-pressure polymerization reaction kettle, adding 20g of initiator ammonium persulfate solution (10 wt%) when the mixture is heated to 70 ℃, and starting the polymerization reaction;
a3, after the reaction starts, the pressure is reduced, the reaction kettle pressure is maintained to be 3.7MPa through periodically and continuously supplementing main polymerized monomers (the molar percentage of the main polymerized monomers is 20:20:15:45, namely perfluoromethyl vinyl ether, vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene), the reaction temperature is controlled to be 88 ℃, meanwhile, the stirring rotation speed is maintained to be 100rpm so as to maintain the reaction rate, and the reaction is terminated after the ammonium persulfate solution (10 wt percent) is respectively supplemented to the reaction for 1.0h, 2.0h, 3.5h, 4.5h and 6h, and the chain transfer agent mixture is 4g and 8 h;
a4, discharging the reaction emulsion after the kettle temperature of the high-pressure polymerization kettle is reduced to room temperature, and performing high-speed stirring demulsification (stirring speed 1000 rpm) to coagulate the emulsion into rubber particles; and (3) repeatedly washing the polymer with deionized water for 8 times after filtering, finally, dishing the polymer, and putting the polymer into a vacuum oven to dry the polymer for 12 hours at the temperature of 120 ℃ to obtain 1.92Kg of dried polymer.
Comparative example 3
The reaction was carried out in a 10L high-pressure polymerization reactor, and the total weight of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene added in this comparative example was 2.0. 2.0 Kg, which comprises the following steps:
a1, adding 5L of deionized water, 3.0g of sodium bicarbonate, 4g of a chain transfer agent mixture (a mixture of diiododifluoromethane and 1, 4-diiodoperfluorobutane 3:1) and 40g of an emulsifier solution (10 wt% emulsifier solution prepared by ammonium perfluor polyether carboxylate) into a high-pressure polymerization reaction kettle, and filling nitrogen to remove oxygen until the oxygen content in the high-pressure polymerization reaction kettle is lower than 30ppm;
a2, adding an initial mixed monomer (the molar percentage of the initial mixed monomer: vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene is 60:5:35) into the high-pressure polymerization reaction kettle by using a compressor until the pressure in the high-pressure polymerization reaction kettle is about 2.2Mpa, starting stirring, and regulating the rotating speed to be 100rpm; starting the mixture in the high-pressure polymerization reaction kettle, adding 20g of initiator ammonium persulfate solution (10 wt%) when the mixture is heated to 70 ℃, and starting the polymerization reaction;
a3, after the reaction starts, the pressure is reduced, the pressure of the reaction kettle is maintained to be 3.7MPa by periodically and continuously supplementing main polymerized monomers (the mol percentage of the main polymerized monomers: vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene is 65:10:25), the reaction temperature is controlled to be 88 ℃, the stirring rotation speed is kept at 100rpm to maintain the reaction rate, and the reaction is terminated after 6g of ammonium persulfate solution (10 wt%) and 4g of chain transfer agent mixture are respectively supplemented for 1.0h, 2.0h, 3.5h, 4.5h and 6 h;
a4, discharging the reaction emulsion after the kettle temperature of the high-pressure polymerization kettle is reduced to room temperature, adding 80ml of magnesium sulfate solution (10%wt) while stirring, and agglomerating the emulsion into rubber particles; and (3) repeatedly washing the polymer with deionized water for 8 times after filtering, finally, dishing the polymer, and putting the polymer into a vacuum oven to dry the polymer for 12 hours at the temperature of 120 ℃ to obtain 1.91Kg of dried polymer.
Comparative example 4
A commercially available conventional peroxyfluororubber SOLVAY P457 with a Mooney viscosity ML121 ℃ 1+10 of 21 and a fluorine content of 67% was taken.
The transparent peroxyfluororubbers prepared in examples 1 to 5, the peroxyfluororubbers prepared in comparative examples 1 to 3 and the commercially available peroxyfluororubbers of comparative example 4 were examined, and the examination results are shown in Table 1 below:
table 1 table of properties of transparent peroxyfluororubbers prepared in examples 1 to 5 and peroxyfluororubbers prepared in comparative examples 1 to 4
2. Intelligent wearing material for preparing transparent peroxyfluororubber
The transparent raw peroxyfluororubbers prepared in examples 1 to 5 and the peroxyfluororubbers prepared in comparative examples 1 to 4 were respectively prepared into smart wear materials, and the preparation was performed according to the following formulation and preparation method:
formula 1:
100 parts of fluororubber (raw rubber); reinforcing filler: 10 parts of anhydrous weather white carbon black; processing aid: 1.5 parts of raw silicone rubber; vulcanizing agent: 3 parts of liquid TAIC (high purity product); vulcanization accelerators: 2.5 parts of liquid bis 2,5 (high purity product);
formula 2:
100 parts of fluororubber (raw rubber); reinforcing filler: 10 parts of anhydrous weather white carbon black; processing aid: WS 280.5 parts; vulcanizing agent: 3 parts of liquid TAIC (high purity product); vulcanization accelerators: 2.5 parts of liquid bis 2,5 (high purity product);
formula 3:
100 parts of fluororubber (raw rubber); reinforcing filler: 10 parts of anhydrous weather white carbon black; processing aid: 1.5 parts of raw silicone rubber; vulcanizing agent: TAIC (Drimix, TAIC 75%) 4 parts; vulcanization accelerators: 3 parts of double 2,5 (Luperox cube 101 XL-45);
formula 4:
100 parts of fluororubber (raw rubber); reinforcing filler: 10 parts of diatomite; processing aid: 1.5 parts of raw silicone rubber; vulcanizing agent: 3 parts of liquid TAIC (high purity product); vulcanization accelerators: 2.5 parts of liquid bis 2,5 (high purity product);
formula 5:
100 parts of fluororubber (raw rubber); reinforcing filler: 20 parts of diatomite; processing aid: WS 280.5 parts; vulcanizing agent: TAIC (Drimix, TAIC 75%) 4 parts; vulcanization accelerators: 3 parts of double 2,5 (Luperox cube 101 XL-45);
the intelligent peroxyfluororubber wearing material is prepared by the following method:
step B1, preparing the transparent peroxyfluororubber raw rubber prepared in the examples 1 to 5 according to the formula 1, and marking the transparent peroxyfluororubber raw rubber as a material 1, a material 2, a material 3, a material 4 and a material 5 respectively; the clear green peroxyfluororubber prepared in example 5 was compounded according to formulation 2 above and labeled material 6; the clear green peroxyfluororubber prepared in example 5 was compounded according to formulation 3 above and labeled as material 7; the clear green peroxyfluororubber prepared in example 5 was compounded according to formulation 4 above and labeled as material 8; the clear green peroxyfluororubber prepared in example 5 was compounded according to formulation 5 above and labeled as material 9; the peroxyfluororubbers prepared in comparative examples 1 to 4 were compounded according to the above formula 1 and labeled as material 10, material 11, material 12, and material 13, respectively;
then, respectively adding the materials 1 to 13 into an internal mixer to be mixed, wherein the mixing temperature is 95 ℃, and the mixing time is 500s; standing at room temperature for 24 hours, reversely refining on an open mill, wherein the reverse refining temperature is 80 ℃, carrying out thin pass for 5 times, and cooling the obtained sheet to prepare transparent peroxyfluororubber compound and peroxyfluororubber compound;
and B2, sequentially carrying out primary vulcanization (vulcanization for 300 seconds at 170 ℃) and secondary vulcanization (vulcanization for 2 hours at 180 ℃) on the transparent peroxyfluororubber compound and the peroxyfluororubber compound prepared in the step B1 to prepare the transparent peroxyfluororubber intelligent wearing material or the peroxyfluororubber intelligent wearing material.
The materials 1 to 13 prepared in the above steps B1 and B2 were subjected to performance test, and the test results are shown in table 2 below:
table 2 intelligent wearing material performance meter
Note that: transparency in table 2 is: A. transparent B, turbid, light transparent C, white, opaque D, light yellow, light transparent.
In table 2, the transparent peroxyfluororubber raw rubber prepared in examples 1 to 5 is excellent in transparency, vulcanization performance and physical and mechanical properties, and the transparent peroxyfluororubber intelligent wearing materials 1 to 5 prepared by compounding in formula 1 are excellent;
in table 2, the transparent raw peroxyfluororubber prepared in example 5 was excellent in vulcanization performance and physical and mechanical properties, but the transparency was expressed as: cloudy, light transparent. The reason for this is that formulation 2 uses a raw silicone rubber in formulation 1 as compared to formulation 1, and a conventional processing aid WS280 in formulation 2. This demonstrates that traditional processing aids affect the transparency of the material, and that raw silicone rubber is the preferred choice of transparent peroxyfluororubber smart wear materials as a processing aid;
in table 2, the transparent raw peroxyfluororubber produced in example 5 was excellent in vulcanization property and physical and mechanical properties, but the transparency was expressed as: cloudy, light transparent. The reason for this is that in formula 3, a liquid vulcanizing agent (TAIC high purity product) and a liquid vulcanizing accelerator (double 2,5 high purity product) are used as compared with formula 1, and in formula 3, a conventional vulcanizing agent (Drimix. RTM. TAIC 75%) and a conventional vulcanizing accelerator (Luperox. RTM. 101 XL-45) are used, and a conventional vulcanizing agent (Drimix. RTM. 75%) and a conventional vulcanizing accelerator (Luperox. RTM. 101 XL-45) are used as carriers to affect transparency. This demonstrates that conventional supported curatives and conventional supported curatives affect the clarity of the material, and that liquid curatives (TAIC high purity) and liquid curatives (bis 2,5 high purity) are preferred for transparent peroxyfluororubber smart wear materials;
in table 2, the transparent raw peroxyfluororubber prepared in example 5 was excellent in vulcanization performance and physical and mechanical properties, but the transparency was expressed as: white is opaque. The reason is that compared with the formula 1, the formula 4 uses anhydrous weather white carbon black as the reinforcing filler in the formula 1 and diatomite as the reinforcing filler in the formula 4, which proves that the traditional reinforcing filler influences the transparency of the material, and the anhydrous weather white carbon black is the preferable choice of the transparent peroxy fluororubber intelligent wearing material as the reinforcing filler;
in table 2, the transparent raw peroxyfluororubber prepared in example 5 was excellent in vulcanization performance and physical and mechanical properties, but the transparency was expressed as: white is opaque. The reason for this is that the technical scheme of the invention is used in formulation 1, and the conventional peroxyfluororubber technical scheme is used in formulation 5, compared with formulation 1. This demonstrates that traditional processing aids affect the transparency of the material, and that raw silicone rubber is the preferred choice of transparent peroxyfluororubber smart wear materials as a processing aid;
in table 2, the peroxide fluororubber prepared in comparative example 1 was excellent in vulcanization performance and physical and mechanical properties, but the transparency was expressed as: cloudy, light transparent. The reason is that compared with the experimental examples 1 to 5, the emulsion aggregation method in the experimental example 1 is high-speed stirring demulsification, the emulsion aggregation method in the experimental example 1 is traditional metal salt demulsification, and the transparency of the material is influenced by the residue of the metal salt, which proves that the transparency of the material is influenced by the traditional metal salt demulsification method, and the high-speed stirring demulsification method is the preference of the transparent intelligent wearing material of the peroxyfluororubber;
in table 2, the peroxide fluororubber produced in comparative example 2 was excellent in vulcanization performance and physical mechanical properties, but the transparency was expressed as: pale yellow, light transparent. The reason is that the comparative example 2 is compared with the examples 1 to 5, the examples 1 to 5 are free of the comonomer vinylidene fluoride, the comonomer vinylidene fluoride is added in the comparative example 2, the monomer vinylidene fluoride contains hydrogen element, and yellowing of the material is caused in vulcanization, which proves that the transparency of the material is influenced by the perfluoro rubber comonomer if the monomer vinylidene fluoride is contained, and the perfluoro methyl vinyl ether is used for replacing the vinylidene fluoride to be a preferable transparent perfluoro rubber intelligent wearing material;
in table 2, the peroxyfluororubbers produced in comparative examples 3 to 4 were excellent in vulcanization property and physical mechanical property of the peroxyfluororubber smart wear materials 12 and 13 produced by compounding in the formulation 1, but exhibited transparency as follows: pale yellow, light transparent. The reason for this is that comparative example 2 is compared with examples 1 to 5, examples 1 to 5 are free of the comonomer vinylidene fluoride, comparative examples 3 and 4 are typical conventional peroxyfluororubbers, the comonomer vinylidene fluoride is present in the molecular chain, the monomer vinylidene fluoride contains hydrogen element, and yellowing of the material is caused in vulcanization, which proves that the conventional peroxyfluororubbers cannot be used for manufacturing transparent peroxyfluororubber smart wear materials.
Through the experiment and test, the transparent peroxyfluororubber intelligent wearing material and the preparation method provided by the invention have the characteristics of excellent vulcanization performance, excellent physical and mechanical properties, excellent material transparency and the like, and the purpose of the invention is completely realized.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention.
Claims (8)
1. The preparation method of the transparent peroxyfluororubber intelligent wearing material is characterized by comprising the following steps of:
(1) Preparing transparent peroxyfluororubber raw rubber:
1-1, adding deionized water, an emulsifying agent, a pH buffering agent and a chain transfer agent into a high-pressure polymerization reaction kettle, and deoxidizing to reduce the oxygen content in the reaction kettle;
1-2, adding an initial mixed monomer into a high-pressure polymerization reaction kettle until the pressure in the high-pressure polymerization reaction kettle is 2.2Mpa, starting stirring, maintaining the stirring speed of 85-105rpm, starting heating, adding an initiator when the temperature in the reaction kettle is raised to 55-80 ℃, and starting polymerization reaction;
1-3, continuously adding main polymerization monomers in the polymerization reaction process, maintaining the pressure of the reaction kettle at 2.5-4.0MPa, simultaneously adding an initiator and a chain transfer agent at intervals, maintaining the stirring speed at 85-105rpm, and maintaining the temperature of the reaction kettle at 80-95 ℃;
1-4, after the reaction is finished, stirring and condensing the emulsion at a high speed, washing, vacuumizing and drying to obtain transparent peroxy fluororubber raw rubber;
wherein the initial mixed monomer and the main polymerized monomer are the mixture of perfluoromethyl vinyl ether, tetrafluoroethylene and hexafluoropropylene, and the mole percentages of the components in the initial mixed monomer and the main polymerized monomer are different; the molar ratio of the perfluoromethyl vinyl ether, the tetrafluoroethylene and the hexafluoropropylene in the initial mixed monomer is 30:5:65, wherein the molar ratio of the perfluoromethyl vinyl ether to the tetrafluoroethylene to the hexafluoropropylene in the main polymerization monomer is 20-40:5-15:75-45;
(2) The transparent peroxyfluororubber intelligent wearing material is prepared by the following steps:
adding the transparent peroxide fluororubber raw rubber prepared in the step (1), a reinforcing filler, a processing aid, a vulcanizing agent and a vulcanization accelerator into an internal mixer for mixing, standing for 24 hours at room temperature, then, carrying out back mixing on the internal mixer to prepare transparent peroxide fluororubber compound, and carrying out vulcanization treatment on the transparent peroxide fluororubber compound to prepare the transparent peroxide fluororubber intelligent wearing material;
the weight portions of the components in the step (2) are as follows: 100 parts of transparent peroxyfluororubber raw rubber, 5-20 parts of reinforcing filler, 0.5-2.0 parts of processing aid, 1.5-3.0 parts of vulcanizing agent and 1.5-3.0 parts of vulcanization accelerator; the reinforcing filler is anhydrous gas-phase white carbon black, the processing aid is raw silicone rubber, the vulcanizing agent is a high-purity triallyl isocyanurate product, and the vulcanizing accelerator is a high-purity 2, 5-di-tert-butyl peroxy-2, 5-dimethylethane product.
2. The method for preparing the transparent peroxy fluororubber intelligent wearing material according to claim 1, wherein the deoxidizing mode in the step 1-1 is to fill nitrogen for deoxidizing or to pump a vacuum pump for deoxidizing.
3. The method for preparing the transparent peroxyfluororubber intelligent wearing material according to claim 1, wherein the Mooney viscosity ML121 ℃ 1+10 of the transparent peroxyfluororubber raw rubber prepared in the step (1) is 20-60.
4. The method for preparing a transparent peroxyfluororubber intelligent wearing material according to claim 1, wherein the stirring speed of the high-speed stirring in the step 1-4 is 800-1500rpm.
5. The method for preparing the transparent peroxyfluororubber intelligent wearing material according to claim 1, wherein the weight parts of the components in the step (1) are as follows: 250 parts of deionized water, 0.03-0.4 part of emulsifying agent, 0.02-0.35 part of pH buffering agent, 0.1-0.35 part of initiator, 0.3-2.5 parts of chain transfer agent and 100 parts of main polymerized monomer of fluororubber, wherein the main polymerized monomer of fluororubber comprises the initial mixed monomer and the main polymerized monomer.
6. The method for preparing a transparent peroxyfluororubber smart wear material according to claim 5, wherein the emulsifier is ammonium perfluoropolyether carboxylate, wherein the ammonium perfluoropolyether carboxylate is made of a trimer of hexafluoropropylene oxide; the pH buffering agent is sodium bicarbonate; the initiator is ammonium persulfate; the chain transfer agent is a mixture of diiododifluoromethane and 1,4 diiodoperfluorobutane, and the weight ratio of the diiododifluoromethane to the 1,4 diiodoperfluorobutane in the mixture is 3:1.
7. the method for preparing the transparent peroxyfluororubber intelligent wearing material according to claim 1, wherein the vulcanization treatment in the step (2) is a sectional vulcanization treatment comprising a primary vulcanization and a secondary vulcanization, wherein the temperature in the primary vulcanization is 160-180 ℃ and the vulcanization time is 180-500 seconds; in the second-stage vulcanization, the temperature is 175-200 ℃, the vulcanization time is 2-4 hours, and the second-stage vulcanization is carried out after the first-stage vulcanization is finished and cooled to room temperature.
8. The transparent peroxyfluororubber smart wear material prepared by the method for preparing a transparent peroxyfluororubber smart wear material according to any one of claims 1 to 7.
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