CN116715927A - Antifouling watchband material and preparation method thereof - Google Patents
Antifouling watchband material and preparation method thereof Download PDFInfo
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- CN116715927A CN116715927A CN202310775622.0A CN202310775622A CN116715927A CN 116715927 A CN116715927 A CN 116715927A CN 202310775622 A CN202310775622 A CN 202310775622A CN 116715927 A CN116715927 A CN 116715927A
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- 239000000463 material Substances 0.000 title claims abstract description 77
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 229920001971 elastomer Polymers 0.000 claims abstract description 59
- 238000004073 vulcanization Methods 0.000 claims abstract description 42
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000000945 filler Substances 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 229920001973 fluoroelastomer Polymers 0.000 claims abstract description 20
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000049 pigment Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000004014 plasticizer Substances 0.000 claims abstract description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 5
- 239000012065 filter cake Substances 0.000 claims abstract description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000011010 flushing procedure Methods 0.000 claims abstract description 4
- 239000003822 epoxy resin Substances 0.000 claims abstract description 3
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 3
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims abstract description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 20
- 150000002484 inorganic compounds Chemical class 0.000 claims description 20
- 229910010272 inorganic material Inorganic materials 0.000 claims description 20
- -1 hexafluoropropylene, tetrafluoroethylene Chemical group 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000004513 sizing Methods 0.000 claims description 11
- 239000012986 chain transfer agent Substances 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229920001690 polydopamine Polymers 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- WHFBTQVXURKRCS-UHFFFAOYSA-N 1-bromo-1,1,2,2,3,3-hexafluoro-3-iodopropane Chemical compound FC(F)(Br)C(F)(F)C(F)(F)I WHFBTQVXURKRCS-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 6
- 235000013539 calcium stearate Nutrition 0.000 claims description 6
- 239000008116 calcium stearate Substances 0.000 claims description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 4
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229960003638 dopamine Drugs 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- YQJDGOJKITVCSR-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctyl hydrogen sulfate Chemical compound OS(=O)(=O)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YQJDGOJKITVCSR-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 3
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 3
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011737 fluorine Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 210000004243 sweat Anatomy 0.000 description 7
- 229920000128 polypyrrole Polymers 0.000 description 6
- 239000004636 vulcanized rubber Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the technical field of watchband materials, and particularly discloses an antifouling watchband material and a preparation method thereof. The antifouling watchband material comprises the following raw materials in parts by weight: 100 parts of fluororubber modified raw rubber, 1-5 parts of vulcanizing agent, 1-2 parts of vulcanization accelerator, 20-40 parts of polypyrrole-graphene filler, 1-5 parts of plasticizer and 20-24 parts of pigment; the preparation method of the polypyrrole-graphene modified waterborne polyurethane-epoxy resin comprises the following steps: the mass ratio is (2.5-4): 1, dispersing ammonium persulfate and hexadecane agent trimethyl ammonium bromide in hydrochloric acid solution to form mixed solution, dispersing graphene in the mixed solution by using ultrasonic dispersion, and dropwise adding pyrrole monomer for reaction, wherein the mass ratio of the graphene to the pyrrole is 1: (100-200), filtering after the reaction is finished, flushing a filter cake by using distilled water and ethanol, and drying in vacuum. According to the application, the fluorine rubber modified raw rubber is used as a main material and is matched with the polypyrrole-graphene filler, so that the antifouling performance of the watchband material is improved.
Description
Technical Field
The application relates to the technical field of watchband materials, in particular to an antifouling watchband material and a preparation method thereof.
Background
The watch is an ornament of the daily life of people, the traditional watchband material is generally made of metal, leather or plastic, the texture is generally offset printed, the comfort is low relatively poor, and the watch has long service life due to deterioration and damage caused by occasional contact with high temperature, water vapor, acid medium, grease and the like. With the continuous expansion of the application field of rubber in recent years, the types of products are continuously increased, and the application of the rubber is gradually promoted from the aerospace field at the design place to the fields of medicine, chemical industry, electronics and the like.
The rubber watchband has good chemical stability, heat resistance, corrosion resistance, aging resistance, flame retardance and the like, is the ideal choice of watchband materials, but the parts contacted with the human body can be worn and corroded due to sweat and friction on the hands of the human body in the use process, and the functionality and the aesthetic property are affected.
Therefore, improving the stain resistance of rubber watchbands is of great importance for better watchband development.
Disclosure of Invention
The application provides an antifouling watchband material and a preparation method thereof in order to improve the antifouling performance of a rubber watchband.
In a first aspect, the application provides an antifouling watchband material, which adopts the following technical scheme:
an antifouling watchband material comprises the following raw materials in parts by weight: 100 parts of fluororubber modified raw rubber, 1-5 parts of vulcanizing agent, 1-2 parts of vulcanization accelerator, 20-40 parts of polypyrrole-graphene filler, 1-5 parts of plasticizer and 20-24 parts of pigment;
the preparation method of the polypyrrole-graphene modified waterborne polyurethane-epoxy resin comprises the following steps: the mass ratio is (2.5-4): 1, dispersing ammonium persulfate and hexadecane agent trimethyl ammonium bromide in hydrochloric acid solution to form mixed solution, dispersing graphene in the mixed solution by using ultrasonic dispersion, and dropwise adding pyrrole monomer for reaction, wherein the mass ratio of the graphene to the pyrrole is 1: (100-200), filtering after the reaction is finished, flushing a filter cake by using distilled water and ethanol, and drying in vacuum.
By adopting the technical scheme, the fluorine element has low surface tension, and the anti-fouling watchband material has good anti-fouling performance by introducing the fluorine element into raw rubber; meanwhile, the nano polypyrrole functional filler is loaded by the graphene, so that on one hand, excellent photo-thermal effect can be realized through the cooperation of the graphene and the nano polypyrrole to inhibit the adhesion of dirty organisms, and the water loss on the surface and the inner layer of the watchband can be accelerated through the photo-thermal effect, and the nano polypyrrole is loaded by the graphene, so that the penetration of sweat to the watchband can be reduced and the hydrolysis of the inner layer anti-fouling groups can be reduced under the condition that the photo-thermal effect is not influenced; on the other hand, the addition of polypyrrole-graphene filler can increase the mechanical property of the watchband system and prolong the service life of the watchband system. According to the application, the fluorine rubber modified raw rubber is used as a main material in the watchband system, and the polypyrrole-graphene filler is added, so that the watchband has excellent antifouling performance under the combined action of the fluorine rubber modified raw rubber and the polypyrrole-graphene filler.
In a specific embodiment, the fluororubber modified raw rubber comprises the following raw materials in parts by weight: 1 to 5.5 parts of monomer, 0.1 to 0.5 part of initiator, 0.05 to 0.75 part of emulsifier, 0.05 to 1.5 parts of chain transfer agent and 100 parts of deionized water; the mass ratio of the monomers is (60-70): (10-20): (15-25) a mixture of vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene and vinyl bromide monomers of 5.
By adopting the technical scheme, the monomer is matched with other raw materials, fluorine atoms have strong electronegativity, and the strong electron withdrawing capability can ensure that the C-C bond energy on a polymer molecular chain is changed greatly, and the main valence bond is more stable; meanwhile, the fluorine atom volume is slightly larger than that of the hydrogen atom, so that a shielding effect can be formed on a molecular chain, and the fluorine rubber elastomer is prevented from being corroded by an external corrosive medium, so that the fluorine rubber elastomer has excellent antifouling performance, and simultaneously has excellent mechanical performance and medium resistance.
In a specific embodiment, the fluororubber modified raw rubber is prepared by the following steps: blowing nitrogen into a polymerization reaction kettle to remove oxygen, and adding deionized water, an emulsifying agent and a chain transfer agent; introducing the monomer mixture into a reaction kettle through a compressor, enabling the pressure in the reaction kettle to reach 2.4-3.6Mpa, starting stirring, and heating the mixture in the reaction kettle to 50-80 ℃; adding initiator, replenishing premixed monomer, initiator and chain transfer agent at intervals during polymerization, and maintaining the pressure at 3.6-7Mpa; simultaneously maintaining a stirring rate of 80-120r/min to maintain a reaction rate; after the reaction is finished, the emulsion is conveyed into a mixing kettle, and is subjected to condensation, washing and drying.
By adopting the technical scheme, the prepared raw rubber can be vulcanized by peroxide, and has excellent fluidity and higher vulcanization speed.
In a specific embodiment, the initiator is one or more of persulfate, persulfate-bisulfite, diisopropyl peroxydicarbonate, t-butyl peroxyisobutyrate; the emulsifier is one or more of sodium salt or ammonium salt of perfluoro caprylic acid and lithium salt of perfluoro octyl sulfuric acid; the chain transfer agent is one or more of 1-bromo-3-iodo-perfluoropropane, 1, 4-diiodoperfluorobutane, isopentane and ethyl acetate.
By adopting the technical scheme, the initiator can smoothly carry out the polymerization reaction at a lower temperature, simultaneously reduce the generation of side reactions such as chain transfer, branching and the like, and improve the polymer performance; the emulsifier has the advantages that the surface tension is reduced in the polymerization reaction to form a stable emulsion system, the water-oil interfacial tension is reduced, meanwhile, the good dispersion effect and the solubilization effect are realized, more importantly, the solubilized monomers in the micelle are diffused into free radicals to initiate polymerization to generate emulsion particles, the micelle formed by the emulsifier is a main source for emulsion particle formation, and the formation of the emulsion particles can accelerate the polymerization reaction; the chain transfer agent can react with free radicals to form a stable free radical intermediate, so that the activity and reaction property of the free radicals are changed, and the rate of polymerization reaction and the distribution of molecular chains are controlled; the desired polymerization product is obtained by the synergistic effect of the three reaction auxiliaries.
In a specific embodiment, the vulcanizing agent is one of dicumyl peroxide, 2, 5-dimethyl-2, 5-di-t-butylperoxy hexane, 1-di-t-butylperoxy-3, 5-trimethylcyclohexane, preferably 2, 5-dimethyl-2, 5-di-t-butylperoxy hexane; the vulcanization accelerator is one of triallyl isocyanurate, triallyl cyanurate and trimethylolpropane trimethacrylate, and preferably triallyl isocyanurate; the plasticizer is one or more of calcium stearate, rhine 27, rhine 54 and polyvinyl alcohol-2000; the pigment is one or more of iron oxide red, iron oxide yellow, phthalocyanine green and iron oxide blue.
By adopting the technical scheme, the vulcanizing agent can lead the molecular structure of vulcanized rubber to carry out chemical crosslinking reaction, so that the linear molecular structure generates a three-dimensional porous structure, the ductility is reduced, and the ductility compressive strength of the rubber is improved; 2, 5-dimethyl-2, 5-di-t-butylperoxy hexane can improve the tensile strength and hardness of the product, and the smell after vulcanization is minimal in alkyl peroxide.
The vulcanization accelerator can accelerate the vulcanization reaction, shorten the vulcanization time, reduce the vulcanization temperature, reduce the consumption of the vulcanizing agent, improve the physical and mechanical properties of vulcanized rubber, improve the vulcanization production efficiency and the quality of vulcanized rubber, ensure that the product has uniform vulcanization degree and reduce the product cost; the triallyl isocyanurate is a trifunctional auxiliary cross-linking agent, can obviously improve the strength, rigidity and heat resistance of the product, and can enable the self-product to be used for a long time in a high-temperature environment.
The plasticizer reduces the intermolecular acting force to reduce the glass transition temperature of the produced rubber, so that the rubber has plasticity and fluidity, is convenient for molding technical operations such as calendaring, extrusion and the like, improves the processing technology of the rubber, improves the qualification rate and dimensional structural stability of products, reduces energy consumption and improves mixing efficiency.
By adding different pigments, the prepared watchband material has rich colors, meets different user requirements, and improves the diversity of products.
In a specific embodiment, the raw materials of the anti-fouling watchband material further comprise 10-20 parts by weight of polydopamine modified lamellar inorganic compound; the preparation method of the polydopamine modified lamellar inorganic compound comprises the following steps: adding 0.1-1g/ml lamellar inorganic compound into alkaline solution with pH of 8-10, adding 0.1-1g/ml dopamine solution, performing oxidation self-polymerization at 20-30deg.C, and reacting for 15-25 h.
In a specific embodiment, the layered inorganic compound is one or more of a layered silicate compound, a layered metal oxide, a layered transition metal disulfide, a diselenide, a layered metal salt compound, and a layered double hydroxide.
By adopting the technical scheme, the lamellar inorganic compound can play a role in strengthening in two-dimensional directions, and the lamellar planes are oriented, so that the lamellar inorganic compound has high barrier property. After being modified by polydopamine, the layered inorganic compound is easier to disperse and interact with polymers, the strength of the watchband can be improved on the premise of not reducing the breaking elongation of the watchband, and meanwhile, the heat resistance, dielectric resistance, flame retardance and dimensional stability of the watchband can also be improved.
In a second aspect, the application provides a method for preparing an antifouling watchband material, which adopts the following technical scheme:
a preparation method of an antifouling watchband material comprises the following steps:
s1, plasticating fluororubber modified raw rubber to obtain plasticated rubber material, and adding other raw materials into the plasticated rubber material to carry out banburying to obtain banburying rubber material;
s2, turning the banburying material, and cooling after turning to obtain a preformed sizing material;
s3, vulcanizing and forming the preformed sizing material.
In a specific embodiment, in S1, the plasticating time is 1 to 3 minutes and the temperature is not more than 100 ℃; the banburying time is 3-5min, and the temperature is not more than 65 ℃; in the step S2, the turning time is 10-15min, and the temperature is not more than 50 ℃; the cooling temperature is not more than 40 ℃.
In a specific embodiment, in S3, the vulcanization molding includes a first-stage vulcanization and a second-stage vulcanization, wherein the temperature of the first-stage vulcanization is 170-180 ℃ and the time is 6-10min; the temperature of the second-stage vulcanization is 180-200 ℃, and the vulcanization time is 6-12h.
By adopting the technical scheme, the preparation method can simplify the process flow, can be applicable to the preparation of conventional rubber production equipment, and can prepare watchband materials by a continuous method called a one-step method or by a stepwise method; the prepared watchband material has excellent antifouling performance, good mechanical strength and greatly prolonged service life.
In summary, the application has at least the following advantages:
1. according to the application, fluororubber modified raw rubber is used as a main material, and polypyrrole-graphene filler is matched, so that the antifouling performance of the watchband is improved under the combined action of the fluororubber modified raw rubber and the polypyrrole-graphene filler;
2. according to the application, the layered inorganic compound modified by polydopamine is added into the watchband material system, so that the mechanical strength of the watchband is improved, and the service life of the watchband is prolonged.
Detailed Description
The present application will be described in further detail with reference to examples and examples.
Preparation example
Preparation example 1
The preparation example discloses a preparation method of fluororubber modified raw rubber, which comprises the following steps:
s10, blowing nitrogen to remove oxygen from the reaction kettle, then adding 100Kg of distilled water, 0.05Kg of ammonium perfluorooctanoate and 0.04Kg of 1-bromo-3-iodo-perfluoropropane, and then adding a monomer mixture composed of 0.12Kg of vinylidene fluoride, 0.04Kg of hexafluoropropylene, 0.03Kg of tetrafluoroethylene and 0.01Kg of vinyl bromide to enable the pressure of the reaction kettle to reach 2.4Mpa; heating the reaction kettle to 80 ℃, and then adding 0.08Kg of tert-butyl isobutyrate peroxide to initiate reaction; wherein the emulsifier is perfluoro caprylic acid, and in other embodiments, one or more of ammonium salt of perfluoro caprylic acid and lithium salt of perfluoro octyl sulfuric acid can be selected; the chain transfer agent is 1-bromo-3-iodo-perfluoropropane, and in other embodiments, one or more of 1, 4-diiodoperfluorobutane, isopentane and ethyl acetate can be used; the initiator is tert-butyl isobutyrate peroxide, and in other embodiments, one or more of persulfate, persulfate-hydrosulfite and diisopropyl peroxydicarbonate can be used;
s20, after the reaction starts, the pressure is reduced, and the reaction rate is ensured by periodically supplementing the monomer mixture for 4 times to maintain the pressure to be stable at 3.6Mpa and simultaneously maintaining the stirring rate of 80 r/min;
s30, after 3 hours of reaction, adding 0.01Kg of 1-bromo-3-iodo-perfluoropropane and 0.02Kg of tert-butyl hydroperoxide by a metering pump; and stopping the reaction after 4 hours, conveying the emulsion into a mixing kettle, condensing, washing, drying, and mixing by an open mill to obtain the emulsion.
Preparation example 2
The preparation example discloses a preparation method of fluororubber modified raw rubber, which comprises the following steps:
s10, blowing nitrogen to remove oxygen from the reaction kettle, then adding 100Kg of distilled water, 0.75Kg of ammonium perfluorooctanoate and 1.2Kg of 1-bromo-3-iodo-perfluoropropane, and then adding a monomer mixture consisting of 0.7Kg of vinylidene fluoride, 0.1Kg of hexafluoropropylene, 0.25Kg of tetrafluoroethylene and 0.05Kg of vinyl bromide to enable the pressure of the reaction kettle to reach 3.6Mpa; heating the reaction kettle to 50 ℃, and then adding 0.4Kg of tert-butyl isobutyrate peroxide to initiate reaction;
s20, after the reaction starts, the pressure is reduced, and the reaction rate is ensured by periodically supplementing the monomer mixture for 4 times to maintain the pressure to be stable at 7Mpa and simultaneously maintaining the stirring rate of 120 r/min;
s30, after 3 hours of reaction, adding 0.3Kg of 1-bromo-3-iodo-perfluoropropane and 0.1Kg of t-butyl hydroperoxide by a metering pump; and stopping the reaction after 4 hours, conveying the emulsion into a mixing kettle, condensing, washing, drying, and mixing by an open mill to obtain the emulsion.
Preparation example 3
The preparation example discloses a preparation method of polypyrrole-graphene filler, which comprises the following steps: dispersing 2.5g of ammonium persulfate and 1g of cetyltrimethylammonium bromide in 500ml of hydrochloric acid solution with the concentration of 4.92g/L, uniformly dispersing 0.02g of graphene in the liquid by using ultrasonic dispersion, dropwise adding 2g of pyrrole monomer under stirring, changing the reactant from milky white to blue black and finally to black, finishing the reaction after 6 hours, filtering, flushing a filter cake by using distilled water and ethanol, and drying in vacuum.
Preparation example 4
The preparation example discloses a preparation method of polypyrrole-graphene filler, which comprises the following steps: 4g of ammonium persulfate and 1g of cetyltrimethylammonium bromide are dispersed in 500ml of hydrochloric acid solution with the concentration of 4.92g/L, 0.02g of graphene is uniformly dispersed in the liquid by using ultrasonic dispersion, 4g of pyrrole monomer is dropwise added under stirring, the reactant turns from milky white to blue black and finally turns to black, the reaction is completed after 6 hours, the filter cake is washed by using distilled water and ethanol, and the product is obtained after vacuum drying.
Preparation example 5
The preparation example discloses a preparation method of a polydopamine modified lamellar inorganic compound, which comprises the following steps: adding 0.1g/ml of layered montmorillonite into ammonia water with pH of 8, adding 0.1g/ml of dopamine solution, performing oxidation self-polymerization at 20deg.C, and reacting for 15 hr. The layered inorganic compound is selected from layered montmorillonite, and in other embodiments one or more of layered metal oxide, layered transition metal disulfide, diselenide, layered metal salt compound, and layered double hydroxide can be selected.
Preparation example 6
The preparation example discloses a preparation method of a polydopamine modified lamellar inorganic compound, which comprises the following steps: adding 1g/ml of layered potassium phosphate into ammonia water with pH of 10, adding 1/ml of dopamine solution, oxidizing and self-polymerizing at 30 ℃ and reacting for 25 h.
Examples
Examples 1 to 11
As shown in Table 1, the main difference between examples 1 to 11 is the raw material ratios of the antifouling watchband materials.
The following description will take example 1 as an example. The embodiment of the application discloses an antifouling watchband material, which is prepared from 100Kg of fluororubber modified raw rubber, 1Kg of 2, 5-dimethyl-2, 5-di-tert-butyl peroxy hexane, 1Kg of triallyl isocyanurate, 20Kg of polypyrrole-graphene filler, 1Kg of calcium stearate and 20Kg of iron oxide red; wherein the fluororubber modified raw rubber is obtained in preparation example 1, the polypyrrole-graphene filler is obtained in preparation example 3, the plasticizer is calcium stearate, one or more of Rhin 27, rhin 54 and polyvinyl alcohol-2000 are also selected in other embodiments, the pigment is iron oxide red, and one or more of iron oxide yellow, phthalocyanine green and iron oxide blue are also selected in other embodiments.
The embodiment of the application also discloses a preparation method of the antifouling watchband material, which comprises the following steps: the method comprises the following steps:
s1, adding fluororubber modified raw rubber into an open mill, plasticating for 1min at 80 ℃ to obtain plasticated rubber; mixing a vulcanizing agent and a vulcanization accelerator in advance, adding the mixture into a plastic sizing material for banburying for 1min, adding other raw materials for banburying for 2min at 60 ℃ to obtain a banburying material;
s2, turning the banburying material for 10min at 45 ℃; cooling after finishing the turning until the cooling temperature is 35 ℃ to obtain a preformed sizing material;
s3, placing the preformed sizing material into a mold for vulcanization molding, and vulcanizing for 10min at 170 ℃ through one-stage vulcanization; and (3) performing two-stage vulcanization, wherein the temperature is 180 ℃, and the vulcanization is performed for 12 hours.
Table 1 raw material ratios of the antifouling watchband materials of examples 1 to 11
The polydopamine-modified layered inorganic compounds of examples 10 and 11 were obtained in preparation example 5.
Example 12
This example differs from example 11 in that fluororubber-modified raw rubber was obtained in preparation example 2, polypyrrole-graphene filler was obtained in preparation example 4, and polydopamine-modified layered inorganic compound was obtained in preparation example 6.
Example 13
The embodiment of the application also discloses a preparation method of the anti-fouling watchband material, which is different from the embodiment 11: the method comprises the following steps:
s1, adding fluororubber modified raw rubber into an open mill, plasticating for 3min at 90 ℃ to obtain plasticated rubber; mixing a vulcanizing agent and a vulcanization accelerator in advance, adding the mixture into a plastic sizing material for banburying, adding other raw materials for banburying after banburying for 2min, and banburying for 3min at the temperature of 55 ℃ to obtain a banburying sizing material;
s2, turning the banburying material for 15min at 40 ℃; cooling after finishing the turning until the cooling temperature is 30 ℃ to obtain a preformed sizing material;
s3, placing the preformed sizing material into a mold for vulcanization molding, and vulcanizing for 6min at 180 ℃ through one-stage vulcanization; and (3) performing two-stage vulcanization, wherein the temperature is 200 ℃, and the vulcanization is performed for 6 hours.
Comparative example
Comparative example 1
This comparative example differs from example 1 in that the fluororubber-modified raw rubber was replaced with a normal rubber raw rubber.
Comparative example 2
This comparative example differs from example 1 in that the polypyrrole-graphene filler is replaced with a general filler such as carbon black.
Comparative example 3
This comparative example differs from example 1 in that the fluororubber-modified raw rubber was replaced with a normal rubber raw rubber, while the polypyrrole-graphene filler was replaced with carbon black.
Performance test
1. Oil stain resistance test: the antifouling watchband materials prepared in the examples 1-13 and the comparative examples 1-3 are made into slices with the same size, edible oil and tomato sauce are evenly coated on a sample test piece after being blended in a ratio of 2:1, then the sample test piece is placed in an oven at 80 ℃ for 6 hours, the sample test piece is cooled to room temperature after being taken out, and a cotton swab dipped with alcohol is used for wiping the surface of the sample test piece to observe the pollution condition of the surface of the sample test piece; the first level is that the pollution is serious, and the coating part is obviously discolored; the second level is that the coating surface has certain color change due to certain pollution; grade 3 is slight contamination, the coating is slightly discolored; the four grades were very slightly contaminated, no apparent discoloration at the coating and the results are shown in table 2.
2. Sweat resistance test: the antifouling watchband materials prepared in examples 1 to 13 and comparative examples 1 to 3 were cut into pieces of the same size, then hung, sprayed with the same amount of sewage (simulating sweat of human body), and the residual amount of sewage on the cut pieces was measured, and the results are shown in Table 2.
3. Mechanical property test: examples 1 to 13 and comparative examples 1 to 3 were tested for tensile strength and elongation at break with reference to GB/T528-2009, and the results are shown in table 2.
TABLE 2 Performance test data tables for examples 1-13 and comparative examples 1-3
Referring to table 2, in combination with example 1 and comparative examples 1 to 3, it can be seen that the materials obtained by using fluororubber modified raw rubber as a main material and simultaneously compounding polypyrrole-graphite filler in the anti-fouling watchband material system have excellent anti-fouling performance and mechanical performance; the fluorine atoms are contained in the chain segments of the fluororubber modified raw rubber, so that the watchband material is endowed with excellent heat resistance, oxidation resistance, oil resistance, corrosion resistance and aging resistance; polypyrrole has a photo-thermal effect, and the polypyrrole-graphene filler prepared by loading the polypyrrole with graphene can slow down the penetration of sweat to the inner layer of the watchband through a graphene lamellar structure so as to protect the antifouling groups of the inner layer of the watchband and reduce the hydrolysis of the fluorine groups, so that fluororubber modified raw rubber and the polypyrrole-graphite filler have a synergistic effect, and the antifouling performance of a watchband material system is improved together; meanwhile, the addition of polypyrrole-graphene filler can improve the mechanical property of the watchband system and prolong the service life of the watchband system.
Referring to Table 2, in combination with examples 1 to 3, it can be seen that changing the content of the vulcanizing agent within an appropriate range gives samples having good stain resistance and mechanical properties; the proper amount of 2, 5-dimethyl-2, 5-di-tert-butyl peroxy hexane can improve the tensile strength of the product, and the smell after vulcanization is minimum in alkyl peroxide.
Referring to Table 2, in combination with examples 2 and 4, it can be seen that the mechanical properties of the test pieces are continuously improved as the amount of the vulcanization accelerator added to the watch material is continuously increased; the triallyl isocyanurate is a trifunctional auxiliary cross-linking agent, can accelerate the vulcanization reaction speed, shorten the vulcanization time, reduce the vulcanization temperature, reduce the consumption of the vulcanizing agent, improve the physical and mechanical properties of vulcanized rubber, improve the vulcanization production efficiency and the quality of the vulcanized rubber, ensure that the product has uniform vulcanization degree and reduce the product cost. Referring to table 2, in combination with examples 4 to 6, it can be seen that, as the addition amount of polypyrrole-graphene filler in the watch material is continuously increased, the antifouling property and mechanical property of the test piece are improved; on one hand, the polypyrrole-graphene filler can realize excellent photo-thermal effect to inhibit the adhesion of fouling organisms through the cooperation of graphene and nano polypyrrole, so that sweat loss on the surface and the inner layer of the watchband is accelerated under the photo-thermal effect on the surface of the watchband material, and meanwhile, the graphene lamellar structure can reduce the penetration of sweat to the watchband and reduce the world of inner antifouling groups; on the other hand, the addition of polypyrrole-graphene filler can increase the mechanical properties of the watchband material and prolong the service life of the watchband material.
Referring to table 2, in combination with examples 5, 7 and 8, it can be seen that calcium stearate is added as a plasticizer in the watchband system, and by reducing the intermolecular force, the glass transition temperature of the produced rubber is reduced, so that the rubber has plasticity and fluidity, is convenient for molding technical operations such as calendaring and extrusion, improves the processing technology of the rubber, improves the qualification rate and dimensional structure stability of the product, reduces energy consumption, and improves the mixing efficiency; the watchband material obtained by properly changing the addition amount of calcium stearate in the system has good antifouling property and mechanical property.
Referring to table 2, in combination with examples 7 and 9, it can be seen that the samples have good antifouling property and mechanical properties by changing the pigment addition amount within an appropriate range; the prepared watchband material has rich colors due to the addition of the pigment, different user requirements are met, and the diversity of products is improved.
Referring to table 2, in combination with examples 7, 10 and 11, it can be seen that the mechanical properties of the test pieces are continuously improved with increasing addition of the polydopamine modified layered inorganic compound in the watch material. The lamellar inorganic compound can play a role in reinforcement in two dimensions and the lamellar planes are oriented, so that it has high barrier properties. After being modified by polydopamine, the layered inorganic compound is easier to disperse between layers and between layers, is easier to interact with polymers, and improves the breaking elongation and the stretching mildness of the watchband.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. An anti-fouling watchband material, which is characterized in that: the composite material is prepared from the following raw materials in parts by weight: 100 parts of fluororubber modified raw rubber, 1-5 parts of vulcanizing agent, 1-2 parts of vulcanization accelerator, 20-40 parts of polypyrrole-graphene filler, 1-5 parts of plasticizer and 20-24 parts of pigment;
the preparation method of the polypyrrole-graphene modified waterborne polyurethane-epoxy resin comprises the following steps: the mass ratio is (2.5-4): 1, dispersing ammonium persulfate and hexadecane agent trimethyl ammonium bromide in hydrochloric acid solution to form mixed solution, dispersing graphene in the mixed solution by using ultrasonic dispersion, and dropwise adding pyrrole monomer for reaction, wherein the mass ratio of the graphene to the pyrrole is 1: (100-200), filtering after the reaction is finished, flushing a filter cake by using distilled water and ethanol, and drying in vacuum.
2. An anti-fouling wristband material according to claim 1, characterised in that: the fluororubber modified raw rubber comprises the following raw materials in parts by weight: 1 to 5.5 parts of monomer, 0.1 to 0.5 part of initiator, 0.05 to 0.75 part of emulsifier, 0.05 to 1.5 parts of chain transfer agent and 100 parts of deionized water; the mass ratio of the monomers is (60-70): (10-20): (15-25) a mixture of vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene and vinyl bromide monomers of 5.
3. An anti-fouling wristband material according to claim 2, characterised in that: the preparation method of the fluororubber modified raw rubber comprises the following steps: blowing nitrogen into a polymerization reaction kettle to remove oxygen, and adding deionized water, an emulsifying agent and a chain transfer agent; introducing the monomer mixture into a reaction kettle through a compressor, enabling the pressure in the reaction kettle to reach 2.4-3.6Mpa, starting stirring, and heating the mixture in the reaction kettle to 50-80 ℃; adding initiator, replenishing premixed monomer, initiator and chain transfer agent at intervals during polymerization, and maintaining the pressure at 3.6-7Mpa; simultaneously maintaining a stirring rate of 80-120r/min to maintain a reaction rate; after the reaction is finished, the emulsion is conveyed into a mixing kettle, and is subjected to condensation, washing and drying.
4. A stain resistant wristband material according to claim 3, wherein: the initiator is one or more of persulfate, persulfate-hydrosulfite, diisopropyl peroxydicarbonate and tert-butyl peroxyisobutyrate; the emulsifier is one or more of sodium salt or ammonium salt of perfluoro caprylic acid and lithium salt of perfluoro octyl sulfuric acid; the chain transfer agent is one or more of 1-bromo-3-iodo-perfluoropropane, 1, 4-diiodoperfluorobutane, isopentane and ethyl acetate.
5. An anti-fouling wristband material according to claim 1, characterised in that: the vulcanizing agent is one of dicumyl peroxide, 2, 5-dimethyl-2, 5-di-tert-butyl peroxy hexane and 1, 1-di-tert-butyl peroxy-3, 5-trimethyl cyclohexane; the vulcanization accelerator is one of triallyl isocyanurate, triallyl cyanurate and trimethylolpropane trimethacrylate; the plasticizer is one or more of calcium stearate, rhine 27, rhine 54 and polyvinyl alcohol-2000; the pigment is one or more of iron oxide red, iron oxide yellow, phthalocyanine green and iron oxide blue.
6. An anti-fouling wristband material according to claim 1, characterised in that: the raw materials of the antifouling watchband material also comprise 10-20 parts by weight of polydopamine modified lamellar inorganic compound; the preparation method of the polydopamine modified lamellar inorganic compound comprises the following steps: adding 0.1-1g/ml lamellar inorganic compound into alkaline solution with pH of 8-10, adding 0.1-1g/ml dopamine solution, performing oxidation self-polymerization at 20-30deg.C, and reacting for 15-25 h.
7. An anti-fouling wristband material according to claim 6, wherein: the layered inorganic compound is one or more of layered silicate compound, layered metal oxide, layered transition metal disulfide, diselenide, layered metal salt compound and layered double hydroxide.
8. A method for preparing an anti-fouling watchband material as claimed in any one of claims 1-7, characterized by: the method comprises the following steps:
s1, plasticating fluororubber modified raw rubber to obtain plasticated rubber material, and adding other raw materials into the plasticated rubber material to carry out banburying to obtain banburying rubber material;
s2, turning the banburying material, and cooling after turning to obtain a preformed sizing material;
s3, vulcanizing and forming the preformed sizing material.
9. The method for preparing an anti-fouling watchband material according to claim 8, wherein: in the step S1, plasticating time is 1-3min, and the temperature is not more than 100 ℃; the banburying time is 3-5min, and the temperature is not more than 65 ℃; in the step S2, the turning time is 10-15min, and the temperature is not more than 50 ℃; the cooling temperature is not more than 40 ℃.
10. The method for preparing an anti-fouling watchband material according to claim 8, wherein: in the step S3, vulcanization molding comprises primary vulcanization and secondary vulcanization, wherein the primary vulcanization temperature is 170-180 ℃ and the time is 6-10min; the temperature of the second-stage vulcanization is 180-200 ℃, and the vulcanization time is 6-12h.
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| CN112080130A (en) * | 2019-06-12 | 2020-12-15 | 万华化学集团股份有限公司 | Thermoplastic polyurethane elastomer/fluororubber blending material and preparation method thereof |
| CN111363076A (en) * | 2020-04-24 | 2020-07-03 | 四川道弘科技有限公司 | Ternary peroxide fluororubber and preparation method thereof, and intelligent wearing material and preparation method thereof |
| CN115703860A (en) * | 2021-08-05 | 2023-02-17 | 中昊晨光化工研究院有限公司 | Tetrafluoroethylene modified peroxide vulcanized binary fluorine rubber and preparation method thereof |
| CN113913100A (en) * | 2021-10-26 | 2022-01-11 | 哈尔滨工程大学 | Polypyrrole-graphene/polyurethane antifouling paint, and preparation method and application thereof |
| CN116102833A (en) * | 2021-11-10 | 2023-05-12 | 中昊晨光化工研究院有限公司 | Fluororubber compound capable of being compositely bonded and preparation method thereof |
| CN116162199A (en) * | 2021-11-25 | 2023-05-26 | 中昊晨光化工研究院有限公司 | Fluororubber raw rubber and preparation method thereof |
| CN115417942A (en) * | 2022-08-29 | 2022-12-02 | 四川道弘新材料有限公司 | Pre-crosslinked ternary peroxide fluororubber intelligent wearing material and preparation method thereof |
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