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CN111100274A - Preparation method of antibacterial nano-silver resin and non-stick coating containing resin - Google Patents

  • ️Tue May 05 2020
Preparation method of antibacterial nano-silver resin and non-stick coating containing resin Download PDF

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Publication number
CN111100274A
CN111100274A CN201911425822.3A CN201911425822A CN111100274A CN 111100274 A CN111100274 A CN 111100274A CN 201911425822 A CN201911425822 A CN 201911425822A CN 111100274 A CN111100274 A CN 111100274A Authority
CN
China
Prior art keywords
resin
nano silver
hyperbranched polyester
antibacterial
agent
Prior art date
2019-12-31
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201911425822.3A
Other languages
Chinese (zh)
Other versions
CN111100274B (en
Inventor
刘海龙
钱涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hangzhou Jihua Polymer Materials Co ltd
Original Assignee
Hangzhou Jihua Polymer Materials Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
2019-12-31
Filing date
2019-12-31
Publication date
2020-05-05
2019-12-31 Application filed by Hangzhou Jihua Polymer Materials Co ltd filed Critical Hangzhou Jihua Polymer Materials Co ltd
2019-12-31 Priority to CN201911425822.3A priority Critical patent/CN111100274B/en
2020-05-05 Publication of CN111100274A publication Critical patent/CN111100274A/en
2021-11-23 Application granted granted Critical
2021-11-23 Publication of CN111100274B publication Critical patent/CN111100274B/en
Status Active legal-status Critical Current
2039-12-31 Anticipated expiration legal-status Critical

Links

  • BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 111
  • 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 75
  • 239000011347 resin Substances 0.000 title claims abstract description 62
  • 229920005989 resin Polymers 0.000 title claims abstract description 61
  • 238000000576 coating method Methods 0.000 title claims abstract description 42
  • 239000011248 coating agent Substances 0.000 title claims abstract description 38
  • 238000002360 preparation method Methods 0.000 title claims abstract description 27
  • 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 77
  • 239000002245 particle Substances 0.000 claims abstract description 60
  • 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
  • XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
  • SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 34
  • LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
  • 239000002253 acid Substances 0.000 claims abstract description 25
  • 238000006243 chemical reaction Methods 0.000 claims abstract description 19
  • 150000007519 polyprotic acids Polymers 0.000 claims abstract description 19
  • XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
  • 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
  • 239000010703 silicon Substances 0.000 claims abstract description 18
  • 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 17
  • 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 16
  • 238000002156 mixing Methods 0.000 claims abstract description 13
  • 239000004645 polyester resin Substances 0.000 claims abstract description 13
  • 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
  • 238000000034 method Methods 0.000 claims description 27
  • 238000010438 heat treatment Methods 0.000 claims description 24
  • PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
  • CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 20
  • LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
  • 239000000049 pigment Substances 0.000 claims description 17
  • QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 14
  • ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 12
  • 239000000945 filler Substances 0.000 claims description 11
  • KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
  • WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
  • SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 10
  • 239000000919 ceramic Substances 0.000 claims description 9
  • 239000000843 powder Substances 0.000 claims description 9
  • SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 9
  • YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 7
  • 239000002270 dispersing agent Substances 0.000 claims description 7
  • 238000003756 stirring Methods 0.000 claims description 7
  • 239000002562 thickening agent Substances 0.000 claims description 7
  • PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 6
  • QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 6
  • ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 5
  • 229930003268 Vitamin C Natural products 0.000 claims description 5
  • 239000001361 adipic acid Substances 0.000 claims description 5
  • 235000011037 adipic acid Nutrition 0.000 claims description 5
  • 235000010323 ascorbic acid Nutrition 0.000 claims description 5
  • 239000011668 ascorbic acid Substances 0.000 claims description 5
  • 229960005070 ascorbic acid Drugs 0.000 claims description 5
  • HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
  • 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
  • 239000012279 sodium borohydride Substances 0.000 claims description 5
  • 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
  • 239000001509 sodium citrate Substances 0.000 claims description 5
  • NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
  • 235000019154 vitamin C Nutrition 0.000 claims description 5
  • 239000011718 vitamin C Substances 0.000 claims description 5
  • 239000008367 deionised water Substances 0.000 claims description 4
  • 229910021641 deionized water Inorganic materials 0.000 claims description 4
  • 150000002009 diols Chemical class 0.000 claims description 4
  • ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 4
  • 239000011261 inert gas Substances 0.000 claims description 4
  • XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
  • 239000012153 distilled water Substances 0.000 claims description 3
  • 235000011083 sodium citrates Nutrition 0.000 claims description 3
  • 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
  • 239000012498 ultrapure water Substances 0.000 claims description 3
  • 239000004599 antimicrobial Substances 0.000 claims description 2
  • 238000004519 manufacturing process Methods 0.000 claims description 2
  • 239000002671 adjuvant Substances 0.000 claims 1
  • 230000000845 anti-microbial effect Effects 0.000 claims 1
  • 239000013530 defoamer Substances 0.000 claims 1
  • 239000000178 monomer Substances 0.000 abstract description 13
  • 239000000463 material Substances 0.000 abstract description 10
  • 238000011065 in-situ storage Methods 0.000 abstract description 3
  • 150000005846 sugar alcohols Polymers 0.000 abstract description 2
  • 230000002194 synthesizing effect Effects 0.000 abstract 1
  • 239000003973 paint Substances 0.000 description 17
  • 238000009826 distribution Methods 0.000 description 16
  • 230000000052 comparative effect Effects 0.000 description 14
  • 238000012360 testing method Methods 0.000 description 10
  • 239000000047 product Substances 0.000 description 9
  • IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
  • UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
  • 229910052709 silver Inorganic materials 0.000 description 7
  • 239000004332 silver Substances 0.000 description 7
  • 239000003242 anti bacterial agent Substances 0.000 description 6
  • 239000002518 antifoaming agent Substances 0.000 description 6
  • 239000006229 carbon black Substances 0.000 description 6
  • 244000005700 microbiome Species 0.000 description 6
  • 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
  • 238000000354 decomposition reaction Methods 0.000 description 5
  • 230000000694 effects Effects 0.000 description 5
  • 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
  • VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
  • 239000012752 auxiliary agent Substances 0.000 description 4
  • XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 4
  • 239000006185 dispersion Substances 0.000 description 4
  • 229910052757 nitrogen Inorganic materials 0.000 description 4
  • 239000004135 Bone phosphate Substances 0.000 description 3
  • 150000008064 anhydrides Chemical class 0.000 description 3
  • 239000003054 catalyst Substances 0.000 description 3
  • 238000001816 cooling Methods 0.000 description 3
  • 125000000524 functional group Chemical group 0.000 description 3
  • 230000036541 health Effects 0.000 description 3
  • 238000005259 measurement Methods 0.000 description 3
  • 239000002082 metal nanoparticle Substances 0.000 description 3
  • 239000000203 mixture Substances 0.000 description 3
  • 230000004048 modification Effects 0.000 description 3
  • 238000012986 modification Methods 0.000 description 3
  • 238000000053 physical method Methods 0.000 description 3
  • 229920000642 polymer Polymers 0.000 description 3
  • 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
  • 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
  • 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
  • -1 silver ions Chemical class 0.000 description 3
  • 239000003381 stabilizer Substances 0.000 description 3
  • 230000000087 stabilizing effect Effects 0.000 description 3
  • 239000012855 volatile organic compound Substances 0.000 description 3
  • 241000894006 Bacteria Species 0.000 description 2
  • DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
  • FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
  • 230000002776 aggregation Effects 0.000 description 2
  • 150000001412 amines Chemical class 0.000 description 2
  • 230000008901 benefit Effects 0.000 description 2
  • 230000015572 biosynthetic process Effects 0.000 description 2
  • 230000003197 catalytic effect Effects 0.000 description 2
  • 210000000170 cell membrane Anatomy 0.000 description 2
  • 238000011161 development Methods 0.000 description 2
  • 238000010586 diagram Methods 0.000 description 2
  • FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
  • 239000002994 raw material Substances 0.000 description 2
  • 239000002904 solvent Substances 0.000 description 2
  • 239000000126 substance Substances 0.000 description 2
  • 238000003786 synthesis reaction Methods 0.000 description 2
  • 241000588724 Escherichia coli Species 0.000 description 1
  • UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
  • 241000191967 Staphylococcus aureus Species 0.000 description 1
  • 239000004480 active ingredient Substances 0.000 description 1
  • 238000005054 agglomeration Methods 0.000 description 1
  • 238000004220 aggregation Methods 0.000 description 1
  • 230000004075 alteration Effects 0.000 description 1
  • 229910052782 aluminium Inorganic materials 0.000 description 1
  • XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
  • 238000000498 ball milling Methods 0.000 description 1
  • 230000009286 beneficial effect Effects 0.000 description 1
  • 230000003115 biocidal effect Effects 0.000 description 1
  • 210000004027 cell Anatomy 0.000 description 1
  • 230000008859 change Effects 0.000 description 1
  • 238000005229 chemical vapour deposition Methods 0.000 description 1
  • 238000009833 condensation Methods 0.000 description 1
  • 230000005494 condensation Effects 0.000 description 1
  • 210000000805 cytoplasm Anatomy 0.000 description 1
  • 230000007547 defect Effects 0.000 description 1
  • 238000013461 design Methods 0.000 description 1
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  • 238000005516 engineering process Methods 0.000 description 1
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  • 150000002148 esters Chemical group 0.000 description 1
  • 238000011156 evaluation Methods 0.000 description 1
  • 230000002349 favourable effect Effects 0.000 description 1
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  • 230000006872 improvement Effects 0.000 description 1
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  • 238000010348 incorporation Methods 0.000 description 1
  • 238000007689 inspection Methods 0.000 description 1
  • 230000001788 irregular Effects 0.000 description 1
  • 230000002045 lasting effect Effects 0.000 description 1
  • 239000007788 liquid Substances 0.000 description 1
  • 229920002521 macromolecule Polymers 0.000 description 1
  • 230000007246 mechanism Effects 0.000 description 1
  • 238000006011 modification reaction Methods 0.000 description 1
  • 239000002086 nanomaterial Substances 0.000 description 1
  • 239000002105 nanoparticle Substances 0.000 description 1
  • 229920000620 organic polymer Polymers 0.000 description 1
  • 238000011056 performance test Methods 0.000 description 1
  • 238000005191 phase separation Methods 0.000 description 1
  • 238000012643 polycondensation polymerization Methods 0.000 description 1
  • 239000002861 polymer material Substances 0.000 description 1
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  • 239000000376 reactant Substances 0.000 description 1
  • 238000011160 research Methods 0.000 description 1
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  • 238000006748 scratching Methods 0.000 description 1
  • 230000002393 scratching effect Effects 0.000 description 1
  • 238000003980 solgel method Methods 0.000 description 1
  • 238000004544 sputter deposition Methods 0.000 description 1
  • 230000001954 sterilising effect Effects 0.000 description 1
  • 238000004659 sterilization and disinfection Methods 0.000 description 1
  • 230000004083 survival effect Effects 0.000 description 1
  • 210000001519 tissue Anatomy 0.000 description 1
  • 230000001988 toxicity Effects 0.000 description 1
  • 231100000419 toxicity Toxicity 0.000 description 1
  • 238000004804 winding Methods 0.000 description 1

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
    • C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to the field of materials, and discloses a preparation method of antibacterial nano-silver resin and a non-stick coating containing the resin, wherein the preparation method of the antibacterial nano-silver resin comprises the following steps: 1) synthesizing a hyperbranched polyester template agent by taking trihydric alcohol, dihydric alcohol, dibasic acid and polybasic acid anhydride as monomers; 2) adjusting the pH value of the hyperbranched polyester template agent to 4-6, adding a silver nitrate solution, and dropwise adding a reducing agent to prepare nano silver particles; 3) and mixing the nano silver particles with the water-based organic silicon modified hyperbranched polyester resin to obtain the antibacterial nano silver resin. The preparation method comprises the steps of firstly preparing a hyperbranched polyester template agent by taking polyhydric alcohol and polybasic acid as monomers, then carrying out in-situ reaction on silver nitrate and a reducing agent in the template agent to generate nano silver particles, finally mixing the nano silver particles with the waterborne organic silicon modified hyperbranched polyester to obtain the antibacterial nano silver resin, and carrying out coating treatment to obtain the non-stick coating containing the resin.

Description

Preparation method of antibacterial nano-silver resin and non-stick coating containing resin

Technical Field

The invention relates to the field of high polymer materials, in particular to a preparation method of antibacterial nano silver resin and a non-stick coating containing the resin.

Background

At present, the coating is mainly solvent-based, and discharged Volatile Organic Compounds (VOCs) cause serious harm to the environment. With the increasing quality of modern life, people are increasingly demanding on water-based paints or paints with low content of VOCs, however, the requirements are limited by the performance of the water-based paint and the level of the coating technology, the domestic water-based paints have a larger promotion space in the application aspect and are not popularized in a large range, and therefore, the development of the high-performance water-based paints is very urgent.

Among them, the water-based paint faces the challenge of the propagation of a large number of microorganisms such as bacteria under the environment with appropriate temperature and humidity, and interferes with the final performance of the paint. Meanwhile, with the development of society and the continuous improvement of living standard, people pay more and more attention to health and environmental protection, microorganisms are ubiquitous in the environment, and the survival and health of people are threatened by various bacteria all the time. The antibacterial requirement exists in a plurality of fields such as facilities, tools, utensils and the like which people contact in daily work and life. The antibacterial coating is coated on the surfaces of various materials to form a coating with antibacterial effect, and is an ideal material meeting various antibacterial requirements. The non-stick coating is mainly used for cookers, small household appliances and the like, the coating is a material which is directly contacted by a user, and the health requirement of the user on antibiosis is very strong, so that the research and application of the antibacterial coating are greatly concerned.

The silver-based antibacterial agent has a strong antibacterial effect, good thermal stability, a lasting antibacterial effect and no obvious toxicity to cells and tissues, and is widely applied. The silver-based antibacterial agents can be classified into conventional ones according to the particle size of the antibacterial particlesType and nano type. Traditional silver based antimicrobial agents release silver ions (Ag) upon contact with liquids+)，Ag+Positively charged, attracting negatively charged microorganisms into contact therewith, through Ag+The biochemical properties of (a), killing microorganisms; the active ingredient of the nano silver particle antibacterial agent is nano silver particles with the particle size of 1-100 nm, and the nano silver particle antibacterial agent can release Ag when in use+Therefore, the nano silver particle antibacterial agent has substantially the same antibacterial mechanism as the conventional silver-based antibacterial agent. In addition, the nano silver particles have obvious volume and surface effects, can be adsorbed on the surfaces of microorganisms, cause the form change of cell membranes, destroy the cell membranes and enable cytoplasm to flow out, and therefore the microorganisms are killed, and the better sterilization effect is achieved.

The preparation method of the nano silver particles mainly comprises a physical method and a chemical method. The commonly used physical methods are a mechanical ball milling method, a sputtering method, an inert gas condensation method, a plasma method and the like, the purity of the product prepared by the method is high, but the cost of the adopted equipment is high, a large amount of energy is consumed to reduce the size of the material to the nanometer level, and the yield is low. The commonly used chemical methods include chemical vapor deposition, electrochemical methods, template methods, sol-gel methods, etc., which have the disadvantages of easy incorporation of impurities and impure obtained products, but have the advantages of regular and uniform obtained nano-materials, easy mass production and simple and convenient equipment compared with physical methods.

In the process of preparing the antibacterial nano silver particles by adopting a template method, the template and the stabilizer are important for controlling the shape and size of nano silver, dispersion stability, the surface activity of nano particles, the release rate of silver ions and the like, the surface activity influences the catalytic performance, the release rate of the silver ions determines the antibacterial property of the material, namely, the selection of the stabilizer is closely related to the catalytic performance, the antibacterial activity and the safety of the material. Among various templates and stabilizers, macromolecules have the advantages of flexible structural design, a large number of functional groups contained in each chain (a plurality of points are provided for stabilizing metal nanoparticles), good stabilizing effect and the like, however, the aggregation and entanglement of linear polymer chains can cause the agglomeration of the metal nanoparticles, and the stabilizing effect on the metal nanoparticles is not ideal.

Disclosure of Invention

In order to solve the technical problems, the invention provides a preparation method of antibacterial nano-silver resin and a non-stick coating containing the resin2+B3The method' simultaneously introduces a central core mode, uses polyalcohol and polybasic acid as monomers to prepare a hyperbranched polyester template agent, then silver nitrate and a reducing agent react in situ in the template agent to generate nano silver particles, and finally the nano silver particles are mixed with the waterborne organic silicon modified hyperbranched polyester to obtain the antibacterial nano silver resin, and the nonstick coating containing the resin is obtained after coating.

The specific technical scheme of the invention is as follows:

a preparation method of antibacterial nano-silver resin comprises the following steps:

1) preparing a hyperbranched polyester template agent: adding the trihydric alcohol into a reaction bottle, heating to 60-80 ℃ until the trihydric alcohol is completely dissolved, then adding the dihydric alcohol, heating to 100-120 ℃ until the dihydric alcohol is completely dissolved, adding the dibasic acid and the polybasic acid anhydride, heating to 140-180 ℃ and reacting until the acid value is 70-100mgKOH/g, thus obtaining the hyperbranched polyester template, wherein the mass ratio of the trihydric alcohol, the dibasic acid, the polybasic acid anhydride and the dihydric alcohol is 1.8-5.4:0.5-0.9:2.4-6.3: 1.

2) Preparing nano silver particles: adjusting the pH value of the hyperbranched polyester template agent prepared in the step 1) to 4-6, adding a silver nitrate solution, uniformly stirring, and slowly dropwise adding a reducing agent under the protection of inert gas to obtain the nano silver particles, wherein the mass ratio of the hyperbranched polyester template agent to the reducing agent to the silver nitrate is 15-35:5-10: 1.

3) Preparing antibacterial nano silver resin: uniformly mixing the nano silver particles prepared in the step 2) with the water-based organic silicon modified hyperbranched polyester resin to obtain the antibacterial nano silver resin, wherein the concentration of the nano silver particles is 20-50 mu g/mL.

The heat-resistant non-stick coating contains antibacterial nano-silver resin, heat-resistant pigment filler and water, wherein the antibacterial nano-silver resin is prepared by the method, and the mass ratio of the antibacterial nano-silver resin to the heat-resistant pigment filler to the water is 2-10:2-5: 2.

The technical principle of the invention is as follows: the hyperbranched polyester prepared by a specific method is used as a template and a protective agent to prepare nano silver particles, and the inorganic reactant is dispersed and embedded by the hyperbranched polyester, so that the hyperbranched net structure can provide a micro chemical reaction environment and a growth space for constructing an ordered inorganic structure, and the inorganic nano silver with controllable size, morphology and orientation can be grown in situ by an organic polymer phase. Therefore, the hyperbranched polyester has rich ester functional groups, no chain winding and large internal cavity, and is an ideal template for preparing nano silver.

The film-forming resin of the non-stick coating is water-based organic silicon modified hyperbranched polyester resin, compared with nano silver particles prepared by other methods, nano silver particles prepared by using hyperbranched polyester as a template have similar structures and better compatibility with the film-forming resin, and the nano silver particles prepared by the method have uniform particle size, good dispersibility and large specific surface area, can achieve excellent antibacterial property by adding a small amount (ppm level), and are suitable for the field of non-stick coatings needing high temperature resistance due to regular structure and excellent heat resistance.

The invention adopts' A2+B3The method (the difunctional monomer and the trifunctional monomer) prepares the hyperbranched polyester template agent in a one-step feeding method (alcohol and acid monomers are added at one time), wherein the triol has the trifunctional degree and can react with the dibasic acid with the difunctional and the polybasic acid anhydride to generate the hyperbranched polyester with the terminal hydroxyl group and the intramolecular carboxyl group (the carboxyl group from the polybasic acid anhydride which does not participate in the reaction of the alcohol and the acid).

However, the inventor finds that A is2And B3The condensation polymerization of the monomer is easy to generate gel, the molecular weight distribution of the obtained polymer is wide, and C is added into the system to relieve the phenomenon2The intermediate diol is used as a central core, the proportion of the dibasic acid, the polybasic acid anhydride and the tribasic alcohol is controlled to avoid the generation of a gel phenomenon, and the distribution and the structure of the molecular weight are controlled to obtain a regular and separate structureA hyperbranched polyester template with narrow molecular weight distribution.

Selected from C2The hydroxyl activity of monomer dihydric alcohol is higher, and the monomer dihydric alcohol preferentially participates in the reaction with polybasic acid with two functionalities compared with the trihydric alcohol, so that a hyperbranched structure is formed by gradually diffusing and stretching branched monomers starting from a central core molecule, the dispersibility of a final product is controlled, the occurrence of gel points is avoided, and the prepared hyperbranched polyester has a regular structure and narrow molecular weight distribution, so that C2The addition of the monomeric diol is necessary and a detailed schematic of the above reaction process is shown in FIG. 1.

The designed and synthesized hyperbranched polyester template agent has various functional groups and is favorable for being combined with nano silver particles. The preparation conditions are mild and green: the catalyst is synthesized by a one-step feeding method, no catalyst is added, no or little solvent is used, and the normal pressure and the temperature are moderate. The prepared nano silver particles are used as an antibacterial component and added into the aqueous organic silicon modified hyperbranched polyester resin according to a certain proportion to obtain antibacterial nano silver resin, and the antibacterial non-stick coating product is prepared according to a paint preparation process.

Preferably, in step 1), the triol is one or more selected from glycerol, trimethylolpropane and trimethylolethane.

Preferably, in step 1), the diol is selected from one or more of ethylene glycol, 1, 4-cyclohexanedimethanol and neopentyl glycol.

Preferably, in step 1), the dibasic acid is selected from one or more of isophthalic acid, terephthalic acid, adipic acid and 1, 4-cyclohexanedicarboxylic acid.

Preferably, in step 1), the polybasic acid anhydride is selected from one or two of trimellitic anhydride and pyromellitic anhydride.

Preferably, in the step 2), the reducing agent is one or more selected from sodium borohydride, vitamin C, ascorbic acid and sodium citrate.

Preferably, the aqueous organosilicon modified hyperbranched polyester resin is prepared by steps of hyperbranched polyester synthesis, anhydride end-capping reaction, organosilicon intermediate modification, organic amine salification and water dispersion.

In the non-stick coating, the heat-resistant pigment is a high-temperature-resistant pigment commonly used in the field, and can be inorganic high-temperature-resistant pigment such as carbon black, iron oxide red and the like, and can also be organic high-temperature-resistant pigment such as phthalocyanine blue and the like.

In the non-stick coating, the heat-resistant filler is a high-temperature-resistant filler commonly used in the field and can be ceramic powder or silicon carbide.

In the non-stick coating, water is distilled water, ultrapure water or deionized water.

The non-stick coating can be added with an auxiliary agent, preferably, the added auxiliary agent is one or more of a dispersing agent, a flatting agent, a defoaming agent and a thickening agent.

Compared with the prior art, the invention has the beneficial effects that:

1. the 'A' is realized by controlling the proportion of dibasic acid, polybasic acid anhydride and tribasic alcohol and introducing the dibasic alcohol as a central core2+B3The method prepares the hyperbranched polyester template agent which has regular structure and narrow molecular weight distribution and is rich in hydroxyl and carboxyl functional groups in a one-step feeding method, and the preparation condition is mild and green.

2. The nano silver particles prepared by the template agent have uniform particle size and good dispersion stability, have a similar structure with the water-based organic silicon modified hyperbranched polyester of the film-forming resin, and have better compatibility.

3. The obtained nano silver particles are used as an antibacterial component, have good heat resistance, have excellent antibacterial performance and do not influence the original performance of the film-forming resin when being added in a small amount (ppm level), and the prepared non-stick coating has excellent antibacterial property, heat resistance and non-stick property.

Drawings

FIG. 1 is a schematic diagram of the reaction principle of a hyperbranched polyester template;

FIG. 2 is a GPC chart of a hyperbranched polyester templating agent prepared in step 1) of example 1; (number average molecular weight 2477, weight average molecular weight 3666, molecular weight distribution index 1.48, molecular weight distribution narrow);

FIG. 3 is a TGA diagram of the antibacterial nanosilver resin prepared in step 3) of example 1; (decomposition temperature was 437 ℃ C., and heat resistance was good).

Detailed Description

The present invention will be further described with reference to the following examples.

General examples

A preparation method of antibacterial nano-silver resin comprises the following steps:

1) preparing a hyperbranched polyester template agent: adding the trihydric alcohol into a reaction bottle, heating to 60-80 ℃ until the trihydric alcohol is completely dissolved, then adding the dihydric alcohol, heating to 100-120 ℃ until the dihydric alcohol is completely dissolved, adding the dibasic acid and the polybasic acid anhydride, heating to 140-180 ℃ and reacting until the acid value is 70-100mgKOH/g, thus obtaining the hyperbranched polyester template, wherein the mass ratio of the trihydric alcohol, the dibasic acid, the polybasic acid anhydride and the dihydric alcohol is 1.8-5.4:0.5-0.9:2.4-6.3: 1.

The trihydric alcohol is selected from glycerol, trimethylolpropane and trimethylolethane. The dihydric alcohol is selected from ethylene glycol, 1, 4-cyclohexanedimethanol and neopentyl glycol. The dibasic acid is selected from isophthalic acid, terephthalic acid, adipic acid and 1, 4-cyclohexanedicarboxylic acid. The polybasic acid anhydride is selected from trimellitic anhydride and pyromellitic anhydride.

2) Preparing nano silver particles: adjusting the pH value of the hyperbranched polyester template agent prepared in the step 1) to 4-6, adding a silver nitrate solution, stirring uniformly, and slowly dropwise adding a newly prepared reducing agent under the protection of inert gas to obtain the nano silver particles, wherein the mass ratio of the hyperbranched polyester template agent to the reducing agent to the silver nitrate is 15-35:5-10: 1.

The reducing agent is selected from sodium borohydride, vitamin C, ascorbic acid and sodium citrate.

3) Preparing antibacterial nano silver resin: uniformly mixing the nano silver particles prepared in the step 2) with self-made water-based organic silicon modified hyperbranched polyester resin to obtain the antibacterial nano silver resin, wherein the concentration of the nano silver particles is 20-50 mu g/mL.

The waterborne organic silicon modified hyperbranched polyester resin is prepared by the procedures of hyperbranched polyester synthesis, anhydride end capping reaction, organic silicon intermediate modification, organic amine salification and water dispersion.

The heat-resistant non-stick coating contains antibacterial nano-silver resin, heat-resistant pigment filler and water, wherein the antibacterial nano-silver resin is prepared by the method, and the mass ratio of the antibacterial nano-silver resin to the heat-resistant pigment filler to the water is 2-10:2-5: 2.

The heat-resistant pigment is a high-temperature resistant pigment commonly used in the field, and can be inorganic high-temperature resistant pigments such as carbon black, iron oxide red and the like, and can also be organic high-temperature resistant pigments such as phthalocyanine blue and the like. The heat-resistant filler is a high-temperature-resistant filler commonly used in the field and can be ceramic powder or silicon carbide. The water is distilled water, ultrapure water or deionized water. The non-stick coating can also be added with an auxiliary agent, preferably, the added auxiliary agent is one or more of a dispersing agent, a flatting agent, a defoaming agent and a thickening agent.

Example 1

1) Preparing a hyperbranched polyester template agent: adding trimethylolpropane into a reaction bottle, heating to 80 ℃ until the trimethylolpropane is completely dissolved, then adding neopentyl glycol, heating to 120 ℃ until the neopentyl glycol is completely dissolved, adding isophthalic acid and pyromellitic dianhydride, heating to 180 ℃, and reacting until the acid value is 100mgKOH/g, thus obtaining the hyperbranched polyester template, wherein the mass ratio of the trimethylolpropane to the isophthalic acid to the pyromellitic dianhydride to the neopentyl glycol is 3.6: 0.6: 3.8: 1. As shown in FIG. 2, the number average molecular weight of the hyperbranched polyester template obtained by GPC measurement is 2477, and the molecular weight distribution index is 1.48.

2) Preparing nano silver particles: adjusting the pH value of the hyperbranched polyester template agent prepared in the step 1) to 6, adding a silver nitrate solution, uniformly stirring, and slowly dropwise adding newly prepared sodium borohydride under the protection of nitrogen to obtain the nano silver particles, wherein the mass ratio of the hyperbranched polyester template agent to the sodium borohydride to the silver nitrate is 35: 10: 1.

3) Preparing antibacterial nano silver resin: uniformly mixing the nano silver particles prepared in the step 2) with the water-based organic silicon modified hyperbranched polyester resin to obtain the antibacterial nano silver resin, wherein the concentration of the nano silver particles is 20 mug/mL. As shown in FIG. 3, the decomposition temperature of the antibacterial nano-silver resin is 437 ℃ by TGA test.

4) Preparation of heat-resistant non-stick paint: mixing the antibacterial nano silver resin, the carbon black, the ceramic powder and water, adding a dispersing agent, a flatting agent, a defoaming agent and a thickening agent, and preparing a finished product according to a paint preparation process, wherein the mass ratio of the antibacterial nano silver resin to the water to the carbon black to the ceramic powder is 2: 1.

The preparation method of the water-based organic silicon modified hyperbranched polyester comprises the following steps: adding 34 parts by mass of trimethylolpropane and 9 parts by mass of neopentyl glycol into a reaction kettle, and heating to 140 ℃ until the trimethylolpropane and the neopentyl glycol are completely dissolved; then adding 32 parts by mass of isophthalic acid, heating to 170 ℃, keeping the temperature for 1h, heating to 220 ℃, and reacting until the acid value is less than 10mgKOH/g to obtain the hyperbranched polyester. And cooling to 160 ℃, adding 13 parts by mass of butyl acetate and 11 parts by mass of trimellitic anhydride, and reacting for 2 hours to obtain the anhydride terminated hyperbranched polyester. Cooling to 130 ℃, adding 13 parts by mass of butyl acetate and 50 parts by mass of organic silicon intermediate

Figure BDA0002350393600000061

IC232 and 0.3 parts by mass of catalyst, modification reaction to clarity. And cooling to 80 ℃, adding 9 parts by mass of N, N-dimethylethanolamine, carrying out salt forming reaction for 30min, adding into 13 parts by mass of deionized water, and dispersing at high speed for 15min to obtain a finished product.

Example 2

1) Preparing a hyperbranched polyester template agent: adding glycerol into a reaction bottle, heating to 60 ℃ until the glycerol is completely dissolved, then adding 1, 4-cyclohexanedimethanol, heating to 100 ℃ until the glycerol is completely dissolved, adding terephthalic acid and trimellitic anhydride, heating to 140 ℃, and reacting until the acid value is 70mgKOH/g, thus obtaining the hyperbranched polyester template, wherein the mass ratio of the glycerol to the terephthalic acid to the trimellitic anhydride to the 1, 4-cyclohexanedimethanol is 1.8: 0.5: 2.4: 1. The number average molecular weight of the hyperbranched polyester template agent is 2598 and the molecular weight distribution index is 1.43 through GPC test.

2) Preparing nano silver particles: adjusting the pH value of the hyperbranched polyester template agent prepared in the step 1) to 4, adding a silver nitrate solution, uniformly stirring, and slowly dropwise adding newly prepared vitamin C under the protection of nitrogen to obtain the nano silver particles, wherein the mass ratio of the hyperbranched polyester template agent to the vitamin C to the silver nitrate is 15: 5: 1.

3) Preparing antibacterial nano silver resin: and (3) uniformly mixing the nano silver particles prepared in the step 2) with the water-based organic silicon modified hyperbranched polyester resin (the preparation method is the same as that of the embodiment 1) to obtain the antibacterial nano silver resin, wherein the concentration of the nano silver particles is 50 mu g/mL. The decomposition temperature of the antibacterial nano silver resin is 428 ℃ through TGA test.

4) Preparation of heat-resistant non-stick paint: mixing the antibacterial nano silver resin, the iron oxide red, the silicon carbide and the water, adding a dispersing agent, a flatting agent, a defoaming agent and a thickening agent, and preparing a finished product according to a paint preparation process, wherein the mass ratio of the antibacterial nano silver resin to the water to the iron oxide red to the silicon carbide is 10: 5: 1.

Example 3

1) Preparing a hyperbranched polyester template agent: adding trimethylolethane into a reaction bottle, heating to 80 ℃ until the trimethylolethane is completely dissolved, then adding ethylene glycol, heating to 100 ℃ until the ethylene glycol is completely dissolved, adding adipic acid and pyromellitic dianhydride, heating to 150 ℃, and reacting until the acid value is 90mgKOH/g, thus obtaining the hyperbranched polyester template, wherein the mass ratio of the trimethylolethane to the adipic acid to the pyromellitic dianhydride to the ethylene glycol is 5.4: 0.9: 6.3: 1. The number average molecular weight of the hyperbranched polyester template agent is 2346 and the molecular weight distribution index is 1.52 through GPC measurement.

2) Preparing nano silver particles: adjusting the pH value of the hyperbranched polyester template agent prepared in the step 1) to 6, adding a silver nitrate solution, uniformly stirring, and slowly dropwise adding newly prepared ascorbic acid under the protection of nitrogen to obtain the nano silver particles, wherein the mass ratio of the hyperbranched polyester template agent to the ascorbic acid to the silver nitrate is 25: 8: 1.

3) Preparing antibacterial nano silver resin: and (3) uniformly mixing the nano silver particles prepared in the step 2) with the water-based organic silicon modified hyperbranched polyester resin (the preparation method is the same as that of the embodiment 1), so as to obtain the antibacterial nano silver resin, wherein the concentration of the nano silver particles is 25 mug/mL. The decomposition temperature of the antibacterial nano silver resin is 413 ℃ through TGA test.

4) Preparation of heat-resistant non-stick paint: mixing the antibacterial nano silver resin, the phthalocyanine blue, the ceramic powder and water, adding a dispersing agent, a flatting agent, a defoaming agent and a thickening agent, and preparing a finished product according to a paint preparation process, wherein the mass ratio of the antibacterial nano silver resin to the water to the phthalocyanine blue to the ceramic powder is 5: 2: 0.5: 1.5.

Example 4

1) Preparing a hyperbranched polyester template agent: adding trimethylolpropane into a reaction bottle, heating to 80 ℃ until the trimethylolpropane is completely dissolved, then adding 1, 4-cyclohexanedimethanol, heating to 120 ℃ until the 1, 4-cyclohexanedicarboxylic acid and trimellitic anhydride are completely dissolved, adding 1, 4-cyclohexanedicarboxylic acid and trimellitic anhydride, heating to 160 ℃, and reacting until the acid value is 80mgKOH/g, thus obtaining the hyperbranched polyester template, wherein the mass ratio of the trimethylolpropane, the 1, 4-cyclohexanedicarboxylic acid, the trimellitic anhydride and the 1, 4-cyclohexanedimethanol is 2.6: 0.5: 2.4: 1. The number average molecular weight of the hyperbranched polyester template agent is 2614 and the molecular weight distribution index is 1.41 through GPC test.

2) Preparing nano silver particles: adjusting the pH value of the hyperbranched polyester template agent prepared in the step 1) to 6, adding a silver nitrate solution, stirring uniformly, and slowly dropwise adding newly prepared sodium citrate under the protection of nitrogen to obtain the nano silver particles, wherein the mass ratio of the hyperbranched polyester template agent to the sodium citrate to the silver nitrate is 30: 10: 1.

3) Preparing antibacterial nano silver resin: and (3) uniformly mixing the nano silver particles prepared in the step 2) with the water-based organic silicon modified hyperbranched polyester resin (the preparation method is the same as that of the embodiment 1), so as to obtain the antibacterial nano silver resin, wherein the concentration of the nano silver particles is 30 mu g/mL. The decomposition temperature of the antibacterial nano silver resin is 452 ℃ through TGA test.

4) Preparation of heat-resistant non-stick paint: mixing the antibacterial nano silver resin, the carbon black, the ceramic powder and the water, adding a dispersing agent, a flatting agent, a defoaming agent and a thickening agent, and preparing a finished product according to a paint preparation process, wherein the mass ratio of the antibacterial nano silver resin to the water to the carbon black to the ceramic powder is 10: 5: 0.5: 1.5.

Comparative example 1

The only difference from example 1 is that the templating agent is polyvinylpyrrolidone (PVP), and the remaining steps and materials and compositions are in accordance with example 1.

Comparative example 2

The only difference from example 1 is that in step 1), no C is added2The monomers neopentyl glycol, the remaining steps and the materials and compositions correspond to those of example 1. The number average molecular weight of the hyperbranched polyester template agent is 4658 and the molecular weight distribution index is 2.98 through GPC test.

Comparative example 3

The only difference from example 1 is that in step 1), the mass ratio of trimethylolpropane, isophthalic acid, pyromellitic anhydride and neopentyl glycol was 10: 2: 5: 1, and the rest of the steps and the materials and compositions were identical to those of example 1. The number average molecular weight of the hyperbranched polyester template agent is 5475 and the molecular weight distribution index is 2.57 through GPC measurement.

The heat-resistant non-stick coatings prepared in the

embodiments

1 to 4 and the comparative examples 1 to 3 are respectively coated on an aluminum pot (the thickness is 20 to 30 μm), and then the hardness, the heat resistance, the antibacterial property, the non-stick property and other properties of the heat-resistant non-stick coatings are detected, wherein the hardness test is performed according to GB/T6739, and the results are evaluated as follows: scratching a paint film; the heat resistance is determined according to the GB/T1735-2009, and the results are evaluated as follows: the color difference is less than or equal to 1.0; the antibacterial property test is carried out according to the ISO 22196 plus 2011, and the result evaluation is as follows: the antibacterial efficacy value to staphylococcus aureus and escherichia coli is more than or equal to 2; the tack free test was performed as specified in GB/T32095.2-2015 and the results rated: 10 omelettes were kept intact and the results are shown in table 1.

Table 1 examples 1-4 and comparative examples 1-3 non-stick coating product performance test results:

hardness of pencil Heat resistance Antibacterial property Non-tackiness
Example 1 3H Qualified Qualified Qualified
Example 2 2H Qualified Qualified Qualified
Example 3 2H Qualified Qualified Qualified
Example 4 3H Qualified Qualified Qualified
Comparative example 1 HB Fail to be qualified Fail to be qualified Fail to be qualified
Comparative example 2 2H Fail to be qualified Fail to be qualified Fail to be qualified
Comparative example 3 2H Fail to be qualified Qualified Fail to be qualified

Through inspection, the prepared nano silver particles are good by adopting the commonly used polymer PVP as a template in the comparative example 1, but the nano silver particles are poor in compatibility with the water-based organic silicon modified hyperbranched polyester resin and difficult to uniformly distribute in the non-stick coating, and various performances are poor due to large defects of the coating due to macroscopic phase separation of the coating; comparative example 2 No C2The monomer is used as a central core, the prepared hyperbranched polyester template has wide molecular weight distribution (the molecular weight distribution index is 2.98), gel is generated in the preparation process, which indicates that the structure of the hyperbranched polyester is irregular, and as the particle size of nano silver particles prepared by the hyperbranched polyester template is large, the same antibacterial property can not be achieved under the same dosage, and the gel influences the heat resistance and the non-adhesiveness of the coating in the coating; similarly, although comparative example 3 uses C2The monomer is used as a central core, the structure of the hyperbranched polyester template is relatively regular, the prepared nano silver particles are good, and the antibacterial property can meet the requirements, but because the proportion of the dibasic acid, the polybasic acid anhydride and the trihydric alcohol is not accurately controlled (the ratio of the hydroxyl to the carboxyl in the reaction of the comparative example 3 is 3.5, and the ratio of the hydroxyl to the carboxyl in the reaction of the comparative example 3 is controlled to be 2.4), gel can also appear, and the heat resistance and the non-adhesiveness of the coating are damaged. The heat-resistant non-stick coatings of examples 1-4 have excellent hardness, heat resistance, antibacterial property and non-stick property compared with comparative examples, which show that by controlling the ratio of dibasic acid, polybasic acid anhydride and tribasic alcohol and introducing dibasic alcohol as a central core, the prepared hyperbranched polyester template has narrow molecular weight distribution and regular structure, and the prepared hyperbranched polyester template has high strength, high toughness and good water resistanceThe obtained nano silver particles have good compatibility with the film-forming resin, and can have excellent antibacterial performance without influencing the original performance of the film-forming resin by adding a small amount of the nano silver particles, so that the prepared non-stick coating has excellent antibacterial performance, heat resistance and non-stick performance.

The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (10)

1. The preparation method of the antibacterial nano-silver resin is characterized by comprising the following steps:

1) preparing a hyperbranched polyester template agent: adding the trihydric alcohol into a reaction vessel, heating to 60-80 ℃ until the trihydric alcohol is completely dissolved, then adding the dihydric alcohol, heating to 100-120 ℃ until the dihydric alcohol is completely dissolved, adding the dibasic acid and the polybasic acid anhydride, heating to 140-180 ℃ and reacting until the acid value is 70-100mgKOH/g, thus obtaining the hyperbranched polyester template agent; the mass ratio of the trihydric alcohol to the dibasic acid to the polybasic acid anhydride to the dihydric alcohol is 1.8-5.4:0.5-0.9:2.4-6.3: 1;

2) preparing nano silver particles: adjusting the pH value of the hyperbranched polyester template agent prepared in the step 1) to 4-6, adding a silver nitrate solution, uniformly stirring, and slowly dropwise adding a reducing agent under the protection of inert gas to obtain nano silver particles, wherein the mass ratio of the hyperbranched polyester template agent to the reducing agent to the silver nitrate is 15-35:5-10: 1;

3) preparing antibacterial nano silver resin: uniformly mixing the nano silver particles prepared in the step 2) with the water-based organic silicon modified hyperbranched polyester resin to obtain the antibacterial nano silver resin, wherein the concentration of the nano silver particles is 20-50 mu g/mL.

2. The method of claim 1, wherein in step 1), the triol is one or more selected from the group consisting of glycerol, trimethylolpropane and trimethylolethane.

3. The method according to claim 1, wherein in step 1), the diol is one or more selected from the group consisting of ethylene glycol, 1, 4-cyclohexanedimethanol, and neopentyl glycol.

4. The method according to claim 1, wherein in step 1), the dibasic acid is one or more selected from the group consisting of isophthalic acid, terephthalic acid, adipic acid and 1, 4-cyclohexanedicarboxylic acid.

5. The production method according to claim 1, wherein in step 1), the polybasic acid anhydride is selected from one or both of trimellitic anhydride and pyromellitic anhydride.

6. The method of claim 1, wherein in step 2), the reducing agent is selected from one or more of sodium borohydride, vitamin C, ascorbic acid, and sodium citrate.

7. A heat resistant non-stick coating comprising an antibacterial nanosilver resin prepared by the method of any one of claims 1 to 6.

8. The heat resistant non-stick coating of claim 7 containing an antimicrobial nanosilver resin, a heat resistant pigment filler and water; the mass ratio of the antibacterial nano silver resin to the water to the heat-resistant pigment filler is 2-10:2-5: 2.

9. The heat resistant non-stick coating of claim 8, wherein the heat resistant pigment is an inorganic high temperature resistant pigment and/or an organic high temperature resistant pigment; the heat-resistant filler is ceramic powder and/or silicon carbide; the water is distilled water and/or ultrapure water and/or deionized water.

10. The heat resistant non-stick coating of claim 7 further comprising an adjuvant which is one or more of a dispersant, a leveling agent, a defoamer and a thickener.

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