CN104974658A - Nano-modified high-corrosion-resistance electric-conduction UV (Ultraviolet) coating material and preparation method therefor - Google Patents
Nano-modified high-corrosion-resistance electric-conduction UV (Ultraviolet) coating material and preparation method therefor Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 42
- 239000011248 coating agent Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000000463 material Substances 0.000 title abstract description 8
- 229960000892 attapulgite Drugs 0.000 claims abstract description 35
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 26
- 238000005260 corrosion Methods 0.000 claims abstract description 11
- 230000007797 corrosion Effects 0.000 claims abstract description 11
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 8
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- -1 (methyl) glycidyl Chemical group 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000013530 defoamer Substances 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical group CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 229920006026 co-polymeric resin Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 3
- NQOGBCBPDVTBFM-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol;prop-2-enoic acid Chemical group OC(=O)C=C.CC(O)COC(C)COC(C)CO NQOGBCBPDVTBFM-UHFFFAOYSA-N 0.000 claims description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- 229920005732 JONCRYL® 678 Polymers 0.000 claims description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 3
- NIPYIXMXODGEES-UHFFFAOYSA-N hexanoyl bromide Chemical group CCCCCC(Br)=O NIPYIXMXODGEES-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- LTOKKZDSYQQAHL-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCC1CO1 LTOKKZDSYQQAHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001262 acyl bromides Chemical class 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011247 coating layer Substances 0.000 abstract 2
- 239000012855 volatile organic compound Substances 0.000 abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000007822 coupling agent Substances 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 abstract 1
- 229920002635 polyurethane Polymers 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 3
- 230000002421 anti-septic effect Effects 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical group C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002118 epoxides Chemical group 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZHUWIYQJHBMTCY-UHFFFAOYSA-N 3-[ethoxy(2,2,2-triethoxyethoxy)silyl]propan-1-amine Chemical compound NCCC[SiH](OCC(OCC)(OCC)OCC)OCC ZHUWIYQJHBMTCY-UHFFFAOYSA-N 0.000 description 1
- QMMBZOSZCYBCDC-UHFFFAOYSA-N NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC Chemical compound NCCNCCC[SiH](OC(OCC)(OCC)OCC)OC QMMBZOSZCYBCDC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention discloses a nano-modified high-corrosion-resistance electric-conduction UV (Ultraviolet) coating material. The nano-modified high-corrosion-resistance electric-conduction UV coating material contains the ingredients in parts by weight: 10-40 parts of polyfunctional polyurethane acrylate, 15-35 parts of epoxy acrylate resin, 5-35 parts of reactive diluent, 2-10 parts of photoinitiator, 5-18 parts of nano conductive attapulgite powder, 0.3-2 parts of carbon nano-tubes, 0.05-1.0 part of silicon coupling agent containing epoxy groups and 0.1-2 parts of dispersant. The UV coating material has outstanding anti-electrostatic capability and corrosion resistance. A coating layer prepared by using the UV coating material disclosed by the invention has the surface resistance of 4.5*10<6> to 5.5*10<7> Omega and the surface hardness not lower than 3H, which are unchanged when the coating layer is soaked with 5% NaOH for 30 hours. The UV coating material is simple and convenient in preparation, low in cost, low in VOC (Volatile Organic Compound) and high in universality and has excellent electromagnetic shielding performance. The UV coating material is a new product which is high in hardness, good in wear resistance and good in transparency and is green, healthy and environment-friendly, thereby having a broad application prospect.
Description
Technical field
The present invention relates to a kind of nano modification height corrosion resistant conduction UV coating and preparation method thereof, belong to paint field.
Background technology
UV curable coating, owing to having preventing pollution, energy-conservation, corrosion-resistant and quick-setting characteristic, be just widely used in the coating processes of the multiple industrial circles such as plastic cement, vacuum plating, PVC floor, shadow mask board, auto bulb, timber floor, cabinet panel and multiple product.But make a general survey of current each UV coating, antistatic, erosion resistance needs improve.As existing technical indicator is: resistance sizes is 4.8 × 10
6-6.5 × 10
8Ω, 5%NaOH soak 24 hours unchanged.And for some field, These parameters just seems not enough.
In order to improve electroconductibility or the antistatic property of coating, often need the consumption increasing electroconductive stuffing, because the consistency between filling surface and resin is poor, even be separated in coating, and then create trickle hole, this can reduce the barrier property of coating to water in air and oxygen, thus reduces the antiseptic property of coating.
Summary of the invention
In order to improve the antistatic effect of UV coating, increasing the corrosion resistance nature of product and improving other performance, the present invention proposes a kind of nano modification height corrosion resistant conduction UV coating and preparation method thereof.
According to the first embodiment of the present invention, provide nano modification height corrosion resistant conduction UV coating, it comprises (with parts by weight):
Polyfunctional group urethane acrylate: 10-40, preferred 15-35;
Epocryl: 15-35, preferred 18-32;
Reactive diluent: 5-35, preferred 10-30, more preferably 15-25;
Light trigger: 2-10, preferred 4-8;
The conductive nano attapulgite of mean particle size 10-90nm, preferably 30-80nm, more preferably 40-70nm: 5-18, preferred 7-16, more preferably 9-13;
Carbon nanotube: 0.3-2, preferred 0.6-1.8, more preferably 0.9-1.5;
Silicone couplet containing epoxy group(ing): 0.05-1.0, preferred 0.1-0.5; With
Dispersion agent: 0.1-2, preferred 0.2-1.5, more preferably 0.3-1.0.
Preferably, above-mentioned dispersion agent is selected from: Disponer 983 dispersion agent (production of De Qian company), THYON SR-675 aqueous solid acrylic resin, THYON SR-625 aqueous solid acrylic resin, Joncryl-678 Styrene-acrylic copolymer resin or Joncryl-672 water-based Styrene-acrylic copolymer resin.
Wherein THYON SR-675: aqueous solid acrylic resin, acid number 215, weight-average molecular weight 9000, Tg is 109 DEG C, and Argentinian DIRANSA company produces.
Wherein THYON SR-625: aqueous solid acrylic resin, belongs to acrylic resin modified, acid number 230, and molecular weight 6500, Tg is 107 DEG C, and Argentinian DIRANSA company produces.
Wherein Joncryl-678: Styrene-acrylic copolymer resin, acid number 215mg KOH/g, weight-average molecular weight 8500, solid content 20wt%, BASF Zhuan Chen company.
Wherein Joncryl-672: water-based Styrene-acrylic copolymer resin, BASF Zhuan Chen company.
Preferably, above-mentioned coating comprises further:
Flow agent: 0.05-1.5, preferred 0.1-1.0, more preferably 0.3-0.7, and
Defoamer: 0.05-1.5, preferred 0.1-1.0, more preferably 0.3-0.7.
Generally, the gross weight of above-mentioned raw materials or component is 100 weight parts.
Preferably, described polyfunctional group urethane acrylate is a kind of resin comprising urethane segment and multiple (such as 3-10, as 4-6) acrylate-functional groups.
Preferably, reactive diluent is tripropylene glycol acrylate (TPGDA), dipentaerythritol acrylate (DPHA) or both combinations.
Preferably, light trigger is: 2-hydroxy-2-methyl-1-phenyl-1-acetone.
Preferably, flow agent is: BYK310, BYK323, BYK3100 or in the middle of them two or three combination.
Defoamer is such as BYK051, BYK052 or both combinations.
Silane coupling agent containing epoxy group(ing) is, such as, and 3-glycidylpropyl Trimethoxy silane (Dow coming Z6040).
Preferably, Epocryl is one or both the mixture in following resins (I) or (II):
Wherein m is the integer of 0-10, preferably 3-8, more preferably 5-7, and n is the integer of 0-10, preferably 3-8, more preferably 5-7, R
2hydrogen or methyl.
Preferably, in order to not affect antiseptic property while raising electroconductibility, consistency between conductive nano concave-convex rod particle and resin can be improved by method of modifying.By forming organic modified layer on inorganic particle surfaces, make the character of modified inorganic particle and coating resin close, thus guarantee to form finer and close coating, make the barrier property of coating increase to water and air, thus significantly improve antiseptic property.Preferably, conductive nano attapulgite carries out modification in the following manner:
Step 1): mean particle size 8-85nm (the preferred 27-75nm adding 12-55 weight part (preferred 15-48 weight part) in churned mechanically reactor successively, more preferably 36-67nm) conductive nano attapulgite raw material, the silane coupling agent of the band amino of 4-22 weight part (preferred 8-16 weight part), the solvent of 100-500 weight part (preferred 200-400 weight part), under 70-90 DEG C (as 75-85 DEG C) and inert atmosphere (as nitrogen), under agitation (such as under rotating speed 80-220rpm stirs) reaction 10-26 hour (preferred 13-23 hour), then, mixture system carried out centrifugation and repeatedly wash, vacuum-drying (such as at 60-80 DEG C) obtains surface containing amino powder,
Step 2): the above step 1 adding 9-52 weight part (preferred 12-40 weight part) in churned mechanically reactor successively) surface of gained contains amino powder, the alpha-brominated tertiary butyl C1-C5 acylbromide (such as alpha-brominated tertiary butyl acetyl bromide) of 8-40 weight part (15-35 weight part), the solvent of 100-600 weight part (preferred 200-400 weight part), react 10-30 hour (preferred 12-24 hour) at 80-100 DEG C and under stirring, finally filter, washing, dry, obtain the functionalized powder of surface containing tert.-butyl bromide functional group,
Step 3): with the functionalized powder obtained in step 2 for initiator, in organic solvent in cuprous salt (as cuprous iodide or cuprous bromide) and nitrogen heterocycles ligand (as 2, 2 '-dipyridyl) existence under, with in nitrogen atmosphere, atom transfer radical polymerization method is adopted to prepare lipophilic polymer oligopolymer from vinylformic acid (ester) monomer, such as prepare oleophilic polymer oligopolymer according to following process: add the powder of surface with tert.-butyl bromide functional group in the reactor successively, catalyzer, part, vinylformic acid (ester) monomer, wherein powder, catalyzer, part, the weight ratio of vinylformic acid (ester) monomer is 5-9: 0.5-1.5: 1.5-5.5: 3-15 (preferred 6-8: 0.7-1.3: 1.8-4.0: 4-10), it is airtightly vacuumized, airtight after inflated with nitrogen three bouts.5-13 hour is reacted at 100-130 DEG C.After reaction terminates, add solvent wherein, filter, wash, dry (such as drying at 100 DEG C), obtain conductive nano attapulgite, the i.e. modified attapulgite powder product of conductive nano type, preferably, the mean particle size 10-90nm of this product, preferably 30-80nm, more preferably 40-70nm.
Containing amino silane coupling agent be: in γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane one or more.
Preferably, vinylformic acid (ester) monomer is in step 3 one or both or the three kinds of acrylate monomers that are selected from methyl methacrylate, β-dimethyl-aminoethylmethacrylate or (methyl) glycidyl acrylate, or this type of acrylate monomer and (methyl) acrylic acid mixture, wherein (acrylate monomer): (methyl) acrylic acid weight ratio=85-95: 15-5, more preferably 88-92: 12-8.Such as, (methyl) glycidyl acrylate: (methyl) acrylic acid weight ratio=85-95: 15-5, more preferably 88-92: 12-8.Again such as, (methyl methacrylate and/or β-dimethyl-aminoethylmethacrylate): (methyl) acrylic acid weight ratio=85-95: 15-5, more preferably 88-92: 12-8.
According to the second embodiment of the present invention, also provide the method preparing above-mentioned UV coating, the method comprises and being mixed by the raw material of following consumption (with parts by weight):
Polyfunctional group urethane acrylate: 10-40, preferred 15-35;
Epocryl: 15-35, preferred 18-32;
Reactive diluent: 5-35, preferred 10-30, more preferably 15-25;
Light trigger: 2-10, preferred 4-8;
Conductive nano attapulgite: 5-18, preferred 7-16, more preferably 9-13;
Carbon nanotube: 0.3-2, preferred 0.6-1.8, more preferably 0.9-1.5;
Silicone couplet containing epoxy group(ing): 0.05-1.0, preferred 0.1-0.5; With
Dispersion agent: 0.1-2, preferred 0.2-1.5, more preferably 0.3-1.0;
Preferably, raw material also comprises:
Flow agent: 0.05-1.5, preferred 0.1-1.0, more preferably 0.3-0.7,
Defoamer: 0.05-1.5, preferred 0.1-1.0, more preferably 0.3-0.7.
More particularly, aforesaid method comprises: silane coupling agent, reactive thinner are added together in clean reactor, high speed dispersion 10-15 minute, slowly adds conductive nano attapulgite, carbon nanotube, high speed dispersion 15-20 minute, be uniformly dispersed, question response thing fluid temperature, in 50 DEG C-60 DEG C time, slowly adds polyfunctional group urethane acrylate, epoxy acrylate, dispersion agent, light trigger, and other auxiliary agents stir, continue to stir 10-15 minute, obtain coating.
According to the third embodiment the present invention, also provide the purposes of UV coating, it is for application plastic cement, vacuum plating, PVC floor, shadow mask board, auto bulb, timber floor or cabinet panel.
In this application, " (methyl) vinylformic acid " represents common implication, namely represents vinylformic acid and methacrylic acid.
Advantageous Effects of the present invention:
The present invention, in the antistatic UV coating of tradition, with the addition of the materials such as conductive nano attapulgite, carbon nanotube, dispersion agent, substantially increases UV coating conductive capability and corrosion resistance nature.The coatingsurface resistance utilizing UV coating of the present invention to prepare is 4.5 × 10
6-5.5 × 10
7Ω, surface hardness>=3H, 5%NaOH soak 30 hours unchanged.Originally the system of being transported to is simple and convenient, and cost is low, low VOC, highly versatile, has excellent capability of electromagnetic shielding.The present invention is that a kind of hardness is large, wear resistance good, transparency is good, green, healthy, the product innovation of environmental protection, is with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is conductive nano attapulgite in preparation example 1 and through the infrared spectrogram of finishing containing the conductive nano attapulgite of bromo functional groups.
Fig. 2 is the infrared spectrogram of the conductive nano Attapulgite powder that in preparation example 1, polymethyl acrylic acid glycidyl ether is modified.
Embodiment
Embodiment 1
By the silicone couplet 3-glycidylpropyl Trimethoxy silane (Dow coming Z6040) containing epoxy group(ing) of 0.04Kg, the tripropylene glycol acrylate (TPGDA) of 2Kg joins in reactor, high-speed stirring dispersion 10-15 minute, then the conductive nano attapulgite (65nm) of 1.3Kg, 0.15Kg carbon nanotube (78nm) is added, high-speed stirring dispersion 15-20 minute.Then mixture is warming up to 50-60 DEG C, slowly adds the polyfunctional group urethane acrylate (average acrylate functionality is 4) of 3.2Kg, (n is 6, R to the Epocryl of the general formula (I) of 2.8Kg
2hydrogen), the light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone of the dispersion agent Disponer of 0.06Kg 983 (De Qian company produces or THYON SR-675), 0.4Kg, 0.05Kg flow agent BYK310 and 0.05Kg defoamer BYK051, continue again after stirring to stir 10-15 minute, obtain UV coating.
Gained UV coating is applied on steel disc, dries.Test performance.
Preparation example 1
The preparation of conductive nano attapulgite grafting poly (glycidyl methacrylate):
The first step: the preparation of the conductive nano attapulgite of the brominated initiator of surface grafting: 1) add 1000g conductive nano attapulgite raw material (particle diameter is 60nm) successively in churned mechanically reactor, 100ml γ-aminopropyltrimethoxysilane, 5000ml toluene, 80 DEG C, under nitrogen atmosphere, reaction 16 hours under rotating speed 100-200rpm stirs; Then system is carried out centrifugation, washing 3 times after, the conductive nano attapulgite of surface band amino within 12 hours, can be obtained 60 DEG C of vacuum-dryings; 2) in churned mechanically reactor, conductive nano attapulgite, 250g alpha-brominated tertiary butyl acetyl bromide, the 5000ml toluene of 1000g with amino is added successively, reaction 12 hours at 100 DEG C, under rotating speed 100-200rpm stirs, finally filter, wash, dry at 100 DEG C and the powder of surface with tert.-butyl bromide functional group within 12 hours, can be obtained.
Examination of infrared spectrum instrument is adopted to characterize product.Fig. 1 is the infrared spectrogram of unmodified conductive nano attapulgite (A) and the conductive nano attapulgite (B) containing bromo functional groups through finishing.Compared to unmodified conductive nano attapulgite (A), from Fig. 1, B, 1733cm-1 are the stretching vibration peak of ester carbonyl group, the saturated C-H stretching vibration peak in 2922cm-1 place, and 1464cm-1 is the flexural vibration peak of C-H.
Consistent with theory.Namely show successfully to synthesize the conductive nano attapulgite with tert.-butyl bromide functional group.
Second step: the preparation of the conductive nano attapulgite of grafted methacrylic acid glycidyl ether
Add conductive nano attapulgite, 85g cuprous bromide, the 250g 2 of 400g surface with tert.-butyl bromide functional group in the reactor successively, 2-dipyridyl, 600ml methyl propenoic acid glycidyl ether, 2000ml toluene, airtightly carry out vacuumizing by it, airtight after inflated with nitrogen three bouts.React 8 hours at 120 DEG C.After reaction terminates, add toluene wherein, filter, wash three times, dry at 100 DEG C, obtain powder product.
Show by analyzing, this powder product has nucleocapsid structure.Its middle shell is the oligopolymer of lipophilicity monomer.Carry out ring-opening reaction with hydrochloric acid to the epoxy group(ing) on composite particles, measure epoxy linkage content, recording average graft polymerization degree is 8.5.
The infrared spectrogram of the conductive nano attapulgite that polymethyl acrylic acid glycidyl ether is modified is see Fig. 2.
As can see from Figure 2,906cm
-1place is the asymmetrical stretching vibration peak of epoxide group, 3004-3065cm
-1for the stretching vibration peak of C-H on epoxide group, 755cm
-1neighbouring is epoxy 12 μ peak, 1733cm
-1near be the stretching vibration peak of carbonyl in methyl propenoic acid glycidyl ether.As can be seen here, the conductive nano attapulgite that polymethyl acrylic acid glycidyl ether is modified successfully is synthesized.
Through modified powder, there is excellent oleophilic drainage performance.Its deployment conditions is observed by unmodified powder and modified powder being dispersed in water.Unmodified powder all precipitates after 24h, and modified powder all swims on the water surface.
Preparation example 2
Repeat preparation example 1, just adopt methyl methacrylate to substitute glycidyl methacrylate.
Preparation example 3
Repeat preparation example 1, just adopt the mixture replacing glycidyl methacrylate of methyl methacrylate and ethyl propenoate (weight ratio 1: 1).
Preparation example 4
Repeat preparation example 1, just adopt the mixture of methyl methacrylate and ethyl propenoate (weight ratio 1: 1) and add the vinylformic acid of 8wt% (gross weight based on three), substituting glycidyl methacrylate.
Embodiment 2
Repeat embodiment 1, just adopt the conductive nano attapulgite in the modified powder alternate embodiment 1 obtained in preparation example 1.
Embodiment 3
Repeat embodiment 1, just adopt the conductive nano attapulgite in the modified powder alternate embodiment 1 obtained in preparation example 4.
Comparative example 1
Repeat embodiment 1, but do not add conductive nano attapulgite.
Table 1: the performance test results
Note: the coat-thickness of all embodiments and comparative example is 350 ± 20 microns.
Result as can be seen from table 1, coating of the present invention has lower resistance, therefore has good antistatic property.In addition, corrosion resistance nature is also more outstanding.Possessed high antistatic property and corrosion resistance nature simultaneously.
Claims (10)
1. nano modification height corrosion resistant conduction UV coating, it comprises (with parts by weight):
Polyfunctional group urethane acrylate: 10-40, preferred 15-35;
Epocryl: 15-35, preferred 18-32;
Reactive diluent: 5-35, preferred 10-30, more preferably 15-25;
Light trigger: 2-10, preferred 4-8;
The conductive nano attapulgite of mean particle size 10-90nm, preferably 30-80nm, more preferably 40-70nm: 5-18, preferred 7-16, more preferably 9-13;
Carbon nanotube: 0.3-2, preferred 0.6-1.8, more preferably 0.9-1.5;
Silicone couplet containing epoxy group(ing): 0.05-1.0, preferred 0.1-0.5; With
Dispersion agent: 0.1-2, preferred 0.2-1.5, more preferably 0.3-1.0.
2. coating according to claim 1, wherein dispersion agent is selected: Disponer 983 dispersion agent, THYON SR-675 aqueous solid acrylic resin, THYON SR-625 aqueous solid acrylic resin, Joncryl-678 Styrene-acrylic copolymer resin, or Joncryl-672 water-based Styrene-acrylic copolymer resin.
3. coating according to claim 1, it comprises further:
Flow agent: 0.05-1.5, preferred 0.1-1.0, more preferably 0.3-0.7,
Defoamer: 0.05-1.5, preferred 0.1-1.0, more preferably 0.3-0.7.
4., according to the coating in claim 1-3 described in any one, wherein said polyfunctional group urethane acrylate is a kind of resin comprising urethane segment and multiple (such as 3-10) acrylate-functional groups; And/or
Reactive diluent is tripropylene glycol acrylate (TPGDA), dipentaerythritol acrylate (DPHA) or both combinations; And/or
Light trigger is: 2-hydroxy-2-methyl-1-phenyl-1-acetone.
5., according to the coating in claim 3 described in any one, wherein flow agent is: BYK310, BYK323, BYK3100 or in the middle of them two or three combination; And/or
Defoamer is: BYK051, BYK052 or both combinations; And/or
Silane coupling agent containing epoxy group(ing) is: 3-glycidylpropyl Trimethoxy silane (Dow corningZ6040).
6., according to the coating in claim 1-5 described in any one, wherein Epocryl is one or both the mixture in following resins (I) or (II):
Wherein m is the integer of 0-10, preferably 3-8, more preferably 5-7, and n is the integer of 0-10, preferably 3-8, more preferably 5-7, R
2hydrogen or methyl.
7., according to the coating in claim 1-6 described in any one, wherein conductive nano attapulgite carries out modification in the following manner:
Step 1): mean particle size 8-85nm (the preferred 27-75nm adding 12-55 weight part (preferred 15-48 weight part) in churned mechanically reactor successively, more preferably 36-67nm) conductive nano attapulgite raw material, the silane coupling agent of the band amino of 4-22 weight part (preferred 8-16 weight part), the solvent of 100-500 weight part (preferred 200-400 weight part), under 70-90 DEG C (as 75-85 DEG C) and inert atmosphere (as nitrogen), under agitation (such as under rotating speed 80-220rpm stirs) reaction 10-26 hour (preferred 13-23 hour), then, mixture system carried out centrifugation and repeatedly wash, vacuum-drying (such as at 60-80 DEG C) obtains surface containing amino powder,
Step 2): the above step 1 adding 9-52 weight part (preferred 12-40 weight part) in churned mechanically reactor successively) surface of gained contains amino powder, the alpha-brominated tertiary butyl C1-C5 acylbromide (such as alpha-brominated tertiary butyl acetyl bromide) of 8-40 weight part (15-35 weight part), the solvent of 100-600 weight part (preferred 200-400 weight part), react 10-30 hour (preferred 12-24 hour) at 80-100 DEG C and under stirring, finally filter, washing, dry, obtain the functionalized powder of surface containing tert.-butyl bromide functional group,
Step 3): with the functionalized powder obtained in step 2 for initiator, in organic solvent in cuprous salt (as cuprous iodide or cuprous bromide) and nitrogen heterocycles ligand (as 2, 2 '-dipyridyl) existence under, with in nitrogen atmosphere, atom transfer radical polymerization method is adopted to prepare lipophilic polymer oligopolymer from vinylformic acid (ester) monomer: to add the powder of surface with tert.-butyl bromide functional group in the reactor successively, catalyzer, part, vinylformic acid (ester) monomer, wherein powder, catalyzer, part, the weight ratio of vinylformic acid (ester) monomer is 5-9: 0.5-1.5: 1.5-5.5: 3-15, vacuumize airtight for gained mixture, airtight after inflated with nitrogen three bouts, 6-12 hour is reacted at 100-120 DEG C, after reaction terminates, add solvent wherein, filter, washing, dry (such as drying at 100 DEG C), obtain conductive nano attapulgite, the i.e. modified attapulgite powder product of conductive nano type, preferably, the mean particle size 10-90nm of this product, preferred 30-80nm, more preferably 40-70nm.
8. coating according to claim 7, wherein vinylformic acid (ester) monomer is in step 3 one or both or the three kinds of acrylate monomers that are selected from methyl methacrylate, β-dimethyl-aminoethylmethacrylate or (methyl) glycidyl acrylate, or this type of acrylate monomer and (methyl) acrylic acid mixture, wherein (acrylate monomer): (methyl) acrylic acid weight ratio=85-95: 15-5, more preferably 88-92: 12-8.
9. prepare the method for the UV coating in claim 1-8 described in any one, the method comprises and being mixed by the raw material of following consumption (with parts by weight):
Polyfunctional group urethane acrylate: 10-40, preferred 15-35;
Epocryl: 15-35, preferred 18-32;
Reactive diluent: 5-35, preferred 10-30, more preferably 15-25;
Light trigger: 2-10, preferred 4-8;
Conductive nano attapulgite: 5-18, preferred 7-16, more preferably 9-13;
Carbon nanotube: 0.3-2, preferred 0.6-1.8, more preferably 0.9-1.5;
Silicone couplet containing epoxy group(ing): 0.05-1.0, preferred 0.1-0.5; With
Dispersion agent: 0.1-2, preferred 0.2-1.5, more preferably 0.3-1.0;
Preferably, raw material also comprises:
Flow agent: 0.05-1.5, preferred 0.1-1.0, more preferably 0.3-0.7,
Defoamer: 0.05-1.5, preferred 0.1-1.0, more preferably 0.3-0.7.
10. the purposes of the UV coating in claim 1-8 described in any one, it is for application plastic cement, vacuum plating, PVC floor, shadow mask board, auto bulb, timber floor or cabinet panel.
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