CN104974658B - High corrosion resistant conduction UV coating of nano modification and preparation method thereof - Google Patents
High corrosion resistant conduction UV coating of nano modification and preparation method thereof Download PDFInfo
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- CN104974658B CN104974658B CN201510196473.8A CN201510196473A CN104974658B CN 104974658 B CN104974658 B CN 104974658B CN 201510196473 A CN201510196473 A CN 201510196473A CN 104974658 B CN104974658 B CN 104974658B
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- 238000000576 coating method Methods 0.000 title claims abstract description 36
- 239000011248 coating agent Substances 0.000 title claims abstract description 34
- 230000004048 modification Effects 0.000 title claims abstract description 12
- 238000005260 corrosion Methods 0.000 title claims abstract description 9
- 230000007797 corrosion Effects 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 238000002715 modification method Methods 0.000 title description 4
- 229960000892 attapulgite Drugs 0.000 claims abstract description 29
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 29
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 28
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- -1 Chloroalkyl Acrylates Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 229920000178 Acrylic resin Polymers 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 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
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229920006026 co-polymeric resin Polymers 0.000 claims description 6
- 239000013530 defoamer Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical group CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000007306 functionalization reaction Methods 0.000 claims description 4
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 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
- 229920005732 JONCRYL® 678 Polymers 0.000 claims description 3
- 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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 3
- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical compound CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004568 cement Substances 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
- 229920003023 plastic Polymers 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 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
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- LTOKKZDSYQQAHL-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCC1CO1 LTOKKZDSYQQAHL-UHFFFAOYSA-N 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000002421 anti-septic effect Effects 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 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
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002118 epoxides Chemical group 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000000463 material 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
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-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
- 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
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical group Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001262 acyl bromides Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 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
- 210000003739 neck Anatomy 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
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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 kind of high corrosion resistant conduction UV coating of nano modification, it is included (in parts by weight)：Polyfunctional group urethane acrylate：10‑40；Epocryl：15‑35；Reactive diluent：5‑35；Light trigger：2‑10；Conductive nano attapulgite：5‑18；CNT：0.3‑2；Silicone couplet containing epoxy radicals：0.05‑1.0；And dispersant：0.1‑2.UV coating has prominent antistatic effect and decay resistance.It is 4.5 × 10 using the coating surface resistance of UV coating preparations of the present invention6‑5.5×107Ω, case hardness >=3H, 5%NaOH soak 30 hours it is unchanged.Originally the system of being transported to is simple and convenient, and cost is low, low VOC, and highly versatile has excellent capability of electromagnetic shielding.The present invention is the new product that a kind of hardness is big, wearability is good, transparency is good, green, healthy, environmentally friendly, is with a wide range of applications.
Description
Technical field
The present invention relates to high corrosion resistant conduction UV coating of a kind of nano modification and preparation method thereof, belong to paint field.
Background technology
UV curable coatings, due to preventing from polluting, save, corrosion-resistant and quick-setting characteristic, positive extensive use
In a variety of industrial circles such as plastic cement, vacuum plating, PVC floor, planar mask, auto bulb, timber floor, cabinet panel and a variety of productions
In the coating processes of product.But current each UV coating is made a general survey of, needs to improve in antistatic, corrosion resistance.It is such as existing
Technical indicator is：Resistance sizes are 4.8 × 106-6.5×108Ω, 5%NaOH soak 24 hours it is unchanged.And for some necks
Domain, These parameters just seem not enough.
In order to improve the electric conductivity or antistatic property of coating, generally require to increase the consumption of electroconductive stuffing, due to filling out
Expect that the compatibility between surface and resin is poor, be even separated in coating, and then generate trickle hole, this can drop
Low coating reduces the antiseptic property of coating to air reclaimed water and the barrier property of oxygen.
The content of the invention
In order to improve the antistatic effect of UV coating, increase the decay resistance of product and improve other performance, the present invention
Propose high corrosion resistant conduction UV coating of a kind of nano modification and preparation method thereof.
According to the first embodiment of the present invention there is provided the high corrosion resistant conduction UV coating of nano modification, it is included (with weight
Part meter)：
Polyfunctional group urethane acrylate：10-40, preferably 15-35；
Epocryl：15-35, preferably 18-32；
Reactive diluent：5-35, preferably 10-30, more preferably 15-25；
Light trigger：2-10, preferably 4-8；
Particle mean size 10-90nm, preferably 30-80nm, more preferably 40-70nm conductive nano attapulgite：5-18, preferably
7-16, more preferably 9-13；
CNT：0.3-2, preferably 0.6-1.8, more preferably 0.9-1.5；
Silicone couplet containing epoxy radicals：0.05-1.0, preferably 0.1-0.5；With
Dispersant：0.1-2, preferably 0.2-1.5, more preferably 0.3-1.0.
Preferably, above-mentioned dispersant is selected from：The dispersants of Disponer 983 (production of De Qian companies), THYON SR-
675 aqueous solid acrylic resins, THYON SR-625 aqueous solid acrylic resins, Joncryl-678 Styrene And Chloroalkyl Acrylates
Copolymer resin or the aqueous Styrene-acrylic copolymer resins of Joncryl-672.
Wherein THYON SR-675：Aqueous solid acrylic resin, acid number 215, weight average molecular weight 9000, Tg is 109 DEG C,
Argentinian DIRANSA companies production.
Wherein THYON SR-625：Aqueous solid acrylic resin, belongs to acrylic resin modified, acid number 230, molecular weight
6500, Tg be 107 DEG C, Argentinian DIRANSA companies production.
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：Aqueous Styrene-acrylic copolymer resin, BASF Zhuan Chen companies.
Preferably, above-mentioned coating further comprises：
Levelling agent：0.05-1.5, preferably 0.1-1.0, more preferably 0.3-0.7, and
Defoamer：0.05-1.5, preferably 0.1-1.0, more preferably 0.3-0.7.
Typically, the gross weight of above-mentioned raw materials or component is 100 parts by weight.
Preferably, the polyfunctional group urethane acrylate be comprising polyurethane segment and it is multiple (such as 3-10,
Such as 4-6) a kind of resins of acrylate-functional groups.
It is preferred that, reactive diluent is tripropylene glycol acrylate (TPGDA), dipentaerythritol acrylate
Or both (DPHA) combination.
It is preferred that, light trigger is：2- hydroxy-2-methyl -1- phenyl -1- acetone.
Preferably, levelling agent is：BYK310, BYK323, BYK3100 or their central two or three combinations.
Defoamer is, for example, BYK051, BYK052 or both combination.
Silane coupler containing epoxy radicals is, for example, 3- glycidylpropyls trimethoxy silane (Dow coming
Z6040)。
Preferably, Epocryl is one or both of following resins (I) or (II) mixture：
Wherein m is 0-10, preferably 3-8, more preferably 5-7 integer, and n is 0-10, preferably 3-8, more preferably 5-7 integer,
R2It is hydrogen or methyl.
Preferably, in order to not influence antiseptic property while electric conductivity is improved, it can be improved by method of modifying
Compatibility between conductive nano concave-convex rod particle and resin.By forming organic modified layer on inorganic particle surfaces so that
Modified inorganic particle and the property of coating resin are close, so that it is guaranteed that forming finer and close coating so that coating increase pair
The barrier property of water and air, so as to significantly improve antiseptic property.Preferably, conductive nano attapulgite is in the following manner
It is modified：
Step 1)：12-55 parts by weight (preferably 15-48 parts by weight) are sequentially added in churned mechanically reactor
Particle mean size 8-85nm (preferably 27-75nm, more preferably 36-67nm) conductive nano attapulgite raw material, 4-22 parts by weight are (excellent
Select 8-16 parts by weight) the silane coupler with amino, the solvent of 100-500 parts by weight (preferably 200-400 parts by weight),
It is anti-(such as under rotating speed 80-220rpm stirrings) under agitation under 70-90 DEG C (such as 75-85 DEG C) and inert atmosphere (such as nitrogen)
Answer 10-26 hours (preferably 13-23 hours)；Then, mixture system is centrifuged and repeatedly washed, be dried in vacuo
(such as at 60-80 DEG C) obtains the powder that amino is contained on surface；
Step 2)：9-52 parts by weight (preferably 12-40 parts by weight) are sequentially added in churned mechanically reactor
Above step 1) obtained by surface contain the powder of amino, the alpha-brominated tert-butyl group C1-C5 of 8-40 parts by weight (15-35 parts by weight)
Acylbromide (such as alpha-brominated tert-butyl group acetyl bromide), the solvent of 100-600 parts by weight (preferably 200-400 parts by weight), in 80-100
At DEG C and lower 10-30 hours (preferably 12-24 hours) of reaction of stirring, finally filters, washs, drying obtains surface and contains tertiary fourth
The functionalization powder of bromide functional group；
Step 3)：The powder of the functionalization obtained using in step 2 is initiator, in organic solvent in cuprous salt (such as iodine
Change cuprous or cuprous bromide) and nitrogen heterocycles ligand (such as 2,2 '-bipyridyl) in the presence of, and in nitrogen atmosphere, use
Atom transfer radical polymerization method prepares lipophilic polymer oligomer from acrylic acid (ester) monomer, such as according to following process system
Standby oleophilic polymer oligomer：Powder of the surface with tert-butyl bromide functional group, catalyst are sequentially added in the reactor, matched somebody with somebody
Body, acrylic acid (ester) monomer, wherein powder, catalyst, part, the weight ratio of acrylic acid (ester) monomer are 5-9: 0.5-1.5:
1.5-5.5: 3-15 (preferably 6-8: 0.7-1.3: 1.8-4.0: 4-10), by its it is closed vacuumized, three bouts of inflated with nitrogen
It is closed afterwards.Reacted 5-13 hours at 100-130 DEG C.After reaction terminates, solvent is added thereto, (example is dried in filtering, washing
Dried such as at 100 DEG C), the modified attapulgite powder product of conductive nano attapulgite, i.e. conductive nano type is obtained, preferably
It is, the particle mean size 10-90nm of the product, preferably 30-80nm, more preferably 40-70nm.
Silane coupler containing amino is: gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, γ-
Aminopropyltriethoxy diethoxy silane, N- β-aminoethyl-γ-aminopropyltrimethoxysilane, N- β-aminoethyl-γ-aminopropyl
It is one or more in methyl dimethoxysilane.
Preferably, in step 3 acrylic acid (ester) monomer is to be selected from methyl methacrylate, methacrylic acid second
One or both of ester or (methyl) glycidyl acrylate or three kinds of acrylate monomers, or such acrylate
The mixture of monomer and (methyl) acrylic acid, wherein (acrylate monomer): weight ratio=85-95: the 15- of (methyl) acrylic acid
5, more preferably 88-92: 12-8.For example, (methyl) glycidyl acrylate: the weight ratio=85-95 of (methyl) acrylic acid:
15-5, more preferably 88-92: 12-8.In another example, (methyl methacrylate and/or EMA): (methyl) acrylic acid
Weight ratio=85-95: 15-5, more preferably 88-92: 12-8.
According to the second embodiment of the present invention, the method for preparing above-mentioned UV coating is also provided, this method is included by under
The raw material of row consumption (in parts by weight) is mixed：
Polyfunctional group urethane acrylate：10-40, preferably 15-35；
Epocryl：15-35, preferably 18-32；
Reactive diluent：5-35, preferably 10-30, more preferably 15-25；
Light trigger：2-10, preferably 4-8；
Conductive nano attapulgite：5-18, preferably 7-16, more preferably 9-13；
CNT：0.3-2, preferably 0.6-1.8, more preferably 0.9-1.5；
Silicone couplet containing epoxy radicals：0.05-1.0, preferably 0.1-0.5；With
Dispersant：0.1-2, preferably 0.2-1.5, more preferably 0.3-1.0；
Preferably, raw material also includes：
Levelling agent：0.05-1.5, preferably 0.1-1.0, more preferably 0.3-0.7,
Defoamer：0.05-1.5, preferably 0.1-1.0, more preferably 0.3-0.7.
More specifically, the above method includes：Silane coupler, reactive diluent are added in clean reactor together,
It is scattered 10-15 minutes at a high speed, conductive nano attapulgite, CNT are slowly added into, it is scattered 15-20 minutes at a high speed, disperse equal
It is even, question response thing liquid temperature when 50 DEG C -60 DEG C, be slowly added to polyfunctional group urethane acrylate, epoxy acrylate,
Dispersant, light trigger, other auxiliary agents stir, and continue to stir 10-15 minutes, obtain coating.
According to the third embodiment the present invention, the purposes of UV coating is also provided, it is used for application plastic cement, vacuum electric
Plating, PVC floor, planar mask, auto bulb, timber floor or cabinet panel.
In this application, " (methyl) acrylic acid " represents common implication, that is, represents acrylic acid and methacrylic acid.
The advantageous effects of the present invention：
The present invention with the addition of the materials such as conductive nano attapulgite, CNT, dispersant in traditional antistatic UV coating
Material, substantially increases UV coating conductive capability and decay resistance.Utilize the coating surface resistance of UV coating preparations of the present invention
For 4.5 × 106-5.5×107Ω, case hardness >=3H, 5%NaOH soak 30 hours it is unchanged.Originally the system of being transported to is simple and convenient, into
This low, low VOC, highly versatile has excellent capability of electromagnetic shielding.The present invention is that a kind of hardness is big, wearability is good, transparency
Good, green, healthy, environmentally friendly new product, is with a wide range of applications.
Brief description of the drawings
Fig. 1 is recessed for the conductive nano attapulgite in preparation example 1 and by conductive nano of the surface modification containing bromo functional groups
The infrared spectrogram of convex rod powder.
Fig. 2 is the infrared light of the conductive nano concave convex rod powder of polymethylacrylic acid glycidol ether modification in preparation example 1
Spectrogram.
Embodiment
Embodiment 1
By 0.04Kg silicone couplet 3- glycidylpropyls trimethoxy silane (the Dow corning containing epoxy radicals
Z6040), 2Kg tripropylene glycol acrylate (TPGDA) is added in reactor, and high-speed stirred is scattered 10-15 minutes,
Then 1.3Kg conductive nano attapulgite (65nm), 0.15Kg CNTs (78nm) is added, high-speed stirred disperses 15-20
Minute.Then mixture is warming up to 50-60 DEG C, is slowly added to 3.2Kg polyfunctional group urethane acrylate (average propylene
Acid esters degree of functionality for 4), (n is 6, R to the Epocryl of 2.8Kg logical formula (I)2Hydrogen), 0.06Kg dispersant
Disponer 983 (De Qian companies produce or THYON SR-675), 0.4Kg light trigger 2- hydroxy-2-methyl -1- phenyl -
1- acetone, 0.05Kg levelling agent BYK310 and 0.05Kg defoamer BYK051 are further continued for stirring 10-15 minutes after stirring,
Produce UV coating.
Gained UV coating is coated on steel disc, dried.Test performance.
Preparation example 1
Conductive nano attapulgite is grafted the preparation of poly (glycidyl methacrylate)：
The first step：The preparation of the conductive nano attapulgite of the brominated initiator of surface grafting：1) with churned mechanically
1000g conductive nano attapulgites raw material (particle diameter is 60nm), 100ml γ-aminopropyl trimethoxy are sequentially added in reactor
Silane, 5000ml toluene under 80 DEG C, nitrogen atmosphere, reacts 16 hours under rotating speed 100-200rpm stirrings；Then by system
It is centrifuged, washs after 3 times, conductive nano concave convex rod of the surface with amino is can obtain within 12 hours in 60 DEG C of vacuum drying
Powder；2) sequentially added in churned mechanically reactor 1000g with the conductive nano attapulgite of amino, 250g α-
Bromo tert-butyl group acetyl bromide, 5000ml toluene, react 12 hours, last mistake at 100 DEG C, under rotating speed 100-200rpm stirrings
Filter, washing, the powder that surface carries tert-butyl bromide functional group is can obtain for 12 hours in 100 DEG C of drying.
Product is characterized using examination of infrared spectrum instrument.Fig. 1 is unmodified conductive nano attapulgite (A) and warp
Cross the infrared spectrogram of conductive nano attapulgite (B) of the surface modification containing bromo functional groups.Compared to unmodified conductive nano
Attapulgite (A), the B from Fig. 1,1733cm-1, which is that saturation C-H is flexible at the stretching vibration peak of ester carbonyl group, 2922cm-1, to shake
Dynamic peak, 1464cm-1 is C-H flexural vibrations peak.
It is consistent with theory.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 glycidol ether
Conductive nano attapulgite, 85g bromines that 400g surfaces carry tert-butyl bromide functional group are sequentially added in the reactor
Change cuprous, 250g 2, its closed progress is taken out true by 2- bipyridyls, 600ml methyl propenoic acid glycidyl ethers, 2000ml toluene
It is closed after empty, three bouts of inflated with nitrogen.Reacted 8 hours at 120 DEG C.After reaction terminates, toluene is added thereto, filters, wash
Wash three times, dried at 100 DEG C, obtain powder product.
By analysis shows, the powder product has nucleocapsid structure.Wherein housing is the oligomer of lipophile monomer.With
Hydrochloric acid carries out ring-opening reaction to the epoxy radicals on compound particle, measures epoxy linkage content, and it is 8.5 to measure average graft polymerization degree.
The infrared spectrogram of the conductive nano attapulgite of polymethylacrylic acid glycidol ether modification is referring to Fig. 2.
From fig. 2 it can be seen that 906cm-1Locate the asymmetric stretching vibration peak for epoxide group, 3004-3065cm-1For
C-H stretching vibration peak, 755cm on epoxide group-1It is nearby the μ peaks of epoxy 12,1733cm-1It is nearby Glycidyl methacrylate
The stretching vibration peak of carbonyl in glycerin ether.As can be seen here, successfully the nanometer of synthesis polymethylacrylic acid glycidol ether modification is led
Electric attapulgite.
There is excellent oleophilic drainage performance by modified powder.By the way that unmodified powder and modified powder are disperseed
Its deployment conditions is observed in water.Unmodified powder after 24h go down by precipitation, and modified powder all swims in water
On face.
Preparation example 2
Preparation example 1 is repeated, GMA is simply substituted using methyl methacrylate.
Preparation example 3
Preparation example 1 is repeated, simply using methyl methacrylate and the mixture replacing of ethyl acrylate (weight is than 1: 1)
GMA.
Preparation example 4
Repeat preparation example 1, simply using methyl methacrylate and ethyl acrylate (weight is than 1: 1) mixture and
8wt% (gross weight based on three) acrylic acid is added, GMA is substituted.
Embodiment 2
Embodiment 1 is repeated, simply using the conductive nano in the modified powder alternate embodiment 1 obtained in preparation example 1
Attapulgite.
Embodiment 3
Embodiment 1 is repeated, simply using the conductive nano in the modified powder alternate embodiment 1 obtained in preparation example 4
Attapulgite.
Comparative example 1
Embodiment 1 is repeated, but without conductive nano attapulgite.
Table 1：The performance test results
Note：The coating layer thickness of all embodiments and comparative example is 350 ± 20 microns.
The coating that can be seen that the present invention from the result in table 1 has lower resistance, therefore with well antistatic
Performance.In addition, decay resistance is also more prominent.It has been provided simultaneously with high antistatic property and decay resistance.
Claims (5)
1. the high corrosion resistant conduction UV coating of nano modification, it is made up of the raw material of following parts by weight：
Polyfunctional group urethane acrylate： 15-35；
Epocryl： 18-32；
Reactive diluent： 15-25；
Light trigger： 4-8；
Particle mean size 40-70nm conductive nano attapulgite：9-13；
CNT： 0.9-1.5；
Silicone couplet containing epoxy radicals： 0.1-0.5；
Dispersant： 0.3-1.0；
Levelling agent： 0.3-0.7；With
Defoamer： 0.3-0.7；
Wherein, Epocryl is following resins (I)：
Wherein n is 5-7 integer, R2It is hydrogen or methyl；
Wherein, conductive nano attapulgite is modified in the following manner：
Step 1)：The particle mean size 36-67nm that 15-48 parts by weight are sequentially added in churned mechanically reactor receives
The conductive attapulgite raw material of rice, the silane coupler with amino of 8-16 parts by weight, the solvent of 200-400 parts by weight, in 70-
90 DEG C, with inert atmosphere, are reacted 13-23 hours under rotating speed 80-220rpm stirrings；Then, mixture system is carried out
Centrifuge and repeatedly washing, vacuum drying obtains the powder that amino is contained on surface at 60-80 DEG C；
Step 2)：The above step 1 of 12-40 parts by weight is sequentially added in churned mechanically reactor) obtained by
The powder of amino, α-bromo tert-butyl group acetyl bromide, the solvent of 200-400 parts by weight of 15-35 parts by weight are contained in surface,
Reacted at 80-100 DEG C and under stirring 12-24 hours, finally filter, wash, drying obtains surface and contains tert-butyl bromide function
The functionalization powder of group；
Step 3)：The powder of the functionalization obtained using in step 2 is initiator, in organic solvent in cuprous salt and 2,2 '-
In the presence of bipyridyl, and in nitrogen atmosphere, using atom transfer radical polymerization method from acrylic acid (ester) monomer system
Standby lipophilic polymer oligomer：Powder of the surface with tert-butyl bromide functional group, catalyst are sequentially added in the reactor, matched somebody with somebody
Body, acrylic acid (ester) monomer, wherein powder, catalyst, part, the weight ratio of acrylic acid (ester) monomer are 5-9: 0.5-
1.5: 1.5-5.5: 3-15, by gained mixture it is closed vacuumized, after three bouts of inflated with nitrogen it is closed, in 100-
Reacted 6-12 hours at 120 DEG C, after reaction terminates, solvent is added thereto, filtering, washing, drying obtain conductive nano recessed
The modified attapulgite powder product of convex rod powder, i.e. conductive nano type, the particle mean size 40-70nm of the product；
Above-mentioned steps 3）In acrylic acid (ester) monomer be two kinds of acrylic acid of methyl methacrylate and EMA
Ester monomer, the wherein mixture with (methyl) acrylic acid, acrylate monomer: the weight ratio=88-92 of (methyl) acrylic acid
∶ 12-8。
2. coating according to claim 1, wherein dispersant are selected：The dispersants of Disponer 983, THYON SR-675
Aqueous solid acrylic resin, THYON SR-625 aqueous solid acrylic resins, Joncryl-678 Styrene And Chloroalkyl Acrylates are total to
Copolymer resin, or the aqueous Styrene-acrylic copolymer resins of Joncryl-672.
3. coating according to claim 1, wherein the polyfunctional group urethane acrylate is to include polyurethane segment
With a kind of resin of 3-10 acrylate-functional groups；Reactive diluent is tripropylene glycol acrylate
(TPGDA), the combination of dipentaerythritol acrylate (DPHA) or both；Light trigger is：2- hydroxyl -2- methyl
- 1- phenyl -1- acetone.
4. coating according to claim 1, wherein levelling agent are：BYK310, BYK323, BYK3100 or they among two
Kind or three kinds of combination；Defoamer is：BYK051, BYK052 or both combination；Silane coupler containing epoxy radicals is：3-
Glycidylpropyl trimethoxy silane.
5. the purposes of the UV coating described in claim 1, it be used for application plastic cement, vacuum plating, PVC floor, planar mask,
Auto bulb, timber floor or cabinet panel.
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