CN102002314A - Nano dispersed water-based conductive primer for vehicle bumper and preparation method thereof - Google Patents
Nano dispersed water-based conductive primer for vehicle bumper and preparation method thereof Download PDFInfo
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- CN102002314A CN102002314A CN 201010295090 CN201010295090A CN102002314A CN 102002314 A CN102002314 A CN 102002314A CN 201010295090 CN201010295090 CN 201010295090 CN 201010295090 A CN201010295090 A CN 201010295090A CN 102002314 A CN102002314 A CN 102002314A
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- chlorinated polypropylene
- bumper
- priming paint
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003973 paint Substances 0.000 claims abstract description 60
- -1 polypropylene Polymers 0.000 claims abstract description 57
- 239000004743 Polypropylene Substances 0.000 claims abstract description 49
- 229920001155 polypropylene Polymers 0.000 claims abstract description 49
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- 229920002635 polyurethane Polymers 0.000 claims abstract description 17
- 239000004814 polyurethane Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 13
- 229920000767 polyaniline Polymers 0.000 claims abstract description 8
- 230000037452 priming Effects 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 150000003673 urethanes Chemical class 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 239000013530 defoamer Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 150000002009 diols Chemical class 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical group O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004970 Chain extender Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- GWGWXYUPRTXVSY-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=C(C)C=C1 Chemical compound N=C=O.N=C=O.CC1=CC=C(C)C=C1 GWGWXYUPRTXVSY-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 3
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229920002961 polybutylene succinate Polymers 0.000 claims description 3
- 239000004631 polybutylene succinate Substances 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 22
- 229920001940 conductive polymer Polymers 0.000 abstract description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 abstract 1
- 229960002796 polystyrene sulfonate Drugs 0.000 abstract 1
- 239000011970 polystyrene sulfonate Substances 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000645 desinfectant Substances 0.000 description 6
- 239000002482 conductive additive Substances 0.000 description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000009503 electrostatic coating Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention provides a nano dispersed water-based conductive primer for a vehicle bumper and a preparation method thereof. The nano dispersed water-based conductive primer for the vehicle bumper is prepared by using water-based conductive polyaniline and a water-based conductive polymer of poly-3,4-ethylene dioxide thiophene-polystyrene sulfonate as conductive mediums and using CPP (Chlorinated polypropylene) modified polyurethane water-based resin as forming resin. The nano dispersed water-based conductive primer for the vehicle bumper can reach the conductance requirement even if less water-based conductive primer which is 1.3-14.2 percent in parts by weight of the total solid of the primer is added. The nano dispersed water-based conductive primer is nano dispersed water-based paint containing no harmful substances, such as toluene, xylene, and the like, thereby causing no pollution to the environment and being an environmental-friendly product.
Description
Technical field
The invention belongs to bumper nano-dispersed aqueous priming paint and preparation method thereof.
Technical background
Bumper is generally the plastic basis materials such as polypropylene of terpolymer EP rubber modification, the general extensive employing electrostatic painting process of its external coating, because this method is compared with traditional aerial spraying, the utilization ratio of coating can be improved 25～40%, thereby reduce the consumption of coating effectively, reduce production costs, reduce the pollution that painting dressing automobiles production brings environment simultaneously.Yet bumper plastic component surface resistivity is generally about 10
12～10
16Ω/sq can't be coated directly onto finish paint on the frosting by electrostatic coating.Therefore, to plastic basis material surface-coated one deck conductive substrate coating, give base material electroconductibility usually, make its sheet resistance value less than 3 * 10
7Behind Ω/sq, carry out electrostatic coating again.
Electrically conducting primer mainly is made of film-forming resin, electroconductive stuffing and auxiliary agent usually.At present, extensively adopting conductive carbon black, electrically conductive graphite, carbon fiber, metal-powder and electroconductibility titania powder is that conducting medium prepares electrically conducting coating, and relevant technology has given report at ZL200510050812.8, CN1221768A, CN 1015266B and ZL 200480020334.X.Above-mentioned these reports all use the inorganic conductive filler as additive, meeting the requirements of electricity leads, the addition that needs is bigger, even always solidify 40% of mass parts up to coating, high mineral filler additive like this, must cause paint film to become fragile, cause the mechanical property of coating to descend, influence the application of topcoat.In addition, film-forming resin adopts urethane resin, Resins, epoxy, resol, acrylic resin or Synolac mostly, yet for the acrylic plastering base material bumper of modification, the characteristics of its low surface tension make above-mentioned these resins that the sticking power that provides on this base material is provided.
The conducting high polymers thing is as conductive additive, not needing to add any wetting dispersing agent just can be compatible well with film-forming resin, can reduce influence that paint film is brought effectively, be to replace the inorganic conductive medium to prepare one of conductive substrate coating method the most effectively.In recent years, along with the day by day strictness of the whole world to the restriction of volatile organic compounds (VOC) quantity discharged, the water-borne coatings of environmental protection becomes the development trend of automotive industry paint field.Waterborne conductive polyaniline (Macromolecules, 2007,2007,40, the 8132-8135 of high conductivity nano-dispersed; Polymer, 2009,50,2674-2679) and poly-3,4-ethene dioxythiophene/polystyrolsulfon acid waterborne conductive polymkeric substance (Chem.Mater.2006,18,4354～4360; Macromolecules2006,39,6071～6074; J.Phys.Chem.B, 2009,113,11378～11383; ACSnano, 2010,4,2242～2248; Chem.Mater.2010,22,3670～3677, ACSApplied Materials and Interfaces, 2010,2,474～483) be the effective high molecular polymer conductive additive of preparation waterborne conductive priming paint.Yet, still the waterborne conductive polymkeric substance is not applied to patent and the report that the bumper aqueous priming paint prepares as conductive additive at present.
For bumper acrylic plastering base material, according to the similar compatibility principle, the resin of Chlorinated Polypropylene III structure can provide excellent sticking power, urethane resin is because the advantage of its excellent abrasive, erosion resistance, can satisfy the demand of bumper, adopt Chlorinated Polypropylene III that urethane resin is carried out the selection that modification is undoubtedly the ideal film-forming resin.
Summary of the invention
The present invention is directed to the problem that exists on the present prior art, provide and be used for bumper nano-dispersed waterborne conductive priming paint and preparation method thereof, be characterized in adopting waterborne conductive polyaniline and poly-3,4-ethene dioxythiophene-polystyrolsulfon acid conductive polymers is a conductive additive, and chlorinated polypropylene modified polyurethane aqueous resin is a film-forming resin.
The composition and the weight part proportioning that are used for bumper nano-dispersed waterborne conductive priming paint are as follows:
Water nano dispersed electro-conductive polymkeric substance is 80～270 parts;
Chlorinated polypropylene modified polyurethane aqueous resin is 25～156 parts;
Water cross-linking agent is 24.5～45 parts;
Aqueous promoter is 15～30 parts;
The water-based flow agent is 0.8～3.2 part;
The water-based defoamer is 1.5～4.0 parts;
Sterilant is 1.2～2.8 parts;
Described water nano dispersed electro-conductive polymkeric substance is for gathering 3,4-ethene dioxythiophene-polystyrolsulfon acid or waterborne conductive polyaniline;
Chlorinated polypropylene modified polyurethane aqueous resin is cation water-based resin of chlorinated polypropylene modified urethane or the anion aqueous resin of chlorinated polypropylene modified urethane;
Water cross-linking agent is a water dispersive polyisocyanate;
Aqueous promoter is one or both mixtures in Virahol, butyl glycol ether and the Diethylene Glycol butyl ether;
The water-based flow agent is selected from ionic acrylic interpolymer and polyether-modified polydimethylsiloxane type flow agent;
The water-based defoamer is selected from organosilicon type defoamer;
Sterilant is an isothiazolinone.
Water nano dispersed electro-conductive polymkeric substance poly-3,4-ethene dioxythiophene-polystyrolsulfon acid (PEDOT-PSS), ACS nano, 2010,4,513～523 have provided its preparation method.It obtains solid content is 1.71%, and molecular weight is 48000 dalton, and specific conductivity is 230S/cm.
Waterborne conductive polyaniline (WPA), CN 101260234A3 has provided its preparation method.It obtains the aqueous dispersions that solid content is 5.7% waterborne conductive polyaniline, and its particle diameter is 30～65nm, and molecular weight is 32000～45000 dalton, and specific conductivity is 30S/cm.
Be used for the method for making of bumper nano-dispersed waterborne conductive priming paint, step and condition are as follows:
(1) preparation of chlorinated polypropylene modified polyurethane aqueous resin
By proportioning, toluene, Chlorinated Polypropylene III, Hydroxyethyl acrylate and benzoyl peroxide are added in the reactor, be 100～110 ℃ of reactions 2.5～3.5 hours in temperature of reaction; Add vulcabond, polyester diol, hydrophilic chain extender and dibutyl tin dilaurate catalyzer then, 75～80 ℃ of reactions 2.5～3 hours; Add TriMethylolPropane(TMP) then, in 80～85 ℃ of reactions 1.5～2 hours; In the agent of 40～45 ℃ of adding pH regulator, reaction 15～20min adds entry then, carries out emulsification 20-30min with 1500～2000rpm rotating speed; Toluene is removed in decompression, and discharging obtains chlorinated polypropylene modified polyurethane aqueous resin;
Described toluene: Chlorinated Polypropylene III: Hydroxyethyl acrylate: benzoyl peroxide: vulcabond: polyester diol: hydrophilic chain extender: dibutyl tin dilaurate: TriMethylolPropane(TMP): pH regulator agent: the mol ratio of water is 2～2.5: 0.001～0.003: 0.38～0.46: 0.01～0.04: 1.8～2.4: 0.1～0.3: 0.8～1: 0.0002～0.0005: 0.4～0.5: 0.6～0.9: 58.9～117.2; Best mol proportioning is 2.1～2.3: 0.0015～0.002: 0.42～0.44: 0.02～0.03: 2～2.2: 0.2～0.25: 0.8～0.95: 0.0003～0.0004: 0.46～0.48: 0.7～0.8: 77.2～82.5;
The preferred chloride weight percent of described Chlorinated Polypropylene III is 10～40%, and more preferably chloride weight percent is 20～35%; Weight-average molecular weight is 10000～150000 dalton, more preferably is preferably 35000～90000 dalton;
Described vulcabond is preferred 2, one or both in 4-Xylene Diisocyanate and the isophorone diisocyanate;
A kind of in the preferred poly adipate succinic acid ester glycol of described polyester diol, the poly butylene succinate two pure and mild polyethylene glycol adipate glycol; Described polyester diol preferred molecular weight is 2000 dalton;
A kind of in the preferred N methyldiethanol amine of described hydrophilic chain extender, N butyl diethanol amine, dimethylolpropionic acid and the dimethylol propionic acid;
A kind of in the preferred dimethylethanolamine of described pH regulator agent, triethylamine, oxyacetic acid, sulfuric acid and the acetate.
(2) be used for the preparation of bumper nano-dispersed waterborne conductive priming paint
By proportioning weighing material;
A) chlorinated polypropylene modified polyurethane aqueous resin, water nano dispersed electro-conductive polymkeric substance, water-based flow agent and aqueous promoter are put in the sand mill jar, the rotating speed of 600～1200rpm stirred 0.5～3 hour;
B) water cross-linking agent, water-based defoamer and the sterilant rotating speed with 900～1500rpm was stirred 0.5～1 hour;
C) with above-mentioned steps a) and b) product that obtains puts into paint mixing tank, stirs 1.5～3 minutes with the rotating speed of 800～1100rpm, discharging obtains being used for bumper nano-dispersed waterborne conductive priming paint.
Beneficial effect: (1) the present invention is first with waterborne conductive polyaniline and poly-3,4-ethene dioxythiophene-polystyrolsulfon acid waterborne conductive polymkeric substance is as conducting medium, with chlorinated polypropylene modified polyurethane aqueous resin, as film-forming resin, prepare bumper nano-dispersed waterborne conductive priming paint.(2) the waterborne conductive priming paint of bumper nano-dispersed provided by the invention meets the requirements of electric conductivity value, and the water-based conducting polymer addition is little, only is 7～13%.(3) environmental type coating: this coating is water-borne coatings, does not contain toluene, dimethylbenzene hazardous and noxious substances, can not pollute environment, and be Green Product.
Embodiment
Embodiment 1: the preparation of the anion aqueous resin of chlorinated polypropylene modified urethane
Pressing the mol ratio, molecular weight 40000 dalton of 2.1mol toluene, 0.002mol, contain Chlorinated Polypropylene III, 0.44mol Hydroxyethyl acrylate and the 0.03mol benzoyl peroxide of chlorine weight percentage 20%, is 105 ℃ of reactions 3 hours in temperature of reaction; Add 2 of 2.2mol then, molecular weight 2000 daltonian poly adipate succinic acid ester glycol, 0.95mol dimethylol propionic acid and the 0.0004mol dibutyl tin dilaurate catalyzer of 4-Xylene Diisocyanate, 0.25mol were 80 ℃ of reactions 2.5 hours; Add the 0.48mol TriMethylolPropane(TMP) then, in 82 ℃ of reactions 2 hours; In the agent of 40 ℃ of adding 0.8mol triethylamine pH regulator, reaction 15min adds 58.9mol water, carries out emulsification 30min with the 1500rpm rotating speed; Toluene is removed in decompression, and discharging obtains the chlorinated polypropylene modified polyurethane aqueous resin of 41% solid content.
Embodiment 2: the preparation of the anion aqueous resin of chlorinated polypropylene modified urethane
Press the mol ratio, 2mol toluene, 0.003mol Chlorinated Polypropylene III (molecular weight 10000 dalton are contained chlorine weight percentage 10%), 0.46mol Hydroxyethyl acrylate and 0.04mol benzoyl peroxide are 105 ℃ of reactions 3.5 hours in temperature of reaction; Add 2 of 2.4mol then, 4-Xylene Diisocyanate, 0.3mol poly butylene succinate glycol (molecular weight 2000 dalton), 1mol dimethylolpropionic acid and 0.0005mol dibutyl tin dilaurate catalyzer were 80 ℃ of reactions 2.5 hours; Add the 0.5mol TriMethylolPropane(TMP) then, in 82 ℃ of reactions 2 hours; In the agent of 40 ℃ of adding 0.9mol dimethylethanolamine pH regulator, reaction 15min adds 117.2mol water, carries out emulsification 30min with the 1500rpm rotating speed; Toluene is removed in decompression, and discharging obtains the chlorinated polypropylene modified polyurethane aqueous resin of 40% solid content.
Embodiment 3: the preparation of the cation water-based resin of chlorinated polypropylene modified urethane
Press the mol ratio, 2.5mol toluene, 0.001mol Chlorinated Polypropylene III (molecular weight 150000 dalton, chloride weight percentage 40%), 0.38mol Hydroxyethyl acrylate and 0.01mol benzoyl peroxide are 110 ℃ of reactions 2.5 hours in temperature of reaction; Add isophorone diisocyanate, the 0.1mol polyethylene glycol adipate glycol (molecular weight 2000 dalton) of 1.8mol, N methyldiethanol amine and the 0.0002mol dibutyl tin dilaurate catalyzer of 0.8mol then, 80 ℃ of reactions 2.5 hours; Add the 0.4mol TriMethylolPropane(TMP) then, in 85 ℃ of reactions 2 hours; In the agent of 45 ℃ of adding 0.6mol oxyacetic acid pH regulator, reaction 20min adds 82.5mol water, carries out emulsification 30min with the 2000rpm rotating speed; Toluene is removed in decompression, and discharging obtains the chlorinated polypropylene modified polyurethane aqueous resin of 42% solid content.
Embodiment 4: the preparation of the cation water-based resin of chlorinated polypropylene modified urethane
Press the mol ratio, 2.3mol toluene, 0.001mol Chlorinated Polypropylene III (molecular weight 100000 dalton, chloride weight percentage 30%), 0.38mol Hydroxyethyl acrylate and 0.01mol benzoyl peroxide are 110 ℃ of reactions 3 hours in temperature of reaction; Add then 1mol isophorone diisocyanate, 0.8mol 2, N butyl diethanol amine and the 0.0002mol dibutyl tin dilaurate catalyzer of 4-Xylene Diisocyanate, 0.1mol polyethylene glycol adipate glycol (molecular weight 2000 dalton), 0.8mol were 80 ℃ of reactions 2.5 hours; Add the 0.4mol TriMethylolPropane(TMP) then, in 85 ℃ of reactions 2 hours; In the agent of 45 ℃ of adding 0.6mol acetate pH regulator, reaction 20min adds 77.2mol water, carries out emulsification 30min with the 2000rpm rotating speed; Toluene is removed in decompression, and discharging obtains the chlorinated polypropylene modified polyurethane aqueous resin of 40% solid content.
Embodiment 5: be used for the preparation of bumper nano-dispersed waterborne conductive priming paint
A) by weight ratio, get 80 parts of PEDOT-PSS (the 1.71%PEDOT aqueous solution), 156 parts of embodiment, 1 preparation the anion aqueous resin of chlorinated polypropylene modified urethane, 2.8 parts of BYK-380N water-based flow agents and 15 parts of Virahol water-based auxiliary agents be put in the sand mill jar, 600 rev/mins rotating speed stirred 3 hours.
B) by weight ratio, the rotating speed that 45 parts of Bayhydur VPLS2306 water cross-linking agents, 1.5 parts of BYK-024 water-based defoamers and 1.2 parts of isothiazolinone disinfecting agents are pressed 1500 rev/mins of rotating speeds stirred 1 hour.
C) with above-mentioned steps a) and b) product two components that obtain put into paint mixing tank, 1100 rev/mins rotating speed stirred 3 minutes, obtained solid content and be 38.5% waterborne conductive priming paint, size distribution is 45～180nm.Film thickness is 7 μ m, and paint film face resistance is 2.3 * 10
7Ω/sq.Pure PEDOT-PSS conductive polymers addition is 1.3% of priming paint total solid weight part.
Embodiment 6: be used for the preparation of bumper nano-dispersed waterborne conductive priming paint
A) by weight ratio, get 170 parts PEDOT-PSS (the 1.71%PEDOT aqueous solution), the anion aqueous resin of chlorinated polypropylene modified urethane, 1.6 parts of BYK-380N water-based flow agents and the 25 parts of ethylene glycol monobutyl ether aqueous promoters among 102 parts of embodiment 2 are put in the sand mill jar, 600 rev/mins rotating speed stirred 3 hours.
B) by weight ratio, the rotating speed that 32 parts Bayhydur XP 2487/1 water cross-linking agent, 3.5 parts of BYK-093 defoamers and 1.7 parts of isothiazolinone disinfecting agents are pressed 1500 rev/mins of rotating speeds stirred 1 hour.
C) by weight ratio, with above-mentioned steps a) and b) product that obtains puts into paint mixing tank, 1100 rev/mins rotating speed stirred 3 minutes, obtained solid content and be 24% waterborne conductive priming paint, size distribution is 52～130nm.Film thickness is 6 μ m, and paint film face resistance is 5.6 * 10
6Ω/sq.Pure PEDOT-PSS conductive polymers addition is 3.8% of priming paint total solid weight part.
Embodiment 7: be used for the preparation of bumper nano-dispersed waterborne conductive priming paint
A) by weight ratio, get the cation water-based resin of chlorinated polypropylene modified urethane among 270 parts of WPA (5.7% solid aqueous solution), the 125 parts of embodiment 3,1.2 parts of BYK-341 and 2 parts of BYK-307 water-based flow agents, 30 parts of Diethylene Glycol butyl ether aqueous promoters and be put in the sand mill jar, 600 rev/mins rotating speed stirred 3 hours.
B) by weight ratio, the rotating speed that 40 parts Bayhydur 3100 water cross-linking agents, 2.8 parts of BYK-011 water-based defoamers and 2.3 parts of isothiazolinone disinfecting agents are pressed 1500 rev/mins of rotating speeds stirred 1 hour.
C) with above-mentioned steps a) and b) product that obtains puts into paint mixing tank, 1100 rev/mins rotating speed stirred 3 minutes, obtained solid content and be 24.5% waterborne conductive priming paint, size distribution is 80～140nm.Film thickness is 8 μ m, and paint film face resistance is 1.1 * 10
6Ω/sq.Pure WPA conductive polymers addition is 14.2% of priming paint total solid weight part.
Embodiment 8: be used for the preparation of bumper nano-dispersed waterborne conductive priming paint
A) by weight ratio, the cation water-based resin of chlorinated polypropylene modified urethane, 1.8 parts of BYK-381 water-based flow agents and 22 parts of butyl glycol ether aqueous promoters of getting among 100 parts of WPA (5.7% solid aqueous solution), the 150 parts of embodiment 4 are put in the sand mill jar, and 600 rev/mins rotating speed stirred 3 hours.
B) by weight ratio, the rotating speed that the BayhydurXP2451 aqueous promoter of 32 parts of Bayhydur XP2570 and 10 parts, 4 parts of BYK-093 water-based defoamers and 1.8 parts of isothiazolinone disinfecting agents are pressed 1500 rev/mins of rotating speeds stirred 1 hour.
C) with above-mentioned steps a) and b) product that obtains puts into paint mixing tank, 1100 rev/mins rotating speed stirred 3 minutes, obtaining solid content is 33.5% waterborne conductive priming paint, coating be distributed as 85～120nm.Film thickness is 9 μ m, and paint film face resistance is 1.7 * 10
7Ω/sq.Pure WPA waterborne conductive polymkeric substance addition is 5.8% of priming paint total solid weight part.
Embodiment 9: be used for the preparation of bumper nano-dispersed waterborne conductive priming paint
A) by weight ratio, the anion aqueous resin of chlorinated polypropylene modified urethane, 2.6g part BYK-380N water-based flow agent and 30 parts of butyl glycol ether aqueous promoters of getting among 230 parts of PEDOT-PSS (the 1.71%PEDOT aqueous solution), the 120 parts of embodiment 2 are put in the sand mill jar, and 600 rev/mins rotating speed stirred 3 hours.
B) by weight ratio, the rotating speed that 38 parts of Bayhydur VPLS2306 water cross-linking agents, 3.5 parts of BYK-024 water-based defoamers and 2.1 parts of isothiazolinone disinfecting agents are pressed 1500 rev/mins of rotating speeds stirred 1 hour.
C) with above-mentioned steps a) and b) product that obtains puts into paint mixing tank, 1000 rev/mins rotating speed stirred 3 minutes, obtaining solid content is 22.4% waterborne conductive priming paint, coating be distributed as 90～105nm.Film thickness is 8 μ m, and paint film face resistance is 1.2 * 10
6Ω/sq.Pure PEDOT-PSS conductive polymers addition is 4.3% of priming paint total solid weight part.
Embodiment 10: be used for the preparation of bumper nano-dispersed waterborne conductive priming paint
A) by weight ratio, the cation water-based resin of chlorinated polypropylene modified urethane, 3 parts of BYK-381 water-based flow agents and 18 parts of butyl glycol ethers and 12 parts of Virahol water-based auxiliary agents of getting among 103 parts of WPA (5.7% solid aqueous solution), the 98 parts of embodiment 4 are put in the sand mill jar, and 600 rev/mins rotating speed stirred 3 hours.
B) by weight ratio, the rotating speed that the BayhydurXP2451 water cross-linking agent of 20 parts of Bayhydur XP2570 and 10 parts, 3 parts of BYK-093 and 0.5 part of BYK-028 water-based defoamer, 2.6 parts of isothiazolinone disinfecting agents are pressed 1500 rev/mins of rotating speeds stirred 1 hour.
C) with above-mentioned steps a) and b) product that obtains puts into paint mixing tank, 1100 rev/mins rotating speed stirred 3 minutes, obtained solid content and be 27.8% waterborne conductive priming paint, coating be distributed as 45～80nm.Film thickness is 10 μ m, and paint film face resistance is 3.4 * 10
4Ω/sq.Pure WPA conductive polymers addition is 7.8% of priming paint total solid weight part.
Embodiment 11: be used for bumper nano-dispersed waterborne conductive priming paint spraying
Embodiment 5～10 preparation is used for bumper nano-dispersed waterborne conductive priming paint in the spraying on the bumper: spray the conductive primer of 6～10 μ m on collision bumper, normal temperature dodges does 6～10min, then, and 80 ℃ of baking 20min.
In the foregoing description 1～11, described water cross-linking agent is a water dispersive polyisocyanate, and Bayhydur 3100, Bayhydur VP LS 2306, Bayhydur XP 2487/1, BayhydurXP 2570 and Bayhydur XP 2451 are Beyer Co., Ltd's product; The water-based defoamer is selected from organosilicon type defoamer, and BYK-024, BYK-028, BYK-011 and BYK-093 are BYK company water-based defoamer; The water-based flow agent is selected from ionic acrylic interpolymer and polyether-modified polydimethylsiloxane type flow agent, and BYK-380N, BYK-307, BYK-341 and BYK-381 are the water-based flow agent product of BYK company.
In sum, the present invention is not limited to above-mentioned embodiment, and persons skilled in the art are in the disclosed technical scope of the present invention, and the variation that can expect easily is all within protection scope of the present invention.
Claims (8)
1. be used for bumper nano-dispersed waterborne conductive priming paint, it is characterized in that, its composition and weight part proportioning are as follows:
Water nano dispersed electro-conductive polymkeric substance is 80～270 parts;
Chlorinated polypropylene modified polyurethane aqueous resin is 25～156 parts;
Water cross-linking agent is 24.5～45 parts;
Aqueous promoter is 15～30 parts;
The water-based flow agent is 0.8～3.2 part;
The water-based defoamer is 1.5～4.0 parts;
Sterilant is 1.2～2.8 parts;
Described water nano dispersed electro-conductive polymkeric substance is for gathering 3,4-ethene dioxythiophene-polystyrolsulfon acid or waterborne conductive polyaniline;
Chlorinated polypropylene modified polyurethane aqueous resin is cation water-based resin of chlorinated polypropylene modified urethane or the anion aqueous resin of chlorinated polypropylene modified urethane;
Water cross-linking agent is a water dispersive polyisocyanate;
Aqueous promoter is one or more mixtures in Virahol, butyl glycol ether and the Diethylene Glycol butyl ether;
The water-based flow agent is selected from ionic acrylic interpolymer or polyether-modified polydimethylsiloxane type flow agent;
The water-based defoamer is selected from organosilicon type defoamer;
Sterilant is an isothiazolinone.
2. the method for making that is used for bumper nano-dispersed waterborne conductive priming paint as claimed in claim 1 is characterized in that its step and condition are as follows:
(1) preparation of chlorinated polypropylene modified polyurethane aqueous resin
By proportioning, toluene, Chlorinated Polypropylene III, Hydroxyethyl acrylate and benzoyl peroxide are added in the reactor, be 100～110 ℃ of reactions 2.5～3.5 hours in temperature of reaction; Add vulcabond, polyester diol, hydrophilic chain extender and dibutyl tin dilaurate catalyzer then, 75～80 ℃ of reactions 2.5～3 hours; Add TriMethylolPropane(TMP) then, in 80～85 ℃ of reactions 1.5～2 hours; In the agent of 40～45 ℃ of adding pH regulator, reaction 15～20min adds entry then, carries out emulsification 20-30min with 1500～2000rpm rotating speed; Toluene is removed in decompression, and discharging obtains chlorinated polypropylene modified polyurethane aqueous resin;
Described polyester diol is a kind of in poly adipate succinic acid ester glycol, the poly butylene succinate two pure and mild polyethylene glycol adipate glycol;
Described toluene: Chlorinated Polypropylene III: Hydroxyethyl acrylate: benzoyl peroxide: vulcabond: polyester diol: hydrophilic chain extender: dibutyl tin dilaurate: TriMethylolPropane(TMP): pH regulator agent: the mol ratio of water is 2～2.5: 0.001～0.003: 0.38～0.46: 0.01～0.04: 1.8～2.4: 0.1～0.3: 0.8～1: 0.0002～0.0005: 0.4～0.5: 0.6～0.9: 58.9～117.2; Best mol proportioning is 2.1～2.3: 0.0015～0.002: 0.42～0.44: 0.02～0.03: 2～2.2: 02～0.25: 0.8～0.95: 0.0003～0.0004: 0.46～0.48: 0.7～0.8: 77.2～82.5;
Described hydrophilic chain extender is a kind of in N methyldiethanol amine, N butyl diethanol amine, dimethylolpropionic acid and the dimethylol propionic acid;
Described pH regulator agent is a kind of in dimethylethanolamine, triethylamine, oxyacetic acid, sulfuric acid and the acetate.
(2) be used for the preparation of bumper nano-dispersed waterborne conductive priming paint
By proportioning weighing material;
A) chlorinated polypropylene modified polyurethane aqueous resin, water nano dispersed electro-conductive polymkeric substance, water-based flow agent and aqueous promoter are put in the sand mill jar, the rotating speed of 600～1200rpm stirred 0.5～3 hour;
B) water cross-linking agent, water-based defoamer and the sterilant rotating speed with 900～1500rpm was stirred 0.5～1 hour;
C) with above-mentioned steps a) and b) product that obtains puts into paint mixing tank, stirs 1.5～3 minutes with the rotating speed of 800～1100rpm, discharging obtains being used for bumper nano-dispersed waterborne conductive priming paint.
3. the method for making that is used for bumper nano-dispersed waterborne conductive priming paint as claimed in claim 2 is characterized in that, described Chlorinated Polypropylene III is that chloride weight percent is 10～40%.
4. the method for making that is used for bumper nano-dispersed waterborne conductive priming paint as claimed in claim 3 is characterized in that, described Chlorinated Polypropylene III is that chloride weight percent is 20～35%.
5. the method for making that is used for bumper nano-dispersed waterborne conductive priming paint as claimed in claim 2 is characterized in that, described Chlorinated Polypropylene III is that weight-average molecular weight is 10000～150000 daltonian Chlorinated Polypropylene IIIs.
6. the method for making that is used for bumper nano-dispersed waterborne conductive priming paint as claimed in claim 5 is characterized in that, described Chlorinated Polypropylene III is that weight-average molecular weight is 35000～90000 daltonian Chlorinated Polypropylene IIIs.
7. the method for making that is used for bumper nano-dispersed waterborne conductive priming paint as claimed in claim 2 is characterized in that described vulcabond is 2, one or both in 4-Xylene Diisocyanate and the isophorone diisocyanate;
8. the method for making that is used for bumper nano-dispersed waterborne conductive priming paint as claimed in claim 2 is characterized in that the molecular weight of described polyester diol is 2000 dalton.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102653659A (en) * | 2012-04-26 | 2012-09-05 | 苏州艾达仕电子科技有限公司 | Conductive coating material based on polyurethane dispersion body |
| CN103525266A (en) * | 2012-07-04 | 2014-01-22 | 中国科学院理化技术研究所 | Water-based antistatic coating and preparation method thereof |
| CN103865464A (en) * | 2014-03-20 | 2014-06-18 | 长春市三化实业有限责任公司 | Water-based conductive adhesive and preparation method thereof |
| CN103865364A (en) * | 2014-03-11 | 2014-06-18 | 苏州斯迪克新材料科技股份有限公司 | Polythiophene antistatic coating liquid and preparation method thereof |
| CN104109427A (en) * | 2014-06-23 | 2014-10-22 | 重庆华辉涂料有限公司 | Light-gray conductive primer for PP material bumper electrostatic coating and preparation method thereof |
| CN106147493A (en) * | 2016-06-29 | 2016-11-23 | 浙江佑谦特种材料有限公司 | A kind of aqueous priming paint for bumper |
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| CN106189765A (en) * | 2015-10-30 | 2016-12-07 | 丹阳市日月漆业有限公司 | A kind of water-based mono-component plastic coating and its preparation method and application |
| CN106189766A (en) * | 2015-10-30 | 2016-12-07 | 丹阳市日月漆业有限公司 | Coating and its preparation method and application |
| CN110205012A (en) * | 2019-07-04 | 2019-09-06 | 苏州市朴力冭材料科技有限公司 | A kind of macromolecule of resistance to alcohol anti-static conductive coating and preparation method thereof for plastic sheet |
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| CN111534215A (en) * | 2020-05-22 | 2020-08-14 | 中国科学院长春应用化学研究所 | Water-based paint for automobile bumpers and preparation method thereof |
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| CN1823146A (en) * | 2003-07-23 | 2006-08-23 | 关西涂料株式会社 | White electrically conducting primer composition and process for forming multilayer coating films |
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| JPH06136316A (en) * | 1992-10-23 | 1994-05-17 | Toyota Motor Corp | Primer for polypropylene |
| CN1823146A (en) * | 2003-07-23 | 2006-08-23 | 关西涂料株式会社 | White electrically conducting primer composition and process for forming multilayer coating films |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102653659A (en) * | 2012-04-26 | 2012-09-05 | 苏州艾达仕电子科技有限公司 | Conductive coating material based on polyurethane dispersion body |
| CN102653659B (en) * | 2012-04-26 | 2014-05-14 | 苏州艾达仕电子科技有限公司 | Conductive coating material based on polyurethane dispersion body |
| CN103525266A (en) * | 2012-07-04 | 2014-01-22 | 中国科学院理化技术研究所 | Water-based antistatic coating and preparation method thereof |
| CN103525266B (en) * | 2012-07-04 | 2015-11-04 | 中国科学院理化技术研究所 | Water-based antistatic coating and preparation method thereof |
| CN103865364A (en) * | 2014-03-11 | 2014-06-18 | 苏州斯迪克新材料科技股份有限公司 | Polythiophene antistatic coating liquid and preparation method thereof |
| CN103865464A (en) * | 2014-03-20 | 2014-06-18 | 长春市三化实业有限责任公司 | Water-based conductive adhesive and preparation method thereof |
| CN103865464B (en) * | 2014-03-20 | 2015-06-24 | 长春市三化实业有限责任公司 | Water-based conductive adhesive and preparation method thereof |
| CN104109427A (en) * | 2014-06-23 | 2014-10-22 | 重庆华辉涂料有限公司 | Light-gray conductive primer for PP material bumper electrostatic coating and preparation method thereof |
| CN106189765A (en) * | 2015-10-30 | 2016-12-07 | 丹阳市日月漆业有限公司 | A kind of water-based mono-component plastic coating and its preparation method and application |
| CN106167671A (en) * | 2015-10-30 | 2016-11-30 | 丹阳市日月漆业有限公司 | Water-based mono-component plastic coating and its preparation method and application |
| CN106189764A (en) * | 2015-10-30 | 2016-12-07 | 丹阳市日月漆业有限公司 | A kind of coating and its preparation method and application |
| CN106189767A (en) * | 2015-10-30 | 2016-12-07 | 丹阳市日月漆业有限公司 | A kind of water paint and its preparation method and application |
| CN106189766A (en) * | 2015-10-30 | 2016-12-07 | 丹阳市日月漆业有限公司 | Coating and its preparation method and application |
| CN106147493A (en) * | 2016-06-29 | 2016-11-23 | 浙江佑谦特种材料有限公司 | A kind of aqueous priming paint for bumper |
| CN110205012A (en) * | 2019-07-04 | 2019-09-06 | 苏州市朴力冭材料科技有限公司 | A kind of macromolecule of resistance to alcohol anti-static conductive coating and preparation method thereof for plastic sheet |
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| CN111534215A (en) * | 2020-05-22 | 2020-08-14 | 中国科学院长春应用化学研究所 | Water-based paint for automobile bumpers and preparation method thereof |
| CN111534215B (en) * | 2020-05-22 | 2021-07-02 | 中国科学院长春应用化学研究所 | Water-based paint for automobile bumpers and preparation method thereof |
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