CN102417779A - Preparation process of bicomponent castor oil polyurethane waterproof coating - Google Patents
Preparation process of bicomponent castor oil polyurethane waterproof coating Download PDFInfo
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- CN102417779A CN102417779A CN2011102299175A CN201110229917A CN102417779A CN 102417779 A CN102417779 A CN 102417779A CN 2011102299175 A CN2011102299175 A CN 2011102299175A CN 201110229917 A CN201110229917 A CN 201110229917A CN 102417779 A CN102417779 A CN 102417779A
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Abstract
A preparation process of a bicomponent castor oil polyurethane waterproof coating is characterized in that the coating is obtained by interpenetrating a component A of polyurethane prepolymer and a component B of a colorful color paste system under the action of an initiator and a catalyst; wherein the component A is obtained by allowing castor oil and 2,4-toluene diisocyanate to react in an organic solvent dissolved with an initiator; the component B is obtained by mixing a blending agent, a solid pigment and/or a solid filler with a coupling agent, milling, orderly adding a alkene monomer, a catalyst, a polymerization inhibitor, and a light stabilizer, and stirring uniformly. The coating of the invention has excellent waterproofness, a good apparent state, abundant colors, good decorative effect, adjustable curing time, adjustable film flexibility and hardness, and simple operations.
Description
Technical field
The present invention relates to a kind of preparation technology of polyurethane water-proof paint
,Especially
BeThe preparation technology of two-pack Viscotrol C polyurethane water-proof paint.
Background technology
Urethane (PU-Polyurethane) is the abbreviation of polyurethane(s), and it is a kind of high molecular polymer.It is the polymkeric substance of being processed by raw materials such as chainextenders such as POLYMETHYLENE POLYPHENYLISOCYANATE and polyether glycol or polyester polyol or small molecules polyvalent alcohol, polyamine or water or linking agents.Through changing raw material type and composition, can change product form and performance thereof significantly, obtain from softness to hard the finished product.Urethane is with respect to other high-molecular coating, and it has lot of advantages, and like the material good mechanical property, the performance adjustable extent is wide, building-up properties is good etc.PU is one of synthetic paint of the world's six great development.With regard to it used range, it had jumped and has been the first place of all kinds of synthetic paint.
(Interpenetrating polymer network IPN) is interleaving network by two or more polymkeric substance interpenetration to interpenetrating net polymer.The notion of interpenetrating net polymer is the Mmllar sixties
[18]Put forward, it is to use chemical method that two or more polymkeric substance is run through one type of novel complex phase polymer coating that formation interweaves netted each other
[19]High-polymer molecular runs through each other and forms the network system, between the polymkeric substance of participation IPN chemical reaction does not take place, permeates but intersect each other, and mechanical interlocking plays " force and dissolve each other " and " synergy ".This internetwork entanglement has improved dispersiveness, the interface wetting ability of system significantly, thereby has improved relative stability, has realized that polymer performance is complementary, reaches the purpose of modification.
Interpenetrating net polymer is polymer blending and compound important means, can regard a kind of innovative techniques that chemically realizes the polymer physics blend as, and IPN is one of the main developing direction of multiphase polymer in modern age.The maximum characteristics of IPN are to have adopted special preparation method, ideally with two kinds not the polymkeric substance of phase mixing intert mutually through network, entangled to each other, force compatible.And original copolymer had both had memory capability, did not lose primary characteristic; Have synergy again, a little less than strong benefit, even obtain the incomparable excellent properties of other polymkeric substance.So to the research and development of IPN coating, countries in the world are all rather paid attention to.In paint field, the application prospect of IPN is encouraging, and through the selection of raw material, the adjustment of formulating of recipe and the change of synthesis technique can make the many kinds with specified property, multiduty IPN, are used to prepare various new exclusive coating.Have this to close the work of this respect, also be in initial stage at present, the IPN that is used for coating mostly is synchronous IPN (SIN) and latex IPN (LIPN).When two kinds of polymer formation IPN, can improve their compatibility, widen the scope of corresponding glass transition temperature.Along with the increase of two kinds of polymeric constituent compatibilities, two second-order transition temperatures of IPN each other near and form a broad glass transition zone, the damping of can effectively shaking in this zone, so IPN has excellent damping capacity.The more next benefit of the application of IPN compound damping paint and noise deadener extensively is divided into extended pattern damping coating and polymer coated two kinds of constraint with it usually.Adopt gradation type IPN can make stretching, extension damping layer and bond course be combined into same integral body.For example: the gradation type IPN with hard surface (playing bond course) and viscoelastic internal layer (damping layer) of people such as Sperling preparation make it that fabulous damping damping capacity arranged, so the IPN damping paint has very broad application prospect.
Present polyurethane interpenetrating network type coating is many, and reaction obtains prepolymer with POLYMETHYLENE POLYPHENYLISOCYANATE by polyvalent alcohol, and again with other synthetic resins copolymerization, remaining isocyano is through moisture absorption formation urethane network and solidify in the last system.Because behind the surface cure, water is hindered to the inner diffusion of filming, the moisture absorption curing ratio of the feasible inner residue isocyano of filming is difficulty, and it is long that system is done solid work the time.In addition, be difficult for discharging, make film be coated with apparent being not in good state, also influence film simultaneously and be coated with sticking power base material because the inner moisture absorption of filming is solidified the bubble that produces.The natural renewable resource of some blending agentss, good fluidity, wettability are strong, can serve as wetting dispersing agent and crosslinking and curing agent in the polyurethane coating.Vinyl monomer such as vinylbenzene are used for the exposed conveying appliance waterproof paint can make filmed excellent abrasive and hardness, and can shorten the surface drying of filming and do solid work the time; TEB 3K, NSC 20956, vinylformic acid, methylacrylic acid are used for the exposed conveying appliance waterproof paint can make film good gloss retention, weather-proof erosion resistance and snappiness.
Summary of the invention
The object of the present invention is to provide a kind of preparation technology of two-pack Viscotrol C polyurethane water-proof paint, it can overcome the deficiency of prior art, and has excellent performance; Apparent state is good, rich color, good decorating effect, and set time is adjustable; The gentle hardness of filming is adjustable, easy and simple to handle.
The technical scheme that realizes the object of the invention is: a kind of preparation technology of two-pack Viscotrol C polyurethane water-proof paint is characterized in that: by base polyurethane prepolymer for use as is that component A and colored mill base system are that B component IPN under the effect of initiator and catalyzer obtains; Wherein component A is reacted in dissolving with the organic solvent of initiator by Viscotrol C and 2,4 toluene diisocyanate and obtains; B component is mixed with coupling agent to mill by blending agents and solid pigment and/or solid packing and is added vinyl monomer, catalyzer, stopper, photostabilizer more successively and stir and obtain.
And, comprise the steps:
(1) raw material is handled: decompression dehydration obtained in 1～2 hour under 100～120 ℃ of blending agentss, the 0.08MPa vacuum tightness; Solid pigment and/or solid packing are dried under 120 ℃ temperature and were obtained in two hours;
(2) solid pigment that blending agents and toning is needed or solid packing mix with coupling agent and are milled to suitable fineness, add vinyl monomer, catalyzer, stopper, photostabilizer stirring again and successively and obtain uniform and stable B component;
(3) will dissolve organic solvent and 2 earlier with initiator; The 4-tolylene diisocyanate adds the Viscotrol C that in batches adds again in the reaction kettle after the vacuum hydro-extraction; Be not more than in water or air cycle condensation and in temperature control under 50 ℃ the condition and reacted 1 ~ 3 hour, stirring obtains component A;
(4) component A and B component are mixed by weight 1:0.5 ~ 4; Add an amount of organic solvent again and be adjusted to appropriate viscosity; Stir; Left standstill 10-60 minute, and brushed under the room temperature or be sprayed on to solidify on the different base materials and obtained colored exposed conveying appliance interpenetrating(polymer)networks two-pack Viscotrol C polyurethane water-proof paint in 30 minutes ~ 8 hours.
And the used blending agents of step (1) is 1 ~ 5 kind in glycerine, glycol ether, tetramethylolmethane, sorbyl alcohol, the TriMethylolPropane(TMP); The used solid pigment of step (1) is 1 ~ 10 kind in white titanium pigment, red iron oxide, carbon black, zinc oxide, zinc sulfide white, medium chrome yellow medium yellow, phthalocyanine blue, phthalocyanine green, ultramarine, the toluidine red; Solid packing is that blue or green cream powder, granularity are 1 ~ 5 kind in 600-800 purpose light calcium carbonate, wilkinite, talcum powder, the tiff; The used vinyl monomer of step (2) is 1～6 kind in vinylbenzene, TEB 3K, NSC 20956, vinyl cyanide, the acrylic or methacrylic acid; Coupling agent is a titanate coupling agent; Catalyzer is 1～4 kind in dibutyl tin dilaurate, stannous octoate, triethylamine, the triethylene diamine; Stopper is a Resorcinol; Photostabilizer is oxidation inhibitor four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester (1010), UV-531 (UV-531), 2-(2-hydroxyl-3; 5-two fourth uncles base phenyl)-5-chlorinated benzotriazole (UV-327), 2-(2 '-hydroxyl-3 ', 5 '-the diamyl phenyl) benzotriazole (UV-328), 2-hydroxyl 4-1～5 kind in the octyloxy UVNUL MS-40 (UV-292).Wherein, 1010, UV-531, UV-327, UV-328, UV-292 are respectively its commodity popular name; The used initiator of step (3) is Lucidol or Diisopropyl azodicarboxylate; Organic solvent is 1～6 kind in toluene, YLENE, ETHYLE ACETATE, butylacetate, acetone, the methylethylketone.
And component A and B component weight ratio are 1:0.5 ~ 4; In component A, by weight percentage, the Viscotrol C consumption is 30% ~ 75%, and the 2,4 toluene diisocyanate consumption is 15% ~ 60%, and consumption of organic solvent is 5% ~ 25%, and initiator amount is 0.2 ~ 2%; In B component, by weight percentage, the blending agents consumption is 10% ~ 30%; Solid pigment or solid packing consumption are 20% ~ 45%, and the vinyl monomer consumption is 20 ~ 55%, and the coupling agent consumption is 0.05 ~ 1%; Catalyst levels is 0.05 ~ 1%, and the stopper consumption is 0.05 ~ 1%, and the photostabilizer consumption is 0.05 ~ 2%.
The present invention utilizes blending agents, vinyl monomer as linking agent; Make cross-linking system contain simultaneously with two keys and hydroxyl; This cross-linking system can either utilize the two keys in its pair key and the base polyurethane prepolymer for use as to carry out copolymerization or self-polymeric reaction forms the polyolefine network; Can utilize remaining isocyano reaction formation urethane network in its hydroxyl and the base polyurethane prepolymer for use as again, make curing reaction can not rely on moisture and accomplish.Simultaneously, use blending agents to make linking agent, enlarged the cross-linker molecules chain, improved the low temperature flexibility of filming, vinyl monomer is made linking agent can improve the apparent condition and adjusting coating performance of filming.Processing unit of the present invention is simple, and is easy to operate, helps industrial mass production; The colored interpenetrating(polymer)networks two-pack of the exposed conveying appliance that obtains Viscotrol C polyurethane water-proof paint has excellent water resistance; Better mechanical property, ageing-resistant performance, resistance to chemical corrosion, and rich color, good decorating effect not only can use at the exposed parts of buildings; Play waterproof and decoration function simultaneously; But also can use at non-exposed parts, having price and environment-friendly advantage, product can use at products such as top-grade building thing, highway, bridge, high-speed railway, drome, large stadiums; Comparatively wide applications is arranged, have fine economic and social benefit.
Description of drawings
Fig. 1 is thermogravimetric and the heat flow curve figure after two-pack Viscotrol C polyurethane water-proof paint varnish solidifies.
Wherein curve a is the thermogravimetric curve after colored exposed conveying appliance interpenetrating(polymer)networks two-pack Viscotrol C polyurethane water-proof paint varnish solidifies, and b is the heat flow curve after colored exposed conveying appliance interpenetrating(polymer)networks two-pack Viscotrol C polyurethane water-proof paint varnish solidifies.
Through test, compositional range involved in the present invention all can realize goal of the invention, below makes further detailed description through embodiment:
A is the thermogravimetric curve figure after colored exposed conveying appliance interpenetrating(polymer)networks two-pack Viscotrol C polyurethane water-proof paint varnish solidifies in the accompanying drawing 1, has three steps weightless; B is the heat flow curve figure after the colored interpenetrating(polymer)networks two-pack of exposed conveying appliance Viscotrol C polyurethane water-proof paint varnish solidifies, and three endotherm(ic)peaks are arranged.Explain that the degraded of the colored interpenetrating(polymer)networks two-pack of exposed conveying appliance Viscotrol C polyurethane water-proof paint varnish divides three ones and carries out.This is because in this is filmed, exist two kinds of cross-linked networks: the polyolefine network of the free-radical polymerized formation of two keys process in contained pair of key of Viscotrol C and the vinyl monomer in the performed polymer; In residue-NCO in the performed polymer and the colored mill base system in the Viscotrol C-OH forms the urethane network.Physics windings through molecular chain of two kinds of networks, hydrogen bond etc. combine the stable IPN system of formation.
Embodiment one:
White exposed conveying appliance waterproof paint: concrete proportioning is: component A: Viscotrol C 20.0%, 2,4 toluene diisocyanate 38.07%, YLENE 8.6%, Diisopropyl azodicarboxylate 0.2%; Component B: glycol ether 8.0.%, white titanium pigment 15.5%, talcum powder 2.0%; Ultramarine 0.05%, coupling agent YB-201A (can adopt the titanate coupling agent of Changzhou Ya Bangya space auxiliary agent ltd) 0.08%, methylacrylic acid formic acid 7.0%; Antioxidant 1010 0.1%, UV-292 0.1%, Resorcinol 0.1%; Stannous octoate 0.1%, triethylene diamine 0.1%.Component A and component B are mixed, add proper amount of diluting, stir, left standstill 30 minutes, be cast under the room temperature on the glass template and be sprayed on the steel plate, 30 ℃ of following constant temperature 7 days.Coating surface drying time on the glass template is 2 hours, and the coating surface drying time on the steel plate is 2 hours; Coating gloss 60.3 on the steel plate, hardness 3H; Filming on the glass template measured its tensile strength according to national polyurethane water-proof paint standard on XLD-3 type electronic tensile test machine be 10.75MPa, and elongation at break is 275%; The electronic waterproof determinator of LTD-A type is measured its watertightness, and 0.4MPa30min is waterproof.
Embodiment two:
White exposed conveying appliance waterproof paint: concrete proportioning is: component A: Viscotrol C 30.07%, 2,4 toluene diisocyanate 20.0%, YLENE 8.6%, Diisopropyl azodicarboxylate 0.2%; Component B: glycol ether 8.0.%, white titanium pigment 15.5%, talcum powder 2.0%; Ultramarine 0.05%, coupling agent YB-201A (can adopt the titanate coupling agent of Changzhou Ya Bangya space auxiliary agent ltd) 0.08%, methylacrylic acid formic acid 7.0%; Antioxidant 1010 0.1%, UV-292 0.1%, Resorcinol 0.1%; Stannous octoate 0.1%, triethylene diamine 0.1%.Component A and component B are mixed, add proper amount of diluting, stir, left standstill 30 minutes, be cast under the room temperature on the glass template and be sprayed on the steel plate, 30 ℃ of following constant temperature 7 days.Coating surface drying time on the glass template is 3 hours, and the coating surface drying time on the steel plate is 2 hours; Coating gloss 60.4 on the steel plate, hardness 3H; Filming on the glass template measured its tensile strength according to national polyurethane water-proof paint standard on XLD-3 type electronic tensile test machine be 8.65MPa, and elongation at break is 363%; The electronic waterproof determinator of LTD-A type is measured its watertightness, and 0.4MPa30min is waterproof.
Embodiment three:
White exposed conveying appliance waterproof paint: concrete proportioning is: component A: Viscotrol C 27.0%, 2,4 toluene diisocyanate 14.85%, YLENE 4.2%, ETHYLE ACETATE 2.1%, Diisopropyl azodicarboxylate 0.3%; Component B: glycol ether 8.5%, white titanium pigment 16.5%, talcum powder 3.0%; Ultramarine 0.15%, coupling agent YB-201A (can adopt the titanate coupling agent of Changzhou Ya Bangya space auxiliary agent ltd) 0.5%, methylacrylic acid formic acid 21.8%; Antioxidant 1010 0.2%, UV-292 0.3%, Resorcinol 0.2%; Stannous octoate 0.2%, triethylene diamine 0.2%.Component A and component B are mixed, add proper amount of diluting, stir, left standstill 30 minutes, be cast under the room temperature on the glass template and be sprayed on the steel plate, 30 ℃ of following constant temperature 7 days.Coating surface drying time on the glass template is 2 hours, and the coating surface drying time on the steel plate is 1.5 hours; Coating gloss 72.8 on the steel plate, hardness 3H; Filming on the glass template measured its tensile strength according to national polyurethane water-proof paint standard on XLD-3 type electronic tensile test machine be 15.22MPa, and elongation at break is 365%; The electronic waterproof determinator of LTD-A type is measured its watertightness, and 0.4MPa30min is waterproof.
Embodiment four:
Yellow exposed conveying appliance waterproof paint: concrete proportioning is: component A: 31.95% kilogram of Viscotrol C, 2,4 toluene diisocyanate 9.9%, YLENE 4.2%, ETHYLE ACETATE 2.1%, Diisopropyl azodicarboxylate 0.3%; Component B: glycol ether 10.0%, white titanium pigment 5.2%, medium chrome yellow medium yellow 18.0%; Talcum powder 4.2%, toluidine red 0.85%, coupling agent YB-201A (can adopt the titanate coupling agent of Changzhou Ya Bangya space auxiliary agent ltd) 0.5%; Vinylbenzene 12.2%; Resorcinol 0.2%, dibutyl tin laurate 0.2%, triethylamine 0.2%.Component A and component B are mixed, add proper amount of diluting, stir, left standstill 30 minutes, be cast under the room temperature on the glass template and be sprayed on the steel plate, 30 ℃ of following constant temperature 7 days.Coating surface drying time on the glass template is 2.5 hours, and the coating surface drying time on the steel plate is 2 hours; Coating gloss 70.9 on the glass template, hardness 4H; Filming on the glass template measured its tensile strength according to national polyurethane water-proof paint standard on XLD-3 type electronic tensile test machine be 7.82 MPa, and elongation at break is 210%; The electronic waterproof determinator of LTD-A type is measured its watertightness, and 0.4MPa30min is waterproof.
Embodiment five:
Smaragdine(-nus) exposed conveying appliance waterproof paint: concrete proportioning is: component A: Viscotrol C 31.95%, 2,4 toluene diisocyanate 9.9%, YLENE 4.2%, ETHYLE ACETATE 2.1%, Diisopropyl azodicarboxylate 0.3%; Component B: glycol ether 10.0%, white titanium pigment 2.0%, medium chrome yellow medium yellow 3.2%; The titanium cyanines are green 18.85%, talcum powder 4.2%, coupling agent YB-201A (can adopt the titanate coupling agent of Changzhou Ya Bangya space auxiliary agent ltd) 0.5%; Vinylformic acid 12.2%; Resorcinol 0.2%, dibutyl tin laurate 0.2%, triethylamine 0.2%.Component A and component B are mixed, add proper amount of diluting, stir, left standstill 30 minutes, be cast under the room temperature on the glass template and be sprayed on the steel plate, 30 ℃ of following constant temperature 7 days.Coating surface drying time on the glass template is 3.5 hours, and the coating surface drying time on the steel plate is 2.5 hours; Coating gloss 67.8 on the glass template, hardness 3H; Filming on the glass template measured its tensile strength according to national polyurethane water-proof paint standard on XLD-3 type electronic tensile test machine be 12.65 MPa, and elongation at break is 190%; The electronic waterproof determinator of LTD-A type is measured its watertightness, and 0.4MPa30min is waterproof.
Claims (4)
1. the preparation technology of a two-pack Viscotrol C polyurethane water-proof paint, it is characterized in that: by base polyurethane prepolymer for use as is that component A and colored mill base system are that B component IPN under the effect of initiator and catalyzer obtains; Wherein component A is reacted in dissolving with the organic solvent of initiator by Viscotrol C and 2,4 toluene diisocyanate and obtains; B component is mixed with coupling agent to mill by blending agents and solid pigment and/or solid packing and is added vinyl monomer, catalyzer, stopper, photostabilizer more successively and stir and obtain.
2. the preparation technology of two-pack Viscotrol C polyurethane water-proof paint according to claim 1 is characterized in that comprising the steps:
(1) raw material is handled: decompression dehydration obtained in 1～2 hour under 100～120 ℃ of blending agentss, the 0.08MPa vacuum tightness; Solid pigment and/or solid packing are dried under 120 ℃ temperature and were obtained in two hours;
(2) solid pigment that blending agents and toning is needed or solid packing mix with coupling agent and are milled to suitable fineness, add vinyl monomer, catalyzer, stopper, photostabilizer stirring again and successively and obtain uniform and stable B component;
(3) will dissolve organic solvent and 2 earlier with initiator; The 4-tolylene diisocyanate adds the Viscotrol C that in batches adds again in the reaction kettle after the vacuum hydro-extraction; Be not more than in water or air cycle condensation and in temperature control under 50 ℃ the condition and reacted 1 ~ 3 hour, stirring obtains component A;
(4) component A and B component are mixed by weight 1:0.5 ~ 4; Add an amount of organic solvent again and be adjusted to appropriate viscosity; Stir; Left standstill 10-60 minute, and brushed under the room temperature or be sprayed on to solidify on the different base materials and obtained colored exposed conveying appliance interpenetrating(polymer)networks two-pack Viscotrol C polyurethane water-proof paint in 30 minutes ~ 8 hours.
3. the preparation technology of two-pack Viscotrol C polyurethane water-proof paint according to claim 1 and 2 is characterized in that: the used blending agents of step (1) is 1 ~ 5 kind in glycerine, glycol ether, tetramethylolmethane, sorbyl alcohol, the TriMethylolPropane(TMP); The used solid pigment of step (1) is 1 ~ 10 kind in white titanium pigment, red iron oxide, carbon black, zinc oxide, zinc sulfide white, medium chrome yellow medium yellow, phthalocyanine blue, phthalocyanine green, ultramarine, the toluidine red; Solid packing is that blue or green cream powder, granularity are 1 ~ 5 kind in 600-800 purpose light calcium carbonate, wilkinite, talcum powder, the tiff; The used vinyl monomer of step (2) is 1～6 kind in vinylbenzene, TEB 3K, NSC 20956, vinyl cyanide, the acrylic or methacrylic acid; Coupling agent is a titanate coupling agent; Catalyzer is 1～4 kind in dibutyl tin dilaurate, stannous octoate, triethylamine, the triethylene diamine; Stopper is a Resorcinol; Photostabilizer is oxidation inhibitor four [β-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, UV-531,2-(2-hydroxyl-3; 5-two fourth uncles base phenyl)-5-chlorinated benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-the diamyl phenyl) benzotriazole, 2-hydroxyl 4-1～5 kind in the octyloxy UVNUL MS-40; The used initiator of step (3) is Lucidol or Diisopropyl azodicarboxylate; Organic solvent is 1～6 kind in toluene, YLENE, ETHYLE ACETATE, butylacetate, acetone, the methylethylketone.
4. the preparation technology of two-pack Viscotrol C polyurethane water-proof paint according to claim 3 is characterized in that: component A and B component weight ratio are 1:0.5 ~ 4; In component A, by weight percentage, the Viscotrol C consumption is 30% ~ 75%, and the 2,4 toluene diisocyanate consumption is 15% ~ 60%, and consumption of organic solvent is 5% ~ 25%, and initiator amount is 0.2 ~ 2%; In B component, by weight percentage, the blending agents consumption is 10% ~ 30%; Solid pigment or solid packing consumption are 20% ~ 45%, and the vinyl monomer consumption is 20 ~ 55%, and the coupling agent consumption is 0.05 ~ 1%; Catalyst levels is 0.05 ~ 1%, and the stopper consumption is 0.05 ~ 1%, and the photostabilizer consumption is 0.05 ~ 2%.
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| CN103666235A (en) * | 2013-11-19 | 2014-03-26 | 长安大学 | Polyurethane water-proof anticorrosive coating and preparation method thereof |
| CN105754388A (en) * | 2016-03-02 | 2016-07-13 | 湖北启利新材料股份有限公司 | Double-component nano polyaniline-epoxy acrylic resin/polyurethane interpenetrating-polymer-network conductive anticorrosive coating |
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| CN102786873A (en) * | 2012-08-21 | 2012-11-21 | 昆明理工大学 | Nano compound anticorrosive paint and preparation method thereof |
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| CN103666235A (en) * | 2013-11-19 | 2014-03-26 | 长安大学 | Polyurethane water-proof anticorrosive coating and preparation method thereof |
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| CN105860817A (en) * | 2016-04-29 | 2016-08-17 | 李强 | Ultravioresistant aqueous polyurethane coating and preparation method thereof |
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| CN109735093A (en) * | 2018-12-29 | 2019-05-10 | 扬州市德运塑业科技股份有限公司 | A kind of preparation method of organosilicon of the use for synthetic leather containing Phthalocyanine Zinc/aqueous polyurethane interpenetrating network polymer emulsion |
| CN109735093B (en) * | 2018-12-29 | 2021-01-15 | 扬州市德运塑业科技股份有限公司 | Preparation method of organic silicon/waterborne polyurethane interpenetrating network polymer emulsion containing zinc phthalocyanine for synthetic leather |
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