CN104559725B - Poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy material and preparation method - Google Patents
Poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy material and preparation method Download PDFInfo
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- CN104559725B CN104559725B CN201510037147.2A CN201510037147A CN104559725B CN 104559725 B CN104559725 B CN 104559725B CN 201510037147 A CN201510037147 A CN 201510037147A CN 104559725 B CN104559725 B CN 104559725B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Abstract
The invention provides a kind of poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material and preparation method thereof and using method, described protective material is mixed to get according to the mass ratio of 3.5 ~ 4.8:1 by component A and B component.Component A is counted by weight, and be made up of 35 ~ 50 parts of isocyanate prepolymers and 50 ~ 68 parts of epoxy resin, in described isocyanate prepolymer, the massfraction of free isocyanate groups is 8 ~ 15%.B component is counted by weight, and be made up of 8.5 ~ 15 parts of hydroxy polyethers, 0.9 ~ 1.5 part of chainextender, 2.5 ~ 8.5 parts of solidifying agent and auxiliary agent and filler/pigment, auxiliary agent is made up of catalyzer, photostabilizer and antioxidant.Poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy coating can be applied to the engineering structure surfacecti proteons such as concrete structure, steel construction, timber structure, improve structure corrosion-resistant, ageing-resistant, resistance to wear, the performance such as shock resistance, the work-ing life of effective extending structure.
Description
Technical field
The invention belongs to Material Field, be specifically related to a kind of long-life protective material, particularly relate to a kind of extra long life and gather isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy coating and preparation method thereof.
Background technology
Along with the development of Chinese society economy and scientific and technological level, Large Infrastructure Projects increases gradually, and its work-ing life under complicated Service Environment requires also more and more higher.For Transbay Bridge, Qingdao, it is located in northern China frost region, the annual temperature difference can reach 50 DEG C, about 2 months ice period, sea water salinity scope 24.9% ~ 32.9%, be subject to the corrosion of typhoon, heavy rain, the impact of seawater and salt fog, Industrial emissions in addition, and its design service life reaches 100 years.The port Zhuhai and Macao Design of Bridge being located in the Delta of the Pearl River then reaches 120 years work-ing life, and residing environment is subtropics oceanic climate, and Service Environment is also very complicated.Reach 100 years and above requirement in work-ing life, except improving the performance of structure and material of construction thereof, also need for building structure provides long-acting, reliable safeguard procedures.
Effective safeguard procedures of the key position of the Infrastructure such as bridge spanning the sea, normally at body structure surface painting anticorrosion coating, with materials such as exclusion of water, air, corrosive mediums, thus generation protective effect, but the common protective system self deterioration life-span is shorter, poor to the tolerance of severe environment, be difficult to the reliable protection that structure provides 30 years, 50 years and even 100 years.After common corrosion protection coating application 3 ~ 5 years will application again, cause the huge waste of human and material resources, financial resources, and the work-ing life after the current application of the heavy-duty coating of China also only has 15 ~ 20 years, the important infrastructure requirement of shelter of more than 100 years far cannot be met.
Application for a patent for invention 200810059347.8 discloses a kind of obdurability protection coating material for thermal shielding vehicle and preparation method thereof, primarily of end silicon imide I (SiO
1-1.5)
2or Duan Gui oxazolidone OX (SiO
1-1.5)
2or end silicon polymeric polyisocyanate-oxazolidone PIOX (SiO
1-1.5)
3, carbon nanotube and metal alkoxide, transition metal coordination complexes in absolute alcohol solvent under acidic conditions back hydrolysis cocondensation, or with inorganic metal salt hydrolysis cocondensation, or above-mentioned composition and previously prepared good function colloidal sol is the colloidal sol made of back hydrolysis cocondensation under these conditions, and add a certain amount of stablizer, can alternate products be obtained.But there is following problem in this application for a patent for invention disclosed protection class coating material: (1) can only be used for metal base, and is not suitable for the substrate surfaces such as concrete; (2) its formula comprises Multimetal oxide and carbon nanotube, cost intensive, is not suitable for spread and uses; (3) complicated process of preparation, preparation process is easily subject to the impact of the many factors such as water, by product.
Patent of invention CN1390905A discloses a kind of novel propylene pimaric acid Huan Yang/oxazolidone urethane broad-spectrum anticorrosion paint, by the series A component made with rosin, vinylformic acid (or maleic anhydride), epoxy resin with by 2,2-dimethyl-1, ammediol is same vulcabond respectively, the serial B component made under DBTDL and DABCD katalysis, adds TMA and auxiliary agent product are prepared from.But broad-spectrum anticorrosion paint product solid content is low disclosed in this application for a patent for invention, solvent is large, does not meet environmental requirement.
Summary of the invention
For the problems referred to above that existing protective coating exists, poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy coating that the invention provides a kind of extra long life and preparation method thereof.Described poly-isocyanide amino acid ester oxazolidone/polyurethane/epoxy coating can be applied to concrete structure, steel construction, timber structure and other engineering structure surfacecti proteon, not only improve structure corrosion-resistant, ageing-resistant, resistance to wear, shock resistance, the performance such as high temperature resistant, the also work-ing life of effective extending structure.
Technical scheme of the present invention is: poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material, is mixed to get according to the mass ratio of 3.5 ~ 4.8:1 by component A and B component.
Described component A is counted by weight, and be made up of 35 ~ 50 parts of isocyanate prepolymers and 50 ~ 68 parts of epoxy resin, in described isocyanate prepolymer, the massfraction of free isocyanate groups is 8-15%.Described isocyanate prepolymer is obtained by isocyanate-monomer/isocyanate semi-prepolymer and polyvalent alcohol building-up reactions; The functionality of described isocyanate-monomer/isocyanate semi-prepolymer is 1.8 ~ 3.0, described polyvalent alcohol functionality be 1.6 ~ 3.5, molecular weight is 400 ~ 9000.
Described isocyanate-monomer is 4,4 '-diphenylmethanediisocyanate, 2, one or more in the semi prepolymer of the many phenyl isocyanate of 4 '-diphenylmethanediisocyanate, polymethine and above-mentioned monomer; The molecular weight of described polyvalent alcohol is 600 ~ 8000, and described polyvalent alcohol is one or more in propylene oxide, oxyethane polyethers, polyglycol ether, polypropylene glycol ether, polyglycerol ether, polypentaerythritol ether, PTMG, the multipolymer of said structure and the polyether glycol of low-unsaturation-degree.Described epoxy resin is bisphenol A-type, and described epoxy resin is one or more in E-44, E-42, E-39-D and E-35.
Described B component is counted by weight, is made up of 8.5 ~ 15 parts of hydroxy polyethers, 0.9 ~ 1.5 part of chainextender, 2.5 ~ 8.5 parts of solidifying agent and auxiliary agent and filler/pigment.Described auxiliary agent is made up of catalyzer, photostabilizer and antioxidant; The massfraction of described catalyzer in protective material is 0.87-1.11 ‰, and the massfraction of described photostabilizer in protective material is 3.45-6.97 ‰, and the massfraction of described antioxidant in protective material is 4.94-7.84 ‰.The massfraction sum of described filler/pigment in protective material is not more than 10%.The hydroxyl value of described hydroxy polyethers is 50 ~ 80mgKOH/g, and described chainextender is polyalcohols chainextender, and described solidifying agent is aliphatic polybasic amine solidifying agent; Described photostabilizer is hindered amines or azimidobenzene base polymer; Described oxidation inhibitor is Hinered phenols polymkeric substance.
Described hydroxy polyethers is one or more in polytetrahydrofuran polyol, copolyether polyvalent alcohol and polyoxytrimethylene ethoxylated polyhydric alcohol, the Acclaim 2200 of such as U.S. Acro company, the POLY TH 2000 of BASF AG.Described chainextender is one or more in BDO, ethylene glycol, propylene glycol, glycol ether, neopentyl glycol, glycerol, TriMethylolPropane(TMP).Described solidifying agent is one or more in diethylenetriamine, Triethylenetetramine (TETA), tetren and hexanediamine.
Described catalyzer is triethylenediamine, four ethylenetriamine, five ethylene tetra or 2,4,6-tri-(dimethylamino methyl) phenol.Catalyzer is mainly used in the chemical reaction between catalysis component A and B component, the generation of Cu Shi oxazolidone structure.
Described photostabilizer is methacrylic acid (1,2,2,6,6-pentamethvl alcohol) ester, the two 1-octyloxy-2 of sebacic acid, 2,6,6-tetramethyl piperidine alcohol ester, 2-(2 '-hydroxyl-5 '-methyl)-benzotriazole, 2-(2 '-hydroxyl-3 ' dodecyl-5 '-[1,1,3,3-tetramethyl butyl])-benzotriazole or 2,2 ' methylene radical-(the tertiary octyl group of 6-(2H-benzotriazole)-4-) phenol.Described oxidation inhibitor is N, N '-bis-[β (3,5-di-tert-butyl-hydroxy phenyl propionyl] hydrazine, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) 2,4,6-Three methyl Benzene, 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl 2,6-dimethyl benzyl) 1,3,5-triazine-2,4.6-(1H, 3H, 5H)-triketone or 2 (1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl)-4,6-di-tert-pentyl-phenyl acrylate.By the introducing of photostabilizer and antioxidant, make protective coating the tolerance of the environmental factorss such as light, water, corrosive medium is significantly improved.Described filler is one or more in mica powder, silicon powder or Graphite Powder 99, and described pigment is one or more in titanium dioxide, phthalocyanine blue and carbon black.
The preparation method of poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material, is characterized in that: comprise the following steps:
(1) component A is prepared: take by 35 ~ 50 parts of isocyanate prepolymers and 50 ~ 68 parts of epoxy resin in reaction vessel, high-speed stirring 30 minutes, namely obtains component A under normal temperature environment and nitrogen protection.The preparation method of described isocyanate prepolymer is: at room temperature, is added drop-wise in the quantitative polyisocyanates at the uniform velocity stirred by the polyvalent alcohol of accurate measurement, and is slowly heated to 60 ~ 75 DEG C; After polyvalent alcohol dropwises, continue to stir, and 85 ~ 95 DEG C of insulations 1 hour, surveying free isocyanate group content was between 8 ~ 15%, namely obtains the semi prepolymer that isocyanate group is excessive; Said process carries out under nitrogen protection environment.
(2) B component is prepared: take 8.5 ~ 15 parts of hydroxy polyethers, 0.9 ~ 1.5 part of chainextender, 2.5 ~ 8.5 parts of solidifying agent and auxiliary agent and filler/pigment.Described auxiliary agent is made up of catalyzer, photostabilizer and antioxidant; The massfraction of described catalyzer in protective material is 0.87-1.11 ‰, and the massfraction of described photostabilizer in protective material is 3.45-6.97 ‰, and the massfraction of described antioxidant in protective material is 4.94-7.84 ‰.The massfraction sum of described filler/pigment in protective material is not more than 10%.Catalyzer, photostabilizer, antioxidant and 5 ~ 10 parts of hydroxy polyethers are ground to fineness and are less than 45 orders, then mix with chainextender, solidifying agent, remaining hydroxy polyethers and filler/pigment, namely obtain B component.The object of grinding is fine grinding particle and disperse agglomerations.
(3) mix: component A and B component are mixed according to mass ratio 3.5 ~ 4.8:1, namely obtains poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material.
The using method of poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material: use spraying equipment, component A and B component is extracted respectively by design proportion, be warming up to 60 ~ 90 DEG C, be forced into 2000 ~ 2500psi, by spray gun spraying to the substrate surface such as concrete, steel, form fine and close poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy coating.Described spraying equipment should possess following functions: (1) has accurate metering, proportion adjustment and takes out material function; (2) there is pressurization, voltage regulation function, can 3000psi be forced into; (3) there is temperature adjustment, heating, heat insulation function, 100 DEG C can be heated to; (4) have atomizing functions, fogging degree is adjustable.The method of spraying application is convenient and swift, and one time coating thickness can environmentally demand adjust between 1.0 ~ 15mm.
The principles of chemistry of the present invention are as follows: in component A and B component mixing process, following reaction occurs:
(1) in component A, the isocyanate group in ending isocyanate prepolymer and the hydroxy polyethers in B component and chainextender react, and generate urethane long-chain.
(2) the solidifying agent generation curing reaction in component A epoxy resin and B component, generates net macromolecular structure.
(3) in component A ending isocyanate prepolymer and epoxy resin catalyzer in B component effect under, there is following reaction, generate stable poly-isocyanide amino acid ester oxazolidone structure, as shown in reaction formula 1.
In formula:
The product of above-mentioned reaction is macromolecular structure, is mutually wound around and hydrogen bond action, makes coating have stable performance between molecular chain, and due to the generation of poly-isocyanide amino acid Zhi oxazolidone, the toughness of protective material is promoted greatly.
Beneficial effect of the present invention: compared with existing protective material, poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material of the present invention has following advantage:
(1) both had that polyurethane material elasticity is high, good toughness, ageing-resistant, resistance to wear and shock proof excellent specific property, also have that epoxy material sticking power is high, the advantage of corrosion resistance and good;
(2) to the better tolerance of the environmental factors such as alternation of wetting and drying, freeze-thaw cycle and high and low temperature alternative, ageing-resistant performance is excellent, solve conventional polyurethanes coating and epoxy coat protection the life-span short, the shortcoming easily peel off under environment under arms, lost efficacy, can improve the work-ing life of structure greatly.
(3) adopt spraying equipment construction, not only film forming speed is fast, and need not before spraying brushing primer, can directly and base material mortise, efficiently convenient; Diamond Search, environmental protection, nuisanceless to environment.
(4) cost is low, has high cost performance, and market application foreground is good.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1:
Poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material, is obtained according to the mass ratio mixing spraying of 4.8:1 by component A and B component.Component A is made up of 3500g isocyanate prepolymer and 6000g E-44, and in isocyanate prepolymer, the massfraction of free isocyanate groups is 8 ~ 15%; B component is by 850g polytetrahydrofuran polyol, 100g 1,4-butyleneglycol, 850g diethylenetriamine, 10g triethylenediamine, 80g methacrylic acid (1,2,2,6,6-pentamethvl alcohol) ester and 90g N, N '-bis-[β (3,5-di-tert-butyl-hydroxy phenyl propionyl] hydrazine composition.
The preparation method of poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material:
(1) component A is prepared:
Prepare isocyanate prepolymer: in the reactor that agitator, temperature sensor and nitrogen protection device are housed, add PTMG (PTMG-2000) 8000g, and slowly stir, period uniform speed slow dropping 4,4 '-diphenylmethanediisocyanate 8000g, and be slowly heated to 60 ~ 75 DEG C; After polyvalent alcohol dropwises, continue to stir, and 85 ~ 95 DEG C of insulations 1 hour, surveying free isocyanate group content was between 8 ~ 15%, namely obtains the isocyanate prepolymer that isocyanate group is excessive.
Take 3500g isocyanate prepolymer and 6000gE-44 in reaction vessel, under normal temperature environment and nitrogen protection, high-speed stirring 30 minutes, namely obtains component A.
(2) B component is prepared: take 850g polytetrahydrofuran polyol (PTMG-2000) (hydroxyl value is 56), 100g 1,4-butyleneglycol, 850g diethylenetriamine, 10g triethylenediamine, 80g methacrylic acid (1,2,2,6,6-pentamethvl alcohol) ester and 90g N, N '-bis-[β (3,5-di-tert-butyl-hydroxy phenyl propionyl] hydrazine.By triethylenediamine, methacrylic acid (1,2,2,6,6-pentamethvl alcohol) ester and N, N '-bis-[β (3,5-di-tert-butyl-hydroxy phenyl propionyl] hydrazine and 500g polytetrahydrofuran polyol be ground to fineness and be less than 45 orders, then mix with diethylene glycol bis-(PABA ester), diethylenetriamine, remaining polytetrahydrofuran polyol and filler/pigment, namely obtain B component.
(3) mix: component A and B component are mixed according to mass ratio 4.8:1, has both obtained poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material.
The using method of poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material: use spraying equipment, component A and B component is extracted respectively by the mass ratio of 4.8:1, be warming up to 85 DEG C, be forced into 2500psi, by spray gun spraying to the concrete substrate surface utilized after shot-blasting machine process, form poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy coating that fine and close coating thickness is 2mm.
Embodiment 2:
Poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material, is mixed to get according to the mass ratio of 3.71:1 by component A and B component.Component A is made up of 4200g isocyanate prepolymer and 6500g E-42, and in described isocyanate prepolymer, the massfraction of free isocyanate groups is 8 ~ 15%.B component is by 1300g polypropylene glycol (PPG-2000) (hydroxyl value is 58), 150g propylene glycol, 550g Triethylenetetramine (TETA), 15g tetra-ethylenetriamine, the two 1-octyloxy-2 of 70g sebacic acid, 2,6,6-tetramethyl piperidine alcohol ester, 95g1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) 2,4,6-Three methyl Benzene, 300g mica powder and 400g titanium dioxide form.
The preparation method of poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material:
(1) component A is prepared:
Prepare isocyanate prepolymer: in the reactor that agitator, temperature sensor and nitrogen protection device are housed, add polypropylene glycol ether (molecular weight is 1025) 7200g, and slowly stir, period uniform speed slow dropping 2,4 '-diphenylmethanediisocyanate (molecular weight is 250) 6000g, and be slowly heated to 60 ~ 75 DEG C; After polyvalent alcohol dropwises, continue to stir, and 85 ~ 95 DEG C of insulations 1 hour, surveying free isocyanate group content was between 8 ~ 15%, namely obtains the isocyanate prepolymer that isocyanate group is excessive.
Take 4200g isocyanate prepolymer and 6500g E-42 in reaction vessel, under normal temperature environment and nitrogen protection, high-speed stirring 30 minutes, namely obtains component A.
(2) B component is prepared: take 1300g polypropylene glycol (PPG-2000) (hydroxyl value is 58), 150g propylene glycol, 550g Triethylenetetramine (TETA), 15g tetra-ethylenetriamine, the two 1-octyloxy-2 of 70g sebacic acid, 2,6,6-tetramethyl piperidine alcohol ester, 95g1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) 2,4,6-Three methyl Benzene, 300g mica powder and 400g titanium dioxide.By four ethylenetriamine, the two 1-octyloxy-2 of sebacic acid, 2,6,6-tetramethyl piperidine alcohol ester, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) 2,4,6-Three methyl Benzene and 900g polypropylene glycol (PPG-2000) are ground to fineness and are less than 45 orders, then mix with 3,5-diamino-4-trifluoromethyl phenyl ethyl ether, Triethylenetetramine (TETA), remaining polypropylene glycol, mica powder and titanium dioxide, namely obtain B component.
(3) mix: component A and B component are mixed according to mass ratio 3.71:1, has both obtained poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material.The using method of poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material: use spraying equipment, component A and B component is extracted respectively by the mass ratio of 3.71:1, be warming up to 90 DEG C, be forced into 2300psi, by spray gun spraying to the steel structure surface after sandblasting with certain roughness, form poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy coating that fine and close coating thickness is 1.5mm.
Embodiment 3:
Poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material, is mixed to get according to the mass ratio of 3.52:1 by component A and B component.Component A is made up of 5000g isocyanate prepolymer and 5500g E-39-D; In isocyanate prepolymer, the massfraction of free isocyanate groups is 8 ~ 15%.B component is by 1500g copolyether polyvalent alcohol (POLY THF 2000) (hydroxyl value is 54), 130g ethylene glycol, 250g diethylenetriamine, 15g five ethylene tetra, 90g 2-(2 '-hydroxyl-5 '-methyl)-benzotriazole, 100g 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl 2,6-dimethyl benzyl) 1,3,5-triazine-2,4.6-(1H, 3H, 5H)-triketone, 600g silicon powder and 300g phthalocyanine blue composition.
The preparation of poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material and use:
(1) component A is prepared:
Prepare isocyanate prepolymer: in the reactor that agitator, temperature sensor and nitrogen protection device are housed, add polypropylene glycol (relative molecular weight is 1025) 7000g, and slowly stir, period uniform speed slow dropping 2,4 '-diphenylmethanediisocyanate (relative molecular mass 250) 7000g, and be slowly heated to 60 ~ 75 DEG C; After polyvalent alcohol dropwises, continue to stir, and 85 ~ 95 DEG C of insulations 1 hour, surveying free isocyanate group content was between 8 ~ 15%, namely obtains the isocyanate prepolymer that isocyanate group is excessive.
Take 5000g isocyanate prepolymer and 5500g E-39-D in reaction vessel, under normal temperature environment and nitrogen protection, high-speed stirring 30 minutes, namely obtains component A.
(2) B component is prepared: take 1500g copolyether polyvalent alcohol (POLY THF 2000) (hydroxyl value is 54), 130g ethylene glycol, 250g diethylenetriamine, 15g five ethylene tetra, 90g 2-(2 '-hydroxyl-5 '-methyl)-benzotriazole, 100g 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl 2,6-dimethyl benzyl) 1,3,5-triazine-2,4.6-(1H, 3H, 5H)-triketone, 600g silicon powder and 300g phthalocyanine blue.By five ethylene tetra, 2-(2 '-hydroxyl-5 '-methyl)-benzotriazole, 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl 2,6-dimethyl benzyl) 1,3,5-triazine-2,4.6-(1H, 3H, 5H)-triketone and 1000g copolyether polyvalent alcohol (POLY THF 2000) are ground to fineness and are less than 45 orders, then mix with methylene-bis (4-amino-3-benzoic ether), tetren, remaining copolyether polyvalent alcohol (POLY THF 2000), silicon powder and phthalocyanine blue, namely obtain B component.
(3) mix: component A and B component are mixed according to mass ratio 3.52:1, has both obtained poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material.
The using method of poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material: use spraying equipment, in mass ratio for the ratio of 3.52:1 extracts component A and B component respectively, be warming up to 85 DEG C, be forced into 2500psi, be sprayed onto the wood structure surface cleaned out after being mixed by spray gun, form poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy coating that fine and close coating thickness is 2.5mm.
Embodiment 4:
As different from Example 1, poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material, is mixed to get according to the mass ratio of 3.80:1 by component A and B component.Component A is made up of 3800g isocyanate prepolymer and 6800g E-35.B component is by 1000g copolyether polyvalent alcohol (PTG-2000) (hydroxyl value is 54-58), 120g propylene glycol, 450g hexanediamine, 12g 2,4,6-tri-(dimethylamino methyl) phenol, 58g 2-(2 '-hydroxyl-3 ' dodecyl-5 '-[1,1,3,3-tetramethyl butyl])-benzotriazole, 70g 2 (1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl)-4,6-di-tert-pentyl-phenyl acrylate, 700g Graphite Powder 99 and 380g carbon black composition.
The preparation method of poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material:
(1) component A is prepared:
Take 3800g isocyanate prepolymer (free isocyanate content is 14.2%) and 6800g E-35 in reaction vessel, under normal temperature environment and nitrogen protection, high-speed stirring 30 minutes, namely obtains component A.
(2) B component is prepared: take 1000g copolyether polyvalent alcohol (PTG-2000) (hydroxyl value is 54), 120g propylene glycol, 450g hexanediamine, 12g 2,4,6-tri-(dimethylamino methyl) phenol, 58g 2-(2 '-hydroxyl-3 ' dodecyl-5 '-[1,1,3,3-tetramethyl butyl])-benzotriazole, 70g 2 (1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl)-4,6-di-tert-pentyl-phenyl acrylate, 700g Graphite Powder 99 and 380g carbon black.By 2,4,6-tri-(dimethylamino methyl) phenol, 2-(2 '-hydroxyl-3 ' dodecyl-5 '-[1,1,3,3-tetramethyl butyl])-benzotriazole, 2 (1-(2-hydroxyls-3,5-di-tert-pentyl-phenyl) ethyl)-4,6-di-tert-pentyl-phenyl acrylate and 800g copolyether polyvalent alcohol (PTG-2000) are ground to fineness and are less than 45 orders, then with 4,4 '-methylene-bis (2,6-diethyl-3-chloroaniline), hexanediamine, remaining copolyether polyvalent alcohol (PTG-2000), Graphite Powder 99 and carbon black mix, and namely obtain B component.
(3) mix: component A and B component are mixed according to mass ratio 3.80:1, has both obtained poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material.
Embodiment 5:
As different from Example 1, poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material, is mixed to get according to the mass ratio of 3.58:1 by component A and B component.Component A is made up of 4500g isocyanate prepolymer (free isocyanate content is 13.5%) and 5000g E-35.B component is by 900g copolyether polyvalent alcohol (PTG-2000) (hydroxyl value is 54), 90g propylene glycol, 350g hexanediamine, 13g 2,4,6-tri-(dimethylamino methyl) phenol, 42g 2,2 ' methylene radical-(the tertiary octyl group of 6-(2H-benzotriazole)-4-) phenol, 60g 2 (1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl)-4,6-di-tert-pentyl-phenyl acrylate, 800g mica powder and 400g phthalocyanine blue composition.
The preparation method of poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material:
(1) component A is prepared:
Take 4500g isocyanate prepolymer and 5000g E-35 in reaction vessel, under normal temperature environment and nitrogen protection, high-speed stirring 30 minutes, namely obtains component A.
(2) B component is prepared: take 900g copolyether polyvalent alcohol (PTG-2000) (hydroxyl value is 54), 90g propylene glycol, 350g hexanediamine, 13g 2,4,6-tri-(dimethylamino methyl) phenol, 42g 2,2 ' methylene radical-(the tertiary octyl group of 6-(2H-benzotriazole)-4-) phenol, 60g 2 (1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl)-4,6-di-tert-pentyl-phenyl acrylate, 800g mica powder and 400g phthalocyanine blue.By 2,4,6-tri-(dimethylamino methyl) phenol, 2,2 ' methylene radical-(the tertiary octyl group of 6-(2H-benzotriazole)-4-) phenol, 2 (1-(2-hydroxyls-3,5-di-tert-pentyl-phenyl) ethyl)-4,6-di-tert-pentyl-phenyl acrylate and 500g copolyether polyvalent alcohol (PTG-2000) are ground to fineness and are less than 45 orders, then with 3-amino-4-chlorophenylmethyl-4 '-Aminobenzoate), hexanediamine, remaining copolyether polyvalent alcohol (PTG-2000), mica powder and phthalocyanine blue mix, and namely obtains B component.
(3) mix: component A and B component are mixed according to mass ratio 3.58:1, has both obtained poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material.
As shown in Table 1, the tensile strength of poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material prepared by embodiment 1-5 is 16.54-20.93MPa, and elongation at break is 338.73-405.67%, and cohesive strength is 1.75-5.71MPa, and hardness is Shao 82-89 A.And the tensile strength of existing protective material epoxy resin is 14MPa, elongation at break is≤15%, and cohesive strength is 5.5MPa, and hardness is 93 Shao A; In existing protective material, the tensile strength of acroleic acid polyurethane is 7MPa, and elongation at break is≤50%, and cohesive strength is 2.8MPa, and hardness is 82 Shao A.
Table 1. gathers the performance index of isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material and existing protective material
Therefore, the elongation at break of poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material much larger than existing protective material, tensile strength slightly larger than existing protective material, cohesive strength and hardness and existing protective material close.This explanation, relative to existing protective material, the poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material of the application has higher intensity and excellent snappiness concurrently, this is because the reaction occurred at high temperature under high pressure by A, B component generates stable crosslinking structure.
Base material in embodiment 3 is timber, and in bonding strength test, the numerical value of wood failure and cohesive strength is lower; And the numerical value of cohesive strength is 3.04-5.71MPa in all the other four embodiments, and protective material and base material have destruction, illustrate that the cohesive strength of protective material is high; The result of embodiment 3 is the results because the problem of timber itself causes, but not the cohesiveness of protective material is low.In prior art, though epoxy coating is high to the cohesive strength of base material, but property is crisp easily to be split, and is not suitable for the surfacecti proteon for engineering structure; The snappiness of Acrylic Polyurethane Coating is better, but water tolerance is poor, is unwell to wet environment.
Table 2. is through the performance index of the poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material of uviolizing in 7200 hours
As shown in Table 2, uviolizing is after 7200 hours, and in example 1-5, the tensile strength of poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material and elongation at break are respectively between 16.12-19.76MPa, 316.14%-380.65%.Compared with before uviolizing, stretching strength retentivity and elongation at break conservation rate are respectively at 94.4%-97.5%, 90.4-94.4%.And similar impregnating material is as serious in uviolizing 7500h rear surface efflorescence in epoxy resin, penetration of cracks coating section, when cutting out sample, embrittlement occurs, acroleic acid polyurethane is at uviolizing 7500h, and tensile strength is down to 4.52, and elongation at break is down to 10.32%.This illustrates, compared with same type of material of the prior art, the poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material of the application is with the obvious advantage, is highly suitable for the extended protection of exterior components structure.
Claims (5)
1. the poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material for spraying, is characterized in that: be mixed to get according to the mass ratio of 3.5 ~ 4.8:1 by component A and B component; Described component A is counted by weight, and be made up of 35 ~ 50 parts of isocyanate prepolymers and 50 ~ 68 parts of epoxy resin, in described isocyanate prepolymer, the massfraction of free isocyanate groups is 8 ~ 15%; Described B component is counted by weight, is made up of 8.5 ~ 15 parts of hydroxy polyethers, 0.9 ~ 1.5 part of chainextender, 2.5 ~ 8.5 parts of solidifying agent; Described B component also comprises catalyzer, photostabilizer and antioxidant composition, the massfraction of described catalyzer in protective material is 0.87-1.11 ‰, the massfraction of described photostabilizer in protective material is 3.45-6.97 ‰, and the massfraction of described antioxidant in protective material is 4.94-7.84 ‰; Described isocyanate prepolymer is obtained by isocyanate-monomer/isocyanate semi-prepolymer and polyvalent alcohol building-up reactions; The functionality of described isocyanate-monomer/isocyanate semi-prepolymer is 1.8 ~ 3.0, described polyvalent alcohol functionality be 1.6 ~ 3.5, molecular weight is 400 ~ 9000; Described epoxy resin is bisphenol A-type, and described epoxy resin is one or more in E-44, E-42, E-39-D and E-35; The hydroxyl value of described hydroxy polyethers is 50 ~ 80mgKOH/g, and described chainextender is polyalcohols chainextender, and described solidifying agent is aliphatic polybasic amine solidifying agent; Described photostabilizer is hindered amines or azimidobenzene base polymer; Described oxidation inhibitor is Hinered phenols polymkeric substance; Described catalyzer is triethylenediamine, four ethylenetriamine, five ethylene tetra or 2,4,6-tri-(dimethylamino methyl) phenol;
The preparation method of described poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material for spraying is:
(1) component A is prepared: take by 35 ~ 50 parts of isocyanate prepolymers and 50 ~ 68 parts of epoxy resin in reaction vessel, high-speed stirring 30 minutes, namely obtains component A under normal temperature environment and nitrogen protection; The preparation method of described isocyanate prepolymer is: at room temperature, is added drop-wise in the quantitative polyisocyanates at the uniform velocity stirred by the polyvalent alcohol of accurate measurement, and is slowly heated to 60 ~ 75 DEG C; After polyvalent alcohol dropwises, continue to stir, and 85 ~ 95 DEG C of insulations 1 hour, surveying free isocyanate group content was between 8 ~ 15%, namely obtains the semi prepolymer that isocyanate group is excessive; Said process carries out under nitrogen protection environment;
(2) B component is prepared: take 8.5 ~ 15 parts of hydroxy polyethers, 0.9 ~ 1.5 part of chainextender, 2.5 ~ 8.5 parts of solidifying agent, 0.10-1.15 part catalyzer, 0.42-0.90 part photostabilizer and 0.6-1.0 part antioxidants, catalyzer, photostabilizer, antioxidant and 5-10 part hydroxy polyethers are ground to fineness and are less than 45 orders, then mix with chainextender, solidifying agent and remaining hydroxy polyethers, both obtained B component;
(3) mix: component A and B component are mixed according to mass ratio 3.5 ~ 4.8:1, has both obtained poly-isocyanide amino acid Zhi oxazolidone protective material.
2. the poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material for spraying according to claim 1, it is characterized in that: described isocyanate-monomer is 4,4 '-diphenylmethanediisocyanate, 2, one or more in the semi prepolymer of the many phenyl isocyanate of 4 '-diphenylmethanediisocyanate, polymethine and above-mentioned monomer; The molecular weight of described polyvalent alcohol is 600 ~ 8000, and described polyvalent alcohol is one or more in propylene oxide, oxyethane polyethers, polyglycol ether, polypropylene glycol ether, polyglycerol ether, polypentaerythritol ether, PTMG, the multipolymer of said structure and the polyether glycol of low-unsaturation-degree.
3. the poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material for spraying according to claim 1, is characterized in that: described hydroxy polyethers is one or more in polytetrahydrofuran polyol, copolyether polyvalent alcohol and polyoxytrimethylene ethoxylated polyhydric alcohol; Described chainextender is one or more in BDO, ethylene glycol, propylene glycol, glycol ether, neopentyl glycol, glycerol, TriMethylolPropane(TMP); Described solidifying agent is one or more in diethylenetriamine, Triethylenetetramine (TETA), tetren and hexanediamine; Described photostabilizer is methacrylic acid (1,2,2,6,6-pentamethvl alcohol) ester, the two 1-octyloxy-2 of sebacic acid, 2,6,6-tetramethyl piperidine alcohol ester, 2-(2 '-hydroxyl-5 '-methyl)-benzotriazole, 2-(2 '-hydroxyl-3 ' dodecyl-5 '-[1,1,3,3-tetramethyl butyl])-benzotriazole or 2,2 ' methylene radical-(the tertiary octyl group of 6-(2H-benzotriazole)-4-) phenol; Described oxidation inhibitor is N, N '-bis-[β (3,5-di-tert-butyl-hydroxy phenyl propionyl] hydrazine, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) 2,4,6-Three methyl Benzene, 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl 2,6-dimethyl benzyl) 1,3,5-triazine-2,4.6-(1H, 3H, 5H)-triketone or 2 (1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl)-4,6-di-tert-pentyl-phenyl acrylate.
4. according to the poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material for spraying in claim 1-3 described in any one, it is characterized in that: described B component is counted by weight, also comprise filler/pigment, described filler and the pigment massfraction sum in protective material is not more than 10%; Described filler is one or more in mica powder, silicon powder and Graphite Powder 99, and described pigment is one or more in titanium dioxide, phthalocyanine blue and carbon black.
5. the using method of the poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy protective material for spraying according to claim 1, it is characterized in that: use spraying equipment, component A and B component is extracted respectively by design proportion, be warming up to 60 ~ 90 DEG C, be forced into 2000 ~ 2500psi, by spray gun spraying to substrate surface, form poly-isocyanide amino acid Zhi oxazolidone/polyurethane/epoxy compound coating.
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