CN101302393A - Spray polyurea elastomer for mine, preparation and construction method thereof - Google Patents
Spray polyurea elastomer for mine, preparation and construction method thereof Download PDFInfo
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- CN101302393A CN101302393A CNA200810016869XA CN200810016869A CN101302393A CN 101302393 A CN101302393 A CN 101302393A CN A200810016869X A CNA200810016869X A CN A200810016869XA CN 200810016869 A CN200810016869 A CN 200810016869A CN 101302393 A CN101302393 A CN 101302393A
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Abstract
The invention provides a spraying polyurea elastomer applied to a mine, a method for making the same and a construction method. The spraying polyurea elastomer can solve the problem of poor wearing resistance in the prior art. The invention comprises the following technical proposals that: the spraying polyurea elastomer applied to the mine comprises two compositions A and R, wherein, the composition A is a semi-prepolymer synthesized by 45 to 65 portions of polyisocyanate and 35 to 55 portions of polyether polyol; the composition R comprises 55 to 80 portions of amine terminated polyether, 15 to 33 portions of chain extender and 5 to 25 portions of antiwear filler; and the compositions A and R are matched for use according to an isocyanate index of between 0.9 and 1.2. The spraying polyurea elastomer has good physical performance, high wearing resistance, good oil resistance, hydrolization resistance, bacteria resistance and aging resistance and good construction performance and can be used in a vibration sieve equipment lining, a flotation equipment lining, etc. of the mine and other application places which have high requirement on wearing resistance.
Description
Technical field
The present invention relates to the macromolecule chemical industry material field of the anti-wear lining of mechanical means of wearing and tearing easily, specifically is a kind of Spray Polyurea Elastomer that is applied to the mine and preparation method thereof and constructional method.
Background technology
Be applied to equipment such as the mechanical means in fields such as mine, building, chemical industry such as vibratory screening apparatus, roller roto-sifter, spiral separator lining, water conservancy separator, in use because serious wear causes equipment attrition and corrosion.In order to reduce this kind equipment wearing and tearing and corrosion, existing way is the wearing surface inner lining protection layer at equipment.The protective layer that generally uses is solids epoxy coating and water-borne coatings at present, needs spraying repeatedly, and speed is slow, and is in uneven thickness etc.The following shortcoming of all these ubiquities: 1) toughness deficiency, very easily ftracture under thermal stresses or shock action.2) system contains organic solvent, and is harmful.3) must adopt multiple working procedure, the cycle is long, efficient is low, and the volatile vacuum that causes of solvent easily makes corrosive medium immerse.
A kind of spray polyurea material of wear resistance is disclosed in European patent 0 431 728 A1 the inside.The semi prepolymer that the liquefied mdi of this patent A component employing carbodiimide modification and the polyvalent alcohol of long-chain obtain.The B component adopts amino-polyether, chainextender, modified filler and isocyanate reaction to obtain.The wear resistance that this patent is compared with not filled system spray polyurea system by the filler that adds modification has improved nearly one times, but the final abrasion of product still have about 200mg.
In United States Patent (USP) 5962618, the Dudley J Primeaux II of U.S. Huntsman company discloses a kind of spraying polyurea elastomer material that is used for the wagon box wear resistance lining.The A component is a semi-prepolymer in the prescription of this patent, by at least 50% 2,4 '-diphenylmethanediisocyanate and 4, the mixture of 4 '-diphenylmethanediisocyanate and polyether glycol are synthetic, wherein diphenylmethanediisocyanate accounts for 36-65 part.The B component is JEFFAMINE Amino Terminated polyether(ATPE) 55-45 part of Huntsman company, amine chain extender 25-40 part, functional epoxy silane 0.3-0.8 such as Sliquest@187 part, the mixture that water 0.2-0.3 part etc. constitute.The volume of A, B component is 1: 1, adopts polycomponent high pressure painting equipment to construct.High by 2 by using in this patent, the isocyanic ester of 4 '-MDI monomer content and silane coupling agent have improved the sticking power and the wear resistance of system.But the wear resistance of whole system still is not very desirable, if be applied to still be apparent not enough in the mining equiment.
At the defective of prior art, the present invention further improves again.
Summary of the invention
The invention provides a kind of Spray Polyurea Elastomer that is applied to the mine and preparation method thereof and constructional method; it can solve the problem that wears no resistance that prior art exists; provide a kind of configuration reasonable; the hardness height; wear-resistant; and the polyurea elastomer wearable lining protection material of long service life can be applied to the attrition resistant spraying polyurea elastomer material on the equipment such as the mechanical means in fields such as mine, building, chemical industry such as vibratory screening apparatus, roller roto-sifter, spiral separator lining, water conservancy separator.The present invention has also introduced the constructional method of using this high-abrasive material simultaneously.
For solving the problems of the technologies described above, the present invention adopts following technical proposals:
A kind of Spray Polyurea Elastomer that is applied to the mine comprises two kinds of components of A, R, it is characterized in that: described A component is polyisocyanates of 45-65 part and the polyether glycol synthetic semi prepolymer of 35-55 part by parts by weight; The R component comprises that parts by weight are the Amino Terminated polyether(ATPE) of 55-80 part, the chainextender of 15-30 part, the wear resistant filler of 5-25 part, and described A, R two components are used between 0.9-1.2 according to isocyanate index.
In technical scheme of the present invention, also have following technical characterictic: the functionality of described polyisocyanates is between 2.0-2.7, and preferred functionality is 2.0-2.2;
Described polyisocyanates is 2,6-tolylene diisocyanate, 4,4 of 4 '-diphenylmethanediisocyanate, carbodiimide-uretonimine-modified, 4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, the many phenyl isocyanate of polymethine, 4, the mixture of one or more in 4 '-dicyclohexyl methane diisocyanate, the isophorone diisocyanate.
In technical scheme of the present invention, also have following technical characterictic: the hydroxyl equivalent of described polyether glycol is 300-2000, and its functionality is between 2-4;
Described polyether glycol is one or more in polyglycol ether, polypropylene glycol ether, polyglycerol ether, polypentaerythritol ether, PTMG, the polycaprolactone glycol; The perhaps multipolymer of one or more of above-mentioned substance is selected one or more of described multipolymer then for use;
Perhaps described polyether glycol is selected low-unsaturation-degree polyether for use, hydroxyl terminated poly-butadiene, hydroxy-end capped polyvalent alcohol and the semi prepolymer of isocyanic ester.
In technical scheme of the present invention, also have following technical characterictic: the Amino Terminated polyether(ATPE) in the described R component is the polyether resin that contains primary amine or secondary amine end, and its functionality is 2-3, and described Amino Terminated polyether(ATPE) resin comprises Huntsman company
D-2000,
T-3000,
D-400,
The mixture of one or more among the T-5000.
In technical scheme of the present invention, also have following technical characterictic: the chainextender in the described R component comprises amine chain extender, the mixture of one or more in the alcohols chainextender, described amine chain extender comprises aromatic diamine, the mixture of one or more in the aliphatic polyamine, described aromatic diamine is a diethyl toluene diamine, diformazan sulfenyl tolylene diamine, N, N ' two sec-butyl methylene dianiline (MDA)s, 4,4 '-diaminodiphenyl-methane, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, described aliphatic polyamine is 1,4-cyclohexyl diamines, isophorone diamine, 4,4 '-dicyclohexyl methyl hydride diamines, 1,4-diamines ethyl methane; Described alcohols chainextender is 1, the mixture of one or more in 4-butyleneglycol, 1,3 butylene glycol, TriMethylolPropane(TMP), glycerol, the trolamine.
In technical scheme of the present invention, also have following technical characterictic: the wear resistant filler in the described R component is selected one or more the mixture in silicon carbide, glass microballon, polytetrafluoroethylene powder, aluminium sesquioxide, titanium dioxide, aluminum oxide, the nanometer inorganic filler for use.
In technical scheme of the present invention, also has following technical characterictic: the auxiliary agent that also comprises parts by weight 0.3-2 part in the described R component, described auxiliary agent comprises wetting dispersing agent, oxidation inhibitor, UV light absorber, wherein wetting dispersing agent is 1～30: 1 with the ratio that cooperates of oxidation inhibitor, and wetting dispersing agent is 1～15: 2 with the ratio that cooperates of UV light absorber.
Described wetting dispersing agent is an Evonik company
430,
410;
Described oxidation inhibitor comprises Hinered phenols antioxidant and aromatic amine kind antioxidant, as the IRGANOX1010,1076 of CIBA GEIGY company;
Described UV light absorber is a benzotriazole compound, for example TINUVIN P, TINUVIN327, TINUVIN328 etc.
In technical scheme of the present invention, also have following technical characterictic: also comprise the color stuffing of 0～20 part of parts by weight in the described R component, for example color stuffing can be one or more the mixture in carbon black, titanium white, phthalein green grass or young crops, the chrome yellow.
A kind of preparation method who is applied to the Spray Polyurea Elastomer in mine, it is characterized in that: the synthetic method of described A component is: with parts by weight is that the polyisocyanates of 45-65 part joins in the reactor of nitrogen protection, at the uniform velocity stir, be heated to 50-60 ℃, in reactor, slowly add the polyether glycol of 35-55 part, under 70-90 ℃, insulation reaction 2.5～3.5 hours, sampling analysis is surveyed free isocyanate content in the gained semi prepolymer between 13-20%, cooling discharging;
The preparation method of described R component is: the R component comprises that parts by weight are the Amino Terminated polyether(ATPE) of 55-80 part, the chainextender of 15-30 part, the wear resistant filler of 5-25 part;
1) if adds filler, comprise wear resistant filler or color stuffing, then at first filler with make mixture according to the part Amino Terminated polyether(ATPE) of the parts by weight in the described R component of claim 1, be dispersed into slurry with grinding plant such as sand mills then, according to prescription ground slurry, remainder Amino Terminated polyether(ATPE), chainextender are joined in the system paint can at last, utilize high-shear dispersing apparatus high-speed stirring to make in 25～35 minutes;
2) if not filled,, Amino Terminated polyether(ATPE), chainextender, auxiliary agent were made with high-shear dispersing apparatus high-speed stirring in 25～35 minutes then according to formula ratio;
In use, the isocyanate index according to A, R component cooperates between 0.9-1.2.
A kind of constructional method that is applied to the Spray Polyurea Elastomer in mine, it is characterized in that: after two components of described A, R are measured, pressurize, heated up in the high pressure collision type mixed spraying equipment of 1: 1 fixed volume ratio, be sprayed onto on the ground by spray gun, solidify spraying polyurea elastomer material.The initial temperature of A, R component is higher than 10 ℃, and setting main frame pressure is 55-77Kg/cm
2, temperature is 50-60 ℃, the spray pressure difference of two components is lower than 14Kg/cm in the spray gun mixing section
2
Isocyanate index is meant the equivalence ratio of A, R component.After the A component prepared, isocyanate index as requested calculated, prepares the R component again.
The hardness of elastomer material of the present invention is between Shao A70-80.
Described filler comprises wear resistant filler or color stuffing, can be added in A component or the R component, preferably is added in the R component.
The isocyanate-terminated semi prepolymer of described A component also can be obtained by one or more composition reactions of polyisocyanates and polyamines, the compound that contains amino and alcohol radical two functional groups and their mixture.
The present invention has the following advantages and positively effect:
1. fast setting does not contain catalyzer, can spray mo(u)lding on arbitrary surface, inclined-plane and vertical surface, do not produce the sagging phenomenon.
2. to moisture, temperature-insensitive, be not subjected to the influence of envrionment temperature, humidity during construction.
3. the thickness range of once constructing can overcome in the past the repeatedly disadvantage of construction from hundreds of microns to several centimetres.
4. can save expensive die cost in the direct spray mo(u)lding in baroque surface.
5. excellent material performance, wear resisting property can reach more than 10 times of carbon steel.Also have excellent flexibility, corrosion-resistant, ageing-resistant performance simultaneously.
6. material sticking power is good, and all kinds of grounds such as steel, cast iron, aluminium, concrete are all had good sticking power.
7. good weatherability, does not ftracture at the not efflorescence of outdoor life-time service.
The spray polyurea material has good physical performance, the wear resistance height, long service life, in light weight, also have excellent oil resistant, hydrolysis, anti-bacterium, ageing-resistant performance simultaneously, and workability is good, but random molding can be widely used in the wear-resisting application places of having relatively high expectations such as equipment linings such as vibratory screening apparatus, floatation equipment lining, roller roto-sifter, spiral separator lining, water conservancy separator lining in mine.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment 1
A by contain have an appointment 15 parts 2,4 of 4 '-diphenylmethanediisocyanate and 41 parts, the molecular weight of 4 '-diphenylmethanediisocyanate and 44 parts is 1000, and functionality is the prepolymer of 2 poly(propylene oxide) ether glycol (TDiol-1000, Plant of Tianjin Petrochemical Company three factories) preparation.The NCO content of prepolymer is (15 ± 0.1) %.The R component by
T-5000 aminoresin,
D-2000,
D-400, DETDA aminoresin and TiO
2Mixture is formed.Various raw materials in the R component are joined after accurately taking by weighing in the system paint can according to prescription, with high speed shear dispersing apparatus high-speed stirring 30 minutes.
The isocyanate index of this system is 1.10.Concrete proportioning is as shown in the table.
A, R component adopted high pressure head-on collision mixed spraying equipment to spray in 1: 1 by volume.With coating spraying to the PVC plate that scribbles releasing agent.Treat behind the coating curing coating taken off and carry out performance test.
The polyureas high-abrasive material performance index of spraying gained are as follows:
Embodiment 2
A by contain have an appointment 15 parts 2,4 '-diphenylmethanediisocyanate and 41 part 4, the molecular weight of 4 '-diphenylmethanediisocyanate and 44 parts is 1000, and functionality is the prepolymer of 2 PTMG (PTMG-1000, German BASF) preparation.The NCO content of prepolymer is (15 ± 0.1) %, and the viscosity in the time of 25 ℃ is about 1200cps.The R component by
T-5000 aminoresin,
D-2000,
D-400, DETDA aminoresin and TiO
2Mixture is formed.Various raw materials in the R component are joined after accurately taking by weighing in the system paint can according to prescription, with high speed shear dispersing apparatus high-speed stirring 30 minutes.
The isocyanate index of this system is 1.10.Concrete proportioning is as shown in the table.
A, R component adopted high pressure head-on collision mixed spraying equipment to spray in 1: 1 by volume.With coating spraying to the PVC plate that scribbles releasing agent.Treat behind the coating curing coating taken off and carry out performance test.
The polyureas high-abrasive material performance index of spraying gained are as follows:
Embodiment 3
A by contain have an appointment 30 parts 2,4 of 4 '-diphenylmethanediisocyanate and 26 parts, the molecular weight of 4 '-diphenylmethanediisocyanate and 44 parts is 1000, and functionality is the prepolymer of 2 PTMG (PTMG-1000, German BASF) preparation.The NCO content of prepolymer is (15 ± 0.1) %, and the viscosity in the time of 25 ℃ is about 1200cps.The R component by
T-5000 aminoresin,
D-2000,
D-4000, DETDA aminoresin, TiO
2, the mica powder mixture forms.Various raw materials in the R component are joined after accurately taking by weighing in the system paint can according to prescription, with high speed shear dispersing apparatus high-speed stirring 30 minutes.
The isocyanate index of this system is 1.10.Concrete proportioning is as shown in the table.
A, R component adopted high pressure head-on collision mixed spraying equipment to spray in 1: 1 by volume.With coating spraying to the PVC plate that scribbles releasing agent.Treat behind the coating curing coating taken off and carry out performance test.
The polyureas high-abrasive material performance index of spraying gained are as follows:
The above only is preferred embodiment of the present invention, is not to be the restriction of the present invention being made other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not break away to any simple modification, equivalent variations and remodeling that above embodiment did, still belongs to the protection domain of technical solution of the present invention according to technical spirit of the present invention.
Claims (10)
1, a kind of Spray Polyurea Elastomer that is applied to the mine comprises two kinds of components of A, R, it is characterized in that: described A component is polyisocyanates of 45-65 part and the polyether glycol synthetic semi prepolymer of 35-55 part by parts by weight; The R component comprises that parts by weight are the Amino Terminated polyether(ATPE) of 55-80 part, the chainextender of 15-30 part, the wear resistant filler of 5-25 part, and described A, R two components are used between 0.9-1.2 according to isocyanate index.
2, Spray Polyurea Elastomer according to claim 1 is characterized in that: the functionality of described polyisocyanates is between 2.0-2.7, and preferred functionality is 2.0-2.2;
Described polyisocyanates is 2,6-tolylene diisocyanate, 4,4 of 4 '-diphenylmethanediisocyanate, carbodiimide-uretonimine-modified, 4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, the many phenyl isocyanate of polymethine, 4, the mixture of one or more in 4 '-dicyclohexyl methane diisocyanate, the isophorone diisocyanate.
3, Spray Polyurea Elastomer according to claim 1 is characterized in that: the hydroxyl equivalent of described polyether glycol is 300-2000, and its functionality is between 2-4;
Described polyether glycol is one or more in polyglycol ether, polypropylene glycol ether, polyglycerol ether, polypentaerythritol ether, PTMG, the polycaprolactone glycol; The perhaps multipolymer of one or more of above-mentioned substance is selected one or more of described multipolymer then for use;
Perhaps described polyether glycol is selected low-unsaturation-degree polyether for use, hydroxyl terminated poly-butadiene, hydroxy-end capped polyvalent alcohol and the semi prepolymer of isocyanic ester.
4, Spray Polyurea Elastomer according to claim 1, it is characterized in that: the Amino Terminated polyether(ATPE) in the described R component is the polyether resin that contains primary amine or secondary amine end, its functionality is 2-3, and described Amino Terminated polyether(ATPE) resin comprises JEFFAMINE D-2000, the JEFFAMINE T-3000 of Huntsman company, one or more the mixture among JEFFAMINE D-400, the JEFFAMINE T-5000.
5, Spray Polyurea Elastomer according to claim 1, it is characterized in that: the chainextender in the described R component comprises amine chain extender, the mixture of one or more in the alcohols chainextender, described amine chain extender comprises aromatic diamine, the mixture of one or more in the aliphatic polyamine, described aromatic diamine is a diethyl toluene diamine, diformazan sulfenyl tolylene diamine, N, N ' two sec-butyl methylene dianiline (MDA)s, 4,4 '-diaminodiphenyl-methane, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, described aliphatic polyamine is 1,4-cyclohexyl diamines, isophorone diamine, 4,4 '-dicyclohexyl methyl hydride diamines, 1,4-diamines ethyl methane; Described alcohols chainextender is 1, the mixture of one or more in 4-butyleneglycol, 1,3 butylene glycol, TriMethylolPropane(TMP), glycerol, the trolamine.
6, Spray Polyurea Elastomer according to claim 1 is characterized in that: the wear resistant filler in the described R component is selected one or more the mixture in silicon carbide, glass microballon, polytetrafluoroethylene powder, aluminium sesquioxide, titanium dioxide, aluminum oxide, the nanometer inorganic filler for use.
7, Spray Polyurea Elastomer according to claim 1, it is characterized in that: the auxiliary agent that also comprises parts by weight 0.3-2 part in the described R component, described auxiliary agent comprises wetting dispersing agent, oxidation inhibitor, UV light absorber, wherein wetting dispersing agent is 1～30: 1 with the ratio that cooperates of oxidation inhibitor, and wetting dispersing agent is 1～15: 2 with the ratio that cooperates of UV light absorber.
8, Spray Polyurea Elastomer according to claim 1 is characterized in that: comprise also in the described R component that parts by weight are 0～20 part color stuffing.
9, the preparation method of the described Spray Polyurea Elastomer of a kind of claim 1, it is characterized in that: the synthetic method of described A component is: will join in the reactor of nitrogen protection according to the polyisocyanates of the described parts by weight metering of claim 1, at the uniform velocity stir, be heated to 50-60 ℃, the polyether glycol that in reactor, slowly adds metering, under 70-90 ℃, insulation reaction 2.5～3.5 hours, sampling analysis, survey free isocyanate content in the gained semi prepolymer between 13-20%, cooling discharging;
The preparation method of described R component is: 1) if add filler, comprise wear resistant filler or color stuffing, then at first filler with make mixture according to the part Amino Terminated polyether(ATPE) of the parts by weight in the described R component of claim 1, be dispersed into slurry with grinding plant such as sand mills then, according to prescription ground slurry, remainder Amino Terminated polyether(ATPE), chainextender are joined in the system paint can at last, utilize high-shear dispersing apparatus high-speed stirring to make in 25～35 minutes; 2) if not filled,, Amino Terminated polyether(ATPE), chainextender, auxiliary agent were made with high-shear dispersing apparatus high-speed stirring in 25～35 minutes then according to formula ratio;
In use, the isocyanate index according to A, R component cooperates between 0.9-1.2.
10, the constructional method of the described Spray Polyurea Elastomer of a kind of claim 1, it is characterized in that: after two components of described A, R are measured, pressurize, heated up in the high pressure collision type mixed spraying equipment of 1: 1 fixed volume ratio, be sprayed onto on the ground by spray gun, solidify spraying polyurea elastomer material, the initial temperature of A, R component is higher than 10 ℃, and setting main frame pressure is 55-77Kg/cm
2, temperature is 50-60 ℃, the spray pressure difference of two components is lower than 14Kg/cm in the spray gun mixing section
2
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2008
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