CN102153944A - Solvent-free polyurethane elastomeric coating with self-lubricating effect - Google Patents
Solvent-free polyurethane elastomeric coating with self-lubricating effect Download PDFInfo
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- CN102153944A CN102153944A CN2011100528409A CN201110052840A CN102153944A CN 102153944 A CN102153944 A CN 102153944A CN 2011100528409 A CN2011100528409 A CN 2011100528409A CN 201110052840 A CN201110052840 A CN 201110052840A CN 102153944 A CN102153944 A CN 102153944A
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Abstract
The invention discloses a solvent-free polyurethane elastomeric coating with self-lubricating effect, and belongs to the field of organic chemistry. The coating consists of two components A and R, wherein the component A is isocyanate blocked quasi-prepolymer; and the component R comprises chain extender, hydroxyl terminated polyether, abrasion-resistant filler and auxiliary agent. The abrasion of the coating prepared by adopting a new formula and a new process can reach 36 to 83mg (1,000hr) and is greatly improved by compared with the traditional spray polyurethane which has abrasion of 200mg (1,000hr), and the coating has excellent abrasion resistance; the friction coefficient of the spray coating is reduced by 20 percent compared with the traditional spray polyurethane under the same working condition, and the coating has low friction coefficient and can reduce flow resistance and reduce the energy loss of a system; and the coating has good construction performance and high construction efficiency, can be used for corrosion and abrasion protection of various products with complex shapes, has good adhesion performance with a base material, and can be applied to solid-liquid slurry conveying pipelines and overflow parts and the occasions with high equipment abrasion and corrosion resistant requirements in the industries of chemical engineering, mines, environmental friendliness and the like.
Description
Technical field
The present invention relates to organic chemistry filed, specifically a kind of no-solvent polyurethane elastomer coatings with self-lubricating function.
Background technology
We know, are applied to the slurry transportation pipeline, flow passage components in fields such as mine, building, chemical industry, environmental protection etc., in use because wearing and tearing and corrosion are serious, cause mechanical means performance failure and a large amount of consumptive materials of generation.In order to reduce the wearing and tearing and the corrosion of this class pipeline, equipment, existing way is the inner lining protection layer at the wearing surface of equipment, as adhesive rubber, wear-resistant paint, spraying polyurethane or polyurea elastomer material etc.Use these methods to alleviate abrasion to a certain extent; improved work-ing life, but the most outstanding shortcoming of generally using at present of polyurethane/polyurea wear-resistant protective layer is exactly that frictional coefficient is big, easily buildup, sizing; reduce transport efficiency, caused the wear resisting property variation simultaneously.In order to improve its resistance to abrasion, the general both at home and abroad method that adopts is to add wear resistant filler, seldom can come modification from the polyurethane/polyurea resin structure, and only in the surface side filler adjustment, the coating resistance to abrasion does not have the raising of essence.
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.This material can be used for the carbon steel sheet ground through shop primer, plays a part wear-resisting, attractive in appearance, easy to clean.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.
Summary of the invention
Purpose of the present invention is exactly the defective that exists at prior art, a kind of wear-resisting application places of having relatively high expectations such as transport pipe, mechanical means such as vibratory screening apparatus that are applied to fields such as mine, building, chemical industry, environmental protection are provided, have low surface friction coefficient, erosion resistant, and the no-solvent polyurethane elastomer coatings of long service life.Adopt new wear-resisting mechanism,, reduce the frictional coefficient of coating surface, improve the wear resistance level of coating, cooperate wear resistant filler simultaneously, obtain the better polyurethane coating of wear resisting property promptly by the adding of fluorine modified resin.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of no-solvent polyurethane elastomer coatings with self-lubricating function, it is characterized in that: form by A, R two components, by weight, wherein the A component is polyisocyanates and the isocyanate-terminated prepolymer of 35-55 part by 45-65 part; The R component is made up of 55-80 part end hydroxy polyether, 15-30 part chainextender, 5-25 part wear resistant filler.
The present invention also can realize by following measure: described polyisocyanates can be selected from 2,6-tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 4 of modification, 4 '-diphenylmethanediisocyanate, the many phenyl isocyanate of polymethine, 4,4 '-dicyclohexyl methane diisocyanate, isophorone diisocyanate is chosen wherein one or more, functionality is preferably between the 1.8-2.0 at 1.8-2.0.
Described polyisocyanates preferentially selects 4 for use, 4 '-diphenylmethanediisocyanate and 2,4 '-diphenylmethanediisocyanate, wherein contain at least 50% 4,4 '-diphenylmethanediisocyanate.
The isocyanate-terminated prepolymer of described A component can be obtained by one or more composition reactions of polyisocyanates and polyvalent alcohol, polyamines, the compound that contains amino and alcohol radical two functional groups and their mixture.
Described many alcohol, polyamines, contain the two compound of amino and alcohol radical, can be that one or more polyvalent alcohols are formed, these polyvalent alcohols can be selected from polyglycol ether, polypropylene glycol ether, polyglycerol ether, polypentaerythritol ether, PTMG, polycaprolactone glycol, low-unsaturation-degree alcohol ether and above-mentioned one or more multipolymer, choose wherein one or more, preferentially select PTMG, polycaprolactone glycol and low-unsaturation-degree polyether for use; The functionality of polyether glycol is 2-4, and hydroxyl equivalent is at least more than 300.
The synthetic method of said A component is: the polyisocyanates of accurate measurement is joined in the reactor of nitrogen protection; at the uniform velocity stir; be heated to 50-80 ℃; the polyether glycol that in reactor, slowly adds metering; under 60-90 ℃, insulation reaction 2-3 hour, sampling analysis; survey free isocyanate content in the gained semi prepolymer between 13-20%, cooling discharging.
Comprise any suitable hydroxy resin in the R component.R component in this patent is made of chainextender, terminal hydroxy group envelope polyethers, wear resistant filler and other auxiliary agent.
Chainextender described in the R component comprises amine chain extender: 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, aliphatic polyamine, choose wherein one or more, cooperate fluorine modified multicomponent amine chainextender; Also comprise the alcohols chainextender: 1,4-butyleneglycol, 1,3 butylene glycol, TriMethylolPropane(TMP), glycerol, trolamine are chosen wherein one or more, cooperate fluorine modified multicomponent amine chainextender; The mixture that also comprises amine chain extender and alcohols chainextender cooperates fluorine modified multicomponent amine chainextender.Wherein, fluorine modified multicomponent amine chainextender general formula:
R
1Can be C1-C20 chain or dendritic perfluoro alkyl group, R
2It can be the alkyl group of C1-C4.In the formula, m represents integer 1 or 2, and n represents integer 1-10.As:
End hydroxy polyether described in the R component is meant the polyether resin that contains primary hydroxyl or secondary hydroxyl end, and its functionality is 2-3.Polyglycol ether, polypropylene glycol ether, polyglycerol ether, polypentaerythritol ether, PTMG, polycaprolactone glycol, low-unsaturation-degree alcohol ether be can select for use, PTMG, polycaprolactone glycol and low-unsaturation-degree polyether preferentially selected for use; The functionality of polyether glycol is 2-4, and hydroxyl equivalent is at least more than 300, selects above-mentioned one or more multipolymer to cooperate fluorine modified polyalcohol, fluorine modified polyalcohol general formula: HOCH
2CH
2(CF
2)
nCH
2CH
2OH, n=1-20 wherein chooses wherein one or more, and as fluorine modified polyalcohol GF-1, molecular formula is HOCH
2CH
2CF
2CH
2CH
2OH; Fluorine modified polyalcohol GF-18, molecular formula is HOCH
2CH
2(CF
2)
18CH
2CH
2OH.
Wear resistant filler can be added in A component or the R component, preferably is added in the R component.Wear resistant filler described in the R component be selected from silicon carbide,, filler such as molybdenumdisulphide, titanium dioxide, glass microballon, polytetrafluoroethylene powder, aluminium sesquioxide, chromium sesquioxide, aluminum oxide, zirconium white, nanometer inorganic filler, can select one or more.The addition of wear resistant filler accounts between the 5-25% of R component resin weight.
Also can add stabilization aids such as oxidation inhibitor, UV light absorber as required in the R component.The IRGANOX1010 of auxiliary agent CIBA GEIGY company commonly used and oxidation inhibitor such as 1076, and UV light absorber such as TINUVIN P, TINUVIN327, TINUVIN328, the consumption of this analog assistant is 0.3-2 part.
In the R component, also can add color stuffing as required.Color stuffings such as carbon black, titanium white, phthalein green grass or young crops, chrome yellow for example.
The preparation method of R component is: 1) if add filler, comprise wear resistant filler and color stuffing, then at first the end hydroxy polyether in filler and the part R component is made mixture, be dispersed into mill base with grinding plant such as sand mills then.According to prescription ground mill base, remainder end hydroxy polyether, chainextender and auxiliary agent thereof are joined in the system paint can at last, utilize high-shear dispersing apparatus high-speed stirring 30min to make.
2) if do not add color stuffing, then according to formula ratio, Amino Terminated polyether(ATPE), chainextender, add usefulness high-shear dispersing apparatus high-speed stirring 30min such as material, auxiliary agent and make.
The equivalence ratio of A, R component, just isocyanate index is between 0.90-1.20.
The constructional method of the wear-resisting spray polyurea ammonia of the present invention ester elastomer is: after two components of A, R are measured, pressurize, heated up in the high pressure painting equipment of 1:1 fixed volume ratio, by spray gun be sprayed onto on the ground, the wear-resisting spraying polyurea elastomer material of solidified.The initial temperature of A, R material 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
The present invention has following advantage: 1. fast setting, can spray mo(u)lding on arbitrary surface, inclined-plane and vertical surface, and do not produce the sagging phenomenon.To moisture, temperature-insensitive, be not subjected to the influence of envrionment temperature, humidity during construction.2. the thickness range of once constructing can overcome in the past the repeatedly disadvantage of construction from hundreds of microns to several centimetres.3. can save expensive die cost in the direct spray mo(u)lding in baroque surface.4. excellent material performance, wear resisting property reaches more than 10 times of carbon steel, and the 3-5 of rubber item has doubly improved work-ing life.Also has excellent flexibility, corrosion-resistant, acidproof/alkalization medium, ageing-resistant simultaneously.5. low surface friction coefficient.Can reduce surface resistance greatly, improve pipeline transmission capacity.6. the fluorine resin of low surface free energy makes its surperficial hydrophobic characteristic, has improved the antiseptic property of material.7. shock-absorbing performance is good, and noise is low, has improved Working environment.8. good weatherability still can keep its good abrasion resistance under cold condition, the not efflorescence of outdoor life-time service, does not ftracture.
Embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1
A by contain have an appointment 25 parts 2,4 of 4 '-diphenylmethanediisocyanate and 100 parts, the molecular weight of 4 '-diphenylmethanediisocyanate and 99.36 parts is 1000, and functionality is the prepolymer of 2 poly(propylene oxide) ether glycol (as TDiol-1000, Plant of Tianjin Petrochemical Company three factories) preparation.Viscosity when the NCO content of prepolymer is 15 ± 0.1%, 25 ℃ is about 1000cps.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 1.15, the equivalent of the NCO that its isocyanic acid acid esters index is the A component and the hydroxyl of R component and the normal ratio of amido (down together), and concrete proportioning is as shown in the table.
| The R resin is formed | Ratio (weight) |
| The poly(propylene oxide) dibasic alcohol | 71.0 |
| Polyether resin | 9.0 |
| Diethyl toluene diamine | 12.0 |
| Titanium dioxide | 8.0 |
A, R component 1:1 by volume adopt high pressure head-on collision mixed spraying equipment to spray.With coating spraying to the PVC plate that scribbles releasing agent.After treating that coating curing fully, it is carried out the wear resisting property test.
The polyureas high-abrasive material performance index of spraying gained are as follows:
| Project | The result |
| Wear resistance/mg(1000r) | 83 |
Embodiment 2
A by contain have an appointment 30 parts 2,4 '-diphenylmethanediisocyanate and 36-52 part 4, the molecular weight of 4 '-diphenylmethanediisocyanate and 95 parts is 1000, and functionality is the prepolymer of 2 PTMG (PTMG-1000, German BASF) preparation.Viscosity when the NCO content of prepolymer is 15 ± 0.1%, 25 ℃ is about 1200cps.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 1.15.Concrete proportioning is as shown in the table.
| The R resin is formed | Ratio (weight) |
| PTMG | 64.0 |
| Polyether resin) | 23.0 |
| Diethyl toluene diamine | 5.0 |
| TiO 2 | 8.0 |
A, R component 1:1 by volume adopt high pressure head-on collision mixed spraying equipment to spray.With coating spraying to the PVC plate that scribbles releasing agent.After treating that coating curing fully, it is carried out the wear resisting property test.
The polyureas high-abrasive material performance index of spraying gained are as follows:
| Project | The result |
| Wear resistance/mg(1000r) | 45 |
Embodiment 3
A by contain have an appointment 62.5 parts 2,4 of 4 '-diphenylmethanediisocyanate and 62.5 parts, the molecular weight of 4 '-diphenylmethanediisocyanate and 99.36 parts is 1000, and functionality is the prepolymer of 2 polycaprolactone dibasic alcohol (210N, U.S. Arch chemical company) preparation.Viscosity when the NCO content of prepolymer is 15 ± 0.1%, 25 ℃ is about 1200cps.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.
| The R resin is formed | Ratio (weight) |
| The polycaprolactone dibasic alcohol | 64.0 |
| Polyether resin | 23.0 |
| Diformazan sulfenyl tolylene diamine | 5.0 |
| MoS 2 | 8.0 |
A, R component 1:1 by volume adopt high pressure head-on collision mixed spraying equipment to spray.With coating spraying to the PVC plate that scribbles releasing agent.After treating that coating curing fully, it is carried out the wear resisting property test.
The polyureas high-abrasive material performance index of spraying gained are as follows:
| Project | The result |
| Wear resistance/mg(1000r) | 27 |
Embodiment 4
A by contain 40 parts 2,4 of 4 '-diphenylmethanediisocyanate and 85 parts, the molecular weight of 4 '-diphenylmethanediisocyanate and 132.5 parts is 4950, and functionality is the prepolymer of 3 polyether polyol with high activity (330N, Plant of Tianjin Petrochemical Company three factories) preparation.Viscosity when the NCO content of prepolymer is 15 ± 0.1%, 25 ℃ is about 1500cps.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 1.15.Concrete proportioning is as shown in the table.
| The R resin is formed | Ratio (weight) |
| The poly(propylene oxide) dibasic alcohol | 44.0 |
| The fluorine modified polyalcohol | 20.0 |
| Polyether resin | 23.0 |
| Diethyl toluene diamine | 4.8 |
| 1,4 butyleneglycol | 0.2 |
| MoS 2 | 8.0 |
A, R component 1:1 by volume adopt high pressure head-on collision mixed spraying equipment to spray.With coating spraying to the PVC plate that scribbles releasing agent.After treating that coating curing fully, it is carried out the wear resisting property test.
The polyureas high-abrasive material performance index of spraying gained are as follows:
| Project | The result |
| Wear resistance/mg(1000r) | 36 |
Claims (9)
1. no-solvent polyurethane elastomer coatings with self-lubricating function, it is characterized in that: be made up of A, R two components, by weight, wherein the A component is polyisocyanates and the isocyanate-terminated prepolymer of 35-55 part by 45-65 part; The R component is made up of 55-80 part end hydroxy polyether, 15-30 part chainextender, 5-25 part wear resistant filler.
2. according to the described no-solvent polyurethane elastomer coatings of claim 1, it is characterized in that said isocyanate-terminated prepolymer can be obtained by one or more composition reactions of polyisocyanates and polyvalent alcohol, polyamines, the compound that contains amino and alcohol radical two functional groups and their mixture with self-lubricating function.
3. according to the described no-solvent polyurethane elastomer coatings of claim 2 with self-lubricating function, it is characterized in that said polyisocyanates can be selected from 2, the 6-tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, 4 of modification, 4 '-diphenylmethanediisocyanate, the many phenyl isocyanate of polymethine, 4,4 '-dicyclohexyl methane diisocyanate, isophorone diisocyanate, choose wherein one or more, functionality is at 1.8-2.7, between.
4. according to the described no-solvent polyurethane elastomer coatings of claim 3 with self-lubricating function, it is characterized in that said polyisocyanates preferentially selects 4 for use, 4 '-diphenylmethanediisocyanate and 2,4 '-diphenylmethanediisocyanate, wherein contain at least 50% 4,4 '-diphenylmethanediisocyanate.
5. according to the described no-solvent polyurethane elastomer coatings of claim 2 with self-lubricating function, it is characterized in that said how pure, polyamines, the two the compound that contains amino and alcohol radical, can be that one or more polyvalent alcohols are formed, these polyvalent alcohols can be selected from polyglycol ether, polypropylene glycol ether, polyglycerol ether, polypentaerythritol ether, PTMG, polycaprolactone glycol, low-unsaturation-degree alcohol ether and above-mentioned one or more multipolymer, choose wherein one or more, preferentially select PTMG for use, polycaprolactone glycol and low-unsaturation-degree polyether; The functionality of polyether glycol is 2-4, and hydroxyl equivalent is at least more than 300.
6. according to the described no-solvent polyurethane elastomer coatings of claim 1 with self-lubricating function, it is characterized in that said chainextender comprises amine chain extender: 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, aliphatic polyamine are chosen wherein one or more, cooperate fluorine modified multicomponent amine chainextender; Also comprise the alcohols chainextender: 1,4-butyleneglycol, 1,3 butylene glycol, TriMethylolPropane(TMP), glycerol, trolamine are chosen wherein one or more, cooperate fluorine modified multicomponent amine chainextender; The mixture that also comprises amine chain extender and alcohols chainextender cooperates fluorine modified multicomponent amine chainextender, wherein, and fluorine modified multicomponent amine chainextender general formula:
R
1Can be C1-C20 chain or dendritic perfluoro alkyl group, R
2Can be the alkyl group of C1-C4, in the formula, m represents integer 1 or 2, and n represents integer 1-10, as:
7. according to the described no-solvent polyurethane elastomer coatings of claim 1 with self-lubricating function, it is characterized in that said end hydroxy polyether is meant the polyether resin that contains primary hydroxyl or secondary hydroxyl end, its functionality is 2-3, polyglycol ether, polypropylene glycol ether, polyglycerol ether, polypentaerythritol ether, PTMG, polycaprolactone glycol, low-unsaturation-degree alcohol ether be can select for use, PTMG, polycaprolactone glycol and low-unsaturation-degree polyether preferentially selected for use; The functionality of polyether glycol is 2-4, and hydroxyl equivalent is at least more than 300, selects above-mentioned one or more multipolymer to cooperate fluorine modified polyalcohol, fluorine modified polyalcohol general formula: HOCH
2CH
2(CF
2)
nCH
2CH
2OH, n=1-20 wherein chooses wherein one or more, and as fluorine modified polyalcohol GF-1, molecular formula is HOCH
2CH
2CF
2CH
2CH
2OH, fluorine modified polyalcohol GF-6, molecular formula is HOCH
2CH
2(CF
2)
6CH
2CH
2OH.
8. according to the described no-solvent polyurethane elastomer coatings of claim 1 with self-lubricating function, it is characterized in that said wear resistant filler is selected from fillers such as silicon carbide, glass microballon, polytetrafluoroethylene powder, aluminium sesquioxide, chromium sesquioxide, molybdenumdisulphide, titanium dioxide, aluminum oxide, zirconium white, nanometer inorganic filler, the addition of wear resistant filler accounts between the 5-25% of R component resin weight.
9. according to the described no-solvent polyurethane elastomer coatings of claim 1, it is characterized in that the isocyanate index of A and R system is 0.90-1.20 in said two components with self-lubricating function.
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| CN104559728A (en) * | 2014-12-12 | 2015-04-29 | 中国航空工业集团公司北京航空材料研究院 | Corrosion-resistant anti-cavitation coating and preparation method thereof |
| CN104830051A (en) * | 2015-05-18 | 2015-08-12 | 吴江市宏宇机械有限公司 | Novel polyurethane elastomer for mold resins and preparation method thereof |
| CN104946068A (en) * | 2015-06-30 | 2015-09-30 | 无锡阳工机械制造有限公司 | Hydraulic part wearing-resistant coating material |
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| CN109535983A (en) * | 2018-12-19 | 2019-03-29 | 福州皇家地坪有限公司 | Solvent-free elastic polyurethane anti-corrosion floor material |
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Application publication date: 20110817 |