CN114149737B - Polyurethane coating and application thereof - Google Patents
Polyurethane coating and application thereof Download PDFInfo
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- CN114149737B CN114149737B CN202111569994.5A CN202111569994A CN114149737B CN 114149737 B CN114149737 B CN 114149737B CN 202111569994 A CN202111569994 A CN 202111569994A CN 114149737 B CN114149737 B CN 114149737B
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
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Abstract
The invention provides a polyurethane coating and application thereof. The polyurethane coating comprises a component A and a component B; the component A comprises 95 to 105 parts of diisocyanate in parts by weight; the component B comprises, by weight, 5-15 parts of modified organosilicon polymer, 60-80 parts of polyether polyol and 15-30 parts of chain extender. According to the invention, the component A is selected from specific diisocyanate, and the component B is selected from specific modified organic silicon polymer, polyether polyol and chain extender, so that the coating comprising the polyurethane coating is good in flexibility, excellent in corrosion resistance, easy to strip, free of solvent volatilization, green and environment-friendly, and high in production efficiency.
Description
Technical Field
The invention belongs to the technical field of materials for chemical milling, and particularly relates to a polyurethane coating and application thereof.
Background
The chemical milling is a special processing technology without a cutter and cutting chips, which is used for obtaining the required processing dimension and process precision by uniformly corroding the exposed part of a workpiece through a chemical solution. The chemical milling has more advantages than the mechanical milling in certain aspects, mainly shows that the chemical milling can process parts which are extremely thin, easy to deform and large in area, is not influenced by the state of a metal material, can be directly processed into an integral structure, does not generate stress, does not deform parts and has high production efficiency. The essential material in the chemical milling process is chemical milling protective coating, also called strippable coating, which is a temporary protective coating in the chemical milling process, can play a role in temporary protection in the processing process, and is removed after the chemical milling process is finished.
With the development requirement of science and technology, several aluminum alloy chemical milling protective strippable coatings are developed in sequence. The first generation chemical milling protection strippable coating is neoprene, and the chemical milling processing technology standard (called as navigation mark for short) of the aluminum alloy in the aviation industry is compiled on the basis of the first generation chemical milling protection strippable coating, but the biggest defect of the neoprene is that 'corrosion leakage' is generated, the toxicity of a solvent is high, the storage stability is poor, and the neoprene is eliminated at present; the second generation chemical milling protection strippable coating is represented by styrene-butadiene rubber, although the toxicity of a solvent is reduced, the process is complex, the problem of corrosion leakage still exists, and the coating is not popularized and used in aviation enterprises at present.
The third generation is thermoplastic elastomer such as styrene-butadiene-styrene elastomer (SBS) and has the properties of both rubber and plastics, for example, CN102010643A discloses a chemical milling protective coating which is a single-component coating consisting of thermoplastic elastomer, pigment, filler, auxiliary agent, solvent and the like, and can be dried by air at normal temperature and low temperature. The paint film is flat and uniform, and has certain adhesive force and better physical and mechanical properties. Meanwhile, the coating has good chemical corrosion resistance and strippability. However, the coating is still a solvent-based product, and a large amount of solvent is volatilized in the construction process, so that the coating is harmful to the environment and workers and is not beneficial to environmental protection.
CN112322112A discloses a water-based chemical milling temporary protective coating and a preparation method thereof. The coating comprises: concentrated natural latex, potassium hydroxide solution, peregal O-20 solution, sulfur dispersion, zinc di-n-dithiocarbamate dispersion, terpene emulsion, antioxidant dispersion, zinc oxide dispersion, magnesium hydroxide dispersion, and deionized water. The water-based chemical milling protective coating is environment-friendly, and is friendly to the environment and workers and nontoxic. However, a large amount of water still needs to be volatilized in the film forming process, and the film forming time is long, so that the process efficiency is low.
Therefore, the development of a chemical milling protective coating with good strippability, excellent corrosion resistance, fast film formation, environmental protection and high process efficiency is an urgent problem to be solved in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a polyurethane coating and application thereof. The polyurethane coating selects the specific modified organic silicon polymer, the polyether polyol, the chain extender and the specific diisocyanate, so that the coating comprising the polyurethane coating has the advantages of good flexibility, excellent corrosion resistance, easy stripping, no solvent volatilization, environmental friendliness and high production efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a polyurethane coating comprising an a-component and a B-component; the component A comprises 95 to 105 parts of diisocyanate in parts by weight; the component B comprises, by weight, 5-15 parts of modified organosilicon polymer, 60-80 parts of polyether polyol and 15-30 parts of chain extender.
In the invention, by selecting the specific modified organic silicon polymer, the compatibility of the component B and the component A can be improved, the adhesion of the coating to a base material can be reduced, and the corrosion resistance of the coating can be improved; the coating comprising the polyurethane coating has excellent mechanical properties by forming a specific ratio of the modified organic silicon polymer, the polyether polyol, the chain extender and the component A, and all components in the polyurethane coating participate in the reaction, so that the polyurethane coating is free of solvent volatilization and environment-friendly.
Preferably, the A component includes 95 to 105 parts of diisocyanate, which may be, for example, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts, 101 parts, 102 parts, 103 parts, 104 parts, 105 parts, etc.
In the invention, the part of the component A is less than 95 parts or more than 105 parts, so that the index of the diisocyanate is lower or higher, and the reaction of the component A and the component B is incomplete, so that the performance of the final coating can not meet the performance requirement.
Preferably, the B component includes 5 to 15 parts of the modified silicone polymer, which may be, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, and the like.
In the invention, when the part of the modified organic silicon polymer is less than 5 parts, the adhesive force of the coating is too large, and the coating is not convenient to peel off after the chemical milling process is finished; when the amount is more than 15 parts, the adhesive force of the coating cannot meet the requirement, so that the alkali-resistant corrosion protection of the coating is insufficient in the chemical milling process.
Preferably, the B component comprises 60 to 80 parts of polyether polyol, and may be, for example, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, 78 parts, 80 parts, and the like.
In the invention, the polyether polyol is less than 60 parts, the flexibility of a paint film is insufficient, and the coating is difficult to peel after the chemical milling process is finished; if the amount of the modified epoxy resin is more than 80 parts, the hydrophilicity of a paint film can be enhanced, and the alkali corrosion resistance of the coating is reduced.
Preferably, the B component includes 15 to 30 parts of chain extender, which may be, for example, 15 parts, 17 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, etc.
Preferably, the diisocyanate includes any one of diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, or hexamethylene diisocyanate, or a combination of at least two thereof.
Preferably, the diisocyanate comprises diphenylmethane diisocyanate and/or carbodiimide modified diphenylmethane diisocyanate.
Preferably, the modified silicone polymer has a number average molecular weight of 2000 to 4000, and may be, for example, 2000, 2500, 3000, 3500, 4000, or the like.
In the invention, the excessively high number average molecular weight of the modified organosilicon polymer affects the reaction speed of the modified organosilicon polymer and diisocyanate, so that incomplete reaction is caused to affect the performance of a paint film; the number average molecular weight is too low, and the branch chains are all organic silicon polymers with small molecular weight after the paint film is cured, so that the flexibility of the paint film can be reduced.
Preferably, the modified silicone polymer raw materials include monohydroxy terminated polydimethylsiloxane, 4,4' -diisocyanate diphenylmethane and trimethylolpropane.
Preferably, the mass ratio of the monohydroxy terminated polydimethylsiloxane, 4,4' -diisocyanate diphenylmethane and trimethylolpropane is 1 (0.06-0.1) (0.04-0.07), and can be, for example, 1.
In the invention, the modified organic silicon polymer obtained by selecting monohydroxy terminated polydimethylsiloxane, 4,4' -diisocyanate diphenylmethane and trimethylolpropane in a specific ratio can improve the compatibility of the component B and the component A during spraying, properly reduce the adhesive force between a coating and a base material, is easy to peel and can improve the alkali corrosion resistance of a paint film.
In the present invention, it is preferable that the mass ratio of monohydroxy-terminated polydimethylsiloxane, 4,4' -diisocyanate diphenylmethane and trimethylolpropane is 100.
Preferably, the modified silicone polymer is prepared by a method comprising: pre-reacting monohydroxy terminated polydimethylsiloxane with 4,4 '-diisocyanate diphenylmethane to obtain 4,4' -diisocyanate diphenylmethane modified polydimethylsiloxane; and reacting 4,4' -diisocyanate diphenylmethane modified polydimethylsiloxane with trimethylolpropane to obtain the modified organic silicon polymer.
Preferably, the temperature of the pre-reaction is 50 to 100 ℃, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 100 ℃ and the like.
Preferably, the pre-reaction time is 2 to 4 hours, for example, 2 hours, 3 hours, 4 hours, and the like.
Preferably, the pre-reaction is preceded by a step of dehydrating the single hydroxyl terminated polydimethylsiloxane.
In the invention, the monohydroxy terminated polydimethylsiloxane is dehydrated before the pre-reaction so as to eliminate the reaction between water in the raw material and 4,4' -diisocyanate diphenylmethane and ensure that the reaction product is not influenced by impurity water.
Preferably, the dehydration temperature is 105~115 ℃, for example, can be 105 degrees, 106 degrees, 107 degrees, 108 degrees, 109 degrees, 110 degrees, 111 degrees, 112 degrees, 113 degrees, 114 degrees.
Preferably, the time for dehydration is 1.5 to 2.5 hours, for example, 1.5 hours, 2 hours, 2.5 hours, and the like.
Preferably, the reaction temperature is 50-100 ℃, for example, can be 50 degrees, 55 degrees, 60 degrees, 65 degrees, 70 degrees, 75 degrees, 80 degrees, 85 degrees, 90 degrees, 100 degrees C.
Preferably, the reaction time is 2 to 4 hours, and for example, 2 hours, 3 hours, 4 hours, and the like can be used.
Preferably, the polyether polyol has a number average molecular weight of 1000 to 2000, and may be, for example, 1000, 1200, 1400, 1600, 1800, 2000, and the like.
Preferably, the polyether polyol comprises a tetrahydrofuran homopolyether.
Preferably, the chain extender comprises a glycol chain extender.
Preferably, the chain extender comprises any one of ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, methyl propylene glycol, dipropylene glycol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,2-pentanediol, or 1,6-hexanediol, or a combination of at least two thereof.
Preferably, the chain extender comprises any one of ethylene glycol, diethylene glycol or 1,3-propylene glycol or a combination of at least two thereof.
In the invention, the preparation method of the polyurethane coating comprises the following steps: and mixing the component A with the component B to obtain the polyurethane coating.
In a second aspect, the present invention provides a polyurethane coating comprising the polyurethane coating of the first aspect.
Preferably, the thickness of the polyurethane coating is controlled to be 200 μm to 300 μm, for example, 220 μm, 240 μm, 260 μm, 280 μm, 300 μm, etc.
In a third aspect, the present invention provides a method for preparing the polyurethane coating according to the second aspect, the method comprising:
and mixing the component A and the component B, spraying and curing to obtain the polyurethane coating.
Preferably, the mixing device is a two-component high-pressure spraying device.
In the invention, the bi-component high-pressure spraying equipment can be selected from an H-3500 or H-20/30 main machine and a GX-7 or GX-8 spray gun of Gusmer company in America, an MX/MH main machine and a Probler spray gun of Glas-Craft company, an H-XP3 main machine or an E-XP2 main machine and a Fusion MP spray gun of Graco company, and the like.
Preferably, the curing time is 20 to 30min, for example, 20min, 22min, 24min, 26min, 28min, 30min, etc.
In the invention, the specific preparation method of the polyurethane coating comprises the following steps: mixing the A and B components in a ratio of 1:1, metering in a double-component high-pressure spraying device, heating to 55-70 ℃, uniformly spraying the mixture onto a substrate after mixing by a spray gun by adjusting the angle of the spray gun and proper spraying pressure, and quickly curing within half an hour to obtain the polyurethane coating.
According to the invention, the polyurethane coating can be rapidly formed into a film by adopting a spraying process, the film is formed without the assistance of processes such as baking and the like, and the production efficiency is high; and the component A and the component B are mixed more fully through a spraying process, so that the film forming speed and the coating quality are improved.
In the invention, the polymer in the polyurethane coating obtained by the spraying process is in a comb-shaped structure, the main chain is polyurethane, and the branched chain is a modified organic silicon polymer, so that the coating has better flexibility and is easy to strip.
In a fourth aspect, the present invention provides a chemical milling protective coating comprising the polyurethane coating according to the first aspect and/or the polyurethane coating according to the second aspect.
The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.
Compared with the prior art, the invention has the beneficial effects that:
according to the polyurethane coating provided by the invention, the component A is selected from specific diisocyanate, and the component B is selected from specific modified organic silicon polymer, polyether polyol and chain extender, so that the polyurethane coating is high in film forming speed; the coating of the polyurethane coating has good flexibility and excellent corrosion resistance, has moderate adhesive force with a base material and is easy to peel; the etching ratio of the coating comprising the polyurethane coating is 0.9-1.1, the peel strength is 300-600N/m, the tensile strength is more than or equal to 4MPa, and the elongation is more than or equal to 750%.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Unless otherwise specified, all of the materials for the polyurethane coatings provided in the examples and comparative examples of the present invention are commercially available or prepared by methods conventional in the art.
Preparation example 1
A modified silicone polymer comprising 100 parts monohydroxy-terminated polydimethylsiloxane (X-22-170 BX, shin-Etsu chemical industries, ltd.), 9 parts 4,4' -diisocyanate diphenylmethane and 5 parts trimethylolpropane.
A preparation method of the modified organic silicon polymer comprises the following specific steps:
adding single-end hydroxyl-terminated polydimethylsiloxane into a three-neck flask according to the formula amount, vacuumizing and dehydrating for 2h at 110 ℃, then reducing the temperature to 50 ℃, adding 4,4' -diisocyanate diphenylmethane (MDI, the purity is more than or equal to 98%), reacting for 3h at 80 ℃, adding trimethylolpropane, and continuing to react for 3h at 80 ℃ to obtain the modified organic silicon polymer.
Preparation example 2
A modified silicone polymer comprising 100 parts monohydroxy-terminated polydimethylsiloxane (X-22-170 BX, shin-Etsu chemical industries, ltd.), 9 parts 4,4' -diisocyanate diphenylmethane and 2 parts trimethylolpropane.
A preparation method of the modified organic silicon polymer comprises the following specific steps:
adding single-end hydroxyl-terminated polydimethylsiloxane into a three-neck flask according to the formula amount, vacuumizing and dehydrating for 2h at 110 ℃, then reducing the temperature to 50 ℃, adding 4,4' -diisocyanate diphenylmethane (MDI, the purity is more than or equal to 98 percent) to react for 3h at 100 ℃, adding trimethylolpropane to continue reacting for 3h at 100 ℃ to obtain the modified organic silicon polymer.
Preparation example 3
A modified organosilicon polymer which is different from the preparation example 1 only in that the trimethylolpropane is 10 parts by weight, and other raw materials and using amounts are the same as the preparation example 1.
The specific steps of the preparation method of the modified organic silicon polymer are the same as those of preparation example 1.
Preparation example 4
A modified silicone polymer differing from preparation example 1 only in that 4,4 '-diisocyanate diphenylmethane was replaced with 4.5 parts of toluene diisocyanate and 4.5 parts of 4,4' -diisocyanate diphenylmethane, and other raw materials and amounts were the same as in preparation example 1.
The specific steps of the preparation method of the modified organic silicon polymer are the same as those of preparation example 1.
Preparation example 5
A modified silicone polymer differing from preparation example 1 only in that the monohydroxy-terminated polydimethylsiloxane was replaced with a polydimethylsiloxane having an equimolar hydroxyl group (X-22-176 DX, shin-Etsu chemical Co., ltd.), and other raw materials and amounts were the same as in preparation example 1.
The specific steps of the preparation method of the modified organic silicon polymer are the same as those of preparation example 1.
Example 1
The embodiment provides a polyurethane coating which comprises a component A and a component B in parts by weight; the A component comprises 100 parts of carbodiimide modified 4,4' -diphenylmethane diisocyanate (MDI-100 LL, tantainwawa polyurethane GmbH); the B component included 10 parts of a modified silicone polymer (preparation example 1), 70 parts of tetrahydrofuran homopolyether (PTMG, number average molecular weight 2000), and 30 parts of ethylene glycol.
The embodiment provides a preparation method of a polyurethane coating, which comprises the following specific steps:
according to the formula, mixing carbodiimide modified 4,4' -diphenylmethane diisocyanate, modified organosilicon polymer, tetrahydrofuran homopolyether and ethylene glycol to obtain the polyurethane coating.
Example 2
The embodiment provides a polyurethane coating which comprises a component A and a component B in parts by weight; the A component comprises 95 parts of carbodiimide modified 4,4' -diphenylmethane diisocyanate (MDI-100 LL, tantainwanhua polyurethane GmbH); the B component comprises 5 parts of modified silicone polymer (preparation example 1), 60 parts of tetrahydrofuran homopolyether (PTMG, number average molecular weight 2000) and 30 parts of 1,6-hexanediol.
The embodiment provides a preparation method of a polyurethane coating, which comprises the following specific steps:
according to the formula, mixing carbodiimide modified 4,4' -diphenylmethane diisocyanate, modified organosilicon polymer, tetrahydrofuran homopolyether and 1,6-hexanediol to obtain the polyurethane coating.
Example 3
This example provides a polyurethane coating which differs from example 1 only in that the carbodiimide-modified 4,4' -diphenylmethane diisocyanate (MDI-100 LL, nicotineam trawawa polyurethane gmbh) was replaced with an equal part by weight of the diisocyanate diphenylmethane (MDI-50, nicotineam trawawa polyurethane gmbh), and the other components, amounts and preparation methods were the same as in example 1.
Example 4
This example provides a polyurethane coating which differs from example 1 only in that 100 parts of carbodiimide-modified 4,4 '-diphenylmethane diisocyanate (MDI-100 LL, cigarette taiwanhua polyurethane gmbh) was replaced with 50 parts of carbodiimide-modified 4,4' -diphenylmethane diisocyanate (MDI-100 LL, cigarette taiwanhua polyurethane gmbh) and 50 parts of diisocyanate diphenylmethane (MDI-50, cigarette taiwanhua polyurethane gmbh), and the other components, amounts and preparation methods were the same as in example 1.
Example 5
This example provides a polyurethane coating which differs from example 1 only in that the modified silicone polymer is the modified silicone polymer provided in preparation example 2, and the other raw materials, amounts and preparation methods are the same as those of example 1.
Example 6
This example provides a polyurethane coating that differs from example 1 only in that the modified silicone polymer is the modified silicone polymer provided in preparation example 3, and the other components, amounts, and preparation methods are the same as in example 1.
Example 7
This example provides a polyurethane coating that differs from example 1 only in that the modified silicone polymer is the modified silicone polymer provided in preparation 4, and the other components, amounts, and preparation methods are the same as in example 1.
Example 8
This example provides a polyurethane coating that differs from example 1 only in that the modified silicone polymer is the modified silicone polymer provided in preparation example 5, and the other components, amounts, and preparation methods are the same as in example 1.
Example 9
This example provides a polyurethane coating which differs from example 1 only in that the polyether of tetrahydrofuran is replaced by polyethylene glycol 2000 with an equal molar multiple of hydroxyl groups, and the other components, amounts and preparation methods are the same as example 1.
Example 10
This example provides a polyurethane coating which differs from example 1 only in that 10 parts of the modified silicone polymer (preparation example 1) are replaced with 5 parts of the modified silicone polymer provided in preparation example 1 and 5 parts of the modified silicone polymer provided in preparation example 5, and the other raw materials, amounts, and preparation methods are the same as in example 1.
Comparative example 1
This comparative example provides a polyurethane coating which differs from example 1 only in that the tetrahydrofuran homopolyether is replaced with polycaprolactone 2000 having the same molar multiple of hydroxyl groups, and the other components, amounts and preparation methods are the same as those of example 1.
Comparative example 2
This comparative example provides a polyurethane coating which differs from example 1 only in that the modified silicone polymer is replaced with polydimethylsiloxane (X-22-176 DX, shin-Etsu chemical industries, ltd.) having an equimolar ratio of hydroxyl groups, and the other components, amounts and preparation methods are the same as those of example 1.
Application example
A polyurethane coating comprising the polyurethane coatings provided in examples 1-10, comparative examples 1 and 2; the preparation method of the polyurethane coating comprises the following steps:
passing the A and B components through an H-XP3 host machine or an E-XP2 host machine and a Fusion MP spray gun of Graco company in the U.S. A, B components according to the volume ratio of 1:1 is sprayed on a 2A12-T4 aluminum alloy test piece, the film thickness is controlled to be about 250 micrometers, and the polyurethane coating is obtained after the coating is cured for 30 min.
After the polyurethane coatings provided by the examples 1-10 and the comparative examples 1 and 2 are constructed according to the method, the polyurethane coatings are subjected to chemical milling processing, and evaluation tests are carried out according to the standard HB 5453-2004-aluminum alloy chemical milling protective coating standard of the PRC and aviation industry.
The specific test results are shown in table 1:
TABLE 1
The above table shows that the component A of the polyurethane coating provided by the invention is selected from specific diisocyanate, and the component B is selected from specific modified organic silicon polymer, polyether polyol and chain extender, so that the coating comprising the polyurethane coating has the advantages of good flexibility, strong corrosion resistance, easiness in stripping, no solvent volatilization, environmental friendliness and high production efficiency.
As can be seen from examples 1 to 4, the polyurethane coating comprising the polyurethane coating has an etching ratio of 0.98 to 1.01, is qualified in acid and alkali resistance, has a peel strength of 400 to 570N/m, a tensile strength of 11 to 13MPa and an elongation of 750 to 800 percent; as can be seen from comparison of example 1 with examples 5 to 10, the polyurethane coating does not use a specific modified silicone polymer or a specific polyether polyol, and the mechanical properties or corrosion resistance of the polyurethane coating is reduced; as can be seen from the comparison of example 1 with comparative examples 1 and 2, the polyurethane coating is not the preferred formulation of the present invention, and the mechanical properties or the acid and alkali corrosion resistance of the polyurethane coating layer are decreased.
In conclusion, the polyurethane coating provided by the invention has the advantages that the component A is the specific diisocyanate, the component B is the specific modified organic silicon polymer, the polyether polyol and the chain extender, and the component A and the component B are compounded, so that the coating comprising the polyurethane coating has good flexibility, excellent acid and alkali corrosion resistance, low adhesive force with a base material and easy stripping, and is suitable for a chemical milling protective coating.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (20)
1. The polyurethane coating is characterized by comprising a component A and a component B;
the component A comprises 95 to 105 parts by weight of diisocyanate;
the component B comprises, by weight, 5 to 15 parts of a modified organic silicon polymer, 60 to 80 parts of a polyether polyol and 15 to 30 parts of a chain extender;
the diisocyanate comprises any one or the combination of at least two of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or hexamethylene diisocyanate;
the raw materials of the modified organic silicon polymer comprise monohydroxy terminated polydimethylsiloxane, 4,4' -diisocyanate diphenylmethane and trimethylolpropane;
the mass ratio of the monohydroxy terminated polydimethylsiloxane, 4,4' -diisocyanate diphenylmethane and trimethylolpropane is 1 (0.06 to 0.1) to (0.04 to 0.07);
the modified organic silicon polymer is prepared by the following method, and the method comprises the following steps: pre-reacting monohydroxy terminated polydimethylsiloxane with 4,4 '-diisocyanate diphenylmethane to obtain 4,4' -diisocyanate diphenylmethane modified polydimethylsiloxane; the 4,4' -diisocyanate diphenylmethane modified polydimethylsiloxane is reacted with trimethylolpropane to obtain the modified organic silicon polymer;
the polyether polyol is tetrahydrofuran homopolyether.
2. The polyurethane coating of claim 1, wherein the diisocyanate comprises diphenylmethane diisocyanate and/or carbodiimide modified diphenylmethane diisocyanate.
3. The polyurethane coating according to claim 1, wherein the modified silicone polymer has a number average molecular weight of 2000 to 4000.
4. The polyurethane coating of claim 1, wherein the mass ratio of the monohydroxy terminated polydimethylsiloxane, 4,4' -diisocyanate diphenylmethane and trimethylolpropane is 1 (0.085 to 0.095) to (0.045 to 0.055).
5. The polyurethane coating according to claim 1, wherein the pre-reaction temperature is 50 to 100 ℃.
6. The polyurethane coating as claimed in claim 1, wherein the pre-reaction time is 2 to 4 hours.
7. The polyurethane coating of claim 1, wherein the pre-reaction is preceded by a step of dehydrating the single hydroxyl terminated polydimethylsiloxane.
8. The polyurethane coating according to claim 7, wherein the temperature for dehydration is 105 to 115 ℃.
9. The polyurethane coating as claimed in claim 7, wherein the dehydration time is 1.5 to 2.5 hours.
10. The polyurethane coating as claimed in claim 1, wherein the reaction temperature is 50 to 100 ℃.
11. The polyurethane coating as claimed in claim 1, wherein the reaction time is 2 to 4 hours.
12. The polyurethane coating according to claim 1, wherein the polyether polyol has a number average molecular weight of 1000 to 2000.
13. The polyurethane coating of claim 1, wherein the chain extender comprises a glycol chain extender.
14. The polyurethane coating of claim 1, wherein the chain extender comprises any one of or a combination of at least two of ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, methyl propanediol, dipropylene glycol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,2-pentanediol, or 1,6-hexanediol.
15. The polyurethane coating of claim 14, wherein the chain extender comprises any one of ethylene glycol, diethylene glycol, or 1,3-propylene glycol, or a combination of at least two thereof.
16. A polyurethane coating, characterized in that the polyurethane coating comprises the polyurethane paint according to any one of claims 1 to 15.
17. A method of preparing a polyurethane coating according to claim 16, comprising:
and mixing the component A and the component B, spraying and curing to obtain the polyurethane coating.
18. The method of claim 17, wherein the mixing device is a two-component high pressure spray device.
19. The method of claim 17, wherein the curing time is 20 to 30 min.
20. A chemical milling protective coating, characterized in that the chemical milling protective coating comprises the polyurethane coating of any one of claims 1 to 15 and/or the polyurethane coating of claim 16.
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