CN110643273A - High-performance waterborne polyurethane composition and preparation method thereof - Google Patents
High-performance waterborne polyurethane composition and preparation method thereof Download PDFInfo
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- 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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- 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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- 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
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- C08G18/348—Hydroxycarboxylic acids
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- 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
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- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
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- C08G18/61—Polysiloxanes
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- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/63—Additives non-macromolecular organic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a high-performance waterborne polyurethane composition and a preparation method thereof, wherein the composition comprises the following components in parts by weight: 90-95 parts of high-performance aqueous polyurethane emulsion; 0.3-0.5 part of nano aluminum oxide; 0.06-0.1 part of grinding aid; 1.4-7.4 parts of a leveling agent; 1-2 parts of a scratch-resistant auxiliary agent; 1-2 parts of an aqueous thickening agent. During preparation, metered nano aluminum oxide and a grinding aid are added into a certain amount of deionized water, fully ground, cooled to normal temperature, sequentially added with metered high-performance aqueous polyurethane emulsion, a leveling agent, an anti-scraping aid and an aqueous thickening agent in a stirring state, fully stirred, filtered by a 300-mesh filter screen, and packaged to obtain the high-performance aqueous polyurethane composition. The composition has good leveling property on a paint panel, and a glue film is tough, transparent, antioxidant and scratch-resistant, and compared with a stealth car coat with a TPU film, the composition has the advantages of simple construction, lower cost and better attaching property to irregular surfaces.
Description
Technical Field
The invention relates to a waterborne polyurethane technology, in particular to a high-performance waterborne polyurethane composition.
Background
The automobile is basically stored in the open air after being taken off line, and bird droppings can seriously affect the automobile paint, so a protective film must be pasted to ensure that the automobile paint is not bad when being sent to a customer; in addition, although the automobile paint surface has high hardness, marks are inevitably generated due to scraping in the using process, the appearance is influenced, and the problems can be solved through polishing or paint repairing, but the maintenance cost and the time cost are increased.
The stealth car clothing product released by 3M company is to coat pressure-sensitive adhesive on a TPU film, then stick the TPU film on the surface of a car body, and solve the problems by means of the elasticity and the scratch resistance of the TPU film. The TPU film is softer and can be applied to a curved surface, but the TPU film is also soft, so that the application difficulty is high; the peeling force between the pressure-sensitive adhesive and the vehicle paint is large, the pressure-sensitive adhesive can not be peeled off almost, once a vehicle needs to be made into a metal plate, the TPU film needs to be removed, the vehicle paint adhered with the TPU film is damaged, and the loss is enlarged.
With the increase of the automobile holding capacity, the development of a paint surface protective film which is convenient to construct, low in price, convenient to maintain and environment-friendly is imperative.
The protection of the paint surface does not mean that the beauty of the paint surface is damaged and the color of the paint surface is changed, so that the paint surface protection film firstly keeps transparent, better gloss and good weather resistance under any temperature condition; materials with good structural symmetry cannot be used in the aspect of material selection so as not to become opaque due to crystallization; the compatibility of each component is good so as not to reduce the transparency of the material due to poor compatibility. Secondly, the protective film must have sufficient strength, and the simplest method for polyurethane materials is to increase the bond energy, such as urea bonds, i.e., amine chain extenders are used instead of alcohol chain extenders. Third, the protective film must resist yellowing, i.e., use aliphatic materials. And fourthly, the protective film has the advantages of scratch resistance, large elastic deformation after the polyurethane material is formed into a film, high strength and good scratch resistance, and further scratch resistance components are introduced, so that the scratch resistance of the polyurethane material can be greatly improved, and the protective film really plays a role in protection. Fifthly, the construction is convenient, the spraying is undoubtedly the most convenient construction method, the appearance is good, but the basic requirements of the spraying are that the spraying nozzle cannot be blocked, a 300-mesh filter screen can be preferably passed, and the proper kinematic viscosity, namely the anti-sagging performance, can be realized. And sixthly, proper stripping force is kept on the painted surface, so that the maintenance is convenient.
It can be seen that providing a paint protective film that meets the above performance requirements is a problem that needs to be addressed in the art.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a paint surface protection film scheme which is convenient to use, stable and reliable in performance and suitable for paint surface protection of automobile delivery and paint surface protection of users in daily use.
In order to achieve the purpose, the invention provides a high-performance waterborne polyurethane composition which comprises the following components in parts by weight:
further, the oligomer polyol of the high-performance polyurethane emulsion is a mixture of polyether polyol polytetrahydrofuran ether glycol (PTMEG) and hydroxyl fluorosilicone oil, wherein the PTMEG is preferably 3-methyl polytetrahydrofuran ether glycol (3-methyl PTMEG) and has a molecular weight of 1400 or 2000.
Further, the hydroxyl fluorosilicone oil of the high-performance polyurethane emulsion is an oligomer of trifluoropropylmethyl siloxane.
Further, the molecular chain segment of the high-performance polyurethane emulsion resin contains a urea bond structure generated by 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane and isocyanate:
wherein R is a high-performance polyurethane emulsion resin main chain.
Furthermore, the molecular linkage of the high-performance polyurethane emulsion resin contains a methoxysilane structure:
wherein R is a high-performance polyurethane emulsion resin main chain.
Further, the nano aluminum oxide is of a y-phase crystal form, and the particle size is 10-20 nm;
further, the grinding aid is a mixture of dimethylethanolamine and alkynediol, and the mass ratio of the dimethylethanolamine to the alkynediol is 9/1.
Further, the leveling agent is an organic silicon leveling agent; the anti-scratch auxiliary agent is an organic silicon anti-scratch auxiliary agent; the aqueous thickener is preferably an associative thickener.
In order to achieve the above object, the present invention provides a method for preparing the above high-performance aqueous polyurethane composition, comprising:
(1) adding metered nano aluminum oxide and grinding aid into a certain amount of deionized water, fully grinding, and cooling to normal temperature;
(2) sequentially adding the high-performance aqueous polyurethane emulsion, the leveling agent, the anti-scraping auxiliary agent and the aqueous thickening agent in a stirring state, and fully stirring;
(3) filtering with a filter screen, and packaging to obtain the high-performance waterborne polyurethane composition.
Further, the preparation process of the high-performance aqueous polyurethane emulsion comprises the following steps:
(11) putting 3-methyl PTMEG and hydroxyl fluorosilicone oil which are measured into a reaction kettle, heating to 110-120 ℃, dehydrating for 2 hours under the vacuum degree of 0.095, adding dry dimethylolbutyric acid (DMBA) which is measured at 100-110 ℃ after pressure relief, and cooling to 70-80 ℃ after the dimethylolbutyric acid is completely dissolved;
(12) adding metered isophorone diisocyanate (IPDI) and antioxidant 1010, reacting for 1h at 83-87 ℃, then adding catalyst XK-651 with the addition of 120ppm of 3-methyl PTMEG, continuing to react for 2h, and cooling to 60-65 ℃;
(13) adding acetone to dilute excessive 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane, maintaining the temperature for reacting for 90min, and cooling to 45-50 ℃;
(14) adding an appropriate amount of acetone for dilution, adding triethylamine with the molar weight of 90% of DMBA for neutralization, and neutralizing for 10 min;
(15) adding metered deionized water at 10-15 ℃, starting an emulsifying machine for emulsification, and emulsifying for 10 min;
(16) adding metered isophorone diamine, N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane and diethylenetriamine diluted by deionized water, and continuing to emulsify for 5 min;
(17) stopping emulsification, slowly heating to 48-52 ℃, stirring for 30min at the temperature, and removing acetone in vacuum;
(18) filtering, discharging and packaging for later use, and taking the mixture as high-performance polyurethane emulsion.
The high-performance polyurethane composition prepared by the invention is safe and environment-friendly, is convenient to construct, and has the performance reaching or exceeding that of TPU film products. The preparation method is simple and easy to implement, the raw materials are easy to obtain, the process controllability is good, the product quality is stable, and the construction difficulty is low.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific examples.
The scheme gives a high-performance waterborne polyurethane composition in consideration of the use environment of the automobile clothes, the composition is prepared by synthesizing a high-performance waterborne polyurethane emulsion, adding a wear-resistant and scratch-resistant additive and other auxiliaries, the composition can be diluted by deionized water, and the VOC emission in the drying process is less than 2%. When the composition is used, the composition is sprayed or brushed on the surface of a paint panel, can be heated or naturally dried to form a film, does not damage the paint panel in the film forming process, and can play a good role in protecting the paint surface of the paint panel. The composition has good leveling property on a paint panel, and a glue film is tough, transparent, antioxidant and scratch-resistant, and compared with a stealth car coat with a TPU film, the composition has the advantages of simple construction, lower cost and better attaching property to irregular surfaces.
Therefore, the high-performance aqueous polyurethane composition provided by the scheme mainly comprises the following components in parts by weight:
when the high-performance polyurethane emulsion in the component is synthesized, the adopted oligomer polyol is a mixture of polyether polyol polytetrahydrofuran ether glycol (PTMEG) and hydroxy fluorosilicone oil, the PTMEG is preferably 3-methyl polytetrahydrofuran ether glycol (3-methyl PTMEG), so that the transparency of the adhesive film cannot be influenced by crystallization at low temperature, and the molecular weight is preferably 1400 or 2000;
the adopted hydroxyl fluorosilicone oil is preferably an oligomer of trifluoropropylmethyl siloxane, and is preferably a product with a hydroxyl value of 95-100 mgKOH/g; the mass ratio of the 3-methyl PTMEG to the hydroxy fluorosilicone oil is 100/5.
Furthermore, the molecular chain segment of the high-performance polyurethane emulsion resin contains a urea bond structure generated by 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane and isocyanate:
wherein R is a high-performance polyurethane emulsion resin main chain.
Furthermore, the molecule connecting segment of the high-performance polyurethane emulsion resin contains a methoxy silane structure:
wherein R is a high-performance polyurethane emulsion resin main chain.
On the basis, the scheme also provides a specific formula with a synergistic effect:
the nano aluminum oxide is preferably of a y-phase crystal form and has a particle size of 10-20 nm.
The grinding aid is a mixture of dimethylethanolamine and alkynediol, the alkynediol is preferably long-chain linear polymer Surfadol 541, the mass ratio of the dimethylethanolamine to the Surfadol 541 is 9/1, and the addition amount of the dimethylethanolamine to the Surfadol 541 is 20% of the mass of aluminum oxide.
The leveling agent is preferably an organic silicon leveling agent, and the preferred grade is BYK 333; the anti-scratch auxiliary agent is preferably an organic silicon anti-scratch auxiliary agent, and is preferably DC 51 with the trade name of Dow Corning; the water-based thickener is preferably an associated thickener, preferably with the trade name of
299。
Aiming at the high-performance waterborne polyurethane composition formed by the components according to the corresponding proportion, the invention also provides a corresponding preparation method. The preparation method comprises the following two steps:
the first step is as follows: synthesizing the high-performance aqueous polyurethane emulsion.
Adding measured 3-methyl PTMEG and hydroxy fluorosilicone oil into a reaction kettle, heating to 110-120 ℃ and dehydrating for 2h under the vacuum degree of 0.095, decompressing, adding measured dry dimethylolbutyric acid (DMBA) at 100-110 ℃, cooling to 70-80 ℃ after the dimethylolbutyric acid is completely dissolved, adding measured isophorone diisocyanate (IPDI) and antioxidant 1010, reacting for 1h at 83-87 ℃, then adding catalyst XK-651 with the addition of 120ppm of 3-methyl PTMEG, continuing to react for 2h, cooling to 60-65 ℃, adding acetone to dilute the measured 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane, reacting for 90min at the temperature, cooling to 45-50 ℃, adding an appropriate amount of acetone for dilution, adding triethylamine with the molar amount of 90% of DMBA for neutralization, neutralizing for 10min, adding measured deionized water at 10-15 ℃, starting an emulsifying machine to emulsify for 10min, adding metered isophorone diamine, N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane and diethylenetriamine diluted by deionized water, continuing to emulsify for 5min, stopping emulsifying, slowly heating to 48-52 ℃, stirring for 30min at the temperature, removing acetone in vacuum, filtering, discharging and packaging for later use, and taking the mixture as high-performance polyurethane emulsion.
The second step is that: preparation of high-performance aqueous polyurethane composition
Adding the measured nano aluminum oxide and the grinding aid into a certain amount of deionized water, fully grinding, cooling to normal temperature, sequentially adding the measured high-performance aqueous polyurethane emulsion, the organic silicon leveling agent, the anti-scraping aid and the aqueous thickening agent under a stirring state, fully stirring, filtering by using a 300-mesh filter screen, and packaging to obtain the high-performance aqueous polyurethane composition.
According to the high-performance aqueous polyurethane composition prepared by the method, the peeling force on the paint surface after the high-performance aqueous polyurethane composition is formed into a film is adjusted by the adding amount of the organic silicon flatting agent, the crystallinity of the polyurethane prepared by the asymmetric 3-methyl PTMEG is obviously lower than that of the polyurethane prepared by the common PTMEG, and the transparency, particularly the transparency at low temperature, is ensured. In the scheme, 3 '-dimethyl-4, 4' -diaminodicyclohexyl methane is adopted as a chain extender, and the prepared polyurethane has excellent mechanical properties.
The hydroxyl fluorosilicone oil is introduced into the high-performance aqueous polyurethane composition, so that the hydrophobicity of the aqueous polyurethane material after film forming is improved and the weather resistance is improved on the basis of ensuring the compatibility. The methoxysilane structure introduced by the scheme can form a coupling structure with inorganic aluminum oxide, so that the dispersibility of the aluminum oxide is improved, and the scratch resistance of the composition after film formation is improved.
Therefore, the high-performance waterborne polyurethane composition is sprayed on a paint surface, has good leveling property and no sagging, the peeling force of the dried film on the paint surface is 400-1000 g/25mm adjustable, the breaking strength is more than 30Mpa, the elongation is more than 600%, steel wool is loaded with 1kg load and wiped for 10 times without scratching, the transparency is more than 90%, the haze is less than 5%, and the surface tension is less than 50 dyne.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards. If there is no corresponding national standard, it is carried out according to the usual international standards, to the conventional conditions or to the conditions recommended by the manufacturer. Unless otherwise indicated, all parts are parts by weight, all percentages are percentages by weight, and the polymer molecular weight is the number average molecular weight.
Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
1. High-performance aqueous polyurethane emulsion
Example 1.1:
putting 200Kg of 3-methyl PTMEG with molecular weight of 2000 and 10Kg of hydroxy fluorosilicone oil into a reaction kettle, dehydrating for 2 hours at 110-120 ℃ under the vacuum degree of 0.095, after pressure relief, adding 14.8Kg of dry DMBA at 100-110 ℃, cooling to 70-80 ℃ after DMPA is completely dissolved, adding 79Kg of IPDI and 200g of antioxidant 1010, reacting for 1 hour at 83-87 ℃, then adding 24g of catalyst XK-651, continuing to react for 2 hours, cooling to 60-65 ℃, adding acetone to dilute 11.9Kg of 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane, maintaining the temperature to react for 90 minutes, cooling to 45-50 ℃, adding an appropriate amount of acetone to dilute, adding 9.09Kg of triethylamine to neutralize, neutralizing for 10 minutes, adding 443Kg of 10-15 Kg of deionized water, starting an emulsifying machine to emulsify for 10 minutes, adding 9.7Kg of isophorone diamine diluted by 50-15 ℃ of deionized water, 2.95Kg of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 0.5Kg of diethylenetriamine, continuously emulsifying for 5min, stopping emulsifying, slowly heating to 48-52 ℃, stirring for 30min at the temperature, removing acetone in vacuum to prepare a light blue semitransparent emulsion, filtering, discharging and packaging for later use, wherein the emulsion is used as a high-performance waterborne polyurethane emulsion.
Example 1.2:
adding 210Kg of 3-methyl PTMEG with the molecular weight of 1400 and 10.5Kg of hydroxy fluorosilicone oil into a reaction kettle, heating to 110-120 ℃, dehydrating for 2h under the vacuum degree of 0.095, decompressing, adding 22.2Kg of dry DMBA at 100-110 ℃, cooling to 70-80 ℃, adding 103Kg of IPDI and 210g of antioxidant 1010 when the DMPA is completely dissolved, reacting for 1h at 83-87 ℃, then adding 25.2g of catalyst XK-651, continuing to react for 2h, cooling to 60-65 ℃, adding acetone to dilute 12.4Kg of 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane, reacting for 90min at the temperature, cooling to 45-50 ℃, adding an appropriate amount of acetone to dilute, adding 13.6Kg of triethylamine to neutralize for 10min, adding 464Kg of deionized water, starting an emulsifying machine to emulsify for 10min, adding 10.3Kg of metered isophorone diamine diluted by 60Kg of deionized water at 10-15 ℃, adding 10.3Kg of metered isophorone diamine, 3.1Kg of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 0.6Kg of diethylenetriamine, continuously emulsifying for 5min, stopping emulsifying, slowly heating to 48-52 ℃, stirring for 30min at the temperature, removing acetone in vacuum to prepare a light blue semitransparent emulsion, filtering, discharging and packaging for later use, wherein the emulsion is used as a high-performance waterborne polyurethane emulsion.
2. High performance polyurethane compositions
Example 2.1
0.5Kg of nano aluminum oxide and 0.1Kg of grinding aid are added into 10.0Kg of deionized water, fully ground, cooled to normal temperature, and sequentially added with 90.0Kg of the high-performance aqueous polyurethane emulsion prepared in example 1.1, BYK-3337.4 Kg, DC-511.0 Kg,
2991.0 Kg, fully stirring, filtering by a 300-mesh filter screen, and packaging to obtain the high-performance aqueous polyurethane composition.
The composition is sprayed on a paint surface, has good leveling property and no sagging, and after drying and film forming, the stripping force on the paint surface is 450g/25mm, the breaking strength is greater than 32Mpa, the elongation is 750 percent, steel wool is loaded with 1kg load and wiped for 10 times without scratching, the transparency is 91 percent, the haze is 4 percent, and the surface tension is 43 dyne.
Example 2.2
0.5Kg of nano aluminum oxide and 0.1Kg of grinding aid are added into 10.0Kg of deionized water, fully ground, cooled to normal temperature, and then sequentially added with 95.0Kg of the high-performance aqueous polyurethane emulsion prepared in example 1.1, BYK-3331.4 Kg, DC-511.0 Kg,
2992.0 Kg, fully stirring, filtering by a 300-mesh filter screen, and packaging to obtain the high-performance aqueous polyurethane composition.
The composition is sprayed on a paint surface, has good leveling property and no sagging, and after drying and film forming, the stripping force on the paint surface is 1000g/25mm, the breaking strength is more than 34Mpa, the elongation is 830%, steel wool is loaded with 1kg load and wiped for 10 times without scratching, the transparency is 91.4%, the haze is 3.7%, and the surface tension is 45 dyne.
Example 2.3
0.3Kg of nano aluminum oxide and 0.06Kg of grinding aid are added into 6.0Kg of deionized water, fully ground, cooled to normal temperature, and sequentially added with 90.0Kg of the high-performance aqueous polyurethane emulsion prepared in the example 1.2, BYK-3336.64 Kg, DC-512.0 Kg, BYK-3336.64 Kg, BYK-512.0 Kg, BYK-B-K,
2991.0 Kg, fully stirring, filtering by a 300-mesh filter screen, and packaging to obtain the high-performance aqueous polyurethane composition.
The composition is sprayed on a paint surface, has good leveling property and no sagging, and after drying and film forming, the peeling force on the paint surface is 650g/25mm, the breaking strength is more than 37Mpa, the elongation is 610%, steel wool is loaded with 1kg load and wiped for 10 times without scratching, the transparency is 91%, the haze is 3.9%, and the surface tension is 47 dyne.
Example 2.4
0.4Kg of nano aluminum oxide and 0.08Kg of grinding aid are added into 8.0Kg of deionized water, fully ground, cooled to normal temperature, and then sequentially added with 95.0Kg of the high-performance aqueous polyurethane emulsion prepared in the example 1.2, BYK-3331.52 Kg, DC-512.0 Kg, BYK-3331.52 Kg, BYK-512.0 Kg,
2991.0 Kg, fully stirring, filtering by a 300-mesh filter screen, and packaging to obtain the high-performance aqueous polyurethane composition.
The composition is sprayed on a paint surface, has good leveling property and no sagging, and after drying and film forming, the stripping force on the paint surface is 850g/25mm, the breaking strength is more than 38Mpa, the elongation is 560 percent, steel wool is loaded with 1kg load and wiped for 10 times without scratching, the transparency is 90.8 percent, the haze is 4.1 percent, and the surface tension is 48 dyne.
Example 2.5
0.5Kg of nano-alumina and 0.1Kg of grinding aid are added into 10.0Kg of deionized water, fully ground and cooledAfter cooling to normal temperature, 90.0Kg of the high performance aqueous polyurethane emulsion prepared in example 1.2, BYK-3337.4 Kg, DC-511.0 Kg, were added in sequence under stirring,2991.0 Kg, fully stirring, filtering by a 300-mesh filter screen, and packaging to obtain the high-performance aqueous polyurethane composition.
The composition is sprayed on a paint surface, has good leveling property and no sagging, and after drying and film forming, the stripping force on the paint surface is 400g/25mm, the breaking strength is more than 39Mpa, the elongation is 590%, steel wool is loaded with 1kg load and wiped for 10 times without scratching, the transparency is 91.5%, the haze is 3.7%, and the surface tension is 44 dyne.
According to the embodiment, the composition scheme provided by the invention has the advantages that the leveling property on the paint panel is good, the glue film is tough and transparent, and is antioxidant and scratch-resistant, and compared with the invisible car cover with a TPU film, the composition scheme is simple in construction, lower in cost and better in attaching property to irregular surfaces.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The high-performance waterborne polyurethane composition is characterized by comprising the following components in parts by weight:
2. the aqueous polyurethane composition of claim 1, wherein the high performance polyurethane emulsion comprises an oligomer polyol, and the oligomer polyol is a polyether polyol comprising a mixture of polytetrahydrofuran ether glycol and hydroxy fluorosilicone oil.
3. The aqueous polyurethane composition according to claim 1, wherein the high-performance polyurethane emulsion contains hydroxyfluorosilicone oil, and the hydroxyfluorosilicone oil is an oligomer of trifluoropropylmethylsiloxane.
4. The aqueous polyurethane composition of claim 1, wherein the molecular chain segment of the high-performance polyurethane emulsion resin contains a urea bond structure formed by 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane and isocyanate:
wherein R is a high-performance polyurethane emulsion resin main chain.
5. The aqueous polyurethane composition of claim 1, wherein the molecular chain segment of the high-performance polyurethane emulsion resin contains a methoxysilane structure:
wherein R is a high-performance polyurethane emulsion resin main chain.
6. The waterborne polyurethane composition of claim 1, wherein the nano aluminum oxide is in a y-phase crystal form and has a particle size of 10-20 nm.
7. The aqueous polyurethane composition according to claim 1, wherein the grinding aid is a mixture of dimethylethanolamine and acetylenic diol in a mass ratio of 9/1.
8. The aqueous polyurethane composition of claim 1, wherein the leveling agent is an organosilicon leveling agent; the anti-scratch auxiliary agent is an organic silicon anti-scratch auxiliary agent; the aqueous thickener is preferably an associative thickener.
9. A method for preparing the high-performance aqueous polyurethane composition according to any one of claims 1 to 8, comprising:
(1) adding metered nano aluminum oxide and grinding aid into a certain amount of deionized water, fully grinding, and cooling to normal temperature;
(2) sequentially adding the high-performance aqueous polyurethane emulsion, the leveling agent, the anti-scraping auxiliary agent and the aqueous thickening agent in a stirring state, and fully stirring;
(3) filtering with a filter screen, and packaging to obtain the high-performance waterborne polyurethane composition.
10. The preparation method of claim 9, wherein the high-performance aqueous polyurethane emulsion is prepared by the following steps:
(11) putting 3-methyl PTMEG and hydroxyl fluorosilicone oil which are measured into a reaction kettle, heating to 110-120 ℃, dehydrating for 2 hours under the vacuum degree of 0.095, adding dry dimethylolbutyric acid (DMBA) which is measured at 100-110 ℃ after pressure relief, and cooling to 70-80 ℃ after the dimethylolbutyric acid is completely dissolved;
(12) adding metered isophorone diisocyanate (IPDI) and antioxidant 1010, reacting for 1h at 83-87 ℃, then adding catalyst XK-651 with the addition of 120ppm of 3-methyl PTMEG, continuing to react for 2h, and cooling to 60-65 ℃;
(13) adding acetone to dilute excessive 3,3 '-dimethyl-4, 4' -diaminodicyclohexyl methane, maintaining the temperature for reacting for 90min, and cooling to 45-50 ℃;
(14) adding an appropriate amount of acetone for dilution, adding triethylamine with the molar weight of 90% of DMBA for neutralization, and neutralizing for 10 min;
(15) adding metered deionized water at 10-15 ℃, starting an emulsifying machine for emulsification, and emulsifying for 10 min;
(16) adding metered isophorone diamine, N- (beta-aminoethyl) -gamma-aminopropyl methyl dimethoxy silane and diethylenetriamine diluted by deionized water, and continuing to emulsify for 5 min;
(17) stopping emulsification, slowly heating to 48-52 ℃, stirring for 30min at the temperature, and removing acetone in vacuum;
(18) filtering, discharging and packaging for later use, and taking the mixture as high-performance polyurethane emulsion.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181605A (en) * | 2022-01-17 | 2022-03-15 | 雨中情防水技术集团股份有限公司 | Single-component water-based polyurethane waterproof coating and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121936A (en) * | 1994-10-26 | 1996-05-08 | 普涂创新有限公司 | Procoat composition for coating and protection of surfaces |
| WO2005116100A1 (en) * | 2004-05-20 | 2005-12-08 | Noveon Ip Holdings Corp. | A hybrid polymer composition, and article therefrom |
| WO2006083343A1 (en) * | 2005-02-01 | 2006-08-10 | Henkel Corporation | Vinyl ether/acrylate block resins, compositions and methods of making same |
| CN102702947A (en) * | 2012-06-18 | 2012-10-03 | 中国石油大学(华东) | Organosilicone-nano compound modified polyurea corrosion-resisting coating for mechanical recovery well environment and preparation method for organosilicone-nano compound modified polyurea corrosion-resisting coating |
| CN104312326A (en) * | 2014-09-28 | 2015-01-28 | 上海维凯光电新材料有限公司 | High-hardness high-rub-resistance die-pressing transfer paint composition applicable to PETG (polyethylene terephthalate glycol) cards |
| CN107400451A (en) * | 2016-05-19 | 2017-11-28 | 河南省超贝工程设备有限公司 | A kind of water-soluble nano transparent wear-resistant coating |
| CN108250969A (en) * | 2018-01-26 | 2018-07-06 | 温州大学 | A kind of fluorescent paint of super homogenizing and preparation method thereof |
-
2019
- 2019-08-14 CN CN201910747100.3A patent/CN110643273A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121936A (en) * | 1994-10-26 | 1996-05-08 | 普涂创新有限公司 | Procoat composition for coating and protection of surfaces |
| WO2005116100A1 (en) * | 2004-05-20 | 2005-12-08 | Noveon Ip Holdings Corp. | A hybrid polymer composition, and article therefrom |
| WO2006083343A1 (en) * | 2005-02-01 | 2006-08-10 | Henkel Corporation | Vinyl ether/acrylate block resins, compositions and methods of making same |
| CN102702947A (en) * | 2012-06-18 | 2012-10-03 | 中国石油大学(华东) | Organosilicone-nano compound modified polyurea corrosion-resisting coating for mechanical recovery well environment and preparation method for organosilicone-nano compound modified polyurea corrosion-resisting coating |
| CN104312326A (en) * | 2014-09-28 | 2015-01-28 | 上海维凯光电新材料有限公司 | High-hardness high-rub-resistance die-pressing transfer paint composition applicable to PETG (polyethylene terephthalate glycol) cards |
| CN107400451A (en) * | 2016-05-19 | 2017-11-28 | 河南省超贝工程设备有限公司 | A kind of water-soluble nano transparent wear-resistant coating |
| CN108250969A (en) * | 2018-01-26 | 2018-07-06 | 温州大学 | A kind of fluorescent paint of super homogenizing and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181605A (en) * | 2022-01-17 | 2022-03-15 | 雨中情防水技术集团股份有限公司 | Single-component water-based polyurethane waterproof coating and preparation method thereof |
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