CN108752563B - Waterborne hyperbranched structure modified polyurethane polymer, preparation method thereof and self-repairing diffuse reflection coating composition - Google Patents
Waterborne hyperbranched structure modified polyurethane polymer, preparation method thereof and self-repairing diffuse reflection coating composition Download PDFInfo
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention discloses a waterborne hyperbranched structure modified polyurethane polymer, a preparation method thereof and a self-repairing diffuse reflection coating composition, wherein the preparation of the polymer comprises the steps of decompressing and vacuumizing aliphatic polyether diol and aliphatic polyester diol at 90-150 ℃, cooling to 60-90 ℃, and adding a catalyst and aliphatic diisocyanate; adding a hydrophilic chain extender to react for 1-3 hours; adding a hydroxyl-terminated hyperbranched polymer, and reacting for 1-2 hours; adding a hydrophilic chain extender, and reacting for 1-2 hours; cooling to normal temperature, and adding a neutralizing agent to adjust the pH value to 7-9; adding a sulfonate hydrophilic chain extender and deionized water to react for 0.5-1 hour to prepare the waterborne hyperbranched structure modified polyurethane polymer. The self-repairing diffuse reflection coating composition comprises the polyurethane polymer, and has the advantages of self-repairing performance, diffuse reflection performance, good transparency, hardness and flexibility.
Description
Technical Field
The invention relates to the field of polyurethane coatings, in particular to a waterborne hyperbranched structure modified polyurethane polymer and a preparation method thereof, and also relates to a self-repairing diffuse reflection coating composition.
Background
With the upgrading of the social industry level and the people consumption level, the requirements of consumers on the appearance, the touch and the experience comfort of daily supplies and industrial supplies are more and more strict. Many premium products are beginning to attract the attention of the public with an aesthetically pleasing appearance and feel. The use of anti-glare coatings has also come into play. The novel automobile interior decoration film has attractive appearance and comfortable physiological touch of human body, gradually occupies a place in industries such as automobile interior decoration, electronic products and the like, and is gradually favored more and more.
Anti-glare materials can be divided into two types: a particle diffusion type and a surface relief type. The particle diffusion type anti-glare material includes a light diffusion layer composed of a binder resin and Light Diffusion Particles (LDP), and light is refracted when passing through an interface between the resin and the particles. At present, the slow reflection type coating is mainly based on the addition of inorganic filler, namely, a certain amount of matting aid, mainly silicon dioxide or aluminum oxide with various particle sizes, is added into a coating system. CN101235244A describes a method for preparing silica particles by inorganic-organic composite method, which is then used together with multifunctional acrylate and initiator to prepare an anti-glare coating, which is then coated to obtain a hard coating layer, and the coating layer has good wear resistance, aging resistance and dirt resistance. In addition, the anti-glare material is required to have high light transmittance and light diffusion property, but the light diffusion effect is increased and is accompanied by the decrease of light transmittance, which is a great challenge for preparing a film having both high light transmittance and light diffusion property. However, the added inorganic filler and the organic system of the coating are difficult to be perfectly mutually soluble, and are inevitably separated and other unstable states after being placed for a long time.
The polyurethane has good light transmission and weather resistance, and the polyurethane synthesized by using the aliphatic diisocyanate has excellent yellowing resistance and ensures high light transmission, thus being an ideal optical coating. The Chinese patent application 2014105797477 discloses a method for synthesizing an anti-glare polyurethane coating, which is simple and low in cost, and the synthesized polyurethane coating has good stability and excellent anti-glare performance, but has poor transparency. Chinese patent application 201710037727.0 discloses a self-repairing anti-glare waterborne polyurethane coating which has good transparency, but because the coating is linear polyurethane prepared from dihydric alcohol and diisocyanate, a compact space network structure cannot be formed, and the coating has good flexibility but insufficient hardness.
Therefore, how to prepare a self-repairable water-based coating with diffuse reflection performance, good transparency and both hardness and flexibility becomes a great challenge.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a waterborne hyperbranched structure modified polymer and a self-repairing diffuse reflection polyurethane coating prepared from the waterborne hyperbranched structure modified polymer. The hyperbranched structure group participates in the reaction of the polyurethane polymer to prepare the polyurethane polymer with a multi-branched tree structure, and the polymer presents a special space three-dimensional network form, has good flexibility and higher hardness; the hyperbranched polymer is of a space core structure, diffuse reflection is generated by the microscopic crystallinity of the hyperbranched polymer and polyether groups, polyester groups and polyurethane groups in the sub-chain segments and the compatibility of the micro-chain segments, and meanwhile, the single-component system ensures good high transmission of the coating. The sulfonate group participates in chain extension, reversible ionic interaction force is generated in the polymer, and when micro cracks appear in molecules, self-repairing can be achieved through reversible ionic bond breaking recombination without adding a repairing agent.
The preparation method of the waterborne hyperbranched structure modified polyurethane polymer comprises the following steps:
(1) weighing a certain amount of aliphatic polyether glycol and aliphatic polyester glycol, decompressing, vacuumizing and dehydrating at 90-150 ℃, cooling to 60-90 ℃, introducing nitrogen, adding a certain amount of catalyst and aliphatic diisocyanate, and reacting for 1-5 hours;
(2) adding a certain amount of hydrophilic chain extender into the product obtained in the step (1), wherein the molar ratio of the added hydrophilic chain extender to the aliphatic diisocyanate used in the step (1) is 0.05-0.3: 1, and reacting for 1-3 hours;
(3) adding a certain amount of hydroxyl-terminated hyperbranched polymer into the product obtained in the step (2), and reacting for 1-2 hours; the ratio of the added hydroxyl-terminated hyperbranched polymer to the total mass of the aliphatic polyether diol, the aliphatic polyester diol and the aliphatic diisocyanate in the step (1) is 0.01-0.2: 1;
(4) continuously adding a certain amount of hydrophilic chain extender, wherein the molar ratio of the added amount to the chain extender in the step (2) is 0.5-1: 1, and reacting for 1-2 hours;
(5) cooling to normal temperature, and adding a neutralizing agent to adjust the pH value of the system to 7-9;
(6) adding a sulfonate hydrophilic chain extender and deionized water into a reaction kettle at one time, and reacting for 0.5-1 hour; the ratio of the deionized water for preparing the aqueous hyperbranched structure modified polyurethane coating to the total solid mass of the hyperbranched structure modified polyurethane polymer is 1: 4-1.
In the step (1), the dosage of the catalyst is 0.01-0.5% of the total mass of the dihydric alcohol, and the catalyst is one or more of triethylamine, triethylene diamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, tetraisopropyl titanate and tetraisobutyl titanate.
In addition, in the step (1), the molar ratio of the aliphatic polyether diol to the aliphatic polyester diol is 1-10: 1; the total molar ratio of the aliphatic diisocyanate to the two diols is 2-5: 1.
In addition, the aliphatic polyether glycol is one or more of polytetramethylene glycol and polypropylene glycol with the molecular weight of 300-6000 g/mol; the aliphatic polyester dihydric alcohol is one or more of polybutylene adipate dihydric alcohol, polycaprolactone dihydric alcohol, polyethylene glycol adipate dihydric alcohol and polycarbonate dihydric alcohol with the molecular weight of 300-6000 g/mol; the aliphatic diisocyanate is one or more of hexamethylene diisocyanate and isophorone diisocyanate.
In addition, the hydrophilic chain extender in the step (2) and the step (4) is one or more of dimethylol propionic acid and diaminebenzoic acid of which the hydrophilic group is carboxyl, or ethylenediamine, di-o-chloro diphenylamine and N-dihydroxy (diisopropyl) aniline of which the hydrophilic group is amino.
In addition, the hydroxyl-terminated hyperbranched polymer in the step (3) is one or more of hydroxyl-terminated hyperbranched polyether and hydroxyl-terminated hyperbranched polyester with the molecular weight of 2000-100000 g/mol and the terminal hydroxyl group content of 10-30.
In addition, the molar ratio of the amount of the neutralizing agent in the step (5) to the chain extender in the step (2) is 1-2: 1; the neutralizer is one or more of triethanolamine, triethylamine, amino acid and terephthalic acid.
In addition, the sulfonate hydrophilic chain extender in the step (6) is one or more of ethylenediamine ethyl sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and diisooctyl succinate sodium sulfonate, wherein the hydrophilic group of the sulfonate hydrophilic chain extender is a sulfonic group, and the molar ratio of the sulfonate hydrophilic chain extender to the neutralizer in the step (5) is 0.1-0.3: 1.
The invention also provides the waterborne hyperbranched structure modified polyurethane polymer prepared by the preparation method.
The invention also provides a self-repairing diffuse reflection coating composition, wherein the solid content of the coating composition is 20-50%, and the average particle size of the emulsion is 110-500 nm; the coating composition comprises the following components in parts by weight:
the hyperbranched structure modified polyurethane polymer aqueous solution is prepared by mixing deionized water and a hyperbranched structure modified polyurethane polymer, wherein the mass ratio of the deionized water to the hyperbranched structure modified polyurethane polymer is 1: 4-1;
wherein the defoaming agent is one or more of BYK-370 and GSK-716; the thickener is Gel LW 44; the leveling agent is one or more of BYK-333 and Tego-482.
Aiming at the defects of the prior art, the invention provides a waterborne hyperbranched structure modified polyurethane coating which has good diffusion performance, high transmission performance, self-repairing function and flexibility and hardness and overcomes the defect of low coating light transmittance under the condition of high light diffusion effect from the aspects of molecular synthesis and structural design, and the preparation method thereof.
In general, when the diffusion property is higher, the transmission property is reduced because the hiding power of the coating film means that strong absorption, scattering and reflection are generated to the light entering into the film, and the hiding power is increased with the more scattered light, that is, the transmission of the light is reduced. In addition, the transmission performance is also related to the ratio of the refractive indices of the filler and the base material. When the coating structure contains polyester, polyether chain segment and polyurethane chain segment with different crystallization capacities, certain light transmittance can be kept when the coating film obtains high diffusion performance while fillers are avoided.
The waterborne hyperbranched structure modified polyurethane coating which is suitable for transparent surfaces and has flexibility and hardness can achieve an excellent diffuse reflection effect without additional auxiliaries or surface treatment. The sulfonate group participates in chain extension, reversible ionic interaction force is generated in the polymer, and self-repairing can be realized through reversible ionic bond breaking recombination without adding a repairing agent when a molecule has a micro crack.
Compared with the prior art, the invention has the following advantages:
(1) the waterborne polyurethane coating is green and environment-friendly in process, free of pollution and VOC emission problem, and meets the low-carbon environment-friendly concept. And the viscosity of the coating system can be adjusted, and the difficulty of the coating process is greatly reduced.
(2) The system has no addition of inorganic filler, is very uniform and stable in the processes of storage and use, and has no problems of layering, precipitation and phase separation.
(3) The diffuse reflection effect is realized by depending on the differences of crystallization properties and microcosmic compatibility of polyester groups, polyether groups and polyurethane groups in a molecular chain, and the diffuse reflection effect is very stable in the using process and cannot be changed along with the prolonging of the using time.
(4) The hyperbranched structure group participates in the reaction of the polyurethane polymer to prepare the polyurethane polymer with a multi-branched tree structure, and the polymer presents a special space three-dimensional network form, has good flexibility and higher hardness; the hyperbranched polymer is of a space core structure, diffuse reflection is generated by the microscopic crystallinity of the hyperbranched polymer and polyether groups, polyester groups and polyurethane groups in the sub-chain segments and the compatibility of the micro-chain segments, and meanwhile, the single-component system ensures good high transmission of the coating.
The waterborne hyperbranched structure-modified polyurethane self-repairing diffuse reflection coating can be widely applied to the decoration industries of automobile interiors, automobile finish, electronic products and the like.
Detailed Description
The description is to be regarded as illustrative and explanatory only and should not be taken as limiting the scope of the invention in any way.
In order to judge the diffuse reflection effect, the hardness and the flexibility of the prepared waterborne hyperbranched structure modified polyurethane self-repairing diffuse reflection coating, the performance of the prepared coating is tested, and the glossiness is measured by a glossmeter according to ISO/2813 to obtain 60-degree glossiness. The light transmittance of the coating is tested by adopting an ultraviolet visible light photometer model Carry60 of Agilent company, the reference sample is a glass slide, the mode is T%, the scanning range is 300-700 nm, and the scanning speed is 600 nm/min. The technical indexes of diffuse reflection are as follows: according to the anti-glare index of paper made by Bachuan of Japan K.K., when the 60-degree gloss is 20-50 and the light transmittance is more than or equal to 87%, the ideal diffuse reflection effect can be achieved.
The hardness of the coating is tested by pencil hardness, and the coating is not marked or damaged after being folded at 180 degrees for 30 times.
Example 1
200g (0.1mol) of aliphatic polyether diol with molecular weight of 2000g/mol and 200g (0.1mol) of aliphatic polyester diol with molecular weight of 2000g/mol are weighed, vacuum-pumping and dehydration are carried out at 100 ℃, the temperature is reduced to 60 ℃, nitrogen is introduced, 0.1g of catalyst dibutyltin dilaurate and 88.7g (0.4mol) of isophorone diisocyanate are added, and the reaction is carried out for 3 hours. 2.7g (0.02mol) of dimethylolpropionic acid were added and reacted for 3 hours. 4.9g of a hydroxyl-terminated hyperbranched polyester having a functionality of 15 and a molecular weight of 5000g/mol (containing 0.015mol of hydroxyl groups) were added and reacted for 2 hours. 1.4g (0.01mol) of dimethylolpropionic acid were added thereto and the reaction was continued for 3 hours. The temperature is reduced to normal temperature, 2g (0.02mol) of neutralizer triethylamine is added, and the mixture is stirred for 10 minutes. And adding 0.8g (0.002mol) of diisooctyl succinate sodium sulfonate to prepare the hyperbranched structure modified polyurethane polymer.
500.5g of deionized water were added, stirred for 0.5 hour and filtered. And adding 20g of defoaming agent BYK-370, 30g of thickener Gel LW44 and 10g of flatting agent BYK-333 to prepare the aqueous hyperbranched structure modified polyurethane coating.
20g of coating is uniformly coated on the surface of the PET film subjected to corona treatment, and the PET film is heated at 100 ℃ for 30 seconds to dry water, wherein the thickness of the coating is 25 mu m. The glossiness of the pencil is 50, the light transmittance is 95%, the pencil hardness is 3H, and no crease exists after 30 times of folding at 180 degrees.
Example 2
200g (0.1mol) of aliphatic polyether diol with molecular weight of 2000g/mol and 100g (0.05mol) of aliphatic polyester diol with molecular weight of 2000g/mol are weighed, vacuum-pumping and dehydration are carried out at 100 ℃, the temperature is reduced to 60 ℃, nitrogen is introduced, 0.1g of catalyst dibutyltin dilaurate and 166.3g (0.75mol) of isophorone diisocyanate are added, and the reaction is carried out for 5 hours. 30.2g (0.225mol) of dimethylolpropionic acid were added and reacted for 3 hours. 99.3g of a hydroxyl-terminated hyperbranched polyester having a functionality of 15 and a molecular weight of 5000g/mol (containing 0.3mol of hydroxyl groups) were added and reacted for 2 hours. 30.2g (0.225mol) of dimethylolpropionic acid were added further and reacted for 3 hours. The temperature is reduced to normal temperature, 45.5g (0.45mol) of neutralizer triethylamine is added, and the mixture is stirred for 10 minutes. And adding 52.8g (0.135mol) of diisooctyl succinate sodium sulfonate to prepare the hyperbranched structure modified polyurethane polymer.
724.3g of deionized water were added, stirred for 0.5 hour and filtered. And 2.9g of defoaming agent BYK-370, 2.9g of thickener Gel LW44 and 1.4g of flatting agent BYK-333 are added to prepare the aqueous hyperbranched structure-modified polyurethane coating.
20g of coating is uniformly coated on the surface of the PET film subjected to corona treatment, and the PET film is heated at 100 ℃ for 30 seconds to dry water, wherein the thickness of the coating is 25 mu m. The glossiness of the pencil is 45, the light transmittance is 95%, the pencil hardness is 3H, and no crease exists after the pencil is folded for 30 times at 180 degrees.
Through comparison between the example 1 and the example 2, it is found that when the content of the polyester diol is large relative to that of the polyether diol in the hyperbranched structure-modified polyurethane waterborne coating, the gloss of the coating is lower, the diffuse reflection effect is better, and the differences of the light transmittance, the hardness and the flexibility are not large.
Example 3
200g (0.1mol) of aliphatic polyether diol with molecular weight of 2000g/mol and 20g (0.01mol) of aliphatic polyester diol with molecular weight of 2000g/mol are weighed, vacuum-pumped and dehydrated at 100 ℃, cooled to 70 ℃, nitrogen is introduced, 0.1g of catalyst dibutyltin dilaurate and 73.2g (0.33mol) of hexamethylene diisocyanate are added, and the reaction is carried out for 3 hours. 8.9g (0.066mol) of dimethylolpropionic acid were added thereto and reacted for 3 hours. 30.2g of a hydroxyl-terminated hyperbranched polyester having a functionality of 15 and a molecular weight of 50000g/mol (containing 0.009mol of hydroxyl groups) were added and reacted for 2 hours. 5.4g (0.04mol) of dimethylolpropionic acid are added further and reacted for 3 hours. The temperature is reduced to normal temperature, 10g (0.099mol) of neutralizing agent triethylamine is added, and the mixture is stirred for 10 minutes. And 7.8g (0.02mol) of diisooctyl succinate sodium sulfonate is added to prepare the hyperbranched structure modified polyurethane polymer.
1422g of deionized water was added, stirred for 0.5 hour and filtered. And adding 17g of defoaming agent BYK-370, 17g of thickener Gel LW44 and 8g of flatting agent BYK-333 to prepare the aqueous hyperbranched structure modified polyurethane coating.
20g of coating is uniformly coated on the surface of the PET film subjected to corona treatment, and the PET film is heated at 100 ℃ for 30 seconds to dry water, wherein the thickness of the coating is 25 mu m. The glossiness of the pencil is 40, the light transmittance is 92%, the pencil hardness is 3H, and no crease exists after 30 times of folding at 180 degrees.
Through comparison between example 1 and example 3, it is found that when the molecular weight of the hyperbranched polymer in the hyperbranched structure-modified polyurethane aqueous coating is increased, the glossiness of the coating is reduced, the diffuse reflection effect is better, but the light transmittance is slightly reduced.
Example 4
200g (0.1mol) of aliphatic polyether diol with molecular weight of 2000g/mol and 200g (0.1mol) of aliphatic polyester diol with molecular weight of 2000g/mol are weighed, vacuum-pumping and dehydration are carried out at 90 ℃, the temperature is reduced to 60 ℃, nitrogen is introduced, 0.04g of catalyst stannous octoate and 133g (0.6mol) of hexamethylene diisocyanate are added, and the reaction is carried out for 3 hours. 13.41g (0.1mol) of dimethylolpropionic acid were added and reacted for 3 hours. 50g of a 20 functionality hydroxyl-terminated hyperbranched polyester having a molecular weight of 50000g/mol (containing 0.02mol of hydroxyl groups) were added and reacted for 2 hours. 13.41g (0.1mol) of dimethylolpropionic acid were added further and reacted for 3 hours. The temperature is reduced to normal temperature, 20.24g (0.2mol) of neutralizer triethylamine is added, and the mixture is stirred for 10 minutes. Adding 15.64g (0.04mol) of sodium diisooctyl succinate sulfonate to prepare the hyperbranched structure modified polyurethane polymer.
1937g of deionized water was added, stirred for 0.5 hour and filtered. 5g of defoaming agent BYK-370, 5g of thickener Gel LW44 and 3g of flatting agent BYK-333 are added to prepare the waterborne hyperbranched structure modified polyurethane coating.
20g of coating is uniformly coated on the surface of the PET film subjected to corona treatment, and the PET film is heated at 100 ℃ for 30 seconds to dry water, wherein the thickness of the coating is 25 mu m. The glossiness of the pencil is 38, the light transmittance is 92%, the pencil hardness is 4H, and no crease exists after 30 times of folding at 180 degrees.
Through comparison between the example 3 and the example 4, when the hyperbranched polymer functionality in the hyperbranched structure-modified polyurethane water-based paint is increased, the glossiness of the coating is reduced, the diffuse reflection effect is better, the light transmittance is unchanged, and the hardness is better.
Example 5
200g (0.1mol) of aliphatic polyether diol with molecular weight of 2000g/mol and 100g (0.05mol) of aliphatic polyester diol with molecular weight of 2000g/mol are weighed, vacuum-pumped and dehydrated at 150 ℃, cooled to 90 ℃, introduced with nitrogen, added with 1.5g of catalyst lead octoate and 133g (0.6mol) of isophorone diisocyanate and reacted for 5 hours. 13.41g (0.1mol) of dimethylolpropionic acid were added and reacted for 3 hours. 50g of a 20 functionality hydroxyl-terminated hyperbranched polyester having a molecular weight of 50000g/mol (containing 0.02mol of hydroxyl groups) were added and reacted for 2 hours. 13.41g (0.1mol) of dimethylolpropionic acid were added further and reacted for 3 hours. The temperature is reduced to normal temperature, 20.24g (0.2mol) of neutralizer triethylamine is added, and the mixture is stirred for 10 minutes. Adding 15.64g (0.04mol) of sodium diisooctyl succinate sulfonate to prepare the hyperbranched structure modified polyurethane polymer.
2182g of deionized water was added, stirred for 0.5 hour and filtered. 5.5g of defoaming agent BYK-370, 15g of thickener Gel LW44 and 8g of flatting agent BYK-333 are added to prepare the waterborne hyperbranched structure modified polyurethane coating.
20g of coating is uniformly coated on the surface of the PET film subjected to corona treatment, and the PET film is heated at 100 ℃ for 30 seconds to dry water, wherein the thickness of the coating is 25 mu m. The glossiness of the pencil is 30, the light transmittance is 90%, the pencil hardness is 5H, and no crease exists after the pencil is folded at 180 degrees for 30 times.
Through comparison between the example 4 and the example 5, when the content of the hyperbranched polymer in the hyperbranched structure-modified polyurethane water-based paint is increased, the glossiness of the coating is reduced, the diffuse reflection effect is better, the light transmittance is slightly reduced, and the hardness is better.
Example 6
200g (0.1mol) of aliphatic polyether diol with molecular weight of 2000g/mol and 20g (0.01mol) of aliphatic polyester diol with molecular weight of 2000g/mol are weighed, vacuum-pumping and dehydration are carried out at 100 ℃, the temperature is reduced to 60 ℃, nitrogen is introduced, 0.22g of catalyst tetraisopropyl titanate and 121.9g (0.55mol) of isophorone diisocyanate are added, and the reaction is carried out for 1 hour. 13.41g (0.1mol) of dimethylolpropionic acid were added and reacted for 3 hours. 50g of a hydroxyl-terminated hyperbranched polyether having a functionality of 20 and a molecular weight of 50000g/mol (containing 0.02mol of hydroxyl groups) were added and reacted for 2 hours. 13.41g (0.1mol) of dimethylolpropionic acid were added further and reacted for 3 hours. The temperature is reduced to normal temperature, 20.24g (0.2mol) of neutralizer triethylamine is added, and the mixture is stirred for 10 minutes. Adding 15.64g (0.04mol) of sodium diisooctyl succinate sulfonate to prepare the hyperbranched structure modified polyurethane polymer.
545g of deionized water was added, stirred for 0.5 hour and filtered. And 2g of defoaming agent BYK-370, 2g of thickener Gel LW44 and 1g of flatting agent BYK-333 are added to prepare the aqueous hyperbranched structure modified polyurethane coating.
20g of coating is uniformly coated on the surface of the PET film subjected to corona treatment, and the PET film is heated at 100 ℃ for 30 seconds to dry water, wherein the thickness of the coating is 25 mu m. The glossiness of the pencil is 30, the light transmittance is 92%, the pencil hardness is 5H, and no crease exists after the pencil is folded at 180 degrees for 30 times.
The comparison between the example 5 and the example 6 shows that, when the hyperbranched polymer in the hyperbranched structure-modified polyurethane aqueous coating is changed from hyperbranched polyester to hyperbranched polyether, the glossiness of the coating is unchanged, the diffuse reflection effect is consistent, and the light transmittance is improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a waterborne hyperbranched structure-modified polyurethane polymer is characterized by comprising the following steps:
(1) weighing a certain amount of aliphatic polyether glycol and aliphatic polyester glycol, decompressing, vacuumizing and dehydrating at 90-150 ℃, cooling to 60-90 ℃, introducing nitrogen, adding a certain amount of catalyst and aliphatic diisocyanate, and reacting for 1-5 hours;
(2) adding a certain amount of hydrophilic chain extender into the product obtained in the step (1), wherein the molar ratio of the added hydrophilic chain extender to the aliphatic diisocyanate used in the step (1) is 0.05-0.3: 1, and reacting for 1-3 hours;
(3) adding a certain amount of hydroxyl-terminated hyperbranched polymer into the product obtained in the step (2), and reacting for 1-2 hours; the ratio of the added hydroxyl-terminated hyperbranched polymer to the total mass of the aliphatic polyether diol, the aliphatic polyester diol and the aliphatic diisocyanate in the step (1) is 0.01-0.2: 1;
(4) continuously adding a certain amount of hydrophilic chain extender, wherein the molar ratio of the added amount to the chain extender in the step (2) is 0.5-1: 1, and reacting for 1-2 hours;
(5) cooling to normal temperature, adding a neutralizing agent to adjust the pH value of the system to 7-9;
(6) adding sulfonate hydrophilic chain extender into a reaction system, and reacting for 0.5-1 hour; to prepare the waterborne hyperbranched structure modified polyurethane polymer.
2. The preparation method according to claim 1, wherein in the step (1), the amount of the catalyst is 0.01 to 0.5% of the total mass of the aliphatic polyether diol and the aliphatic polyester diol, and the catalyst is one or more of triethylamine, triethylenediamine, stannous octoate, dibutyltin dilaurate, lead octoate, cobalt octoate, iron octoate, zinc naphthenate, tetraisopropyl titanate, and tetraisobutyl titanate.
3. The preparation method according to claim 1, wherein in the step (1), the molar ratio of the aliphatic polyether glycol to the aliphatic polyester glycol is 1-10: 1; the total molar ratio of the aliphatic diisocyanate to the two diols is 2-5: 1.
4. The preparation method according to claim 3, wherein the aliphatic polyether glycol is one or more of polytetramethylene glycol and polypropylene glycol with the molecular weight of 300-6000 g/mol; the aliphatic polyester dihydric alcohol is one or more of polybutylene adipate dihydric alcohol, polycaprolactone dihydric alcohol, polyethylene glycol adipate dihydric alcohol and polycarbonate dihydric alcohol with the molecular weight of 300-6000 g/mol; the aliphatic diisocyanate is one or more of hexamethylene diisocyanate and isophorone diisocyanate.
5. The preparation method according to claim 1, wherein the hydrophilic chain extender in the steps (2) and (4) is one or more of dimethylolpropionic acid, diaminobenzoic acid, or N-dihydroxy (diisopropyl) aniline, the hydrophilic group of which is carboxyl, or amino.
6. The preparation method according to claim 1, wherein the hydroxyl-terminated hyperbranched polymer in the step (3) is one or more of hydroxyl-terminated hyperbranched polyether and hydroxyl-terminated hyperbranched polyester with molecular weight of 2000-100000 g/mol and terminal hydroxyl group content of 10-30.
7. The preparation method according to claim 1, wherein the molar ratio of the amount of the neutralizing agent in the step (5) to the chain extender in the step (2) is 1-2: 1; the neutralizer is one or more of triethanolamine, triethylamine, amino acid and terephthalic acid.
8. The preparation method of claim 1, wherein the sulfonate hydrophilic chain extender in the step (6) is one or more of ethylenediamine ethyl sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and diisooctyl succinate sodium sulfonate, and the hydrophilic group of the sulfonate hydrophilic chain extender is a sulfonic acid group, and the molar ratio of the sulfonate hydrophilic chain extender to the neutralizer in the step (5) is 0.1-0.3: 1.
9. An aqueous hyperbranched structurally-modified polyurethane polymer obtainable by the process according to any one of claims 1 to 8.
10. The self-repairing diffuse reflection coating composition is characterized in that the solid content of the coating composition is 20-50%, and the average particle size of emulsion is 110-500 nm; the coating composition comprises the following components in parts by weight:
wherein the hyperbranched structurally-modified polyurethane polymer is the hyperbranched structurally-modified polyurethane polymer of claim 9;
the defoaming agent is one or more of BYK-370 and GSK-716; the thickener is Gel LW 44; the leveling agent is one or more of BYK-333 and Tego-482.
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