CN114933690A - Method for preparing stain-resistant ultraviolet curing resin by utilizing core-shell structure - Google Patents
Method for preparing stain-resistant ultraviolet curing resin by utilizing core-shell structure Download PDFInfo
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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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
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- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
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- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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Abstract
The invention provides a method for preparing stain-resistant ultraviolet curing resin by utilizing a core-shell structure, which comprises the following steps: preparing an isocyanate end group prepolymer by reacting organic silicon hydroxyl dihydric alcohol, polyol, dihydroxy carboxylic acid and diisocyanate, and then carrying out end capping by adopting a high-functionality acrylic acid hydroxyl-containing monomer to prepare a prepolymer A; preparing a prepolymer B by adopting diisocyanate, a polyacrylic acid hydroxyl monomer, polyol, organosilicon hydroxyl diol and hydroxyl-containing fluoride; and fully mixing the prepolymer A and the prepolymer B, and performing neutralization, emulsification, chain extension, vacuum pumping and solvent removal treatment to obtain the stain-resistant ultraviolet curing resin. According to the invention, the organic silicon long chain segment is introduced through the core-shell proportion design of the core-shell structure and the synthetic branching mode, so that the ultraviolet curing water-based dispersion has the self stain resistance, no additional additive or auxiliary agent or auxiliary component is needed, and the stain resistance effect of a solvent type product after coating is achieved on the premise of low VOC (volatile organic compound) emission through a physical mixing process.
Description
Technical Field
The invention belongs to the field of resin preparation, and particularly relates to a method for preparing stain-resistant ultraviolet curing resin by utilizing a core-shell structure.
Background
At present, high-performance stain-resistant easy-to-clean coatings used for consumer electronics and plastic coating on the market are mainly traditional solvent-based coatings, so that VOC (volatile organic compounds) emission cannot be overcome. Most of the existing water-based stain-resistant systems achieve the stain-resistant effect through an auxiliary agent or other auxiliary means, and the durability and the stain-resistant result are different from those of solvent-based products.
Disclosure of Invention
An object of the present invention is to provide a method for preparing a stain resistant uv curable resin using a core-shell structure and to provide at least the advantages which will be described later.
The invention also aims to provide a method for preparing the stain-resistant ultraviolet curing resin by utilizing the core-shell structure, wherein the organic silicon long chain segment is introduced by designing the core-shell proportion of the core-shell structure and synthesizing the branched mode to enable the ultraviolet curing aqueous dispersion to have the stain resistance per se, and the durable stain resistance can be achieved without additionally adding additives or auxiliaries and auxiliary components; the stain resistant effect of solvent type products after coating is achieved through a physical mixing process on the premise of low VOC emission.
The technical scheme of the invention is as follows:
the method for preparing the stain-resistant ultraviolet curing resin by utilizing the core-shell structure comprises the following steps:
preparing an isocyanate end group prepolymer by reacting organic silicon hydroxyl dihydric alcohol, polyol, dihydroxy carboxylic acid and diisocyanate, and then carrying out end capping by adopting a high-functionality acrylic acid hydroxyl-containing monomer to prepare a prepolymer A;
preparing a prepolymer B with theoretical NCO micro-excess by adopting diisocyanate, a polyacrylic acid hydroxyl monomer, polyol, organic silicon hydroxyl diol and hydroxyl-containing fluoride;
and (3) mixing prepolymer A and prepolymer B according to the mass ratio of 1: and 0.3-1, fully mixing, and performing neutralization, emulsification, chain extension and vacuum-pumping solvent removal treatment to obtain the stain-resistant ultraviolet curing resin.
Preferably, in the method for preparing the stain-resistant ultraviolet curing resin by using the core-shell structure, the prepolymer a is prepared by the following method:
step one, adding 10-30 parts by weight of organic silicon hydroxyl dihydric alcohol and 10-30 parts by weight of diisocyanate monomer at normal temperature, uniformly mixing, then adding 0.01-0.1 part of catalyst, and stirring and reacting at 50-80 ℃ for 1-2 hours to obtain isocyanate-terminated organic silicon prepolymer I;
step two, uniformly mixing 3-8 parts by weight of dihydroxy carboxylic acid, 1-5 parts by weight of micromolecular polyol and butanone, dropwise adding the mixture into the product obtained in the step one, stirring and reacting for 1-3 hours at the temperature of 70-80 ℃, and carrying out chain extension to obtain an isocyanate-terminated prepolymer II;
and step three, uniformly mixing 20-30 parts by weight of hydroxyl acrylate monomer, 0.01-0.2 part by weight of catalyst and 0.05-0.1 part by weight of polymerization inhibitor, slowly adding the mixture into the product obtained in the step two, and stirring and reacting for 2-4 hours at the temperature of 70-80 ℃ to obtain prepolymer A which is not only blocked by isocyanate but also blocked by acrylic acid.
Preferably, in the method for preparing the stain-resistant ultraviolet curing resin by using the core-shell structure, the prepolymer B is prepared by the following method:
step one, adding 0-20 parts by weight of organic silicon hydroxyl dihydric alcohol, 0-5 parts by weight of hydroxyl-containing fluoride and 10-30 parts by weight of diisocyanate monomer at normal temperature, uniformly mixing, adding 0-5 parts by weight of micromolecule polyol and then 0.01-0.1 part by weight of catalyst, and stirring and reacting at 80-100 ℃ for 1-2 hours to obtain an isocyanate-terminated prepolymer I;
and step two, adding 30-70 parts by weight of polyacrylic acid hydroxyl monomer and 0.05-0.1 part by weight of polymerization inhibitor into the product obtained in the step one, and stirring and reacting for 2-4h at the temperature of 70-80 ℃ to obtain prepolymer B which is not only isocyanate but also acrylic acid terminated.
Preferably, in the method for preparing the stain-resistant ultraviolet curing resin by utilizing the core-shell structure,
fully mixing the prepolymer A, the prepolymer B and acetone, adding 2-5 parts of an amine salt neutralizing agent for neutralization, stirring and reacting at 50-70 ℃ for 20-30 min, then adding deionized water for emulsification under the condition of high-speed dispersion, adding polyamine for secondary chain extension after full emulsification to obtain an aqueous ultraviolet curing dispersion with organic silicon as a main chain, and controlling the final pH value within 6-8 after emulsification;
finally, at the temperature of 50-60 ℃, vacuumizing for 4-6 hours to remove the solvent, and obtaining the water-based ultraviolet curing dispersion taking the solvent-free organic silicon as the main chain.
Preferably, in the method for preparing the stain-resistant ultraviolet curing resin by using the core-shell structure,
the organic silicon hydroxyl dihydric alcohol is dihydric alcohol terminated by carbon hydroxyl, wherein the content of metal salt is less than 5PPM, and the molecular weight is one or more of 1000, 2000 and 3000;
the fluoride containing hydroxyl is hydroxyl-terminated perfluoroheptane and/or hydroxyl-terminated perfluorooctane;
the dihydroxy carboxylic acid is dihydroxy propionic acid and/or dihydroxy butyric acid;
the diisocyanate is one or more of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and hydrogenated diphenylmethane diisocyanate.
The polyhydric alcohol is one of 1, 4 butanediol, trihydroxypropane, trimethylolethane, glycerol, polyester or polyether branched polyhydric alcohol;
the hydroxyl acrylate monomer is pentaerythritol triacrylate and/or pentaerythritol diacrylate.
Preferably, in the method for preparing the stain-resistant ultraviolet curing resin by utilizing the core-shell structure,
the catalyst is dibutyl tin dilaurate and/or organic bismuth.
The polymerization inhibitor is one of p-hydroxyanisole, hydroquinone, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone;
the neutralizing agent is triethylamine and/or dimethylethanolamine;
the polyamine is isophorone diamine and/or diethylenetriamine.
The invention at least comprises the following beneficial effects:
1. solves the problems that the existing high-performance stain-resistant products in consumer electronics and plastic coating have dominant oil solvent systems and the VOC content is too high to meet the relevant national emission requirements.
2. Meanwhile, the stability of the introduced stain-resistant groups synthesized in the synthesis process is good, and the problems that the manufacturing process is complicated and the stability is to be evaluated due to the addition of auxiliary components besides the existing waterborne photocuring stain-resistant easy-to-clean products are solved.
3. While providing low VOC, fast photocuring and durable stain resistance, the user can adjust different gloss requirements through a common matting agent, and the appearance limitation of gloss limited by the use of the product is solved.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The present invention is described in further detail below to enable those skilled in the art to practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The invention provides a preparation method of an easily-cleaned water-based ultraviolet curing resin with a core-shell structure, which comprises the following steps:
and (3) preparing an isocyanate end group prepolymer by reacting organic silicon-carbon hydroxyl dihydric alcohol, polyol, dihydroxy carboxylic acid and diisocyanate, and then carrying out end capping by adopting a high-functionality acrylic acid hydroxyl-containing monomer.
Prepolymer B is prepared from diisocyanate, polyacrylate hydroxyl-containing monomer, polyol, carbon hydroxyl organosilicon diol and hydroxyl-containing fluoride, and is prepared into prepolymer with slightly excessive theoretical NCO.
And finally, with the assistance of a cosolvent, mixing the raw materials in a mass ratio of 1: 0.3-1, fully mixing the prepolymers A and B, neutralizing by adopting an ammonium salt reagent, emulsifying, carrying out chain extension, vacuumizing and desolventizing to obtain the aqueous ultraviolet curing dispersion with organic silicon as a main chain (containing fluorine and silicon).
In an embodiment of the method for preparing the stain-resistant uv-curable resin by using the core-shell structure, the prepolymer a is prepared by the following method:
step one, adding 10-30 parts by weight of organic silicon hydroxyl dihydric alcohol and 10-30 parts by weight of diisocyanate monomer at normal temperature, uniformly mixing, then adding 0.01-0.1 part of catalyst, and stirring and reacting at 50-80 ℃ for 1-2h to obtain an isocyanate-terminated organic silicon prepolymer I;
step two, uniformly mixing 3-8 parts by weight of dihydroxy carboxylic acid, 1-5 parts by weight of micromolecular polyol and butanone, dropwise adding the mixture into the product obtained in the step one, stirring and reacting for 1-3 hours at the temperature of 70-80 ℃, and carrying out chain extension to obtain an isocyanate-terminated prepolymer II;
and step three, uniformly mixing 20-30 parts by weight of hydroxyl acrylate monomer, 0.01-0.2 part by weight of catalyst and 0.05-0.1 part by weight of polymerization inhibitor, slowly adding the mixture into the product obtained in the step two, and stirring and reacting for 2-4 hours at the temperature of 70-80 ℃ to obtain prepolymer A which is not only blocked by isocyanate but also blocked by acrylic acid.
In an embodiment of the method for preparing the stain-resistant ultraviolet-curable resin by using the core-shell structure, the prepolymer B is prepared by the following method:
step one, adding 0-20 parts by weight of organic silicon hydroxyl dihydric alcohol, 0-5 parts by weight of hydroxyl-containing fluoride and 10-30 parts by weight of diisocyanate monomer at normal temperature, uniformly mixing, adding 0-5 parts by weight of micromolecule polyol and then 0.01-0.1 part by weight of catalyst, and stirring and reacting at 80-100 ℃ for 1-2 hours to obtain an isocyanate-terminated prepolymer I;
and step two, adding 30-70 parts by weight of polyacrylic acid hydroxyl monomer and 0.05-0.1 part by weight of polymerization inhibitor into the product obtained in the step one, and stirring and reacting for 2-4 hours at 70-80 ℃ to obtain prepolymer B which is not only isocyanate but also acrylic acid terminated.
In one embodiment of the method for preparing the stain resistant uv curable resin using the core-shell structure provided by the present invention,
fully mixing the prepolymer A, the prepolymer B and acetone, adding 2-5 parts of an amine salt neutralizing agent for neutralization, stirring and reacting at 50-70 ℃ for 20-30 min, then adding deionized water for emulsification under the condition of high-speed dispersion, adding polyamine for secondary chain extension after full emulsification to obtain an aqueous ultraviolet curing dispersion with organic silicon as a main chain, and controlling the final pH value within 6-8 after emulsification;
finally, at the temperature of 50-60 ℃, vacuumizing for 4-6 hours to remove the solvent, and obtaining the water-based ultraviolet curing dispersoid taking the solvent-free organic silicon as the main chain.
In one embodiment of the method for preparing the stain resistant uv curable resin using the core-shell structure provided by the present invention,
the organic silicon hydroxyl dihydric alcohol is dihydric alcohol terminated by carbon hydroxyl, wherein the content of metal salt is less than 5PPM, and the molecular weight is one or more of 1000, 2000 and 3000;
the fluoride containing hydroxyl is hydroxyl-terminated perfluoroheptane and/or hydroxyl-terminated perfluorooctane;
the dihydroxy carboxylic acid is dihydroxy propionic acid and/or dihydroxy butyric acid;
the diisocyanate is one or more of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and hydrogenated diphenylmethane diisocyanate.
The polyalcohol is one of 1, 4 butanediol, trihydroxypropane, trimethylolethane, glycerol, polyester or polyether branched polyalcohol;
the hydroxyl acrylate monomer is pentaerythritol triacrylate and/or pentaerythritol diacrylate.
In one embodiment of the method for preparing the stain resistant uv curable resin using the core-shell structure provided by the present invention,
the catalyst is dibutyl tin dilaurate and/or organic bismuth.
The polymerization inhibitor is one of p-hydroxyanisole, hydroquinone, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone;
the neutralizing agent is triethylamine and/or dimethylethanolamine;
the polyamine is isophorone diamine and/or diethylenetriamine.
The invention relates to the technical field of solvent-free polyurethane synthesis and aqueous polyurethane dispersion synthesis.
Example (b):
preparation of prepolymer A
Step one, adding 90 g of 1000 molecular weight organic silicon hydroxyl dihydric alcohol and 70 g of diisocyanate monomer at normal temperature, uniformly mixing, then adding 0.1 g of dibutyltin dilaurate, and reacting at 65 ℃ for 1 hour;
step two, uniformly mixing 13.5 g of dihydroxypropionic acid, 1 g of trimethylolpropane and 40 g of butanone, dropwise adding the mixture into the product obtained in the step one, stirring the mixture at the temperature of 80 ℃ for reaction for 3 hours, and carrying out chain extension to obtain an isocyanate-terminated prepolymer II;
step three, uniformly mixing 80 g of pentaerythritol triacrylate monomer, 0.1 g of dibutyltin dilaurate catalyst and 0.3 g of p-hydroxyanisole, slowly adding the mixture into the product obtained in the step two, and stirring and reacting at 75 ℃ for 2.5 hours to obtain the prepolymer A which is not only isocyanate but also acrylic acid terminated.
Preparation of prepolymer B:
step one, adding 55 g of 1000 molecular weight organic silicon hydroxyl dihydric alcohol, 4.5 g of hydroxyl-containing fluoride of dodecafluoroheptanol and 30 g of diisocyanate monomer at normal temperature, uniformly mixing, and stirring and reacting 0.1 g of dibutyltin dilaurate catalyst at the temperature of 90 ℃ for 2 hours to obtain an isocyanate prepolymer I;
step two, 65 g of pentaerythritol triacrylate monomer and 0.05 g of p-hydroxyanisole are added into the product obtained in the step one, and the mixture is stirred and reacted for 2 hours at the temperature of 75 ℃ to obtain prepolymer B which is not only isocyanate but also acrylic acid terminated.
Prepolymer a, prepolymer B and 110 g of acetone were mixed thoroughly, 10.5 g of triethylamine was added and neutralized at 50 degrees for 30 minutes.
Then 650 g of deionized water is added for emulsification under the condition of high-speed dispersion, and after full emulsification. Adding 20 g of isophorone diamine diluted to 20% while stirring at high speed for secondary chain extension, and continuing to neutralize for 30 minutes, wherein the chain extension temperature can be within a range of about 40-50 ℃.
Finally, at the temperature of 60 ℃, vacuumizing for 4-6 hours to remove the solvent, and obtaining the water-based ultraviolet curing dispersoid taking the solvent-free organic silicon as the main chain.
Preparing a basic sample plate:
1) adding 3% of DPM cosolvent into the emulsion under stirring, and then adding 3% of 1173/184 (1/1) mixed initiator; the coated preparation was obtained by adding 0.2% of the modesty 699 associated thickener after stirring.
2) Coating with a 30um wire bar on an ABS/PC plastic substrate. After being flash dried for about 3 minutes, the mixture is put into a 60-DEG C oven to be baked for 10 minutes and then is cured by a mercury lamp, and the curing energy is 800mj/cm 2 。
The water drop angle can reach 105 degrees through observation of a water drop angle test.
The invention has the following characteristics:
1) the organosilicon raw material is selected from polyurethane systems, is directly synthesized into a chain segment of a dispersion shell, and achieves the optimal stain resistance effect and the stability of the dispersion through chain extension and branching.
2) By utilizing the design method of the core-shell structure, the core-shell structure can be made into the high-performance ultraviolet curing resin which is the same as a solvent-free system and is used as a cured thick film-forming framework. Thus, the core-shell principle is utilized to reach the same performance as that of the traditional solvent type stain-resistant ultraviolet curing resin to the maximum extent.
3) The stain-resistant use of the present invention is based on photocuring and aqueous properties. Avoids the high VOC volatilization of solvent-type light-cured coatings, and has shorter curing time and lower energy consumption compared with the curing time of water-based heat-cured coatings.
4) The main body has the stain resistant components introduced, the process is simplified as much as possible in the process of preparing the coating, and the stain resistant effect after coating and curing can be achieved only by adding the basic material.
5) The product has simple formula, good stability, wide practicability and capability of adjusting the luster without influencing the stain resistance effect through the common matting powder.
Compared with other aqueous photocuring stain-resistant technologies, the method provided by the invention has the following specific steps that the main film-forming substance has stain resistance:
1) the stain resistant effect is close to that of the current oily products of the same type. The water contact angle of a full optical system can reach 105 degrees; the water contact angle of the semi-optical system can reach 100 degrees.
2) Longer than the time-dependent nature of the external contamination-resistant component. After 24-hour testing according to GB/T2423.3-2006, the marking pen can still keep the easy-to-clean effect under the full-light state.
3) The front-end synthesis process route is mature, and the quality stability of the product batch is well controlled.
4) The rear-end preparation process is simple in process, pollution-resistant products with different gloss can be prepared by simply mixing according to different requirements, and the large-scale production efficiency is high.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (6)
1. The method for preparing the stain-resistant ultraviolet curing resin by utilizing the core-shell structure is characterized by comprising the following steps of:
preparing an isocyanate end group prepolymer by reacting organic silicon hydroxyl dihydric alcohol, polyalcohol, dihydroxy carboxylic acid and diisocyanate, and then carrying out end capping by adopting a high-functionality acrylic acid hydroxyl-containing monomer to prepare a prepolymer A;
preparing a prepolymer B with a theoretical NCO micro-excess by diisocyanate, a polyacrylic acid hydroxyl monomer, polyol, organosilicon hydroxyl diol and fluoride containing hydroxyl;
and (3) mixing prepolymer A and prepolymer B according to a mass ratio of 1: and 0.3-1, fully mixing, and performing neutralization, emulsification, chain extension and vacuum-pumping solvent removal treatment to obtain the stain-resistant ultraviolet curing resin.
2. The method for preparing the stain resistant uv curable resin using the core-shell structure according to claim 1, wherein the prepolymer a is prepared by the following method:
step one, adding 10-30 parts by weight of organic silicon hydroxyl dihydric alcohol and 10-30 parts by weight of diisocyanate monomer at normal temperature, uniformly mixing, then adding 0.01-0.1 part of catalyst, and stirring and reacting at 50-80 ℃ for 1-2 hours to obtain isocyanate-terminated organic silicon prepolymer I;
step two, uniformly mixing 3-8 parts by weight of dihydroxy carboxylic acid, 1-5 parts by weight of micromolecular polyol and butanone, dropwise adding the mixture into the product obtained in the step one, stirring and reacting for 1-3 hours at the temperature of 70-80 ℃, and carrying out chain extension to obtain an isocyanate-terminated prepolymer II;
and step three, uniformly mixing 20-30 parts by weight of hydroxyl acrylate monomer, 0.01-0.2 part by weight of catalyst and 0.05-0.1 part by weight of polymerization inhibitor, slowly adding the mixture into the product obtained in the step two, and stirring and reacting for 2-4 hours at the temperature of 70-80 ℃ to obtain prepolymer A which is not only blocked by isocyanate but also blocked by acrylic acid.
3. The method for preparing the stain resistant uv curable resin using the core-shell structure according to claim 2, wherein the prepolymer B is prepared by the following method:
firstly, adding 0-20 parts by weight of organic silicon hydroxyl dihydric alcohol, 0-5 parts by weight of hydroxyl-containing fluoride and 10-30 parts by weight of diisocyanate monomer at normal temperature, uniformly mixing, adding 0-5 parts by weight of micromolecular polyalcohol and then 0.01-0.1 part by weight of catalyst, and stirring and reacting at the temperature of 80-100 ℃ for 1-2 hours to prepare an isocyanate-terminated prepolymer I;
and step two, adding 30-70 parts by weight of polyacrylic acid hydroxyl monomer and 0.05-0.1 part by weight of polymerization inhibitor into the product obtained in the step one, and stirring and reacting for 2-4h at the temperature of 70-80 ℃ to obtain prepolymer B which is not only isocyanate but also acrylic acid terminated.
4. The method for preparing a stain resistant UV curable resin using a core-shell structure according to claim 3,
fully mixing the prepolymer A, the prepolymer B and acetone, adding 2-5 parts of an amine salt neutralizing agent for neutralization, stirring and reacting at 50-70 ℃ for 20-30 min, then adding deionized water for emulsification under the condition of high-speed dispersion, adding polyamine for secondary chain extension after full emulsification to obtain an aqueous ultraviolet curing dispersion with organic silicon as a main chain, and controlling the final pH value within 6-8 after emulsification;
finally, at the temperature of 50-60 ℃, vacuumizing for 4-6 hours to remove the solvent, and obtaining the water-based ultraviolet curing dispersoid taking the solvent-free organic silicon as the main chain.
5. The method for preparing a stain resistant UV curable resin using a core-shell structure according to claim 4,
the organic silicon hydroxyl dihydric alcohol is dihydric alcohol terminated by carbon hydroxyl, wherein the content of metal salt is less than 5PPM, and the molecular weight is one or more of 1000, 2000 and 3000;
the fluoride containing hydroxyl is hydroxyl-terminated perfluoroheptane and/or hydroxyl-terminated perfluorooctane;
the dihydroxy carboxylic acid is dihydroxy propionic acid and/or dihydroxy butyric acid;
the diisocyanate is one or more of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and hydrogenated diphenylmethane diisocyanate.
The polyhydric alcohol is one of 1, 4 butanediol, trihydroxypropane, trimethylolethane, glycerol, polyester or polyether branched polyhydric alcohol;
the hydroxyl acrylate monomer is pentaerythritol triacrylate and/or pentaerythritol diacrylate.
6. The method for preparing a stain resistant UV curable resin using a core-shell structure according to claim 5,
the catalyst is dibutyl tin dilaurate and/or organic bismuth.
The polymerization inhibitor is one of p-hydroxyanisole, hydroquinone, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone;
the neutralizing agent is triethylamine and/or dimethylethanolamine;
the polyamine is isophorone diamine and/or diethylenetriamine.
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| CN116217863A (en) * | 2023-02-20 | 2023-06-06 | 黄山联固新材料科技有限公司 | Water-based UV (ultraviolet) light-cured stain-resistant resin and preparation method thereof |
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| CN104017169A (en) * | 2014-06-05 | 2014-09-03 | 武汉长盈通光电技术有限公司 | Preparation method of core-shell type waterborne polyurethane emulsion with crosslinked and hybrid structures |
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| CN104017169A (en) * | 2014-06-05 | 2014-09-03 | 武汉长盈通光电技术有限公司 | Preparation method of core-shell type waterborne polyurethane emulsion with crosslinked and hybrid structures |
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