CN110408313B - Polyacrylonitrile hollow microsphere modified waterborne polyurethane extinction resin and preparation method thereof - Google Patents
Polyacrylonitrile hollow microsphere modified waterborne polyurethane extinction resin and preparation method thereof Download PDFInfo
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- CN110408313B CN110408313B CN201910543380.6A CN201910543380A CN110408313B CN 110408313 B CN110408313 B CN 110408313B CN 201910543380 A CN201910543380 A CN 201910543380A CN 110408313 B CN110408313 B CN 110408313B
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- 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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- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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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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- C14—SKINS; HIDES; PELTS; LEATHER
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- C14C11/00—Surface finishing of leather
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Abstract
The invention relates to polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin and a preparation method thereof. The average particle size of the polyacrylonitrile hollow microspheres is 500-1500 nm, the mass of the polyacrylonitrile hollow microspheres is 3% of that of the aqueous polyurethane extinction resin, and the aqueous polyurethane extinction resin has good stability; the modified waterborne polyurethane matting resin is coated on leather, and the glossiness (at 60 ℃) of the leather is 1.6-3.4. According to the invention, an oil phase and a water phase are mixed by a miniemulsion method, a polyacrylonitrile hollow microsphere emulsion is prepared by heating in a water bath at a constant temperature, and then the polyacrylonitrile hollow microsphere emulsion and an aqueous polyurethane prepolymer are blended and emulsified to prepare the acrylonitrile hollow microsphere modified aqueous polyurethane matting resin. The aqueous polyurethane extinction resin has good strength, and can not crack even under the action of strong external force and high-speed collision of a high-speed mixer and an extruder, so that the formed aqueous polyurethane adhesive film has good extinction property and excellent mechanical property, and the stability of the aqueous polyurethane extinction resin is improved.
Description
Technical Field
The invention belongs to the technical field of water-based matte coatings, and particularly relates to polyacrylonitrile hollow microsphere modified water-based polyurethane extinction resin and a preparation method thereof.
Background requirements
The water-based matte coating is not only noble and elegant, but also soft and flat, and is more beneficial to protecting eyesight due to the characteristics of soft surface color and luster and low glossiness, so that the water-based matte coating is deeply favored and widely applied. Most of the traditional matte coatings are prepared by adding a flatting agent externally. The external addition of the flatting agent is to add the flatting agent into the aqueous polyurethane dispersion, and after the water of the coating film is evaporated, the flatting agent can float on the surface of the coating film to generate microscopic unevenness, so that the flatting effect is achieved. If the board-like forever adopts the flatting agent silicon dioxide modified aqueous polyurethane flatting leather finishing agent, the flatting property of the prepared aqueous polyurethane flatting leather is obviously enhanced, and the hand feeling is good. However, the external flatting agent is not easily matched with the polyurethane resin, so that the emulsion is unstable, the brittleness of the coating is increased, the friction resistance is poor, and the surface of the coating film is whitened, frosted and the like, so that the appearance quality of the coated product is reduced. Another embodiment of the inventionCN101709550A discloses a leather matting coating composition and a preparation method thereof. The extinction coating is prepared by blending solvent type polyurethane and a silicon dioxide extinction agent. On one hand, the solvent-based coating has serious environmental pollution; on the other hand, the silica flatting agent has poor compatibility with the coating, is easy to migrate out, and influences the performance of the polyurethane. The preparation method of the extinction type aqueous polyurethane emulsion comprises the following steps of coating a polyurethane molecular chain on functionalized SiO by a chemical bonding method2Or forming polyurethane microsphere emulsion on the polystyrene hollow microspheres, and mixing the polyurethane microsphere emulsion with the aqueous polyurethane emulsion with smaller particle size to obtain the matt aqueous polyurethane emulsion; however, how to bond the polyurethane molecular chain to the hollow microsphere is not described in detail, the particle size of the selected microsphere is 1000-2000 nm, the particle size is larger after the microsphere is coated with polyurethane, and the uniformity of the particle size is difficult to control.
Disclosure of Invention
In order to improve the stability of polyurethane matting resin, solve the technical problems in the prior art and make up for the performance defects caused by adding a matting agent, the invention provides polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin and a preparation method of the hollow microsphere modified waterborne polyurethane matting resin.
In the polyacrylonitrile hollow microsphere modified waterborne polyurethane extinction resin, the mass of polyacrylonitrile hollow microspheres is 3% of the total mass of the waterborne polyurethane extinction resin, and the average particle size of the polyacrylonitrile hollow microspheres is 500-1500 nm; the polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin is coated on leather, and the glossiness (at 60 ℃) is 1.6-3.4.
The preparation operation steps of the polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin are as follows:
(1) preparation of Polyacrylonitrile hollow microsphere Pre-emulsion
(1.1) magnetically stirring 96-160 g of 3% polyvinyl alcohol solution, 0.4-0.75 g of sodium nitrite and 8-15 drops of triethylamine, and uniformly mixing to obtain a water phase;
(1.2) magnetically stirring and uniformly mixing 11-20 g of acrylonitrile, 2.8-5.3 g of isooctane, 0.24-0.45 g of azobisisobutyronitrile, 4.8-9 g of tetraethoxysilane, 0.1-0.18 g of polystyrene, 0.16-0.3 gKH570 silane coupling agent and 1.4-2.7 gKH550 silane coupling agent to obtain an oil phase;
(1.3) slowly adding the oil phase into the water phase, and mixing for 1h by magnetic stirring to obtain a pre-emulsion; homogenizing and emulsifying for 5min at 10000r/min by a high-speed dispersion machine in ice water bath to obtain fine emulsion;
carrying out polymerization reaction for 8 hours at the temperature of 65 ℃ under the protection of nitrogen to obtain polyacrylonitrile hollow microsphere emulsion, wherein the particle size of the polyacrylonitrile hollow microsphere is 500-1500 nm;
(2) preparation of aqueous polyurethane matting resin
(2.1) mixing 16-30 g of polymer polyol and 13.0-15.0 g of polyisocyanate, and reacting for 2 hours at 80 ℃ to obtain a substance A;
(2.2) adding 1.2-2.9 g of hydrophilic chain extender and 1.0-2.7 g of micromolecular chain extender 1, 4-butanediol, and continuing to react for 1h at the temperature of 80 ℃ to obtain a substance B;
(2.3) cooling to 50 ℃, adding 0.04-0.05 g of catalyst stannous octoate, and reacting for 3 hours to obtain a prepolymer; when the temperature of the prepolymer is reduced to below 40 ℃, 1.1-2.2 g of triethylamine is added into the prepolymer for neutralization for 5min, 115-195 g of polyacrylonitrile hollow microsphere emulsion is added under the stirring condition of 3000rpm of rotation speed, and emulsification is carried out for 30min, so as to obtain the polyacrylonitrile hollow microsphere modified waterborne polyurethane extinction resin.
The technical scheme for further limiting is as follows:
in step (1.1), each drop was 0.1 mL.
In the step (2.1), the molecular weight of the polymer polyol is 1000-2000; the polymer polyol is one of polytetramethylene ether glycol and poly adipic acid 1, 4-butanediol ester glycol polycarbonate diol; the polymer polyol is dehydrated for 2 hours at 120 ℃ by vacuum pumping before use.
In the step (2.1), the polyisocyanate is one of toluene diisocyanate, 1, 6-hexamethylene diisocyanate and isophorone diisocyanate (IPDI).
In the step (2.2), the hydrophilic chain extender is one of dimethylolpropionic acid and dimethylolbutyric acid, and the hydrophilic chain extender is dried in a vacuum drying oven for 1h at 50 ℃ before use.
Compared with the prior art, the invention has the following beneficial technical effects:
1. according to the invention, an oil phase and a water phase are mixed by a miniemulsion method, a polyacrylonitrile hollow microsphere emulsion is prepared by heating in a water bath at a constant temperature, and then the polyacrylonitrile hollow microsphere emulsion and an aqueous polyurethane prepolymer are blended and emulsified to prepare the acrylonitrile hollow microsphere modified aqueous polyurethane matting resin. The aqueous polyurethane extinction resin obtained by emulsifying the aqueous polyurethane prepolymer with the polyacrylonitrile hollow microsphere emulsion has strong stability and remains-NH in the emulsion2The polyurethane resin can react with residual-NCO in the waterborne polyurethane prepolymer, and the residual-NCO and the stable urea bond can be formed, so that the stability of the waterborne polyurethane matting resin is greatly enhanced, and the problem of poor physical mixing compatibility of the waterborne polyurethane matting resin and the residual-NCO is solved. The polyacrylonitrile hollow microsphere modified waterborne polyurethane extinction resin emulsion is stable and has no sedimentation when being centrifuged for 30min on a centrifuge of 3000 r/min. The gloss (60 ℃) can reach 1.6 by controlling n (-NCO) n (-OH) to be about 1.5.
2. The preparation method is simple and controllable, has low cost and does not need complex production equipment.
Drawings
FIG. 1 is a schematic diagram of a reaction mechanism for preparing polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin.
FIG. 2 is a TEM photograph of polyacrylonitrile hollow microsphere.
Detailed Description
The invention will now be further described with reference to specific examples.
Example 1
Referring to fig. 1, the preparation operation steps of the polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin are as follows:
(1) preparation of polyacrylonitrile hollow microsphere emulsion
(1.1) 96g of 3% polyvinyl alcohol solution, 0.4g of sodium nitrite and 8 drops of triethylamine are weighed, each drop is 0.1mL, and the mixture is uniformly mixed into a water phase by magnetic stirring.
(1.2) 11.2g of acrylonitrile, 2.8g of isooctane, 0.24g of azobisisobutyronitrile, 4.8g of ethyl orthosilicate, 0.1g of polystyrene, 0.16gKH570 of a silane coupling agent and 1.44gKH550 of a silane coupling agent were weighed, and mixed uniformly by magnetic stirring to obtain an oil phase.
(1.3) slowly adding the oil phase into the water phase, and mixing for 1h by magnetic stirring to obtain a pre-emulsion. Homogenizing and emulsifying for 5min at 10000r/min by a high-speed dispersion machine in ice water bath to obtain fine emulsion. Transferring the miniemulsion into a three-neck flask provided with a stirring device, a reflux condenser tube and a thermometer, and carrying out polymerization reaction for 8 hours at the temperature of 65 ℃ under the protection of nitrogen to obtain the polyacrylonitrile hollow microsphere emulsion, wherein the particle size of the polyacrylonitrile hollow microsphere is 500-1500 nm.
(2) Preparation of polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin
(2.1) (R = 1.75) weighing 16g of polycarbonate diol, vacuumizing and dehydrating for 2.5h at 110 ℃, cooling to 50 ℃, putting into a three-neck flask reactor, adding 13.12g of isophorone diisocyanate, and reacting for 2h at 80 ℃; the molecular weight of the polycarbonate diol is 1000;
(2.2) cooling to 50 ℃, adding 1.25g of dimethylolbutyric acid and 1.1g of micromolecule chain extender 1, 4-butanediol, heating to 80 ℃, and reacting for 1 h; drying dimethylolbutyric acid in a vacuum drying oven at 50 ℃ for 1h before use;
(2.3) cooling to 50 ℃, adding 0.04g of catalyst stannous octoate, reacting at 80 ℃ for 3h to obtain the prepolymer. When the temperature of the prepolymer is reduced to below 40 ℃, adding 1.152g of triethylamine into the prepolymer for neutralization for 5min, adding 115g of polyacrylonitrile hollow microsphere emulsion under the stirring condition of the rotating speed of 3000rpm, and emulsifying for 30min to obtain the polyacrylonitrile hollow microsphere modified waterborne polyurethane extinction resin; a TEM photograph of polyacrylonitrile hollow microspheres is shown in FIG. 2.
The polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin in the embodiment 1 is coated on leather, and the glossiness (at 60 ℃) is 3.4.
Example 2
The preparation operation steps of the polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin are as follows:
(1) preparation of polyacrylonitrile hollow microsphere emulsion
(1.1) 120g of 3% polyvinyl alcohol solution, 0.5g of sodium nitrite and 10 drops of triethylamine are weighed, each drop is 0.1mL, and the mixture is uniformly mixed into a water phase by magnetic stirring.
(1.2) 14g of acrylonitrile, 3.5g of isooctane, 0.3g of azobisisobutyronitrile, 6g of ethyl orthosilicate, 0.12g of polystyrene, 0.2gKH570 of a silane coupling agent and 1.8gKH550 of a silane coupling agent were weighed, and the weighed materials were magnetically stirred and mixed uniformly to obtain an oil phase.
(1.3) slowly adding the oil phase into the water phase, and mixing for 1h by magnetic stirring to obtain a pre-emulsion. Homogenizing and emulsifying with high speed dispersant at 10000r/min for 5min in ice water bath to obtain fine emulsion.
Transferring the miniemulsion into a three-neck flask provided with a stirring device, a reflux condenser tube and a thermometer, setting the polymerization temperature to 65 ℃, and reacting for 8 hours at constant temperature under the protection of nitrogen to obtain the polyacrylonitrile hollow microsphere emulsion, wherein the particle size of the polyacrylonitrile hollow microsphere is 500-1500 nm.
(2) Preparation of polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin
(2.1) (R = 1.5) weighing 20g of poly (1, 4-butylene glycol adipate) glycol, vacuumizing and dehydrating for 2.5h at 110 ℃, cooling to 50 ℃, putting into a three-neck flask reactor, adding 10.4g of toluene diisocyanate, controlling the reaction temperature at 80 ℃, and reacting for 2 h; the molecular weight of the poly (1, 4-butylene adipate) glycol is 2000;
(2.2) cooling to 50 ℃, adding 1.92g of dimethylolpropionic acid and 1.42g of micromolecule chain extender 1, 4-butanediol, heating to 80 ℃, and reacting for 1 h; drying dimethylolpropionic acid in a vacuum drying oven at 50 ℃ for 1h before use;
(2.3) cooling to 50 ℃, adding 0.05g of catalyst stannous octoate, and reacting for 3h to obtain the prepolymer. When the temperature of the prepolymer is reduced to below 40 ℃, 1.44g of triethylamine is added into the prepolymer for neutralization for 5min, 145g of polyacrylonitrile hollow microsphere emulsion is added under the stirring condition of the rotating speed of 3000rpm, and emulsification is carried out for 30min, so as to obtain the polyacrylonitrile hollow microsphere modified waterborne polyurethane extinction resin.
The polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin of example 2 is coated on leather, and the glossiness (at 60 ℃) is 1.6.
Example 3
The preparation operation steps of the polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin are as follows:
(1) preparation of polyacrylonitrile hollow microsphere emulsion
(1.1) 150g of 3% polyvinyl alcohol solution, 0.63g of sodium nitrite and 12 drops of triethylamine are weighed, each drop is 0.1mL, and the mixture is uniformly mixed into a water phase by magnetic stirring.
(1.2) 17.5g of acrylonitrile, 4.38g of isooctane, 0.4g of azobisisobutyronitrile, 7.5g of ethyl orthosilicate, 0.15g of polystyrene, 0.25g of 0.25gKH570 of a silane coupling agent and 2.3g of 2.3gKH550 of a silane coupling agent were weighed and mixed uniformly by magnetic stirring to obtain an oil phase.
(1.3) slowly adding the oil phase into the water phase, and mixing for 1h by magnetic stirring to obtain a pre-emulsion. Homogenizing and emulsifying with high speed dispersant at 10000r/min for 5min in ice water bath to obtain fine emulsion.
Transferring the miniemulsion into a three-neck flask provided with a stirring device, a reflux condenser tube and a thermometer, setting the polymerization temperature to 65 ℃, and reacting for 8 hours at constant temperature under the protection of nitrogen to obtain the polyacrylonitrile hollow microsphere emulsion, wherein the particle size of the polyacrylonitrile hollow microsphere is 500-1500 nm.
(2) Preparation of polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin
(2.1) (R = 1.25) weighing 25g of polytetramethylene ether glycol, vacuumizing and dehydrating at 110 ℃ for 2.5h, cooling to 50 ℃, putting into a three-neck flask reactor, adding 13g of 1, 6-hexamethylene diisocyanate, controlling the reaction temperature at 80 ℃, and reacting for 2 h; the molecular weight of polytetramethylene ether glycol is 2000;
(2.2) cooling to 50 ℃, adding 2.4g of dimethylolpropionic acid and 2.66g of micromolecule chain extender 1, 4-butanediol, heating to 80 ℃, and reacting for 1 h; drying dimethylolpropionic acid in a vacuum drying oven at 50 ℃ for 1h before use;
(2.3) cooling to 50 ℃, adding 0.05g of catalyst stannous octoate, and reacting for 3h to obtain the prepolymer. When the temperature of the prepolymer is reduced to below 40 ℃, 1.8g of triethylamine is added into the prepolymer for neutralization for 5min, 180g of polyacrylonitrile hollow microsphere emulsion is added under the stirring condition of the rotating speed of 3000rpm, and emulsification is carried out for 30min, so as to obtain the polyacrylonitrile hollow microsphere modified waterborne polyurethane extinction resin.
The polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin of example 3 is coated on leather, and the glossiness (at 60 ℃) is 2.1.
Example 4
The preparation operation steps of the polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin are as follows:
(1) preparation of polyacrylonitrile hollow microsphere emulsion
(1.1) 160g of 3% polyvinyl alcohol solution, 0.75g of sodium nitrite and 15 drops of triethylamine are weighed, each drop is 0.1mL, and the mixture is evenly mixed into a water phase by magnetic stirring.
(1.2) 20g of acrylonitrile, 5.3g of isooctane, 0.45g of azobisisobutyronitrile, 9g of ethyl orthosilicate, 0.18g of polystyrene, 0.3g of 0.3gKH570 silane coupling agent and 2.7g of 2.7gKH550 silane coupling agent were weighed, and mixed uniformly by magnetic stirring to obtain an oil phase.
(1.3) slowly adding the oil phase into the water phase, and mixing for 1h by magnetic stirring to obtain a pre-emulsion. Homogenizing and emulsifying with high speed dispersant at 10000r/min for 5min in ice water bath to obtain fine emulsion.
Transferring the miniemulsion into a three-neck flask provided with a stirring device, a reflux condenser tube and a thermometer, setting the polymerization temperature to 65 ℃, and reacting for 8 hours at constant temperature under the protection of nitrogen to obtain the polyacrylonitrile hollow microsphere emulsion, wherein the particle size of the polyacrylonitrile hollow microsphere is 500-1500 nm.
(2) Preparation of polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin
(2.1) (R = 1.15) weighing 30g of 1, 4-butanediol adipate glycol, vacuumizing and dehydrating for 2.5h at 110 ℃, cooling to 50 ℃, putting into a three-neck flask reactor, adding 15g of isophorone diisocyanate, controlling the reaction temperature at 80 ℃, and reacting for 2 h; the molecular weight of the poly (1, 4-butylene adipate) glycol is 2000;
(2.2) cooling to 50 ℃, adding 2.84g of dimethylolpropionic acid and 2.03g of micromolecule chain extender 1, 4-butanediol, heating to 80 ℃, and reacting for 1 h; drying dimethylolpropionic acid in a vacuum drying oven at 50 ℃ for 1h before use;
(2.3) cooling to 50 ℃, adding 0.05g of catalyst stannous octoate, and reacting for 3h to obtain the prepolymer. When the temperature of the prepolymer is reduced to below 40 ℃, 2.16g of triethylamine is added into the prepolymer for neutralization for 5min, 195g of polyacrylonitrile hollow microsphere emulsion is added under the stirring condition of the rotating speed of 3000rpm, and emulsification is carried out for 30min, so as to obtain the polyacrylonitrile hollow microsphere modified waterborne polyurethane extinction resin.
The polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin of example 4 is coated on leather, and the glossiness (at 60 ℃) is 3.1.
The appearance and the extinction performance of leather coated with the hollow microsphere modified waterborne polyurethane extinction resin obtained in the embodiment 1 and the embodiment 4 of the invention are tested, and the results are shown in the following table 1:
as can be seen from Table 1, the polyacrylonitrile hollow microsphere modified waterborne polyurethane extinction resin has good stability and excellent extinction performance. And the extinction performance is best when n (-NCO) n (-OH) is controlled to be about 1.5. In addition, the polyacrylonitrile hollow microsphere modified waterborne polyurethane extinction resin is good in airtightness and good in film coating property, can ensure the mechanical property and the water resistance of a coating, and is environment-friendly, non-toxic and safe.
The above examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Claims (3)
1. A polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin is characterized in that: the mass of the polyacrylonitrile hollow microspheres in the aqueous polyurethane extinction resin is 3% of the total mass of the aqueous polyurethane extinction resin, and the average particle size of the polyacrylonitrile hollow microspheres is 500-1500 nm; the polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin is coated on leather, and when the polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin emulsion is centrifuged for 30min on a centrifuge with the speed of 3000 r/min, the emulsion is stable and has no sedimentation; controlling n (-NCO) n (-OH) at 1.5, gloss at 60 deg.C and 1.6;
the preparation operation steps of the polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin are as follows:
(1) preparation of Polyacrylonitrile hollow microsphere Pre-emulsion
(1.1) magnetically stirring 96-160 g of 3% polyvinyl alcohol solution, 0.4-0.75 g of sodium nitrite and 8-15 drops of triethylamine, and uniformly mixing to obtain a water phase; the dropping amount is 0.1 mL;
(1.2) magnetically stirring and uniformly mixing 11-20 g of acrylonitrile, 2.8-5.3 g of isooctane, 0.24-0.45 g of azobisisobutyronitrile, 4.8-9 g of tetraethoxysilane, 0.1-0.18 g of polystyrene, 0.16-0.3 gKH570 silane coupling agent and 1.4-2.7 gKH550 silane coupling agent to obtain an oil phase;
(1.3) slowly adding the oil phase into the water phase, and mixing for 1h by magnetic stirring to obtain a pre-emulsion; homogenizing and emulsifying for 5min at 10000r/min by a high-speed dispersion machine in ice water bath to obtain fine emulsion;
carrying out polymerization reaction for 8 hours at the temperature of 65 ℃ under the protection of nitrogen to obtain polyacrylonitrile hollow microsphere emulsion, wherein the particle size of the polyacrylonitrile hollow microsphere is 500-1500 nm;
(2) preparation of aqueous polyurethane matting resin
(2.1) mixing 16-30 g of polymer polyol and 13.0-15.0 g of polyisocyanate, and reacting for 2 hours at 80 ℃ to obtain a substance A;
the molecular weight of the polymer polyol is 1000-2000; the polymer polyol is one of polytetramethylene ether glycol and poly adipic acid 1, 4-butanediol ester glycol polycarbonate diol;
the polyisocyanate is one of toluene diisocyanate, 1, 6-hexamethylene diisocyanate and isophorone diisocyanate (IPDI);
(2.2) adding 1.2-2.9 g of hydrophilic chain extender and 1.0-2.7 g of micromolecular chain extender 1, 4-butanediol, and continuing to react for 1h at the temperature of 80 ℃ to obtain a substance B;
the hydrophilic chain extender is one of dimethylolpropionic acid and dimethylolbutyric acid;
(2.3) cooling to 50 ℃, adding 0.04-0.05 g of catalyst stannous octoate, and reacting for 3 hours to obtain a prepolymer; when the temperature of the prepolymer is reduced to below 40 ℃, 1.1-2.2 g of triethylamine is added into the prepolymer for neutralization for 5min, 115-195 g of polyacrylonitrile hollow microsphere emulsion is added under the stirring condition of 3000rpm of rotation speed, and emulsification is carried out for 30min, so as to obtain the polyacrylonitrile hollow microsphere modified waterborne polyurethane extinction resin.
2. The polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin as claimed in claim 1, wherein: in the step (2.1), the polymer polyol is dehydrated for 2 hours at 120 ℃ by vacuumizing before use.
3. The polyacrylonitrile hollow microsphere modified waterborne polyurethane matting resin as claimed in claim 1, wherein: in the step (2.2), the hydrophilic chain extender is dried in a vacuum drying oven at 50 ℃ for 1h before use.
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