CN115584175A - Silica sol-hydroxy acrylic resin composite-dispersion and preparation method thereof - Google Patents
Silica sol-hydroxy acrylic resin composite-dispersion and preparation method thereof Download PDFInfo
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Abstract
The application relates to the technical field of polymer composite materials, in particular to a silica sol-hydroxy acrylic resin composite-dispersion and a preparation method thereof. The application provides a silica sol-hydroxy acrylic resin composite-dispersion which comprises a first component and a second component, wherein raw material components in the first component comprise silica sol, the silica sol is used as a source of nano silicon dioxide and a reaction medium during modification of the nano silicon dioxide, and modified organic silicon is provided to introduce a long hydrophilic chain segment, so that the grafting rate of the organic silicon on the surface of a nano silicon dioxide particle is greatly improved; because the nano silicon dioxide in the silica sol is well modified, the silica sol-hydroxyacrylic acid dispersoid prepared by the method has good storage stability, has high film hardness and good dulling performance compared with the common hydroxyacrylic acid dispersoid, has better water resistance compared with the conventional silica sol-hydroxyacrylic acid composite dispersoid, and is more beneficial to wide application.
Description
Technical Field
The application belongs to the technical field of polymer composite materials, and particularly relates to a silica sol-hydroxy acrylic resin composite-dispersion and a preparation method thereof.
Background
The nano silicon dioxide is an inorganic material which is cheap and easy to obtain, has excellent weather resistance and good chemical inertness, and can obviously improve the performances of hardness, mechanical strength, weather resistance and the like when used for modifying an organic polymer material. The polyacrylate emulsion has wide application in the fields of coatings, printing ink, adhesives and the like, and in order to overcome the defects of hot sticking, cold brittleness, low hardness and the like, the nano silicon dioxide-polyacrylate composite emulsion is widely researched. The nano-silica has poor compatibility with organic polymer materials, and the effect of direct modification is not good, so that other materials are needed to modify the nano-silica, such as organosilicon monomers (or silane coupling agents) or oligomers thereof.
Zhu Wei (2010) reports a nano SiO prepared by using TEOS, gamma-methacryloxypropyltrimethoxysilane and acrylate monomer through an in-situ hydrolysis method 2 Polyacrylate composite emulsion, the coating hardness can reach 3H, wherein the nano silicon dioxide is obtained by TEOS hydrolysis, and the cost is higher. Shouyanhong (2018) uses hexamethyl disilazane (HMDS) as modifier to nano SiO 2 Performing surface hydrophobic modification, and taking the modified nano SiO2 as a stabilizer to prepare stable Pickering emulsion (polyacrylate-nano silicon dioxide composite emulsion), wherein the modification of the nano silicon dioxide requires absolute ethyl alcohol as a reaction solvent and reacts for 6 hours. Patents CN1654489 and CN112280043A modify nano silica by different methods, and also obtain nano silica-acrylate composite emulsion by emulsion polymerization. The modified silica sol can also modify the aqueous acrylic resin (or acrylic dispersion) to provide a composite material with better properties. In patent CN105482585A, ethanol is used as a solvent, KH-570 is used for modifying nano silicon dioxide, and then the nano silicon dioxide, waterborne acrylic resin and other additives form a nano silicon dioxide-acrylic resin composite coating, and the coating has strong corrosion resistance and stain resistance. In patent CN106833244A, an organosilicone/inorganic silica sol hybrid polyacrylate aqueous dispersion with high silicon content is prepared from a functional silica sol and an aqueous acrylic resin mixed with polyorganosiloxane, wherein the functional silica sol is prepared by insulating epoxy group organosilicone and silica sol at 40-70 ℃ for 4-16. Using ethanol as solvent, and organic silicon monomer (or oligomer) as pairThe nano-silica is modified, so that the high grafting rate of an organic silicon monomer (or oligomer) on the surface of the nano-silica can be ensured, but the obtained modified nano-silica has large particle size and wide particle size distribution, can generate adverse effect on the appearance or transparency of a coating film, and has high VOC content. The method for modifying by adding the organic silicon monomer into the silica sol has the advantages of environmental protection and low cost, but the organic silicon monomer is more prone to self-polymerization after hydrolysis in the silica sol, and the grafting rate on the surface of the nano silicon dioxide is difficult to ensure.
In the prior art, various modification methods have various defects, which affect the wide application of modified organosilicon, so that an organosilicon material with high safety, high grafting ratio and excellent product performance is urgently needed to be provided.
Disclosure of Invention
The application aims to provide a silica sol-hydroxy acrylic resin composite-dispersion and a preparation method thereof, and aims to solve the problem of how to improve the grafting rate of nano silicon dioxide in silica sol in the prior art.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a silica sol-hydroxyacrylic resin composite-dispersion comprising a first component and a second component,
wherein the first component comprises the following components in parts by weight:
the second component comprises the following components in parts by weight:
and the mass ratio of the first component to the second component is 10:8 to 25.
In a second aspect, the present application provides a method for preparing a silica sol-hydroxyacrylic resin composite-dispersion, comprising the steps of:
providing each weight component of a first component of a silica sol-hydroxy acrylic resin composite-dispersion body, and carrying out first heating mixing treatment on polyethylene glycol, an anhydride or diisocyanate monomer and a first organic silicon monomer to obtain a first mixture;
then carrying out second mixing treatment on the first mixture, silica sol and water to obtain a first component;
providing each weight component of a second component of the silica sol-hydroxy acrylic resin composite-dispersion, carrying out third heating and mixing treatment on an active solvent and the solvent to obtain a second mixture, mixing part of acrylate monomers, hydroxy monomers, an initiator, a molecular weight regulator, a carboxyl monomer and a vinyl monomer with corresponding molar weights to obtain a third mixture, dropwise adding the third mixture into the second mixture at a constant speed, and carrying out heat preservation treatment to obtain a fourth mixture;
mixing the residual acrylate monomer, the hydroxyl monomer with the corresponding molar weight, the initiator, the molecular weight regulator, the carboxyl monomer and the second organosilicon monomer to obtain a fifth mixture, dropwise adding the fifth mixture into the fourth mixture at a constant speed, and carrying out heat preservation treatment to obtain a sixth mixture;
mixing the sixth mixture and a neutralizing agent to obtain a second component;
and mixing the first component, the second component and water to obtain the silica sol-hydroxy acrylic resin composite-dispersion.
The silica sol-hydroxy acrylic resin composite-dispersion provided by the first aspect of the application comprises a first component and a second component, wherein the raw material component in the first component comprises silica sol which is used as a nano silica source and a reaction medium during modification of the nano silica, and compared with the use of solvents such as ethanol and the like, the silica sol-hydroxy acrylic resin composite-dispersion is safe, environment-friendly and low in cost; in addition, a long hydrophilic chain segment is introduced into the provided modified organic silicon, the chain segment can play a steric hindrance role in silica sol, can block or slow self-polymerization of siloxane after hydrolysis, and can be adsorbed to the surface of the nano silicon dioxide particles through a hydrogen bond effect, so that the grafting rate of the organic silicon on the surface of the nano silicon dioxide particles is greatly improved; because the nano silicon dioxide in the silica sol is well modified, the silica sol-hydroxyacrylic acid dispersoid prepared by the invention has good storage stability, has high film hardness and good dulling performance compared with the common hydroxyacrylic acid dispersoid, has better water resistance compared with the conventional silica sol-hydroxyacrylic acid composite dispersoid, and is more beneficial to wide application.
In the preparation method, raw materials of a first component and a second component are respectively provided, the first component and the second component are respectively prepared, and then the first component, the second component and water are mixed according to a proportion to obtain the silica sol-hydroxy acrylic resin composite-dispersion.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, which means that there may be three relationships, for example, a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In this application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the specification of the embodiments of the present application may not only refer to the specific content of each component, but also refer to the proportional relationship of the weight of each component, and therefore, the proportional enlargement or reduction of the content of the related components according to the specification of the embodiments of the present application is within the scope disclosed in the specification of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The first aspect of the embodiments of the present application provides a silica sol-hydroxyacrylic resin composite-dispersion, which comprises a first component and a second component,
wherein the first component comprises the following components in parts by weight:
the second component comprises the following components in parts by weight:
and the mass ratio of the first component to the second component is 10:8 to 25.
The silica sol-hydroxyacrylic acid resin composite-dispersion provided by the first aspect of the embodiment of the application comprises a first component and a second component, wherein the raw material component in the first component comprises silica sol, the silica sol is used as both a nano silica source and a reaction medium during modification of the nano silica, and compared with the use of solvents such as ethanol and the like, the silica sol is safe, environment-friendly and low in cost; in addition, a long hydrophilic chain segment is introduced into the provided modified organic silicon, the chain segment can play a steric hindrance role in silica sol, can block or slow self-polymerization of siloxane after hydrolysis, and can be adsorbed to the surface of the nano silicon dioxide particles through a hydrogen bond effect, so that the grafting rate of the organic silicon on the surface of the nano silicon dioxide particles is greatly improved; because the nano silicon dioxide in the silica sol is well modified, the silica sol-hydroxyacrylic acid dispersoid prepared by the invention has good storage stability, has high film hardness and good dulling property compared with the common hydroxyacrylic acid dispersoid, has better water resistance compared with the conventional silica sol-hydroxyacrylic acid composite dispersoid, and is more favorable for wide application.
In the first component of the silica sol-hydroxyacrylic resin composite-dispersion, the first component comprises 100 parts of silica sol. In some embodiments, the silica sol is an aqueous dispersion of nano-silica, wherein the aqueous dispersion of nano-silica has a solid content of 15% to 35%, a pH of 2 to 11, and an average particle size of 15 to 70nm.
In the first component of the silica sol-hydroxy acrylic resin composite-dispersion, the first component comprises 1.2-20 parts of polyethylene glycol. In some embodiments, the polyethylene glycol has a molecular weight of 100 to 1000. In some embodiments, the polyethylene glycol has a molecular weight of 100 to 400; further, the molecular weight of the polyethylene glycol is 100 to 200.
In some embodiments, the added parts of the polyethylene glycol in the first component of the silica sol-hydroxyacrylic resin composite-dispersion are selected from 1.2 parts, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts.
In the first component of the silica sol-hydroxy acrylic resin composite-dispersion, the first component comprises 1.2-5.6 parts of anhydride or diisocyanate monomer.
In some embodiments, the anhydride comprises at least one of phthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, trimellitic anhydride. In some embodiments, the anhydride is selected from at least one of phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, adipic anhydride.
In some embodiments, the diisocyanate monomer comprises at least one of toluene diisocyanate, diphenylmethane, diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethylene diisocyanate. In some embodiments, the diisocyanate monomer is selected from hexamethylene diisocyanate.
In some embodiments, the number of anhydride or diisocyanate monomers in the first component of the silica sol-hydroxyacrylic resin composite-dispersion is selected from 1.2 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts. 5 parts, 5 parts and 5.6 parts.
In the first component of the silica sol-hydroxy acrylic resin composite-dispersion, the first component comprises 3-9 parts of a first organic silicon monomer.
In some embodiments, the first silicone monomer is selected from silicone monomers having only one epoxy group as a functional group or silicone monomers having only one amino group as a functional group.
In some embodiments, the silicone monomer having one and only one epoxy group as a functional group is selected from gamma- (2, 3-glycidoxy) propyltrimethoxysilane.
In some embodiments, the silicone monomer having one and only one amino group as a functional group is selected from the group consisting of gamma-aminopropyltriethoxysilane.
In some embodiments, when the anhydride is selected in the first component, the first silicone monomer is selected from silicone monomers having one and only one epoxy group as a functional group.
In some embodiments, when the diisocyanate monomer is selected in the first component, the first silicone monomer is selected from silicone monomers having one and only one amino group as a functional group.
In some embodiments, the added parts of the first silicone monomer in the first component of the silica sol-hydroxyacrylic resin composite-dispersion are selected from 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts.
In the first component of the silica sol-hydroxyacrylic resin composite-dispersion, the first component comprises 50 to 100 parts of water, and the provision of water as a solvent can facilitate the mixing of the raw materials.
The silica sol-hydroxy acrylic resin composite-dispersion comprises a second component, and the second component comprises 22-82 parts of acrylate monomers.
In some embodiments, the acrylate monomer includes at least one of an ester compound of acrylic acid, methacrylic acid. In some embodiments, the ester of methacrylic acid compound comprises at least one of methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, benzyl methacrylate, cyclohexyl acrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, n-butyl methacrylate, isooctyl methacrylate, dodecyl acrylate, dodecyl methacrylate, n-hexyl methacrylate.
In the silica sol-hydroxy acrylic resin composite-dispersoid, the addition parts of the acrylate monomer are selected from 22 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts and 82 parts.
The silica sol-hydroxy acrylic resin composite-dispersion comprises a second component, and the second component comprises 1-15 parts of vinyl monomer.
In some embodiments, the vinyl monomer comprises at least one of vinyl acetate, acrylonitrile, methacrylonitrile, styrene, methylstyrene, vinyl versatate. In some embodiments, the vinyl monomer is selected from styrene.
In some embodiments, the vinyl monomer is added in a number of parts selected from 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, and 15 parts of the second component of the silica sol-hydroxyacrylic resin composite-dispersion.
The silica sol-hydroxy acrylic resin composite-dispersion comprises a second component, and the second component comprises 5-25 parts of hydroxy monomer.
In some embodiments, the hydroxyl monomer comprises at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate. In some embodiments, the hydroxyl monomer is selected from hydroxyethyl methacrylate.
In some embodiments, the added parts of the hydroxyl monomer of the second component of the silica sol-hydroxyacrylic resin composite-dispersion are selected from 5 parts, 10 parts, 15 parts, 20 parts, 25 parts.
The silica sol-hydroxy acrylic resin composite-dispersion comprises a second component, and the second component comprises 2-9 parts of carboxyl monomer. Wherein the amount of the carboxyl monomer is not less than that of the active solvent.
In some embodiments, the carboxyl monomer comprises at least one of acrylic acid, methacrylic acid.
In some embodiments, the added parts of the carboxyl monomer of the second component of the silica sol-hydroxyacrylic resin composite-dispersion are selected from 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts.
The silica sol-hydroxy acrylic resin composite-dispersoid comprises a second component and the second component comprises 0.1 to 15 parts of active solvent. In some embodiments, the reactive solvent is selected from glycidyl versatate.
The silica sol-hydroxy acrylic resin composite-dispersion comprises a second component, and the second component comprises 0.5-3 parts of initiator.
In some embodiments, the initiator comprises at least one of dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, di-t-amyl peroxide, t-amyl peroxyacetate, t-butyl peroxybenzoate, t-amyl peroxybenzoate, and cyclohexanone peroxide. In some preferred embodiments, the initiator is selected from the group consisting of di-t-butyl peroxide, di-t-amyl peroxide, t-butyl peroxybenzoate, t-amyl peroxybenzoate.
In some embodiments, the added parts of the initiator in the second component of the silica sol-hydroxyacrylic resin composite-dispersion include 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts.
The silica sol-hydroxy acrylic resin composite-dispersoid comprises a second component, and the second component comprises 0.15 to 1.5 parts of molecular weight regulator.
In some embodiments, the molecular weight regulator comprises at least one of mercaptoethanol, mercaptoacetic acid, mercaptopropanol, mercaptopropionic acid, alpha-methylstyrene linear dimer, dodecyl mercaptan.
In some embodiments, the added parts of the molecular weight regulator in the second component of the silica sol-hydroxyacrylic resin composite-dispersion include 0.15 parts, 0.5 parts, 1 part, 1.5 parts.
The silica sol-hydroxy acrylic resin composite-dispersion comprises a second component, and the second component comprises 4-10 parts of solvent.
In some embodiments, the solvent comprises at least one of ethylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, diethylene glycol butyl ether, dipropylene glycol butyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, N-methylpyrrolidone, and # 100 mineral spirits.
In some embodiments, the added parts of the solvent in the second component of the silica sol-hydroxyacrylic resin composite-dispersion include 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, and 10 parts.
The silica sol-hydroxy acrylic resin composite-dispersion comprises a second component, and the second component comprises 0.1-3 parts of a second organic silicon monomer.
In some embodiments, the second silicone monomer is selected from silicone monomers containing double bonds.
In some embodiments, the double bond containing silicone monomer includes at least one of gamma-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, methylvinyldimethoxysilane.
In some embodiments, the added parts of the second silicone monomer include 0.1 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts.
The silica sol-hydroxy acrylic resin composite-dispersoid comprises a second component and the second component comprises 2.5 to 6 parts of neutralizer.
In a second aspect of the embodiments of the present application, there is provided a method for preparing a silica sol-hydroxyacrylic resin composite-dispersion, including the following steps:
s01, providing each weight component of a first component of a silica sol-hydroxy acrylic resin composite-dispersion body, and carrying out first heating mixing treatment on polyethylene glycol, anhydride or diisocyanate monomer and a first organic silicon monomer to obtain a first mixture;
s02, performing second mixing treatment on the first mixture, silica sol and water to obtain a first component;
s03, providing each weight component of a second component of the silica sol-hydroxy acrylic resin composite-dispersion, carrying out third heating and mixing treatment on an active solvent and the solvent to obtain a second mixture, mixing part of acrylate monomers, hydroxy monomers, an initiator, a molecular weight regulator, carboxyl monomers and vinyl monomers with corresponding molar weights to obtain a third mixture, dropwise adding the third mixture into the second mixture at a constant speed, and carrying out heat preservation treatment to obtain a fourth mixture;
s04, mixing the residual acrylate monomer, the hydroxyl monomer with the corresponding molar weight, the initiator, the molecular weight regulator, the carboxyl monomer and the second organic silicon monomer to obtain a fifth mixture, dropwise adding the fifth mixture into the fourth mixture at a constant speed, and carrying out heat preservation treatment to obtain a sixth mixture;
s05, mixing the sixth mixture and a neutralizing agent to obtain a second component;
and S06, mixing the first component, the second component and water to obtain the silica sol-hydroxy acrylic resin composite-dispersion.
In the preparation method of the silica sol-hydroxyacrylic acid resin composite-dispersion provided in the second aspect of the embodiment of the present application, raw materials of the first component and the second component are provided, the first component and the second component are obtained by preparation, and the first component, the second component and water are mixed according to a ratio to obtain the silica sol-hydroxyacrylic acid resin composite-dispersion.
In step S01, providing each weight component of the first component of the silica sol-hydroxyacrylic acid resin composite-dispersion, and performing a first heating and mixing treatment on a polyethylene glycol, an anhydride or diisocyanate monomer, and a first organic silicon monomer to obtain a first mixture.
In some embodiments, the temperature of the first heat mixing treatment is 70 to 135 ℃ for 2 to 4 hours.
In step S02, the first mixture, silica sol, and water are subjected to a second mixing process to obtain a first component.
In some embodiments, the step of subjecting the first mixture, silica sol and water to a second mixing process includes: and cooling the first mixture to 35-65 ℃, adding silica sol within 10-30 min, stirring for 1-2 h, adding water, adjusting the solid content to 20-35%, and gradually cooling to room temperature to obtain the first component.
In step S03, providing each weight component of the second component of the silica sol-hydroxyacrylic resin composite-dispersion, performing a third heating and mixing process on the active solvent and the solvent to obtain a second mixture, mixing a part of the acrylate monomer, the hydroxyl monomer, the initiator, the molecular weight regulator, the carboxyl monomer, and the vinyl monomer in the corresponding molar weight to obtain a third mixture, dropwise adding the third mixture into the second mixture at a constant speed, and performing a heat preservation process to obtain a fourth mixture.
In some embodiments, the temperature of the third heat mixing process is 130 to 160 ℃.
In some embodiments, the step of dropping the third mixture into the second mixture at a constant speed and performing heat preservation treatment to obtain the fourth mixture includes: and dropwise adding the third mixture into the second mixture at a constant speed within 3-5 hours, and carrying out heat preservation treatment for 0.5-1 hour to obtain a fourth mixture.
In step S04, mixing the remaining acrylate monomer, the hydroxyl monomer, the initiator, the molecular weight regulator, the carboxyl monomer, and the second organosilicon monomer in a corresponding molar amount to obtain a fifth mixture, dropwise adding the fifth mixture at a constant speed to the fourth mixture, and performing heat preservation to obtain a sixth mixture.
In some embodiments, the step of dropping the fifth mixture into the fourth mixture at a constant speed and performing heat preservation treatment to obtain a sixth mixture includes: and dropwise adding the fifth mixture into the fourth mixture at a constant speed within 1-2 hours, and carrying out heat preservation treatment for 1.5-3 hours to obtain a sixth mixture.
In step S05, the sixth mixture and the neutralizing agent are mixed to obtain the second component.
In some embodiments, the step of mixing the sixth mixture and the neutralizing agent comprises: and cooling the sixth mixture to 70-90 ℃, adding a neutralizing agent, mixing for 0.5-1 hour, and cooling to 60-80 ℃ to obtain a second component.
In step S06, the first component, the second component and water are mixed to obtain the silica sol-hydroxy acrylic resin composite-dispersion.
In some embodiments, the step of mixing the first component, the second component and water comprises: adding the first component into the second component at a constant speed within 1-2 hours, adding water at a constant speed within 0.5-1 hour, and mixing for 0.5 hour to obtain the silica sol-hydroxy acrylic resin composite-dispersion.
The following description is given with reference to specific examples.
Example 1
Silica sol-hydroxy acrylic resin composite-dispersion and preparation method thereof
(1) The first component of the silica sol-hydroxyacrylic resin composite dispersion is as follows in table 1:
TABLE 1
The preparation method comprises the following steps: adding PEG200, phthalic anhydride and KH-560 into a reaction kettle, starting stirring, heating to 125 ℃, keeping the temperature, cooling to 40 ℃ after 2.5h, increasing the stirring speed, adding silica sol within 30min at constant speed, continuing stirring for 1h, adding water, and cooling to room temperature to obtain modified silica sol with the solid content of 25.0%.
(2) The second component of the silica sol-hydroxyacrylic resin composite-dispersion is as follows in table 2:
TABLE 2
The preparation method comprises the following steps: adding ethylene glycol monobutyl ether, 100# solvent and E10P into a reaction kettle, starting stirring, heating to 150 ℃, dropwise adding M1 at a constant speed for 4h, keeping the temperature for 1h after dropwise adding, dropwise adding M2 at a constant speed for 1.5h, and keeping the temperature for 2h after dropwise adding. After the heat preservation is finished, the temperature is reduced to 80 ℃, DMEA is added at a constant speed within 15min, and the mixture is continuously stirred for 0.5h to obtain the hydroxyl acrylic resin (the temperature is maintained at 80 ℃ for standby).
(3) Mixing the first component and the second component to obtain the silica sol-hydroxy acrylic resin composite-dispersoid, wherein the addition parts of the components are shown in Table 3,
TABLE 3
The preparation method comprises the following steps: and (3) increasing the stirring speed, adding the modified silica sol into the hydroxyacrylic acid resin at a constant speed within 1h, continuously stirring for 0.5h, then adding water at a constant speed within 0.5h, stirring, cooling to room temperature, and filtering to obtain the silica sol-hydroxyacrylic acid resin composite-dispersion.
The properties are shown in table 4 below,
TABLE 4
Comparative example 1
Composite dispersion and method for producing same
(1) A conventional silica sol modification formulation is shown in table 5,
TABLE 5
| Name(s) | Dosage per gram | Remarks for note |
| KH-560 | 45 | Same as example 1 |
| Silica sol | 1000 | Same as example 1 |
| Water (W) | 335 | Self-made deionized water |
The preparation method comprises the following steps: adding silica sol into a reaction kettle, starting stirring, heating to 45 ℃, adding KH-560 at a constant speed within 30min, continuously stirring for 6h, adding water, and cooling to room temperature to obtain modified silica sol (comparative example) with a solid content of 25.0%.
(2) The composite dispersion formulations are shown in table 6,
TABLE 6
| Name(s) | Dosage per gram | Remarks to note |
| Hydroxyacrylic resin (80 ℃ C.) | 95 | Example 1 |
| Modified silica Sol (comparative example) | 100 | Comparative example 1 |
| Water (W) | 40 | Self-made deionized water |
The preparation method comprises the following steps: and (3) increasing the stirring speed, adding the hydroxyl acrylic acid resin into the modified silica sol at a constant speed within 1 hour, continuously stirring for 0.5 hour, then adding water at a constant speed within 0.5 hour, stirring, cooling to room temperature, and filtering to obtain the composite dispersion.
The properties are shown in table 7 below,
TABLE 7
Comparative example 2
Composite dispersion and method for producing same
The formulation of the composite dispersion is shown in table 8,
TABLE 8
| Name (R) | Parts by mass | Remarks to note |
| Hydroxyacrylic acid resin (80 ℃ C.) | 100 | Example 1 |
| Water (I) | 90 | Self-made deionized water |
The preparation method comprises the following steps: increasing the stirring speed, adding the hydroxyacrylic acid resin into the water at a constant speed within 1h, continuously stirring for 0.5h, cooling to room temperature, and filtering to obtain the dispersion.
The properties are shown in table 9 below,
TABLE 9
Performance testing and results analysis
The varnish was prepared from the products obtained in example 1, comparative example 1 and comparative example 2 according to the formulation shown in Table 10 below.
Watch 10
Note: the dosage of each material is mass portion, the solid content of the component A and the component B after being mixed with the diluent is 40 (+/-1)%.
A. After the component B and the thinner were mixed uniformly, a coating film of 100 μm (wet film thickness) was prepared on a UV-primed wood board (700 mesh sandpaper), and after the coating film had dried, it was baked in an oven at 50 ℃ for 2 hours, and then cured in a standard environment (temperature 23 (+ -2) ° C, humidity 50% RH) for 7 days, and the properties of the coating film were tested, as shown in Table 11 below, it can be seen that the varnish containing the product of example 1 had high hardness, excellent gloss, and only slight whitening after 48 hours of soaking in water, and excellent properties.
TABLE 11
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A silica sol-hydroxy acrylic resin composite-dispersion is characterized in that the silica sol-hydroxy acrylic resin composite-dispersion comprises a first component and a second component,
wherein the first component comprises the following components in parts by weight:
the second component comprises the following components in parts by weight:
and the mass ratio of the first component to the second component is 10:8 to 25.
2. The silica sol-hydroxyacrylic resin composite-dispersion according to claim 1, wherein the silica sol is an aqueous dispersion of nanosilica, wherein the aqueous dispersion of nanosilica has a solid content of 15% to 35%, a pH of 2 to 11, and wherein the nanosilica has an average particle diameter of 15 to 70nm.
3. The silica sol-hydroxyacrylic resin composite-dispersion according to claim 1, wherein said acid anhydride comprises at least one of phthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, trimellitic anhydride; and/or the presence of a gas in the gas,
the diisocyanate monomer comprises at least one of toluene diisocyanate, diphenylmethane, diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexyl methylene diisocyanate; and/or the presence of a gas in the gas,
the first organic silicon monomer is selected from organic silicon monomers with only one epoxy group as a functional group or organic silicon monomers with only one amino group as a functional group; and/or the presence of a gas in the atmosphere,
the molecular weight of the polyethylene glycol is 100-1000.
4. The silica sol-hydroxyacrylic resin composite-dispersion according to claim 3, wherein the organosilicon monomer having one and only one epoxy group as functional group is selected from the group consisting of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane; and/or the presence of a gas in the gas,
the organosilicon monomer with only one amino group as a functional group is selected from gamma-aminopropyl triethoxysilane.
5. The silica sol-hydroxyacrylic resin composite-dispersion according to claim 3, characterized in that when an acid anhydride is selected in the first component, the first silicone monomer is selected from silicone monomers having only one epoxy group as a functional group; or the like, or, alternatively,
when a diisocyanate monomer is selected in the first component, the first organosilicon monomer is selected from organosilicon monomers having only one amino group as a functional group.
6. The silica sol-hydroxyacrylic resin composite-dispersion according to claim 1, wherein the acrylate monomer comprises at least one of ester compounds of acrylic acid, methacrylic acid; and/or the presence of a gas in the gas,
the vinyl monomer comprises at least one of vinyl acetate, acrylonitrile, methacrylonitrile, styrene, methyl styrene and vinyl versatate; and/or the presence of a gas in the gas,
the hydroxyl monomer comprises at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; and/or the presence of a gas in the gas,
the carboxyl monomer comprises at least one of acrylic acid and methacrylic acid.
7. The silica sol-hydroxyacrylic resin composite-dispersion according to claim 1, characterized in that the reactive solvent is selected from the group consisting of glycidyl versatate; and/or the presence of a gas in the gas,
the initiator comprises at least one of dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, di-tert-amyl peroxide, tert-amyl peroxyacetate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate and cyclohexanone peroxide; and/or the presence of a gas in the gas,
the molecular weight regulator comprises at least one of mercaptoethanol, mercaptoacetic acid, mercaptopropanol, mercaptopropionic acid, an alpha-methyl styrene linear dimer and dodecyl mercaptan; and/or the presence of a gas in the atmosphere,
the solvent comprises at least one of ethylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, diethylene glycol butyl ether, dipropylene glycol butyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, N-methyl pyrrolidone and 100# solvent oil; and/or the presence of a gas in the gas,
the second organosilicon monomer is selected from organosilicon monomers containing double bonds.
8. The silica sol-hydroxyacrylic resin composite-dispersion according to claim 7, wherein the double bond-containing silicone monomer comprises at least one of gamma-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and methylvinyldimethoxysilane.
9. A process for the preparation of the silica sol-hydroxyacrylic resin composite dispersion according to claim 1 to 8, characterized in that it comprises the following steps:
providing each weight component of a first component of the silica sol-hydroxy acrylic resin composite-dispersion, and carrying out first heating mixing treatment on a polyethylene glycol, an anhydride or diisocyanate monomer and a first organic silicon monomer to obtain a first mixture;
then carrying out second mixing treatment on the first mixture, silica sol and water to obtain a first component;
providing each weight component of a second component of the silica sol-hydroxy acrylic resin composite-dispersion, carrying out third heating and mixing treatment on an active solvent and the solvent to obtain a second mixture, mixing part of acrylate monomers, hydroxy monomers, an initiator, a molecular weight regulator, a carboxyl monomer and a vinyl monomer with corresponding molar weights to obtain a third mixture, dropwise adding the third mixture into the second mixture at a constant speed, and carrying out heat preservation treatment to obtain a fourth mixture;
mixing the rest acrylate monomer, the hydroxyl monomer with the corresponding molar weight, the initiator, the molecular weight regulator, the carboxyl monomer and the second organic silicon monomer to obtain a fifth mixture, dropwise adding the fifth mixture into the fourth mixture at a constant speed, and carrying out heat preservation treatment to obtain a sixth mixture;
mixing the sixth mixture and a neutralizing agent to obtain a second component;
and mixing the first component, the second component and water to obtain the silica sol-hydroxy acrylic resin composite-dispersion.
10. The method for preparing the silica sol-hydroxyacrylic resin composite-dispersion according to claim 9, wherein the temperature of the first heating and mixing treatment is 70 to 135 ℃ for 2 to 4 hours; and/or the presence of a gas in the atmosphere,
the step of subjecting the first mixture, silica sol and water to a second mixing treatment includes: cooling the first mixture to 35-65 ℃, adding the silica sol within 10-30 min, stirring for 1-2 h, adding water, adjusting the solid content to 20-35%, and gradually cooling to room temperature to obtain a first component; and/or the presence of a gas in the gas,
the temperature of the third heating and mixing treatment is 130-160 ℃; and/or the presence of a gas in the gas,
the step of dropwise adding the third mixture into the second mixture at a constant speed and carrying out heat preservation treatment to obtain a fourth mixture comprises the following steps: dropwise adding the third mixture into the second mixture at a constant speed within 3-5 hours, and carrying out heat preservation treatment for 0.5-1 hour to obtain a fourth mixture; and/or the presence of a gas in the atmosphere,
and dropwise adding the fifth mixture into the fourth mixture at a constant speed, and performing heat preservation treatment to obtain a sixth mixture, wherein the method comprises the following steps: dropwise adding the fifth mixture into the fourth mixture at a constant speed within 1-2 hours, and carrying out heat preservation treatment for 1.5-3 hours to obtain a sixth mixture; and/or the presence of a gas in the gas,
the step of mixing the sixth mixture and the neutralizing agent comprises: cooling the sixth mixture to 70-90 ℃, adding a neutralizing agent, mixing for 0.5-1 hour, and cooling to 60-80 ℃ to obtain a second component; and/or the presence of a gas in the gas,
the step of mixing the first component, the second component and water comprises: and adding the first component into the second component at a constant speed within 1-2 hours, and adding water at a constant speed within 0.5-1 hour to perform mixing treatment for 0.5 hour to obtain the silica sol-hydroxy acrylic resin composite-dispersion.
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