Reactive acrylate dispersing agent as well as preparation method and application thereof

Abstract

The invention discloses a reactive acrylate dispersing agent as well as a preparation method and application thereof. The reactive acrylate dispersant is prepared from the following raw materials: a hydrophilic monomer, an oleophylic monomer, a polymerization additive and an isocyanate-containing acrylate compound, wherein the oleophylic monomer comprises a high refractive index monomer of which the refractive index is greater than 1.5 at the temperature of 20 DEG C, and the polymerization additive comprises at least one of a hydroxyl type chain transfer agent and a peroxide initiator. The reactive acrylate dispersant has good compatibility with an acrylate compound, can stably disperse nanoparticles in the acrylate compound, and has a significant viscosity reduction effect; meanwhile, the reaction type acrylate dispersing agent can react with an acrylate compound so as to improve the weather resistance of an acrylate compound system coating.

Description

Technical Field

[0001] The present application relates to the field of dispersants, and in particular to a reactive acrylate dispersant and a preparation method and application thereof. Background Art

[0002] In many current application fields, such as optical communication technology, photonic computers, and display panels, high refractive index materials are needed for photon integration to increase system efficiency or protect devices. However, the refractive index of most photocurable resins is relatively low, such as acrylate resins, which are usually in the range of 1.4 to 1.55. Generally, a certain amount of inorganic nanoparticles need to be added to the photocurable resin to increase the refractive index of the photocurable resin. However, inorganic nanoparticles are inorganic materials, and photocurable resins are organic materials. The two are incompatible, and due to the surface effect of nanoparticles, the nanoparticles are easy to agglomerate and have poor stability. Therefore, adding inorganic nanoparticles to photocurable resins can easily cause thickening of the photocurable resin system. Moreover, the poor stability of nanoparticles will cause subsequent coating difficulties or product defects, which does not meet market demand.

[0003] In the prior art, a certain amount of dispersant is usually added to the photocurable resin system containing inorganic nanoparticles to reduce the viscosity of the photocurable resin system, improve the dispersibility of the nanoparticles, and facilitate the subsequent coating of the photocurable resin system. However, conventional dispersants not only have limited viscosity reduction effects, but the addition of conventional dispersants will also reduce the refractive index of the photocurable resin system and affect the refractive index of the photocurable resin system. In addition, after the photocurable resin system is cured to form a coating, the dispersant is prone to precipitation due to the weak interaction between the dispersant and the photocurable resin, which affects the weather resistance, solvent resistance and light transmittance of the coating.

[0004] Therefore, in order to meet market demand, it is necessary to design a reactive acrylate dispersant with good compatibility with photocurable resin, good nanoparticle dispersibility, significant viscosity reduction effect, the ability to react with photocurable resin and high refractive index, so as to realize the preparation of high refractive index photocurable resin system. Summary of the invention

[0005] Therefore, the technical problem to be solved by the present application is to overcome the above-mentioned defects in the prior art, and its purpose is to provide a reactive acrylate dispersant, which not only has a hydrophilic group and a lipophilic group, but can be respectively affinity with nanoparticles and acrylate compounds, thereby achieving the effect of significantly reducing the viscosity of the system and improving the stable dispersion of nanoparticles in acrylate compounds. More importantly, the reactive acrylate dispersant is reactive and can react with acrylate compounds to improve the stability and weather resistance of the acrylate compound system coating. Moreover, the lipophilic monomer in the reactive acrylate dispersant includes a high-refractive monomer, which can reduce the effect of adding the reactive acrylate dispersant on the refractive index of the acrylate compound system containing nanoparticles.

[0006] In a first aspect of the present application, a reactive acrylate dispersant is provided, which is prepared from the following raw materials: a hydrophilic monomer, a lipophilic monomer, a polymerization aid, and an acrylate compound containing isocyanate;

[0007] The lipophilic monomer includes a high-refractive monomer having a refractive index greater than 1.5 at 20° C., and the polymerization aid includes at least one of a hydroxyl chain transfer agent and a peroxide initiator.

[0008] On the one hand, the reactive acrylic dispersant has a hydrophilic group and a lipophilic group, which can be respectively affinity with nanoparticles and acrylic compounds, can significantly reduce the viscosity of the acrylic compound system, and improve the dispersion stability of nanoparticles in acrylic compounds. More importantly, the reactive acrylic dispersant is reactive and can react with acrylic compounds to form chemical bonds during the curing process, which is beneficial to improving the temperature resistance and weather resistance of the acrylic resin system coating; on the other hand, the lipophilic monomer in the reactive acrylic dispersant adopts a high refractive index monomer, so that the reactive acrylic dispersant has a higher refractive index, which minimizes the effect of the introduction of the reactive acrylic dispersant on the overall refractive index of the acrylic compound system, and is beneficial to the preparation of a high refractive index acrylic compound system. In addition, the acrylic compound containing isocyanate in the reactive acrylic dispersant not only introduces a carbon-carbon double bond that can react with the acrylic compound, but also improves the compatibility between the reactive acrylic dispersant and the acrylic compound, further improving the stability and weather resistance of the acrylic compound system.

[0009] In any embodiment, the raw materials for preparing the reactive acrylate dispersant further include vinyl silicone oil monomers.

[0010] The introduction of vinyl silicone oil monomers can significantly reduce the viscosity of the acrylic compound system, further significantly improve the dispersion stability of nanoparticles in the acrylic compound, and improve the refractive index of the acrylic compound system coating, while also playing a role in leveling and defoaming.

[0011] In any embodiment, the raw materials for preparing the reactive acrylate dispersant further include a hydroxyl-containing monomer.

[0012] The introduction of hydroxyl-containing monomers can increase the active sites for reaction with isocyanate-containing acrylate compounds, further effectively improve the grafting of isocyanate-containing acrylate compounds, increase the content of carbon-carbon double bonds in the reactive acrylate dispersant, and further improve the reaction activity of the reactive acrylate dispersant.

[0013] In any embodiment, the mass ratio of the hydrophilic monomer to the lipophilic monomer is 1:(1-10), and can be optionally 1:(4-8).

[0014] If the content of the hydrophilic monomer is too high, the polarity of the reactive acrylate dispersant can be enhanced, which is beneficial to improving the dispersion stability of the nanoparticles in the acrylate compound, but is not conducive to the viscosity reduction effect of the reactive acrylate dispersant on the acrylate compound system; if the content of the hydrophilic monomer is too low, the surface adsorption between the reactive acrylate dispersant and the nanoparticles is weak, the adsorption layer is weak, the steric hindrance effect between the nanoparticles is affected, and it is not conducive to the dispersion stability of the nanoparticles in the acrylate compound, resulting in an increase in the viscosity of the acrylate compound system. Therefore, the mass ratio of the hydrophilic monomer to the lipophilic monomer is controlled within an appropriate range to take into account both the viscosity reduction effect and the dispersion stability of the nanoparticles.

[0015] In any embodiment, the number average molecular weight of the reactive acrylate dispersant is 200 to 20,000, and can be optionally 400 to 10,000.

[0016] If the number average molecular weight of the reactive acrylate dispersant is too small, the adsorption between the reactive acrylate dispersant and the nanoparticles and acrylate compounds is weak, and the dispersion effect of the nanoparticles in the acrylate compounds is limited. If the number average molecular weight of the reactive acrylate dispersant is too large, the risk of intermolecular entanglement of the reactive acrylate dispersant increases, resulting in the generation of flocculation, which significantly affects the dispersion of the nanoparticles in the acrylate compounds. Therefore, the number average molecular weight of the reactive acrylate dispersant is controlled within an appropriate range to effectively improve the dispersibility of the nanoparticles in the acrylate.

[0017] In any embodiment, the hydrophilic monomer includes at least one of the compound of formula I, the compound of formula II, and the compound of formula III.

[0018]

[0019] wherein R1, R4, R6, R7, R8, and R9 each independently include hydrogen, substituted or unsubstituted C 1-4 R2 and R3 each independently include hydrogen, substituted or unsubstituted C 1-4 Alkyl, substituted or unsubstituted C 1-7 Alkoxy, substituted or unsubstituted C 1-7 R5 includes at least one of hydrogen, carboxyl, tetrahydrofuranyl, sulfonic acid, and boric acid.

[0020] In any embodiment, the isocyanate-containing acrylate compound includes a compound having a structure shown in Formula IV,

[0021]

[0022] Among them, R 11 including hydrogen, substituted or unsubstituted C 1-6 At least one of the alkyl groups, R 12 Including substituted or unsubstituted C 1-6 At least one of the alkylene groups.

[0023] In any embodiment, the hydroxyl chain transfer agent includes a compound of the structure shown in Formula V,

[0024]

[0025] Among them, R 13 Including substituted or unsubstituted C 1-6 At least one of an alkylene group and an ester group.

[0026] In any embodiment, the peroxide initiator comprises a compound having a structure shown in Formula VI,

[0027]

[0028] Among them, R 14 The moiety includes at least one of hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted benzoyl, and substituted or unsubstituted benzyl.

[0029] In any embodiment, the vinyl silicone oil monomer includes a compound of the structure shown in Formula VII,

[0030]

[0031] Among them, R 15 , R 16Each independently includes substituted or unsubstituted C 1-3 At least one of an alkyl group, a substituted or unsubstituted phenyl group, R 17 , R 18 , R 19 Each independently includes substituted or unsubstituted C 1-3 At least one of the alkyl groups.

[0032] In any embodiment, the hydroxyl-containing monomer comprises a compound of the structure shown in Formula VIII,

[0033]

[0034] Among them, R 20 including hydrogen, substituted or unsubstituted C 1-3 At least one of the alkyl groups of R 21 Including substituted or unsubstituted C 1-5 Alkyl, C 1-5 At least one of the alkoxy groups.

[0035] In any embodiment, the high-fold monomer includes a monofunctional acrylate monomer, and the monofunctional acrylate monomer includes at least one of o-phenylphenoxyethyl acrylate, (2-ethoxy)o-phenylphenoxyethyl acrylate, (ethoxy)phenol acrylate, benzyl acrylate, 3-phenoxybenzyl acrylate, 2(ethoxy)phenol acrylate, 4(ethoxy)phenol acrylate, o-phenylphenoxyethyl acrylate, 3(ethoxy)o-phenylphenoxyethyl acrylate, diphenylmethanol acrylate and modified products thereof, and optionally includes at least one of 3-phenoxybenzyl acrylate and (ethoxy)phenol acrylate.

[0036] Monofunctional acrylate monomers can form branched macromolecular segments with hydrophilic monomers under the action of polymerization aids, which can not only improve the compatibility between reactive acrylate dispersants and acrylate compounds, but also avoid cross-linking reactions to form a network structure that affects the performance of reactive acrylate dispersants due to the monofunctionality of the high-fold monomers.

[0037] In any embodiment, the number average molecular weight of the vinyl silicone oil monomer is 300-1000.

[0038] In any embodiment, the mass ratio of the hydrophilic monomer to the hydroxyl type initiator is 1:(0.015-0.6), and can be optionally 1:(0.03-0.3).

[0039] In any embodiment, the mass ratio of the hydrophilic monomer to the peroxide initiator is 1:(0.015-0.6), and can be optionally 1:(0.03-0.3).

[0040] In any embodiment, the mass ratio of the vinyl silicone oil monomer to the hydrophilic monomer is no more than 3.

[0041] In any embodiment, the mass ratio of the hydroxyl-containing monomer to the hydrophilic monomer is not higher than 0.8.

[0042] In a second aspect of the present application, a method for preparing a reactive acrylate dispersant is provided, the preparation method comprising:

[0043] Mixing initial raw materials including a hydrophilic monomer, a lipophilic monomer and a polymerization aid, and performing a first reaction to prepare a hydroxyl-containing acrylate dispersant;

[0044] The hydroxyl-containing acrylate dispersant, the isocyanate-containing acrylate compound and the catalyst are mixed to carry out a second reaction to prepare the reactive acrylate dispersant;

[0045] The lipophilic monomer comprises a high-refractive monomer having a refractive index greater than 1.5 at 20° C., the polymerization aid comprises a chain transfer agent and an initiator, the chain transfer agent comprises a hydroxyl chain transfer agent and / or the initiator comprises a peroxide initiator.

[0046] In any embodiment, the initial raw material further comprises vinyl silicone oil monomer.

[0047] In any embodiment, the initial raw material further includes a hydroxyl-containing monomer.

[0048] The third aspect of the present application provides an application of a reactive acrylate dispersant in any embodiment or a reactive acrylate dispersant prepared by a preparation method in any embodiment in nanoimprinting, 3D printing, and display panels. DETAILED DESCRIPTION

[0049] The following specifically discloses the implementation methods of the reactive acrylate dispersant and its preparation method and application of the present application. However, there may be cases where unnecessary detailed descriptions are omitted. For example, there are cases where detailed descriptions of well-known matters and repeated descriptions of actually the same structure are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the following description is provided for those skilled in the art to fully understand the present application and is not intended to limit the subject matter described in the claims. Any product that is identical or similar to the present application and is obtained by anyone under the inspiration of the present application or by combining the features of the present application with other prior arts falls within the scope of protection of the present application.

[0050] The "range" disclosed in the present application is defined in the form of a lower limit and an upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of a particular range. The range defined in this way can include or exclude end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range. For example, the numerical range "ab" represents an abbreviated representation of any real number combination between a and b, where a and b are both real numbers. For example, the numerical range "0-7" means that all real numbers between "0-7" have been fully listed in this article, and "0-7" is just an abbreviated representation of these numerical combinations. In addition, when a certain parameter is expressed as an integer ≥3, it is equivalent to disclosing that the parameter is, for example, an integer of 3, 4, 5, 6, 7, 8, 9, 10, 11, etc.

[0051] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0052] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0053] Unless otherwise specified, all steps of the present application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (1) and (2), which means that the method may include steps (1) and (2) performed sequentially, or may include steps (2) and (1) performed sequentially. For example, mentioning that the method may also include step (3) means that step (3) may be added to the method in any order, for example, the method may include steps (1), (2) and (3), or may include steps (1), (3) and (2), or may include steps (3), (1) and (2, etc.

[0054] If there is no special explanation, the "include" and "comprising" mentioned in this application represent open-ended or closed-ended expressions. For example, the "include" and "comprising" may represent that other components not listed may also be included or only the listed components may be included or only the listed components may be included.

[0055] If not specifically stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0056] The present application proposes a reactive acrylate dispersant, which is prepared from the following raw materials: a hydrophilic monomer, a lipophilic monomer, a polymerization aid, and an acrylate compound containing isocyanate;

[0057] The lipophilic monomer includes a high-refractive monomer with a refractive index greater than 1.5 at 20° C., and the polymerization aid includes at least one of a hydroxyl chain transfer agent and a peroxide initiator.

[0058] In this article, the term "reactive acrylate dispersant" refers to an acrylate dispersant having a hydrophilic group, a lipophilic group and a reactive site at the same time. Reactive acrylate dispersants include but are not limited to anionic dispersants, cationic dispersants, nonionic dispersants or zwitterionic dispersants. Reactive acrylate dispersants are used to disperse particles in a liquid to form a stable dispersion system. For example, reactive acrylate dispersants can be used to disperse nanoparticles in acrylate compounds and have reaction sites that react with acrylate compounds at the same time. For example, reactive acrylate dispersants have carbon-carbon double bonds that can react with acrylate compounds under the action of photocuring agents and light to form chemical bonds. Reactive acrylate dispersants can also disperse other types of particles in liquids, and this application is not limited here. For ease of description, the following description is based on the dispersion of nanoparticles in an acrylate compound system by reactive acrylate dispersants.

[0059] As used herein, the term "hydrophilic monomer" refers to a compound that contains at least one carbon-carbon unsaturated double bond in the molecule that can undergo free radical polymerization, and has at least one hydrophilic group in the molecular structure of the compound, and the hydrophilic group includes but is not limited to an amide group, a carboxyl group, a tetrahydrofuran group, a pyrrolidone group, an acylmorpholine group, a phosphate or a sulfonate group.

[0060] Herein, the term "high-refractive monomer" refers to a monofunctional compound having a refractive index greater than 1.5 at 20°C, and the high-refractive monomer includes a monofunctional acrylate monomer.

[0061] In this article, the term "hydroxyl type chain transfer agent" refers to a chain transfer agent containing a hydroxyl group, and the hydroxyl group in the hydroxyl type chain transfer agent does not react with hydrophilic monomers and lipophilic monomers. The hydroxyl group in the hydroxyl type chain transfer agent reacts with an acrylate compound containing isocyanate to introduce a carbon-carbon double bond, so that the reactive acrylate dispersant has reaction activity.

[0062] In this article, the term "peroxide initiator" refers to an initiator that can generate hydroxyl free radicals, and the generated hydroxyl free radicals initiate the polymerization of hydrophilic monomers and lipophilic monomers to form hydroxyl polymer segments, and the generated hydroxyl polymer segments react with acrylate compounds containing isocyanate to introduce carbon-carbon double bonds, so that the reactive acrylate dispersant has reaction activity.

[0063] In this article, the term "polymerization aid" refers to auxiliary substances added in the polymerization reaction. In addition to hydroxyl chain transfer agents and peroxide initiators, polymerization aids also include but are not limited to catalysts, emulsifiers, dispersants or terminators.

[0064] In some embodiments, the polymerization aid includes a hydroxyl-type chain transfer agent and a peroxide initiator.

[0065] In some embodiments, the polymerization aid includes a hydroxyl type chain transfer agent and a polymerization initiator.

[0066] Herein, the term "polymerization initiator" refers to an initiator that does not generate hydroxyl radicals, and the polymerization initiator includes but is not limited to azobisisobutyronitrile, azobisisoheptanenitrile or benzoyl peroxide.

[0067] In some embodiments, the polymerization aid includes a relative molecular mass regulator and a peroxide initiator.

[0068] Herein, the term "relative molecular weight regulator" refers to a chain transfer agent that does not contain a hydroxyl group. The relative molecular weight regulator is not a hydroxyl type chain transfer agent. The relative molecular weight regulator includes but is not limited to thioglycolic acid, aliphatic mercaptan or dodecyl mercaptan.

[0069] It can be understood that, on the one hand, the reactive acrylate dispersant in the present application has a hydrophilic group and a lipophilic group, which can be respectively affinity with nanoparticles (nanoparticles have hydroxyl groups on their surfaces) and acrylate compounds, significantly reduce the viscosity of the acrylate compound system, and improve the dispersion stability of the nanoparticles in the acrylate compounds. In addition, the reactive acrylate dispersant in the present application has excellent temperature resistance and can broaden its process window. On the other hand, in the present application, at least one of a hydroxyl chain transfer agent and a peroxide initiator is used to generate a hydroxyl active site on the molecular chain segment formed by copolymerization of a hydrophilic monomer and a lipophilic monomer, which is conducive to reacting with the isocyanate group in the isocyanate acrylate compound, so as to introduce a carbon-carbon double bond into the reactive acrylate dispersant, thereby The reactive acrylate dispersant is made reactive, and the reactive acrylate dispersant can react with the acrylate compound to form a chemical bond during the curing process, which is beneficial to improving the temperature resistance, weather resistance and stability of the acrylic resin system, and preventing the poor stability of the nanoparticles during the curing process, which causes the acrylate compound system coating to turn white or the nanoparticles to agglomerate, causing the acrylate compound system coating to have an undesirable phenomenon; at the same time, the lipophilic monomer in the reactive acrylate dispersant uses a high refractive index monomer, so that the reactive acrylate dispersant has a higher refractive index, which minimizes the effect of the introduction of the reactive acrylate dispersant on the overall refractive index of the acrylate compound system coating, and is beneficial to the preparation of an acrylate compound system with a high refractive index. In addition, the acrylate compound containing isocyanate in the reactive acrylate dispersant not only introduces a carbon-carbon double bond that can react with the acrylate compound, but also improves the compatibility between the reactive acrylate dispersant and the acrylate compound, further improving the overall stability and weather resistance of the acrylate compound system.

[0070] As used herein, the term "acrylate compounds" refers to compounds containing carbon-carbon double bonds and ester bonds, and acrylate compounds include acrylate oligomers and / or acrylate monomers; acrylate compounds include but are not limited to 2-phenoxyethyl acrylate, benzyl acrylate, 3-phenoxybenzyl acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, 2-acrylate-[[1,1-binaphthyl]-2,2-di(oxy-2,1-ethylidene)] ester, ethoxylated bisphenol A diacrylate, tris(2-hydroxyethyl)isocyanuric acid triacrylate and oligomers thereof.

[0071] In this article, the term "acrylate compound system" refers to a curing liquid containing nanoparticles, acrylate compounds and reactive acrylate dispersants, and the curing liquid also includes but is not limited to some additives, such as photocuring agents, diluents, leveling agents or wetting agents.

[0072] In this article, the term "acrylate compound system coating" refers to a coating prepared by an acrylate compound system under light or heating conditions, and the coating can be widely used in various optical products. The acrylate compound system can be used to prepare a coating under light conditions or under heating conditions, and this application does not limit this. For ease of description, the following description is based on a coating prepared by an acrylate compound system containing a photocuring agent under light conditions.

[0073] In some embodiments, the raw materials for preparing the reactive acrylate dispersant further include vinyl silicone oil monomers.

[0074] The introduction of vinyl silicone oil monomers can significantly reduce the viscosity of the acrylic compound system, and can further reduce the viscosity growth rate of the acrylic compound system at room temperature / high temperature, greatly improving the room temperature / high temperature dispersion stability of nanoparticles in the acrylic compound system, thereby improving the storage stability of the acrylic compound system and the weather resistance of the acrylic compound system coating, and reducing the defects on the surface of the acrylic compound system coating. At the same time, the reactive acrylic dispersant can also play a role in leveling and defoaming.

[0075] In some embodiments, the raw materials for preparing the reactive acrylate dispersant further include a hydroxyl-containing monomer.

[0076] The introduction of hydroxyl-containing monomers can increase the active sites for reaction with isocyanate-containing acrylate compounds, so that more isocyanate-containing acrylate compounds can participate in the reaction, increase the content of carbon-carbon double bonds in the reactive acrylate dispersant, and further enhance the reaction activity of the reactive acrylate dispersant.

[0077] In some embodiments, the mass ratio of the hydrophilic monomer to the lipophilic monomer is 1:(1-10). In some embodiments, the mass ratio of the hydrophilic monomer to the lipophilic monomer may be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, or any ratio within the range of any two of the above ratios.

[0078] If the content of hydrophilic monomer is too high, the polarity of reactive acrylic dispersant can be enhanced, which is beneficial to improve the dispersibility of nanoparticles in acrylic compounds. However, if the polarity of reactive acrylic dispersant is too high, it is not conducive to the viscosity reduction effect of reactive acrylic dispersant on acrylic compound system. If the content of hydrophilic monomer is too low, the surface adsorption between reactive acrylic dispersant and nanoparticles is weak, and the force of adsorption layer is weak, which affects the steric effect between nanoparticles, is not conducive to the dispersion of nanoparticles in acrylic compounds, and leads to the increase of viscosity of acrylic compound system. Therefore, the mass ratio of hydrophilic monomer to lipophilic monomer is controlled within a suitable range to achieve the best viscosity reduction effect, so that nanoparticles can be stably dispersed in acrylic compounds.

[0079] In some embodiments, the number average molecular weight of the reactive acrylate dispersant is 200 to 20000. In some embodiments, the number average molecular weight of the reactive acrylate dispersant can be 200, 400, 500, 1000, 5000, 10000, 15000, 20000, or any value in the range formed by any two of the above points.

[0080] The number average molecular weight of the reactive acrylate dispersant can be tested by any known test method in the art. For example, the end group analysis method is used for determination, and the hydroxyl value in the acrylate dispersant containing hydroxyl is determined according to the standard GB / T 7193.2-1987, and the molecular weight of the acrylate dispersant containing hydroxyl is calculated, and then combined with the molecular weight of the acrylate compound containing isocyanate and the reaction amount of the two, the number average molecular weight of the reactive acrylate dispersant is obtained.

[0081] It is understandable that reactive acrylic ester dispersants are mainly prepared by polymerization reaction. Reactive acrylic ester dispersants control their number average molecular weight by adding a large amount of chain transfer agents. The main termination mode of polymerization reaction is chain transfer termination. When the chain transfer agent is a hydroxyl-containing chain transfer agent and the initiator is a peroxide initiator that produces hydroxyl free radicals, there are hydroxyl groups at both ends of the polymer chain segment. The hydroxyl content is detected by end group analysis to calculate the hydroxyl equivalent. At this time, the number average molecular weight of the polymer chain segment is twice the hydroxyl equivalent. When the raw materials for preparing reactive acrylic ester dispersants include hydroxyl-containing monomers, the calculation of hydroxyl equivalents should deduct the effect of hydroxyl-containing monomers on hydroxyl content. Under the same conditions, the number average molecular weight of reactive acrylic ester dispersants decreases with the increase of hydroxyl content.

[0082] In addition, the number average molecular weight of the reactive acrylate dispersant can be adjusted by factors such as the content of the initiator, the content of the chain transfer agent, the reaction temperature, the activity of the added raw monomers, etc. Increasing the content of the initiator and the chain transfer agent reduces the number average molecular weight of the reactive acrylate dispersant, increasing the polymerization temperature reduces the number average molecular weight of the reactive acrylate dispersant, and high comonomer activity is conducive to the preparation of a high number average molecular weight reactive acrylate dispersant. Since an excessively large number average molecular weight of the reactive acrylate dispersant will cause nano-nano particle flocculation, in the present application, the number average molecular weight of the reactive acrylate dispersant is controlled by increasing the content of the initiator and the chain transfer agent, and under this condition, the reaction temperature and the activity of the raw monomers have little influence on its number average molecular weight.

[0083] The study found that if the number average molecular weight of the reactive acrylate dispersant is too small, the adsorption between the reactive acrylate dispersant and the nanoparticles and acrylate compounds is weak, and the dispersion effect of the nanoparticles in the acrylate compounds is limited. If the number average molecular weight of the reactive acrylate dispersant is too large, the risk of intermolecular entanglement of the reactive acrylate dispersant increases, and even leads to the generation of flocculation, which significantly affects the dispersion of the nanoparticles in the acrylate compounds. Therefore, the number average molecular weight of the reactive acrylate dispersant is controlled within an appropriate range to effectively improve the dispersibility of the nanoparticles in the acrylate.

[0084] In some embodiments, the hydrophilic monomer includes at least one of the compound of formula I, the compound of formula II, and the compound of formula III.

[0085]

[0086]

[0087] R1, R4, R6, R7, R8, and R9 each independently include hydrogen, substituted or unsubstituted C 1-4 R2 and R3 each independently include hydrogen, substituted or unsubstituted C 1-4 Alkyl, substituted or unsubstituted C 1-7 Alkoxy, substituted or unsubstituted C 1-7 R5 includes at least one of hydrogen, carboxyl, tetrahydrofuranyl, sulfonic acid, and boric acid.

[0088] In some embodiments, the compound of the structure shown in Formula I includes at least one of acrylamide, methacrylamide, (1,1-dimethyl-3-oxobutyl) methacrylamide, N,N-dimethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-n-butoxymethyl acrylamide, N-isobutoxymethyl acrylamide, acryloyl morpholine, and methacryloyl morpholine. In some embodiments, the compound of the structure shown in Formula I includes acrylamide. In some embodiments, the compound of the structure shown in Formula I includes N-hydroxymethyl (meth) acrylamide.

[0089] In some embodiments, the compound of the structure shown in formula II includes at least one of acrylic acid, methacrylic acid, maleic acid, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, sodium methacrylate 2-ethanesulfonate, potassium 3-methacrylic acid sulfonate, hydroxypropyl methacrylate phosphate, and 2-hydroxyethyl methacrylate phosphate. In some embodiments, the compound of the structure shown in formula II includes acrylic acid. In some embodiments, the compound of the structure shown in formula II includes tetrahydrofuran acrylate.

[0090] In some embodiments, the compound of the structure shown in formula III includes at least one of vinyl pyrrolidone, 4-methyl-1-vinyl-2-pyrrolidone, and 1-vinyl-3-methyl-2-pyrrolidone. In some embodiments, the compound of the structure shown in formula III includes vinyl pyrrolidone.

[0091] The hydrophilic monomers with hydrophilic groups can be adsorbed on the surface of nanoparticles, have good affinity, and can effectively improve the dispersibility of nanoparticles in acrylate compounds. In addition, both carboxyl groups and amide groups can react with hydroxyl groups on the surface of nanoparticles to further improve the dispersibility of nanoparticles. For example, acrylic acid and acrylamide can react with hydroxyl groups on the surface of nanoparticles to form chemical bonds, thereby improving the bonding strength between the reactive acrylate dispersant and the nanoparticles, and thus improving the dispersion stability of the nanoparticles. In addition, the hydrophilic monomer has a relatively high refractive index, which can improve the refractive index of the reactive acrylate dispersant, and is conducive to the preparation of high-refractive-index acrylate compound system coatings. For example, acryloylmorpholine and vinylpyrrolidone have relatively high refractive indices, which can reduce the influence of the introduction of reactive acrylate dispersants on the overall refractive index of the coating.

[0092] In some embodiments, the hydrophilic monomer includes at least two of the compounds of formula I, II, and III. In some embodiments, the hydrophilic monomer includes the compounds of formula I, II, and III.

[0093] The study found that hydrophilic monomers including compounds with structures shown in Formula I and compounds with structures shown in Formula II are more conducive to improving the dispersion of nanoparticles in acrylate compounds. For example, the reactive acrylate dispersant obtained by the simultaneous copolymerization of acrylic acid and acrylamide in the polymerization reaction can more effectively improve the dispersibility of nanoparticles in acrylate compounds.

[0094] In some embodiments, the high-fold monomer includes a monofunctional acrylate monomer, and the monofunctional acrylate monomer includes at least one of o-phenylphenoxyethyl acrylate (OPPEA), (2-ethoxy) o-phenylphenoxyethyl acrylate (OPP(EO)2A), (ethoxy)phenol acrylate (PHEA), benzyl acrylate, 3-phenoxybenzyl acrylate (PBA), 2(ethoxy)phenol acrylate (PH(EO)2A), 4(ethoxy)phenol acrylate (PH(EO)4A), o-phenylphenoxyethyl acrylate (OPPEA), 3(ethoxy) o-phenylphenoxyethyl acrylate (OPP(EO)3A), and biphenylmethanol acrylate (BPMA). In some embodiments, the high-fold monomer is o-phenylphenoxyethyl acrylate. In some embodiments, the high-fold monomer is (ethoxy)phenol acrylate.

[0095] The study found that compared with weakly polar compounds such as butyl acrylate, octyl acrylate, isobornyl acrylate or isobornyl methacrylate as lipophilic monomers, the high refractive index monomers including monofunctional acrylate monomers not only have high refractive index, but also can form branched macromolecular segments with hydrophilic monomers under the action of polymerization aids, which can effectively improve the compatibility between reactive acrylate dispersants and acrylate compounds, greatly reduce the effect of the introduction of reactive acrylate dispersants on the refractive index of acrylate compound system coatings, and realize the preparation of high refractive index coatings. In addition, since the high refractive index monomers are monofunctional, it can also avoid the cross-linking reaction to form a network structure that affects the performance of reactive acrylate dispersants.

[0096] In some embodiments, the acrylate compound containing isocyanate includes a compound of the structure shown in Formula IV,

[0097]

[0098] Among them, R 11 including hydrogen, substituted or unsubstituted C 1-6 At least one of the alkyl groups, R 12 Including substituted or unsubstituted C 1-6 At least one of the alkylene groups.

[0099] In some embodiments, the isocyanate-containing acrylate compound includes at least one of isocyanate ethyl acrylate and isocyanoethyl methacrylate.

[0100] The above-mentioned acrylate compound containing isocyanate can introduce carbon-carbon double bonds into the copolymerized chain segments of hydrophilic monomers and lipophilic monomers through the reaction between hydroxyl-isocyanate groups, so that the reactive acrylate dispersant has reaction activity, and the urethane bond formed by the hydroxyl-isocyanate group is beneficial to improving the dispersing effect of the reactive acrylate dispersant, and improving the stability, temperature resistance and weather resistance of the acrylate compound system.

[0101] In some embodiments, the hydroxyl chain transfer agent includes a compound of the structure shown in Formula V,

[0102]

[0103] Among them, R 13 Including substituted or unsubstituted C 1-6 At least one of an alkylene group and an ester group.

[0104] In some embodiments, the hydroxyl-type chain transfer agent includes at least one of mercaptoethanol, mercaptopropanol, and 2-hydroxyethyl mercaptopropionate.

[0105] The above-mentioned hydroxyl chain transfer agent can not only effectively control the number average molecular weight of the reactive acrylate dispersant, but also introduce hydroxyl groups into the chain segments of the hydrophilic monomer and the lipophilic monomer polymerization, so as to facilitate the subsequent hydroxyl-isocyanate reaction with the acrylate compound containing isocyanate, so as to make the reactive acrylate dispersant reactive.

[0106] In some embodiments, the peroxide initiator comprises a compound of the structure shown in Formula VI,

[0107]

[0108] Among them, R 14 The moiety includes at least one of hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted benzoyl, and substituted or unsubstituted benzyl.

[0109] In some embodiments, the peroxide initiator includes at least one of hydrogen peroxide, benzoic acid peroxide, and cumene hydroperoxide.

[0110] The peroxide initiator can introduce hydroxyl groups into the polymerized chain segments of the hydrophilic monomer and the lipophilic monomer, so as to facilitate the subsequent hydroxyl-isocyanate reaction with the acrylate compound containing isocyanate, so as to make the reactive acrylate dispersant reactive.

[0111] In some embodiments, the vinyl silicone oil monomer includes a compound of the structure shown in Formula VII,

[0112]

[0113] Among them, R 15 , R 16 Each independently includes substituted or unsubstituted C 1-3 At least one of an alkyl group, a substituted or unsubstituted phenyl group, R 17 , R 18 , R 19 Each independently includes substituted or unsubstituted C 1-3 At least one of the alkyl groups.

[0114] In some embodiments, the vinyl silicone oil monomer includes at least one of single-terminal vinyl phenyl silicone oil, single-terminal vinyl methyl phenyl silicone oil, and single-terminal vinyl silicone oil.

[0115] As used herein, the term "single-end" means that the vinyl silicone oil monomer contains a vinyl group at only one end.

[0116] Since the single-ended vinyl silicone oil monomer has a vinyl group at only one end, it can undergo polymerization reaction with the hydrophilic monomer and the lipophilic monomer while avoiding the cross-linking reaction to form a network structure that affects the performance of the reactive acrylate dispersant.

[0117] In some embodiments, the number average molecular weight of the vinyl silicone oil monomer is 300 to 1000. In some embodiments, the number average molecular weight of the vinyl silicone oil monomer can be 300, 400, 500, 600, 700, 800, 900, 1000, or any value in the range formed by any two of the above points.

[0118] The number average molecular weight of the vinyl silicone oil monomer is controlled within a suitable range so that the reactive acrylate dispersant has a suitable number average molecular weight and achieves an excellent viscosity reduction effect.

[0119] In some embodiments, the hydroxyl-containing monomer comprises a compound of the structure shown in Formula VIII,

[0120]

[0121] Among them, R 20 including hydrogen, substituted or unsubstituted C 1-3 At least one of the alkyl groups of R 21 Including substituted or unsubstituted C 1-5 Alkyl, C 1-5 At least one of the alkoxy groups.

[0122] In some embodiments, the hydroxyl-containing monomer includes at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate.

[0123] The above-mentioned hydroxyl-containing monomers can undergo polymerization reaction with hydrophilic monomers, lipophilic monomers, and vinyl silicone oil monomers to introduce hydroxyl groups, which is convenient for subsequent reaction with acrylate compounds containing isocyanate. In addition, since the polymerization reaction between the hydroxyl-containing monomers and the hydrophilic monomers, lipophilic monomers, and vinyl silicone oil monomers is random polymerization, it is beneficial to introduce hydroxyl groups in the middle of the main chain segment, so that the acrylate compound containing isocyanate can be used as a side chain of the molecular chain segment of the reactive acrylate dispersant, further improving the bonding strength between the reactive acrylate dispersant and the acrylate compound.

[0124] In some embodiments, the hydrophilic monomer has a refractive index greater than 1.5 at 20°C.

[0125] At 20° C., the refractive index of the hydrophilic monomer is controlled to be higher than 1.5 so that the reactive acrylate dispersant has a high refractive index and the effect of the introduction of the reactive acrylate dispersant on the refractive index of the acrylate compound system is reduced. For example, the refractive index of N-vinyl pyrrolidone or acryloylmorpholine is higher than 1.5.

[0126] In some embodiments, the refractive index of the vinyl silicone oil monomer is greater than 1.5 at 20°C.

[0127] At 20°C, the refractive index of the vinyl silicone oil monomer is controlled to be higher than 1.5, so that the reactive acrylate dispersant has a high refractive index and reduces the effect of the introduction of the reactive acrylate dispersant on the refractive index of the acrylate compound system. For example, the refractive index of the single-end vinyl phenyl silicone oil is higher than 1.5.

[0128] Controlling the hydrophilic monomer, lipophilic monomer and vinyl silicone oil monomer to have a higher refractive index so that the reactive acrylate dispersant has a high refractive index can effectively reduce the effect of the introduction of the reactive acrylate dispersant on the overall refractive index of the acrylate compound system.

[0129] The present application also provides a method for preparing a reactive acrylate dispersant, the preparation method comprising:

[0130] Under polymerizable conditions, initial raw materials including a hydrophilic monomer, a lipophilic monomer and a polymerization aid are mixed to carry out a first reaction to prepare a hydroxyl-containing acrylate dispersant;

[0131] Under polymerizable conditions, a hydroxyl-containing acrylate dispersant, an isocyanate-containing acrylate compound and a catalyst are mixed to carry out a second reaction to prepare a reactive acrylate dispersant;

[0132] The lipophilic monomer includes a high-refractive monomer with a refractive index greater than 1.5 at 20° C., the polymerization aid includes a chain transfer agent and an initiator, the chain transfer agent includes a hydroxy chain transfer agent and / or the initiator includes a peroxide initiator.

[0133] It can be understood that the hydrophilic monomer and the lipophilic monomer undergo a polymerization reaction under the action of a hydroxyl chain transfer agent and / or a peroxide initiator to prepare an acrylate dispersant containing a hydrophilic group, a lipophilic group and a hydroxyl group at the same time, and then, under the action of a catalyst, a hydroxyl-isocyanate reaction occurs with an acrylate compound containing an isocyanate to prepare a reactive acrylate dispersant having a carbon-carbon double bond. The preparation method is simple and easy to operate, and has a low production cost.

[0134] It should be noted that the polymerization aid may only include a hydroxyl chain transfer agent and may not include a peroxide initiator, but the polymerization aid must include a free radical initiator that can initiate the polymerization reaction; the polymerization aid may only include a peroxide initiator and may not include a hydroxyl chain transfer agent, but the polymerization aid must include a relative molecular mass regulator that can control the number average molecular weight of the reactive acrylate dispersant; the polymerization aid may also include a hydroxyl chain transfer agent and a peroxide initiator at the same time, but not a free radical initiator and a relative molecular mass regulator. When the chain transfer agent is a hydroxyl chain transfer agent, such as mercaptoethanol, the hydroxyl chain transfer agent can form a hydroxyl group at the end of the chain segment of the hydrophilic monomer and the lipophilic monomer copolymerization, which is convenient for subsequent reaction with the acrylate compound containing isocyanate, and each end of the chain segment of the hydrophilic monomer and the lipophilic monomer copolymerization has a hydroxyl group; when the initiator is a peroxide initiator, such as hydrogen peroxide or isopropylbenzene hydroperoxide, the residue of the peroxide initiator can form a hydroxyl group at the end of the chain segment of the hydrophilic monomer and the lipophilic monomer copolymerization, which is convenient for subsequent reaction with the acrylate compound containing isocyanate.

[0135] In some embodiments, the peroxide initiator comprises hydrogen peroxide.

[0136] Hydrogen peroxide has two hydroxyl groups. As an initiator, it can make each hydrophilic monomer and lipophilic monomer copolymerized chain segment have a hydroxyl group at the end, thereby making each reactive acrylate dispersant chain segment have a carbon-carbon double bond.

[0137] In some embodiments, the initial raw material further comprises vinyl silicone oil monomer.

[0138] Vinyl silicone oil monomers can undergo polymerization reactions with hydrophilic monomers and lipophilic monomers. Vinyl silicone oil monomers can significantly reduce the viscosity of the acrylic compound system, which is beneficial to the preparation of solvent-free high-particle content acrylic compound system coatings.

[0139] In some embodiments, the initial raw material further includes a hydroxyl-containing monomer.

[0140] The hydroxyl-containing monomer can undergo polymerization reaction with the hydrophilic monomer and the lipophilic monomer. The introduction of the hydroxyl-containing monomer can provide more hydroxyl reaction sites. The hydroxyl reaction active site can be at the end of the chain segment copolymerized with the hydrophilic monomer and the lipophilic monomer, or in the middle of the chain segment copolymerized with the hydrophilic monomer and the lipophilic monomer, thereby further improving the quality of the acrylate compound containing isocyanate participating in the reaction, thereby improving the bonding strength between the reactive acrylate dispersant and the acrylate compound, and improving the weather resistance of the acrylate compound system coating.

[0141] In some embodiments, the initial raw material further comprises a vinyl silicone oil monomer and a hydroxyl-containing monomer.

[0142] In some embodiments, the mass ratio of the hydrophilic monomer to the lipophilic monomer is 1:(1-10).

[0143] In some embodiments, the mass content of the vinyl silicone oil is not more than 20% based on the total mass of the initial raw materials. In some embodiments, the mass content of the vinyl silicone oil is 0.01%, 0.05%, 0.1%, 0.5%, 1%, 2%, 4%, 5%, 6%, 8%, 10%, 12%, 14%, 15%, 16%, 18%, 20%, or any value in the range formed by any two of the above points based on the total mass of the initial raw materials.

[0144] The introduction of vinyl silicone oil can reduce the viscosity of the acrylic compound system. If the mass content of vinyl silicone oil is too high, it will affect the compatibility between the reactive acrylic dispersant and the acrylic compound, thereby reducing its dispersion performance, and it is easy to cause adverse phenomena such as precipitation of the reactive acrylic dispersant, which seriously affects the quality of the product. Therefore, controlling the mass content of vinyl silicone oil within an appropriate range can take into account both dispersion performance and viscosity reduction effect.

[0145] In some embodiments, the mass content of the hydroxyl-containing monomer is not higher than 5% based on the total mass of the initial raw materials. In some embodiments, the mass content of the hydroxyl-containing monomer is 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, or any value in the range formed by any two of the above points based on the total mass of the initial raw materials.

[0146] The mass content of the hydroxyl-containing monomer is controlled within a suitable range, that is, it can provide enough hydroxyl groups to react with the acrylate compound containing isocyanate, and avoid too many active sites of hydroxyl groups resulting in excessive mass content of the acrylate compound containing isocyanate. The mass content of the hydrophilic monomer and the lipophilic monomer is relatively low, which affects the dispersibility of the reactive acrylate dispersant.

[0147] In some embodiments, the mass content of the chain transfer agent is 0.5% to 4% based on the total mass of the initial raw materials. In some embodiments, the mass content of the chain transfer agent is 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, or any value in the range formed by any two of the above points based on the total mass of the initial raw materials.

[0148] In some embodiments, the mass content of the initiator is 0.5% to 4% based on the total mass of the initial raw materials. In some embodiments, the mass content of the initiator is 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, or any value in the range formed by any two of the above points based on the total mass of the initial raw materials.

[0149] Initiator and chain transfer agent can control the number average molecular weight of reactive acrylate dispersant by synergistic effect. Too much mass content of initiator and / or chain transfer agent will cause the number average molecular weight of reactive acrylate dispersant to decrease, and too little mass content of initiator and / or chain transfer agent will cause the polymerization reaction to fail to initiate normally or the number average molecular weight of reactive acrylate dispersant to be too large. Therefore, the mass content of initiator and chain transfer agent is controlled within a suitable range, taking into account the number average molecular weight of reactive acrylate dispersant and the normal progress of polymerization reaction. In addition, when chain transfer agent is hydroxyl type chain transfer and / or initiator is peroxide initiator, the mass content of chain transfer agent and / or initiator affects the number of hydroxyl reaction sites, thereby affecting the content of reactive active sites of reactive acrylate dispersant.

[0150] In some embodiments, the sum of the mass contents of the chain transfer agent and the initiator is not less than 2% based on the total mass of the initial raw materials. In some embodiments, the sum of the mass contents of the chain transfer agent and the initiator can be 2%, 2.2%, 2.4%, 2.5%, 2.6%, 3%, 3.2%, 3.4%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, or any value in the range formed by any two of the above points based on the total mass of the initial raw materials. Avoid excessive number average molecular weight of the reactive acrylate dispersant.

[0151] In some embodiments, the temperature of the first reaction is 60°C to 100°C, and the time of the first reaction is 2h to 8h. In some embodiments, the temperature of the first reaction can be selected as 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, or any value in the range formed by any two of the above points, and the time of the first reaction can be selected as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, or any value in the range formed by any two of the above points.

[0152] If the temperature of the first reaction is too high, it is easy to cause implosion and it is difficult to control the polymerization reaction. If the temperature of the first reaction is too low, the reaction time will be too long, increasing the time cost. Therefore, the reaction time and reaction temperature of the first reaction are controlled within a suitable range to make the first reaction proceed smoothly and quickly.

[0153] In some embodiments, the temperature of the second reaction is 40°C to 70°C, and the time of the second reaction is 0.5h to 3h. In some embodiments, the temperature of the second reaction can be 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, or any value in the range formed by any two of the above points, and the time of the second reaction can be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, or any value in the range formed by any two of the above points.

[0154] The study found that the second reaction is an exothermic reaction. Further controlling the temperature of the second reaction to 40°C to 70°C can prevent the explosion of the second reaction and prepare a reactive acrylate dispersant with a suitable number average molecular weight.

[0155] In some embodiments, the catalyst in the second reaction includes at least one of dibutyltin dilaurate, N-ethylmorpholine, and triethylamine.

[0156] In some embodiments, the mass content of the catalyst is 0.1% to 0.3% based on the total mass of the hydroxyl-containing acrylate dispersant and the isocyanate-containing acrylate compound. In some embodiments, the mass content of the catalyst can be 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, or any value in the range formed by any two of the above points, based on the total mass of the hydroxyl-containing acrylate dispersant and the isocyanate-containing acrylate compound.

[0157] In some embodiments, the mass ratio of the isocyanate acrylate compound to the hydroxyl group in the hydroxyl-containing acrylate dispersant is 1:(1-1.2). In some embodiments, the mass ratio of the isocyanate acrylate compound to the hydroxyl group in the hydroxyl-containing acrylate dispersant can be 1:1, 1:1.02, 1:1.04, 1:1.05, 1:1.06, 1:1.08, 1:1.1, 1:1.12, 1:1.14, 1:1.15, 1:1.16, 1:1.18, or any ratio in the range of any two of the above ratios.

[0158] The hydroxyl value of the acrylate dispersant containing hydroxyl groups can be tested by any known test method in the art, for example, by using the end group analysis method and referring to the standard GB / T 7193.2-1987 to determine the hydroxyl value.

[0159] Controlling the mass ratio of the isocyanate acrylate compound to the hydroxyl group in the hydroxyl-containing acrylate dispersant within an appropriate range can provide enough isocyanate acrylate compounds for reaction so that the reactive acrylate dispersant has more reactive sites, avoid residual hydroxyl groups in the reactive acrylate dispersant affecting its stability, and avoid excessive isocyanate acrylate compound residues affecting the stability of the reactive acrylate dispersant.

[0160] In some embodiments, at 25°C, the initial viscosity of the acrylate compound system containing the reactive acrylate dispersant is 50cps to 1500cps, and after standing at 50°C for 7 days, the viscosity growth rate of the acrylate compound system containing the reactive acrylate dispersant at 25°C is not higher than 10%.

[0161] The reactive acrylate dispersant in the present application has excellent dispersibility and high-temperature dispersion stability, can avoid the influence of temperature increase on its dispersibility, and broadens its application field.

[0162] The present application also provides applications of reactive acrylate dispersants in some embodiments or reactive acrylate dispersants prepared by preparation methods in nanoimprinting, 3D printing, and display panels.

[0163] Example

[0164] The following examples are provided for a better understanding of the present invention, are not limited to the best mode of implementation, and do not limit the content and scope of the present invention. If no specific experimental steps or conditions are specified in the examples, the operation or conditions of the conventional experimental steps described in the literature in this area can be carried out. If the manufacturer is not specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially. If not otherwise specified, the raw materials in the examples and comparative examples are purchased from Sigma-Aldrich.

[0165] 1. Preparation method

[0166] Example 1

[0167] 1) Preparation of reactive acrylate dispersant

[0168] Acrylic acid and o-phenylphenoxyethyl acrylate (OPPEA) were added into a reaction flask, and mercaptoethanol and hydrogen peroxide were added, and the temperature was raised to 80° C. for reaction for 4 hours to obtain a hydroxyl-containing acrylate dispersant, and the hydroxyl content of the hydroxyl-containing acrylate dispersant was measured;

[0169] Add dibutyltin dilaurate to the above hydroxyl-containing acrylate dispersant, add ethyl isocyanate acrylate dropwise at 60° C., and after the addition is completed, keep the mixture at 60° C. for 2 hours to obtain a reactive acrylate dispersant with a number average molecular weight of 3000;

[0170] The mass ratio of acrylic acid to OPPEA is 1:5, the mass of the initiator hydrogen peroxide accounts for 2% of the total mass of acrylic acid, OPPEA, mercaptoethanol and hydrogen peroxide, the mass of the chain transfer agent mercaptoethanol accounts for 2% of the total mass of acrylic acid, OPPEA, mercaptoethanol and hydrogen peroxide, the mass of the catalyst dibutyltin dilaurate accounts for 0.2% of the total mass of the hydroxyl-containing acrylate dispersant and isocyanate ethyl acrylate, and the mass ratio of the hydroxyl group in the isocyanate ethyl acrylate and the hydroxyl group in the hydroxyl-containing acrylate dispersant is 1:1.

[0171] 2) Preparation of photocurable liquid

[0172] The above-mentioned reactive acrylate dispersant, ZrO2 nanoparticles and OPPEA were stirred and evenly mixed in a mass ratio of 2:50:47, and ultrasonically dispersed for 1 hour until the solution became clear and transparent, and then 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator 1173, the mass ratio of reactive acrylate dispersant to photoinitiator 1173 was 2:1) was added and stirred until the photoinitiator 1173 was completely dissolved to obtain the photocurable liquid of Example 1.

[0173] Example 2

[0174] The preparation methods of the reactive acrylate dispersant and the photocurable liquid of Example 2 are similar to those of the reactive acrylate dispersant and the photocurable liquid of Example 1, except that: a single-terminal vinyl phenyl silicone oil is introduced into the preparation of the reactive acrylate dispersant of Example 2. The specific preparation method is as follows:

[0175] 1) Preparation of reactive acrylate dispersant

[0176] Acrylic acid, o-phenylphenoxyethyl acrylate (OPPEA) and single-end vinyl phenyl silicone oil are added into a reaction flask, and then mercaptoethanol and hydrogen peroxide are added and the temperature is raised to 80° C. for reaction for 4 hours to obtain a hydroxyl-containing acrylate dispersant, and the hydroxyl content of the hydroxyl-containing acrylate dispersant is measured;

[0177] Add dibutyltin dilaurate to the above hydroxyl-containing acrylate dispersant, and dropwise add ethyl isocyanate acrylate at 60° C. After the dropwise addition is completed, keep the mixture at 60° C. for 2 hours to obtain a reactive acrylate dispersant;

[0178] The mass ratio of acrylic acid, OPPEA and single-end vinyl phenyl silicone oil is 1:5:0.5, the mass of the initiator accounts for 2% of the total mass of acrylic acid, OPPEA, single-end vinyl phenyl silicone oil, mercaptoethanol and hydrogen peroxide, the mass of the chain transfer agent accounts for 2% of the total mass of acrylic acid, OPPEA, single-end vinyl phenyl silicone oil, mercaptoethanol and hydrogen peroxide, the mass of the catalyst accounts for 0.2% of the total mass of the hydroxyl-containing acrylate dispersant and isocyanate ethyl acrylate, and the mass ratio of the hydroxyl group in the isocyanate ethyl acrylate and the hydroxyl group in the hydroxyl-containing acrylate dispersant is 1:1.

[0179] Example 3

[0180] The preparation methods of the reactive acrylate dispersant and the photocurable liquid of Example 3 are similar to those of the reactive acrylate dispersant and the photocurable liquid of Example 2, except that the initiator in Example 2 is adjusted to azobisisobutyronitrile, as shown in Table 2.

[0181] Example 4

[0182] The preparation methods of the reactive acrylate dispersant and the photocurable liquid of Example 4 are similar to those of the reactive acrylate dispersant and the photocurable liquid of Example 2, except that the chain transfer agent in Example 2 is adjusted to thioglycolic acid, as shown in Table 2.

[0183] Example 5

[0184] The preparation methods of the reactive acrylate dispersant and the photocurable liquid of Example 5 are similar to those of the reactive acrylate dispersant and the photocurable liquid of Example 2, except that hydroxyethyl acrylate is introduced into the preparation of the reactive acrylate dispersant of Example 5. The specific preparation method is as follows:

[0185] 1) Preparation of reactive acrylate dispersant

[0186] Acrylic acid, o-phenylphenoxyethyl acrylate (OPPEA), single-end vinyl phenyl silicone oil and hydroxyethyl acrylate are added into a reaction flask, and then mercaptoethanol and hydrogen peroxide are added and the temperature is raised to 80° C. for reaction for 4 hours to obtain a hydroxyl-containing acrylate dispersant, and the hydroxyl content of the hydroxyl-containing acrylate dispersant is measured;

[0187] Add dibutyltin dilaurate to the above hydroxyl-containing acrylate dispersant, and dropwise add ethyl isocyanate acrylate at 60° C. After the dropwise addition is completed, keep the mixture at 60° C. for 2 hours to obtain a reactive acrylate dispersant;

[0188] The mass ratio of acrylic acid, OPPEA, single-end vinyl phenyl silicone oil and hydroxyethyl acrylate is 1:5:0.5:0.1, the mass of the initiator hydrogen peroxide accounts for 2% of the total mass of acrylic acid, OPPEA, single-end vinyl phenyl silicone oil, mercaptoethanol and hydrogen peroxide, the mass of the chain transfer agent mercaptoethanol accounts for 2% of the total mass of acrylic acid, OPPEA, single-end vinyl phenyl silicone oil, mercaptoethanol and hydrogen peroxide, the mass of the catalyst dibutyltin dilaurate accounts for 0.2% of the total mass of the hydroxyl-containing acrylate dispersant and isocyanate ethyl acrylate, and the mass ratio of the hydroxyl group in the isocyanate ethyl acrylate and the hydroxyl group in the hydroxyl-containing acrylate dispersant is 1:1.

[0189] Embodiment 6-7

[0190] The reactive acrylate dispersants and photocurable liquids of Examples 6 to 7 and the reactive acrylate dispersants, curing agents, acrylic acid+acrylamide (mass ratio of 1:1) of Example 5 are specifically shown in Table 1.

[0191] Example 8

[0192] The preparation methods of the reactive acrylate dispersant and the photocurable liquid of Example 8 are similar to those of the reactive acrylate dispersant and the photocurable liquid of Example 5, except that the lipophilic monomer in the reactive acrylate dispersant in Example 5 is adjusted to 3-phenoxybenzyl acrylate (PBA), and the OPPEA in the photocurable liquid is adjusted to 3-phenoxybenzyl acrylate (PBA). The specific preparation method is as follows:

[0193] 1) Preparation of reactive acrylate dispersant

[0194] Acrylic acid, 3-phenoxybenzyl acrylate (PBA), single-end vinyl phenyl silicone oil and hydroxyethyl acrylate are added into a reaction flask, and then mercaptoethanol and hydrogen peroxide are added and the temperature is raised to 80° C. for reaction for 4 hours to obtain a hydroxyl-containing acrylate dispersant, and the hydroxyl content of the hydroxyl-containing acrylate dispersant is measured;

[0195] Add dibutyltin dilaurate to the above hydroxyl-containing acrylate dispersant, and dropwise add ethyl isocyanate acrylate at 60° C. After the dropwise addition is completed, keep the mixture at 60° C. for 2 hours to obtain a reactive acrylate dispersant;

[0196] The mass ratio of acrylic acid, PBA, single-end vinyl phenyl silicone oil and hydroxyethyl acrylate is 1:5:0.5:0.1, the mass of the initiator hydrogen peroxide accounts for 2% of the total mass of acrylic acid, PBA, single-end vinyl phenyl silicone oil, mercaptoethanol and hydrogen peroxide, the mass of the chain transfer agent mercaptoethanol accounts for 2% of the total mass of acrylic acid, PBA, single-end vinyl phenyl silicone oil, mercaptoethanol and hydrogen peroxide, the mass of the catalyst dibutyltin dilaurate accounts for 0.2% of the total mass of the hydroxyl-containing acrylate dispersant and isocyanate ethyl acrylate, and the mass ratio of isocyanate ethyl acrylate to the hydroxyl group in the hydroxyl-containing acrylate dispersant is 1:1.

[0197] 2) Preparation of photocurable liquid

[0198] The above-mentioned reactive acrylate dispersant, ZrO2 nanoparticles and PBA were stirred and evenly mixed in a mass ratio of 2:50:47, and ultrasonically dispersed for 1 hour until the solution became clear and transparent, and then 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator 1173, the mass ratio of reactive acrylate dispersant to photoinitiator 1173 was 2:1) was added and mixed and stirred until the photoinitiator 1173 was completely dissolved to obtain the photocurable liquid of Example 1.

[0199] Embodiments 9 to 11

[0200] The preparation methods of the reactive acrylate dispersants and photocurable liquids of Examples 9 to 11 are similar to those of the reactive acrylate dispersants and photocurable liquids of Example 5, except that the mass ratios of the hydrophilic monomer to the lipophilic monomer in Example 5 are adjusted to 1:1, 1:8, and 1:10, respectively, as shown in Table 1.

[0201] Example 12

[0202] The preparation methods of the reactive acrylate dispersant and photocurable liquid of Example 12 are similar to those of the reactive acrylate dispersant and photocurable liquid of Example 5, except that the isocyanate-containing acrylate compound in Example 5 is adjusted to isocyanoethyl methacrylate, as shown in Table 1.

[0203] Embodiment 13

[0204] The preparation methods of the reactive acrylate dispersant and the photocurable liquid of Example 13 are similar to those of the reactive acrylate dispersant and the photocurable liquid of Example 5, except that the chain transfer agent in Example 5 is adjusted to 2-hydroxyethyl mercaptopropionate, as shown in Table 2.

[0205] Embodiment 14

[0206] The preparation methods of the reactive acrylate dispersant and the photocurable liquid of Example 14 are similar to those of the reactive acrylate dispersant and the photocurable liquid of Example 5, except that the initiator in Example 5 is adjusted to benzoyl peroxide, as shown in Table 2.

[0207] Embodiment 15

[0208] The preparation methods of the reactive acrylate dispersant and photocurable liquid of Example 15 are similar to those of the reactive acrylate dispersant and photocurable liquid of Example 5, except that the vinyl silicone oil monomer in Example 5 is adjusted to single-end vinyl silicone oil, as shown in Table 1.

[0209] Embodiments 16 to 17

[0210] The preparation methods of the reactive acrylate dispersants and photocurable liquids of Examples 16 to 17 are similar to those of the reactive acrylate dispersants and photocurable liquids of Example 5, except that the mass contents of the chain transfer agent in Example 5 are adjusted to 0.5% and 4%, respectively. See Table 2 for details.

[0211] Embodiments 18 to 19

[0212] The preparation methods of the reactive acrylate dispersants and photocurable liquids of Examples 18 to 19 are similar to those of the reactive acrylate dispersants and photocurable liquids of Example 5, except that the mass contents of the initiators in Example 5 are adjusted to 0.5% and 4%, respectively. See Table 2 for details.

[0213] Table 1 Preparation parameters of the reactive acrylate dispersant of Example

[0214]

[0215]

[0216] “ / ” means that the corresponding substance is not added.

[0217] Table 2 Preparation parameters of the reactive acrylate dispersant of Example

[0218]

[0219]

[0220] Embodiment 20

[0221] The preparation method of the reactive acrylate dispersant of Example 20 is the same as that of the reactive acrylate dispersant of Example 5, but the preparation method of the photocurable liquid of Example 20 is different from that of the photocurable liquid of Example 5, which is specifically as follows:

[0222] 2) Preparation of photocurable liquid

[0223] Modified ZrO2 nanoparticles: ZrO2 nanoparticles, ethanol, water and 3-(trimethoxysilyl)propyl methacrylate (KH-570) were mixed and stirred in a mass ratio of 1:9:1:0.1, ultrasonically dispersed for 0.5 h, and then reacted at 60°C for 1 h. The mixture was centrifuged and washed to obtain KH-570 modified ZrO2 particles.

[0224] The reactive acrylate dispersant, modified ZrO2 nanoparticles and OPPEA of Example 5 were stirred and evenly mixed in a mass ratio of 2:50:47, and ultrasonically dispersed for 1 hour until the solution became clear and transparent. Then, photoinitiator 1173 (the mass ratio of reactive acrylate dispersant to photoinitiator 1173 was 2:1) was added and stirred until the photoinitiator 1173 was completely dissolved to obtain the photocurable liquid of Example 20.

[0225] Embodiment 21

[0226] The preparation method of the reactive acrylate dispersant of Example 21 is the same as that of the reactive acrylate dispersant of Example 5, but the preparation method of the photocurable liquid of Example 21 is different from that of the photocurable liquid of Example 5, which is specifically as follows:

[0227] 2) Preparation of photocurable liquid

[0228] The reactive acrylate dispersant of Example 5, the ZrO2 nanoparticles of Example 5 and propylene glycol methyl ether acetate (PMA) were stirred and mixed in a mass ratio of 2:50:47, and ultrasonically dispersed for 1 hour until the solution became clear and transparent, to obtain the photocurable liquid of Example 21.

[0229] Comparative Example 1

[0230] The preparation methods of the dispersant and the photocurable liquid of Comparative Example 1 are similar to those of the reactive acrylate dispersant and the photocurable liquid of Example 1, except that no acrylate compound containing isocyanate is added in the preparation of the dispersant of Comparative Example 1. The specific preparation method is as follows:

[0231] 1) Preparation of dispersant

[0232] Acrylic acid and o-phenylphenoxyethyl acrylate (OPPEA) were added into a reaction flask, and then mercaptoethanol and hydrogen peroxide were added and the temperature was raised to 80°C for reaction for 4 hours to obtain a dispersant;

[0233] The mass ratio of acrylic acid to OPPEA is 1:5, the mass of the initiator hydrogen peroxide accounts for 2% of the total mass of acrylic acid, OPPEA, mercaptoethanol and hydrogen peroxide, and the mass of the chain transfer agent mercaptoethanol accounts for 2% of the total mass of acrylic acid, OPPEA, mercaptoethanol and hydrogen peroxide.

[0234] Comparative Example 2

[0235] The preparation methods of the dispersant and the photocurable liquid of Comparative Example 2 are similar to those of the reactive acrylate dispersant and the photocurable liquid of Comparative Example 1, except that the lipophilic monomer in Comparative Example 1 is adjusted to octyl acrylate, as shown in Table 3.

[0236] Comparative Example 3

[0237] The preparation methods of the dispersant and photocurable liquid of Comparative Example 3 are similar to those of the reactive acrylate dispersant and photocurable liquid of Comparative Example 2, except that the chain transfer agent in Comparative Example 2 is adjusted to thioglycolic acid and the initiator is adjusted to benzoyl peroxide, as shown in Table 3.

[0238] Comparative Example 4

[0239] The preparation methods of the dispersant and the photocurable liquid of Comparative Example 4 are similar to those of the reactive acrylate dispersant and the photocurable liquid of Example 2, except that no acrylate compound containing isocyanate is added in the preparation of the dispersant of Comparative Example 4, and the lipophilic monomer in Example 2 is adjusted to octyl acrylate. The specific preparation method is as follows:

[0240] 1) Preparation of dispersant

[0241] Add acrylic acid, octyl acrylate and single-end vinyl phenyl silicone oil into a reaction flask, then add mercaptoethanol and hydrogen peroxide and heat to 80°C for 4 hours to obtain a dispersant;

[0242] The mass ratio of acrylic acid, octyl acrylate and single-end vinyl phenyl silicone oil is 1:5:0.5, the mass of the initiator hydrogen peroxide accounts for 2% of the total mass of acrylic acid, octyl acrylate, single-end vinyl phenyl silicone oil, mercaptoethanol and hydrogen peroxide, and the mass of the chain transfer agent mercaptoethanol accounts for 2% of the total mass of acrylic acid, octyl acrylate, single-end vinyl phenyl silicone oil, mercaptoethanol and hydrogen peroxide.

[0243] Comparative Example 5

[0244] The preparation methods of the dispersant and the photocurable liquid of Comparative Example 5 are similar to those of the reactive acrylate dispersant and the photocurable liquid of Example 5, except that no acrylate compound containing isocyanate is added in the preparation of the dispersant of Comparative Example 5, and the lipophilic monomer in Example 5 is adjusted to octyl acrylate. The specific preparation method is as follows:

[0245] Add acrylic acid, octyl acrylate, single-end vinyl phenyl silicone oil and hydroxyethyl acrylate into a reaction flask, then add mercaptoethanol and hydrogen peroxide and heat to 80°C for 4 hours to obtain a dispersant;

[0246] The mass ratio of acrylic acid, octyl acrylate, single-end vinyl phenyl silicone oil and hydroxyethyl acrylate is 1:5:0.5:0.1, the mass of the initiator accounts for 2% of the total mass of acrylic acid, octyl acrylate, single-end vinyl phenyl silicone oil, mercaptoethanol and hydrogen peroxide, and the mass of the chain transfer agent accounts for 2% of the total mass of acrylic acid, octyl acrylate, single-end vinyl phenyl silicone oil, mercaptoethanol and hydrogen peroxide.

[0247] Comparative Example 6

[0248] The preparation methods of the dispersant and photocurable liquid of Comparative Example 6 are similar to those of the reactive acrylate dispersant and photocurable liquid of Comparative Example 1, except that the dispersant of Comparative Example 6 is a commercially available dispersant LD1122 (purchased from Sinopharm), as shown in Table 3.

[0249] Table 3 Preparation parameters of reactive acrylate dispersants of comparative examples

[0250]

[0251] “ / ” means that the corresponding substance is not added.

[0252] Comparative Example 7

[0253] The dispersant of Comparative Example 7 is the same as that of Comparative Example 6, both of which are commercially available dispersant BYK 163 (purchased from BYK Chemicals), but the preparation method of the photocurable liquid of Comparative Example 7 is different from that of the photocurable liquid of Comparative Example 6, which is specifically as follows:

[0254] 2) Preparation of photocurable liquid

[0255] The preparation method of modified ZrO2 nanoparticles is the same as the preparation method of KH-570 modified ZrO2 nanoparticles in Example 21.

[0256] The dispersant, modified ZrO2 nanoparticles and OPPEA of comparative example 6 were stirred and evenly mixed in a mass ratio of 1:50:47, and ultrasonically dispersed for 1 hour until the solution became clear and transparent. Then, photoinitiator 1173 (the mass ratio of dispersant to photoinitiator 1173 was 5:2) was added and stirred until the photoinitiator 1173 was completely dissolved to obtain the photocurable liquid of comparative example 7.

[0257] Comparative Example 8

[0258] The dispersant in Comparative Example 8 is the same as the dispersant in Comparative Example 6, both of which are commercially available dispersant LD1122 (purchased from Sinopharm), but the preparation method of the photocurable liquid in Comparative Example 8 is different from that of the photocurable liquid in Comparative Example 6, as follows:

[0259] 2) Preparation of photocurable liquid

[0260] The dispersant of Comparative Example 6, the modified ZrO2 nanoparticles of Comparative Example 6 and PMA were stirred and mixed uniformly in a mass ratio of 5:50:45, and ultrasonically dispersed for 1 hour until the solution became clear and transparent, thereby obtaining the photocurable liquid of Comparative Example 8.

[0261] 2. Test Method

[0262] 1) Determination of hydroxyl content in hydroxyl-containing acrylic dispersants

[0263] The hydroxyl content in the acrylate dispersant containing hydroxyl was determined with reference to standard GB / T 7193.2-1987 and the end group analysis method was used for determination.

[0264] 2) Refractive index test

[0265] The reactive acrylate dispersant was tested with reference to GB / T 6488-2008 standard. The refractive index of the reactive acrylate dispersant to be tested was tested at 20°C using an Abbemat 300 refractometer.

[0266] 3) Test of initial viscosity and high temperature storage viscosity

[0267] Refer to GB / T 10247 standard to test the viscosity of photocurable liquid.

[0268] Initial viscosity: At 25°C, the initial viscosity of the photocurable liquid just prepared to be tested is tested using a lamella viscometer. The model of the lamella viscometer is DVNXRNCP, and the accuracy of the lamella viscometer is ±5cps.

[0269] High temperature storage viscosity: After the photocurable liquid to be tested is placed at 50°C for 7×24h, its viscosity at 25°C is tested again using a lamella viscometer, which is the hot storage viscosity.

[0270] 4) Dispersion stability test

[0271] Place the photocurable liquid to be tested in a glass cup, let it stand for 6 hours, and then observe whether there is precipitation in the photocurable liquid to be tested in the glass cup. If "no precipitation is produced", the dispersion stability is judged to be "good", if "precipitation is produced", the dispersion stability is judged to be "poor".

[0272] 5) Haze test of coating + substrate

[0273] The haze test was carried out with reference to GB 2410-80 standard.

[0274] Using PET as the substrate, a wire rod coater was used to coat the photocurable liquid to be tested on the PET substrate to prepare a coating with a thickness of 1 um. The PET sheet was then placed on a hot plate at 70°C and baked for 1.5 min. It was then cured under a mercury lamp with a curing energy of 7000 mJ to prepare an optical film.

[0275] A haze meter is used to test the haze of the coating + PET substrate as a whole, and the test equipment model is NDH8000 produced by Japan Denshoku.

[0276] 6) Test of coating surface granularity

[0277] Take the above-prepared coating with a size of 3cm×3cm and place it under a light source to observe whether there are protrusions on the coating surface. If the number of protrusions on the coating surface is less than 10, the coating surface granularity test is judged to be "passed"; if the number of protrusions on the coating surface observed by the naked eye is more than 10, the coating surface granularity test is judged to be "failed".

[0278] 7) Weather resistance test of coating

[0279] The weather resistance test of the coating was carried out with reference to GB / T 2423.50-2012 and GB / T 1766-2008 standards. The coating prepared as above with a size of 3cm×3cm was placed in an environment of 85% humidity and 85°C for 7×24 hours, and then the coating was observed for loss of gloss, discoloration, powdering, cracking, blistering, peeling, etc. If there was no adverse phenomenon or slight discoloration, the weather resistance test of the coating was judged to be "passed", and if the adverse phenomenon changed area greater than 5% or there was obvious discoloration, the weather resistance test of the coating was judged to be "failed".

[0280] Table 4 Performance test parameters of the embodiments and comparative examples

[0281]

[0282]

[0283] “-” means that the corresponding coating cannot be prepared for the corresponding performance parameter test (haze, surface graininess, and weather resistance of Example 21) due to the lack of photoinitiator, or the photocurable liquid is stratified or precipitated and the corresponding parameter test cannot be carried out (thermal storage viscosity of Comparative Examples 2 to 6 and 8), or nanoparticles are precipitated during the curing process of the photocurable liquid, resulting in the inability to prepare the coating for the corresponding performance parameter test (haze, surface graininess, and weather resistance of Comparative Examples 2 to 6 and 8).

[0284] III. Analysis of test results of various embodiments and comparative examples

[0285] From the comparison of Examples 1 to 19 with Comparative Example 6, Example 20 with Comparative Example 7, and Example 21 with Comparative Example 8, it can be seen that conventional dispersants are unable to disperse nanoparticles in OPPEA or PMA to form a stable photocurable liquid. Compared with conventional dispersants, the reactive acrylate dispersant in the present application can not only stably disperse the nanoparticles in OPPEA / PMA, but also significantly reduce the viscosity of the photocurable liquid and improve the room temperature / high temperature dispersion stability of the photocurable liquid, improve the coating process of the photocurable liquid, reduce the haze of the coating and improve the weather resistance of the coating, thereby broadening the application window of the reactive acrylate dispersant.

[0286] From the comparison between Example 1 and Comparative Examples 1 to 3, Examples 2 to 4 and Comparative Example 4, and Examples 5 to 19 and Comparative Example 5, it can be seen that compared with the dispersant without reactive active sites, the reactive acrylate dispersant in the present application is more conducive to improving the high-temperature dispersion stability of the photocurable liquid and the weather resistance of the coating.

[0287] From the comparison between Example 2 and Example 1, it can be seen that the introduction of single-terminal vinyl phenyl silicone oil into the reactive acrylate dispersant is beneficial to further reduce the viscosity of the photocurable liquid and facilitate the preparation of a solvent-free coating.

[0288] From the comparison between Example 2 and Examples 3-4, and Example 5 and Examples 13-14, it can be seen that compared with only the chain transfer agent generating hydroxyl groups or the initiator generating hydroxyl groups, the chain transfer agent and the initiator generating hydroxyl groups at the same time are beneficial to improving the dispersion stability of the photocurable liquid. Example 4 has poor weather resistance due to the undesirable phenomenon of coating aging and whitening, indicating that the chain transfer agent dominates the control of molecular weight during the preparation of the reactive acrylate dispersant. When a hydroxyl-free chain transfer agent is used, some polymer segments will be unable to form hydroxyl active sites and thus unable to form a reactive acrylate dispersant with reactive activity.

[0289] From the comparison between Example 5 and Example 2, it can be seen that the introduction of hydroxyl-containing monomers into the reactive acrylate dispersant is beneficial to improving the dispersion stability of the photocurable liquid.

[0290] It can be seen from Examples 4 to 8, 12, and 15 that the hydrophilic monomer is at least one of acrylic acid, acryloylmorpholine, and acrylamide, the lipophilic monomer is at least one of OPPEA and PBA, the acrylate compound containing isocyanate is at least one of isocyanate ethyl acrylate and isocyanoethyl methacrylate, and the vinyl silicone oil monomer is at least one of single-end vinyl phenyl silicone oil and single-end vinyl silicone oil, all of which can make the photocurable liquid have suitable viscosity and room temperature / high temperature dispersion stability, coating surface properties and weather resistance.

[0291] From the comparison between Examples 6 to 7 and Example 5, it can be seen that compared with the reactive acrylate dispersant containing only one hydrophilic monomer or lipophilic monomer, the reactive acrylate dispersant contains two hydrophilic monomers or lipophilic monomers, which is more conducive to reducing the viscosity and high-temperature dispersion stability of the photocurable liquid, and reducing the haze of the coating.

[0292] It can be seen from Examples 5, 9 to 11 that controlling the mass ratio of the hydrophilic monomer to the lipophilic monomer in the reactive acrylate dispersant to be 1:(1 to 10) can make the photocurable liquid have suitable viscosity and room temperature / high temperature dispersion stability, coating surface properties and weather resistance. It can be seen from the comparison between Examples 1, 10 to 11 and Example 9 that controlling the mass ratio of the hydrophilic monomer to the lipophilic monomer in the reactive acrylate dispersant to be 1:(5 to 10) is conducive to further reducing the viscosity of the photocurable liquid and the haze of the coating.

[0293] It can be seen from Examples 5, 16 to 19 that, based on the total mass of the raw materials, controlling the mass content of the chain transfer agent to 0.5% to 4% or the mass content of the initiator to 0.5% to 4% can make the photocurable liquid have a suitable viscosity and room temperature / high temperature dispersion stability, coating surface properties and weather resistance. From the comparison of Examples 5, 17, 19 with Examples 16 and 18, it can be seen that controlling the ratio of the mass content of the chain transfer agent and the initiator within a suitable range is conducive to further reducing the viscosity and high temperature dispersion stability of the photocurable liquid. From the comparison of Examples 5, 17, 19 with Examples 16 and 18, it can be seen that controlling the sum of the mass content of the chain transfer agent and the initiator within a suitable range so that the reactive acrylate dispersant has a suitable number average molecular weight range is conducive to further reducing the viscosity and high temperature dispersion stability of the photocurable liquid.

[0294] It can be seen from Examples 5 and 20 to 21 that the reactive acrylate dispersant in the present application can stably disperse hydroxylated nanoparticles / acrylate-modified nanoparticles in OPPEA or PMA to prepare a low-viscosity photocurable liquid.

[0295] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them; although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application, and they should all be included in the scope of the claims and specification of the present application. In particular, as long as there is no structural conflict, the various technical features mentioned in the various embodiments can be combined in any way. The present application is not limited to the specific embodiments disclosed herein, but includes all technical solutions that fall within the scope of the claims.

Claims

1. A reactive acrylate dispersant, characterized in that: The method is prepared from the following raw materials: a hydrophilic monomer, a lipophilic monomer, a polymerization aid and an acrylate compound containing isocyanate; The lipophilic monomer includes a high-refractive monomer having a refractive index greater than 1.5 at 20° C., and the polymerization aid includes at least one of a hydroxyl chain transfer agent and a peroxide initiator.

2. The reactive acrylate dispersant according to claim 1, characterized in that The raw materials for preparing the reactive acrylate dispersant also include vinyl silicone oil monomer; and / or The raw materials for preparing the reactive acrylate dispersant further include hydroxyl-containing monomers; and / or The mass ratio of the hydrophilic monomer to the lipophilic monomer is 1:(1-10), and can be optionally 1:(4-8); and / or The number average molecular weight of the reactive acrylate dispersant is 200 to 20,000, and can be optionally 400 to 10,000.

3. The reactive acrylate dispersant according to claim 2, characterized in that: The hydrophilic monomer includes at least one of the compound of formula I, the compound of formula II, and the compound of formula III. wherein R1, R6, R7, R8, and R9 are independently hydrogen, substituted or unsubstituted C 1-4 R2 and R3 each independently include hydrogen, substituted or unsubstituted C 1-4 Alkyl, substituted or unsubstituted C 1-7 Alkoxy, substituted or unsubstituted C 1-7 At least one of epoxy, hydroxyl, and keto groups, R4 includes hydrogen, substituted or unsubstituted C 1-4 R5 comprises at least one of hydrogen, tetrahydrofuranyl, sulfonic acid, and boric acid; and / or The isocyanate-containing acrylate compound includes a compound having a structure shown in Formula IV, Among them, R 11 including hydrogen, substituted or unsubstituted C 1-6 At least one of the alkyl groups, R 12 Including substituted or unsubstituted C 1-6 At least one of the alkylene groups; and / or The hydroxyl chain transfer agent includes a compound having a structure shown in Formula V, Among them, R 13 Including substituted or unsubstituted C 1-6 At least one of an alkylene group and an ester group; and / or The peroxide initiator comprises a compound having a structure shown in Formula VI, Among them, R 14 comprises at least one of hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted benzoyl, substituted or unsubstituted benzyl; and / or The vinyl silicone oil monomer includes a compound with a structure shown in Formula VII, Among them, R 15 , R 16 Each independently includes substituted or unsubstituted C 1-3 At least one of an alkyl group, a substituted or unsubstituted phenyl group, R 17 , R 18 , R 19 Each independently includes substituted or unsubstituted C 1-3 At least one of the alkyl groups of The hydroxyl-containing monomer includes a compound of the structure shown in Formula VIII, Among them, R 20 including hydrogen, substituted or unsubstituted C 1-3 At least one of the alkyl groups of R 21 Including substituted or unsubstituted C 1-5 Alkyl, C 1-5 At least one of the alkoxy groups.

4. The reactive acrylate dispersant according to claim 3, characterized in that: The compound of the structure shown in Formula I includes at least one of amide monomers including acrylamide, methacrylamide, (1,1-dimethyl-3-oxobutyl) methacrylamide, N,N-dimethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-n-butoxymethyl acrylamide, N-isobutoxymethyl acrylamide, acryloyl morpholine, and methacryloyl morpholine, and optionally includes at least one of acrylamide, N-hydroxymethyl (meth) acrylamide, and acryloyl morpholine; and / or The compound of the structure shown in Formula II includes at least one of acrylic acid, methacrylic acid, maleic acid, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, sodium 2-ethanesulfonate of methacrylate, potassium 3-methacrylic acid sulfonate, hydroxypropyl methacrylate phosphate, and 2-hydroxyethyl methacrylate phosphate, and optionally includes tetrahydrofuran; and / or The compound of the structure represented by formula III comprises at least one of vinyl pyrrolidone, 4-methyl-1-vinyl-2-pyrrolidone, and 1-vinyl-3-methyl-2-pyrrolidone, and optionally comprises vinyl pyrrolidone; and / or The high-refractive monomer includes a monofunctional acrylate monomer, and the monofunctional acrylate monomer includes at least one of o-phenylphenoxyethyl acrylate, (2-ethoxy) o-phenylphenoxyethyl acrylate, (ethoxy) phenol acrylate, benzyl acrylate, 3-phenoxybenzyl acrylate, 2 (ethoxy) phenol acrylate, 4 (ethoxy) phenol acrylate, 3 (ethoxy) o-phenylphenoxyethyl acrylate, biphenylmethanol acrylate and modified products thereof, and optionally includes at least one of 3-phenoxybenzyl acrylate, o-phenylphenoxyethyl acrylate and (ethoxy) phenol acrylate; and / or The isocyanate-containing acrylate compound includes at least one of isocyanate ethyl acrylate and isocyanoethyl methacrylate; and / or The vinyl silicone oil monomer includes at least one of single-terminal vinyl phenyl silicone oil, single-terminal vinyl methyl phenyl silicone oil, and single-terminal vinyl silicone oil, and optionally includes single-terminal vinyl phenyl silicone oil; and / or The hydroxyl-containing monomer includes at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate, and optionally includes at least one of hydroxyethyl acrylate and hydroxyethyl methacrylate; and / or The hydroxyl chain transfer agent includes at least one of mercaptoethanol, mercaptopropanol, and 2-hydroxyethyl mercaptopropionate, and optionally includes mercaptoethanol; and / or The peroxide initiator includes at least one of hydrogen peroxide, benzoyl peroxide, and cumene hydroperoxide, and optionally includes hydrogen peroxide.

5. The reactive acrylate dispersant according to claim 2, characterized in that: The number average molecular weight of the vinyl silicone oil monomer is 300 to 1000; and / or The mass ratio of the hydrophilic monomer to the hydroxyl type initiator is 1:(0.015-0.6), and can be optionally 1:(0.03-0.3); and / or The mass ratio of the hydrophilic monomer to the peroxide initiator is 1:(0.015-0.6), and can be optionally 1:(0.03-0.3); and / or The mass ratio of the vinyl silicone oil monomer to the hydrophilic monomer is not higher than 3; and / or The mass ratio of the hydroxyl-containing monomer to the hydrophilic monomer is not higher than 0.

8.

6. A method for preparing the reactive acrylate dispersant according to any one of claims 1 to 5, characterized in that: The preparation method comprises: Mixing initial raw materials including a hydrophilic monomer, a lipophilic monomer and a polymerization aid, and performing a first reaction to prepare a hydroxyl-containing acrylate dispersant; The hydroxyl-containing acrylate dispersant, the isocyanate-containing acrylate compound and the catalyst are mixed to carry out a second reaction to prepare the reactive acrylate dispersant; The lipophilic monomer comprises a high-refractive monomer having a refractive index greater than 1.5 at 20° C., the polymerization aid comprises a chain transfer agent and an initiator, the chain transfer agent comprises a hydroxyl chain transfer agent and / or the initiator comprises a peroxide initiator.

7. The preparation method according to claim 6, characterized in that: The initial raw material also includes vinyl silicone oil monomer; and / or The initial raw material also includes a hydroxyl-containing monomer.

8. The preparation method according to claim 7, characterized in that: The mass ratio of the hydrophilic monomer to the lipophilic monomer is 1:(1-10), and can be 1:(4-8); and / or Based on the total mass of the initial raw materials, the mass content of the vinyl silicone oil is not higher than 20%; and / or Based on the total mass of the initial raw materials, the mass content of the hydroxyl-containing monomer is not higher than 5%; and / or Based on the total mass of the initial raw materials, the mass content of the chain transfer agent is 0.5% to 4%; and / or Based on the total mass of the initial raw materials, the mass content of the initiator is 0.5% to 4%; and / or Based on the total mass of the initial raw materials, the sum of the mass contents of the chain transfer agent and the initiator is not less than 2%; and / or The mass content of the catalyst is 0.1% to 0.3% based on the total mass of the hydroxyl-containing acrylate dispersant and the isocyanate-containing acrylate compound; and / or The mass ratio of the isocyanate-containing acrylate compound to the hydroxyl group in the hydroxyl-containing acrylate dispersant is 1:(1-1.2).

9. The preparation method according to any one of claims 6 to 8, characterized in that: The temperature of the first reaction is 60°C to 100°C, and may be 70°C to 90°C, and the time of the first reaction is 2h to 8h, and may be 3h to 7h; and / or The temperature of the second reaction is 40°C to 70°C, and may be 50°C to 60°C, and the time of the second reaction is 0.5h to 3h, and may be 0.5h to 2h; and / or The catalyst in the second reaction includes at least one of dibutyltin dilaurate, N-ethylmorpholine, and triethylamine.

10. Use of the reactive acrylate dispersant according to any one of claims 1 to 5 or the reactive acrylate dispersant prepared by the preparation method according to any one of claims 6 to 9 in nanoimprinting, 3D printing, and display panels.

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