CN107602767B - Core-shell particles, method for producing same, and use thereof - Google Patents
Core-shell particles, method for producing same, and use thereof Download PDFInfo
- Publication number
- CN107602767B CN107602767B CN201710673762.1A CN201710673762A CN107602767B CN 107602767 B CN107602767 B CN 107602767B CN 201710673762 A CN201710673762 A CN 201710673762A CN 107602767 B CN107602767 B CN 107602767B
- Authority
- CN
- China
- Prior art keywords
- core
- silane
- shell particles
- vinyl
- shell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to a core-shell particle, a preparation method and application thereof. The core of the core-shell particles includes a vinyl polymer. The shell of the core-shell particle includes a hydrophobic silane bonded to the surface of the core via a silane coupling agent. The core-shell particles are suitable for use in matting materials and can be used as matting agents.
Description
[ technical field ] A method for producing a semiconductor device
The present invention relates to core-shell particles and a method for producing the same. The invention also relates to matting compositions comprising core-shell particles as matting agent.
[ background of the invention ]
As the standard of living has increased, consumers have begun to prefer matte surfaces over glossy surfaces in many everyday applications, such as furniture, or the interior of buildings or vehicles. High gloss surfaces reflect a large portion of the light and thus can cause damage to the viewer's eyes. Conversely, a low gloss or matte surface has antireflective properties, reflects less light, and thus can reduce such damage. In addition, scratches on low gloss or matte surfaces are less noticeable due to their antireflective properties. Thus, rapid market growth of matting agents can be expected due to rising consumer demand.
Gloss is known to be related to the smoothness of the surface of an object. Thus, one way to reduce gloss (i.e., achieve a matting effect) is to increase surface roughness by applying a coating of a matting composition to the surface. The matting composition contains matting particles that produce a relief microstructure on the coating, whereby gloss can be reduced.
Silica particles (silica) are commonly used in industry as matting agents due to their low cost and ready availability. However, a problem associated with the use of silica particles as matting agents is that the density of the silica particles can be as high as 2.2g/cm3And therefore the silica particles are easily settled in the emulsion. This makes it impossible to maintain the storage stability for a long period of time. In addition, the compatibility between the inorganic silica particles and the organic resin binder is not good.
Accordingly, the present invention provides a novel core-shell particle having not only good matting ability but also good compatibility with an organic resin binder.
[ summary of the invention ]
An object of the present invention is to provide a core-shell particle. The core of the core-shell particles includes a vinyl polymer. The shell of the core-shell particle includes a hydrophobic silane bonded to the surface of the core via a silane coupling agent.
It is another object of the present invention to provide a matting composition comprising core-shell particles.
It is still another object of the present invention to provide a method for preparing core-shell particles, which comprises performing soap-free emulsion polymerization to form a core and performing a sol-gel reaction to form a shell.
The present invention provides at least the following advantages: (1) the core-shell particles can be synthesized by soap-free emulsion polymerization; the manufacturing process is simple and environmentally friendly and can be carried out as a continuous process. In addition, the soap-free emulsion polymerization method does not affect the subsequent emulsion polymerization. (2) The core-shell particles have high hydrophobicity and low density, and thus can bulge to the film surface, increase surface roughness, and reduce surface gloss. (3) Due to the presence of the organic core, the core-shell particles not only have good matting ability but also have good compatibility with the organic resin binder, and therefore, the stability of the matting composition during storage or transportation can be improved as compared with conventional matting compositions. (4) The matting composition containing the core-shell particles of the present invention has an excellent matting effect.
[ detailed description ] embodiments
The present inventors have extensively and intensively studied and found that a core-shell particle includes: a core comprising a vinyl polymer and a shell comprising a hydrophobic silane, and the hydrophobic silane is bonded to the surface of the core via a silane coupling agent.
In one embodiment, the glass transition temperature (Tg) of the core-shell particles of the present invention is in the range of 0 ℃ to 60 ℃, preferably in the range of 5 ℃ to 50 ℃, more preferably 20 ℃ to 40 ℃.
The present inventors have found that when a polymer having a Tg in the range of 0 to 60 ℃ is used as the core of the core-shell particles, the resulting matting composition has a better matting effect. Without being bound by theory, when the Tg of the core polymer is too low (e.g., less than 0 ℃), the strength of the core polymer is insufficient to maintain a spherical shape; when the Tg of the core polymer is too high (e.g., higher than 60 ℃), the hardness of the core polymer becomes too high, which results in poor film-forming ability of the matting composition. In addition, when the Tg of the core polymer is too low (e.g., less than 0 ℃), the core-shell particles tend to aggregate with each other at room temperature and are not well dispersed in the composition, and thus the matting effect becomes poor; on the other hand, when the Tg of the core polymer is too high (e.g., higher than 60 ℃), the core-shell particles are less compatible with the binder resin, and thus it is more difficult to form a uniform and continuous film, and the matting effect will be poor.
The glass transition temperature (Tg) of the core polymer can be adjusted by the kind of monomers forming the core polymer or the ratio (e.g., weight ratio) thereof.
The core polymer may be a copolymer or a homopolymer.
In one embodiment, the core of the core-shell particles of the present invention comprises a vinyl polymer.
In another embodiment, the core of the core-shell particles of the present invention consists essentially of a vinyl polymer.
The vinyl polymers of the present invention are derived from vinyl monomers containing carbon-carbon double bonds. Vinyl monomers useful in the present invention are exemplified by, but not limited to: styrenic monomers, (meth) acrylate monomers, vinyl ester monomers, alkyl vinyl ether monomers, (meth) acrylamide monomers, nitrile monomers, or combinations thereof. In addition to the vinyl monomers described above, the vinyl polymers of the present invention may optionally contain units derived from other monomers.
Examples of styrenic monomers include, but are not limited to: styrene, alpha-methylstyrene, para-methylstyrene, ortho-methylstyrene, meta-methylstyrene, vinyltoluene, ethylstyrene, propylstyrene, butylstyrene, pentylstyrene, hexylstyrene, heptylstyrene, octylstyrene, and the like.
Examples of (meth) acrylate monomers include, but are not limited to: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, 2-phenoxyethyl acrylate, ethoxylated 2-phenoxyethyl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, cyclic trimethylolpropane formal acrylate, beta-carboxyethyl acrylate, lauryl methacrylate, isooctyl acrylate, isooctyl methacrylate, octadecyl acrylate, octadecyl methacrylate, isodecyl acrylate, isodecyl methacrylate, isobornyl acrylate, isobornyl methacrylate, benzyl acrylate, benzyl methacrylate, 2-hydroxyethyl phosphate (meth) acrylate, 2-hydroxyethyl phosphate, n-butyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-phenoxyethyl, Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and the like.
Examples of vinyl ester monomers include, but are not limited to: vinyl acetate, vinyl propionate, vinyl butyrate, and the like.
Examples of alkyl vinyl ether monomers include, but are not limited to: methyl vinyl ether, ethyl vinyl ether, and the like.
Examples of (meth) acrylamide monomers include, but are not limited to: n-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide.
Examples of nitrile monomers include, but are not limited to: acrylonitrile, methacrylonitrile, and the like.
The monomer species of the polymer and their proportions contribute to the glass transition temperature (Tg) of the polymer. One of ordinary skill in the art can derive the glass transition temperature of the polymer according to the Flory FoxEquation and adjust the monomer species and ratio accordingly:
wherein T isgIs the glass transition temperature of the polymer; w1、W2、…WnIs the weight fraction of component 1,2 … n; and Tg1、Tg2、…TgnIs the glass transition temperature of component 1,2 … n.
In embodiments according to the invention, the monomer ratio (weight ratio) may be adjusted such that the Tg of the core polymer is in the range of 0 ℃ to 60 ℃, e.g.0 ℃, 5 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃ or 60 ℃.
In one embodiment, the Tg of the core of the vinyl-containing polymer of the present invention is in the range of from 0 ℃ to 60 ℃, preferably in the range of from 5 ℃ to 50 ℃, more preferably from 20 ℃ to 40 ℃. The Tg of the core can be adjusted by the type of monomers forming the vinyl polymer or their proportions, for example, the vinyl polymer of the present invention can be derived from at least the following monomers: the desired Tg can be obtained by appropriately adjusting the weight ratio of the styrene monomer and the (meth) acrylate monomer. The (meth) acrylic ester monomer may be a C1-C18 alkyl ester of (meth) acrylic acid, preferably a C1-C10 alkyl ester of (meth) acrylic acid, more preferably a C1-C6 alkyl ester of (meth) acrylic acid.
In one embodiment, the vinyl polymer of the present invention may be styrene- (meth) acrylate copolymer such as polystyrene-methyl acrylate (P (St-MA)), polystyrene-ethyl acrylate (P (St-EA)), polystyrene-n-butyl acrylate (P (St-BA)), polystyrene-n-butyl acrylate-acrylic acid (P (St-BA-AA)).
According to the invention, the vinyl polymer can be functionalized with hydrophobic silanes, so that the particles to be synthesized present a hydrophobic surface, i.e. a hydrophobic shell. Due to the hydrophobicity of the shell, the core-shell particles will bulge to the surface of the film in the film forming process, so as to generate the surface roughness of nanometer level and obtain the ideal extinction effect.
According to the invention, suitable hydrophobic silanes are those having long-chain alkyl radicals, meaning alkyl radicals of 3 to 25, preferably 5 to 20, more preferably 8 to 18 carbon atoms. The long carbon chain alkyl group may be unsubstituted or substituted with a halo group, preferably fluoro. The long-chain alkyl group may be a straight-chain or branched alkyl group, but has at least 3 carbon atoms arranged in a straight chain. The long carbon chain alkyl group is preferably a straight chain alkyl group.
In one embodiment of the invention, the hydrophobic silane is a long carbon chain alkyl silane and has the following formula (I):
(R2)ySi(OR1)4-y(I)
wherein:
R1is C1-C3Alkyl, preferably methyl or ethyl;
R2is- (CH)2)2-R3；
R3Is an alkyl or perhaloalkyl group having 1 to 23 carbon atoms; and
y is an integer from 1 to 3, preferably 1.
In one embodiment of the invention, R3Is an alkyl or perhaloalkyl group having 1 to 23 carbon atoms, preferably 3 to 18 carbon atoms and more preferably 6 to 16 carbon atoms.
In one embodiment of the invention, R3Is a perfluoroalkyl group having 3 to 10 carbon atoms, preferably 4 to 8 carbon atoms, more preferably 5 to 7 carbon atoms.
Exemplary hydrophobic silanes include, but are not limited to: 1H,1H,2H,2H perfluorooctyltrimethoxysilane, 1H,2H,2H perfluorooctyltriethoxysilane, trimethoxy (propyl) silane, trimethoxy (octyl) silane (OTS-silane), trimethoxy (octadecyl) silane (ODS-silane), decyl (triethoxy) silane, dodecyltriethoxysilane, trimethoxy (tetradecyl) silane, hexadecyltrimethoxysilane, isobutyl (trimethoxy) silane, and combinations thereof.
In one embodiment of the present invention, the amount of the hydrophobic silane is in the range of 5 wt% to 30 wt% based on the total weight of the core-shell particles, generally, the more hydrophobic silane is bonded to the core and the more core-shell particles are protruded to the film surface, thereby increasing the surface roughness and improving the matting effect. However, when the amount of the hydrophobic silane exceeds, for example, 30 wt%, the core-shell particles may aggregate with each other, which adversely affects the light-degrading effect. On the other hand, strong cohesive force of fluorine atoms or steric hindrance by long carbon chains may prevent hydrophobic silane having fluorine atoms or long carbon chains from attaching to the core-shell particles. Therefore, the amount of hydrophobic silane should not be too high. Further, when the amount of the hydrophobic silane is less than, for example, 5 wt%, the hydrophobic silane will be difficult to attach to the core-shell particles. In one embodiment of the invention, the amount of hydrophobic silane ranges from 5 wt% to 30 wt%, such as 5 wt%, 6 wt%, 8 wt%, 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, or 30 wt%, based on the total weight of the core-shell particles.
In the present invention, the silane coupling agent is used to improve the interfacial properties between the core and the shell of the core-shell particles, and modify the surface of the core, so that the surface of the core is chemically bonded to the hydrophobic silane via the silane coupling agent. The silane coupling agent of the present invention has at least one ethylenically unsaturated group and at least one hydroxyl group or alkoxy group. The ethylenic unsaturated group of the silane coupling agent reacts with the carbon-carbon double bond of the remaining vinyl polymer on the surface of the core through addition polymerization to form a chemical bond between the silane coupling agent and the vinyl polymer of the core. On the other hand, the alkoxy group of the silane coupling agent can be reduced to a hydroxyl group by reacting with water present in the reaction medium. The hydroxyl group (including a hydroxyl group derived from an alkoxy group) of the silane coupling agent undergoes a sol-gel reaction to form a chemical bond between the silane coupling agent and the hydrophobic silane of the shell.
The present inventors have found that by using a silane coupling agent that can chemically bond to both the vinyl polymer of the core and the hydrophobic silane of the shell, the resulting core-shell particles have high hydrophobicity and can protrude to the surface of the film to increase the roughness of the film, increase physical light scattering, and improve the racemization gloss. Furthermore, the organic core allows the core-shell particles of the present invention to have a lower density compared to silica particles conventionally used in the art. The core-shell particles of the invention have lower density and compact arrangement of the core-shell structure, and the core-shell particles of the invention can be compatible with adhesive resin, so the extinction composition containing the core-shell particles of the invention is more stable. In addition, the process for preparing the core-shell particles of the present invention is easy to handle. The amount of hydrophobic silane bonded to the core surface can be easily controlled or adjusted and thus it is easier to design and prepare core-shell particles with desired properties.
Exemplary silane coupling agents include, but are not limited to: styrylethyltrimethoxysilane, methacryloxypropyl-trimethoxysilane, triethoxysilyl-modified poly-1, 2-butadiene, vinylethoxysiloxane homopolymers, vinylmethoxysiloxane homopolymers, allyltrimethoxysilane, vinyltriisopropoxysilane, (3-acryloxypropyl) trimethoxysilane or triethoxyvinylsilane.
In one embodiment, the silane coupling agent is a vinyl silane having the following formula (II):
(R4)pSi(OR5)4-p(II)
wherein R is4Is an alkene is an unsaturated group; r5Is H or C1-C3Alkyl (e.g., methyl, ethyl, or propyl); and p is an integer from 1 to 3, preferably 1. Examples of where the alkene is an unsaturated group include, but are not limited to: vinyl, propenyl, butenyl, vinylphenyl, propenylphenyl, vinylphenylethyl, propenoxymethyl, propenoxyethyl, propenoxypropyl, propenoxybutyl, propenoxypentyl, propenoxyhexyl, methacryloxymethyl, methacryloxyethyl, methacryloxypropyl, methacryloxyButyl, methacryloxypentyl, methacryloxyhexyl, a group of the following formula (7) and a group of the following formula (8):
wherein R is12Is phenylene, straight or branched chain C1-C8Alkylene, straight or branched C2-C8Alkenylene radical, C3-C8Cycloalkylene radicals or straight or branched chains C1-C8A hydroxy alkylene group; and R is13Is hydrogen or a straight or branched chain C1-C4An alkyl group.
The amount of the silane coupling agent is not particularly limited and may be adjusted depending on the required amount of the hydrophobic silane. In embodiments of the present invention, the amount of the silane coupling agent is in the range of 5 wt% to 25 wt%, for example, 5 wt%, 6 wt%, 8 wt%, 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, 22 wt%, or 24 wt%, based on the total weight of the core-shell particles. It was found that when the amount of the silane coupling agent exceeds, for example, 25% by weight, a sol-gel reaction of the silane coupling agent itself may occur, which adversely affects the sol-gel reaction between the silane coupling agent and the hydrophobic silane. In contrast, when the amount of the silane coupling agent is less than, for example, 5 wt%, the amount of the hydrophobic silane chemically bonded to the vinyl polymer of the core via the silane coupling agent may be insufficient.
In some embodiments of the present invention, the average particle size of the core-shell particles is 10 to 1,000nm, particularly, preferably 10 to 500nm, and more preferably 10 to 300 nm.
The core-shell particles of the present invention may be prepared by any suitable method known in the art. In one embodiment, the core-shell particles of the present invention are prepared by performing soap-free emulsion polymerization to form a core and performing a sol-gel process to form a shell. For example, the core-shell particles of the present invention can be prepared by, for example, the following steps:
(a) polymerizing a vinyl monomer in an aqueous solution to form vinyl polymer particles;
(b) swelling vinyl polymer particles by adding a silane coupling agent;
(c) reacting the vinyl polymer particles with a silane coupling agent to bond the silane coupling agent to the surfaces of the vinyl polymer particles; and
(d) reacting the hydrophobic silane with a silane coupling agent bonded to the surface of the vinyl polymer particles.
It is known in the art to use surfactants (or emulsifiers) in emulsion polymerization; however, this technique suffers from several drawbacks, including environmental pollution and the complexity of removing the surfactant (or emulsifier) after polymerization. According to a preferred embodiment of the invention, in step (a), the core is prepared by soap-free emulsion polymerization (i.e. without using surfactants or emulsifiers) comprising polymerizing vinyl monomers in aqueous solution at high temperature (e.g. 75 ℃) under nitrogen atmosphere and in the presence of an initiator until a conversion of 60% to 80% is reached. The conversion rates mentioned herein are defined as follows:
conversion (%) - (total number of monomers of reactants) - (total of corresponding units in product)
Number) ]/[ total monomer number of reactants ]
Incomplete conversion of the soap-free emulsion polymerization leaves a sufficient amount of carbon-carbon double bonds in the core. Since the carbon-carbon double bond from the monomer is not completely consumed, the unreacted carbon-carbon double bond may react with the vinylsilane coupling agent in a subsequent step and form the core-shell particle of the present invention. Compared to emulsion polymerization, soap-free emulsion polymerization can not only reduce the disadvantages as described above, but also provide advantages such as monodispersity (monodispersity) of particle size and smaller molecular weight of the resulting polymer. In addition, the polymerization rate of soap-free emulsion polymerization is much slower than that of emulsion polymerization, and therefore soap-free emulsion polymerization is suitable for obtaining a predetermined conversion rate.
In the step (b), the vinyl polymer particles are swollen by adding a silane coupling agent, preferably by adding a silane coupling agent and styrene dissolved in a solvent such as methanol and the like. The addition of styrene is beneficial for directing the silane coupling agent to the vinyl polymer particles due to the affinity between the newly added styrene and unreacted vinyl monomers in the vinyl polymer (e.g., styrene and n-butyl acrylate in the case of polystyrene-n-butyl acrylate polymers). The amount of styrene is preferably in the range of 3 wt% to 5 wt%, such as 3 wt%, 3.3 wt%, 3.5 wt%, 3.8 wt%, 4 wt%, 4.3 wt%, 4.5 wt%, 4.8 wt%, or 5 wt%, based on the total weight of the core particle. If the amount of styrene added is too large, the styrene itself tends to self-polymerize due to its high hydrophobicity and intermolecular force (π - π attraction), and the hydrophobic silane coupling agent itself undergoes a sol-gel reaction, so that the styrene content is not too high. In the presence of methanol or a similar solvent, styrene can move together with the silane coupling agent. The amount of the silane coupling agent is preferably in the range of 5 wt% to 25 wt%, for example, 5 wt%, 8 wt%, 10 wt%, 13 wt%, 15 wt%, 18 wt%, 20 wt%, 23 wt%, or 25 wt%, based on the total weight of the core-shell particles. An excessive amount of the silane coupling agent may cause the silane coupling agent itself to undergo a sol-gel reaction. An insufficient amount of the silane coupling agent will decrease the amount of the hydrophobic silane bonded to the core, thereby affecting the matting effect.
In the step (c), the vinyl polymer particles are reacted with a silane coupling agent in the presence of an initiator so that the silane coupling agent is bonded to the surfaces of the vinyl polymer particles.
Suitable initiators for use in steps (a) and (c) may be, for example, but not limited to, peroxides. Examples of peroxides include, but are not limited to: tertiary butyl hydroperoxide, hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate.
In step (d), the hydrophobic silane and the silane coupling agent bonded to the surface of the vinyl polymer particles react in the sol-gel process and form the core-shell particles of the present invention. Suitable amounts of hydrophobic silane are as described above. If more hydrophobic silane is present in the system, the core is more likely to encounter and undergo a sol-gel reaction with the hydrophobic silane. Conversely, if the amount of hydrophobic silane is too small, only a few hydrophobic silanes bond to the core surface, adversely affecting the matting effect.
The advantages of the sol-gel reaction are as follows:
(1) the precursor may be removed by distillation or other simple purification methods to obtain a high purity product.
(2) The low reaction temperature prevents the material from reacting with the container wall.
(3) The shape and size of the particles can be precisely controlled by varying experimental conditions.
(4) The sol-gel reaction can be catalyzed using a nano-scale catalyst having a large specific area.
Depending on the type of hydrophobic silane and the desired particle characteristics (e.g., particle size), the sol-gel reaction can be carried out in an acid or base environment. Under acidic conditions, the rate of hydrolysis of hydrophobic silanes is faster, but the rate of condensation under acidic conditions is much slower. The fast hydrolysis rate and the slow condensation rate result in smaller core-shell particles. In contrast, under alkaline conditions, the rate of condensation is faster than the rate of hydrolysis, resulting in larger core-shell particles. The sol-gel reaction can be carried out under acidic or basic conditions, and the pH value involved can be determined according to the required reaction rate and the required characteristics of the core-shell particles. In one embodiment of the invention, the sol-gel reaction is carried out at a pH of 2 to 11, for example: 3. a pH of 4, 5, 6, 7, 8, 9 or 10.
The invention also provides a matting composition comprising the core-shell particles of the invention as a matting agent. In an embodiment of the invention, the matting composition includes the core-shell particles and a binder resin.
The binder resin of the present invention is used to disperse the core-shell particles, and the binder resin suitable for use in the present invention may be any suitable resin, such as a thermosetting resin. Examples of thermosetting resins include, but are not limited to: acrylic or acrylate resins, methacrylic or methacrylate resins, polyamide resins, polyurethane resins, polyester resins, polyimide resins, alkyd resins, epoxy resins, phenolic resins, or combinations thereof, preferably acrylate resins or methacrylate resins.
In some embodiments of the invention, the binder resin is an acrylic emulsion (Etersol 1135-9; Eternal materials Co. Ltd.).
In some embodiments of the present invention, the matting composition comprises, based on the total weight of solids content of the matting composition: 3 to 25 wt%, preferably 5 to 20 wt% and more preferably 10 to 17 wt% of core-shell particles.
The matting compositions of the invention may optionally include water, solvents, or suitable additives known in the art, such as film formers, surfactants, fillers, pigments, or other processing aids.
The invention will be described in connection with the following examples. In addition to the following examples, the invention may be carried out in other ways without departing from the spirit of the invention; the scope of the invention should not be construed and limited solely by the disclosure of the specification. In addition, unless otherwise indicated herein, the terms "a" and "an" and "the" and similar terms used in the specification, especially in the appended claims, are to be construed to cover both the singular and the plural. The term "about" is used to describe measured values, including acceptable errors, depending in part on how the measurement is performed by the ordinary artisan. The word "or" in reference to a list of two or more items encompasses all interpretations of the word: any one of the list, all of the items in the list, and any combination of the items in the list. Additionally, the words "herein," "above," "below," and words of similar import, when used in this application, shall refer to this application as a whole and not to any particular portions of this application.
Examples of the invention
Example 1: preparation of matting compositions
1. Formation of vinyl polymer core via soap-free emulsion polymerization
To the reactor was added 200g of deionized water and a total weight of 20g of styrene (Across organics, 99% purity) and butyl acrylate (Across organics, 99% purity). For each sample, the weight ratio of styrene to butyl acrylate is reported in table 1. The mixture was degassed under nitrogen for 30 minutes with stirring at 300rpm and then heated to 75 ℃, followed by the addition of 1g of potassium persulfate dissolved in 20g of deionized water. The mixture was held at 75 ℃ for 4 hours to produce (P (St-BA)) copolymer cores at conversions of 60% to 70%.
2. Forming a shell via a sol-gel reaction
P (St-BA) copolymer latex particles were swelled at room temperature for 24 hours by adding triethoxyvinylsilane (silane coupling agent; Across organics, 97% purity) dissolved in 40g of methanol and 1.6g of styrene (15.2 mmol; Across organics, 99% purity). For each sample, the amount of silane coupling agent is reported in table 1. The mixture was degassed under nitrogen for 30 minutes with stirring at 300rpm and then heated to 75 ℃, followed by the addition of 2g of potassium persulfate dissolved in 40g of deionized water. The mixture was held at 75 ℃ for 24 hours to produce P (St-BA) copolymer latex particles modified with triethoxyvinylsilane on the surface.
The modified P (St-BA) copolymer latex particles were cooled to room temperature and then blended with a hydrophobic silane dissolved in 40g of methanol. The type and amount of hydrophobic silane used for each sample is reported in table 1. The sol-gel reaction was performed at room temperature for 2 hours to produce core-shell particles with a hydrophobic silane shell and a P (St-BA) copolymer core.
3. Preparation of matting compositions
The prepared core-shell particles were blended with an acrylic emulsion (Etersol 1135-9; Eternal materials Co. Ltd.) containing 1 wt% of an anionic surfactant to prepare a matting composition. The kind of the anionic surfactant is not particularly limited and may be any anionic surfactant suitable for the matting composition of the present invention. The examples provided herein use Sodium Dodecyl Sulfate (SDS) as the anionic surfactant. In addition, the blending method is not particularly limited and may be performed, for example, by the following steps:
(a) 50g of Etersol1135-9 acrylic emulsion was poured into a 250ml beaker and 1% SDS surfactant solution (containing 1g SDS and 99g water) was added and stirred at 1000rpm for about 3 minutes in a water bath at 40 to 45 ℃ to prepare an acrylic emulsion.
(b) 3.75g of core-shell particles were added to the acrylic emulsion prepared in (a).
(c) 5g of film former (dipropylene glycol n-butyl ether (DPnB)) was then added to the acrylic emulsion containing the core-shell particles.
(d) The mixture was stirred well at a stirring speed of 1000rpm for 30 minutes and left to stand for 1 day.
Example 2: analysis of the extinction Effect
The matting effect of the matting composition was evaluated by heating the glass substrate and film at 50 ℃ for 3 days in an oven to dry and remove DPnB from the film, measuring the 60 ℃ Gloss of the film by a Novo-Gloss60 ℃ Gloss meter according to ASTM D523 (60 ℃ Gloss 53936 to 40; 2 41 to 70; Δ 71 to 90;
>90)。
TABLE 1
1Taking the total weight of the core-shell particles (taking sample 1 as an example, the total weight of the core-shell particles is 20/(100% -12% -14%)
2F-silane: 1H,1H,2H,2H perfluorooctyltriethoxysilane
318-silane: trimethoxy (octadecyl) silane (ODS-silane)
48-silane: trimethoxy (octyl) silane (OTS-silane)
53-silane: trimethoxy (propyl) silane
6The theoretical Tg temperature obtained based on the Flory-Focus equation described in the specification, where the Tg of polystyrene is 373K and the Tg of polybutyl acrylate is 219K.
The matting composition of comparative sample 1 contained P (St-BA) particles without any surface modification. The 60 ° gloss of the film prepared from comparative sample 1 was too high, showing that the P (St-BA) particles without any surface modification failed to provide the desired matting effect.
The matting compositions of samples 1 to 5 contained P (St-BA) particles, the surface of which was modified with 14 wt% of F-silane, based on the total weight of the core-shell particles. The 60 ° gloss of the films prepared from samples 1 to 5 was lower than that of the films prepared from the comparative examples, demonstrating that the F-silane modified P (St-BA) particles can achieve the desired matting effect.
The matting compositions of samples 6 to 11 contained P (St-BA) particles whose surfaces were modified with varying amounts of long-carbon alkanesilanes (OTS-silanes or ODS-silanes). The 60 ° gloss rating of the films prepared from samples 6 to 10 is "o" or "Δ", demonstrating that the desired matting effect can be achieved with long-carbon chain alkylsilane modified P (St-BA) particles.
The matting results of the films prepared by comparing samples 2 and 3 and samples 1 to 5 show that when the Tg of the P (St-BA) particles is less than 0 ℃ (e.g., -10.8 ℃) or exceeds 60 ℃ (e.g., 75.5 ℃), the matting effect becomes poor.
The 60 ° gloss values of the films prepared from samples 6 to 10 and comparative sample 4 found that the more hydrophobic silane used, the better the matting effect; however, when the amount of the hydrophobic silane exceeds 30 wt% (e.g., 35 wt%), the matting effect becomes poor and particle aggregation can be observed.
Claims (9)
1. A core-shell particle, comprising:
a core of a vinyl-containing polymer; and
a shell containing a hydrophobic silane bonded to the core surface via a silane coupling agent; wherein the core of the vinyl-containing polymer has a Tg in the range of 0 ℃ to 60 ℃;
the hydrophobic silane is a long carbon alkanesilane having 3 to 25 carbon atoms;
wherein the silane coupling agent is a vinylsilane having the following formula (II):
(R4)pSi(OR5)4-p(II)
wherein R is4Is an ethylenically unsaturated group; r5Is H or C1-C3An alkyl group; and p is an integer from 1 to 3;
wherein the hydrophobic silane is present in an amount of 5 wt% to 30 wt%, based on the total weight of the core-shell particles; the amount of the silane coupling agent is 5 to 25 wt%.
2. Core-shell particles according to claim 1, wherein the hydrophobic silane has the following formula (I):
(R2)ySi(OR1)4-y(I)
wherein:
R1is C1-C3An alkyl group;
R2is- (CH)2)2-R3；
R3Is an alkyl group having 1 to 23 carbon atoms or a perhaloalkyl group having 1 to 23 carbon atoms; and
y is an integer from 1 to 3.
3. Core-shell particles according to claim 2, wherein the hydrophobic silane is selected from the group consisting of 1H,2H perfluorooctyltrimethoxysilane, 1H,2H perfluorooctyltriethoxysilane, trimethoxy (propyl) silane, trimethoxy (octyl) silane, trimethoxy (octadecyl) silane, decyl (triethoxy) silane, dodecyltriethoxysilane, trimethoxy (tetradecyl) silane, hexadecyltrimethoxysilane, isobutyl (trimethoxy) silane and combinations thereof.
4. Core-shell particles according to claim 1, wherein said vinyl polymer is derived from a vinyl monomer containing a carbon-carbon double bond.
5. Core-shell particles according to claim 4, wherein said vinyl monomer is selected from the group consisting of styrenic monomers, (meth) acrylate monomers, vinyl ester monomers, alkyl vinyl ether monomers, (meth) acrylamide monomers, and combinations thereof.
6. Core-shell particles according to claim 4, wherein said vinyl polymer is derived from vinyl monomers containing carbon-carbon double bonds and nitrile monomers.
7. Core-shell particles according to claim 1, wherein the silane coupling agent is styrylethyltrimethoxysilane, methacryloxypropyl-trimethoxysilane, triethoxysilyl-modified poly-1, 2-butadiene, vinylethoxysiloxane homopolymer, vinylmethoxysiloxane homopolymer, allyltrimethoxysilane, vinyltriisopropoxysilane, (3-acryloxypropyl) trimethoxysilane or triethoxyvinylsilane.
8. A process for preparing core-shell particles according to any one of claims 1 to 7, comprising performing soap-free emulsion polymerization to form a core and performing a sol-gel reaction to form a shell.
9. A matting composition comprising core-shell particles according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710673762.1A CN107602767B (en) | 2017-08-09 | 2017-08-09 | Core-shell particles, method for producing same, and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710673762.1A CN107602767B (en) | 2017-08-09 | 2017-08-09 | Core-shell particles, method for producing same, and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107602767A CN107602767A (en) | 2018-01-19 |
| CN107602767B true CN107602767B (en) | 2020-08-28 |
Family
ID=61064888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710673762.1A Active CN107602767B (en) | 2017-08-09 | 2017-08-09 | Core-shell particles, method for producing same, and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107602767B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651558B (en) * | 2018-11-06 | 2021-05-18 | 广州集泰化工股份有限公司 | Self-crosslinking core-shell structure water-based acrylic acid dispersion and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532554A (en) * | 2011-12-30 | 2012-07-04 | 山东省产品质量监督检验研究院 | Preparation method for organic silicon modified acrylic ester core-shell material |
| CN102827379A (en) * | 2012-08-16 | 2012-12-19 | 华南理工大学 | Redispersible latex powder and preparation method thereof |
| CN103204508A (en) * | 2013-04-12 | 2013-07-17 | 中国科学院化学研究所 | Janus nano material with double properties and preparation method of Janus nano material |
| CN103756395A (en) * | 2014-01-22 | 2014-04-30 | 上海赛肯森材料科技有限公司 | Nano hybrid particle for anti-reflection coating combination as well as preparation method and purpose of nano hybrid particle |
| CN107082868A (en) * | 2017-04-26 | 2017-08-22 | 运研材料科技（上海）有限公司 | A kind of nuclear shell structure nano hybrid particle, its preparation method and its anti-reflective coating compositions |
-
2017
- 2017-08-09 CN CN201710673762.1A patent/CN107602767B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532554A (en) * | 2011-12-30 | 2012-07-04 | 山东省产品质量监督检验研究院 | Preparation method for organic silicon modified acrylic ester core-shell material |
| CN102827379A (en) * | 2012-08-16 | 2012-12-19 | 华南理工大学 | Redispersible latex powder and preparation method thereof |
| CN103204508A (en) * | 2013-04-12 | 2013-07-17 | 中国科学院化学研究所 | Janus nano material with double properties and preparation method of Janus nano material |
| CN103756395A (en) * | 2014-01-22 | 2014-04-30 | 上海赛肯森材料科技有限公司 | Nano hybrid particle for anti-reflection coating combination as well as preparation method and purpose of nano hybrid particle |
| CN107082868A (en) * | 2017-04-26 | 2017-08-22 | 运研材料科技（上海）有限公司 | A kind of nuclear shell structure nano hybrid particle, its preparation method and its anti-reflective coating compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107602767A (en) | 2018-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2559599B2 (en) | Method for producing aqueous dispersion | |
| EP3344705B1 (en) | Copolymers containing polysiloxane macromonomer units, process of their preparation and their use in coating compositions and polymeric moulding compounds | |
| CN112898479B (en) | Unsaturated fatty acid modified waterborne acrylic resin dispersion and preparation method thereof | |
| US5621058A (en) | Hydrophilic crosslinked polymer fine particles and process for production thereof | |
| TW200936614A (en) | Emulsion polymers, aqueous dispersions and processes for preparing them | |
| US10287386B2 (en) | Core-shell particle, method of manufacturing the same and applications thereof | |
| KR101886395B1 (en) | New and stable aqueous hybrid binder | |
| EP4048742A1 (en) | Aqueous composition of organic polymeric microspheres, binder particles, and ion exchange resin | |
| WO1993010184A1 (en) | Highly weather-resistant one-pack cross-linking emulsion | |
| CN107602767B (en) | Core-shell particles, method for producing same, and use thereof | |
| EP0780411B1 (en) | Hydrophilic crosslinked polymer fine particles and process for production thereof | |
| JP2000109703A (en) | Aqueous dispersion | |
| US5539051A (en) | Resin composition for coating and paint | |
| JP5881496B2 (en) | Undercoat for release substrate | |
| KR100290596B1 (en) | Process for producing cationic emulsion | |
| TWI664197B (en) | Core-shell particle, method of manufacturing the same and applications thereof | |
| US5681889A (en) | Hydrophilic crosslinked polymer fine particles and process for production thereof | |
| JPH04268305A (en) | Production of aqueous self-dispersible vinyl resin | |
| CN112239518A (en) | Acrylic acid copolymer emulsion for improving early water resistance and glossiness of coating and application thereof | |
| CN112534021A (en) | Resin composition for vibration damping material | |
| CN109400791B (en) | Silicone-acrylic emulsion and preparation method thereof | |
| JP2018080297A (en) | Aqueous coating composition | |
| US20240067841A1 (en) | Additives for water-based wood stains | |
| JP7273478B2 (en) | water-based damping composition | |
| JP4294765B2 (en) | Room temperature curable coating composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |