CN113354960A - Modified inorganic nano particle and preparation method thereof - Google Patents
Modified inorganic nano particle and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified inorganic nanoparticle, which comprises an inorganic nanoparticle and a surface grafting modified chain segment bonded with the inorganic nanoparticle; the surface graft modification segment comprises at least one polymerizable group; the surface grafting modified chain segment passes through-SiR1R2A radical and/or-R1OTiOR2-bonding to said inorganic nanoparticles; wherein R is1R2Is at least one of alkyl, alkoxy, alkynyl, aryl, acrylic group, ester group, ether group and carboxyl. The modified inorganic nanoparticles of the inventionWhen the organic silicon/inorganic nano-particles are used in the hardening liquid, the using amount of the dispersing agent can be reduced, even the inorganic nano-particles can be stably dispersed without adding the dispersing agent, so that the negative influence of the dispersing agent, especially a macromolecular dispersing agent, on the hardening effect of the inorganic nano-particles in the coating can be effectively reduced, and the mechanical property of the coating can be effectively improved.
Description
Technical Field
The invention relates to modification of inorganic nanoparticles, in particular to modified inorganic nanoparticles applied to the field of coatings and a modification method thereof.
Background
The coating is a complex multiphase dispersion system consisting of a film forming material, a dispersion medium, a filler and an auxiliary agent, wherein each component plays a role in the process of forming a coating, and the filler is dispersed in the film forming material in a fine solid state to increase the mechanical strength of the coating and the like. The filler opens the aggregate by mechanical force in the dispersion process, and simultaneously, the filler and the dispersion medium interact with the film-forming material, namely the wetting, dispersion and stabilization processes are carried out to form a stable dispersion system. The dispersibility of the filler is therefore related to its crystal form, particle size and particle size distribution, and more importantly to its surface characteristics-surface tension, polar groups and water content, etc. Different fillers have different surface characteristics and different interactions with film formers having different molecular sizes and chemical structures. If the dispersion medium and the film former do not wet the surface of the filler particles, no mention is made of the dispersion; if good wetting is achieved, but uniform dispersion is not achieved, it can adversely affect the physical and chemical properties of the coating, such as surface leveling, poor transparency, and uneven hardness. The filler must therefore be uniformly dispersed in the dispersion medium to be a stable dispersion to function. Therefore, the dispersion of the filler and the dispersion stability are important.
The coating material having the optical property is generally used with a nano filler, and the nano filler itself has a large specific surface area, and van der waals force effect and brownian motion are strong, and an aggregate is easily formed. The stable dispersed nanoparticles are cut in mainly from two angles of electrostatic repulsion or steric hindrance effect. The steric hindrance effect is mainly generated by anchoring the macromolecular dispersant on the surface of the particles after opening the nanoparticle aggregate through mechanical force, so that the re-aggregation of the macromolecular dispersant is hindered. However, the surface is coated with a large amount of soft macromolecular dispersing agent, so that the improvement effect of the nano particles on mechanical properties such as hardness and the like in a hardened coating is greatly reduced; if the mechanical properties are enhanced by increasing the loading of the nanoparticles, the optical properties such as the transparency of the coating are reduced. Therefore, how to achieve high dispersibility of inorganic nanoparticles and effectively improve the mechanical properties of the hardened coating is a problem to be solved.
Patent CN1886469A mentions a coating solution containing surface-modified nanoparticles, which can improve the compatibility of nanoparticles with organic matrix and effectively improve the dispersibility of nanoparticles by modifying the surface of nanoparticles to adjust the polarity or hydrophilicity and hydrophobicity of the surface. But on one hand, the magnetic stirrer used for modification is weak in mechanical force and difficult to open nanoparticle agglomerates, so that the surface of the particles is not completely modified; on the other hand, the modifier is selected to be only dispersed for dispersion, the combination between the nano particles and the organic matrix is not tight, and when the coating resists external damage, the solvent of the nano particles slips or falls off, so that the improvement of the mechanical property of the coating is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide modified inorganic nanoparticles which are fully grafted with modified groups on the surface, avoid the reaggregation of the inorganic nanoparticles, have better dispersibility and effectively improve the mechanical property of a coating after being applied to a coating.
In order to achieve the purpose, the invention adopts the technical scheme that: a modified inorganic nanoparticle comprising an inorganic nanoparticle, a surface graft modification segment bonded to the inorganic nanoparticle; the surface graft modification segment comprises at least one polymerizable group;
the surface grafting modified chain segment passes through-SiR1R2A radical and/or-R1OTiOR2-bonding to said inorganic nanoparticles; wherein R is1R2Is at least one of alkyl, alkoxy, alkynyl, aryl, acrylic group, ester group, ether group and carboxyl.
The invention passes through-SiR1R2A radical and/or-R1OTiOR2-grafting a surface graft modification segment onto the surface of the inorganic nanoparticles, the surface graft modification segment comprising a segment of at least one member selected from the group consisting ofThe surface of the inorganic nano particle is fully grafted by at least one polymerizable group, so that the re-coagulation of the inorganic nano particle is avoided, and the dispersibility of the inorganic nano particle is effectively improved.
As a preferred embodiment of the modified inorganic nanoparticle of the present invention, the polymerizable group is at least one of an acryloxy group, methacryloxy group, epoxy group, and vinyl group.
As a preferred embodiment of the modified inorganic nanoparticles of the present invention, the surface graft modification segment further comprises at least one group that can increase the compatibility of the inorganic nanoparticles. In a more preferred embodiment of the modified inorganic nanoparticles of the present invention, the group capable of increasing the compatibility of the inorganic nanoparticles is at least one of an alkyl group, a hydrocarbon group, an aliphatic group, an acryloxy group, an epoxy group, and an ether group. The groups that can increase the compatibility of the inorganic nanoparticles are preferably identical or similar to the polymeric groups of the curable resin contained in the coating when the inorganic nanoparticles are applied in the coating. By matching the modifying group grafted on the surface of the inorganic nano particle with the polymeric group of the curable resin in the coating, the compatibility of the inorganic nano particle in the coating can be improved, the dispersibility is improved, and simultaneously, the chemical bonding between at least part of the modifying chain segment grafted on the surface of the inorganic nano particle and the curable resin can be realized in the curing process, so that the inorganic nano particle and a film-forming material are firmly combined, and the mechanical property of the coating is effectively improved
As a preferred embodiment of the modified inorganic nanoparticles of the present invention, the surface graft modification segment covers at least one layer on the surface of the inorganic nanoparticles. The surface grafting modification chain segment covers one layer, two layers or more layers on the surface of the inorganic nano particle, and the surface grafting modification chain segment fully covers the surface of the inorganic nano particle, so that the dispersibility of the inorganic nano particle can be effectively improved.
In a preferred embodiment of the modified inorganic nanoparticles of the present invention, the inorganic nanoparticles are at least one of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, chromium oxide, antimony oxide, and tin oxide.
As a preferred embodiment of the modified inorganic nanoparticles of the present invention, the inorganic nanoparticles have a particle size distribution D99Is 20-200 nm. As a more preferred embodiment of the modified inorganic nanoparticles of the present invention, the inorganic nanoparticles have a particle size distribution D99Is 80-150 nm.
In addition, the invention also provides a preparation method of the modified inorganic nanoparticles, which comprises the following steps:
(1) premixing: uniformly mixing a modifier with a solvent;
(2) grinding modification: adding inorganic nano particles under the condition of superfine grinding, grinding and modifying, and drying by hot drying or spray drying after modification to obtain the modified inorganic nano particles.
In the preparation method of the modified inorganic nano particles, the modifier and the solvent are firstly premixed, then the inorganic nano particles are added under the condition of superfine grinding, the inorganic nano particles are modified in the grinding process, and are dried by hot drying or spray drying after being modified, and are sealed and stored for later use after being dried.
As a preferable embodiment of the method for preparing the modified inorganic nanoparticles, the modifier is at least one of a silane coupling agent, a titanate coupling agent, and a polyol.
As a more preferred embodiment of the method for preparing the modified inorganic nanoparticles of the present invention, the modifier is gamma-methacryloyloxytrimethoxysilane, gamma-methacryloyloxypropylmethyltrimethoxysilane, gamma-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriisopropoxysilane, acetoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriacetoxysilane, vinyltributoxysilane, gamma-glycidyloxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltriisopropoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-2-methoxyethoxy-vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriisopropoxysilane, vinyltriethoxysilane, vinyltris-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltris-methacryloxypropyltrimethoxysilane, vinyltris-vinyltrimethoxysilane, vinyltris-trimethoxysilane, vinyltris-vinyltris (2-vinyltris-acetoxy-trimethoxysilane, vinyltris-vinyltrimethoxysilane, vinyltris-hydroxytrimethoxysilane, vinyltris-or a-vinyltris-hydroxywith a-or-vinyltris-or a-or-hydroxy-or-vinyltris-or-type-or-hydroxy-or-type-or-hydroxy-or, 3-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, isopropyldioleate acyloxy (dioctylphosphate acyloxy) titanate, isopropyltris (dioctylphosphate) titanate, isopropyltrioleate acyloxy titanate, isopropyl triisostearate, and bis (dioctyloxypyrophosphate) ethylene titanate.
As a preferred embodiment of the method for preparing the modified inorganic nanoparticles of the present invention, the molecular weight of the modifier is not more than 500; as a more preferred embodiment of the method for preparing modified inorganic nanoparticles of the present invention, the molecular weight of the modifier does not exceed 300. The modifier has overlarge molecular weight, can produce a good effect when the particle size is required to be micron or submicron, and when the particle size is reduced to be within two-three hundred nanometers, the surface of the inorganic nano particle is occupied by barriers such as a monomer or a grafted high molecular weight modifier and the like when the modifier is used, and the modifier is difficult to diffuse into the fresh surface of the inorganic nano particle. And the small molecular modifier can be quickly diffused on the surface of the inorganic nano particle and grafted to a new surface, so that the recombination of the inorganic nano particle is prevented.
In a preferred embodiment of the method for preparing modified inorganic nanoparticles of the present invention, the mass ratio of the modifier to the inorganic nanoparticles is 0.5 to 3. The mass ratio of the modifier to the inorganic nanoparticles is generally calculated based on the specific surface area or oil absorption of the inorganic nanoparticles.
As a preferred embodiment of the preparation method of the modified inorganic nanoparticles, the superfine grinding is carried out by a sand mill with adjustable temperature, the grinding temperature is 10-100 ℃, and the grinding time is 1-100 h. As a more preferable embodiment of the preparation method of the modified inorganic nanoparticles, the grinding temperature is 40-80 ℃, and the grinding time is 3-50 h; as the most preferable embodiment of the preparation method of the modified inorganic nanoparticles, the grinding temperature is 50-70 ℃ and the grinding time is 3-50 h. The grinding temperature can be regulated and controlled by externally connecting circulating water.
As a preferred embodiment of the method for preparing modified inorganic nanoparticles of the present invention, the grinding medium is at least one of zirconium beads, aluminum beads, and glass beads; the volume filling rate of the grinding medium in the grinding cavity is 70-90%; the particle size of the grinding medium is 0.03-0.3 mm.
As a preferable embodiment of the preparation method of the modified inorganic nanoparticles, the volume filling rate of the grinding medium in the grinding cavity is 80-90%.
As a preferred embodiment of the preparation method of the modified inorganic nanoparticles, when the particle size of the inorganic nanoparticles is 20-40nm, the particle size of the grinding medium is 0.1-0.3 mm.
As a preferred embodiment of the method for preparing modified inorganic nanoparticles of the present invention, the solvent in step (1) is at least one of water, acetic acid, absolute ethanol, isopropanol, and ethanol; the mass ratio of the modifier to the solvent is 1: 1.5-27.
In the preparation method of the modified inorganic nano-particle, when the adopted modifier needs to be pre-hydrolyzed, the modifier needs to be pre-hydrolyzed before pre-mixing.
The preparation of the modified inorganic nano-particles can adopt a full-automatic production line in actual industrial application, and comprises the following processes:
(1) pre-hydrolysis: adding a solvent into a reaction kettle, adding a modifier under a stirring state, adjusting the pH value (generally adjusting the pH value to 4, different modifiers have different requirements on the pH value), heating (generally heating to 50-70 ℃), performing prehydrolysis (generally the prehydrolysis time is 40 min-5 h), and stopping heating for later use; this step can be omitted if the modifier does not require prehydrolysis;
(2) grinding modification:
a) conveying the solvent into a sand mill through a pipeline, and circulating in the sand mill;
b) the modifier (after prehydrolysis) is conveyed to a sand mill through a pipeline;
c) the inorganic nano particles are gradually added into the sand mill through a powder feeding station, the grinding modification is started, and the temperature in the grinding cavity can be regulated and controlled by regulating the temperature of the water chiller; the temperature range required for different modifiers is different;
d) in the grinding process, the inorganic nanoparticle aggregate is opened, hydroxyl on the surface of the inorganic nanoparticle aggregate can be bonded with a modifier, and after a certain time, surface modification is finished;
e) and drying the modified slurry by a spray drying tower to obtain modified inorganic nanoparticles for later use.
Finally, the invention also provides the application of the modified inorganic nano particles in the coating. The modified inorganic nanoparticles can be applied to coatings, and because the modified inorganic nanoparticles have better dispersibility, when the modified inorganic nanoparticles are applied to the field of coatings, the use amount of a dispersing agent can be effectively reduced, even the inorganic nanoparticles can be stably dispersed without adding the dispersing agent, so that the negative influence of the dispersing agent, especially a macromolecular dispersing agent, on the hardening effect of the inorganic nanoparticles in the coatings can be effectively reduced, and the mechanical property of the coatings can be effectively improved by the modified inorganic nanoparticles.
According to the modified inorganic nanoparticles, the modified inorganic nanoparticles are formed by modifying under the superfine grinding process, the superfine grinding process can effectively open the aggregate of the inorganic nanoparticles, so that the inorganic nanoparticles are grafted with the modified groups on the surfaces when in a dispersed state, the surfaces of the inorganic nanoparticles can be fully grafted, the grinding efficiency is improved while re-agglomeration is avoided, the use amount of the dispersing agent is reduced, even the inorganic nanoparticles can be stably dispersed without adding the dispersing agent, and the negative influence of the dispersing agent, especially a macromolecular dispersing agent, on the hardening effect of the inorganic nanoparticles in a coating can be effectively reduced. More importantly, the polymerizable group grafted on the surface of the inorganic nano particle can ensure that at least part of the nano particle can be bonded with the organic matrix in the coating curing process, thereby effectively improving the mechanical property of the coating. And the slurry containing the modified inorganic nanoparticles can be applied to a solvent-free system, so that the VOC emission in the construction process is reduced.
Drawings
FIG. 1 is a graph showing comparative tests of dispersibility of inorganic nanoparticles before and after modification according to one embodiment of the present invention;
FIG. 2 is a graph showing the comparison of particle sizes of inorganic nano-alumina containing different contents of dispersant before modification;
FIG. 3 is a comparison graph of particle sizes of modified inorganic nano-alumina containing different contents of dispersant;
FIG. 4 is a graph showing the comparison of particle sizes of inorganic nano-alumina containing a small amount of dispersant before and after modification;
FIG. 5 is a comparison graph of particle sizes of inorganic nano alumina before and after modification without dispersant.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
Example 1
In an embodiment of the modified inorganic nanoparticles of the present invention, the modified inorganic nanoparticles of this embodiment are prepared by the following method:
(1) pre-hydrolysis: according to H2Mixing ethanol and water, adding gamma-methacryloxy trimethoxy silane (KH570) while stirring with magnetons, stirring for 3min, adding acetic acid dropwise, adjusting pH to 4 (measured by a pH meter), and hydrolyzing at 50 deg.C for 3 h;
(3) premixing: adding isopropanol into the hydrolyzed solution to 400g for later use, wherein the solution is solution A;
(4) grinding modification: filling zirconium beads with the diameter of 0.6mm into a grinding cavity of a 0.3L sand mill, wherein the volume filling rate of the zirconium beads in the grinding cavity is 80%; pouring the solution A from a feeding hole, starting a sand mill, and gradually adding nano silicon oxide powder (90G), wherein the mass ratio of the nano silicon oxide powder to the modifier is SiO2Gamma-methacryloxy trimethoxysilane (KH570) 1: 1; adjusting the temperature of the water chiller to enable the grinding chamber to be internally provided with a grinding chamberThe temperature is stabilized at about 60 ℃, the operation is continued for 5 hours, the nano silicon oxide dispersion liquid with the surface grafted with the gamma-methacryloxy functional group is obtained, the particle size D100 of the dispersion liquid is tested to be less than 300nm, the modified nano silicon oxide dispersion liquid is repeatedly centrifugally cleaned for 3 times by isopropanol, oligomers of the silane coupling agent which are not grafted in the nano silicon oxide dispersion liquid are removed, and then the modified nano silicon oxide powder is obtained by drying.
The amount of each raw material of the modified inorganic nanoparticles described in this example can be increased or decreased by an equal ratio. When the modifier selected does not require pre-hydrolysis, step (1) above may be omitted.
Example 2
In an embodiment of the modified inorganic nanoparticles of the present invention, the modified inorganic nanoparticles of this embodiment are prepared by the following method:
(1) pre-hydrolysis: according to H2Mixing ethanol and water, adding gamma-methacryloxy trimethoxy silane (KH570) while stirring with magnetons, stirring for 3min, adding acetic acid dropwise, adjusting pH to 4 (measured by a pH meter), and hydrolyzing at 50 deg.C for 3 h;
(2) premixing: adding isopropanol into the hydrolyzed solution to 400g for later use, wherein the solution is solution A;
(3) grinding modification: then filling zirconium beads with the diameter of 0.6mm into a grinding cavity of a 0.3L sand mill, wherein the volume filling rate of the zirconium beads in the grinding cavity is 80%; pouring the solution A from a feeding hole, starting a sand mill, and gradually adding nano alumina powder, wherein the ratio of the nano alumina powder to the modifier is Al2O3Gamma-methacryloxy trimethoxysilane (KH570) 1: 1; adjusting the temperature of a water chiller to enable the temperature in the grinding cavity to be stabilized at about 60 ℃, continuously operating for 5 hours to obtain nano aluminum oxide dispersion liquid with the surface grafted with gamma-methacryloxy functional groups, and testing the particle size of the dispersion liquid; repeatedly centrifuging and cleaning the modified nano-alumina dispersion liquid for 3 times by using isopropanol, removing oligomers of the silane coupling agent which are not grafted in the dispersion liquid, and drying the oligomers to obtain the modified nano-aluminaAluminum powder.
The amount of each raw material of the modified inorganic nanoparticles described in this example can be increased or decreased by an equal ratio. When the modifier selected does not require pre-hydrolysis, step (1) above may be omitted.
Example 3
In an embodiment of the modified inorganic nanoparticles of the present invention, the modified inorganic nanoparticles of this embodiment are prepared by the following method:
(1) pre-hydrolysis: according to H2Mixing ethanol and water at a ratio of 13.5: 9: 27g, adding KH560 with magneton under stirring, stirring for 3min, adding acetic acid dropwise, adjusting pH to 4 (measured by pH meter), heating in water bath at 50 deg.C, and hydrolyzing for 3 hr;
(2) premixing: adding isopropanol into the hydrolyzed solution to 400g for later use, wherein the solution is solution A;
(3) grinding modification: filling zirconium beads with the diameter of 0.6mm into a grinding cavity of a 0.3L sand mill, wherein the volume filling rate of the zirconium beads in the grinding cavity is 80%; pouring the solution A from a feeding hole, starting a sand mill, and gradually adding the nano silicon oxide powder, wherein the ratio of the powder to the modifier is SiO2KH560 is 1: 1; and (3) adjusting the temperature of the water cooler to enable the temperature in the grinding cavity to be stabilized at about 60 ℃, continuously operating for 5 hours to obtain the nano silicon oxide dispersion liquid with the surface grafted with the epoxy group, and testing the particle size of the dispersion liquid. And repeatedly centrifuging and cleaning the modified nano silicon oxide dispersion liquid for 3 times by using isopropanol, removing oligomers of the silane coupling agent which is not grafted in the dispersion liquid, and drying to obtain the modified nano silicon oxide powder.
The amount of each raw material of the modified inorganic nanoparticles described in this example can be increased or decreased by an equal ratio. When the modifier selected does not require pre-hydrolysis, step (1) above may be omitted.
When the materials adopt other proportions in the range of the invention, and the other components in the invention are selected from the substances such as the modifier, the inorganic nanoparticles and the like, the modified inorganic nanoparticles with the structure can be obtained by modification according to the modification method (different grinding process conditions are selected), and the details are not repeated.
Example 4
Dispersion test of the modified inorganic nanoparticles of the present invention
In this example, the modified nano alumina particles prepared in example 2 and the nano alumina particles before modification were used as test objects, the nano alumina powder before modification and the modified nano alumina powder prepared in example 2 were dissolved in water and a solvent (octane), and the dispersion of the nano alumina before modification and the nano alumina after modification in water and the solvent (octane) were observed, respectively, and the test results are shown in fig. 1.
As can be seen from the attached figure 1, the left one is the dispersion condition of the unmodified nano alumina in water, and the unmodified nano alumina is slightly dispersed in water, which indicates that the unmodified nano alumina has certain hydrophilicity; the second left is the dispersion condition of the modified nano-alumina in water, and the modified nano-alumina completely floats on the water surface, which shows that the modified nano-alumina has good hydrophobicity; the left third is the dispersion condition of the unmodified nano alumina in the solvent (octane), and part of the unmodified nano alumina enters the solvent (octane), which indicates that the unmodified nano alumina has certain lipophilicity; the left four is the dispersion condition of the modified nano-alumina in the solvent (octane), and the modified nano-alumina completely enters the solvent (octane), which shows that the modified nano-alumina has good lipophilicity.
Example 5
Particle size test before and after modification of modified inorganic nanoparticles of the invention
In this embodiment, the modified nano alumina particles prepared in example 2 and the nano alumina particles before modification are used as test objects, and the test results are shown in table 1 and fig. 2-5, where unmodified nano alumina with a large amount of dispersant added (a large amount of dispersant BYK111 is added, the addition amount of the dispersant is 70% of the weight of the unmodified nano alumina), unmodified nano alumina with a small amount of dispersant added (a small amount of dispersant BYK111 is added, the addition amount of the dispersant is 5% of the weight of the unmodified nano alumina), unmodified nano alumina particles without dispersant, modified nano alumina with a small amount of dispersant added (a small amount of dispersant BYK111 is added, the addition amount of the dispersant is 5% of the weight of the modified nano alumina), and the particle size of the modified nano alumina without dispersant added (D100 value).
TABLE 1 particle size test results of nano-alumina before and after modification
| Sample (I) | Unmodified | Has been modified |
| No dispersant | 300μm | 0.3μm |
| Small amount of dispersant | 18μm | 0.28μm |
| A plurality of dispersants | 0.35μm |
As can be seen from Table 1 and accompanying drawings 2-5, the particle size of the inorganic nano-alumina is significantly reduced after modification.
Example 6
Haze test of a product coated with a hardening liquid prepared from the modified inorganic nanoparticles of the present invention
In this example, a test group 1 and control groups 1 to 2 were set, and the hardening liquid used in each group had the following formulation:
the hardening liquid used in test group 1 contained the following components in parts by weight: DSM-X30670 parts, initiator 1104 (main component: 1-hydroxycyclohexyl phenyl ketone) 5 parts, ethyl acetate 10 parts, butyl acetate 15 parts, modified inorganic alumina 30 parts (modified inorganic alumina prepared in example 2 was used).
The hardening liquid used in the control group 1 contains the following components in parts by weight: DSM-X30670 parts, initiator 1104 (main component: 1-hydroxy cyclohexyl phenyl ketone) 5 parts, ethyl acetate 10 parts, butyl acetate 15 parts and unmodified inorganic alumina 30 parts.
The hardening liquid used in the control group 2 contains the following components in parts by weight: DSM-X30670 parts, initiator 1104 (main component: 1-hydroxycyclohexyl phenyl ketone) 5 parts, ethyl acetate 10 parts, butyl acetate 15 parts, unmodified inorganic alumina 30 parts, dispersant BYK111 (the amount of dispersant is 5% of the weight of the unmodified inorganic alumina).
The preparation method of the hardening liquid of the test group and the control group comprises the following steps:
(1) mixing the rest components except the modified inorganic nano particles or the unmodified inorganic nano particles, and uniformly stirring to obtain a hardening liquid varnish;
(2) starting a sand mill, using zirconium beads with the diameter of 0.6mm as grinding media, wherein the volume filling rate of the grinding media in a grinding cavity is 80%; and adding the hardening liquid varnish into a sand mill, gradually adding the modified inorganic nanoparticles or unmodified inorganic nanoparticles, and continuously grinding for 3 hours to obtain the hardening liquid.
Respectively adopting the hardening liquid of the test group 1 and the hardening liquid of the control group 1-2 to coat samples, and then testing the haze of the obtained samples, wherein the test result is as follows: the haze of test 1 was 0.45, the haze of control 1 was 15, and the haze of control 2 was 6.
According to the test result, the hardening liquid with the same formula can effectively reduce the haze of the sample obtained by coating by adopting the modified inorganic nano alumina compared with the unmodified inorganic nano alumina.
Example 7
Friction resistance test of product obtained by coating after hardening liquid is prepared from modified inorganic nanoparticles
In this example, a test group 1 and control groups 1 to 2 were set, and the hardening liquid used in each group had the following formulation:
the hardening liquid used in test group 1 contained the following components in parts by weight: DSM-X30670 parts, an initiator 1104 (main component: 1-hydroxycyclohexyl phenyl ketone) 5 parts, ethyl acetate 10 parts, butyl acetate 15 parts, modified inorganic alumina 30 parts (the modified inorganic alumina prepared in example 2 is adopted), and a dispersant BYK111 (the using amount of the dispersant is 5% of the weight of the modified inorganic alumina).
The hardening liquid used in the control group 1 contains the following components in parts by weight: DSM-X30670 parts, initiator 1104 (main component: 1-hydroxy cyclohexyl phenyl ketone) 5 parts, ethyl acetate 10 parts and butyl acetate 15 parts.
The hardening liquid used in the control group 2 contains the following components in parts by weight: DSM-X30670 parts, initiator 1104 (main component: 1-hydroxycyclohexyl phenyl ketone) 5 parts, ethyl acetate 10 parts, butyl acetate 15 parts, unmodified inorganic alumina 30 parts, dispersant BYK111 (the amount of dispersant is 5% of the weight of the unmodified inorganic alumina).
The preparation method of the hardening liquid of the test group and the control group comprises the following steps:
(1) mixing the rest components except the modified inorganic nano particles or the unmodified inorganic nano particles, and uniformly stirring to obtain a hardening liquid varnish;
(2) starting a sand mill, using zirconium beads with the diameter of 0.6mm as grinding media, wherein the volume filling rate of the grinding media in a grinding cavity is 80%; and adding the hardening liquid varnish into a sand mill, gradually adding the modified inorganic nanoparticles or unmodified inorganic nanoparticles, and continuously grinding for 3 hours to obtain the hardening liquid.
Respectively adopting the hardening liquid of a test group 1 and a control group 1-2 to coat samples, and then testing the friction resistance of the obtained samples (test method: steel wool resistance, 1.5 x 1.5 square head, bonstar0000#, 5000 times), wherein the test result is as follows: the sample of the test group 1 has 8000 times of wear resistance and no obvious scratch; the sample of the control group 1 has 1000 wear-resisting times and serious scratch; the control 2 sample was 1500 times wear resistant with obvious scratches.
According to the test result, the hardening liquid with the same formula can effectively improve the friction resistance of a sample obtained by the coating by adopting the modified inorganic nano alumina compared with the unmodified inorganic nano alumina.
Example 8
Hardness, haze and steel wool resistance tests of products obtained by coating after modified inorganic nanoparticles are prepared into hardening liquid
In the present embodiment, test groups 1 to 3 and control groups 1 to 4 were provided, and the formula of each hardening liquid is shown in table 2:
TABLE 2 formulation of hardening liquid for test group and control group (each component is in weight portion)
| Name of Material | Test group 1 | Test group 2 | Test group 3 | Control group 1 | Control group 2 | Control group 3 | Control group 4 |
| DSM-X306 | 70 | 70 | 70 | 70 | 70 | ||
| DSM-1030 | 70 | 70 | |||||
| 1104 | 5 | 5 | 5 | 5 | 5 | ||
| 651 | 3 | 5 | |||||
| BYK-111 | 21 | ||||||
| |
10 | 15 | 15 | 15 | 15 | 15 | 15 |
| Acetic |
15 | 15 | 15 | 15 | 15 | 15 | 15 |
| Modified nano alumina | 30 | ||||||
| Modified nano silicon oxide | 30 | 30 | 30 | 30 | |||
| Unmodified nano silicon oxide | 30 | 30 |
Note: DSM-X306 and DSM-1030 find the only corresponding products according to the number 1104 refers to initiator 1104, the main components of which are: 1-hydroxycyclohexyl phenyl ketone; 651 refers to benzil dimethyl ether.
In the test group 1, the modified nano-silica contained in the curing fluid was prepared in example 1. Test group 2 the hardening liquid contained the modified nano alumina prepared in example 2. Test group 3 the hardening liquid contained the modified nano-silica prepared in example 3.
The modified nano-silica contained in the control group 1 was prepared by the following method:
(1) pre-hydrolysis: according to H2Mixing ethanol and water, adding gamma-methacryloxy trimethoxy silane (KH570) while stirring with magnetons, stirring for 3min, adding acetic acid dropwise, adjusting pH to 4 (measured by a pH meter), and hydrolyzing at 50 deg.C for 3 h;
(2) premixing: adding isopropanol into the hydrolyzed solution to 400g for later use, wherein the solution is solution A;
(3) grinding modification: filling zirconium beads with the diameter of 0.6mm into a grinding cavity of a 0.3L sand mill, wherein the volume filling rate of the zirconium beads in the grinding cavity is 80%; pouring the solution A from a feeding hole, starting a sand mill, and gradually adding nano silicon oxide powder (90G), wherein the ratio of the nano silicon oxide powder to the modifier is SiO2Gamma-methacryloxy trimethoxysilane (KH570) 1: 1; adjusting the temperature of a water cooling machine to enable the temperature in the grinding cavity to be stabilized at about 60 ℃, continuously operating for 5 hours to obtain nano silicon oxide dispersion liquid with the surface grafted with gamma-methacryloxy functional groups, and testing the particle size D100 of the dispersion liquid to be less than 300 nm; and repeatedly centrifuging and cleaning the modified nano silicon oxide dispersion liquid for 3 times by using isopropanol, removing oligomers of the silane coupling agent which is not grafted in the dispersion liquid, and drying to obtain the modified nano silicon oxide powder.
The modified nano-silica contained in the control group 2 was prepared by the following method:
(1) pre-hydrolysis: according to H2O.gamma. -methacryloyloxytrimethoxysilane (KH570) to ethanol (13.5: 9: 27 g) in the first place, ethyleneMixing alcohol and water, adding gamma-methacryloxy trimethoxy silane (KH570) with magneton under stirring, stirring for 3min, adding acetic acid dropwise, adjusting pH to 4 (measured by pH meter), and hydrolyzing at 50 deg.C for 3 hr;
(2) premixing: adding isopropanol into the hydrolyzed solution to 400g for later use, wherein the solution is solution A;
(3) grinding modification: filling zirconium beads with the diameter of 0.6mm into a grinding cavity of a 0.3L sand mill, wherein the volume filling rate of the zirconium beads in the grinding cavity is 80%; pouring the solution A from a feeding hole, starting a sand mill, and gradually adding nano silicon oxide powder, wherein the ratio of the nano silicon oxide powder to the modifier is SiO2Gamma-methacryloxy trimethoxysilane (KH570) 1: 0.1; adjusting the temperature of a water chiller to enable the temperature in the grinding cavity to be stabilized at about 60 ℃, continuously operating for 5 hours to obtain nano silicon oxide dispersion liquid with the surface grafted with gamma-methacryloxy functional groups, and testing the particle size of the dispersion liquid; and repeatedly centrifuging and cleaning the modified nano silicon oxide dispersion liquid for 3 times by using isopropanol, removing oligomers of the silane coupling agent which is not grafted in the dispersion liquid, and drying to obtain the modified nano silicon oxide powder.
The preparation method of the hardening liquid of the test group and the control group comprises the following steps:
(1) mixing the rest components except the modified inorganic nano particles or the unmodified inorganic nano particles, and uniformly stirring to obtain a hardening liquid varnish;
(2) starting a sand mill, using zirconium beads with the diameter of 0.6mm as grinding media, wherein the volume filling rate of the grinding media in a grinding cavity is 80%; and adding the hardening liquid varnish into a sand mill, gradually adding the modified inorganic nanoparticles or unmodified inorganic nanoparticles, and continuously grinding for 3 hours to obtain the hardening liquid.
Samples of each hardening liquid group are coated to prepare sample sheets, and then the hardness (tested by a hardness tester), the haze (tested by a haze meter) and the steel wool resistance (tested by a friction resistance tester) of each sample sheet group are tested respectively, and the test results are shown in table 3.
TABLE 3 hardness, haze, Steel wool resistance test results of samples coated with the hardening liquid of the test group and the control group
| Performance of | Test group 1 | Test group 2 | Test group 3 | Control group 1 | Control group 2 | Control group 3 | Control group 4 |
| Hardness of | 4H | 4H | 3.5H | 3H | 3H | 3H | 3H |
| Steel wire resistant velvet | 8000 | 8000 | 5000 | 3000 | 1500 | 1500 | 2500 |
| Haze degree | 0.35 | 0.42 | 0.38 | 0.89 | 6 | 15 | 0.67 |
As can be seen from the results in Table 3, the hardness, steel wool resistance and haze of the test group are significantly better than those of the control group. In comparison with the test group, the modified inorganic nanoparticles in the control group 1 are grafted with the acryloxy group, and the epoxy resin is used in the hardening liquid, and the polymeric groups of the acryloxy group and the epoxy resin are not consistent, so that the performance of the modified inorganic nanoparticles is slightly inferior to that of the test group. Compared with the test group, in the modification process of the modified inorganic nanoparticles in the control group 2, the amount of the modifier is too small, so that the modified inorganic nanoparticles are not sufficiently modified, and the performance of the control group 2 is poor compared with the test group.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A modified inorganic nanoparticle comprising an inorganic nanoparticle, a surface graft modification segment bonded to the inorganic nanoparticle; the surface graft modification segment comprises at least one polymerizable group;
the surface grafting modified chain segment passes through-SiR1R2A radical and/or-R1OTiOR2-bonding to said inorganic nanoparticles; wherein R is1R2Is at least one of alkyl, alkoxy, alkynyl, aryl, acrylic group, ester group, ether group and carboxyl.
2. The modified inorganic nanoparticle of claim 1, wherein the polymerizable group is at least one of an acryloxy group, methacryloxy group, epoxy group, vinyl group.
3. The modified inorganic nanoparticle of claim 1 or claim 2, wherein the surface graft-modified segment further comprises at least one group that increases the compatibility of the inorganic nanoparticle; preferably, the group capable of increasing the compatibility of the inorganic nanoparticles is at least one of alkyl, hydrocarbon, aliphatic, acryloxy, epoxy and ether.
4. The modified inorganic nanoparticle of claim 1, wherein the surface graft modification segment covers at least one layer of the surface of the inorganic nanoparticle.
5. The modified inorganic nanoparticle of claim 1, wherein the inorganic nanoparticle is at least one of silica, alumina, zirconia, titania, chromia, antimony oxide, tin oxide; preferably, the inorganic nanoparticles have a particle size distribution D99Is 20-200 nm.
6. A method for preparing modified inorganic nanoparticles according to any one of claims 1 to 5, comprising the steps of:
(1) premixing: uniformly mixing a modifier with a solvent;
(2) grinding modification: adding inorganic nano particles under the condition of superfine grinding, grinding and modifying, and drying by hot drying or spray drying after modification to obtain the modified inorganic nano particles.
7. The method of claim 6, wherein the modifier is at least one of a silane coupling agent, a titanate coupling agent, a polyol; preferably, the modifier is gamma-methacryloxypropyltrimethoxysilane, gamma-methacryloxypropylmethyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriisopropoxysilane, acetoxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriacetoxysilane, vinyltributenoximosilane, gamma-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-isopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or mixtures thereof, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, isopropyldioleate acyloxy (dioctylphosphate acyloxy) titanate, isopropyltris (dioctylphosphate acyloxy) titanate, isopropyltrioleate acyloxy titanate, triisostearate isopropyl ester, and bis (dioctyloxypyrophosphate) ethylene titanate.
8. The method of claim 6 or 7, wherein the mass ratio of the modifier to the inorganic nanoparticles is 0.5 to 3.
9. The method for preparing modified inorganic nanoparticles according to claim 6, wherein the superfine grinding is performed by a temperature-controllable sand mill, the grinding temperature is 10-100 ℃, and the grinding time is 1-100 h; the grinding medium is at least one of zirconium beads, aluminum beads and glass beads; the volume filling rate of the grinding medium in the grinding cavity is 70-90%; the particle size of the grinding medium is 0.03-0.3 mm; the solvent in the step (1) is at least one of water, acetic acid, absolute ethyl alcohol, isopropanol and ethanol; the mass ratio of the modifier to the solvent is 1: 1.5-27.
10. Use of the modified inorganic nanoparticles of any one of claims 1 to 5 in a coating.
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