TWI503352B - Copolysilsesquioxane microspheres, the preparing method and the application thereof - Google Patents

Description

Copolypyridamole microspheres and preparation method and application thereof

The present invention relates to the field of organic polymer compounds. In particular, the present invention relates to a copolymerized sesquioxane microsphere and a preparation method and application thereof.

The polysesquioxanes are composed of a ruthenium atom and an oxygen atom alternately, and a plurality of organic groups (such as a methyl group, an ethyl group, a phenyl group, etc.) connected to the ruthenium atom are polymers having a stable skeleton. Polysilsesquioxane microspheres have high hardness, high melting point, abrasion resistance, smoothness, water resistance, flame retardancy, non-toxicity, odorlessness, transparency, luster, physiological inertness, etc., and are structurally stable and environmentally friendly. Therefore, they are widely used. As a filler and modifier for plastics, rubber, cosmetics, paints and other products, it has become an important and indispensable new polymer material in the national economy.

The existing polysesquioxanes are mainly homopolysesquioxanes, and the preparation method of homopolysesquioxanes is mainly based on the Stöber method (the Stupper method is described by Stob (Stöber), etc., a method of hydrolyzing ethyl ortho-ruthenate (TEOS) in an alcoholic water medium and ammonia catalyzed to prepare monodisperse cerium oxide microspheres having a particle size ranging from 0.1 to 10 μm. Arkhireeva and other improvements were cited in the preparation of alkoxysilane microspheres to produce methyl, ethyl, propyl, phenyl polysesquioxanes with a particle size of 60 to 180 nm. Oxysilane particles. At present, the preparation of polysilsesquioxane microspheres is dominated by homopolysesquioxane microspheres, and the properties and applications of the microspheres are limited. For example, (1) the refractive index of the microspheres is difficult to adjust, in the diffusion plate. In applications such as light transmission and haze, there is a problem that cannot be taken into consideration; (2) According to the comprehensive performance requirements of cosmetics, the current organic microspheres have limitations and need to be developed and have different properties (such as slipperiness). , soft focus effect, oil absorption value, etc.).

Therefore, there is an urgent need in the art to develop a polysilsesquioxane microsphere which is excellent in performance and widely used.

One of the objects of the present invention is to provide a polysilsesquioxane microsphere which is excellent in performance and widely used, and which is a copolymerized sesquioxane microsphere.

Another object of the present invention is to provide a method for preparing the above-described copolymerized sesquioxane microspheres and an application thereof.

The first aspect of the present invention provides a copolymerized sesquioxane microsphere prepared by the following method, which comprises the steps of: in an inert solvent in the presence of a base catalyst, The two structurally different oxirane monomers are reacted; the two oxoxane monomers are each independently selected from the group consisting of the general formula R ₁ Si(OR ₄ ) ₃ , and the general formula R ₂ R ₃ Si(OR ₄ ) ₂ or a general formula Si(OR ₄ ) ₄ ; wherein R ₁ , R ₂ , and R ₃ are each independently hydrogen, substituted or unsubstituted C _1-6 alkyl, substituted or unsubstituted C _{2 a -6} alkenyl group, a substituted or unsubstituted C _2-6 alkynyl group, a substituted or unsubstituted C _6-12 aryl group, or a substituted or unsubstituted C _5-12 heteroaryl group; , the substituent is amino, the substituted C _1-6 aminoalkyl, C _1-6 alkoxy, substituted alkoxy, oxy C _1-6 acyl or C _1-6 hydrocarbon group; R & lt ₄ is a C _1-6 alkyl group; the mass ratio of the two oxoxane monomers is 1:99 to 99:1; and the additional condition is that when the two oxoxane monomers are each selected from the formula R ₁ Si ( oR _{4) 3,} wherein the at least one monomer of the general formula wherein R ₁ is not hydrogen, methyl or ethylene .

In another preferred embodiment, each of R ₁ , R ₂ and R _{3 is} independently substituted or unsubstituted C _2-6 alkyl, substituted or unsubstituted C _3-6 alkenyl, substituted Or an unsubstituted C _2-6 alkynyl group, a substituted or unsubstituted C _6-12 aryl group, or a substituted or unsubstituted C _5-12 heteroaryl group, wherein the substituent is an amino group, It is substituted with amino group of C _1-6 alkylamino, C _1-6 alkoxy, substituted alkoxy, oxy C _1-6 acyl or C _1-6 hydrocarbon group.

In another preferred embodiment, the mass ratio of the two oxoxane monomers is from 1:9 to 9:1.

In another preferred embodiment, R ₁ , R ₂ , and R ₃ are each independently hydrogen, phenyl, methyl, ethyl, vinyl, γ-aminopropyl, γ-(2,3-epoxy) Propoxy)-propyl, or γ-(methacryloxy)-propyl or N-(β-aminoethyl)-γ-aminopropyl.

In another preferred embodiment, R ₄ is methyl or ethyl.

In another preferred embodiment, the inert solvent is water or a mixed solvent of water and a C _1-6 alcohol.

In another preferred embodiment, the C _1-6 alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol, and combinations thereof.

In another preferred embodiment, the mass ratio of water to C _1-6 alcohol is from 50 to 100:0 to 50; preferably from 80 to 100:0 to 20.

In another preferred embodiment, the base catalyst is an aqueous solution of an alkali metal hydroxide or ammonia.

In another preferred embodiment, the base catalyst is an aqueous solution of sodium hydroxide (NaOH); preferably an aqueous NaOH solution of 0.1 to 10 mTorr/liter; more preferably an aqueous NaOH solution of 0.5 to 2 mol/liter.

In another preferred embodiment, the reaction is carried out at 20 to 90 ° C; and/or the reaction is carried out for 0.5 to 4 hours.

In another preferred embodiment, the reaction is carried out at 50 to 70 ° C; and/or the reaction is carried out for 1 to 2 hours.

In another preferred embodiment, the copolymerized sesquioxane microspheres have an average particle diameter of from 0.01 to 20 microns.

In another preferred embodiment, the copolymerized sesquioxane microspheres have an average particle diameter of 0.01 to 0.1 μm or 0.1 to 10 μm (preferably 1 to 5 μm) or 10 to 20 μm.

The second aspect of the present invention provides a method for preparing a copolymerized sesquioxane microsphere, which comprises the steps of: carrying out two different structural oxirane monomers in an inert solvent in the presence of a base catalyst. Reaction; the two oxoxane monomers are each independently selected from the group consisting of the general formula R ₁ Si(OR ₄ ) ₃ , the general formula R ₂ R ₃ Si(OR ₄ ) ₂ or the general formula Si(OR ₄ ) ₄ ; R ₁ , R ₂ , and R ₃ are each independently hydrogen, substituted or unsubstituted C _1-6 alkyl, substituted or unsubstituted C _2-6 alkenyl, substituted or unsubstituted C _{a 2-6} alkynyl group, a substituted or unsubstituted C _6-12 aryl group, or a substituted or unsubstituted C _5-12 heteroaryl group, wherein the substituent is an amino group, a C _1-6 ammonia group the substituted alkylamino, C _1-6 alkoxy, substituted alkoxy, oxy C _1-6 acyl or C _1-6 hydrocarbon group; R ₄ is C _1-6 alkyl; the two kinds of silicon The mass ratio of the oxyalkylene monomer is 1:99 to 99:1; the additional condition is that when the two oxoxane monomers are each selected from the formula R ₁ Si(OR ₄ ) ₃ , at least one of the monomers In the formula, R _{1 is} not hydrogen, methyl or vinyl.

In another preferred embodiment, the reaction is followed by hydrolysis followed by polymerization.

In another preferred embodiment, the mass ratio of the two oxoxane monomers is from 1:9 to 9:1.

In another preferred embodiment, R ₁ , R ₂ , and R ₃ are each independently hydrogen, phenyl, methyl, ethyl, vinyl, γ-aminopropyl, or γ-(2,3- Epoxypropoxy)-propyl, γ-(methacrylofluorene)-propyl or N-(β-aminoethyl)-γ-aminopropyl; and/or R ₄ is methyl or ethyl.

In another preferred embodiment, the mass ratio of the total amount of the two oxoxane monomers to the base catalyst is from 1:0.0005 to 1:0.005.

In another preferred embodiment, the inert solvent is water or a mixed solvent of water and a C _1-6 alcohol.

In another preferred embodiment, the C _1-6 alcohol is methanol, ethanol, propanol, butanol, or a combination thereof; and/or in the inert solvent, the mass ratio of water to C _1-6 alcohol is 50 to 100: 0 to 50.

In another preferred embodiment, the mass ratio of water to C _1-6 alcohol is from 80 to 100:0 to 20.

In another preferred embodiment, the base catalyst is an aqueous solution of an alkali metal hydroxide or ammonia.

In another preferred embodiment, the base catalyst is an aqueous NaOH solution.

In another preferred embodiment, the base catalyst is an aqueous NaOH solution of 0.1 to 10 moles per liter.

In another preferred embodiment, the base catalyst is a 0.5 to 2 moles per liter aqueous NaOH solution.

In another preferred embodiment, the reaction is carried out at 20 to 90 ° C; and/or the reaction is carried out for 0.5 to 4 hours.

In another preferred embodiment, the reaction is carried out at 50 to 70 ° C; and/or the reaction is carried out for 1 to 2 hours.

A third aspect of the invention provides the use of a copolymerized sesquioxaxane microsphere as described in the first aspect of the invention for use as a filler or modifier for plastics, cosmetics, rubber, or paints.

A fourth aspect of the present invention provides a light diffusing plate comprising 0.3 to 5% by weight of the copolymerized sesquioxane microspheres according to the first aspect of the present invention, based on the total weight of the light diffusing plate.

In another preferred embodiment, the light diffusing plate comprises 0.5 to 2% by weight of the copolymerized sesquioxane microspheres of the first aspect of the invention.

A fifth aspect of the present invention provides a cosmetic comprising 0.5 to 20% by weight of the copolymerized sesquioxane microspheres according to the first aspect of the present invention, based on the total weight of the cosmetic.

In another preferred embodiment, the cosmetic comprises 0.5 to 5% by weight of the copolymerized sesquioxane microspheres of the first aspect of the invention.

A sixth aspect of the present invention provides an encapsulant comprising 0.5 to 10% by weight of the copolymerized sesquioxane microspheres according to the first aspect of the present invention, based on the total weight of the sub-package.

In another preferred embodiment, the encapsulant comprises from 0.5 to 5% by weight of the copolymerized sesquioxane microspheres as described in the first aspect of the invention.

It should be understood that within the scope of the present invention, the above various technical features of the present invention and the technical features specifically described in the following (such as the embodiments) may be combined with each other to constitute a new or preferred technical solution. . Due to space limitations, we will not repeat them here.

Fig. 1 is an electron microscopic microscope photograph of the copolymerized sesquioxane microspheres prepared in Example 1.

Fig. 2 is an electron microscopic microscope photograph of the copolymerized sesquioxane microspheres prepared in Example 2.

Fig. 3 is an electron microscopic micrograph of the copolymerized sesquioxane microspheres prepared in Example 3.

Fig. 4 is an electron microscopic micrograph of the copolymerized sesquioxane microspheres prepared in Example 4.

Fig. 5 is an electron microscopic microscope photograph of the copolymerized sesquioxane microspheres prepared in Example 5.

Fig. 6 is an electron microscopic microscope photograph of the copolymerized sesquioxane microspheres prepared in Example 8.

Fig. 7 is an electron microscopic microscope photograph of the copolymerized sesquioxane microspheres prepared in Example 10.

Fig. 8 is an electron microscopic micrograph of the copolymerized sesquioxane microspheres prepared in Example 14.

Fig. 9 is an electron microscopic micrograph of the copolymerized sesquioxane microspheres prepared in Example 19.

Fig. 10 is a graph showing the haze and transmittance of the light diffusing plate tested in Example 43.

Fig. 11 is a graph showing the haze and transmittance of the light diffusing plate tested in Example 55.

The present inventors have unexpectedly discovered that by using long-term and intensive research, it is possible to prepare copolymerized sesquioxane microspheres by using two kinds of oxoxane monomers of different structures as raw materials, by changing the structure of the siloxane monomer and/or The weight ratio of the two monomers, the obtained product has a variety of excellent properties, and thus has a good application prospect in light diffusing plates, cosmetics and the like. On this basis, the inventors completed the present invention.

the term

As used herein, the term " _C1-6 hydrocarbyl" refers to an alkyl, alkenyl or alkynyl group having from 1 to 6 carbon atoms and the like. For example, C _1-6 alkyl, C _2-6 alkenyl, C _2-6 alkynyl and the like.

The term "C _1-6 alkyl" means a straight or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. Base, tert-butyl, or the like.

The term "C _1-6 alkoxy" means a straight or branched alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy. , isobutoxy, sec-butoxy, tert-butoxy, or the like.

The term "C _2-6 alkenyl" means a straight or branched alkenyl group having 2 to 6 carbon atoms, such as a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group. , 2-butenyl, or the like.

The term "C _2-6 alkynyl" refers to a straight or branched alkynyl group having 2 to 6 carbon atoms, such as ethynyl, propynyl and the like.

The term "C _6-12 aryl" refers to a monocyclic or bicyclic aromatic hydrocarbon group such as phenyl, naphthyl, or the like.

The term "C _5-12 heteroaryl" refers to an aryl group containing one or more heteroatoms (eg, heteroatoms such as N, S, O, etc.), such as pyrimidine, quinoline, indole, thiazole, thiophene, furan, pyrrole. , pyrazole ring and the like.

The term "C _1-6 alcohol" means an alkyl alcohol having 1 to 6 carbon atoms, such as methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, etc. .

The term "C _1-6 aminoalkyl" means an amino-substituted C _1-6 alkyl group, that is, any position of a C _1-6 alkyl group is substituted with an amino group.

The term " _C1-6 hydrocarbyloxy" refers to a _C1-6 hydrocarbyl substituted anthracene ( _C1-6 hydrocarbyl-(C=O)O-).

Oxane monomer

The oxirane single system for preparing the copolymer sesquisiloxane microspheres according to the present invention is a structurally different two oxoxane monomers, each independently selected from the group consisting of: R ₁ Si(OR ₄ ) ₃ , a formula R ₂ R ₃ Si(OR ₄ ) ₂ or a formula Si(OR ₄ ) ₄ ; wherein R ₁ , R ₂ and R ₃ are each independently hydrogen, substituted or unsubstituted C _{1 -6} alkyl, substituted or unsubstituted C _2-6 alkenyl, substituted or unsubstituted C _2-6 alkynyl, substituted or unsubstituted C _6-12 aryl, or substituted or unsubstituted aryl group of C _5-12 heteroaryl, wherein the substituent is amino, the substituted C _1-6 aminoalkyl, C _1-6 alkoxy, C _1-6 substituted as oxygen Alkoxy or C _1-6 hydrocarbyl methoxy; R ₄ is C _1-6 alkyl; and when both oxosiloxane monomers are selected from the formula R ₁ Si(OR ₄ ) ₃ , then In the formula of at least one monomer, R _{1 is} not hydrogen, methyl or vinyl.

In other words, the two oxoxane monomers may be a combination of: (1) one selected from the group consisting of R ₁ Si(OR ₄ ) ₃ and selected from the group consisting of R ₂ R ₃ Si(OR ₄ ) in a compound of any of claims _2; or (2) is selected from the formula R ₁ Si ₍₄ oR) ₃ in the compound and is selected from any one of the general formula Si (oR ₄₎ a compound according to any of the _4; or (3) is selected from Any one of the compounds of the formula R ₂ R ₃ Si(OR ₄ ) ₂ and any one selected from the group consisting of Si(OR ₄ ) ₄ ; or (4) selected from the formula R ₁ Si(OR ₄ ) ₃ is different from any of the two compound structure; or (5) is selected from the formula Si (oR _{4) 4} differs from any one of two or structure of the compound (6) is selected from the general formula R ₂ R ₃ Si (oR ₄ Any two structurally different compounds of ₂ ).

In another preferred embodiment, when the two oxoxane monomers are selected from any two structurally different compounds of the formula R ₁ Si(OR ₄ ) ₃ , R ₁ of one monomer is C _{6 -12} aryl (preferably phenyl).

In another preferred embodiment, R ₁ , R ₂ , and R ₃ are each independently hydrogen, phenyl, methyl, ethyl, vinyl, γ-aminopropyl, or γ-(2,3- Glycidoxypropoxy)-propyl, γ-(methacryloxy)-propyl or N-(β-aminoethyl)-γ-aminopropyl. In another preferred embodiment, R ₄ is methyl or ethyl.

Method for preparing copolymerized sesquioxane microspheres

The invention provides a preparation method of copolymerized sesquioxane microspheres, which comprises the steps of: reacting two different structural oxirane monomers in an inert solvent in the presence of a base catalyst, thereby obtaining copolymerization Sesquiterpene alkane microspheres.

In another preferred embodiment, the mass ratio of the two oxoxane monomers is from 1:99 to 99:1 (preferably from 1:90 to 90:1; more preferably from 1:50 to 50:1; The best is 1:9 to 9:1).

This reaction means that after the hydrolysis reaction of the siloxane monomer, a polymerization reaction is carried out to obtain the above-mentioned copolymer sesquioxane microspheres.

Wherein, the inert solvent is water or a mixed solvent of water and a C _1-6 alcohol. The C _1-6 alcohol is preferably methanol, ethanol, propanol, butanol, or a combination thereof.

In another preferred embodiment, the mass ratio of water to C _1-6 alcohol is from 50 to 100:0 to 50 (preferably from 50 to 100:0-20 or from 80 to 100:0 to 50, more preferably 80 to 100: 0 to 20).

The alkali catalyst is preferably an aqueous solution of an alkali metal hydroxide or ammonia water. Wherein, the alkali metal hydroxide is an alkali metal hydroxide commonly used in the art, and includes, for example, lithium hydroxide (LiOH), potassium hydroxide (KOH), NaOH, etc.; the aqueous solution of the alkali metal hydroxide is preferably 0.1 to 10 mol/liter of aqueous NaOH; more preferably 0.5 to 2 mol/liter of aqueous NaOH. The molar concentration of the aqueous solution of the alkali metal hydroxide is controlled within this range, and the particle diameter of the formed microspheres has good uniformity. The ammonia water is any concentration of ammonia water, and may be a commercially available saturated ammonia water or an ammonia water diluted by a certain amount by an experimenter.

The reaction temperature is preferably from 20 to 90 ° C (preferably from 30 to 80 ° C or from 50 to 70 ° C). The reaction time is preferably from 0.1 to 10 hours (preferably from 0.5 to 4 hours or from 1 to 2 hours). In the preparation method, the higher the reaction temperature, the smaller the particle size; the longer the reaction time, the larger the particle size.

The copolymerized sesquioxaxane microspheres of the present invention have a uniform particle size distribution and an average particle diameter of 0.01 to 20 μm. Preferably, the copolymer sesquioxane microspheres have an average particle diameter of 0.01 to 0.1 μm or 0.1 to 10 μm (preferably 1 to 5 μm) or 10 to 20 μm.

application

The copolymerized sesquioxane microspheres of the present invention comprise a soft organic group, and the molecules themselves not only have an organic/inorganic hybrid structure, but also have complementary effects due to the presence of different organic functional groups. Moreover, by changing the structure of the siloxane monomer and/or the weight ratio of the monomers, the obtained microspheres have various structures, various properties, and can be adjusted. Therefore, it has broad application prospects, for example, it can be used as a filler or modifier for plastics, cosmetics, rubber, or paints.

Preferably, the present invention provides a light diffusing plate comprising 0.3 to 5% by weight (preferably 0.5 to 2% by weight) of the copolymerized sesquioxaxane micro of the present invention, based on the total weight of the light diffusing plate. ball. The light diffusing plate has both good light transmittance and haze.

Preferably, the present invention provides a cosmetic comprising 0.5 to 20% by weight (preferably 0.5 to 5% by weight) of the copolymerized sesquioxaxane microspheres of the present invention, based on the total weight of the cosmetic. The cosmetic may also comprise raw materials commonly used in cosmetics, and the raw materials commonly used in the cosmetics are generally classified into general matrix materials and natural additives. The general matrix materials mainly include: oily raw materials, surfactants, humectants, binders, powders, pigments, dyes, preservatives, antioxidants, perfumes, and other raw materials such as ultraviolet absorbers. The natural additive is a commonly used additive in the field, and mainly includes: hydrolyzed gelatin, hyaluronic acid, superoxide dismutase (SOD), pearl, aloe vera, pollen, Chinese herbal medicine, and the like. The cosmetics include powder cosmetics (such as powder, powder, talcum powder, rouge, etc.); cream cosmetics (such as moisturizer, cold cream, lipstick, etc.); cream cosmetics (such as cream, lipstick, etc.); and liquid cosmetics (such as liquid foundation, lotion, etc.). The cosmetic of the invention has many advantages, such as good spreadability, good resistance to water and oil, good concealing effect, and more natural senses.

Preferably, the present invention provides an encapsulant comprising 0.5 to 10% by weight (preferably 0.5 to 5% by weight) of the copolymerized sesquioxaxane microspheres of the present invention, based on the total weight of the sub-packaging gum. .

The main advantages of the invention include:

1. The present invention provides a copolymerized sesquioxane microsphere having excellent spherical, micron-sized particle size and narrow distribution, diverse structure, diverse properties, and adjustable properties, and the copolymerized sesquiterpene of the present invention. Oxygenane microspheres have a wide range of applications, such as fillers for plastics, cosmetics, rubber, and coatings, as light diffusing powders for use in light diffusing panels or lampshades, as modifiers for use in cosmetics, as an anti-adhesive agent. In the film or encapsulant, etc. Compared with the existing microspheres, the performance of the microspheres of the invention is significantly improved, for example, applied to a light diffusing plate, which can simultaneously consider the light transmittance and haze of the light diffusing plate; and applied to cosmetics, the soft focus effect and the smoothness Saturation, oil absorption, and water resistance are improved.

2. The invention further provides a preparation method of copolymerized sesquioxane microspheres, which has the advantages of simple method, short production cycle and low economic cost, and is suitable for industrial production.

The invention is further illustrated below in conjunction with specific implementations. It is to be understood that the examples are not intended to limit the scope of the invention. the following The experimental methods in the examples which do not specify the specific conditions are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise stated. Unless otherwise stated, the apparatus or reagents used in the present invention are commercially available.

Preparation of copolymerized sesquioxane microspheres Example 1 Phenyltrimethoxydecane and methyltrimethoxydecane copolymerized sesquioxane microspheres

Take 300 grams of water, add 60 grams of methanol, heat to 50 ° C, add 60 grams of phenyltrimethoxydecane and 6 grams of methyltrimethoxydecane (phenyltrimethoxydecane and methyltrimethoxydecane) with stirring The ratio is 10:1), 3 g of 2 mol/liter NaOH solution is added, and after reacting for 2 hours, it is filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain an average particle diameter of A 1 micron copolymerized sesquioxane microsphere having an electron microscopic microscope photograph as shown in Fig. 1.

Example 2 Phenyltrimethoxydecane and methyltrimethoxydecane copolymerized sesquioxane microspheres

Take 300 grams of water, add 75 grams of methanol, heat to 50 ° C, add 60 grams of phenyltrimethoxydecane and 20 grams of methyltrimethoxydecane (phenyltrimethoxydecane and methyltrimethoxydecane) with stirring The ratio was 3:1), 1.5 g of 1 mol/liter NaOH solution was added, and after reacting for 2 hours, it was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain a particle size of 5 Micron copolymerized sesquioxane microspheres, as shown in Fig. 2, are shown in Fig. 2.

Example 3 Phenyltrimethoxydecane and methyltrimethoxydecane copolymerized sesquioxane microspheres

Take 300 grams of water, add 30 grams of ethanol, heat to 50 ° C, add 30 grams of phenyltrimethoxydecane and 30 grams of methyltrimethoxydecane (phenyltrimethoxydecane and methyltrimethoxydecane) with stirring The ratio is 7:3), 1.5 g of 2 mol/liter NaOH solution is added, and after reacting for 2 hours, it is filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain a particle size of 2 The micron-sized copolymerized sesquioxane microspheres, which are shown in Fig. 3, are shown in Fig. 3.

Example 4 Phenyltrimethoxydecane and methyltrimethoxydecane copolymerized sesquioxane microspheres

Take 300 grams of water, heat to 70 ° C, and add 10 grams of phenyltrimethoxydecane and 90 grams of methyltrimethoxydecane (1:9 ratio of phenyltrimethoxydecane to methyltrimethoxydecane) with stirring. Adding 1.1 gram of 0.5 mol/liter NaOH solution, reacting for 1 hour, filtering under reduced pressure, washing with deionized water, and drying in an oven at 100 ° C for 2 hours to obtain a copolymer halved particle having a particle diameter of 1.5 μm. The electron microscopic micrograph of the aerobicane microspheres is shown in Fig. 4.

Example 5 Phenyltrimethoxydecane and γ-aminopropyltrimethoxydecane Copolysesquioxane Microspheres

Take 300 grams of water, add 75 grams of propanol, heat to 60 ° C, add 60 grams of phenyl trimethoxy decane and γ-aminopropyl trimethoxy decane (phenyl trimethoxy decane and γ-aminopropyl) with stirring The mass ratio of trimethoxydecane was 9:1), 4.2 g of 2 mol/liter NaOH solution was added, and after reacting for 2 hours, it was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours. A copolymerized sesquioxane microsphere having a particle diameter of 4 μm was obtained, and an electron microscopic microscope photograph thereof is shown in Fig. 5.

Example 6 Phenyltrimethoxydecane and γ-aminopropyltrimethoxydecane Copolysesquioxane Microspheres

Take 300 grams of water, add 30 grams of methanol, heat to 50 ° C, add 40 grams of phenyl trimethoxy decane and γ-aminopropyl trimethoxy decane (phenyl trimethoxy decane and γ-aminopropyl trimethacrylate) with stirring The mass ratio of oxoxane was 5:1), 3 g of 1 mol/liter NaOH solution was added, and after reacting for 2 hours, it was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain A copolymerized sesquioxane microsphere having a particle diameter of 2 μm.

Example 7 Phenyltrimethoxydecane and γ-aminopropyltrimethoxydecane Copolysesquioxane Microspheres

Take 300 grams of water, heat to 70 ° C, add 20 grams of phenyl trimethoxy decane and γ-aminopropyl trimethoxy decane (phenyl trimethoxy decane to γ-aminopropyl trimethoxy decane mass ratio) 2:1), 2.5 g of 0.5 mol/liter NaOH solution was added, and after reacting for 1 hour, it was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain a particle size of 1 μm. The copolymerized sesquioxane microspheres.

Example 8 Phenyltrimethoxydecane and Ethyltriethoxydecane Co-sesquioxane microspheres

Take 300 grams of water, add 30 grams of ethanol, heat to 50 ° C, add 60 grams of phenyl trimethoxy decane and ethyl triethoxy decane (phenyl trimethoxy decane and ethyl triethoxy decane quality) with stirring The ratio was 1:9), 1.5 g of 2 mol/liter NaOH solution was added, and after reacting for 2 hours, it was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain a particle size of 4.5. Micron-sized copolymerized sesquioxane microspheres, which are shown in Fig. 6 by electron microscopy.

Example 9 Phenyltrimethoxydecane and vinyltrimethoxydecane copolymerized sesquioxane microspheres

Take 300 grams of water, add 50 grams of ethanol, heat to 50 ° C, add 60 grams of phenyl trimethoxy decane and vinyl trimethoxy decane (the ratio of phenyl trimethoxy decane to vinyl trimethoxy decane) 1:1), adding 2.5 g of 2 mol/L NaOH solution, reacting for 2 hours, filtering under reduced pressure, washing with deionized water, and drying in an oven at 100 ° C for 2 hours to obtain a copolymer having a particle diameter of 2 μm. Sesquiterpene alkane microspheres.

Example 10 Phenyltrimethoxydecane and dimethyldimethoxydecane copolymerized sesquioxane microspheres

Take 300 grams of water, add 30 grams of methanol, heat to 50 ° C, and add 50 grams of phenyltrimethoxydecane and dimethyldimethoxydecane (phenyltrimethoxydecane and dimethyldimethoxy) with stirring. The mass ratio of decane was 9:1), 1.8 g of 2 mol/liter NaOH solution was added, and after reacting for 2 hours, it was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain a particle size. The electron microscope micrograph of the 1.8 micron copolymerized sesquioxane microsphere is shown in Fig. 7.

Example 11 Phenyltrimethoxydecane and Diphenyldimethoxydecane Copolysesquioxane Microspheres

Take 300 grams of water, add 30 grams of methanol, heat to 70 ° C, and add 10 grams of phenyltrimethoxydecane and diphenyldimethoxydecane (phenyltrimethoxydecane and diphenyldimethoxy) with stirring. The mass ratio of decane was 1:1), and 1.0 g of a 2 mol/liter NaOH solution was added. After reacting for 1 hour, the mixture was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain a particle size. It is a 1 micron copolymerized sesquioxane microsphere.

Example 12 Phenyltrimethoxydecane and methylphenyldimethoxydecane copolymerized sesquioxane microspheres

Take 300 grams of water, add 30 grams of methanol, heat to 50 ° C, add 40 grams of phenyl trimethoxy decane and methyl phenyl dimethoxy decane (phenyl trimethoxy decane and methyl phenyl dimethyl ether) with stirring The mass ratio of oxoxane was 4:1), 1 gram of 2 mol/liter NaOH solution was added, and after reacting for 2 hours, it was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain The copolymerized sesquioxane microspheres having a particle diameter of 1 μm.

Example 13 Phenyltrimethoxydecane and methylvinyldimethoxydecane Copolysesquioxane Microspheres

Take 300 grams of water, heat to 70 ° C, add 20 grams of phenyl trimethoxy decane and methyl vinyl dimethoxy decane (phenyl trimethoxy decane and methyl vinyl dimethoxy decane) by mass 1:5), 1 gram of 0.5 mol/liter NaOH solution was added, and after reacting for 1 hour, it was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain a particle size of 1.5 μm. The copolymerized sesquioxane microspheres.

Example 14 Phenyltrimethoxydecane and Tetraethyloxane Copolysesquioxane Microspheres

Take 300 grams of water, add 20 grams of ethanol, heat to 50 ° C, add 60 grams of phenyl trimethoxydecane and tetraethyl decane with the mass ratio of phenyl trimethoxy decane to tetraethyl decane 6:1), adding 2.1 g of 2 mol/liter NaOH solution, reacting for 2 hours, filtering under reduced pressure, washing with deionized water, and drying in an oven at 100 ° C for 2 hours to obtain a particle size of 2.2 μm. The electron microscopic micrograph of the copolymerized sesquioxane microspheres is shown in Fig. 8.

Example 15 Methyltrimethoxydecane and Tetraethyloxane Copolysesquioxane Microspheres

Take 300 grams of water, heat to 70 ° C, and add 30 grams of methyltrimethoxydecane and tetraethyloxirane (methylene trimethoxydecane to tetraethyl decane mass ratio of 1:1) with stirring. Add 1.3 g of 2 mol/L NaOH solution, react for 1 hour, filter under reduced pressure, wash with deionized water, and dry in an oven at 100 ° C for 2 hours. Dry, a copolymerized sesquioxane microsphere having a particle diameter of 2 μm was obtained.

Example 16 γ-aminopropyltrimethoxydecane and tetraethylphosphorane copolymerized sesquioxane microspheres

Take 300 grams of water, add 20 grams of propanol, heat to 50 ° C, add 40 grams of γ-aminopropyltrimethoxydecane and tetraethyloxirane (γ-aminopropyltrimethoxydecane and tetraethyl) with stirring The mass ratio of sulfoxane was 3:7), 1.1 gram of 2 mol/liter NaOH solution was added, and after reacting for 2 hours, it was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours. A copolymerized sesquioxane microsphere having a particle diameter of 5 μm was obtained.

Example 17 Vinyl trimethoxy decane and tetraethyl decane copolymerized sesquioxane microspheres

Take 300 grams of water, add 20 grams of methanol, heat to 50 ° C, add 40 grams of vinyl trimethoxy decane and tetraethyl decane with stirring (the mass ratio of vinyl trimethoxy decane to tetraethyl decane is 1:9), 1.5 g of 2 mol/liter NaOH solution was added, and after reacting for 2 hours, it was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain a particle size of 4 μm. Copolysesquioxane microspheres.

Example 18 Ethylene triethoxy decane and tetraethyl decane copolymerized sesquioxane microspheres

Take 300 grams of water, heat to 70 ° C, add 20 grams of ethyl triethoxy decane and tetraethyl decane with stirring (the ratio of ethyl triethoxy decane to tetraethyl decane is 9:1) Adding 2.5 g of a 0.5 mol/liter NaOH solution, reacting for 1 hour, filtering under reduced pressure, washing with deionized water, and drying in an oven at 100 ° C for 2 hours to obtain a copolymer sesquifer having a particle diameter of 1.8 μm. Alkane microspheres.

Example 19 Dimethyl methoxy decane and tetraethyl decane copolymerized sesquioxane microspheres

Take 300 grams of water, heat to 70 ° C, add 50 grams of dimethyl dimethoxydecane and tetraethyl decane with stirring (mass ratio of dimethyl dimethoxy decane to tetraethyl decane is 9 :1), adding 2.5 g of 1 mol/L NaOH solution, reacting for 1 hour, filtering under reduced pressure, washing with deionized water, and drying in an oven at 100 ° C for 2 hours After drying, a copolymerized sesquioxane microsphere having a particle diameter of 2 μm was obtained, and an electron microscopic microscope photograph thereof is shown in Fig. 9.

Example 20 Diphenyldimethoxydecane and Tetraethyloxane Copolysesquioxane Microspheres

Take 300 grams of water, add 10 grams of methanol, heat to 50 ° C, add 30 grams of diphenyl dimethoxydecane and tetraethyl decane (diphenyl dimethoxy decane and tetraethyl oxime) with stirring The mass ratio of the alkane was 2:5), and 0.6 g of a 2 mol/liter NaOH solution was added. After reacting for 1 hour, the mixture was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain a particle size. It is a 2 micron copolymerized sesquioxane microsphere.

Example 21 methyl phenyl dimethoxy decane and tetraethyl decane copolymerized sesquioxane microspheres

Take 300 grams of water, heat to 70 ° C, add 30 grams of methyl phenyl dimethoxy decane and tetraethyl decane (mixture of methyl phenyl dimethoxy decane and tetraethyl decane) 2:3), 1.5 kg of 0.5 mol/liter NaOH solution was added, and after reacting for 1 hour, it was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain a particle size of 5 μm. The copolymerized sesquioxane microspheres.

Example 22 Vinyl dimethoxydecane and tetraethyloxirane copolymerized sesquioxane microspheres

Take 300 grams of water, add 10 grams of methanol, heat to 50 ° C, add 50 grams of vinyl dimethoxy decane and tetraethyl decane (the quality of vinyl dimethoxy decane and tetraethyl decane) with stirring The ratio was 1:9), 1.8 g of 2 mol/liter NaOH solution was added, and after reacting for 2 hours, it was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain a particle size of 4 Micron copolymerized sesquioxane microspheres.

Example 23 Phenyltrimethoxydecane and methyltrimethoxydecane copolymerized sesquioxane microspheres

Take 300 grams of water, heat to 60 ° C, and add 0.3 grams of phenyltrimethoxydecane to 29.7 grams of methyltrimethoxydecane (1:99 mass ratio of phenyltrimethoxydecane to methyltrimethoxydecane) with stirring. ), adding 0.5 mol / liter of NaOH solution After 1.5 hours of the reaction, the mixture was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain copolymerized sesquioxane microspheres having an average particle diameter of 2 μm.

Example 24 Phenyltrimethoxydecane and methyltrimethoxydecane copolymerized sesquioxane microspheres

Take 300 g of water, heat to 70 ° C, and add 29.7 g of phenyltrimethoxydecane and 0.3 g of methyltrimethoxydecane (the mass ratio of phenyltrimethoxydecane to methyltrimethoxydecane is 99:1) with stirring. Add 1 gram of 1 mol/L NaOH solution, react for 2 hours, filter under reduced pressure, wash with deionized water, and dry in an oven at 100 ° C for 1 hour to obtain a copolymerization average particle size of 3 μm. Semi-aluminoxane microspheres.

Example 25 Phenyltrimethoxydecane and γ-(2,3-epoxypropoxy)propyltrimethoxydecane Copolysesquioxane Microspheres

Take 300 grams of water, heat to 70 ° C, and add 3 grams of phenyltrimethoxydecane and 27 grams of γ-(2,3-epoxypropoxy)propyltrimethoxydecane (phenyltrimethoxydecane) with stirring. Γ-(2,3-epoxypropoxy)propyltrimethoxydecane in a mass ratio of 1:9), adding 4 g of 0.5 mol/liter NaOH solution, reacting for 2 hours, filtering under reduced pressure, using deionized After washing with water, it was dried in an oven at 100 ° C for 2 hours to obtain copolymerized sesquioxane microspheres having an average particle diameter of 5 μm.

Example 26 Phenyltrimethoxydecane and γ-(methylpropylphosphonium)propyltrimethoxydecane Copolysesquioxane Microspheres

Take 300 g of water, heat to 70 ° C, and add 27 g of phenyltrimethoxydecane and 3 g of γ-(methylpropylphosphonium)propyltrimethoxydecane (phenyltrimethoxydecane and γ- with stirring). (Methyl propyl oxime) propyl trimethoxy decane mass ratio of 9:1), adding 3 gram of 0.5 mol / liter NaOH solution, after 2 hours of reaction, filtered under reduced pressure, washed with deionized water, It was dried in an oven at 100 ° C for 2 hours to obtain copolymerized sesquioxane microspheres having an average particle diameter of 2 μm.

Example 27 Phenyltrimethoxydecane and N-(β-aminoethyl)-γ-aminopropyltrimethoxydecane Copolysesquioxane Microspheres

Take 300 grams of water, heat to 50 ° C, add 30 grams of phenyl trimethoxy with stirring Quality of decane and N-(β-aminoethyl)-γ-aminopropyltrimethoxydecane (phenyltrimethoxydecane and N-(β-aminoethyl)-γ-aminopropyltrimethoxydecane The ratio is 9:1), 1 kg of 0.5 mol/liter NaOH solution is added, and after reacting for 2 hours, it is filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain an average particle diameter of 1 micron copolymerized sesquioxane microspheres.

Example 28 Dimethyldimethoxydecane and Diphenyldimethoxydecane Copolysesquioxane Microspheres

Take 300 grams of water, heat to 70 ° C, add 60 grams of dimethyl dimethoxydecane and diphenyl dimethoxydecane (dimethyl dimethoxy decane and diphenyl dimethoxy decane) with stirring. The mass ratio was 1:1), adding 2.6 g of 1 mol/liter NaOH solution, after reacting for 4 hours, filtering under reduced pressure, washing with deionized water, and drying in an oven at 100 ° C for 2 hours to obtain a particle size of 2 micron copolymerized sesquioxane microspheres.

Example 29 Dimethyldimethoxydecane and methylvinyldimethoxydecane Copolysesquioxane Microspheres

Take 300 grams of water, heat to 70 ° C, add 40 grams of dimethyl dimethoxydecane and methyl vinyl dimethoxy decane (dimethyl dimethoxy decane and methyl vinyl dimethoxy) with stirring The mass ratio of decane was 1:9), 1.5 gram of 2 mol/liter NaOH solution was added, and after reacting for 4 hours, it was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain granules. The copolymerized sesquioxane microspheres having a diameter of 1 μm.

Example 30 Phenyltrimethoxydecane and ethynyltrimethoxydecane Copolysesquioxane Microspheres

Take 300 grams of water, heat to 50 ° C, and add 15 grams of phenyltrimethoxydecane and 15 grams of ethynyltrimethoxydecane (the ratio of phenyltrimethoxydecane to ethynyltrimethoxydecane) is 1:1. 2 g of 0.5 mol/liter NaOH solution was added, and after reacting for 1 hour, it was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain a copolymerization ratio of an average particle diameter of 2 μm. Semi-aluminoxane microspheres.

Example 31 Phenyltrimethoxydecane and trimethoxyhydrodecane copolymerized sesquioxane microspheres

Take 300 grams of water, heat to 50 ° C, and add 15 grams of phenyltrimethoxydecane and 15 grams of trimethoxyhydroquinane (1:1 mass ratio of phenyltrimethoxynonane to trimethoxyhydrodecane) with stirring. 1.5 g of 0.5 mol/liter NaOH solution was added, and after reacting for 1 hour, it was filtered under reduced pressure, washed with deionized water, and dried in an oven at 100 ° C for 2 hours to obtain a copolymerized sesquiterpene having an average particle diameter of 2 μm. Oxysilane microspheres.

In summary, the copolymerized sesquioxaxane microspheres of the present invention have a good shape and a narrow and uniform particle size distribution.

Comparative Example 1 Methyltriethoxydecane and triethoxyhydrodecane copolymerized sesquioxane microspheres

Take 300 grams of water, heat to 50 ° C, add 40 grams of methyl triethoxy decane and triethoxyhydrofuran (the ratio of methyl triethoxy decane to triethoxyhydrodecane) is 1:1. Adding 1.9 g of a 0.5 mol/liter NaOH solution, reacting for 2 hours, filtering under reduced pressure, washing with deionized water, and drying in an oven at 100 ° C for 2 hours to obtain a copolymerization ratio of an average particle diameter of 2 μm. Semi-aluminoxane microspheres.

Comparative Example 2 Methyltriethoxydecane and vinyltriethoxydecane copolymerized sesquioxane microspheres

Take 300 grams of water, heat to 60 ° C, add 50 grams of methyl triethoxy decane and vinyl triethoxy decane (methylene triethoxy decane and vinyl triethoxy decane) mass ratio of 1 :1), adding 2.5 g of 0.5 mol/liter NaOH solution, reacting for 2 hours, filtering under reduced pressure, washing with deionized water, and drying in an oven at 100 ° C for 2 hours to obtain an average particle diameter of 2 μm. Copolysesquioxane microspheres.

Comparative Example 3 Methyltriethoxydecane and vinyltriethoxydecane copolymerized sesquioxane microspheres

Take 300 grams of water, heat to 60 ° C, add 40 grams of methyl triethoxy decane and vinyl triethoxy decane (methylene triethoxy decane and vinyl triethoxy decane mass ratio 2) :1), adding 2.1 gram of 0.5 mol/liter NaOH solution, reacting for 2 hours, filtering under reduced pressure, washing with deionized water, and drying in an oven at 100 ° C for 2 hours to obtain an average particle diameter of 2 μm. Copolysesquioxane microspheres.

Copolyhexamoxysilane microspheres applied to light diffusing plates Example 32 Addition of the copolymerized sesquioxane microparticle prepared in Example 1 Ball light diffuser

The PC was dried at 200 ° C for 12 hours, and then the copolymerized sesquioxane microspheres prepared in Example 1 were respectively 0.2% by weight, 0.5% by weight, 1.0% by weight, 1.5% by weight, and 2% by weight based on the total weight of the materials used. % is added to the PC for premixing, and the mixed raw materials are extruded and granulated at 280 ° C by a twin-screw extruder, and then dried and then injection molded at 280 ° C to prepare a light diffusing plate, which are sequentially recorded separately. It is a light diffusing plate 1A, 1B, 1C, 1D, 1E.

Example 33 Adding a light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 2

The preparation method was the same as that in Example 32, except that the copolymerized sesquioxaxane microspheres prepared in Example 2 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 2A, 2B, 2C, 2D, 2E.

Example 34 Adding a light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 3

The preparation method was the same as that of Example 32, except that the copolymerized sesquioxaxane microspheres prepared in Example 3 were used in place of the copolymerized sesquioxaxane microspheres prepared in Example 1, respectively, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 3A, 3B, 3C, 3D, 3E.

Example 35 Adding a light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 4

The preparation method was the same as that of Example 32, except that the copolymerized sesquioxaxane microspheres prepared in Example 4 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 4A, 4B, 4C, 4D, 4E.

Example 36 The light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 6 was added.

The preparation method was the same as that of Example 32, except that the copolymerized sesquioxaxane microspheres prepared in Example 6 were used instead of the copolymerized sesquioxane microspheres prepared in Example 1, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 5A, 5B, 5C, 5D, 5E.

Example 37 The light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 25 was added.

The preparation method was the same as that of Example 32 except that the preparation of Example 25 was respectively carried out. The copolymerized sesquioxane microspheres were used in place of the copolymerized sesquioxane microspheres prepared in Example 1, to obtain light-diffusing sheets, which are respectively referred to as light-diffusing sheets 6A, 6B, 6C, 6D, and 6E.

Example 38 The light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 31 was added.

The preparation method was the same as that of Example 32, except that the copolymerized sesquioxaxane microspheres prepared in Example 31 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 7A, 7B, 7C, 7D, 7E.

Example 39 Adding a light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 10

The preparation method was the same as that of Example 32, except that the copolymerized sesquioxaxane microspheres prepared in Example 10 were used in place of the copolymerized sesquioxaxane microspheres prepared in Example 1, respectively, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 8A, 8B, 8C, 8D, 8E.

Example 40 The light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 14 was added.

The preparation method was the same as that of Example 32, except that the copolymerized sesquioxaxane microspheres prepared in Example 14 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, which were respectively recorded as Light diffusing plates 9A, 9B, 9C, 9D, 9E.

Example 41 The light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 20 was added.

The preparation method was the same as that of Example 32, except that the copolymerized sesquioxaxane microspheres prepared in Example 20 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 10A, 10B, 10C, 10D, 10E.

Example 42 The light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 28 was added.

The preparation method was the same as that of Example 32, except that the copolymerized sesquioxaxane microspheres prepared in Example 28 were used in place of the copolymerized sesquioxaxane microspheres prepared in Example 1, respectively, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 11A, 11B, 11C, 11D, 11E.

Comparative Example 4 was added to the light diffusing plate of the copolymerized sesquioxane microspheres prepared in Comparative Example 1.

The preparation method was the same as that in Example 32, except that the copolymerized sesquioxaxane microspheres prepared in Comparative Example 1 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, respectively. They are light diffusing plates 12A, 12B, 12C, 12D, and 12E.

Comparative Example 5 A light diffusing plate of the copolymerized sesquioxane microspheres prepared in Comparative Example 2 was added.

The preparation method was the same as that of Example 32, except that the copolymerized sesquioxaxane microspheres prepared in Comparative Example 2 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, respectively. They are light diffusing plates 13A, 13B, 13C, 13D, and 13E.

Comparative Example 6 A light diffusing plate of the copolymerized sesquioxane microspheres prepared in Comparative Example 3 was added.

The preparation method was the same as that of Example 32, except that the copolymerized sesquioxaxane microspheres prepared in Comparative Example 3 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, respectively. They are light diffusing plates 14A, 14B, 14C, 14D, and 14E.

Comparative Example 7 Comparative light diffusing plate to which homopolysesquioxane microspheres were added

The preparation method was the same as that of Example 32, except that the homopolymerized polyphenylsesquioxane microspheres were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a comparative light diffusing plate, respectively. The light diffusing plates 15A, 15B, 15C, 15D, and 15E are compared.

Example 43 Light diffusion plate performance test

The haze and light transmittance were measured using an NDH 2000N haze meter (purchased from Nippon Denshoku Industries Co., Ltd.) and the test method was ISO 14782. 32-42, and haze and light transmittance of the diffuser plate than the ratio in Example 4 to 7 was prepared separately by test examples, the results of FIG. 10 and shown in Table 1.

As can be seen from Tables 1 and 10, the PC light diffusing plate to which the copolymerized sesquioxane microspheres of the present invention are added and the PC light diffusing plate of the comparative example both exhibit an increase in the amount of addition of the microspheres, and haze. There has been an increase but the change has been small and the light transmittance has decreased. However, when the amount of the microspheres is the same, the light diffusing plate of the present invention has a higher light transmittance than the comparative example, and the light transmittance can be effectively increased by reducing the amount of addition of the microspheres, and Still maintain a high haze. Therefore, a light diffusing plate excellent in haze and light transmittance can be obtained by controlling the amount of addition of the microspheres of the present invention. It can be seen that the copolymerized sesquioxane microspheres of the present invention are currently advanced products of microspheres.

The copolymerized sesquioxaxane microspheres prepared in Examples 5, 7 to 9, 11 to 13, 15 to 19, 21 to 24, 26 to 27, and 29 to 30, respectively, were used in place of the copolymerized sesquioxane oxygen prepared in Example 1. Alkane microspheres, a light diffusing plate was prepared (preparation method is the same as in Example 32). The light diffusing plate performance test was carried out on the prepared light diffusing plate (method as in Example 43), and the results showed that these light diffusing plates also had excellent haze and light transmittance.

Example 44 The light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 1 was added.

The PMMA was dried at 200 ° C for 12 hours, and then the copolymerized sesquioxane microspheres prepared in Example 1 were 0.2% by weight, 0.5% by weight, 1.0% by weight, 1.5% by weight, and 2.0% by weight based on the total weight of the materials used. It is added to PMMA for premixing, and the mixed raw materials are extruded and granulated by a twin-screw extruder at 260 ° C, and then dried and then injection molded at 260 ° C to prepare a light diffusing plate, which is respectively recorded as light diffusion. Plates 16A, 16B, 16C, 16D, 16E.

Example 45 Adding a light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 2

The preparation method was the same as that of Example 44, except that the copolymerized sesquioxaxane microspheres prepared in Example 2 were used in place of the copolymerized sesquioxaxane microspheres prepared in Example 1, respectively, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 17A, 17B, 17C, 17D, 17E.

Example 46 The light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 3 was added.

The preparation method was the same as that of Example 44, except that the copolymerized sesquioxaxane microspheres prepared in Example 3 were used in place of the copolymerized sesquioxaxane microspheres prepared in Example 1, respectively, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 18A, 18B, 18C, 18D, 18E.

Example 47 Adding a light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 4

The preparation method was the same as that of Example 44, except that the copolymerized sesquioxaxane microspheres prepared in Example 4 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain light diffusion plates, which were respectively recorded as Light diffusing plates 19A, 19B, 19C, 19D, 19E.

Example 48 The light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 6 was added.

The preparation method was the same as that of Example 44, except that the copolymerized sesquioxaxane microspheres prepared in Example 6 were used in place of the copolymerized sesquioxaxane microspheres prepared in Example 1, respectively, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 20A, 20B, 20C, 20D, 20E.

Example 49 A light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 25 was added.

The preparation method was the same as that of Example 44, except that the copolymerized sesquioxaxane microspheres prepared in Example 25 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 21A, 21B, 21C, 21D, 21E.

Example 50 The light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 31 was added.

The preparation method was the same as that of Example 44, except that the copolymerized sesquioxaxane microspheres prepared in Example 31 were used in place of the copolymerized sesquioxaxane microspheres prepared in Example 1, respectively, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 22A, 22B, 22C, 22D, 22E.

Example 51 The light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 10 was added.

The preparation method was the same as that of Example 44, except that the copolymerized sesquioxaxane microspheres prepared in Example 10 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 23A, 23B, 23C, 23D, 23E.

Example 52 The light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 14 was added.

The preparation method was the same as that of Example 44, except that the copolymerized sesquioxaxane microspheres prepared in Example 14 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 24A, 24B, 24C, 24D, 24E.

Example 53 The light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 20 was added.

The preparation method was the same as that of Example 44, except that the copolymerized sesquioxaxane microspheres prepared in Example 20 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 25A, 25B, 25C, 25D, 25E.

Example 54 The light diffusing plate of the copolymerized sesquioxane microspheres prepared in Example 28 was added.

The preparation method was the same as that of Example 44, except that the copolymerized sesquioxaxane microspheres prepared in Example 28 were used in place of the copolymerized sesquioxaxane microspheres prepared in Example 1, respectively, to obtain light diffusing plates, which were respectively recorded as Light diffusing plates 26A, 26B, 26C, 26D, 26E.

Comparative Example 8 A light diffusing plate of the copolymerized sesquioxane microspheres prepared in Comparative Example 1 was added.

The preparation method was the same as that in Example 44, except that the copolymerized sesquioxaxane microspheres prepared in Comparative Example 1 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, respectively. They are light diffusing plates 27A, 27B, 27C, 27D, and 27E.

Comparative Example 9 A light diffusing plate of the copolymerized sesquioxane microspheres prepared in Comparative Example 2 was added.

The preparation method was the same as that of Example 44, except that the copolymerized sesquioxaxane microspheres prepared in Comparative Example 2 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, respectively. They are light diffusing plates 28A, 28B, 28C, 28D, 28E.

Comparative Example 10 A light diffusing plate of the copolymerized sesquioxane microspheres prepared in Comparative Example 3 was added.

The preparation method was the same as that of Example 44, except that the copolymerized sesquioxaxane microspheres prepared in Comparative Example 3 were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, respectively. They are light diffusing plates 29A, 29B, 29C, 29D, 29E.

Comparative Example 11 Comparative light diffusing plate to which homopolysesquioxane microspheres were added

The preparation method was the same as that in Example 44, except that the homopolymerized polyphenylsesquioxane microspheres were used instead of the copolymerized sesquioxaxane microspheres prepared in Example 1, to obtain a light diffusing plate, which was respectively recorded as Light diffusing plates 30A, 30B, 30C, 30D, 30E.

Example 55 Light diffusion plate performance test

The haze and light transmittance of the light-diffusing sheets obtained in Examples 44 to 53 and Comparative Examples 8 to 11 were tested in accordance with the method described in Example 43. The test results are shown in Figure 11 and Table 2.

It can be seen from Table 2 and Figure 11 that the PMMA light diffusing plate to which the copolymerized sesquioxaxane microspheres of the present invention are added and the PMMA light diffusing plate of the comparative example both exhibit an increase in the amount of addition of the microspheres, and the haze has The increase but the change is small, and the light transmittance decreases. However, when the amount of the microspheres is the same, the light diffusing plate of the present invention has a higher light transmittance than the comparative example, and the light transmittance can be effectively increased by reducing the amount of the microspheres added, and still Maintain a good haze. Therefore, a light diffusing plate excellent in haze and light transmittance can be obtained by controlling the amount of addition of the microspheres of the present invention. It can be seen that the copolymerized sesquioxane microspheres of the present invention are currently advanced products of microspheres.

The copolymerized sesquioxaxane microspheres prepared in Examples 5, 7 to 9, 11 to 13, 15 to 19, 21 to 24, 26 to 27, and 29 to 30, respectively, were used in place of the copolymerized sesquioxane oxygen prepared in Example 1. Alkane microspheres, a light diffusing plate was prepared (preparation method is the same as in Example 44). The light diffusion plate performance test was carried out on the prepared light diffusion plate (the method is the same as in Example 55), and the results show that these light diffusion plates also have excellent haze and light transmittance.

In summary, the light diffusing plate of the copolymerized sesquioxane microspheres of the present invention can effectively adjust the light transmittance of the diffusing plate by controlling the amount of microspheres added while maintaining high haze. Light diffusing plate with excellent light transmittance and haze.

Copolysesquioxane microspheres for cosmetics Example 56 The liquid foundation of the copolymerized sesquioxane microspheres prepared in Example 2 was added.

Take 38.48 grams of water, add 5 grams of propylene glycol, 3 grams of glycerin, 0.7 grams of sodium chloride and mix well to make an aqueous phase. Take 15 grams of eucalyptus oil, add 8 grams of cyclodecane/dimethyl methoxyalkanol copolymer, 10 grams of squalane, 2.0 grams of cetyl polyethylene glycol, 1.5 grams of polyglycerol-4 isostearate 9 g of titanium dioxide, 0.9 of yellow iron oxide, 0.27 g of red iron oxide, and 0.15 g of black iron oxide, and 5 g of the copolymerized sesquioxane microspheres of Example 2 were mixed to form an oil phase. The aqueous phase was slowly added to the oil phase and emulsified for 5 minutes at a stirring speed of 1000 rpm, and 1.0 g of bentonite was added thereto to be uniformly stirred to prepare a liquid foundation.

Example 57 The liquid foundation of the copolymerized sesquioxane microspheres prepared in Example 3 was added.

The preparation method was the same as that of Example 56, except that the copolymer prepared by Example 3 was used. The sesquioxane microspheres were substituted for the copolymerized sesquioxane microspheres prepared in Example 2.

Comparative Example 12 The liquid foundation of the copolymerized sesquioxane microspheres prepared in Comparative Example 1 was added.

The preparation method was the same as that of Example 56 except that the copolymerized sesquioxane microspheres prepared in Comparative Example 1 were used instead of the copolymerized sesquioxane microspheres prepared in Example 2.

Comparative Example 13 The liquid foundation of the copolymerized sesquioxane microspheres prepared in Comparative Example 2 was added.

The preparation method was the same as that of Example 56 except that the copolymerized sesquioxane microspheres prepared in Comparative Example 2 were used instead of the copolymerized sesquioxane microspheres prepared in Example 2.

Comparative Example 14 Adding a comparative liquid foundation of homopolysesquioxane microspheres

The preparation method was the same as that of Example 56 except that the homopolymerized polymethylsesquioxane microspheres were used instead of the copolymerized sesquioxane microspheres prepared in Example 2.

Example 58 Liquid Foundation Performance Test

The soft focus effect, slip property, oil absorption effect and water resistance of the liquid foundations obtained in Examples 56 to 57 and Comparative Examples 12 to 14 were tested by the following methods, and the results are shown in Table 3.

Soft focus effect: The finished product was uniformly coated on the glass surface with a coating bar. The test was carried out using an NDH 2000N haze meter (purchased from Nippon Denshoku Industries Co., Ltd.), and the test method was tested for haze and light transmittance using ASTM D2457. The higher the haze, the better the soft focus effect.

Gloss: The finished product was uniformly applied to a smooth iron sheet and dried for a certain period of time. The gloss was measured using a gloss meter ZGM1020.

Sensory effect: Apply the prepared finished product to the skin, feel the ease of pushing it away, and feel the skin after drying.

Water resistance: The finished product is applied to the glass piece, dried for a certain period of time, and a quantitative amount of water is taken on it (droplet shape) to observe changes in the finished product and the ball over time: the more complete the sphere, the better the water resistance.

Oil resistance: The finished product is applied to the glass sheet and dried for a certain period of time. A quantitative amount of linseed oil is dripped on it (droplet shape) to observe changes in the finished product and the ball over time: the more complete the sphere, the better the oil resistance.

Viscosity: The viscosity of the finished product was measured using a viscometer (BROOKFEILD DV-1+ viscometer), 63# rotor, and 30 rpm.

The results show that the liquid foundation of the copolymerized sesquioxane microspheres of the invention has the advantages of good viscosity, better soft focus effect, smear resistance, water resistance, oil resistance and concealing effect, lower gloss and more natural sense. .

Preparing a liquid foundation by using the copolymerized sesquioxaxane microspheres prepared in Examples 1, 4 to 31 instead of the copolymerized sesquioxaxane microspheres prepared in Example 2, respectively. The preparation method is the same as in the example 56). The performance test of the prepared liquid foundation (the same method as in Example 58) shows that the liquid foundations also have the following advantages: suitable viscosity, soft focus effect, spreadability, water resistance, oil resistance and concealing effect are better. The gloss is lower and the senses are more natural.

Example 59 The emulsion of the copolymerized sesquioxane microspheres prepared in Example 2 was added.

Take 74.4 grams of deionized water, 4 grams of propylene glycol, 4 grams of glycerin, 0.1 grams of xanthan gum into a 200 ml beaker, mix well at 80 ° C to make an aqueous phase.

Take 1.5 grams of polyoxyethylene-21 stearyl ether, 1.5 grams of stearyl ether-2, 3.5 grams of eucalyptus oil, 2 grams of squalane, 0.5 grams of palmitic acid oligopeptide, 1.5 grams of isooctyl palmitate, 2 grams Tris(ethylhexanoic acid) glyceride, 5 g of the copolymerized sesquioxaxane microspheres prepared in Example 2 were placed in a 50 ml beaker, heated to 80 ° C and uniformly mixed to prepare an oil phase.

The prepared aqueous phase was added to the oil phase under stirring to be emulsified, and emulsified for 5 minutes to prepare an emulsion RY-8.

Example 60 The emulsion of the copolymerized sesquioxane microspheres prepared in Example 3 was added.

The method was the same as that of Example 59 except that the copolymerized sesquioxane microspheres prepared in Example 3 were used instead of the copolymerized sesquioxane microspheres prepared in Example 2.

Comparative Example 15 An emulsion of the copolymerized sesquioxane microspheres prepared in Comparative Example 1 was added.

The procedure was the same as in Example 59 except that the copolymerized sesquioxane microspheres prepared in Comparative Example 1 were used instead of the copolymerized sesquioxane microspheres prepared in Example 2.

Comparative Example 16 The emulsion of the copolymerized sesquioxane microspheres prepared in Comparative Example 2 was added.

The procedure was the same as in Example 59 except that the copolymerized sesquioxane microspheres prepared in Comparative Example 2 were used instead of the copolymerized sesquioxane microspheres prepared in Example 2.

Comparative Example 17 Comparative emulsion in which homopolysesquioxane microspheres were added

The method is the same as that in Example 59, except that the homopolymerized polymethyl sesquiterpene oxygen is used. The alkane microspheres were substituted for the copolymerized sesquioxane microspheres prepared in Example 2.

Example 61 Emulsion Performance Test

The properties of the emulsions prepared in Examples 59 to 60 and the emulsions prepared in Comparative Examples 15 to 17 were respectively examined in accordance with the performance test method of Example 58, and the results are shown in Table 4.

The results showed that the emulsion of the copolymerized sesquioxaxane microspheres of the present invention was suitable in pH value and viscosity, and the copolymerized sesquioxaxane microspheres prepared by the invention were added as compared with the emulsion prepared in the comparative example. The emulsion has higher haze and better soft focus effect. The skin is white and natural after application.

The copolymer was prepared by substituting the copolymerized sesquioxaxane microspheres prepared in Examples 1, 4 to 31 for the copolymerized sesquioxaxane microspheres prepared in Example 2 (the preparation method is the same as in Example 59). The performance of the prepared emulsion was tested (the same method as in Example 58). The results showed that the emulsions also had the following advantages: pH value and viscosity were suitable, haze was higher, soft focus effect was better, and the skin was white and tender after application. natural.

In summary, the cosmetic using the copolymerized sesquioxane microspheres of the present invention has better spreadability, is excellent in water and oil resistance, has a good concealing effect, and is more natural in sense. As the amount of microspheres increases, the spreadability of cosmetics increases, and the resistance to water and oil increases. It is especially used for powders, creams, creams, and liquid products. As the amount of addition increases, the soft focus effect increases, and the makeup becomes more natural.

All documents mentioned in the present application are hereby incorporated by reference in their entirety in their entireties in the the the the the the the the the the In addition, it is to be understood that those skilled in the art can make various modifications and/or modifications of the present invention, which are also within the scope of the appended claims.

Claims (11)

A copolymerized sesquioxane microsphere, wherein the copolymer sesquioxane microspheres have an average particle diameter of 0.01 to 20 μm, wherein the copolymer sesquioxane microspheres are prepared by a method comprising the following steps: In the solvent, in the presence of a base catalyst, reacting two different structural oxirane monomers; the two oxoxane monomers are each independently selected from the general formula R ₁ Si(OR ₄ ) ₃ R ₂ R ₃ Si(OR ₄ ) ₂ or the general formula Si(OR ₄ ) ₄ ; wherein R ₁ , R ₂ and R ₃ are each independently hydrogen, substituted or unsubstituted C _1-6 alkyl , substituted or unsubstituted C _2-6 alkenyl, substituted or unsubstituted C _2-6 alkynyl, substituted or unsubstituted C _6-12 aryl, substituted or unsubstituted C _5-12 heteroaryl; wherein the substituent is amino, the substituted C _1-6 aminoalkyl, C _1-6 alkoxy, the oxygen is substituted with C _1-6 alkoxy or a C _{1 -6} hydrocarbyl methoxy group; R ₄ is C _1-6 alkyl group; the mass ratio of the two oxoxane monomers is 1:99 to 99:1; the additional condition is when the two oxoxane single when the body are selected from the general formula _{R 1 Si (OR 4) 3} , wherein the at least one monomer of the through Wherein R ₁ is not hydrogen, methyl or vinyl. The copolymerized sesquioxane microsphere of claim 1, wherein R ₁ , R ₂ , and R ₃ are each independently hydrogen, phenyl, methyl, ethyl, vinyl, ethynyl, γ-aminopropyl , γ-(2,3-epoxypropoxy)-propyl, γ-(methacryloxy)-propyl or N-(β-aminoethyl)-γ-aminopropyl; and/or R ₄ is a methyl group or an ethyl group. The copolymerized sesquioxaxane microsphere of claim 1, wherein the copolymerized sesquioxane microsphere has an average particle diameter of 0.01 to 10 μm. A method for preparing a copolymerized sesquioxane microsphere, wherein the copolymer sesquioxane microsphere has an average particle diameter of 0.01 to 20 μm, comprising the steps of: in an inert solvent, in the presence of a base catalyst, The two siloxane oxide monomers having different structures are reacted; the two oxoxane monomers are each independently selected from the group consisting of the general formula R ₁ Si(OR ₄ ) ₃ and the general formula R ₂ R ₃ Si(OR ₄ ) ₂ Or a general formula Si(OR ₄ ) ₄ ; wherein R ₁ , R ₂ , and R ₃ are each independently hydrogen, substituted or unsubstituted C _1-6 alkyl, substituted or unsubstituted C _{2 -6} alkenyl, substituted or unsubstituted C _2-6 alkynyl, substituted or unsubstituted C _6-12 aryl, substituted or unsubstituted C _5-12 heteroaryl , wherein the substituent is amino, the substituted C _1-6 aminoalkyl, C _1-6 alkoxy, substituted alkoxy, oxy C _1-6 acyl or C _1-6 hydrocarbon group And R ₄ is a C _1-6 alkyl group; the mass ratio of the two oxoxane monomers is 1:99 to 99:1; and the additional condition is that when the two oxoxane monomers are selected from the the formula R ₁ Si (OR _{4) 3,} then at least one monomer of the general formula _wherein, R ₁ is not hydrogen, Or vinyl group. The preparation method of claim 4, wherein the inert solvent is water or a mixed solvent of water and a C _1-6 alcohol. The preparation method of claim 5, wherein the C _1-6 alcohol is methanol, ethanol, propanol, butanol, or a combination thereof; and/or the mass ratio of water to C _1-6 alcohol in the inert solvent is 50 to 100: 0 to 50. The preparation method of claim 4, wherein the alkali catalyst is an aqueous solution of an alkali metal hydroxide or ammonia water. The preparation method of claim 4, wherein the reaction is carried out at 20 to 90 ° C; and/or the reaction is carried out for 0.5 to 4 hours. A use of the copolymerized sesquioxane microspheres according to claim 1, which is used as a filler or modifier for plastics, cosmetics, rubber, or paints. A light diffusing plate comprising 0.3 to 5% by weight of the copolymerized sesquioxane microspheres according to claim 1 in terms of the total weight of the light diffusing plate. A cosmetic comprising 0.5 to 20% by weight of the copolymerized sesquioxane microspheres as claimed in claim 1 in terms of the total weight of the cosmetic.