CN108676116A - A kind of modified manometer silicon dioxide and the organic inorganic hybridization polyacrylate dispersion using the modified manometer silicon dioxide - Google Patents
A kind of modified manometer silicon dioxide and the organic inorganic hybridization polyacrylate dispersion using the modified manometer silicon dioxide Download PDFInfo
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- CN108676116A CN108676116A CN201810528902.0A CN201810528902A CN108676116A CN 108676116 A CN108676116 A CN 108676116A CN 201810528902 A CN201810528902 A CN 201810528902A CN 108676116 A CN108676116 A CN 108676116A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/36—Silica
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- C08K9/00—Use of pretreated ingredients
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The present invention relates to the organic inorganic hybridization polyacrylate dispersions of a kind of modified manometer silicon dioxide and the use modified manometer silicon dioxide.The modified manometer silicon dioxide includes with 100 parts of nano silicon dioxide, 0.2 2 parts of γ aminopropyl triethoxysilanes, 4 40 parts of ethyl alcohol, 0.2 2 parts of Diacetone Acrylamide, 1000 parts of solvent.The present invention solves prepares nano silicon dioxide and polyacrylate consistency problem in organic inorganic hybridization polyacrylate dispersion using nano silicon dioxide in the prior art, by being modified to nano-silica surface, introduce the diacetone group with reactivity, the group can keep stablizing in emulsion polymerization process and during storage, curing cross-linking reaction can be participated in during hybridisation emulsion film-forming, nano silicon dioxide and polyacrylate are connected by chemical bond, reaches and improves compatibility purpose between nano silicon dioxide and polyacrylate.
Description
Technical field
The present invention relates to the organic inorganic hybridizations of a kind of modified manometer silicon dioxide and the use modified manometer silicon dioxide
Polyacrylate dispersion belongs to aqueous high molecular materials synthesis field.
Background technology
Polyacrylate resin has excellent weatherability, water resistance, chemical-resistant and glossiness are high, gloss retention is good etc.
Advantage.Polyacrylate resin is typically all to construct in a liquid state when in use as materials such as coating, adhesives,
To environment, there are larger impact, water polyacrylic acids because to discharge a large amount of solvents when in use for solvent type polyacrylate resin
Resin is because having volatile organic matter（VOC）The advantages that discharge is less, price is low, safe to use, environmentally friendly, it has also become current development
Main way.
Performance is centainly limited to when water polyacrylic acid resin is used alone, thus is often needed in use to tree
Fat is modified.Organic-inorganic materials are a kind of homogeneous multiple phases materials being made of organic phase and inorganic phase, wherein
At least the size of a phase or there are one dimension in nanometer scale.This material is different from traditional organic phase-inorganic phase
Filler systems are not the simple adduction of organic phase and inorganic phase, but organic phase and inorganic phase nanometer to submicron order very
It combines and is formed on to molecular level, this material not only has both the good feature of the good film-forming property of organic material, the transparency, and has nothing
The advantages that high rigidity of machine material, thus hybrid inorganic-organic materials more areas is made to have broad application prospects.
It is a kind of side for preparing polyacrylate/inorganic hybrid material using nano-silicon dioxide modified polyacrylate
Method, since unmodified nano silicon dioxide is easy to reunite, and unmodified nano silicon dioxide and polyacrylate resin
Between interface binding power it is poor, influence the comprehensive performance of material, thus generally needed when in use to nano silicon dioxide carry out table
Face is modified, and the quality of the binding force and structural regularity between nano silicon dioxide and polyacrylate is to finally obtained poly- third
The stability and mechanical property of olefin(e) acid ester/nano silicon dioxide hybridization material play an important role.
State Intellectual Property Office discloses a Publication No. CN101899128A in 2010.12.1, entitled " hollow to receive
The invention of rice silica microsphere modified polyacrylate nuclear shell structure composite emulsion and film ", is mentioned silane coupled in literary
Y is the active function groups for having with polymer molecule affinity or respond in agent, does not carry specific group.
State Intellectual Property Office discloses a Publication No. CN102030873A in 2011.4.27, and entitled " one kind is received
The invention of the preparation method of rice silica/poly acrylate composite emulsion "；State Intellectual Property Office discloses in 2012.11.7
One Publication No. CN102766241A, it is entitled " a kind of nuclear shell structure nano silica/polyacrylate dispersion and its
The invention of preparation method "；State Intellectual Property Office discloses a Publication No. CN105061700A, title in 2015.11.18
For the invention of " nano silicon dioxide/polyacrylate organic inorganic hybridization water-dispersed resin and preparation method thereof ".Above-mentioned three
It is the silane coupling agent with double bond group that silane coupling agent is mentioned in part document.
The technical solution of above-mentioned four patent documents is only modified using silane coupling agent, modified nano-silica
SiClx surface is the residual groups of coupling agent.
Invention content
Present invention seek to address that preparing organic inorganic hybridization polyacrylate breast using nano silicon dioxide in the prior art
Nano silicon dioxide and polyacrylate consistency problem and dispersing uniformity and the problem of stability in liquid, provide one kind
Modified manometer silicon dioxide, using the modified manometer silicon dioxide prepare organic inorganic hybridization polyacrylate dispersion in, receive
Compatibility is improved between rice silica and polyacrylate, and nano silicon dioxide is in the polyacrylate being prepared
Dispersing uniformity and stability in lotion are improved.
In order to achieve the above-mentioned object of the invention, specific technical solution is as follows：
A kind of modified manometer silicon dioxide, it is characterised in that：Including following raw materials by weight：
100 parts of nano silicon dioxide, 0.2-2 parts of gamma-aminopropyl-triethoxy-silane, 4-40 parts of ethyl alcohol, Diacetone Acrylamide
0.2-2 parts, 1000 parts of solvent.
A kind of organic inorganic hybridization polyacrylate dispersion using the modified manometer silicon dioxide, feature exist
In：Including following raw materials by weight：
300-450 parts of one or two kinds of arbitrary proportion mixing in acrylate and methacrylate, modified nano-silica
8-20 parts of one or two kinds of arbitrary proportion mixing in 5-50 parts of SiClx, acrylic acid and methacrylic acid, diacetone acrylamide acyl
4-20 parts of amine, 2-10 parts of adipic dihydrazide, 10-20 parts of emulsifier, 1-2 parts of initiator, 5 parts of buffer, deionized water 500-700
Part.
Currently preferred, the acrylate is that methyl acrylate, ethyl acrylate, butyl acrylate and acrylic acid are different
One or two kinds of any of the above ratio mixing in monooctyl ester.
Currently preferred, the methacrylate is one kind in methyl methacrylate and butyl methacrylate
Or two kinds of arbitrary proportion mixing.
Currently preferred, the emulsifier is nonionic emulsifier and anion emulsifier.
Above-mentioned nonionic emulsifier is one or more of OP-10, OP-15, NP-10 and NP-15 arbitrary proportions
Mixing；Anion emulsifier is mixed for one or both of neopelex and sodium dodecyl benzene sulfonate arbitrary proportion
It closes.
It is currently preferred, the initiator be one or both of potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate with
Upper arbitrary proportion mixing.
Currently preferred, the buffer is one or more of sodium carbonate, sodium bicarbonate and ammonium hydrogen carbonate
Arbitrary proportion mixes.
It is currently preferred, the solvent be dichloromethane, chloroform, tetrachloromethane, dichloroethanes, trichloroethanes and
One or more of tetrachloroethanes arbitrary proportion mixes.
Currently preferred, the preparation method of the modified manometer silicon dioxide comprises the following steps that：
A, at room temperature, after gamma-aminopropyl-triethoxy-silane being dissolved in ethyl alcohol, nanometer titanium dioxide of the even spraying in stirring
Silicon continues uniform stirring and disperses 15-60 minutes, be put into 50-80 DEG C of baking oven 0.5-2 hours, takes out and place room temperature grinding distribution,
Obtain the nano silicon dioxide of the end group containing amino；
B, it after the nano silicon dioxide of the end group containing amino prepared in step A being dispersed in solvent at room temperature, is added double
Acetone acrylamide, constant temperature react 4-16h to 10-40 DEG C, centrifuge removal upper solution after reaction, solvent is added
The nano silicon dioxide of the end group containing amino is uniformly dispersed again, is stirred 15-60 minutes, upper solution is centrifuged, will wash
The modified manometer silicon dioxide of the base side chain containing diacetone is obtained after drying materials grinding afterwards.
It is currently preferred, using the organic inorganic hybridization polyacrylate dispersion of the modified manometer silicon dioxide
Preparation method is：Ionized water is removed at room temperature, and emulsifier and buffer is added, is put into water-bath and heats up after stirring and dissolving is uniform
To 80-90 DEG C, while being added and weighing the good and uniform mix monomer of dispersion mixing/modified manometer silicon dioxide component, double in advance
Acetone acrylamide and initiator solution, feed time are 3-5 hours, and heat preservation 0.5-2 is small at 80-90 DEG C after the completion of charging
When, be warming up to 85-90 DEG C and continue heat preservation reaction was completed in 0.5-2 hour, be cooled to 50 DEG C be added ammonium hydroxide by lotion neutralization to pH=
7.5 ± 0.5, addition adipic dihydrazide continues stirring and is cooled to 35 DEG C, and filtering blowing obtains organic inorganic hybridization polyacrylate breast
Liquid.
In step, the ratio of gamma-aminopropyl-triethoxy-silane and ethyl alcohol is 1:20, γ-methacryloxies
The dosage of propyl trimethoxy silicane is the 0.2-2% of nano silicon dioxide mass ratio.
In stepb, the dosage of Diacetone Acrylamide is contained three ethoxy of γ-aminopropyl in modified manometer silicon dioxide
1.3 times of base silane molal quantity, solvent quality are 10 with modified manometer silicon dioxide mass ratio：1.
The principle of the present invention is to prepare a kind of nano silicon dioxide with reactivity first, and specific method is to utilize to contain
It is reacted with the silicone hydroxyl of nano-silica surface after the siloxy group hydrolysis of amino silicane coupling agent, amino is introduced into nanometer two
Silicon oxide surface adds Diacetone Acrylamide component, will after being reacted with the double bond in Diacetone Acrylamide by amino
Diacetone key with reactivity introduces nano-silica surface, and nano silicon dioxide is made to be provided with and with self-cross linking groups
Acrylic resin cross-linking reaction ability.Second step is to prepare polyacrylate/nano silicon dioxide hybridization lotion, first will
Modified manometer silicon dioxide is dispersed in crylic acid ester mixture monomer, then carry out emulsion polymerizing preparation acrylate/
Nano silicon dioxide hybridization material.
The advantageous effects that the present invention is brought：
1, the present invention solves is prepared using nano silicon dioxide in organic inorganic hybridization polyacrylate dispersion in the prior art
Nano silicon dioxide and polyacrylate consistency problem, by being modified to nano-silica surface, introducing has instead
Answer active diacetone group, the group that can keep stablizing in emulsion polymerization process and during storage, it is solid in hybridisation emulsion
Curing cross-linking reaction can be participated in chemical conversion membrane process, is connected nano silicon dioxide and polyacrylate by chemical bond,
Reach and improves compatibility purpose between nano silicon dioxide and polyacrylate.
2, since nano-silica surface has carried out organically-modified, the interface in acrylate organic monomer is compatible
Property and dispersion stabilization are better than unmodified nano silicon dioxide, while also having part propylene acid ester monomer in the course of the polymerization process
It is grafted in the organic chain on modified manometer silicon dioxide surface, makes nano silicon dioxide in the polyacrylate dispersion being prepared
In dispersing uniformity and stability be improved, the diacetone key on modified manometer silicon dioxide surface and poly- in the curing process
Diacetone key on acrylate molecule chain can crosslink reaction with adipic dihydrazide, further by nano silicon dioxide and
Polyacrylate molecular is connected by chemical bond, so as to get polyacrylate/nano silicon dioxide hybridization material
The other performance of uniformity, storage stability and material is improved.
3, organic inorganic hybridization polyacrylate dispersion prepared by the present invention can be by contained in the drying process that forms a film
Cross-linking reaction group generates chemical reaction, and polyacrylate segment and nano silicon dioxide is bonded, thus with organic
The features such as inorganic component binding strength is good, and film forming compactness is good, good emulsion stability.
Specific implementation mode
Embodiment 1
A kind of modified manometer silicon dioxide, including following raw materials by weight：
100 parts of nano silicon dioxide, 0.2 part of gamma-aminopropyl-triethoxy-silane, 4 parts of ethyl alcohol, 0.2 part of Diacetone Acrylamide,
1000 parts of solvent.
Embodiment 2
A kind of modified manometer silicon dioxide, including following raw materials by weight：
It is 100 parts of nano silicon dioxide, 2 parts of gamma-aminopropyl-triethoxy-silane, 40 parts of ethyl alcohol, 2 parts of Diacetone Acrylamide, molten
1000 parts of agent.
Embodiment 3
A kind of modified manometer silicon dioxide, including following raw materials by weight：
100 parts of nano silicon dioxide, 1.1 parts of gamma-aminopropyl-triethoxy-silane, 22 parts of ethyl alcohol, Diacetone Acrylamide 1.1
Part, 1000 parts of solvent.
Embodiment 4
A kind of modified manometer silicon dioxide, including following raw materials by weight：
100 parts of nano silicon dioxide, 0.5 part of gamma-aminopropyl-triethoxy-silane, 33 parts of ethyl alcohol, Diacetone Acrylamide 1.3
Part, 1000 parts of solvent.
Embodiment 5
A kind of organic inorganic hybridization polyacrylate dispersion, including following raw materials by weight：
One or two kinds of arbitrary proportion in acrylate and methacrylate mixes 300 parts, modified manometer silicon dioxide 5
8 parts of one or two kinds of arbitrary proportion mixing in part, acrylic acid and methacrylic acid, 4 parts of Diacetone Acrylamide, adipyl
2 parts of hydrazine, 10 parts of emulsifier, 1 part of initiator, 5 parts of buffer, 500 parts of deionized water.
Embodiment 6
A kind of organic inorganic hybridization polyacrylate dispersion, including following raw materials by weight：
One or two kinds of arbitrary proportion in acrylate and methacrylate mixes 450 parts, modified manometer silicon dioxide
One or two kinds of arbitrary proportion in 50 parts, acrylic acid and methacrylic acid mix 20 parts, 20 parts of Diacetone Acrylamide, oneself
Two 10 parts of hydrazides, 20 parts of emulsifier, 2 parts of initiator, 5 parts of buffer, 700 parts of deionized water.
Embodiment 7
A kind of organic inorganic hybridization polyacrylate dispersion, including following raw materials by weight：
One or two kinds of arbitrary proportion in acrylate and methacrylate mixes 375 parts, modified manometer silicon dioxide
One or two kinds of arbitrary proportion in 27 parts, acrylic acid and methacrylic acid mix 14 parts, 12 parts of Diacetone Acrylamide, oneself
Two 6 parts of hydrazides, 15 parts of emulsifier, 1.5 parts of initiator, 5 parts of buffer, 600 parts of deionized water.
Embodiment 8
A kind of organic inorganic hybridization polyacrylate dispersion, including following raw materials by weight：
One or two kinds of arbitrary proportion in acrylate and methacrylate mixes 320 parts, modified manometer silicon dioxide
One or two kinds of arbitrary proportion in 10 parts, acrylic acid and methacrylic acid mix 18 parts, 19 parts of Diacetone Acrylamide, oneself
Two 5 parts of hydrazides, 12 parts of emulsifier, 1.2 parts of initiator, 5 parts of buffer, 550 parts of deionized water.
Embodiment 9
A kind of preparation method of modified manometer silicon dioxide comprises the following steps that：
A, at room temperature, after gamma-aminopropyl-triethoxy-silane being dissolved in ethyl alcohol, nanometer titanium dioxide of the even spraying in stirring
Silicon continues uniform stirring and disperses 15 minutes, be put into 50 DEG C of baking ovens 0.5 hour, takes out and place room temperature grinding distribution, obtains containing ammonia
The nano silicon dioxide of cardinal extremity base；
B, it after the nano silicon dioxide of the end group containing amino prepared in step A being dispersed in solvent at room temperature, is added double
Acetone acrylamide, constant temperature react 4h to 10 DEG C, centrifuge removal upper solution after reaction, and solvent, which is added, will contain ammonia
The nano silicon dioxide of cardinal extremity base is uniformly dispersed again, stirs 15 minutes, centrifuges upper solution, and the material after washing is dried
The modified manometer silicon dioxide of the base side chain containing diacetone is obtained after dry grinding.
Embodiment 10
A kind of preparation method of modified manometer silicon dioxide comprises the following steps that：
A, at room temperature, after gamma-aminopropyl-triethoxy-silane being dissolved in ethyl alcohol, nanometer titanium dioxide of the even spraying in stirring
Silicon continues uniform stirring and disperses 60 minutes, be put into 80 DEG C of baking ovens 2 hours, takes out and place room temperature grinding distribution, obtains containing amino
The nano silicon dioxide of end group；
B, it after the nano silicon dioxide of the end group containing amino prepared in step A being dispersed in solvent at room temperature, is added double
Acetone acrylamide, constant temperature react 16h to 40 DEG C, centrifuge removal upper solution after reaction, and solvent, which is added, will contain ammonia
The nano silicon dioxide of cardinal extremity base is uniformly dispersed again, stirs 60 minutes, centrifuges upper solution, and the material after washing is dried
The modified manometer silicon dioxide of the base side chain containing diacetone is obtained after dry grinding.
Embodiment 11
A kind of preparation method of modified manometer silicon dioxide comprises the following steps that：
A, at room temperature, after gamma-aminopropyl-triethoxy-silane being dissolved in ethyl alcohol, nanometer titanium dioxide of the even spraying in stirring
Silicon continues uniform stirring and disperses 37 minutes, be put into 65 DEG C of baking ovens 1.25 hours, takes out and place room temperature grinding distribution, contained
The nano silicon dioxide of amino end group；
B, it after the nano silicon dioxide of the end group containing amino prepared in step A being dispersed in solvent at room temperature, is added double
Acetone acrylamide, constant temperature react 10h to 25 DEG C, centrifuge removal upper solution after reaction, and solvent, which is added, will contain ammonia
The nano silicon dioxide of cardinal extremity base is uniformly dispersed again, stirs 38 minutes, centrifuges upper solution, and the material after washing is dried
The modified manometer silicon dioxide of the base side chain containing diacetone is obtained after dry grinding.
Embodiment 12
A kind of preparation method of modified manometer silicon dioxide comprises the following steps that：
A, at room temperature, after gamma-aminopropyl-triethoxy-silane being dissolved in ethyl alcohol, nanometer titanium dioxide of the even spraying in stirring
Silicon continues uniform stirring and disperses 18 minutes, be put into 75 DEG C of baking ovens 1 hour, takes out and place room temperature grinding distribution, obtains containing amino
The nano silicon dioxide of end group；
B, it after the nano silicon dioxide of the end group containing amino prepared in step A being dispersed in solvent at room temperature, is added double
Acetone acrylamide, constant temperature react 15h to 26 DEG C, centrifuge removal upper solution after reaction, and solvent, which is added, will contain ammonia
The nano silicon dioxide of cardinal extremity base is uniformly dispersed again, stirs 30 minutes, centrifuges upper solution, and the material after washing is dried
The modified manometer silicon dioxide of the base side chain containing diacetone is obtained after dry grinding.
Embodiment 13
Use the preparation method of the organic inorganic hybridization polyacrylate dispersion of modified manometer silicon dioxide for：
Ionized water is removed at room temperature, and emulsifier and buffer is added, is put into after stirring and dissolving is uniform in water-bath and is warming up to 80 DEG C,
It is added simultaneously and weighs good and the uniform mix monomer of dispersion mixing/modified manometer silicon dioxide component, diacetone acrylamide acyl in advance
Amine and initiator solution, feed time are 3 hours, keep the temperature 0.5 hour at 80 DEG C after the completion of charging, are warming up to 85 DEG C after continuation of insurance
Reaction was completed in 0.5 hour for temperature, is cooled to 50 DEG C and ammonium hydroxide is added by lotion neutralization to pH=7, adipic dihydrazide is added and continues stirring cooling
To 35 DEG C, filtering blowing obtains organic inorganic hybridization polyacrylate dispersion.
Embodiment 14
Use the preparation method of the organic inorganic hybridization polyacrylate dispersion of modified manometer silicon dioxide for：
Ionized water is removed at room temperature, and emulsifier and buffer is added, is put into after stirring and dissolving is uniform in water-bath and is warming up to 90 DEG C,
It is added simultaneously and weighs good and the uniform mix monomer of dispersion mixing/modified manometer silicon dioxide component, diacetone acrylamide acyl in advance
Amine and initiator solution, feed time are 5 hours, keep the temperature 2 hours at 90 DEG C after the completion of charging, are warming up to 90 DEG C and continue to keep the temperature
Reaction was completed within 2 hours, is cooled to 50 DEG C and ammonium hydroxide is added by lotion neutralization to pH=8, addition adipic dihydrazide continues stirring and is cooled to 35
DEG C, filtering blowing obtains organic inorganic hybridization polyacrylate dispersion.
Embodiment 15
Use the preparation method of the organic inorganic hybridization polyacrylate dispersion of modified manometer silicon dioxide for：
Ionized water is removed at room temperature, and emulsifier and buffer is added, is put into after stirring and dissolving is uniform in water-bath and is warming up to 85 DEG C,
It is added simultaneously and weighs good and the uniform mix monomer of dispersion mixing/modified manometer silicon dioxide component, diacetone acrylamide acyl in advance
Amine and initiator solution, feed time are 4 hours, keep the temperature 1.25 hours at 85 DEG C after the completion of charging, are warming up to 88 DEG C of continuation
Reaction was completed within 1.25 hours for heat preservation, is cooled to 50 DEG C and ammonium hydroxide is added by lotion neutralization to pH=7.5, adipic dihydrazide is added and continues to stir
It mixes and is cooled to 35 DEG C, filtering blowing obtains organic inorganic hybridization polyacrylate dispersion.
Embodiment 16
Use the preparation method of the organic inorganic hybridization polyacrylate dispersion of modified manometer silicon dioxide for：
Ionized water is removed at room temperature, and emulsifier and buffer is added, is put into after stirring and dissolving is uniform in water-bath and is warming up to 88 DEG C,
It is added simultaneously and weighs good and the uniform mix monomer of dispersion mixing/modified manometer silicon dioxide component, diacetone acrylamide acyl in advance
Amine and initiator solution, feed time are 3.5 hours, keep the temperature 1 hour at 82 DEG C after the completion of charging, are warming up to 87 DEG C after continuation of insurance
Reaction was completed in 1 hour for temperature, is cooled to 50 DEG C and ammonium hydroxide is added by lotion neutralization to pH=7.5, adipic dihydrazide is added and continues stirring cooling
To 35 DEG C, filtering blowing obtains organic inorganic hybridization polyacrylate dispersion.
Embodiment 17
(1) at room temperature, after 0.04 gram of gamma-aminopropyl-triethoxy-silane being dissolved in 0.8 gram of ethyl alcohol, even spraying is in stirring
8 grams of nano silicon dioxides, continue uniform stirring disperse 30 minutes, be put into 70 DEG C of baking ovens 1 hour, take out place grinding at room temperature
Dispersion, obtains the nano silicon dioxide of the end group containing amino.
It (2) at room temperature will be above-mentioned（1）The modified manometer silicon dioxide of middle preparation is dispersed in 0.4 gram of dichloromethane
Afterwards, 0.0403 gram of Diacetone Acrylamide is added, constant temperature reacts 10h to 20 DEG C, and it is molten to centrifuge removal upper layer after reaction
Liquid is added 0.4 gram of dichloromethane and modified manometer silicon dioxide is uniformly dispersed again, stir 30 minutes, it is molten to centrifuge upper layer
Liquid will obtain the modified manometer silicon dioxide of the base containing diacetone after the nano silicon dioxide drying grinding after washing.
(3) self-crosslinking polyacrylates/nano silicon dioxide hybridization lotion is prepared, the self-crosslinked polyacrylic emulsion
Synthesis material and proportioning are as follows：
Methyl methacrylate 240
Butyl acrylate 122
Modified manometer silicon dioxide 8
Methacrylic acid 12
Diacetone Acrylamide 12
Adipic dihydrazide 6
OP-10 12
Lauryl sodium sulfate 8
Potassium peroxydisulfate 2
Sodium bicarbonate 5
Deionized water 570
The preparation process of the self-crosslinked polyacrylic emulsion is as follows：
A certain amount of deionized water is weighed at room temperature, emulsifier and buffer is added, be put into water-bath and heat up after stirring and dissolving is uniform
To 85 DEG C, while being added and weighing good and the uniform mix monomer of dispersion mixing/modified manometer silicon dioxide component and initiation in advance
Agent solution, feed time are 4 hours, and mix monomer and initiator keep the temperature 1 hour after adding at 85 DEG C, are warming up to 90 DEG C of continuation
Reaction was completed within 1 hour for heat preservation, is cooled to 50 DEG C and ammonium hydroxide is added by lotion neutralization to pH=7.5 ± 0.5, adipic dihydrazide is added and continues
Stirring is cooled to 35 DEG C.Filtering blowing obtains organic inorganic hybridization polyacrylate dispersion.
Embodiment 18
(1) at room temperature, after 0.18 gram of gamma-aminopropyl-triethoxy-silane being dissolved in 3.6 grams of ethyl alcohol, even spraying is in stirring
15 grams of nano silicon dioxides, continue uniform stirring disperse 30 minutes, be put into 70 DEG C of baking ovens 1 hour, take out place room temperature grind
Mill dispersion, obtains the nano silicon dioxide of the end group containing amino.
It (2) at room temperature will be above-mentioned（1）The modified manometer silicon dioxide of middle preparation is dispersed in 1.8 grams of chloroforms
Afterwards, 0.179 gram of Diacetone Acrylamide is added, constant temperature reacts 16h to 10 DEG C DEG C, centrifuges removal upper layer after reaction
Solution is added 1.8 grams of chloroforms and modified manometer silicon dioxide is uniformly dispersed again, stir 30 minutes, centrifuges upper layer
Solution will obtain the modified manometer silicon dioxide of the base containing diacetone after the nano silicon dioxide drying grinding after washing.
(3) self-crosslinking polyacrylates/nano silicon dioxide hybridization lotion is prepared, the self-crosslinked polyacrylic emulsion
Synthesis material and proportioning are as follows：
Methyl methacrylate 162
Butyl methacrylate 50
Methyl acrylate 10
Butyl acrylate 70
Modified manometer silicon dioxide 15
Acrylic acid 8
Diacetone Acrylamide 4
Adipic dihydrazide 2
OP-15 12
Dodecyl sodium sulfate 8
Ammonium persulfate 2
Ammonium hydrogen carbonate 5
Deionized water 700
The preparation process of the self-crosslinked polyacrylic emulsion is as follows：
A certain amount of deionized water is weighed at room temperature, emulsifier and buffer is added, be put into water-bath and heat up after stirring and dissolving is uniform
To 85 DEG C, while being added and weighing good and the uniform mix monomer of dispersion mixing/modified manometer silicon dioxide component and initiation in advance
Agent solution, feed time are 3 hours, and mix monomer and initiator keep the temperature 1 hour after adding at 85 DEG C, are warming up to 90 DEG C of continuation
Reaction was completed within 1 hour for heat preservation, is cooled to 50 DEG C and ammonium hydroxide is added by lotion neutralization to pH=7.5 ± 0.5, adipic dihydrazide is added and continues
Stirring is cooled to 35 DEG C.Filtering blowing obtains organic inorganic hybridization polyacrylate dispersion.
Embodiment 19
(1) at room temperature, after 0.1 gram of gamma-aminopropyl-triethoxy-silane being dissolved in 2 grams of ethyl alcohol, even spraying in stirring 5
Gram nano silicon dioxide continues uniform stirring and disperses 30 minutes, be put into 70 DEG C of baking ovens 1 hour, takes out and place grinding at room temperature point
It dissipates, obtains the nano silicon dioxide of the end group containing amino.
It (2) at room temperature will be above-mentioned（1）The modified manometer silicon dioxide of middle preparation is dispersed in 1 gram of tetrachloromethane
Afterwards, 0.099 gram of Diacetone Acrylamide is added, constant temperature reacts 4h to 40 DEG C, and it is molten to centrifuge removal upper layer after reaction
Liquid is added 1 gram of tetrachloromethane and modified manometer silicon dioxide is uniformly dispersed again, stir 30 minutes, centrifuges upper solution,
The modified manometer silicon dioxide of the base containing diacetone will be obtained after nano silicon dioxide drying grinding after washing.
(3) self-crosslinking polyacrylates/nano silicon dioxide hybridization lotion is prepared, the self-crosslinked polyacrylic emulsion
Synthesis material and proportioning are as follows：
Methyl methacrylate 162
Methyl acrylate 30
Ethyl acrylate 20
Butyl acrylate 120
Modified manometer silicon dioxide 5
Acrylic acid 10
Diacetone Acrylamide 20
Adipic dihydrazide 10
NP-10 12
Lauryl sodium sulfate 8
Potassium peroxydisulfate 2
Sodium bicarbonate 5
Deionized water 500
The preparation process of the self-crosslinked polyacrylic emulsion is as follows：
A certain amount of deionized water is weighed at room temperature, emulsifier and buffer is added, be put into water-bath and heat up after stirring and dissolving is uniform
To 85 DEG C, while being added and weighing good and the uniform mix monomer of dispersion mixing/modified manometer silicon dioxide component and initiation in advance
Agent solution, feed time are 5 hours, and mix monomer and initiator keep the temperature 1 hour after adding at 85 DEG C, are warming up to 90 DEG C of continuation
Reaction was completed within 1 hour for heat preservation, is cooled to 50 DEG C and ammonium hydroxide is added by lotion neutralization to pH=7.5 ± 0.5, adipic dihydrazide is added and continues
Stirring is cooled to 35 DEG C.Filtering blowing obtains organic inorganic hybridization polyacrylate dispersion.
Embodiment 20
(1) at room temperature, after 0.1 gram of gamma-aminopropyl-triethoxy-silane being dissolved in 2 grams of ethyl alcohol, even spraying is in stirring
50 grams of nano silicon dioxides continue uniform stirring and disperse 30 minutes, be put into 70 DEG C of baking ovens 1 hour, take out and place grinding at room temperature
Dispersion, obtains the nano silicon dioxide of the end group containing amino.
It (2) at room temperature will be above-mentioned（1）The modified manometer silicon dioxide of middle preparation is dispersed in 1 gram of dichloroethanes
Afterwards, 0.099 gram of Diacetone Acrylamide is added, constant temperature reacts 6h to 30 DEG C, and it is molten to centrifuge removal upper layer after reaction
Liquid is added 1 gram of dichloroethanes and modified manometer silicon dioxide is uniformly dispersed again, stir 30 minutes, centrifuges upper solution,
The modified manometer silicon dioxide of the base containing diacetone will be obtained after nano silicon dioxide drying grinding after washing.
(3) self-crosslinking polyacrylates/nano silicon dioxide hybridization lotion is prepared, the self-crosslinked polyacrylic emulsion
Synthesis material and proportioning are as follows：
Methyl methacrylate ester 230
Butyl acrylate 80
Isooctyl acrylate monomer 30
Modified manometer silicon dioxide 50
Methacrylic acid 20
Diacetone Acrylamide 10
Adipic dihydrazide 5
NP-15 12
Dodecyl sodium sulfate 8
Sodium peroxydisulfate 2
Sodium carbonate 5
Deionized water 600
The preparation process of the self-crosslinked polyacrylic emulsion is as follows：
A certain amount of deionized water is weighed at room temperature, emulsifier and buffer is added, be put into water-bath and heat up after stirring and dissolving is uniform
To 85 DEG C, while being added and weighing good and the uniform mix monomer of dispersion mixing/modified manometer silicon dioxide component and initiation in advance
Agent solution, feed time are 4.5 hours, and mix monomer and initiator keep the temperature 1 hour after adding at 85 DEG C, be warming up to 90 DEG C after
Reaction was completed in 1 hour for continuation of insurance temperature, is cooled to 50 DEG C ammonium hydroxide are added and neutralize lotion to pH=7.5 ± 0.5, be added adipic dihydrazide after
Continuous stirring is cooled to 35 DEG C.Filtering blowing obtains organic inorganic hybridization polyacrylate dispersion.
Embodiment 21
(1) at room temperature, after 0.24 gram of gamma-aminopropyl-triethoxy-silane being dissolved in 4.8 grams of ethyl alcohol, even spraying is in stirring
30 grams of nano silicon dioxides, continue uniform stirring disperse 30 minutes, be put into 70 DEG C of baking ovens 1 hour, take out place room temperature grind
Mill dispersion, obtains the nano silicon dioxide of the end group containing amino..
It (2) at room temperature will be above-mentioned（1）The modified manometer silicon dioxide of middle preparation is dispersed in 2.4 grams of trichloroethanes
Afterwards, 0.239 gram of Diacetone Acrylamide is added, constant temperature reacts 12h to 15 DEG C, and it is molten to centrifuge removal upper layer after reaction
Liquid is added 2.4 grams of trichloroethanes and modified manometer silicon dioxide is uniformly dispersed again, stir 30 minutes, it is molten to centrifuge upper layer
Liquid will obtain the modified manometer silicon dioxide of the base containing diacetone after the nano silicon dioxide drying grinding after washing.
(3) self-crosslinking polyacrylates/nano silicon dioxide hybridization lotion is prepared, the self-crosslinked polyacrylic emulsion
Synthesis material and proportioning are as follows：
Methyl methacrylate ester 250
Ethyl acrylate 40
Butyl acrylate 100
Modified manometer silicon dioxide 30
Acrylic acid 12
Diacetone Acrylamide 8
Adipic dihydrazide 4
OP-10 12
Lauryl sodium sulfate 8
Ammonium persulfate 2
Sodium bicarbonate 5
Deionized water 600
The preparation process of the self-crosslinked polyacrylic emulsion is as follows：
A certain amount of deionized water is weighed at room temperature, emulsifier and buffer is added, be put into water-bath and heat up after stirring and dissolving is uniform
To 85 DEG C, while being added and weighing good and the uniform mix monomer of dispersion mixing/modified manometer silicon dioxide component and initiation in advance
Agent solution, feed time are 4.5 hours, and mix monomer and initiator keep the temperature 1 hour after adding at 85 DEG C, be warming up to 90 DEG C after
Reaction was completed in 1 hour for continuation of insurance temperature, is cooled to 50 DEG C ammonium hydroxide are added and neutralize lotion to pH=7.5 ± 0.5, be added adipic dihydrazide after
Continuous stirring is cooled to 35 DEG C.Filtering blowing obtains organic inorganic hybridization polyacrylate dispersion.
Embodiment 22
Comparative example（It is compared with embodiment 17）
Self-crosslinking polyacrylates/nano silicon dioxide hybridization lotion is prepared, the synthesis of the self-crosslinked polyacrylic emulsion is former
Material and proportioning are as follows：
Methyl methacrylate 240
Butyl acrylate 122
Unmodified nano silicon dioxide 8
Methacrylic acid 12
Diacetone Acrylamide 12
Adipic dihydrazide 6
OP-10 12
Lauryl sodium sulfate 8
Potassium peroxydisulfate 2
Sodium bicarbonate 5
Deionized water 570
The preparation process of the self-crosslinked polyacrylic emulsion is as follows：
A certain amount of deionized water is weighed at room temperature, emulsifier and buffer is added, be put into water-bath and heat up after stirring and dissolving is uniform
To 85 DEG C, while being added and weighing good and the uniform mix monomer of dispersion mixing/modified manometer silicon dioxide component and initiation in advance
Agent solution, feed time are 4 hours, and mix monomer and initiator keep the temperature 1 hour after adding at 85 DEG C, are warming up to 90 DEG C of continuation
Reaction was completed within 1 hour for heat preservation, is cooled to 50 DEG C and ammonium hydroxide is added by lotion neutralization to pH=7.5 ± 0.5, adipic dihydrazide is added and continues
Stirring is cooled to 35 DEG C.Filtering blowing obtains organic inorganic hybridization polyacrylate dispersion.
Comparative sample performance test：
Sample prepared by embodiment 17 and sample prepared by embodiment 22 are taken out respectively and are partially placed into polytetrafluoroethylene (PTFE) into model
On, after being put into 50 DEG C of baking oven drying film forming, constant temperature 24 hours at room temperature are placed, water resistance contrast test is carried out；It takes respectively
Go out partial emulsion and is put into the storage stability for being placed in closed sample bottle and placing 7 days test lotions in 50 DEG C of baking oven.Sample
Test result is as follows for product：
Claims (10)
1. a kind of modified manometer silicon dioxide, it is characterised in that：Including following raw materials by weight：
100 parts of nano silicon dioxide, 0.2-2 parts of gamma-aminopropyl-triethoxy-silane, 4-40 parts of ethyl alcohol, Diacetone Acrylamide
0.2-2 parts, 1000 parts of solvent.
2. a kind of organic inorganic hybridization polyacrylate dispersion using modified manometer silicon dioxide described in claim 1,
It is characterized in that：Including following raw materials by weight：
300-450 parts of one or two kinds of arbitrary proportion mixing in acrylate and methacrylate, modified nano-silica
8-20 parts of one or two kinds of arbitrary proportion mixing in 5-50 parts of SiClx, acrylic acid and methacrylic acid, diacetone acrylamide acyl
4-20 parts of amine, 2-10 parts of adipic dihydrazide, 10-20 parts of emulsifier, 1-2 parts of initiator, 5 parts of buffer, deionized water 500-700
Part.
3. a kind of organic inorganic hybridization polyacrylate dispersion according to claim 2, it is characterised in that：The acrylic acid
Ester is one or two kinds of any of the above ratio in methyl acrylate, ethyl acrylate, butyl acrylate and Isooctyl acrylate monomer
Example mixing.
4. a kind of organic inorganic hybridization polyacrylate dispersion according to claim 2 or 3, it is characterised in that：The first
Base acrylate is one or two kinds of arbitrary proportion mixing in methyl methacrylate and butyl methacrylate.
5. a kind of organic inorganic hybridization polyacrylate dispersion according to claim 2, it is characterised in that：The emulsifier
For nonionic emulsifier and anion emulsifier.
6. a kind of organic inorganic hybridization polyacrylate dispersion according to claim 2, it is characterised in that：The initiator
It is mixed for one or more of potassium peroxydisulfate, sodium peroxydisulfate and ammonium persulfate arbitrary proportion.
7. a kind of organic inorganic hybridization polyacrylate dispersion according to claim 2, it is characterised in that：The buffer
It is mixed for one or more of sodium carbonate, sodium bicarbonate and ammonium hydrogen carbonate arbitrary proportion.
8. a kind of modified manometer silicon dioxide according to claim 1, it is characterised in that：The solvent be dichloromethane,
One or more of chloroform, tetrachloromethane, dichloroethanes, trichloroethanes and tetrachloroethanes arbitrary proportion mixes.
9. a kind of modified manometer silicon dioxide according to claim 1, it is characterised in that：The modified manometer silicon dioxide
Preparation method comprise the following steps that：
A, at room temperature, after gamma-aminopropyl-triethoxy-silane being dissolved in ethyl alcohol, nanometer titanium dioxide of the even spraying in stirring
Silicon continues uniform stirring and disperses 15-60 minutes, be put into 50-80 DEG C of baking oven 0.5-2 hours, takes out and place room temperature grinding distribution,
Obtain the nano silicon dioxide of the end group containing amino；
B, it after the nano silicon dioxide of the end group containing amino prepared in step A being dispersed in solvent at room temperature, is added double
Acetone acrylamide, constant temperature react 4-16h to 10-40 DEG C, centrifuge removal upper solution after reaction, solvent is added
The nano silicon dioxide of the end group containing amino is uniformly dispersed again, is stirred 15-60 minutes, upper solution is centrifuged, will wash
The modified manometer silicon dioxide of the base side chain containing diacetone is obtained after drying materials grinding afterwards.
10. a kind of organic inorganic hybridization polyacrylate dispersion according to claim 2, it is characterised in that：Using described
The preparation method of organic inorganic hybridization polyacrylate dispersion of modified manometer silicon dioxide be：Ionized water is removed at room temperature,
Emulsifier and buffer is added, is put into water-bath after stirring and dissolving is uniform and is warming up to 80-90 DEG C, while be added and weighing in advance
And the uniform mix monomer of dispersion mixing/modified manometer silicon dioxide component, Diacetone Acrylamide and initiator solution, charging
Time be 3-5 hour, keep the temperature 0.5-2 hours at 80-90 DEG C after the completion of charging, be warming up to 85-90 DEG C continue heat preservation 0.5-2 it is small
When reaction was completed, be cooled to 50 DEG C ammonium hydroxide be added and neutralize lotion to pH=7.5 ± 0.5, adipic dihydrazide is added and continues stirring cooling
To 35 DEG C, filtering blowing obtains organic inorganic hybridization polyacrylate dispersion.
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| CN113354960A (en) * | 2021-05-24 | 2021-09-07 | 广东海浦倍尔新材料有限公司 | Modified inorganic nano particle and preparation method thereof |
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Application publication date: 20181019 |