CN104530302B - A kind of Ludox/polyacrylate dispersion of high silicon content and preparation method thereof - Google Patents
A kind of Ludox/polyacrylate dispersion of high silicon content and preparation method thereof Download PDFInfo
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- CN104530302B CN104530302B CN201410764940.8A CN201410764940A CN104530302B CN 104530302 B CN104530302 B CN 104530302B CN 201410764940 A CN201410764940 A CN 201410764940A CN 104530302 B CN104530302 B CN 104530302B
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Abstract
Ludox/polyacrylate dispersion that the invention discloses a kind of high silicon content and preparation method thereof.The method uses water-soluble macromolecule that Ludox is carried out physical modification, modified Ludox and acrylic ester monomer is carried out in-situ polymerization and prepares Ludox/polyacrylate dispersion.In terms of mass fraction, the formula of raw material consists of: deionized water 50～70 parts, Ludox 5～30 parts, water-soluble macromolecule 0.01～0.5 part, acrylic ester monomer 20～53 parts, methacrylic acid or acrylic acid 1～5 parts, emulsifying agent 1～5 parts, initiator 0.1～0.5 part, pH buffer agent 0.1～0.5 part；With SiO2Meter, in emulsion, silicone content accounts for the 5～30% of whole solid content；Latex particle size is 60～100nm；Carboxyl on Inventive polymers strand and hydroxyl, SiO2The hydroxyl on micelle surface can occur esterification and crosslinking, makes the hardness of film reach more than 5H, and has prominent resistance to water and weatherability.
Description
Technical field
The present invention relates to a kind of polyacrylate composite polymer latex, the silicon particularly relating to a kind of high silicon content is molten
Glue/polyacrylate dispersion and preparation method thereof.
Technical background
In recent years, on the basis of emulsion polymerization theory and technology develop, occur in that composite polymer latex, particularly have
Machine inorganic compounding emulsion causes the extensive concern of people.
After the concept of the Okubo proposition eighties in 20th century " particle design ", use seed emulsion polymerization, prepare
There is the new polymers emulsion of out-phase (core-shell structure copolymer) structure latex particle.Due to latex particle with core shell structure core, shell it
Between there may be grafting, interpenetrating networks or ionic bonding, same materials form in the case of, there is the emulsion particle of this structure
Son be possible not only to significantly improve wear-resisting, water-fast, weather-proof, resistant, the shielding property of polymer and tensile strength, resistance to impact and
Adhesion strength, improves the transparency, but also can significantly reduce film-forming temperature, improve processing characteristics.According to polymer emulsion
Nucleocapsid structure theoretical model, uses seeded emulsion polymerization technique, introduces inorganic nano material in the course of the polymerization process, define with nothing
Machine nano material be core, macromolecular material be the complex emulsions of shell, this Core-Shell Type Hybrid Emulsions had both overcome nano material
Easily reunite when being introduced directly into coating system and the shortcoming such as Organic substance poor compatibility, maintain again traditional polymer emulsion film forming good,
The advantage that the film transparency is excellent with pliability, before having a wide range of applications in terms of preparation high-performance and specific function coating
Scape.
Chinese invention patent application CN 102649835 A discloses a kind of nanometer processed with silane coupler surface
SiO2For seed, suitable emulsion polymerization technique is used to prepare Nano-meter SiO_22The method of-poly acrylate composite emulsion.The method
Both overcome nano material easily to reunite and the shortcoming such as Organic substance poor compatibility, and maintained again that traditional polymer emulsion film forming is good, be coated with
The advantage that the film transparency is excellent with pliability.
Chinese invention patent application CN 102140217 A discloses one to be prepared at Core-Shell Polyacrylic-ester Copolymer shell
During add the method preparing polyacrylate/silica solution composite material through modified Ludox.The method silicon
Ludox is modified by alkane coupling agent, and the emulsion of preparation has nucleocapsid structure.
Chinese invention patent application CN 1036269ll A discloses a kind of with the coupling agent modified Ludox system of fluorine containing silane
The method of standby hydrophobicity organic-inorganic high silicon content acrylate polymer emulsion, emulsion nano silicon dioxide prepared by the method
Being uniformly dispersed, film has the hardness and hydrophobicity become reconciled.
Above-mentioned prior art is all to SiO first with silane coupler2Carry out chemical modification, the most on this basis
Prepare the SiO of organic inorganic hybridization2/ polyacrylate dispersion.At silane coupler to SiO2During carrying out chemical modification,
Easily cause SiO2Reunion, cause the particle diameter being difficult to control to organic inorganic hybridization emulsion, thus affect emulsion film film property,
The combination property such as hardness, chemical-resistant.
Summary of the invention
It is an object of the invention to the deficiency overcoming prior art to exist, it is provided that a kind of SiO2Good with polymer compatibility,
Emulsion particle diameter is little, hardness of film is high and Ludox/poly-third of the high silicon content of the function admirable such as film property, resistance to water, weatherability
Olefin(e) acid ester emulsion and preparation method thereof.
The present invention uses emulsion polymerization in situ, with Ludox (Nano-meter SiO_22The colloidal sol of particle) it is raw material, with water solublity
Macromole, to its physical modification, prepares the Ludox/polypropylene of the high silicon content that emulsion particle is 60～100nm on this basis
Acid esters nano-composite emulsion.This emulsion had both overcome nano material and had easily reunited and the shortcoming such as Organic substance poor compatibility, maintained again
The advantage that traditional polymer emulsion film forming is good, film is transparent and pliability is excellent, also has prominent resistance to water, weatherability etc.
Performance.
The method that invention also provides preparation above-mentioned emulsion, realizes especially by following technical scheme:
The preparation method of the Ludox/polyacrylate dispersion of a kind of high silicon content, comprises the steps:
1) take account for ionized water gross mass 10～the deionized water of 30%, water-soluble macromolecule is dissolved in deionized water
Make water-soluble macromolecule aqueous solution, water-soluble macromolecule aqueous solution is mixed with Ludox, stirs, obtain water solublity and divide greatly
Sub-modified silicasol；
2) using water-soluble macromolecule modified silicasol as still liquid, and addition accounts for emulsifying agent gross mass 1～the emulsifying of 40%
Agent and account for ionized water gross mass 1～the deionized water of 50%, whole pH buffer agents, stirring, mix homogeneously；
3) formula hydroxy acryl acid ester monomer, acrylic or methacrylic acid monomers, esters of acrylic acid list are weighed respectively
Body or methacrylate-based monomer, take account for total monomer quality 10～45% monomer mix as nuclear monomer, by remaining list
Body mixes as shell monomer；
Take remaining emulsifying agent and mix with the deionized water of account for ionized water total amount 25～70%, fully dissolve, obtain emulsifying
Agent solution, the emulsifier solution of taking-up 10～30% mass is for emulsifying nuclear monomer, remaining for emulsifying shell monomer；
In the emulsifier solution for emulsifying nuclear monomer, add nuclear monomer, prepare nuclear monomer pre-emulsion；For breast
Change and the emulsifier solution of shell monomer adds shell monomer, prepare shell monomer pre-emulsion；Cause with remaining deionized water dissolving
Agent, makes initiator solution；
4) by step 2) solution temperature that obtains is increased to 60～90 DEG C, and it is simultaneously added dropwise and accounts for 30～50% initiator of mass
Solution and nuclear monomer pre-emulsion, carry out polyreaction, drips complete insulation 15～45min；
5) add remaining initiator solution and shell monomer pre-emulsion, at 70～90 DEG C, proceed polyreaction；
Treating that the dropping of shell monomer pre-emulsion is complete, be incubated 1.5～4h, regulation pH value is 7～8, filters discharging；
Described water-soluble macromolecule is carboxymethyl cellulose (CMC), hydroxymethyl cellulose (HMC), hydroxyethyl cellulose
(HEC), hydroxypropyl methyl cellulose (HPMC), hydroxyethylmethyl-cellulose (HEMC), polyvinyl alcohol (PVA), Polyethylene Glycol
(PEG), polyacrylamide (PAM), hydrolyzed polyacrylamide (HPAM)), polyvinylpyrrolidone (PVP), sodium polyacrylate and
One or more in water soluble starch；
Described hydroxy acryl acid ester monomer is 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate, Hydroxypropyl acrylate, first
Other hydroxy acryl acid ester monomers that base Hydroxypropyl acrylate, N hydroxymethyl acrylamide and the art are conventional, emulsion
Preparation process is chosen one or more in above-mentioned monomer；
Described acrylic ester monomer or methacrylate-based monomer are acrylic acid methyl ester., ethyl acrylate, propylene
Acid butyl ester, methyl methacrylate, ethyl methacrylate, butyl methacrylate, N-Hexyl methacrylate, methacrylic acid
Two or more in monooctyl ester and acrylic acid-2-ethyl caproite；
Described emulsifying agent be anionic emulsifier and nonionic emulsifier obtained by compounding emulsifying agent, anionic
The mass ratio of emulsifying agent and nonionic emulsifier is 1～3:1, and wherein anionic emulsifier gathers selected from allyloxy nonyl phenol
Oxygen vinyl Ether series, sodium vinyl sulfonate, methallylsulfonic acid sodium, allyloxy hydroxide sodium dimercaptosulphanatein, enuatrol, stearic acid
One in sodium, sodium lauryl sulphate, dodecyl sodium sulfate, dodecylbenzene sodium sulfonate and double dodecylbenzene sodium sulfonate
Or it is multiple；Described nonionic emulsifier selects fatty alcohol polyethenoxy ether class, alkylphenol polyoxyethylene class and polyoxyethylene
One or more of sorbitan fatty acid ester apoplexy due to endogenous wind；
Described water soluble starter is one or both in Ammonium persulfate., potassium peroxydisulfate and sodium peroxydisulfate.
For realizing the object of the invention further, it is preferable that described pH buffer agent is sodium bicarbonate, dibastic sodium phosphate and di(2-ethylhexyl)phosphate
One or more in hydrogen sodium.
Described nuclear monomer pre-emulsion is prepared via a method which: under the mixing speed of 800～2000rpm, will be used for
The emulsifier solution stirring 10～25min of emulsifying nuclear monomer, drips nuclear monomer, after dropping, continues with 1000-2000rpm
Rotating speed stirring 20～30min.
Described shell monomer pre-emulsion is prepared via a method which: under the mixing speed of 800～2000rpm, will be used for
The emulsifier solution stirring 10～25min of emulsifying shell monomer, drips shell monomer, after dropping, continues with 1000-2000rpm
Rotating speed stirring 20～30min.
Described dropping account for 30～50% mass initiator solution and the time for adding of nuclear monomer pre-emulsion be 30～
90min。
The time of the remaining initiator solution of described addition and shell monomer pre-emulsion is 2.5～3.5h.
Step 1) in be stirred at 30～75 DEG C stirring 6～24h.
Step 5) in pH value by add ammonia regulate.
Ludox/the polyacrylate dispersion of a kind of high silicon content, is prepared by above-mentioned preparation method.Described high silicon content
Ludox/polyacrylate dispersion, it is characterised in that the solid content of described Ludox/polyacrylate dispersion be 25～
40%；In terms of SiO2, inorganic silicon accounts for the 5～30% of whole emulsion solid content；Emulsion appearance is light blue translucent liquid, latex
Grain particle diameter is 60～100nm；Emulsion infusion process or brushing method are coated on the glass after washes clean or metal substrate,
Toasting 5～30min under the conditions of 120 DEG C, the hardness of film obtained reaches more than 5H, and adhesive force reaches 0 grade, and film room temperature water soaks
Within 20 days, not whitening, resistance to neutral salt spray 30 days is unchanged.
Present invention water soluble polymer is to SiO2Micelle processes so that it is surface forms an Adsorption of Organic layer, and
Shield SiO2The negative charge on micelle surface, thus add the affinity of it and monomer, with such SiO2Micelle is core, enters
Row seeded emulsion polymerization, makes monomer radical energy targeting SiO2Micelle, it is thus achieved that SiO2-water soluble polymer/PBA-MMA complex nucleus
Shell mould micelle.
Compared with prior art, the invention have the advantages that
1) preparation of the Ludox/polyacrylate dispersion of a kind of high silicon content of the present invention, uses water-soluble macromolecule pair
The modification of alkaline silica sol, belongs to physical modification, can retain SiO2The hydroxyl on micelle surface.Become at high temperature (90～130 DEG C)
Carboxyl on polymer molecular chain and hydroxyl, SiO during film2The hydroxyl on micelle surface can occur esterification and crosslinking generation esterification and crosslinking,
Improve the hardness of film, resistance to water and weatherability further.
2) emulsion preparation method disclosed by the invention, inorganic nano silicon dioxide gel and the use of water-soluble macromolecule,
Relative to traditional method, both reduced the particle diameter of emulsion particle, enhanced product performance, the production cost of emulsion can have been reduced again.
3) emulsion prepared by the present invention, its emulsion particle is in the micropore that nanoscale can penetrate into base material, hydroxyl simultaneously
Acrylate monomer ensure that on polymer chain containing hydroxyl for necessary monomer so that the adhesive force of film is higher, reaches 0 grade.
4) Ludox/polyacrylate dispersion of a kind of high silicon content of the present invention, by physical modification Ludox with acrylic acid
Esters monomer in-situ polymerization and prepare, method is simple.
Specific implementation method
For being more fully understood that the present invention, below in conjunction with embodiment, the invention will be further described, but embodiment is not constituted
Limiting the scope of the present invention.The raw material related in embodiment, is commercially available in addition to specified otherwise.
In example below, HEC selects viscosity to be 50mPa s, and HEMC selects viscosity to be 100mPa s, is Shanghai brilliant
Pure biochemical technology limited company produces；The Ludox that glass factory of flooding in Foshan produces selected by Ludox, and mass content is
30%, alkalescence.
Embodiment 1
0.18g HEC is dissolved in 5g deionized water, then HEC solution is added in 56g Ludox, stir at 41 DEG C
Reaction 12h, obtains modified silicasol.
By 3.2g DNS-86 (allyloxy nonyl phenol propanol polyoxyethylene (10) ether ammonium sulfate) and X-405 (octylphenol polyethylene
Oxygen vinyl Ether) compound emulsifying agent (mass ratio: 2:1) is dissolved in 38g deionized water and prepares emulsified solution, is classified as three parts: take
8g is nuclear monomer emulsifier solution, and 25g is as shell monomer emulsifier solution, and residual emulsifier solution mixes work with modified silicasol
For still liquid.
Monomer pre-emulsification: respectively nuclear monomer emulsifier solution and shell monomer emulsifier solution are added in two wide mouthed bottles,
Stir 25min with the speed of 1500rpm, and backward two bottles are respectively dropped into 11g nuclear monomer (methyl methacrylate and propylene
Acid butyl ester mass ratio is 1:1) and 32.2g shell monomer (methyl methacrylate, butyl acrylate and acrylic acid three's mass ratio are
2:1:0.1), after dropping, continue with 1500rpm magnetic agitation 30min, prepare nuclear monomer pre-emulsion and the pre-breast of shell monomer
Change liquid.And 0.65g Ammonium persulfate. is dissolved in 10.8g deionized water.
In the four-hole boiling flask being provided with stirring paddle, thermometer, reflux condensing tube, add still liquid, and add 0.6g
NaHCO3, stirs with the speed of 200rpm and is warming up to 75 DEG C, is incubated 30min.Nuclear monomer pre-emulsion is contained by constant pressure funnel,
And at the uniform velocity dripping 4g initiator ammonium sulfate solution, time for adding is 30min.Insulation 30min.It is warming up to 81 DEG C, leaks by constant voltage
Bucket contains shell monomer pre-emulsion, and at the uniform velocity dropping 6.8g initiator ammonium sulfate solution, and time for adding is 3h, is incubated 3h.Cold
But to less than 50 DEG C, with ammonia, the pH value being dissolved in is adjusted to about 8, obtains stable Ludox/polyacrylate dispersion.Through inspection
Surveying, the silicone content of this Ludox/polyacrylate dispersion is 28%；Latex particle size (particle diameter of micelle in emulsion) is
98.5nm/PDI=0.303 (Malvern laser particle size analyzer)；Emulsion is coated tinplate 120 DEG C baking 15min, and it is coated with
Film smoothness, transparency, hardness reaches 5H (GB/T6739-2006), and adhesive force is 0 grade of (GB/T1720-1979) film water logging
Steep within 21 days, do not whiten (GB/T 1733-1993), resistance to neutral salt spray 31 days unchanged (GB/T1771-2007).
Performance comparison: the present embodiment gained hardness of film reaches 5H, and (GB/T6739-2006, with patent CN102649835A
Suitable with patent CN1O2731735A)；Due to the effect adhesive force of nano-emulsion micelle and hydroxyl be 0 grade (GB/T1720-1979,
Patent CN102649835A is 1 grade, patent CN1O2731735A is 0～1 grade)；Hydroxyl on polymer molecular chain in baking
Base and carboxyl crosslink so that the present embodiment gained film is soaked in water 21 days (GB/T 1733-1993, the patent of not whitening
CN102649835A does not explicitly point out water resistance, patent CN1O2731735A is 7～10 days)；Film is resistant to neutrality
Salt fog 31 days is unchanged, and (GB/T1771-2007 does not explicitly point out salt spray resistance, patent in patent CN102649835A
It CN1O2731735A is 12～20 days).
Visible present embodiments provide a kind of SiO2Good with polymer compatibility, latex particle size is little, hardness of film is high and becomes
Ludox/the polyacrylate dispersion of the high silicon content of the function admirables such as film, resistance to water, weatherability.
Embodiment 2
0.01g HEC is dissolved in 5g deionized water, then HEC solution is added in 30g Ludox, stir at 41 DEG C
Reaction 12h, obtains modified silicasol.
1.6g DNS-86 and OP-10 (NPE) compound emulsifying agent (mass ratio: 2:1) is dissolved in 20g
Ionized water, is divided into three parts: taking 3g is nuclear monomer emulsifier solution；11g is nuclear monomer emulsifier solution；Residual emulsifier solution
Mix as still liquid with modified silicasol.
Monomer pre-emulsification: respectively nuclear monomer emulsifier solution and shell monomer emulsifier solution are added in two wide mouthed bottles,
Stir 15min with the speed of 1500rpm, in two bottles, instill 7g nuclear monomer (methyl methacrylate and propylene the most respectively
Acid butyl ester mass ratio is 1:1) and 23g shell monomer (methyl methacrylate, butyl acrylate, methacrylic acid and metering system
Acid hydroxypropyl acrylate three's mass ratio is 2:1:0.1:0.1), after dropping, continue with 1500rpm magnetic agitation 30min, make respectively
Obtain nuclear monomer pre-emulsion and shell monomer pre-emulsion, standby.0.25g Ammonium persulfate. is dissolved in 30g deionized water, makes and draw
Send out agent aqueous solution.
Still liquid (residual emulsifier and 39g is added in the four-hole boiling flask being provided with stirring paddle, thermometer, reflux condensing tube
Modified silicasol), and add 0.4g NaHCO3, stir with the speed of 200rpm and be warming up to 75 DEG C, being incubated 30min.Use constant voltage
Funnel contains nuclear monomer pre-emulsion, and at the uniform velocity dropping 10g initiator solution, and time for adding is 30min, is incubated 30min, rises
Temperature, to 81 DEG C, contains shell monomer pre-emulsion, and at the uniform velocity dropping 21g initiator solution by constant pressure funnel, and time for adding is 3h,
Insulation 2.5h.It is cooled to less than 50 DEG C, with ammonia, the pH value of emulsion is adjusted to about 8, obtain stable Ludox/polyacrylic acid
Ester emulsion.The silicone content of this Ludox/polyacrylate dispersion is 22% (quality), and latex particle size is 63.4nm/PDI=
0.350 (Malvern laser particle size analyzer)；Emulsion is coated tinplate 120 DEG C baking 15min, its photocatalytic coating film slippery, thoroughly
Lightness, hardness reaches 5H (GB/T6739-2006), and adhesive force is that 0 grade of (GB/T1720-1979) film is soaked in water 20 days and does not whitens
(GB/T 1733-1993), resistance to neutral salt spray 30 days unchanged (GB/T1771-2007).
Embodiment 3
0.08g PEG (molecular weight 20000,1Guanghua Chemical Plant Co., Ltd., Guangdong) is dissolved in 5g deionized water, then
Being added in 25g Ludox by PEG solution, at 60 DEG C, stirring reaction 10h, obtains modified silicasol.
By 3.5gSVS (sodium vinyl sulfonate) and AEO40 (fatty alcohol polyethenoxy ether class emulsifying agent) compound emulsifying agent (matter
Amount ratio: 1:4) be dissolved in 25g deionized water, be divided into three parts: taking 5g as nuclear monomer emulsifier solution, 15g is as shell monomer breast
Agent solution, residual emulsifier solution mixes as still liquid with modified silicasol.
Monomer pre-emulsification: respectively nuclear monomer emulsifier solution and shell monomer emulsifier solution are added in two wide mouthed bottles,
Stirring 10min with the speed of 1500rpm, (methyl methacrylate and butyl acrylate mass ratio are then to instill 7g nuclear monomer
1:1) and 23g shell monomer (methyl methacrylate, butyl acrylate and methacrylic acid three's mass ratio are 2:1:0.1:
0.2), after dropping, continue with 1500rpm magnetic agitation 30min, prepare nucleocapsid pre-emulsion.And by 0.25g Ammonium persulfate.
It is dissolved in 30g deionized water.
Still liquid (residual emulsifier and 39g is added in the four-hole boiling flask being provided with stirring paddle, thermometer, reflux condensing tube
Modified silicasol), and add 0.4g NaHCO3 and 0.5g methacrylic acid, stir with the speed of 200rpm and be warming up to 75 DEG C,
Insulation 30min.Containing nuclear monomer pre-emulsion, and at the uniform velocity dropping 10g initiator solution by constant pressure funnel, time for adding is
30min.Insulation 30min.It is warming up to 81 DEG C, contains shell monomer pre-emulsion, and at the uniform velocity dropping 21g initiator water by constant pressure funnel
Solution, time for adding is 3h, is incubated 4h.It is cooled to less than 50 DEG C, with ammonia, the pH value being dissolved in is adjusted to about 8, is stablized
Ludox/polyacrylate dispersion.The silicone content of this emulsion is 20%, and emulsion particle diameter is 62.5nm/PDI=0.377 (Ma Er
Literary composition laser particle size analyzer), emulsion is coated tinplate 120 DEG C baking 15min, its photocatalytic coating film slippery, transparent excellence, hardness
Reaching 5H (GB/T6739-2006), adhesive force is 0 grade (GB/T1720-1979), and film is soaked in water 20 days (GB/T that do not whiten
1733-1993), resistance to neutral salt spray 30 days unchanged (GB/T1771-2007).
Embodiment 4
0.06g HEMC is dissolved in 5g deionized water, then HEMC solution is added in 42.5g Ludox, at 65 DEG C
Stirring reaction 12h, obtains modified silicasol.
2.8g dodecylbenzene sodium sulfonate and OP-10 compound emulsifying agent (mass ratio: 1:1) are dissolved in 25g deionized water, point
Be three parts: take 5g as nuclear monomer emulsifier solution, 15g as shell monomer emulsifier solution, residual emulsifier solution with change
Property Ludox mix as still liquid.
Monomer pre-emulsification: respectively nuclear monomer emulsifier solution and shell monomer emulsifier solution are added in two wide mouthed bottles,
Stir 10min with the speed of 1500rpm, in two bottles, instill 7g nuclear monomer (methyl methacrylate and propylene the most respectively
Acid butyl ester mass ratio is 1:1) and 23g shell monomer (methyl methacrylate, butyl acrylate and methacrylic acid three's mass ratio
For 2:1:0.1:0.2), after dropping, continue with 1500rpm magnetic agitation 30min, prepare nucleocapsid pre-emulsion.And will
0.25g Ammonium persulfate. is dissolved in 30g deionized water.
Still liquid (residual emulsifier and 39g is added in the four-hole boiling flask being provided with stirring paddle, thermometer, reflux condensing tube
Modified silicasol), and add 0.4g NaHCO3 and 0.5g methacrylic acid, stir with the speed of 200rpm and be warming up to 75 DEG C,
Insulation 30min.Containing nuclear monomer pre-emulsion, and at the uniform velocity dropping 10g initiator solution by constant pressure funnel, time for adding is
30min.Insulation 30min.It is warming up to 81 DEG C, contains shell monomer pre-emulsion, and at the uniform velocity dropping 21g initiator water by constant pressure funnel
Solution, time for adding is 3h, is incubated 3h.It is cooled to less than 50 DEG C, with ammonia, the pH value being dissolved in is adjusted to about 8, is stablized
Ludox/polyacrylate dispersion.The silicone content of this emulsion is 30%, and latex particle size is 99.2nm/PDI=0.377 (horse
You literary composition laser particle size analyzer), emulsion is coated tinplate 120 DEG C baking 15min, its photocatalytic coating film slippery, excellent clarity,
Hardness reaches 6H (GB/T6739-2006), and adhesive force is that 0 grade of (GB/T1720-1979) film is soaked in water 21 days (GB/T that do not whiten
1733-1993), resistance to neutral salt spray 30 days unchanged (GB/T1771-2007).
Embodiment 5
0.02g PVA (low viscosity uses standard USP25) is dissolved in 5g deionized water, then HEMC solution is added to
In 18g Ludox, at 50 DEG C, stirring reaction 12h, obtains modified silicasol.
By 1.6g DNS-86 and polysorbate60 (polyoxyethylene sorbitan fatty acid ester emulsifying agent) compound emulsifying agent
(mass ratio: 2:1) is dissolved in 25g deionized water, is divided into three parts: taking 5g as nuclear monomer emulsifier solution, 15g is as shell monomer
Emulsifier solution, residual emulsifier solution mixes as still liquid with modified silicasol.
Monomer pre-emulsification: respectively nuclear monomer emulsifier solution and shell monomer emulsifier solution are added in two wide mouthed bottles,
Stir 15min with the speed of 1500rpm, in two bottles, instill 7g nuclear monomer (methyl methacrylate and propylene the most respectively
Acid butyl ester mass ratio is 1:1) and 23g shell monomer (methyl methacrylate, butyl acrylate, hydroxyethyl methylacrylate and first
Base acrylic acid mass ratio is 2:1:0.1:0.2), after dropping, continue with 1500rpm magnetic agitation 30min, prepare core
Shell pre-emulsion.And 0.25g Ammonium persulfate. is dissolved in 30g deionized water.
Still liquid (residual emulsifier and 39g is added in the four-hole boiling flask being provided with stirring paddle, thermometer, reflux condensing tube
Modified silicasol), and add 0.4g NaHCO3,1.5gN-n-methylolacrylamide and 0.5g methacrylic acid, with 200rpm's
Speed stirs and is warming up to 75 DEG C, is incubated 30min.Contain nuclear monomer pre-emulsion by constant pressure funnel, and at the uniform velocity dropping 10g causes
Agent aqueous solution, time for adding is 30min.Insulation 30min.It is warming up to 81 DEG C, contains shell monomer pre-emulsion by constant pressure funnel, and
At the uniform velocity dropping 21g initiator solution, time for adding is 3h, is incubated 3h.It is cooled to less than 50 DEG C, the pH value being dissolved in ammonia
It is adjusted to about 8, obtains stable hud typed Ludox/polyacrylate dispersion.The silicone content of this emulsion is 20%, emulsion particle grain
Footpath is 75.3nm/PDI=0.321 (Malvern laser particle size analyzer), and emulsion is coated tinplate 120 DEG C baking 15min,
Its photocatalytic coating film slippery, excellent clarity, hardness reaches 5H (GB/T6739-2006), and adhesive force is that 0 grade (GB/T1720-1979) is coated with
Film is soaked in water 20 days do not whiten (GB/T 1733-1993), resistance to neutral salt spray 30 days unchanged (GB/T1771-2007).
Embodiment 6
Emulsion in Example 5 coats tinplate drying and forming-film at room temperature, and its photocatalytic coating film slippery, transparency are excellent
Different, hardness has 4H (GB/T6739-2006), and adhesive force is 0 grade (GB/T1720-1979)；Film is soaked in water 7 days and does not whitens
(GB/T 1733-1993)；Film is resistant to neutral salt spray 8 days unchanged (GB/T1771-2007).
Claims (10)
1. the preparation method of the Ludox/polyacrylate dispersion of a high silicon content, it is characterised in that comprise the steps:
1) take account for ionized water gross mass 10～the deionized water of 30%, water-soluble macromolecule is dissolved in deionized water and makes
Water-soluble macromolecule aqueous solution, mixes water-soluble macromolecule aqueous solution with Ludox, stirs, and obtains water-soluble macromolecule and changes
Property Ludox；
2) using water-soluble macromolecule modified silicasol as still liquid, and add account for emulsifying agent gross mass 1～the emulsifying agent of 40% and
The ionized water gross mass that accounts for 1～the deionized water of 50%, whole pH buffer agents, stirring, mix homogeneously；
3) hydroxy acryl acid ester monomer, acrylic or methacrylic acid monomers, acrylic ester monomer in formula are weighed respectively
Or methacrylate-based monomer, take account for total monomer quality 10～45% monomer mix as nuclear monomer, by remaining monomer
Mixing is as shell monomer；
Take remaining emulsifying agent and mix with the deionized water of account for ionized water gross mass 25～70%, fully dissolve, obtain emulsifying agent
Solution, the emulsifier solution of taking-up 10～30% mass is for emulsifying nuclear monomer, remaining for emulsifying shell monomer；
In the emulsifier solution for emulsifying nuclear monomer, add nuclear monomer, prepare nuclear monomer pre-emulsion；For emulsifying shell
The emulsifier solution of monomer adds shell monomer, prepares shell monomer pre-emulsion；By remaining deionized water dissolving initiator, system
Become initiator solution；
4) by step 2) solution temperature that obtains is increased to 60～90 DEG C, and it is simultaneously added dropwise and accounts for 30～50% initiator solution of mass
With nuclear monomer pre-emulsion, carry out polyreaction, drip complete insulation 15～45min；
5) add remaining initiator solution and shell monomer pre-emulsion, at 70～90 DEG C, proceed polyreaction；Treat shell
The dropping of monomer pre-emulsion is complete, is incubated 1.5～4h, and regulation pH value is 7～8, filters discharging；
Described water-soluble macromolecule is carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl fiber
Element, hydroxyethylmethyl-cellulose, polyvinyl alcohol, Polyethylene Glycol, polyacrylamide, hydrolyzed polyacrylamide, polyvinylpyrrolidine
One or more in ketone, sodium polyacrylate and water soluble starch；
Described hydroxy acryl acid ester monomer is 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate, Hydroxypropyl acrylate, methyl-prop
One or more in other hydroxy acryl acid ester monomers that olefin(e) acid hydroxypropyl acrylate and the art are commonly used；
Described acrylic ester monomer or methacrylate-based monomer are acrylic acid methyl ester., ethyl acrylate, acrylic acid fourth
Ester, methyl methacrylate, ethyl methacrylate, butyl methacrylate, N-Hexyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester
Two or more with in acrylic acid-2-ethyl caproite；
Emulsifying agent, the anionic emulsifying obtained by compounding that is anionic emulsifier and nonionic emulsifier of described emulsifying agent
The mass ratio of agent and nonionic emulsifier is 1～3:1, and wherein anionic emulsifier is selected from allyloxy polyoxyethylene nonyl phenyl second
Alkene ether series, sodium vinyl sulfonate, methallylsulfonic acid sodium, allyloxy hydroxide sodium dimercaptosulphanatein, enuatrol, sodium stearate, ten
One or many in sodium dialkyl sulfate, dodecyl sodium sulfate, dodecylbenzene sodium sulfonate and double dodecylbenzene sodium sulfonate
Kind；Described nonionic emulsifier selects fatty alcohol polyethenoxy ether class, alkylphenol polyoxyethylene class and polyoxyethylene sorbitan
One or more of Span apoplexy due to endogenous wind；
Described water soluble starter is one or both in Ammonium persulfate., potassium peroxydisulfate and sodium peroxydisulfate.
The preparation method of the Ludox/polyacrylate dispersion of high silicon content the most according to claim 1, it is characterised in that
Described pH buffer agent is one or more in sodium bicarbonate, dibastic sodium phosphate and sodium dihydrogen phosphate.
The preparation method of the Ludox/polyacrylate dispersion of high silicon content the most according to claim 1, it is characterised in that
Described nuclear monomer pre-emulsion is prepared via a method which: under the mixing speed of 800～2000rpm, will be used for emulsifying vouching
The emulsifier solution stirring 10～25min of body, drips nuclear monomer, after dropping, continues to stir with 1000-2000rpm rotating speed
20～30min.
The preparation method of the Ludox/polyacrylate dispersion of high silicon content the most according to claim 1, it is characterised in that
Described shell monomer pre-emulsion is prepared via a method which: under the mixing speed of 800～2000rpm, will be used for emulsifying shell list
The emulsifier solution stirring 10～25min of body, drips shell monomer, after dropping, continues to stir with 1000-2000rpm rotating speed
20～30min.
The preparation method of the Ludox/polyacrylate dispersion of high silicon content the most according to claim 1, it is characterised in that
Described dropping account for 30～50% mass initiator solution and the time for adding of nuclear monomer pre-emulsion be 30～90min.
The preparation method of the Ludox/polyacrylate dispersion of high silicon content the most according to claim 1, it is characterised in that
The time of the remaining initiator solution of described addition and shell monomer pre-emulsion is 2.5～3.5h.
The preparation method of the Ludox/polyacrylate dispersion of high silicon content the most according to claim 1, it is characterised in that
Step 1) in be stirred at 30～75 DEG C stirring 6～24h.
The preparation method of the Ludox/polyacrylate dispersion of high silicon content the most according to claim 1, it is characterised in that
Step 5) in pH value by add ammonia regulate.
9. Ludox/the polyacrylate dispersion of a high silicon content, it is characterised in that it is by described in any one of claim 1-8
Preparation method prepares.
Ludox/the polyacrylate dispersion of high silicon content the most according to claim 9, it is characterised in that described silicon is molten
The solid content of glue/polyacrylate dispersion is 25～40%；With SiO2Meter, inorganic silicon accounts for the 5～30% of whole emulsion solid content；
Emulsion appearance is light blue translucent liquid, and latex particle size is 60～100nm；Emulsion infusion process or brushing method are coated on
On glass after washes clean or metal substrate, under the conditions of 120 DEG C, toast 5～30min, the hardness of film obtained reach 5H with
On, adhesive force reaches 0 grade, and film room temperature water soaks and do not whitens for 20 days, and resistance to neutral salt spray 30 days is unchanged.
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585272A (en) * | 2015-10-22 | 2016-05-18 | 湖州绿色建材开发有限公司 | Novel concrete reinforcing agent |
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| CN116715982A (en) * | 2023-06-09 | 2023-09-08 | 江苏苏博特新材料股份有限公司 | Inorganic exterior wall building coating with high color retention and preparation method thereof |
| CN117070115A (en) * | 2023-08-17 | 2023-11-17 | 宁波勤邦新材料科技股份有限公司 | Moisture-heat aging resistant photovoltaic backboard base film and preparation method and preparation device thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649835A (en) * | 2012-04-26 | 2012-08-29 | 华南理工大学 | Organic-inorganic hybrid high-silicon-content acrylic ester emulsion and preparation method thereof |
| CN102731735A (en) * | 2012-06-05 | 2012-10-17 | 华南理工大学 | Organosilicon modified silica sol/polyacrylate composite emulsion and its preparation method |
| CN103304719A (en) * | 2013-07-05 | 2013-09-18 | 广东天龙油墨集团股份有限公司 | Acrylic emulsion and preparation method and application in waterborne polyvinyl chloride (PVC) wallpaper ink thereof |
| CN103554341A (en) * | 2013-10-30 | 2014-02-05 | 华南理工大学 | Low-temperature self-crosslinking acrylate emulsion with core-shell structure as well as preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4517590B2 (en) * | 2003-06-05 | 2010-08-04 | 三菱化学株式会社 | Antifouling agent and antifouling article using the same |
-
2014
- 2014-12-11 CN CN201410764940.8A patent/CN104530302B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649835A (en) * | 2012-04-26 | 2012-08-29 | 华南理工大学 | Organic-inorganic hybrid high-silicon-content acrylic ester emulsion and preparation method thereof |
| CN102731735A (en) * | 2012-06-05 | 2012-10-17 | 华南理工大学 | Organosilicon modified silica sol/polyacrylate composite emulsion and its preparation method |
| CN103304719A (en) * | 2013-07-05 | 2013-09-18 | 广东天龙油墨集团股份有限公司 | Acrylic emulsion and preparation method and application in waterborne polyvinyl chloride (PVC) wallpaper ink thereof |
| CN103554341A (en) * | 2013-10-30 | 2014-02-05 | 华南理工大学 | Low-temperature self-crosslinking acrylate emulsion with core-shell structure as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Facile Fabrication of Superhydrophobic Cotton Fabric from Stearyl Methacrylate Modified Polysiloxane/Silica Nanocomposite";Lifen Hao等;《Fibers and Polymers》;20121130;第13卷(第9期);第1145-1153页 * |
| "纳米二氧化硅/聚丙烯酸酯复合乳液的合成及其涂膜性能";张佼如等;《电镀与涂饰》;20120915;第31卷(第9期);第59-62页 * |
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