CN102659972A - Self-crosslinking nano-SiO2 styrene acrylic composite emulsion and preparation method thereof - Google Patents
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Abstract
The invention discloses a self-crosslinking nano-SiO2 styrene acrylic composite emulsion and a preparation method thereof. The self-crosslinking nano-SiO2 styrene acrylic composite emulsion is a styrene acrylic composite emulsion which is acquired through a self-crosslinking method and contains nano-SiO2. The self-crosslinking nano-SiO2 styrene acrylic composite emulsion is applicable to the paint of coated paper, and has the advantages of a high binding capacity with fibers, a good film forming ability, and good water resistance. When the self-crosslinking nano-SiO2 styrene acrylic composite emulsion is applied to the paint of coated paper, the self-crosslinking nano-SiO2 styrene acrylic composite emulsion can significantly improve surface strength of paper compared with ordinary emulsions, and is a high-performance and environmental protection product which can satisfy the requirement of surface sizing of papermaking paint printing.
Description
Technical field
The present invention relates to a kind of styrene-acrylic composite emulsion that is applied to White Board.
Background technology
Benzene emulsion is nontoxic and have advantages such as higher weathering resistance, pollution resistance and production cost are low because of it, in water-borne coatings such as trade sales coating, floor coating, frie retardant coating and paper tackiness agent, tackiness agent, is used widely.But,,, its range of application is restricted with shortcomings such as basic material bonding force such as cement are not strong because the phenylpropyl alcohol latex film exists that hardness is low, scrub resistance, solvent resistance and thermotolerance are relatively poor.Be distributed in the monomer after inorganic nano particle modified, and make inorganic nano-particle/polymkeric substance composite emulsion, increase substantially emulsion property, widen its Application Areas through emulsion polymerization in situ.
Chinese patent CN101280035A discloses a kind of preparation method of emulsion, and the emulsion applications for preparing is in paper coating, and coating is mobile, but coating back surface strength of paper is relatively poor and the water tolerance of emulsion own is relatively poor on paper.
Summary of the invention
The object of the invention discloses a kind of self-crosslinking nanometer SiO
2Styrene-acrylic composite emulsion and preparation method thereof is to overcome the defective that prior art exists.
Described self-crosslinking nanometer SiO
2Styrene-acrylic composite emulsion contains nanometer SiO for a kind of through what the self-crosslinking method obtained
2Styrene-acrylic composite emulsion;
Said styrene-acrylic composite emulsion comprises the component of following weight part:
Said (methyl) propenoate is selected from vinyl cyanide, methyl acrylate, ethyl propenoate, n-butyl acrylate, NSC 20949, ethyl acrylate, TEB 3K, Jia Jibingxisuanyizhi, n-BMA, methylacrylic acid-2-ethylhexyl, acrylic or methacrylic acid C
8～C
16At least a in the alkyl ester;
Said cross-linking monomer is selected from least a in vinylformic acid-2-hydroxyl ethyl ester, vinylformic acid-2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, the methylacrylic acid-2-hydroxypropyl acrylate; Said promotor is selected from least a in USAF RH-1 ethyl ethylene-urea, the diacetone-acryloamide(DAA).
Said silane coupling agent is selected from γ-An Bingjisanyiyangjiguiwan, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane; γ-(methacryloxypropyl) propyl trimethoxy silicane; γ-mercaptopropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl front three (second) TMOS, two-(the silica-based propyl group of 3-γ-triethoxy) tetrasulfide; N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, one or more in the vinyltrimethoxy silane; Said emulsifying agent is the mixture of anionic emulsifier and nonionic emulsifying agent; Weight ratio is 1: 5～5: 1;
Said initiator is selected from least a in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate;
Said buffer reagent is selected from sodium hydrogencarbonate, yellow soda ash, sodium-acetate or Sodium phosphate, dibasic.
Said alkali aqueous solution is selected from least a in aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, the ammonium hydroxide aqueous solution.
The anionic emulsifier agent is selected from C
10～C
20Sodium alkyl benzene sulfonate, C
10～C
20Sodium alkyl naphthalene sulfonate, C
10～C
20At least a in sodium alkyl sulfate, dialkyl group-2-sodium sulfosuccinate, dicyclohexyl-2-sodium sulfosuccinate, Succinic Acid sodium sulfonate, sodium oleate, potassium oleate, the Emulphor FM;
Nonionic emulsifying agent is selected from Witconol AL 69-66; Anhydrous sorbitol tristearate (this dish 65); Glycol fatty acid ester; Propylene glycol fatty acid ester; Anhydrous sorbitol list hard fatty acid ester (this dish 60); Sorbitan monooleate (span 80); The Diethylene Glycol fatty ester; Anhydrous sorbitol monopalmitate (this dish 40); The polyoxytrimethylene hard fatty acid ester; Sorbitan mono-laurate (this dish 20); The polyoxyethylene hard fatty acid ester; The LAURIC ACID 99 MIN polyoxyethylene ester; Polyoxyethylene (4) anhydrous sorbitol list hard fatty acid ester (tween 61); Polyoxyethylene (5) sorbitan monooleate (sorbimacrogol oleate100); Polyoxyethylene (20) anhydrous sorbitol tristearate (polysorbate65); Polyoxyethylene (20) Witconol AL 69-66 (polysorbate85); The polyoxyethylene monoleate; Fatty alcohol amine polyoxyethylene ether; TX10; The polyoxyethylene mono-laurate; Polyoxyethylene castor oil; Polyoxyethylene (4) sorbitan mono-laurate (tween 21); Polyoxyethylene (20) anhydrous sorbitol list hard fatty acid ester (polysorbate60); Polyoxyethylene (20) sorbitan monooleate (tween 80); Polyoxyethylene (20) anhydrous sorbitol monopalmitate (polysorbate40); At least a in polyoxyethylene (20) sorbitan mono-laurate (polysorbas20).
Said self-crosslinking nanometer SiO
2The method of styrene-acrylic composite emulsion comprises the steps:
(1) nanometer SiO
2Surface-treated:
With nanometer SiO
2, after silane coupling agent water mixed diluting disperses, the pH value is transferred to 2～4 with hydrochloric acid soln, stir 1～3h then; Using weight concentration again is that 28～32% ammonia soln transfers to 9～10 with the pH value, and restir 25～35min filters; Drying, the nanometer SiO of acquisition surface-treated
2
(2) preparation of mix monomer pre-emulsion:
Nanometer SiO with (methyl) propenoate, (methyl) vinylbenzene, (methyl) vinylformic acid, cross-linking monomer, emulsifying agent, surface-treated
2Mix with water, under 20～50 ℃ of temperature, stirred 10～30 minutes, carry out the preparatory emulsification of UW 10～50 minutes again, obtain the mix monomer pre-emulsion;
(3) preparation of seed emulsion:
The emulsifying agent and the water of the mix monomer pre-emulsion of the step (2) of gross weight 5～20%, buffer reagent, gross weight 20～60% are mixed, be warming up to 60 ℃～95 ℃, add the initiator of gross weight 20～50% then, reacted 10～30 minutes, promptly get seed emulsion;
(4) with the mix monomer pre-emulsion of step (2) remainder and the initiator of remainder, in 1～3 hour, splash into simultaneously respectively in the said seed emulsion, 60 ℃～95 ℃ were reacted 1～3 hour;
(5) 50～80 ℃ of insulations 1～2 hour are cooled to 20～30 ℃, and using weight concentration is that 28～32% alkali aqueous solution is neutralized to pH=7～10, filters, and make the weight solid content and be 30～50% self-crosslinking nanometer SiO
2Styrene-acrylic composite emulsion.
Described self-crosslinking nanometer SiO
2Styrene-acrylic composite emulsion can be applicable to coated paper coatings;
The method that the present invention adopts machinery emulsification and the preparatory emulsification of UW to combine prepares the mix monomer pre-emulsion earlier, has improved modification SiO
2With the consistency of acrylic ester monomer, thereby improve the stability of mix monomer pre-emulsion, and then improved nanometer SiO
2The stability of styrene-acrylic composite emulsion, the hydroxyl of introducing, carboxyl isoreactivity group make SiO
2Styrene-acrylic composite emulsion has multiple performances such as bridging property, color stuffing consistency, polarity; Add the thiazolinyl carboxylic acid monomer, obtain the polymer segment of carboxylate-containing, improve the stable dispersion property of emulsion particle in water, thereby reduce the emulsifying agent consumption, improved the water tolerance of filming.Among the present invention, add a small amount of nanometer SiO
2, unexpected, be applied to obviously improve the surface strength of paper in the coating of White Board.This maybe because, the compound nano silicon can act on the mineral dyes such as lime carbonate in the coating mutually in benzene emulsion, and the bonding force of styrene-acrylic latex and paper fibre is stronger, plays the crosslinked effect of building bridge, the effect of raising benzene emulsion.
Said self-crosslinking nanometer SiO
2Styrene-acrylic composite emulsion has with fibrous binding force higher, good film-forming properties and water tolerance advantage.Be applied to the coating of White Board, compare, can obviously improve the surface strength of paper, can satisfy the papermaking paint printing with the product of top sizing with high-performance, environmental protection for a kind of with ordinary emulsion.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Embodiment 1
With 10g nanometer SiO
2With γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane of 0.1g with the dilution of 100g water, stirrer stir down blending dispersion evenly after, using weight concentration is that 10% hydrochloric acid soln transfers to 3 with the pH value, stirs 2h then; Using weight concentration again is that 32% ammonia soln transfers to 10 with the pH value, and the about 30min of restir puts into 80 ℃ baking oven after the filtration, dry for use;
Mixture with 20g n-butyl acrylate, 74g vinylbenzene and 6g vinylformic acid, 2g 2-hydroxyethyl methacrylate are formed adds 0.25g X 2073,0.1g polyoxyethylene (20) sorbitan monooleate (tween 80), 1g modified Nano SiO
2In the mixed aqueous solution of the composition of 60g deionized water, and then JB90-D type powerful motor stirs on the machine, stirs 30 minutes with the rotating speed of 1000rpm, obtains monomer pre-emulsion;
In the four-hole bottle that 0.2g sodium hydrogencarbonate, 0.25g X 2073,0.1g polyoxyethylene (20) sorbitan monooleate (tween 80), 90g deionized water are housed, add the above-mentioned pre-emulsion of 15g; Be warmed up to 60 ℃, add the aqueous solution that the 0.1g Potassium Persulphate is dissolved in the 10g deionized water, react to emulsion change basket; Drip the aqueous solution of remaining pre-emulsion and 0.3g Potassium Persulphate simultaneously; After 3h drips off, be incubated 1 hour, be cooled to room temperature after; Add weight concentration and be 32% ammoniacal liquor and regulate and be neutralized to pH=10, filter and promptly get ambient self-crosslinking nanometer SiO
2Styrene-acrylic composite emulsion.
Embodiment 2
With 10g nanometer SiO
2With γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane of 0.1g with the dilution of 100g water, stirrer stir down blending dispersion evenly after, using weight concentration is that 10% hydrochloric acid soln transfers to 3 with the pH value, stirs 2h then; Ammonia soln with weight concentration 32% transfers to 9 with the pH value again, and the about 30min of restir puts into 80 ℃ baking oven after the filtration, dries for use.
Mixture with 40g ethyl propenoate, 50g vinyl toluene and 10g methylacrylic acid, 1g vinylformic acid-2-hydroxyl ethyl ester composition; Add 0.1g dialkyl group-2-sodium sulfosuccinate; 0.4g in the mixed aqueous solution of the composition of sorbitan mono-laurate (this dish 20), 1.5g polyoxyethylene monoleate, 1g modified Nano SiO2 and 60g deionized water; And then JB90-D type powerful motor stirs on the machine, stirs 30 minutes with the rotating speed of 1500rpm, obtains monomer pre-emulsion.
In the four-hole bottle that 0.3g sodium hydrogencarbonate, 1.5g dodecyl sodium naphthalene sulfonate, 1g sorbitan mono-laurate (this dish 20), 90g deionized water are housed, add the above-mentioned pre-emulsion of 15g; Be warmed up to 95 ℃, add the aqueous solution that the 1g Potassium Persulphate is dissolved in the 10g deionized water, react to emulsion change basket; Drip the aqueous solution of remaining pre-emulsion and 3g Potassium Persulphate simultaneously; After 1h drips off, 80 ℃ the insulation 1 hour, be cooled to room temperature after; Add weight concentration and be 32% ammoniacal liquor and regulate and be neutralized to pH=7, filter and promptly get ambient self-crosslinking nanometer SiO
2Styrene-acrylic composite emulsion.
Embodiment 3
With 10g nanometer SiO
2With γ-(methacryloxypropyl) propyl trimethoxy silicane of 0.1g with the dilution of 100g water, stirrer stir down blending dispersion evenly after, using weight concentration is that 10% hydrochloric acid soln transfers to 3 with the pH value, stirs 2h then; Using weight concentration again is that 32% ammonia soln transfers to 10 with the pH value, and the about 30min of restir puts into 80 ℃ baking oven after the filtration, dry for use.
Mixture with 10g TEB 3K, 34g ethyl acrylate, 48g vinyl toluene and 8g methylacrylic acid, 1.5g methylacrylic acid-2-hydroxypropyl acrylate composition; Add 0.1g Succinic Acid sodium sulfonate; 0.2g polyoxytrimethylene hard fatty acid ester, 0.5g sodium lauryl sulphate; 0.2g in the mixed aqueous solution of the composition of sorbitan monooleate (span 80), 2g modified Nano SiO2 and 60g deionized water; And then JB90-D type powerful motor stirs on the machine, stirs 20 minutes with the rotating speed of 2000rpm, obtains monomer pre-emulsion.In the four-hole bottle that 0.2g sodium hydrogencarbonate, 0.2g potassium oleate, 0.8g Diethylene Glycol fatty ester, 0.3g sodium lauryl sulphate, 90g deionized water are housed, add the above-mentioned pre-emulsion of 15g; Be warmed up to 75 ℃, add the aqueous solution that the 0.8g Potassium Persulphate is dissolved in the 10g deionized water, react to emulsion change basket; Drip the aqueous solution of remaining pre-emulsion and 1.5g Potassium Persulphate simultaneously; 1.5h after dripping off, be incubated 1 hour, be cooled to room temperature after; Add weight concentration and be 32% ammoniacal liquor and regulate and be neutralized to pH=8, filter and promptly get ambient self-crosslinking nanometer SiO
2Styrene-acrylic composite emulsion.
Embodiment 4
Comparative Examples: the emulsion of pressing the method preparation of CN101280035A
With embodiment 1～3 and Comparative Examples, by following formulated coating
95 grades of water-ground limestone 400g
Brazil china clay 100g
Emulsion (dry weight) 50g
Deionized water is an amount of, and adjustment coating weight solid content is 65%.
Experimentation: 1) 95 grades of water-ground limestones, Brazilian china clay and appropriate amount of deionized water are added high speed dispersor, the back high speed dispersion 20～30min that stirs, qualified to fineness, low speed adds emulsion down, after stirring, discharging, 100 eye mesh screens filter.2) will adopt embodiment 1～5 with Comparative Examples emulsion coatings formulated with the 10# spreading rod at 75g/m
2Be coated with glue spread 20g/m on the art base paper
2, subsequent use.3) coating rolling condition: get above-mentioned coating pattern respectively with twice of the hard press polish of small-sized rolling press (0.3Mpa, 85 ℃).Subsequent use.
A) adopt IGT printability appearance (Japanese KRK) to detect above-mentioned White Board:
Criterion: surface strength shows that more greatly the emulsion effect is good more
| Surface strength m/s | |
| Comparative Examples | 0.65 |
| Embodiment 1 | 0.95 |
| Embodiment 2 | 0.97 |
| Embodiment 3 | 0.91 |
B) the emulsion water tolerance detects
Criterion: filming bleaches from transparent gradually, the water tolerance variation
Emulsion water tolerance detection method: with deionized water emulsion is diluted to 30%, coating one deck emulsion on clean sheet glass is then 25 ℃, the fixed temperature and humidity condition held of relative humidity 60% 24 hours.Afterwards the sheet glass of coating being put into deionized water observes.Every state of observing primary coating after a while.
| Sample | 24 hours | 48 hours |
| Comparative Examples | Become blue | Bleach |
| Embodiment 1 | No change | The slight indigo plant that becomes |
| Embodiment 2 | No change | The slight indigo plant that becomes |
| Embodiment 3 | No change | The slight indigo plant that becomes |
Can find out from above-mentioned application result: use the self-crosslinking nanometer SiO2 styrene-acrylic composite emulsion of the embodiment of the invention 1～3 preparation, compare, be applied to the coating of White Board, can significantly improve the surface strength of White Board, and water tolerance is better with Comparative Examples.
Claims (6)
1. self-crosslinking nanometer SiO
2Styrene-acrylic composite emulsion is characterized in that, contains nanometer SiO for a kind of through what the self-crosslinking method obtained
2Styrene-acrylic composite emulsion.
2. self-crosslinking nanometer SiO
2Styrene-acrylic composite emulsion is characterized in that, comprises the component of following weight part:
3. self-crosslinking nanometer SiO according to claim 2
2Styrene-acrylic composite emulsion; It is characterized in that said (methyl) propenoate is selected from vinyl cyanide, methyl acrylate, ethyl propenoate, n-butyl acrylate, NSC 20949, ethyl acrylate, TEB 3K, Jia Jibingxisuanyizhi, n-BMA, methylacrylic acid-2-ethylhexyl, acrylic or methacrylic acid C
8～C
16At least a in the alkyl ester;
Said cross-linking monomer is selected from least a in vinylformic acid-2-hydroxyl ethyl ester, vinylformic acid-2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, the methylacrylic acid-2-hydroxypropyl acrylate; Said promotor is selected from least a in USAF RH-1 ethyl ethylene-urea, the diacetone-acryloamide(DAA).
4. self-crosslinking nanometer SiO according to claim 3
2Styrene-acrylic composite emulsion is characterized in that, said silane coupling agent is selected from γ-An Bingjisanyiyangjiguiwan; γ-(2; 3-epoxy third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane; N-(β-aminoethyl)-γ-aminopropyl front three (second) TMOS; Two-(the silica-based propyl group of 3-γ-triethoxy) tetrasulfide, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, one or more in the vinyltrimethoxy silane; Said emulsifying agent is the mixture of anionic emulsifier and nonionic emulsifying agent; Weight ratio is 1: 5～5: 1;
Said initiator is selected from least a in Potassium Persulphate, Sodium Persulfate, the ammonium persulphate;
Said buffer reagent is selected from sodium hydrogencarbonate, yellow soda ash, sodium-acetate or Sodium phosphate, dibasic;
Said alkali aqueous solution is selected from least a in aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, the ammonium hydroxide aqueous solution.
5. self-crosslinking nanometer SiO according to claim 4
2Styrene-acrylic composite emulsion is characterized in that, the anionic emulsifier agent is selected from C
10～C
20Sodium alkyl benzene sulfonate, C
10～C
20Sodium alkyl naphthalene sulfonate, C
10～C
20At least a in sodium alkyl sulfate, dialkyl group-2-sodium sulfosuccinate, dicyclohexyl-2-sodium sulfosuccinate, Succinic Acid sodium sulfonate, sodium oleate, potassium oleate, the Emulphor FM;
Nonionic emulsifying agent is selected from Witconol AL 69-66; Anhydrous sorbitol tristearate (this dish 65); Glycol fatty acid ester; Propylene glycol fatty acid ester; Anhydrous sorbitol list hard fatty acid ester (this dish 60); Sorbitan monooleate (span 80); The Diethylene Glycol fatty ester; Anhydrous sorbitol monopalmitate (this dish 40); The polyoxytrimethylene hard fatty acid ester; Sorbitan mono-laurate (this dish 20); The polyoxyethylene hard fatty acid ester; The LAURIC ACID 99 MIN polyoxyethylene ester; Polyoxyethylene (4) anhydrous sorbitol list hard fatty acid ester (tween 61); Polyoxyethylene (5) sorbitan monooleate (sorbimacrogol oleate100); Polyoxyethylene (20) anhydrous sorbitol tristearate (polysorbate65); Polyoxyethylene (20) Witconol AL 69-66 (polysorbate85); The polyoxyethylene monoleate; Fatty alcohol amine polyoxyethylene ether; TX10; The polyoxyethylene mono-laurate; Polyoxyethylene castor oil; Polyoxyethylene (4) sorbitan mono-laurate (tween 21); Polyoxyethylene (20) anhydrous sorbitol list hard fatty acid ester (polysorbate60); Polyoxyethylene (20) sorbitan monooleate (tween 80); Polyoxyethylene (20) anhydrous sorbitol monopalmitate (polysorbate40); At least a in polyoxyethylene (20) sorbitan mono-laurate (polysorbas20).
6. prepare each described self-crosslinking nanometer SiO of claim 1～5
2The method of styrene-acrylic composite emulsion comprises the steps:
(1) nanometer SiO
2Surface-treated:
With nanometer SiO
2, after silane coupling agent water mixed diluting disperses, pH value is transferred to 2～4 with hydrochloric acid soln, stir 1～3h then, with ammonia soln pH value is transferred to 9～10 again, restir 25～35min, filtration, drying, the nanometer SiO of acquisition surface-treated
2
(2) preparation of mix monomer pre-emulsion:
Nanometer SiO with (methyl) propenoate, (methyl) vinylbenzene, (methyl) vinylformic acid, cross-linking monomer, emulsifying agent, surface-treated
2Mix with water, under 20～50 ℃ of temperature, stirred 10～30 minutes, carry out the preparatory emulsification of UW 10～50 minutes again, obtain the mix monomer pre-emulsion;
(3) preparation of seed emulsion:
The emulsifying agent and the water of the mix monomer pre-emulsion of the step (2) of gross weight 5～20%, buffer reagent, gross weight 20～60% are mixed, be warming up to 60 ℃～95 ℃, add the initiator of gross weight 20～50% then, reacted 10～30 minutes, promptly get seed emulsion;
(4) with the mix monomer pre-emulsion of step (2) remainder and the initiator of remainder, in 1～3 hour, splash into simultaneously respectively in the said seed emulsion, 60 ℃～95 ℃ were reacted 1～3 hour;
(5) 50～80 ℃ of insulations 1～2 hour are cooled to 20～30 ℃, and using weight concentration is that 28～32% alkali aqueous solution is neutralized to pH=7～10, filters, and make the weight solid content and be 30～50% self-crosslinking nanometer SiO
2Styrene-acrylic composite emulsion.
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