CN106947030B - POSS base hydridization polyacrylate dispersion and the preparation method and application thereof - Google Patents
POSS base hydridization polyacrylate dispersion and the preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/022—Emulsions, e.g. oil in water
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
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Abstract
The present invention relates to a kind of POSS base hydridization polyacrylate dispersions and the preparation method and application thereof.POSS base hydridization polyacrylate dispersion of the present invention, formula comprise the following components in parts by weight raw material: 95~120 parts of deionized water, 155.1~190.95 parts of nuclear monomer pre-emulsion, 80.9~106.8 parts of shell monomer pre-emulsion, 18~54 parts of initiator.The aqueous woodware paint that the present invention is prepared using POSS base hydridization polyacrylate dispersion as film forming binder, hardness height, good luster, richness height, scratch resistance, anti-after tack and excellent water resistance, prepared product processes are simple, cost performance is high, it has good workability, there are very high application value and market prospects.
Description
Technical field
The present invention relates to macromolecule material preparation area, in particular to a kind of POSS base hydridization polyacrylate dispersion and its
Preparation method and application.
Background technique
As environmental protection is paid more and more attention increasingly strict with environmental regulation, have to traditional solvent type coating volatility
The limitation of machine compound (VOC) and hazardous air pollutants (HAP) discharge, coatings industry is gradually to greenization, functionalization side
To development, developing high-performance water-based resin material becomes the emphasis and hot spot of coatings industry development.
Domestic interior decoration and furniture market cause serious interior still based on solvent wood coatings at present
Environmental pollution, promoting the use of aqueous woodware paint is the main path for solving room air pollution.It is single-component water-based currently on the market
Woodcare paint is mainly using aqueous pure acrylate lotion, aqueous polyurethane dispersing liquid, polymerization of acrylic modified polyurethane as film forming matter.
But the problem of the generally existing hardness of film of the said goods, scratch resistance and anti-after tack performance deficiency, constrain aqueous wooden ware
Coating promotion and application.So improving water-borne wood coating hardness of paint film, damage resistant type and anti-after tack is current aqueous wooden ware
Coating critical issue anxious to be resolved.
Acrylic acid ester emulsion has many advantages, such as that pollution-free, at low cost, filming performance is good, the weatherability of latex film, flexible
The function admirables such as property, adhesive force, have obtained relatively broad application, but its latex in fields such as building, automobile, packaging, printings
Heat resistance, the hardness of film etc. are poor, limit its application to a certain extent.To it is acrylic acid modified there are many ways to, than if any
Polyester modification, it is organic-silicon-modified, it is epoxy-modified, it is alkyd modified, it is polyurethane-modified etc..Organosilicon have excellent water resistance,
The features such as resistant of high or low temperature, surface can be low.In aqueous acrylic emulsion polymerization, organic silicon monomer modification by copolymerization is introduced, it can be with
The crosslink density of latex film is improved, so as to improve the comprehensive performance (hardness, water resistance, salt fog resistance etc.) of film.Cage model sesquialter
Siloxanes POSS (Polyhedral OligomericSilsesquioxane) is that skeleton symbol is (RSiO1.5) n (n >=4)
Compound, R group can be the functional groups such as hydrogen atom, alkyl, alkenyl, amino, aryl in molecule.Cage-type silsesquioxane is one
The functional form organosilicon polymeric monomer of kind nanoscale three-dimensional structure, can significantly improve the physical and mechanical property of polymer.
Such as Chinese invention patent (CN 101875707A) discloses a kind of preparation of fluorin-containing POSS acrylate polymer
Method and coating containing the fluorin-containing POSS acrylate polymer, by controlling the addition sequence of fluorinated acrylate monomer,
The fluorin-containing POSS acrylate polymer that fluorinated acrylate structural unit is distributed in copolymer both ends is obtained, obtained coating
With low-surface-energy, high antifouling capacity.
Such as Chinese invention patent (CN103923248A) inventor utilizes methacryloxy cagelike silsesquioxane,
Under the action of conventional emulsifier dodecyl sodium sulfate, third is prepared for styrene, methyl methacrylate, butyl acrylate
Olefin(e) acid ester lotion.
Low molecule or conventional emulsifier that emulsion polymerization generally uses at present, generally all have stronger water imbibition and easily
The shortcomings that flocculation, so that the water resistance to emulsion film generates large effect.Therefore it is badly in need of developing a kind of comprehensive performance
Good POSS base hydridization polyacrylate dispersion.
Summary of the invention
In order to solve the above-mentioned problems in the prior art, the present invention has synthesized a kind of good POSS base of comprehensive performance
Hydridization polyacrylate dispersion.
Technical purpose of the invention is achieved through the following technical solutions: POSS base hydridization poly- third of the present invention
Olefin(e) acid ester lotion, formula comprise the following components in parts by weight raw material: 95~120 parts of deionized water, nuclear monomer pre-emulsion
155.1~190.95 parts, 80.9~106.8 parts of shell monomer pre-emulsion, 18~54 parts of initiator.
Further, the nuclear monomer pre-emulsion includes following raw material component: stratum nucleare acrylate to the present invention
121.5~151.8 parts of class monomer, 1.8~4.5 parts of POSS base reactive emulsifier, 25~38 parts of deionized water.
Further, the shell monomer pre-emulsion includes following raw material component: shell acrylic acid to the present invention
45.7~81 parts of esters monomer, 2~7.2 parts of POSS base acrylate monomer, 1~3 part of POSS base reactive emulsifier, deionization
18~27 parts of water.
Preferably, the molecular formula of the POSS base reactive emulsifier is (C to the present invention21H40NO)8(SiO1.5)8, structure
Formula are as follows:
Wherein R1For
The POSS base acrylate monomer can be methacryloxypropyl cage-type silsesquioxane, commercial products.Its
Molecular formula is (C7H11O2)8(SiO1.5)8Or (C6H9O2)8(SiO1.5)8, structural formula are as follows:
Wherein,
The present invention specifically, the preparation of the POSS base reactive emulsifier the following steps are included:
The preparation of S1:POSS-Cl solid: by r-chloropropyl trimethoxyl silane, concentrated hydrochloric acid (mass fraction be 30~36%) and
Methanol is 40g in 35~40 DEG C of 70~72h of back flow reaction, the r-chloropropyl trimethoxyl silane, concentrated hydrochloric acid and methanol usage ratio:
30ml~35ml:150ml~200ml is filtered, washing, recrystallization, drying；
S2: by POSS-Cl solid, oleamide and n,N-Dimethylformamide obtained by step S1,95~100 DEG C of reflux are anti-
5~6h is answered, the POSS-Cl solid, oleamide and N,N-dimethylformamide amount ratio are 160g:320~360g:
200ml~300ml, then remove n,N-Dimethylformamide obtain milky wax solid product to get.
Preferably, recrystallization uses ethyl acetate/petroleum ether mixed liquor to the present invention in the step S1, and mixed proportion is
VEthyl acetate:VPetroleum ether=1:6.Preferably, the stratum nucleare acrylic ester monomer is selected from methacrylic acid, methacrylic acid to the present invention
Methyl esters, ethyl methacrylate, butyl methacrylate, acrylic acid, methyl acrylate, ethyl acrylate, in butyl acrylate
Two or more combinations.Preferably, the initiator is potassium peroxydisulfate or ammonium persulfate.
Further, the shell acrylic ester monomer is the mixing of first kind monomer and the second class monomer to the present invention
Object, the first kind monomer are selected from butyl acrylate, ethyl acrylate, n-octyl, Isooctyl acrylate monomer, metering system
The different monooctyl ester of acid, lauryl ester, methyl acrylate, methyl methacrylate, ethyl methacrylate, metering system
It is two or more in sour N-butyl；The second class monomer is selected from Diacetone Acrylamide and acrylic acid, methacrylic acid, methyl
One or more of hydroxypropyl acrylate, trimethylolpropane trimethacrylate.Preferably, it is preferable that described first
The weight part ratio of the pre- second class monomer of class monomer is 45~75:0.7~2.7.
Another technical object of the present invention is to provide a kind of preparation methods of POSS base hydridization polyacrylate dispersion, including
Following steps:
S1: nuclear monomer pre-emulsion: 25~38 parts of deionized waters and 1.8~4.5 parts of POSS base reactive emulsifiers are stirred
10~20min of dispersion is mixed, 121.5~151.8 parts of stratum nucleare acrylic ester monomers are then added, continue 20~30min of stirring, i.e.,
?；
S2: the preparation of shell monomer pre-emulsion: by 18~27 parts of deionized waters and 1~3 part of POSS base reactive emulsifier
After being dispersed with stirring 10~20min, 2~7.2 parts of POSS base acrylate monomers and 45.7~81 parts of shell esters of acrylic acid are added
Monomer continues 20~30min of stirring to obtain the final product；
The preparation of S3:POSS base hydridization polyacrylate dispersion: by nuclear monomer pre-emulsion total weight 10 obtained by step S1
~20% nuclear monomer pre-emulsion and the initiator of initiator total weight 25~35% are warming up to 50~60 DEG C, and heat preservation 20~
40min；70~80 DEG C are then heated to, the initiation of remaining nuclear monomer pre-emulsion and initiator total weight 25~35% is added dropwise
Agent, 2~3h are added dropwise, then are warming up to 85 DEG C of 0.5~1.0h of heat preservation；Then shell monomer pre-emulsion obtained by a dropping step S2 and
Remaining initiator, 1~2h are added dropwise, and then 0.5~1h of heat preservation under the conditions of 85~90 DEG C to obtain the final product.
Another technical object of the present invention is to provide a kind of containing the preparation of above-mentioned POSS base hydridization polyacrylate dispersion
Aqueous woodware paint coating, includes the raw material components of following parts by weight: 80~100 parts of polyacrylate dispersion of POSS base hydridization；Wetting
0.2~0.6 part of agent；0.1~0.5 part of defoaming agent；3~5 parts of coalescing agent；0.2~0.5 part of levelling agent；Thickener 0.3~0.8
Part.
The present invention preferably, the wetting agent be selected from TEGO Wet 270, TEGO Wet 500, TEGO Twin 4000,
The mixing of one or more of BYK346, BYK2010, BYK2015；Preferably, the defoaming agent is selected from TEGO
The mixing of one or more of Airex 902W, TEGO Foamex 825, BYK093, BYK019, BYK022；It is preferred that
Ground, the coalescing agent are selected from alcohol ester-12, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol methyl ether and ethylene glycol
The mixing of one or more of monobutyl ether；Preferably, the levelling agent is BYK-333, BYK-349, TEGO Rad
One or more of 2200N, TEGO Glide 410 and TEGO Glide 440 combination；Preferably, the thickener
Selected from TEGO ViscoPlus 3060, TEGO ViscoPlus 3030, TEGO ViscoPlus 3010, BYK425, RM-8W
With one or more of RM-12W mixing.
Another technical purpose of the present invention is to provide the preparation method of above-mentioned aqueous woodware paint coating, comprising the following steps:
1), each raw material component is weighed by formula ratio；
2) the POSS base hydridization polyacrylate cream, is added in the wetting agent, the defoaming agent under agitation
In liquid, stir 5~10 minutes；
3), then by after mixing the coalescing agent be added 2) gained mixture at 400~600rpm of revolving speed after
Continuous stirring 5~10 minutes；Sequentially add the levelling agent and the thickener, disperse 5~10 minutes to get.
Technical solution of the present invention compared with prior art, has the following beneficial effects:
1, the present invention uses monomer pre-emulsification semi-continuous seed emulsion polymerization technique, with the replacement of POSS base reactive emulsifier
Conventional emulsifier introduces functionality POSS base acrylate monomer in shell, synthesizes the good POSS base hydridization of comprehensive performance
Polyacrylate dispersion significantly improves hardness, scratch resistance, anti-after tack and the water-fast, solvent resistant and stain resistant of latex film
Etc. performances.
2, simple production process of the present invention, cost performance is high, has good workability, resulting single-component water-based woodcare paint hardness
Height, scratch resistance, anti-after tack and excellent water resistance have very high application value and market prospects.
Specific embodiment
In order to make the object, technical solutions and advantages of the present invention definitely, below to the preferred embodiment of the present invention into
The detailed description of row.
The preparation of 1 POSS base reactive emulsifier of embodiment
The specific step of preparation process of the POSS base reactive emulsifier (OA-POSS) is as follows:
1, equipped with thermometer, reflux condensing tube three-necked flask in be added 40.0g r-chloropropyl trimethoxyl silane,
30.0ml concentrated hydrochloric acid and 200ml methanol, 40 DEG C of back flow reaction 72h, suction filtration are washed 2~3 times with 50~100ml methanol, are used in combination
60ml ethyl acetate/petroleum ether (VEthyl acetate:VPetroleum ether=1:6) mixed liquor recrystallization, 50 DEG C of vacuum drying obtain white solid for 24 hours
POSS-Cl。
2, equipped with thermometer, reflux condensing tube three-necked flask in be added 160gPOSS-Cl, 346.2g oleamide and
N,N-Dimethylformamide is removed under reduced pressure after reaction and obtains by 200mlN, dinethylformamide, 100 DEG C of back flow reaction 6h
Milky wax solid product POSS base reactive emulsifier (OA-POSS).POSS base reactive emulsifier molecular formula is
(C21H40NO)8(SiO1.5)8, structural formula is as follows:
Wherein R1For
Embodiment 2
One, the preparation of POSS base hydridization polyacrylate dispersion
1. the preparation of nuclear monomer pre-emulsion
After addition 30.0g deionized water and 4.5g OA-POSS are dispersed with stirring 15min in four-hole boiling flask, 40.0g is added
Methyl methacrylate, 80.0g butyl acrylate and 2.0g acrylic acid continue stirring 20min and obtain nuclear monomer pre-emulsion.
2. the preparation of shell monomer pre-emulsion
After addition 20.0g deionized water and 3.0g OA-POSS are dispersed with stirring 15min in four-hole boiling flask, 2.0g first is added
Base acryloxypropyl cage-type silsesquioxane, 60.0g methyl methacrylate, 20.0g butyl acrylate and 1.0g acrylic acid,
Continue stirring 20min and obtains shell monomer pre-emulsion.
The preparation of 3.POSS base hydridization polyacrylate dispersion
100.0g deionized water, 30.0g nuclear monomer are added in the four-hole boiling flask that blender, condenser pipe, thermometer are housed
The potassium peroxydisulfate of pre-emulsion and 12.0g are warming up to 60 DEG C of heat preservation 20min, and it is pre- to then heat to 80 DEG C of remaining nuclear monomers of dropwise addition
The potassium peroxydisulfate of emulsion and 12.0g, 2h are added dropwise, and are warming up to 85 DEG C of heat preservation 0.5h.Be added dropwise shell monomer pre-emulsion and
The potassium peroxydisulfate of 16.0g1%, 2h are added dropwise, and then heat to 90 DEG C of heat preservation 0.5h, obtain POSS base hydridization polyacrylate
Lotion.
Two, using the preparation method for preparing aqueous woodware paint of POSS base hydridization polyacrylate dispersion
By above-mentioned POSS base hydridization polyacrylate dispersion 100.0g, in the case where 400rpm stirs humidity, the lower 0.3g that is added is soaked
Agent TEGO Twin 4000 and 0.5g defoaming agent TEGO Airex 920 is stirred 5 minutes, then by 5.0g coalescing agent ethylene glycol
Butyl ether addition continues stirring 5 minutes；Sequentially add 0.2g levelling agent TEGO Rad 2200N and 0.8g thickener TEGO
ViscoPlus 3060, continues to be dispersed with stirring 10 minutes and obtains aqueous woodware paint.
Three, the performance detection of aqueous woodware paint as described in example 2
Test performance after being placed at room temperature for 7 days according to GBT 23999-2009 film, paint film correlated performance test result are shown in Table
1。
Embodiment 3
One, the preparation of POSS base hydridization polyacrylate dispersion
1. the preparation of nuclear monomer pre-emulsion
After addition 30.0g deionized water and 3.6g OA-POSS are dispersed with stirring 10min in four-hole boiling flask, 35.0g is added
Methyl methacrylate, 85.0g butyl acrylate and 1.5g acrylic acid continue stirring 25min and obtain nuclear monomer pre-emulsion.
2. the preparation of shell monomer pre-emulsion
After addition 18.0g deionized water and 2.1g OA-POSS are dispersed with stirring 10min in four-hole boiling flask, 3.8g first is added
Base acryloxypropyl cage-type silsesquioxane, 50.0g methyl methacrylate, 20.0g butyl acrylate, 2g acrylic acid hydroxyl second
Ester and 1.5g acrylic acid continue stirring 25min and obtain shell monomer pre-emulsion.
The preparation of 3.POSS base hydridization polyacrylate dispersion
120.0g deionized water, 25.0g nuclear monomer are added in the four-hole boiling flask that blender, condenser pipe, thermometer are housed
The potassium peroxydisulfate of pre-emulsion and 15.0g1% are warming up to 50 DEG C of heat preservation 40min, then heat to 75 DEG C, remaining vouching is added dropwise
The potassium peroxydisulfate of body pre-emulsion and 15.0g, 2.5h are added dropwise, and are warming up to 85 DEG C of heat preservation 0.5h.It is pre- to continue dropwise addition shell monomer
The potassium peroxydisulfate of emulsion and 18.0g, 1.5h are added dropwise, and then heat to 88 DEG C of heat preservation 1h, obtain POSS base hydridization poly- third
Olefin(e) acid ester lotion.
Two, using the preparation method for preparing aqueous woodware paint of POSS base hydridization polyacrylate dispersion
By above-mentioned POSS base hydridization polyacrylate dispersion 100.0g, in the case where 400rpm stirs humidity, the lower 0.5g that is added is soaked
Agent BYK346 and 0.3g defoaming agent BYK093 is stirred 5 minutes, then 5.0g coalescing agent dipropylene glycol monomethyl ether is added and continues
Stirring 5 minutes；0.3g levelling agent BYK333 and 0.4g thickener BYK420 is sequentially added, continues to be dispersed with stirring 10 minutes and obtains
Aqueous woodware paint.
Three, the performance detection of aqueous woodware paint described in embodiment 3
Test performance after being placed at room temperature for 7 days according to GBT 23999-2009 film, paint film correlated performance test result are shown in Table
1。
Embodiment 4
One, the preparation of POSS base hydridization polyacrylate dispersion
1. the preparation of nuclear monomer pre-emulsion
After addition 35.0g deionized water and 3.0gOA-POSS are dispersed with stirring 20min in four-hole boiling flask, 37.5g first is added
Base methyl acrylate, 112.5g butyl acrylate and 1.8g acrylic acid continue stirring 25min and obtain nuclear monomer pre-emulsion.
2. the preparation of shell monomer pre-emulsion
After addition 22.0g deionized water and 1.5g OA-POSS are dispersed with stirring 20min in four-hole boiling flask, 5.6g first is added
Base acryloxypropyl cage-type silsesquioxane, 60.0g methyl methacrylate, 15.0g butyl acrylate, 1.5g metering system
Sour hydroxypropyl acrylate and 1.2g acrylic acid continue stirring 25min and obtain shell monomer pre-emulsion.
The preparation of 3.POSS base hydridization polyacrylate dispersion
110.0g deionized water, 20.0g nuclear monomer are added in the four-hole boiling flask that blender, condenser pipe, thermometer are housed
The potassium peroxydisulfate of pre-emulsion and 18.0g are warming up to 55 DEG C of heat preservation 30min, and it is pre- to then heat to 70 DEG C of remaining nuclear monomers of dropwise addition
The potassium peroxydisulfate of emulsion and 18.0g, 3h are added dropwise, and are warming up to 85 DEG C of heat preservation 0.5h.Be added dropwise shell monomer pre-emulsion and
The potassium peroxydisulfate of 18.0g, 1.5h are added dropwise, and then heat to 88 DEG C of 1h, obtain POSS base hydridization polyacrylate dispersion.
Two, using the preparation method for preparing aqueous woodware paint of POSS base hydridization polyacrylate dispersion
By above-mentioned POSS base hydridization polyacrylate dispersion 100.0g, in the case where 400rpm stirs humidity, the lower 0.4g that is added is soaked
Agent TEGO Wet 270,0.2g defoaming agent TEGO Foamex825 are stirred 5 minutes, then by 5.0g coalescing agent tripropylene glycol
N-butyl ether addition continues stirring 5 minutes；0.5g levelling agent TEGO Glide 410 and 0.6g thickener BYK425 is sequentially added,
Continue to be dispersed with stirring 10 minutes and obtains aqueous woodware paint.
Three, the performance detection of aqueous woodware paint as described in example 4
Test performance after being placed at room temperature for 7 days according to GBT 23999-2009 film, paint film correlated performance test result are shown in Table
1。
Embodiment 5
One, the preparation of POSS base hydridization polyacrylate dispersion
1. the preparation of nuclear monomer pre-emulsion
After addition 38.0g deionized water and 2.75g OA-POSS are dispersed with stirring 15min in four-hole boiling flask, 33.0g is added
Methyl methacrylate, 117.0g butyl acrylate and 1.2g acrylic acid continue stirring 25min and obtain nuclear monomer pre-emulsion.
2. the preparation of shell monomer pre-emulsion
After addition 18.0g deionized water and 1.5g OA-POSS are dispersed with stirring 15min in four-hole boiling flask, 6.0g third is added
Alkene monomethacryloxypropyl cage-type silsesquioxane, 40.0g methyl methacrylate, 20.0g butyl acrylate and 0.8g acrylic acid continue
Stirring 25min obtains shell monomer pre-emulsion.
The preparation of 3.POSS base hydridization polyacrylate dispersion
105.0g deionized water, 35.0g nuclear monomer are added in the four-hole boiling flask that blender, condenser pipe, thermometer are housed
The ammonium persulfate of pre-emulsion and 12.0g are warming up to 55 DEG C of heat preservation 30min, and it is pre- to then heat to 70 DEG C of remaining nuclear monomers of dropwise addition
The ammonium persulfate of emulsion and 12.0g, 3h are added dropwise, and are warming up to 85 DEG C of heat preservation 0.5h.Be added dropwise shell monomer pre-emulsion and
The ammonium persulfate of 12.0g, 1h are added dropwise, and then heat to 90 DEG C of 0.5h, obtain POSS base hydridization polyacrylate dispersion.
Two, using the preparation method for preparing aqueous woodware paint of POSS base hydridization polyacrylate dispersion
By above-mentioned POSS base hydridization polyacrylate dispersion 100.0g, in the case where 400rpm stirs humidity, the lower 0.6g that is added is soaked
Agent TEGO Wet 500,0.4g defoaming agent BYK019 are stirred 5 minutes, are then added 4.0g coalescing agent dipropylene glycol n-butyl ether
Enter to continue stirring 5 minutes；0.4g levelling agent TEGO glide440 and 0.5g thickener RM-12W is sequentially added, continues to stir
Dispersion obtains aqueous woodware paint in 10 minutes.
Three, the performance detection of aqueous woodware paint described in embodiment 5
Test performance after being placed at room temperature for 7 days according to GBT 23999-2009 film, paint film correlated performance test result are shown in Table
1。
Embodiment 6
One, the preparation of POSS base hydridization polyacrylate dispersion
1. the preparation of nuclear monomer pre-emulsion
After addition 25.0g deionized water and 1.8g OA-POSS are dispersed with stirring 20min in four-hole boiling flask, 27.0g is added
Methyl methacrylate, 108.0g butyl acrylate and 1.0g acrylic acid continue stirring 30min and obtain nuclear monomer pre-emulsion.
2. the preparation of shell monomer pre-emulsion
After addition 27.0g deionized water and 1.0g OA-POSS are dispersed with stirring 20min in four-hole boiling flask, 7.2g third is added
Alkene monomethacryloxypropyl cage-type silsesquioxane, 35.0g methyl methacrylate, 10.0g butyl acrylate and 0.7g acrylic acid continue
Stirring 30min obtains shell monomer pre-emulsion.
The preparation of 3.POSS base hydridization polyacrylate dispersion
It is pre- that 95.0g deionized water, 28.0g nuclear monomer are added in the four-hole boiling flask that blender, condenser pipe, thermometer are housed
The ammonium persulfate of emulsion and 4.5g are warming up to 50 DEG C of heat preservation 40min, then heat to 75 DEG C and the remaining pre- cream of nuclear monomer is added dropwise
Change the ammonium persulfate of liquid and 4.5g, 2.5h is added dropwise, and is warming up to 85 DEG C of heat preservation 0.5h.Shell monomer pre-emulsion and 9.0g is added dropwise
Ammonium persulfate, 3h is added dropwise, then keeps the temperature 1h, obtain POSS base hydridization polyacrylate dispersion.
Two, using the preparation method for preparing aqueous woodware paint of POSS base hydridization polyacrylate dispersion
By above-mentioned POSS base hydridization polyacrylate dispersion 100.0g, in the case where 400rpm stirs humidity, the lower 0.2g that is added is soaked
Agent BYK2015,0.1g defoaming agent BYK022 is stirred 5 minutes, then by 3.0g coalescing agent butyl glycol ether and 1.0g alcohol ester-
12 additions continue stirring 5 minutes；0.5g levelling agent BYK349 and 0.3g thickener RM-8W is sequentially added, continues to be dispersed with stirring
Obtain aqueous woodware paint within 10 minutes.
Three, the performance detection of aqueous woodware paint described in embodiment 6
Test performance after being placed at room temperature for 7 days according to GBT 23999-2009 film, paint film correlated performance test result are shown in Table
1。
Reference examples 1
One, the preparation of POSS base hydridization polyacrylate dispersion
1. the preparation of nuclear monomer pre-emulsion
After addition 30.0g deionized water and 3.0gSDS and 1.5gOP-10 are dispersed with stirring 15min in four-hole boiling flask, it is added
40.0g methyl methacrylate, 80.0g butyl acrylate and 2.0g acrylic acid continue stirring 20min and obtain nuclear monomer pre-emulsification
Liquid.
2. the preparation of shell monomer pre-emulsion
After addition 20.0g deionized water and 2.0gSDS and 1.0gOP-10 are dispersed with stirring 15min in four-hole boiling flask, it is added
60.0g methyl methacrylate, 20.0g butyl acrylate and 1.0g acrylic acid continue stirring 20min and obtain shell monomer pre-emulsification
Liquid.
The preparation of 3.POSS base hydridization polyacrylate dispersion
100.0g deionized water, 30.0g nuclear monomer are added in the four-hole boiling flask that blender, condenser pipe, thermometer are housed
The potassium peroxydisulfate of pre-emulsion and 12.0g are warming up to 60 DEG C of heat preservation 20min, and it is pre- to then heat to 80 DEG C of remaining nuclear monomers of dropwise addition
The potassium peroxydisulfate of emulsion and 12.0g, 2h are added dropwise, and are warming up to 85 DEG C of heat preservation 0.5h.Be added dropwise shell monomer pre-emulsion and
The potassium peroxydisulfate of 16.0g, 2h are added dropwise, and then heat to 90 DEG C of heat preservation 0.5h, obtain POSS base hydridization polyacrylate cream
Liquid.
Two, using the preparation method for preparing aqueous woodware paint of POSS base hydridization polyacrylate dispersion
0.3g wetting agent TEGO is added in the case where 400rpm is stirred under humidity in above-mentioned Core-shell type acrylate emulsion 100.0g
Twin 4000 and 0.5g defoaming agent TEGO Airex 920 is stirred 5 minutes, is then added 5.0g coalescing agent butyl glycol ether
Enter to continue stirring 5 minutes；Sequentially add 0.2g levelling agent TEGO Rad 2200N and 0.8g thickener TEGO ViscoPlus
3060, continue to be dispersed with stirring 10 minutes and obtains aqueous woodware paint.
Three, the performance detection of aqueous woodware paint described in embodiment 1
Test performance after being placed at room temperature for 7 days according to GBT 23999-2009 film, paint film correlated performance test result are shown in Table
1。
The performance of the self-crosslinking aqueous woodcare paint of 1 one component room temperature of table
As can be seen from Table 1, using POSS base hydridization polyacrylate dispersion obtained in embodiment 2~6 preparation from
Cross-linking aqueous woodcare paint has good comprehensive performance relative to relative to self-crosslinking aqueous woodcare paint obtained by reference examples 1,
By significantly improving the hardness, tough of polyacrylic acid latex film in the addition aqueous woodware paint of POSS base hydridization polyacrylate dispersion
Property and glossiness.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate examples made by the present invention, and is not to this
The restriction of the embodiment of invention.It for those of ordinary skill in the art, on the basis of the above description can be with
It makes other variations or changes in different ways.Here all embodiments can not be exhaustive.It is all to belong to the present invention
The obvious changes or variations extended out of technical solution still in the scope of protection of the present invention.
Claims (7)
1. a kind of POSS base hydridization polyacrylate dispersion, which is characterized in that its formula comprises the following components in parts by weight raw material:
95~120 parts of deionized water, 155.1~190.95 parts of nuclear monomer pre-emulsion, 80.9~106.8 parts of shell monomer pre-emulsion,
18~54 parts of initiator；The nuclear monomer pre-emulsion includes following raw material component: stratum nucleare acrylic ester monomer
121.5~151.8 parts, 1.8~4.5 parts of POSS base reactive emulsifier, 25~38 parts of deionized water；The shell monomer pre-emulsification
Liquid includes following raw material component: 45.7~81 parts of shell acrylic ester monomer, POSS base acrylate monomer 2~
7.2 parts, 1~3 part of POSS base reactive emulsifier, 18~27 parts of deionized water；The molecule of the POSS base reactive emulsifier
Formula is (C21H40NO)8(SiO1.5)8, structural formula is as follows:
Wherein R1ForThe POSS base third
The molecular formula of olefin(e) acid ester monomer is (C7H11O2)8(SiO1.5)8Or (C6H9O2)8(SiO1.5)8, structural formula is as follows:
Wherein,
2. POSS base hydridization polyacrylate dispersion according to claim 1, which is characterized in that the POSS base response type
The preparation of emulsifier the following steps are included:
S1:POSS-Cl solid preparation: by r-chloropropyl trimethoxyl silane, concentrated hydrochloric acid and methanol in 35~40 DEG C of back flow reactions 70
~72h, the r-chloropropyl trimethoxyl silane, concentrated hydrochloric acid and methanol usage ratio are 40g:30ml~35ml:150ml~200ml,
It filters, wash, recrystallize, be dried to obtain white solid；
S2: by POSS-Cl solid, oleamide and N,N-dimethylformamide obtained by step S1 in 95~100 DEG C of back flow reactions 5
~6h, the POSS-Cl solid, oleamide and N,N-dimethylformamide amount ratio be 160g:320~360g:200ml~
300ml, then remove n,N-Dimethylformamide obtain milky wax solid product to get.
3. POSS base hydridization polyacrylate dispersion according to claim 1, which is characterized in that the stratum nucleare esters of acrylic acid
Monomer is selected from methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylic acid, acrylic acid
Methyl esters, ethyl acrylate, the two or more combinations in butyl acrylate.
4. POSS base hydridization polyacrylate dispersion according to claim 1, which is characterized in that the shell esters of acrylic acid
Monomer be first kind monomer and the second class monomer mixture, the first kind monomer selected from butyl acrylate, ethyl acrylate,
N-octyl, Isooctyl acrylate monomer, isooctyl methacrylate, lauryl ester, methyl acrylate, methyl
It is methyl acrylate, ethyl methacrylate, two or more in n-BMA；The second class monomer is selected from double third
One of ketone acrylamide and acrylic acid, methacrylic acid, hydroxy propyl methacrylate, trimethylolpropane trimethacrylate
Or it is two or more.
5. a kind of preparation method of POSS base hydridization polyacrylate dispersion, which comprises the steps of:
S1: nuclear monomer pre-emulsion: by 25~38 parts of deionized waters and 1.8~4.5 parts of POSS base reactive emulsifier stirrings point
Dissipate 10~20min, then be added 121.5~151.8 parts of stratum nucleare acrylic ester monomers, continue 20~30min of stirring to get；
S2: the preparation of shell monomer pre-emulsion: by 18~27 parts of deionized waters and 1~3 part of POSS base reactive emulsifier stirring
After dispersing 10~20min, 2~7.2 parts of POSS base acrylate monomers and 45.7~81 parts of shell acrylic ester monomers are added
Continue 20~30min of stirring to obtain the final product；
The preparation of S3:POSS base hydridization polyacrylate dispersion: by nuclear monomer pre-emulsion total weight 10 obtained by step S1~
20% nuclear monomer pre-emulsion and the initiator of initiator total weight 25~35% are warming up to 50~60 DEG C, and heat preservation 20~
40min；70~80 DEG C are then heated to, the initiation of remaining nuclear monomer pre-emulsion and initiator total weight 25~35% is added dropwise
Agent, 2~3h are added dropwise, then are warming up to 85 DEG C of 0.5~1.0h of heat preservation；Then shell monomer pre-emulsion obtained by a dropping step S2 and
Remaining initiator, 1~2h are added dropwise, and then 0.5~1h of heat preservation under the conditions of 85~90 DEG C to obtain the final product；
The molecular formula of the POSS base reactive emulsifier is (C21H40NO)8(SiO1.5)8, structural formula is as follows:
Wherein R1ForThe POSS base third
The molecular formula of olefin(e) acid ester monomer is (C7H11O2)8(SiO1.5)8Or (C6H9O2)8(SiO1.5)8, structural formula is as follows:
Wherein,
6. a kind of water containing the POSS base hydridization polyacrylate dispersion preparation as described in any one of Claims 1 to 4
Property woodcare paint coating, which is characterized in that the raw material components including following parts by weight: POSS base hydridization polyacrylate dispersion 80-
100 parts；0.2~0.6 part of wetting agent；0.1~0.5 part of defoaming agent；3~5 parts of coalescing agent；0.2~0.5 part of levelling agent；Thickening
0.3~0.8 part of agent.
7. a kind of preparation method of aqueous woodware paint coating as claimed in claim 6, which comprises the following steps:
1), each raw material component is weighed by formula ratio；
2), the wetting agent, the defoaming agent are added in the POSS base hydridization polyacrylate dispersion under agitation,
Stirring 5~10 minutes；
3), then the coalescing agent after mixing is added in 2) gained mixture, continues stirring 5~10 minutes；Again successively
Be added the levelling agent and the thickener, disperse 5~10 minutes to get.
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| CN107936188A (en) * | 2017-11-27 | 2018-04-20 | 湖南辰砾新材料有限公司 | A kind of polyimide modified acrylic acid anti-corrosion lotion and preparation method thereof |
| CN109535351B (en) * | 2018-11-22 | 2021-03-19 | 陕西科技大学 | POSS/fluorine-silicon co-modified polymethyl methacrylate resin and preparation and forming method thereof |
| CN110452490B (en) * | 2019-08-29 | 2021-09-17 | 安徽立兴化工有限公司 | Dual POSS polyether hybrid water-based acrylic resin dispersion, preparation method and composition for preparing resin coating film |
| CN111533860B (en) * | 2020-06-10 | 2021-10-01 | 青岛天祥环保工程有限公司 | Super-hydrophobic modifier for water-based paint and preparation method thereof |
| CN112812643B (en) * | 2021-02-05 | 2023-10-20 | 青岛中氟氟碳材料有限公司 | Outdoor water-based wood coating, preparation method thereof and wood product |
| CN113913801B (en) * | 2021-10-29 | 2024-03-22 | 南京科润工业介质股份有限公司 | Organic-inorganic hybridization-based waste heat black liquor |
| CN115490864B (en) * | 2022-09-29 | 2023-08-15 | 长兴化学（天津）有限公司 | POSS hybridized waterborne polyurethane emulsion and preparation method and application thereof |
| CN115947904A (en) * | 2023-03-10 | 2023-04-11 | 北京奇点势能科技有限公司 | POSS composite polyacrylate water dispersion and preparation method thereof |
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