CN110041473A - A kind of silicon modified aqueous acrylic emulsion and the preparation method and application thereof - Google Patents
A kind of silicon modified aqueous acrylic emulsion and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110041473A CN110041473A CN201910274661.6A CN201910274661A CN110041473A CN 110041473 A CN110041473 A CN 110041473A CN 201910274661 A CN201910274661 A CN 201910274661A CN 110041473 A CN110041473 A CN 110041473A
- Authority
- CN
- China
- Prior art keywords
- silicon
- mesoporous inorganic
- modified aqueous
- acrylic emulsion
- vinylsiloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- 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
- 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
- C09D151/10—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 inorganic materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Silicon Polymers (AREA)
- Silicon Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of silicon modified aqueous acrylic emulsions and the preparation method and application thereof, mesoporous inorganic silica is prepared for using sol-gel method first, mesoporous inorganic silica is modified with vinylsiloxane, obtain the mesoporous inorganic silica that load has vinylsiloxane, i.e. modified mesoporous inorganic silica, then modified mesoporous inorganic silica is mixed with acrylic monomers, the vinylsiloxane and acrylic monomers reactive polymeric being supported on mesoporous inorganic silica, it neutralizes, it filters to get silicon modified aqueous acrylic emulsion is arrived.Silicon modified aqueous acrylic emulsion prepared by the present invention has the characteristics of organosilicon and acrylic emulsion, it can be applied after HDI trimer solidifies in various substrate surfaces, it is its coating machinery good strength formed, acid and alkali-resistance, water-fast, there is certain hydrophobic oleophobic performance.
Description
Technical field
The invention belongs to functional high molecule material fields, and in particular to a kind of silicon modified aqueous acrylic emulsion and its system
Preparation Method and application.
Technical background
Aqueous acrylic emulsion have extraordinary guarantor's light colour retention, weatherability, be widely used in leather, coating,
The industries such as fiber process, plastic products, anti-corrosion of metal, the wooden wall decoration.
The combination of organosilicon and acrylic emulsion can make up organosilicon bad mechanical property, film is excessively soft the problems such as,
The problem of acrylic emulsion water resistance and resistance to soiling deficiency can be improved, organic silicon modified aqueous acrylic emulsion has become to be ground now
Study carefully the hot spot of exploitation.
Organosilicon is introduced into aqueous acrylic emulsion there are two types of mode, and one is utilize to contain hydroxyl, amino or epoxy
The organosiloxane of base isoreactivity functional group is reacted with active group corresponding on strand, so that organosiloxane be introduced
In aqueous acrylic emulsion.The shortcomings that this grafting method is that grafting rate is lower, and excessive organosiloxane need to be added to guarantee
Enough organosiloxanes are grafted on molecular weight.Another kind is to utilize organosiloxane and acrylic monomers with double bond
Double bond copolymerization, the grafting rate of this method is higher, but there is the organosiloxane with double bond and be easy during reaction, storage
The problem of hydrolyzing, polycondensation, causing product gel, such as patent application CN106009943A and CN106366228A.
How to inhibit organosiloxane the problem of reacting and storing the hydrolysis of process, polycondensation, is second of grafting side
The key of formula.In this regard, the present invention is situated between by using meso-porous titanium dioxide silicon carrier as the buffering between organosiloxane and water
Matter effectively inhibits hydrolysis, the polycondensation of organosiloxane.Also, due to the addition of mesoporous inorganic silica, effectively enhance third
The weatherability and resistance to soiling of olefin(e) acid lotion.
Summary of the invention
In order to solve the deficiencies in the prior art, the object of the present invention is to provide a kind of systems of silicon modified aqueous acrylic emulsion
Preparation Method and application react vinylsiloxane with acrylic monomers by using mesoporous silicon oxide as buffer medium
It tends towards stability, without gel.Silicon modified aqueous acrylic emulsion of the invention has certain hydrophobic oleophobic performance, can apply
In substrate surfaces such as metal, woodenware, glass.
To achieve the goals above, the present invention provides following technical schemes.
The present invention provides a kind of preparation methods of silicon modified aqueous acrylic emulsion, the described method comprises the following steps:
(1) modified mesoporous inorganic silica is prepared, is specifically comprised the following steps:
(1.1) pore-foaming agent, catalyst are mixed with water, stirs to homogeneous system, then instills silicon source, kept the temperature after dripping off
Gained colloid is centrifuged by colloid, is washed, and drying obtains silica；
(1.2) it disperses gained silica in the ethanol solution of concentrated hydrochloric acid, flows back, be then centrifuged for, wash, dry
It is dry, obtain mesoporous inorganic silica；
(1.3) it disperses mesoporous inorganic silica in dehydrated alcohol, adds vinylsiloxane, be uniformly mixed,
Mixed liquor, mixed liquor flow back 2-10h under nitrogen protection, be then centrifuged for, wash, dry, obtaining load has vinyl silicon oxygen
The mesoporous inorganic silica of alkane, i.e., modified mesoporous inorganic silica；
(2) by the modified mesoporous inorganic silica and polymerizable acrylic monomer, specifically includes the following steps:
(2.1) in terms of mass fraction, 47-70 parts of acrylic monomers, 2-6 parts of emulsifier, 10-20 parts of load are had
The pre-emulsification for having blender is added in the deionized water of the mesoporous inorganic silica suspension and 20-40 of vinylsiloxane part
Pre-emulsification is carried out in kettle, obtains pre-emulsion；
(2.2) 20wt%-30wt% step (2.1) are added in the reaction kettle for having blender, condenser, thermometer to obtain
The initiator of the pre-emulsion and 0.67-1 that arrive part, turn on agitator heat up reaction kettle；When there is the formation of blue light lotion, benefit
With the peristaltic pump remaining pre-emulsion that a dropping step (2.1) obtains into reaction kettle, it is added dropwise to what the step (2.1) obtained
Remaining pre-emulsion adds 0.33-0.5 parts of the initiator when remaining 1/4-1/3；Completion of dropwise addition is reacted at 82~84 DEG C
After 1.5-2h, cooling is added 3-8 parts of neutralizer and neutralizes, filters to get silicon modified aqueous acrylic emulsion.
Preferably, in the step (1.1), washing refers to is washed 2-4 times with dehydrated alcohol and deionized water respectively；
The pore-foaming agent is cetyl trimethylammonium bromide, polyethylene glycol 2000, one in triblock copolymer P123
Kind or more than one；
One in ammonium hydroxide, concentrated hydrochloric acid or formic acid that the catalyst is sodium hydroxide, mass fraction range is 20-25%
Kind；
The silicon source is tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyl diethoxy
One of base silane or methyltriethoxysilane.
Preferably, the mass volume ratio of step (1.1) pore-foaming agent and water is 1-4.35mg/ml；
The silicon source, catalyst, pore-foaming agent molar ratio be (1-3): (0.1-1): (0.1-0.6).
Preferably, the speed of step (1.1) described stirring is 300-600r/min；The time of stirring is 0.5-2h；It is described
The rate of addition of silicon source is 0.1~0.5mL/min；When mixing and the temperature of heat preservation is 60-90 DEG C；The time of the heat preservation is 1-
4h；The rate of the centrifugation is 3000-6000r/min；The time of the drying is 10-16h；The temperature of the drying is 60-
90℃。
Preferably, the volume ratio of concentrated hydrochloric acid and dehydrated alcohol is in the ethanol solution of step (1.2) described concentrated hydrochloric acid
1-100；
The mass volume ratio of the ethanol solution of the silica and concentrated hydrochloric acid is 10-40mg/ml.
Preferably, the time of step (1.2) described reflux is 24-48h；The temperature of the reflux is 60-100 DEG C；It is described
The rate of centrifugation is 3000-6000r/min；Washing solution used is dehydrated alcohol and deionized water；With dehydrated alcohol and go
The number of ion water washing is respectively 2-4 times；The time of the drying is 10-16h；The temperature of the drying is 60-90 DEG C.
Preferably, the mass volume ratio of step (1.3) the mesoporous inorganic silica and dehydrated alcohol is 1-10mg/
ml；
The volume ratio of the vinylsiloxane and dehydrated alcohol is 0.01-0.1；
The vinylsiloxane is vinyltriethoxysilane, the vinyltrimethoxysilane, (β-first of vinyl three
Oxygroup ethyoxyl) silane, one of vinyl silane triisopropoxide or more than one；
The time of the reflux is 2-10h, and the temperature of the reflux is 60-100 DEG C；
The rate of the centrifugation is 3000-6000r/min；Washing solution used is dehydrated alcohol and deionized water；With
Dehydrated alcohol and the number of deionized water washing are respectively 2-4 times；
The time of the drying is 10-16h；The temperature of the drying is 60-90 DEG C.
Preferably, step (2) acrylic monomers is one kind of hard monomer, soft monomer, carboxylic monomer and carboxylic monomer
Or more than one；
The hard monomer is methyl acrylate, methyl methacrylate, Isobutyl methacrylate, the different ice of methacrylic acid
One of piece ester, styrene, vinyl chloride or more than one；
The soft monomer be butyl acrylate, ethyl acrylate, isobutyl acrylate, butyl methacrylate, butadiene,
One of ethylene, acrylic acid-2-ethyl caproite or more than one；
The carboxylic monomer is one of acrylic acid, methacrylic acid；
The carboxylic monomer is one of hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or one
Kind or more；
The mesoporous inorganic silica suspension for having vinylsiloxane that loads is that load has vinylsiloxane
The mixed liquor of mesoporous inorganic silica and dehydrated alcohol, wherein 4-8 parts of load has the mesoporous inorganic two of vinylsiloxane
Silica, 6-12 parts of dehydrated alcohol；
The initiator is azo-bis-isobutyl cyanide, benzoyl peroxide, ammonium persulfate, any one in sodium sulfite；
The emulsifier is neopelex, dodecyl sodium sulfate, OP-10, Tween80, dodecyl
The one or more of mercaptan, alkyl phenol polyoxyethylene ether；
The neutralizer is ammonium hydroxide, sodium hydroxide, triethylamine, potassium hydroxide, N, one of N- dimethylethanolamine.
The present invention also provides a kind of silicon modified aqueous acrylic emulsions of upper the method preparation.
The present invention also provides a kind of silicon modified aqueous acrylic emulsion as described above as binder resin aqueous antifouling
Coating, aqueous architectural coating, the application in water-borne wood coating field.
Silicon modified aqueous acrylic emulsion of the present invention, basic framework pass through emulsion polymerization by a variety of acrylic monomers
It obtains.The soft or hard suitable ratio of monomer imparts the good hardness of emulsion coating, flexibility, and enough carboxylic monomers improve poly-
The crosslinking degree for closing object, makes emulsion coating have more plumpness, the stabilization of basic structure, so that emulsion coating be made to have good power
Learn performance.Therefore it can be used as binder resin to apply in the neck such as waterborne anti-fouling coatings, aqueous architectural coating, water-borne wood coating
Domain.
Silicon modified aqueous acrylic emulsion of the present invention is dispersed on polymer molecular chain and loads vinyl silicon oxygen
The mesoporous inorganic silica of alkane is reacted using vinylsiloxane with polymerizable acrylic monomer, to obtain having both antifouling, water
The silicon modified aqueous acrylic emulsion of lower oleophobic.Coating after silicon modified aqueous acrylic emulsion film forming prepared by the present invention is to oil
Contact angle it is 90 ° big, show certain oleophobic effects.
Silicon modified aqueous acrylic emulsion prepared by the present invention can be applied to various substrate surfaces, including metal, woodenware,
The substrate surfaces such as glass.
Compared to the prior art, the beneficial effects of the present invention are:
(1) present invention has the mesoporous inorganic silica of vinylsiloxane to react synthesis with acrylic monomers using load
Silicon modified aqueous acrylic emulsion can provide a kind of new thinking to the synthesis of fluorine-silicon modified acrylic lotion；
(2) silicon modified aqueous acrylic emulsion prepared by the present invention has the characteristics of organosilicon and acrylic emulsion, through HDI
The coating machinery good strength formed in various substrate surfaces, acid and alkali-resistance, water-fast can be applied after tripolymer solidification, there is one
Fixed hydrophobic oleophobic performance.
Detailed description of the invention
Fig. 1 is the tinplate of siliceous modified aqueous acrylic acid lotion paint film and the contact angle test figure of water.
Specific embodiment
Embodiment 1:
A kind of preparation method of silicon modified aqueous acrylic emulsion is present embodiments provided, the method includes following steps
It is rapid:
(1) preparation of modified mesoporous inorganic silica:
1g cetyl trimethylammonium bromide CTAB, 3.5mL NaOH (2M) and 480mL deionized water are mixed at 80 DEG C
It closes uniformly, is slowly dropped into 5mL tetraethoxysilane TEOS, drips off within 40 minutes.In 80 DEG C of heat preservation 2h after dripping off, colloid is obtained, then
Gained colloid is centrifuged, obtains silica (SiO in 80 DEG C of baking 12h with dehydrated alcohol and water washing 3 times respectively2)；
To remove template agent removing, disperse gained silica in the ethanol solution of concentrated hydrochloric acid, silica with it is dense
The mass volume ratio 20mg/ml of the ethanol solution of hydrochloric acid, concentrated hydrochloric acid is (with commercially available in the ethanol solution of the concentrated hydrochloric acid
Obtain) volume be 2ml, the volume of dehydrated alcohol is 98ml, then 80 DEG C of reflux for 24 hours, centrifugation, washing, drying (centrifugation speed
Rate 4500r/min, washing three times, 80 DEG C of drying temperature and drying 12h), obtain mesoporous inorganic silica；
It disperses 0.1g mesoporous inorganic silica in 50mL dehydrated alcohol, 1mL vinyltriethoxysilane is added,
It is uniformly mixed, obtains mixed liquor.Mixed liquor flows back 3h under nitrogen protection, and reflux temperature is 80 DEG C, is then centrifuged for, washs, dries
(centrifugation rate 4500r/min, washing three times, 80 DEG C of drying temperature and drying 12h), obtain load have vinyl triethoxyl silicon
Mesoporous inorganic silica, that is, modified inorganic silica of alkane.
(2) modified mesoporous inorganic silica and polymerizable acrylic monomer
A kind of silicon modified aqueous acrylic emulsion, is prepared by the raw material of following quality: methyl methacrylate and first
Base isobornyl acrylate total 30g, butyl acrylate 25g, acrylic acid 5g, load have mesoporous the two of vinyltriethoxysilane
Silica suspension 10g (in the suspension load have the mesoporous inorganic silica of vinyltriethoxysilane quality be
4g, the quality of dehydrated alcohol are 6g), N, N- dimethylethanolamine 4g, deionized water 25g, ammonium persulfate 1g, detergent alkylate sulphur
Sour sodium and the total 3g of alkyl phenol polyoxyethylene ether.
By methyl methacrylate and isobornyl methacrylate total 30g, butyl acrylate 25g, acrylic acid 5g, load
There are the mesoporous silicon oxide suspension 10g of vinyltriethoxysilane, neopelex and alkylphenol-polyethenoxy
Ether total 3g, deionized water 25g are added in the pre-emulsification kettle with blender and carry out pre-emulsification, obtain pre-emulsion；
With blender, condenser, thermometer reaction kettle in the obtained pre-emulsion of 20wt% and 0.67g is added
Ammonium persulfate, turn on agitator, heating；When there is the formation of blue light lotion, 80wt% is added dropwise into reaction kettle using peristaltic pump and obtains
The pre-emulsion arrived is added dropwise to when pre-emulsion remains 1/3 and adds 0.33g ammonium persulfate；Completion of dropwise addition reacts 2h at 84 DEG C
Afterwards, cool down, the N of 4g is added, N- dimethylethanolamine neutralizes, and filters to get silicon modified aqueous acrylic emulsion.
Embodiment 2:
A kind of preparation method of silicon modified aqueous acrylic emulsion is present embodiments provided, the method includes following steps
It is rapid:
(1) preparation of modified mesoporous inorganic silica:
1g cetyl trimethylammonium bromide CTAB, 3.5mL NaOH (2M) and 480mL deionized water are mixed at 80 DEG C
It closes uniformly, is slowly dropped into 5ml tetraethoxysilane TEOS, drips off within 40 minutes.In 80 DEG C of heat preservation 2h after dripping off, colloid is obtained, then
Gained colloid is centrifuged, obtains silica (SiO in 80 DEG C of baking 12h with dehydrated alcohol and water washing 3 times respectively2)；
To remove template agent removing, disperse gained silica in the ethanol solution of concentrated hydrochloric acid, silica with it is dense
The mass volume ratio 20mg/ml of the ethanol solution of hydrochloric acid, concentrated hydrochloric acid is (with commercially available in the ethanol solution of the concentrated hydrochloric acid
Obtain) volume be 2ml, the volume of dehydrated alcohol is 98ml, then 80 DEG C of reflux for 24 hours, centrifugation, washing, drying (centrifugation speed
Rate 4500r/min, washing three times, 80 DEG C of drying temperature and drying 12h), obtain mesoporous inorganic silica；
It disperses 0.1g mesoporous inorganic silica in 50mL dehydrated alcohol, three isopropoxy silicon of 1mL vinyl is added
Alkane is uniformly mixed, obtains mixed liquor.Mixed liquor flows back 3h under nitrogen protection, and reflux temperature is 80 DEG C, is then centrifuged for, washs, dries
Dry (centrifugation rate 4500r/min, washing three times, 80 DEG C of drying temperature and drying 12h), obtaining load has three isopropyl oxygen of vinyl
The mesoporous inorganic silica of base silane, i.e., modified mesoporous inorganic silica.
(2) modified mesoporous inorganic silica and polymerizable acrylic monomer
A kind of silicon modified aqueous acrylic emulsion, is prepared by the raw material of following quality: methyl methacrylate and first
Base isobornyl acrylate total 25g, butyl acrylate 30g, acrylic acid 4g, load have the mesoporous of vinyl silane triisopropoxide
(load has the matter of the mesoporous inorganic silica of vinyl silane triisopropoxide to silica suspension 10g in the suspension
Amount is 4g, and the quality of dehydrated alcohol is 6g), N, N- dimethylethanolamine 3.25g, deionized water 25g, ammonium persulfate 1g, 12
Sodium alkyl benzene sulfonate and the total 3.5g of alkyl phenol polyoxyethylene ether.
By methyl methacrylate and isobornyl methacrylate total 25g, butyl acrylate 30g, acrylic acid 4g, load
Have a mesoporous silicon oxide suspension 10g of vinyl silane triisopropoxide, deionized water 25g, neopelex and
The total 3.5g of alkyl phenol polyoxyethylene ether, which is added in the pre-emulsification kettle with blender, carries out pre-emulsification, obtains pre-emulsion；
With blender, condenser, thermometer reaction kettle in the obtained pre-emulsion of 20wt% and 0.67g is added
Ammonium persulfate, turn on agitator, heating；When there is the formation of blue light lotion, 80wt% is added dropwise into reaction kettle using peristaltic pump and obtains
The pre-emulsion arrived is added dropwise to when pre-emulsion remains 1/3 and adds 0.33g ammonium persulfate；Completion of dropwise addition reacts 2h at 84 DEG C
Afterwards, cool down, the N of 3.25g is added, N- dimethylethanolamine neutralizes, and filters to get silicon modified aqueous acrylic emulsion.
Embodiment 3:
A kind of preparation method of silicon modified aqueous acrylic emulsion is present embodiments provided, the method includes following steps
It is rapid:
(1) preparation of modified mesoporous inorganic silica:
1g cetyl trimethylammonium bromide CTAB, 4mL NaOH (2M) are mixed at 80 DEG C with 480mL deionized water
Uniformly, it is slowly dropped into 5ml tetraethoxysilane TEOS, is dripped off within 40 minutes.In 80 DEG C of heat preservation 2h after dripping off, colloid is obtained, then will
The centrifugation of gained colloid, obtains silica (SiO in 80 DEG C of baking 12h with dehydrated alcohol and water washing 3 times respectively2)；
To remove template agent removing, disperse gained silica in the ethanol solution of concentrated hydrochloric acid, silica with it is dense
The mass volume ratio 25mg/ml of the ethanol solution of hydrochloric acid, concentrated hydrochloric acid is (with commercially available in the ethanol solution of the concentrated hydrochloric acid
Obtain) volume be 2ml, the volume of dehydrated alcohol is 98ml, then 80 DEG C of reflux for 24 hours, centrifugation, washing, drying (centrifugation speed
Rate 4500r/min, washing three times, 80 DEG C of drying temperature and drying 12h), obtain mesoporous inorganic silica；
It disperses 0.1g mesoporous inorganic silica in 50mL dehydrated alcohol, 1mL vinyltriethoxysilane is added,
It is uniformly mixed, obtains mixed liquor.Mixed liquor flows back 3h under nitrogen protection, and reflux temperature is 80 DEG C, is then centrifuged for, washs, dries
(centrifugation rate 4500r/min, washing three times, 80 DEG C of drying temperature and drying 12h), obtaining load has Jie of vinylsiloxane
Hole inorganic silicon dioxide, that is, modified inorganic silica.
(2) modified mesoporous inorganic silica and polymerizable acrylic monomer
A kind of silicon modified aqueous acrylic emulsion, is prepared by the raw material of following quality: methyl methacrylate and first
Base isobornyl acrylate total 30g, butyl acrylate 30g, acrylic acid 5g, load have mesoporous the two of vinyltriethoxysilane
Silica suspension 15g (in the suspension load have the mesoporous inorganic silica of vinyltriethoxysilane quality be
6g, the quality of dehydrated alcohol are 9g), N, N- dimethylethanolamine 4g, deionized water 30g, ammonium persulfate 1g, detergent alkylate sulphur
Sour sodium and the total 4g of alkyl phenol polyoxyethylene ether.
By methyl methacrylate and isobornyl methacrylate total 30g, butyl acrylate 30g, acrylic acid 5g, load
There are the mesoporous silicon oxide suspension 15g of vinyltriethoxysilane, deionized water 30g, neopelex and alkane
The total 4g of base phenol polyethenoxy ether, which is added in the pre-emulsification kettle with blender, carries out pre-emulsification, obtains pre-emulsion；
With blender, condenser, thermometer reaction kettle in the obtained pre-emulsion of 20wt% and 0.67g is added
Ammonium persulfate, turn on agitator, heating；When there is the formation of blue light lotion, 80wt% is added dropwise into reaction kettle using peristaltic pump and obtains
The pre-emulsion arrived is added dropwise to when pre-emulsion remains 1/3 and adds 0.33g ammonium persulfate；Completion of dropwise addition reacts 2h at 84 DEG C
Afterwards, cool down, the N of 4g is added, N- dimethylethanolamine neutralizes, and filters to get silicon modified aqueous acrylic emulsion.
Embodiment 4:
A kind of preparation method of silicon modified aqueous acrylic emulsion is present embodiments provided, the method includes following steps
It is rapid:
(1) preparation of modified mesoporous inorganic silica:
1g cetyl trimethylammonium bromide CTAB, 3.5mL NaOH (2M) and 480mL deionized water are mixed at 80 DEG C
It closes uniformly, is slowly dropped into 5ml tetraethoxysilane TEOS, drips off within 40 minutes.In 80 DEG C of heat preservation 2h after dripping off, colloid is obtained, then
Gained colloid is centrifuged, obtains silica (SiO in 80 DEG C of baking 12h with dehydrated alcohol and water washing 3 times respectively2)；
To remove template agent removing, disperse gained silica in the ethanol solution of concentrated hydrochloric acid, silica with it is dense
The mass volume ratio 25mg/ml of the ethanol solution of hydrochloric acid, concentrated hydrochloric acid is (with commercially available in the ethanol solution of the concentrated hydrochloric acid
Obtain) volume be 2ml, the volume of dehydrated alcohol is 100ml, then 80 DEG C of reflux for 24 hours, centrifugation, washing, drying (centrifugation
Rate 4500r/min, washing three times, 80 DEG C of drying temperature and drying 12h), obtain mesoporous inorganic silica；
It disperses 0.1g mesoporous inorganic silica in 50mL dehydrated alcohol, three isopropoxy silicon of 1mL vinyl is added
Alkane is uniformly mixed, obtains mixed liquor.Mixed liquor flows back 3h under nitrogen protection, and reflux temperature is 80 DEG C, is then centrifuged for, washs, dries
Dry (centrifugation rate 4500r/min, washing three times, 80 DEG C of drying temperature and drying 12h), obtaining load has three isopropyl oxygen of vinyl
Mesoporous inorganic silica, that is, modified inorganic silica of base silane.
(2) modified mesoporous inorganic silica and polymerizable acrylic monomer
A kind of silicon modified aqueous acrylic emulsion, is prepared by the raw material of following quality: methyl methacrylate and first
Base isobornyl acrylate total 25g, butyl acrylate 30g, acrylic acid 5g, load have the mesoporous of vinyl silane triisopropoxide
Silica suspension 15g, N, N- dimethylethanolamine 4g, deionized water 25g, ammonium persulfate 1g, neopelex
With the total 3g of alkyl phenol polyoxyethylene ether.
By methyl methacrylate and isobornyl methacrylate total 25g, butyl acrylate 30g, acrylic acid 5g, load
Have vinyl silane triisopropoxide mesoporous silicon oxide suspension 15g (in the suspension load have vinyl triethoxyl
The quality of the mesoporous inorganic silica of silane is 6g, and the quality of dehydrated alcohol is 9g), deionized water 25g, detergent alkylate sulphur
Sour sodium and the total 3g of alkyl phenol polyoxyethylene ether are added in the pre-emulsification kettle with blender and carry out pre-emulsification, obtain pre-emulsion；
With blender, condenser, thermometer reaction kettle in the obtained pre-emulsion of 20wt% and 0.67g is added
Ammonium persulfate, turn on agitator, heating；When there is the formation of blue light lotion, 80wt% is added dropwise into reaction kettle using peristaltic pump and obtains
The pre-emulsion arrived is added dropwise to the ammonium persulfate that 0.33g is added when pre-emulsion remains 1/3；Completion of dropwise addition reacts 2h at 84 DEG C
Afterwards, cool down, the N of 4g is added, N- dimethylethanolamine neutralizes, and filters to get silicon modified aqueous acrylic emulsion.
The test of coating basic performance: the fluorine-silicon modified acrylic lotion for taking 5g embodiment 1-4 to prepare respectively, it is even with coating device
Speed is streaked on tinplate, and paint film obtained toasts 0.5 hour at 120 DEG C, respectively obtains siliceous modified acrylic acid emulsion
The tinplate of paint film.The siliceous modified acrylic acid emulsion paint film that the fluorine-silicon modified acrylic lotion prepared using embodiment 4 is obtained
Tinplate and water contact angle be 99.6 °, more than 90 °, as shown in Fig. 1.
The test result of respective performances such as table 1:
Table 1
The acid resistance test is H of the coating in 0.1mol/L2SO4It is impregnated in solution for 24 hours, acid resistance test is that coating exists
It is impregnated in the NaOH solution of 0.1mol/L for 24 hours, water resistance test is that coating impregnates 48h in 25 DEG C of distilled water.
By above data it is found that can apply after silicon modified aqueous acrylic emulsion solidification prepared by the present invention in substrate
Surface, it is the coating machinery good strength formed, acid and alkali-resistance, water-fast, there is certain hydrophobic oleophobic performance.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other any without departing from changes, modifications, substitutions, combinations, simplifications made by the principle of the present invention, it should be equivalent
Substitute mode is included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of silicon modified aqueous acrylic emulsion, which is characterized in that the described method comprises the following steps:
(1) modified mesoporous inorganic silica is prepared, is specifically comprised the following steps:
(1.1) pore-foaming agent, catalyst are mixed with water, stirs to homogeneous system, then instills silicon source, glue is kept the temperature to obtain after dripping off
Gained colloid is centrifuged by body, is washed, and drying obtains silica；
(1.2) it disperses gained silica in the ethanol solution of concentrated hydrochloric acid, flows back, be then centrifuged for, wash, dry,
Obtain mesoporous inorganic silica；
(1.3) it disperses mesoporous inorganic silica in dehydrated alcohol, adds vinylsiloxane, be uniformly mixed, obtain mixed
Liquid is closed, mixed liquor flows back 2-10h under nitrogen protection, is then centrifuged for, washs, dries, and obtaining load has vinylsiloxane
Mesoporous inorganic silica, i.e., modified mesoporous inorganic silica；
(2) by the modified mesoporous inorganic silica and polymerizable acrylic monomer, specifically includes the following steps:
(2.1) by acrylic monomers, emulsifier, load have the mesoporous inorganic silica suspension of vinylsiloxane and go from
Sub- water is added in the pre-emulsification kettle with blender and carries out pre-emulsification, obtains pre-emulsion；
(2.2) with blender, condenser, thermometer reaction kettle in be added 20wt%-30wt% step (2.1) obtain it is pre-
Emulsion and initiator, turn on agitator heat up reaction kettle；When there is the formation of blue light lotion, using peristaltic pump to reaction kettle
Remaining pre-emulsion obtained by interior a dropping step (2.1) is added dropwise to when remaining pre-emulsion remains 1/4-1/3 and adds the initiation
Agent；Completion of dropwise addition, after reacting 1.5-2h at 82 ~ 84 DEG C, cooling is added neutralizer and neutralizes, filters to get silicon modified aqueous third
Olefin(e) acid lotion.
2. the preparation method of silicon modified aqueous acrylic emulsion according to claim 1, which is characterized in that the step
(1.1) in, washing refers to is washed 2-4 times with dehydrated alcohol and deionized water respectively；
The pore-foaming agent be one of cetyl trimethylammonium bromide, polyethylene glycol 2000, triblock copolymer P123 or
More than one；
The catalyst is sodium hydroxide, one of ammonium hydroxide, concentrated hydrochloric acid or formic acid that mass fraction range is 20-25%；
The silicon source is tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyl diethoxy silicon
One of alkane or methyltriethoxysilane.
3. the preparation method of silicon modified aqueous acrylic emulsion according to claim 1, which is characterized in that step (1.1) institute
The mass volume ratio for stating pore-foaming agent and water is 1-4.35 mg/ml；
The silicon source, catalyst, pore-foaming agent molar ratio be (1-3): (0.1-1): (0.1-0.6).
4. the preparation method of silicon modified aqueous acrylic emulsion according to claim 1, which is characterized in that step (1.1) institute
The speed for stating stirring is 300-600 r/min；The time of stirring is 0.5-2 h；The rate of addition of the silicon source is 0.1 ~ 0.5
mL/min；When mixing and the temperature of heat preservation is 60-90 DEG C；The time of the heat preservation is 1-4 h；The rate of the centrifugation is
3000-6000 r/min；The time of the drying is 10-16h；The temperature of the drying is 60-90 DEG C.
5. the preparation method of silicon modified aqueous acrylic emulsion according to claim 1, which is characterized in that step (1.2) institute
Stating the volume ratio of concentrated hydrochloric acid and dehydrated alcohol in the ethanol solution of concentrated hydrochloric acid is 1-100；
The mass volume ratio of the ethanol solution of the silica and concentrated hydrochloric acid is 10-40mg/ml.
6. the preparation method of silicon modified aqueous acrylic emulsion according to claim 1, which is characterized in that step (1.2) institute
The time for stating reflux is 24-48h；The temperature of the reflux is 60-100 DEG C；The rate of the centrifugation is 3000-6000 r/
min；Washing solution used is dehydrated alcohol and deionized water；It is respectively 2-4 with the number that dehydrated alcohol and deionized water are washed
It is secondary；The time of the drying is 10-16h；The temperature of the drying is 60-90 DEG C.
7. the preparation method of silicon modified aqueous acrylic emulsion according to claim 1, which is characterized in that step (1.3) institute
The mass volume ratio for giving an account of hole inorganic silicon dioxide and dehydrated alcohol is 1-10mg/ml；
The volume ratio of the vinylsiloxane and dehydrated alcohol is 0.01-0.1；
The vinylsiloxane is vinyltriethoxysilane, vinyltrimethoxysilane, three ('beta '-methoxy of vinyl
Ethyoxyl) silane, one of vinyl silane triisopropoxide or more than one；
The time of the reflux is 2-10h, and the temperature of the reflux is 60-100 DEG C；
The rate of the centrifugation is 3000-6000 r/min；Washing solution used is dehydrated alcohol and deionized water；With anhydrous
Ethyl alcohol and the number of deionized water washing are respectively 2-4 times；
The time of the drying is 10-16h；The temperature of the drying is 60-90 DEG C.
8. the preparation method of silicon modified aqueous acrylic emulsion according to claim 1, which is characterized in that with mass fraction
Meter, 47-70 part of acrylic monomers in step (2.1), load the mesoporous inorganic dioxy for having vinylsiloxane at 2-6 parts of emulsifier
10-20 parts and deionized water 20-40 parts of SiClx suspension；The initiator 0.67-1 being added before turn on agitator in step (2.2)
3-8 parts of 0.33-0.5 parts of initiator, the neutralizer added after part, turn on agitator；
The acrylic monomers is the one or more of hard monomer, soft monomer, carboxylic monomer and carboxylic monomer；
The hard monomer is methyl acrylate, methyl methacrylate, Isobutyl methacrylate, methacrylic acid isoborneol
One of ester, styrene, vinyl chloride or more than one；
The soft monomer is butyl acrylate, ethyl acrylate, isobutyl acrylate, butyl methacrylate, butadiene, second
One of alkene, acrylic acid-2-ethyl caproite or more than one；
The carboxylic monomer is one of acrylic acid, methacrylic acid；
The carboxylic monomer be one of hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or it is a kind of with
On；
The mesoporous inorganic silica suspension for having vinylsiloxane that loads is that load has the mesoporous of vinylsiloxane
The mixed liquor of inorganic silicon dioxide and dehydrated alcohol, wherein 4-8 parts of load has the mesoporous inorganic titanium dioxide of vinylsiloxane
Silicon, 6-12 parts of dehydrated alcohol；
The initiator is azo-bis-isobutyl cyanide, benzoyl peroxide, ammonium persulfate, any one in sodium sulfite；
The emulsifier be neopelex, dodecyl sodium sulfate, OP-10, Tween80, lauryl mercaptan,
The one or more of alkyl phenol polyoxyethylene ether；
The neutralizer is ammonium hydroxide, sodium hydroxide, triethylamine, potassium hydroxide, N, one of N- dimethylethanolamine.
9. a kind of silicon modified aqueous acrylic emulsion prepared such as any one of claim 1 to 8 the method.
10. a kind of silicon modified aqueous acrylic emulsion as claimed in claim 9 is as binder resin in waterborne anti-fouling coatings, aqueous
Application in building coating, water-borne wood coating field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910274661.6A CN110041473B (en) | 2019-04-08 | 2019-04-08 | Silicon-modified water-based acrylic emulsion and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910274661.6A CN110041473B (en) | 2019-04-08 | 2019-04-08 | Silicon-modified water-based acrylic emulsion and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110041473A true CN110041473A (en) | 2019-07-23 |
| CN110041473B CN110041473B (en) | 2021-10-22 |
Family
ID=67276286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910274661.6A Expired - Fee Related CN110041473B (en) | 2019-04-08 | 2019-04-08 | Silicon-modified water-based acrylic emulsion and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110041473B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551455A (en) * | 2019-08-05 | 2019-12-10 | 安佐化学有限公司 | low-odor low-VOC benzene-free acrylate adhesive |
| CN111019567A (en) * | 2019-12-24 | 2020-04-17 | 李智远 | Water-based environment-friendly acrylic emulsion adhesive and preparation method thereof |
| CN111921481A (en) * | 2020-09-10 | 2020-11-13 | 合肥谷口化工科技有限公司 | Synthesis process of water-based acrylic emulsion |
| CN112635909A (en) * | 2020-12-18 | 2021-04-09 | 汕头市广油美联新材料研究院有限公司 | Preparation method of in-situ synthesized water-based ceramic slurry |
| CN112646444A (en) * | 2020-12-18 | 2021-04-13 | 汕头市广油美联新材料研究院有限公司 | Preparation method of mesoporous silica water-based ceramic slurry |
| CN116004074A (en) * | 2022-12-20 | 2023-04-25 | 浙江双金粉末涂料有限公司 | Building exterior wall heat insulation coating and preparation method thereof |
| CN116218320A (en) * | 2023-03-24 | 2023-06-06 | 广西科学院 | Preparation method of super-hydrophobic self-cleaning aluminum alloy coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1446827A (en) * | 2003-04-09 | 2003-10-08 | 吉林大学 | Method for synthesizing nano microsphere of inorganic/polymer huds with narrow decentralization |
| CN1654533A (en) * | 2005-01-19 | 2005-08-17 | 南京工业大学 | Nano silicon dioxide/acrylate composite emulsion and preparation method thereof |
-
2019
- 2019-04-08 CN CN201910274661.6A patent/CN110041473B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1446827A (en) * | 2003-04-09 | 2003-10-08 | 吉林大学 | Method for synthesizing nano microsphere of inorganic/polymer huds with narrow decentralization |
| CN1654533A (en) * | 2005-01-19 | 2005-08-17 | 南京工业大学 | Nano silicon dioxide/acrylate composite emulsion and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 张佼如: "SiO2溶胶/聚丙烯酸酯复合乳液的合成及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 郑林萍等: "介孔二氧化硅复合微球的制备及药物控释应用", 《河南科技大学学报（自然科学版）》 * |
| 陈师等: "高SiO2 含量硅溶胶/聚丙烯酸酯复合乳液的制备", 《北京化工大学学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110551455A (en) * | 2019-08-05 | 2019-12-10 | 安佐化学有限公司 | low-odor low-VOC benzene-free acrylate adhesive |
| CN111019567A (en) * | 2019-12-24 | 2020-04-17 | 李智远 | Water-based environment-friendly acrylic emulsion adhesive and preparation method thereof |
| CN111921481A (en) * | 2020-09-10 | 2020-11-13 | 合肥谷口化工科技有限公司 | Synthesis process of water-based acrylic emulsion |
| CN112635909A (en) * | 2020-12-18 | 2021-04-09 | 汕头市广油美联新材料研究院有限公司 | Preparation method of in-situ synthesized water-based ceramic slurry |
| CN112646444A (en) * | 2020-12-18 | 2021-04-13 | 汕头市广油美联新材料研究院有限公司 | Preparation method of mesoporous silica water-based ceramic slurry |
| CN112635909B (en) * | 2020-12-18 | 2023-05-09 | 汕头市广油美联新材料研究院有限公司 | Preparation method of in-situ synthesized water-based ceramic slurry |
| CN116004074A (en) * | 2022-12-20 | 2023-04-25 | 浙江双金粉末涂料有限公司 | Building exterior wall heat insulation coating and preparation method thereof |
| CN116218320A (en) * | 2023-03-24 | 2023-06-06 | 广西科学院 | Preparation method of super-hydrophobic self-cleaning aluminum alloy coating |
| CN116218320B (en) * | 2023-03-24 | 2024-03-12 | 广西科学院 | Preparation method of super-hydrophobic self-cleaning aluminum alloy coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110041473B (en) | 2021-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110041473A (en) | A kind of silicon modified aqueous acrylic emulsion and the preparation method and application thereof | |
| CN109868026B (en) | Organic silicon modified acrylate resin, preparation method thereof and hydrophobic weather-resistant slow-release modified acrylic resin coating | |
| CN105384864B (en) | A kind of multiple self-crosslinking nano acrylic ester copolymer emulsion of room temperature and preparation method thereof and using the lotion as the aqueous woodware paint of base-material | |
| CN101250369B (en) | Aqueous composite paint containing amphiphilic fluorine-containing acrylate blocking copolymer and preparation thereof | |
| CN103613702B (en) | A kind of water-soluble multifunctional acrylic matting resin and preparation method thereof | |
| CN104558447B (en) | Inorganic nano composite anti-doodling resin and preparation method thereof | |
| CN108395800B (en) | Three-in-one colorful emulsion and preparation method thereof | |
| CN102898578B (en) | Self-crosslinking silicone-acrylate copolymer emulsion and preparation method | |
| CN104672403A (en) | Environment-friendly silicon-acrylate emulsion and preparation method thereof | |
| CN105237675A (en) | Polyacrylic woodware emulsion with core-shell bi-crosslinking structure and preparation method thereof | |
| CN110218275B (en) | Reentrant corner cracking resistant acrylic emulsion and water-based damping coating containing same | |
| CN106519107A (en) | Nanoparticle-modified acrylate emulsion and preparation method and application thereof | |
| CN109666111A (en) | A kind of Nano-meter SiO_22/ organosilicon-modified acrylate emulsion | |
| CN104293062B (en) | Soft raw matter antifouling paint of aqueous and preparation method thereof | |
| CN106146755A (en) | A kind of preparation method of high solids content silicone acrylic emulsion | |
| CN102627741B (en) | Preparation method of fluoride silicon macromolecular emulsion modified acrylic ester emulsion | |
| CN112851850A (en) | Preparation method of silicon-acrylic emulsion for preparing polymer cement-based waterproof coating | |
| CN106632791B (en) | One kind resisting fresh cement accumulation of salt in the surface soil priming paint styrene-acrylic emulsion and preparation method thereof | |
| CN105254795A (en) | Emulsion for outer wall engineering coating and preparation method thereof | |
| CN110437776A (en) | A kind of double-component aqueous redwood splicing adhesive and its application | |
| CN100532478C (en) | Composite coating containing fluorine-containing acrylic ester block copolymer and producing method thereof | |
| CN103864996A (en) | Silicon-fluorine-acrylic acid ternary polymerization latex and preparation method thereof | |
| CN102675518A (en) | Preparation method for organic-inorganic hybrid fluorine-silicon modified nano waterborne resin | |
| CN104017146A (en) | Water-based acrylate adhesive for reflective coatings and preparation method thereof | |
| CN109762095A (en) | Organic-silicon-modified hydroxy acrylate lotion and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20211022 |