CN106543381A - A kind of hydroxyl polyacrylate aqueous dispersion and preparation method thereof - Google Patents
A kind of hydroxyl polyacrylate aqueous dispersion and preparation method thereof Download PDFInfo
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- CN106543381A CN106543381A CN201611097679.6A CN201611097679A CN106543381A CN 106543381 A CN106543381 A CN 106543381A CN 201611097679 A CN201611097679 A CN 201611097679A CN 106543381 A CN106543381 A CN 106543381A
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- 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
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Abstract
The invention discloses a kind of hydroxyl polyacrylate aqueous dispersion, including the component of following weight portion：400～1000 parts of solvent, Part I monomer mixture include 50～200 parts of hydroxyl monomer, 200～450 parts of acrylate monomer, 0～150 part of vinyl monomer；Part II monomer mixture includes 50～150 parts of hydroxyl monomer, 15～30 parts of carboxyl group-containing monomer, 50～150 parts of acrylate monomer, 0～150 part of vinyl monomer, 10～80 parts of hydrophilic acrylate's derivant；20～40 parts of initiator, 18～25 parts of nertralizer, 800～1200 parts of deionized water.The hydroxyl polyacrylate aqueous dispersion of excellent in stability prepared by the present invention, due to having imported hydrophilic acrylate's derivant, stores more than one month without any layering, sedimentation change under the conditions of 50 DEG C, particle diameter, acid value, pH are held essentially constant.
Description
Technical field
The invention belongs to technical field of coatings, be related to a kind of excellent in stability hydroxyl polyacrylate aqueous dispersion and
Its preparation method.
Background technology
In recent years, with enhancing and a series of national environmental regulations successively put into effect of people's environmental consciousness, high VOC rows
The solvent based coating put just is being subject to increasingly stricter restriction.Water paint due to its have it is nontoxic, do not fire, environmental friendliness, section
The advantages of saving the energy, it has also become the study hotspot of current coating industry, within the following quite a long time, Water-borne modification with it is high
The development trend for being coating industry is located by solid part and powdery paints etc..
Water paint is various with matrix resin species, wherein with excellent film property, good weatherability properties and splendid guarantor's color
The water-borne acrylic resin of the features such as gloss retention is widely used in the covering with paint in the fields such as exterior wall, woodenware, metal, plastic and glass.
And the water based acrylic resin for importing functional group is used cooperatively with amino resins or aqueous polyisocyanate curing agent, energy
The combination property of paint film is enough significantly improved, can be compared favourably with solvent based coating.
Water soluble acrylic acid ester dispersion is generally divided into one-level dispersion and secondary breakup body.One obtained using emulsion polymerization
That the characteristics of level dispersion is particle diameter is larger with molecular weight, without solvent, the large usage quantity in exterior wall latex paint, but using should
Amino-stoving varnish gloss prepared by class dispersion is generally relatively low, and outward appearance is also not satisfactory, and due to the presence of additional emulsifying agent, paint
The resistance to water of film is generally poor.From unlike one-level dispersion, acrylate secondary breakup body is obtained by polymerisation in solution
To containing hydrophilic radical resin, then hydrophilic group partly or entirely neutralize into salt, be scattered in water finally by phase inversion process
In.
Generally hydroxy acrylate secondary breakup body (anionic) need to draw to pursue its dispersibility and storage stability
Enter more carboxyl, and the increase of carboxyl-content causes the acid number of resin to greatly improve, too high acid number causes hydroxy acrylic acid
Declining occur in the water-fast of resin, alkali resistance, and the raising of acid number makes the viscosity of resulting dispersion larger, Gu set containing after being down to 30%
Fat just has certain fluidity, and this causes the construction of its made coating admittedly containing substantially low.
In addition, play the stable anion (mainly carboxylic acid ion) with peptizaiton to be vulnerable in system or outward
Strengthen electrolyte, acid or the impact of alkali, acrylate and be stablizing for the standby water paint of main body resin-made with which
Property is generally unsatisfactory.And contain substantial amounts of ester bond on hydroxyl acrylic resin side chain, these ester bonds are under acid, alkali environment
Hydrolysis is easier, impact is produced on the performance of coating on the one hand, on the other hand also further deteriorate resin and made coating
Stability, the application of serious restriction resin.
In view of this, it is necessary to provide a kind of storage stability excellent hydroxyl polyacrylate aqueous dispersion, with solution
The problem that certainly prior art is present.
The content of the invention
For the problem that polyacrylate secondary breakup body described above is present, it is an object of the invention to provide a kind of synthesis
The simple operable, storage stability of process is excellent, low solvent hydroxyl polyacrylate aqueous dispersion and preparation method thereof；Institute
Stating aqueous dispersion can be used as the hydroxy resin component of bicomponent polyurethane coating, and aqueouss diisocyanate component prepares high-performance
Aqueous polyurethane coating, also can prepare high temperature baking vanish with amino resins.
To reach above-mentioned purpose, the technical solution used in the present invention is as follows：
One aspect of the present invention provide a kind of excellent in stability hydroxyl polyacrylate aqueous dispersion, including with
The component of lower weight portion：
400～1000 parts of solvent；
Part I monomer mixture, including：
50～200 parts of hydroxyl monomer,
200～450 parts of acrylate monomer,
0～150 part of vinyl monomer；
Part II monomer mixture, including：
Preferably, the hydroxyl monomer is selected from (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate, (methyl)
At least one in hy-droxybutyl.
Preferably, the carboxyl group-containing monomer selected from acrylic acid, methacrylic acid, itaconic acid, fumaric acid, in maleic acid extremely
Few one kind, preferred acrylic or methacrylic acid.
Preferably, the acrylate monomer is selected from (methyl) acrylic acid methyl ester., (methyl) sec-butyl acrylate, (methyl)
Ethyl acrylate, (methyl) n-butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) third
The different monooctyl ester of olefin(e) acid, (methyl) dodecylacrylate, (methyl) acrylic acid cocinin, (methyl) octadecyl base
Ester, (methyl) dimethylaminoethyl acrylate, (methyl) diethylaminoethyl acrylate, (methyl) acrylate third
Ester, (methyl) glycidyl acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, Propylene Glycol two (methyl) acrylate, Isosorbide-5-Nitrae-
Butanediol two (methyl) acrylate, Polyethylene Glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, three hydroxyls
At least one in methylpropane three (methyl) acrylate.
Preferably, the vinyl monomer is selected from vinyl acetate, vinyl chloride, dichloro- ethylene, styrene, acrylonitrile, (first
Base) acrylamide, N- (1,1- dimethyl -3- oxo butyl) (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide,
N- methylols (methyl) acrylamide, N- n-butoxies (methyl) acrylamide, N- isobutoxies (methyl) acrylamide, diethyl
At least one in alkenyl benzene.
Preferably, hydrophilic acrylate's derivant be and meanwhile have can addition polymerization double bond and multiple-CH2-CH2-O-
And/or-CH (CH3)-CH2One class compound ACX of-O- chain links, shown in structural formula such as formula (1)：
CH2=C (CH3)-CH2-CH2-O-(CH2-CH2-O)m-(CH(CH3)-CH2-O)n- H formulas (1)
Wherein：M, n are chain number, m=10～60, n=0～10.
Preferably, the initiator is azodiisobutyronitrile, dibenzoyl peroxide, dilauroyl peroxide, peroxidating
Diisopropylbenzene (DIPB), peroxidating tert-butyl acetate, peroxidating acetic acid tert-pentyl ester, peroxidized t-butyl perbenzoate, perbenzoic acid uncle
Pentyl ester, peroxide -2-ethyl hexanoic acid tert-butyl, peroxidating -2 ethyl hexanoic acid tert-pentyl ester, the peroxidating trimethylacetic acid tert-butyl ester, two uncles
At least one in butylperoxide, two t-amyl peroxy compounds.
Preferably, the nertralizer is selected from ammonia, triethylamine, triethanolamine, dimethylethanolamine, 2- methyl-2-aminos
At least one in propanol, dimethylisopro panolamine, methyl diethanolamine, ethyl diisopropylamine, diethyl ethylene diamine；Degree of neutralization
For 50-100%, preferably 75-90%.
Preferably, the solvent is butyl acetate, diethylene glycol dimethyl ether, No. 100 solvent naphthas, No. 200 solvent naphthas, first
Benzene, dimethylbenzene, ethanol, isopropanol, n-butyl alcohol, acetone, butanone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, isophorone, two acetone
Alcohol, ethylene glycol, butyl glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propandiol butyl ether, ethylene glycol ethyl ethers
Ether acetate, 2-Butoxyethyl acetate, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethyl
At least one in glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene, dimethyl ether.Root
The mixture of solvent or solvent is selected according to the principle of solvent boiling point slightly above reaction temperature.
Another aspect of the present invention provides a kind of system of the hydroxyl polyacrylate aqueous dispersion of excellent in stability
Preparation Method, comprises the following steps：
400-1000 part solvents are added, reaction temperature, Deca Part I monomer are heated under the protection of nitrogen
Mixture and Part I initiator, the Part I monomer mixture include 200-450 part acrylate monomers, 50-200
Part hydroxyl monomer, 0～150 part of vinyl monomer, are incubated for the first time, continue Deca Part II monomer mixture and second
Second insulation is carried out after dividing initiator, the Part II monomer mixture includes 50-150 part acrylate monomers, 50-
150 parts of hydroxyl monomers, 0～150 part of vinyl monomer, 15～30 parts of carboxyl group-containing monomers, 10～80 parts of hydrophilic acrylates
Derivant, continues Deca Part III initiator, and third time is incubated, then cooling removing excess of solvent, adds the neutralization of 18-25 parts
4th insulation after agent, last Deca 800-1200 part deionized water, filtering and discharging after the 5th insulation obtain the stability
Excellent hydroxyl polyacrylate aqueous dispersion, wherein：Total part of Part I, Part II and Part III initiator
Number is 20-40 parts.
The first time insulation, second insulation, third time insulation, the 4th insulation, the time of the 5th insulation are
0.5-2 hours.
There is advantages below and beneficial effect due to adopting above-mentioned technical proposal, the present invention：
The hydroxyl polyacrylate aqueous dispersion of the excellent in stability prepared by the present invention, due to having imported hydrophilic third
Olefin(e) acid ester derivant, on the one hand the presence of non-ionic segments can reduce anion is easily affected by strong electrolyte and soda acid,
On the other hand play a part of again to protect the ester bond of polymer lateral chain and then suppress its hydrolysis, so that the storage of dispersion is steady
It is qualitative very excellent, more than one month is stored under the conditions of 50 DEG C without any layering, sedimentation change, particle diameter, acid value, pH are protected substantially
Hold constant.
The hydroxyl polyacrylate aqueous dispersion of the excellent in stability prepared by the present invention and traditional polyacrylate
Secondary breakup body phase ratio, the presence of nucleocapsid structure make resin viscosity lower and admittedly containing higher, while the decline of acid number causes tree
The resistance to water of fat is significantly improved.
The hydroxyl polyacrylate aqueous dispersion of excellent in stability obtained in of the invention and water-compatible amino resin or aqueouss
The film that diisocyanate curing agent is prepared have gloss it is high, it is water-fast it is good, the characteristics of weatherability is excellent.
Specific embodiment
In order to be illustrated more clearly that the present invention, with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, and should not limit this with this
The protection domain of invention.
In the case of being clear to the purpose of the present invention by following examples, being explained, the component of the compositionss
Released bright as the universal standard with weight portion.In the case of without special instruction, for simplicity's sake, institute in the embodiment of the present invention
" part " stated has identical meaning with weight portion.
Embodiment 1
800 parts of propylene glycol methyl ether acetates are added, 130 DEG C is heated under the protection of nitrogen, Deca Part I
Monomer mixture (includes 70 parts of n-butyl acrylates, 300 parts of n-BMAs, 10 parts of ethyleneglycol dimethacrylates
Ester, 100 parts of hydroxyethyl methylacrylates) and 15 parts of peroxidating acetic acid tert-pentyl esters, Deca the is continued in insulation 1.5 hours for the first time
Two partial monosomy mixture (include 20 parts of n-butyl acrylates, 100 parts of n-BMAs, 150 parts of hydroxyethyl methacrylates
Ethyl ester, 25 parts of acrylic acid, 40 parts of hydrophilic acrylate's derivants ACX (m=30, n=5)) and 10 parts of peroxidating acetic acid uncles penta
Second insulation 1 hour after ester, continues 5 parts of peroxidating acetic acid tert-pentyl esters of Deca, and then third time insulation 0.5 hour is cooled to
Excess of solvent is removed after uniform temperature, the 4th insulation 0.5 hour, 1000 parts of last Deca after 20 parts of dimethylethanolamines of addition
Deionized water, the 5th time insulation 1 hour after filtering and discharging, obtain the excellent in stability hydroxyl polyacrylate moisture dissipate
Body.
Embodiment 2
1000 parts of dipropylene glycol methyl ethers are added, 150 DEG C is heated under the protection of nitrogen, Deca Part I monomer
Mixture (includes 70 parts of sec-butyl acrylates, 300 parts of methyl methacrylates, 70 parts of styrene, 100 parts of hy-droxybutyls)
With 18 part of two t-amyl peroxy compound, insulation 1.5 hours, continue Deca Part II monomer mixture (including 20 parts for the first time
Isooctyl acrylate monomer, 100 parts of n-BMAs, 150 parts of methacrylates, 25 parts of acrylic acid, 40 parts it is hydrophilic
Property acrylate derivative ACX (m=20, n=0)) and 12 part of two t-amyl peroxy compound after carry out second insulation 1 hour,
Continue 7 part of two t-amyl peroxy compound of Deca, third time insulation 0.5 hour is removed after being then cooled to uniform temperature unnecessary molten
Agent, the 4th insulation 0.5 hour after 20 parts of dimethylethanolamines of addition, 800 parts of deionized waters of last Deca, the 5th insulation 1
Filtering and discharging after hour, obtains the hydroxyl polyacrylate aqueous dispersion of the excellent in stability.
Embodiment 3
400 parts of dimethylbenzene are added, 130 DEG C is heated under the protection of nitrogen, Deca Part I monomer mixture
(including 70 parts of 2-Propenoic acid, 2-methyl-, isooctyl esters, 300 parts of acrylic acid methyl ester .s, 150 parts of styrene, 100 parts of Hydroxypropyl acrylates) and 18
Part peroxidating acetic acid tert-pentyl ester, insulation 2 hours, continue Deca Part II monomer mixture (including 20 parts of acrylic acid for the first time
Different monooctyl ester, 100 parts of n-BMAs, 150 parts of methacrylates, 25 parts of acrylic acid, 40 parts of hydrophilic propylene
Acid ester derivant ACX (m=50, n=6)) and 12 parts of peroxidating acetic acid tert-pentyl esters after carry out second insulation 1 hour, continue drop
Plus 7 parts of peroxidating acetic acid tert-pentyl esters, third time insulation 1 hour, excess of solvent is removed after being then cooled to uniform temperature, 20 are added
1 hour is incubated 4th time after part triethylamine, 1200 parts of deionized waters of last Deca, filtering and discharging after the 5th insulation 1 hour are obtained
To the hydroxyl polyacrylate aqueous dispersion of the excellent in stability.
Embodiment 4
1000 parts of butyl glycol ethers are added, 150 DEG C are heated under the protection of nitrogen, Deca Part I monomer is mixed
Compound (includes 30 parts of 2-Propenoic acid, 2-methyl-, isooctyl esters, 170 parts of acrylic acid methyl ester .s, 100 parts of styrene, 100 parts of Hydroxypropyl acrylates)
With 12 parts of di-tert-butyl peroxides, insulation 1 hour, continues Deca Part II monomer mixture (including 20 parts of first for the first time
Base Isooctyl acrylate monomer, 50 parts of n-BMAs, 50 parts of styrene, 50 parts of methacrylates, 15 parts of methyl
Acrylic acid, 20 parts of hydrophilic acrylate's derivants ACX (m=60, n=2)) and 6 parts of di-tert-butyl peroxides after carry out
Secondary insulation 1 hour, continues 2 parts of di-tert-butyl peroxides of Deca, and then third time insulation 1 hour is cooled to uniform temperature
After remove excess of solvent, be incubated 1 hour the 4th time after adding 25 parts of ammonia, 1000 parts of deionized waters of last Deca, the 5th guarantor
Temperature filtering and discharging after 1 hour, obtains the hydroxyl polyacrylate aqueous dispersion of the excellent in stability.
Embodiment 5
600 parts of dipropylene glycol methyl ethers are added, 150 DEG C is heated under the protection of nitrogen, Deca Part I monomer
Mixture (includes 30 parts of octadecyl acrylates, 170 parts of acrylic acid methyl ester .s, 100 parts of n-butyl acrylates, 30 parts of acetic acid second
Alkene, 200 parts of hy-droxybutyls) and 24 parts of di-tert-butyl peroxides, insulation 1.5 hours, continue Deca second for the first time
Monomer mixture is divided (to include 20 parts of octadecyl acrylates, 130 parts of methyl methacrylates, 10 parts of vinyl acetates, 50 parts of first
Base 2-(Acryloyloxy)ethanol, 30 parts of methacrylic acids, 17 parts of hydrophilic acrylate's derivants ACX (m=50, n=10)) and 14 parts
Second insulation 1 hour is carried out after di-tert-butyl peroxide, continues 2 parts of di-tert-butyl peroxides of Deca, third time insulation 1
Hour, excess of solvent is removed after being then cooled to uniform temperature, after adding 25 parts of methyl diethanolamines, the 4th insulation 0.5 is little
When, 1000 parts of deionized waters of last Deca, the 5th time insulation 1 hour after filtering and discharging, obtain the excellent in stability containing hydroxyl
Based polyacrylic acid ester aqueous dispersion.
Embodiment 6
800 parts of Ketohexamethylene are added, 80 DEG C is heated under the protection of nitrogen, Deca Part I monomer mixture
(include 30 parts of ethyl acrylate, 150 parts of acrylic acid methyl ester .s, 180 parts of n-butyl acrylates, 30 parts of acrylonitrile, 200 parts of acrylic acid
Hydroxy butyl ester) and 24 parts of azodiisobutyronitriles, insulation 2 hours, continue Deca Part II monomer mixture (including 20 parts for the first time
Ethyl acrylate, 130 parts of methyl methacrylates, 10 parts of acrylonitrile, 50 parts of hydroxyethyl methylacrylates, 30 parts of metering systems
Acid, 15 parts of hydrophilic acrylate's derivants ACX (m=50, n=10)) and 14 parts of azodiisobutyronitriles after carry out second guarantor
Temperature 1 hour, continues 2 parts of azodiisobutyronitriles of Deca, and third time is incubated 1 hour, and it is unnecessary to remove after being then cooled to uniform temperature
Solvent, the 4th insulation 0.5 hour after 25 parts of dimethylisopro panolamines of addition, 950 parts of deionized waters of last Deca, the 5th guarantor
Temperature filtering and discharging after 2 hours, obtains the hydroxyl polyacrylate aqueous dispersion of the excellent in stability.
Embodiment 7
800 parts of diethylene glycol dimethyl ethers are added, 80 DEG C is heated under the protection of nitrogen, Deca Part I monomer
Mixture (including 15 parts of acrylic acid methyl ester .s, 150 parts of methyl methacrylates, 180 parts of n-butyl acrylates, 30 parts of styrene,
200 parts of hy-droxybutyls) and 24 parts of azodiisobutyronitriles, insulation 2 hours, continue the mixing of Deca Part II monomer for the first time
Thing (including 20 parts of ethyl acrylate, 130 parts of tert-butyl acrylates, 70 parts of hydroxyethyl methylacrylates, 25 parts of methacrylic acids,
12 parts of hydrophilic acrylate's derivants ACX (m=50, n=10)) and 14 parts of azodiisobutyronitriles after carry out second insulation 1
Hour, continuing 2 parts of azodiisobutyronitriles of Deca, third time insulation 0.5 hour is removed after being then cooled to uniform temperature unnecessary molten
Agent, the 4th insulation 1 hour after 25 parts of dimethylisopro panolamines of addition, 950 parts of deionized waters of last Deca, the 5th insulation 1
Filtering and discharging after hour, obtains the hydroxyl polyacrylate aqueous dispersion of the excellent in stability.
Embodiment 8
800 parts of diethylene glycol dimethyl ethers are added, 120 DEG C is heated under the protection of nitrogen, Deca Part I list
Body mixture (including 15 parts of methyl methacrylates, 150 parts of acrylic acid methyl ester .s, 180 parts of n-butyl acrylates, 30 parts of styrene,
200 parts of hy-droxybutyls) and 17 parts of peroxidized t-butyl perbenzoates, insulation 1 hour, continues Deca Part II list for the first time
Body mixture (includes 20 parts of ethyl acrylate, 130 parts of tert-butyl acrylates, 70 parts of hydroxyethyl methylacrylates, 25 parts of methyl-props
Olefin(e) acid, 80 parts of hydrophilic acrylate's derivants ACX (m=50, n=10)) and 14 parts of peroxidized t-butyl perbenzoates carry out
Secondary insulation 1 hour, continues 2 parts of peroxidized t-butyl perbenzoates of Deca, and then third time insulation 1 hour is cooled to a constant temperature
Excess of solvent is removed after degree, the 4th insulation 1 hour, 1050 parts of deionizations of last Deca after 25 parts of dimethylisopro panolamines of addition
Water, the 5th time insulation 1.5 hours after filtering and discharging, obtain the hydroxyl polyacrylate aqueous dispersion of the excellent in stability.
Embodiment 9
700 parts of dipropylene glycol methyl ethers are added, 120 DEG C is heated under the protection of nitrogen, Deca Part I monomer
Mixture (includes 150 parts of methyl methacrylates, 180 parts of n-butyl acrylates, 30 parts of styrene, 150 parts of acrylic acid hydroxyl fourths
Ester) and 17 parts of peroxidized t-butyl perbenzoates, insulation 1 hour, continues Deca Part II monomer mixture (including 20 for the first time
Part ethyl acrylate, 130 parts of tert-butyl acrylates, 70 parts of hydroxyethyl methylacrylates, 25 parts of methacrylic acids, 50 parts of hydrophilic
Acrylate derivative ACX (m=50, n=6)) and 14 parts of peroxidized t-butyl perbenzoates carry out second insulation 1 hour, after
2 parts of peroxidized t-butyl perbenzoates of continuous Deca, third time insulation 1 hour, remove excess of solvent after being then cooled to uniform temperature,
4th insulation 1 hour after 18 parts of dimethylisopro panolamines of addition, 800 parts of deionized waters of last Deca, the 5th insulation 1 hour
Filtering and discharging, obtains the hydroxyl polyacrylate aqueous dispersion of the excellent in stability afterwards.
Comparative example 1
800 parts of propylene glycol methyl ether acetates are added, 130 DEG C is heated under the protection of nitrogen, 90 parts of propylene of Deca
Sour N-butyl, 400 parts of n-BMAs, 10 parts of methacrylic acid glycol esters, 250 parts of hydroxyethyl methylacrylates,
25 parts of acrylic acid, 40 parts of hydrophilic acrylate's derivants ACX (m=30, n=5) and 25 parts of peroxidating acetic acid tert-pentyl esters, are carried out
Insulation 2 hours, continues 5 parts of peroxidating acetic acid tert-pentyl esters of Deca, is incubated 1 hour, and it is unnecessary to remove after being then cooled to uniform temperature
Solvent, is incubated 1 hour after adding 20 parts of dimethylethanolamines, and 1000 parts of deionized waters of last Deca, insulation were filtered out after 1 hour
Material, obtains hydroxyl polyacrylate aqueous dispersion.
Comparative example 2
800 parts of propylene glycol methyl ether acetates are added, 130 DEG C is heated under the protection of nitrogen, Deca Part I
Monomer mixture (including 70 parts of n-butyl acrylates, 300 parts of n-BMAs, 10 parts of methacrylic acid glycol esters,
100 parts of hydroxyethyl methylacrylates) and 15 parts of peroxidating acetic acid tert-pentyl esters, 2 hours are incubated, are continued Deca Part II monomer and is mixed
Compound (including 20 parts of n-butyl acrylates, 100 parts of n-BMAs, 150 parts of hydroxyethyl methylacrylates, 25 part third
Olefin(e) acid) and 10 parts of peroxidating acetic acid tert-pentyl esters after carry out insulation 2 hours, continue 5 parts of peroxidating acetic acid tert-pentyl esters of Deca, insulation 1
Hour, excess of solvent is removed after being then cooled to uniform temperature, 1 hour is incubated after adding 20 parts of dimethylethanolamines, is finally dripped
Plus 1000 parts of deionized waters, filtering and discharging after being incubated 1 hour, obtain hydroxyl polyacrylate aqueous dispersion.
Comparative example 3
800 parts of propylene glycol methyl ether acetates are added, 130 DEG C is heated under the protection of nitrogen, Deca Part I
Monomer mixture (including 70 parts of n-butyl acrylates, 300 parts of n-BMAs, 10 parts of methacrylic acid glycol esters,
100 parts of hydroxyethyl methylacrylates) and 15 parts of peroxidating acetic acid tert-pentyl esters, 2 hours are incubated, are continued Deca Part II monomer and is mixed
Compound (including 20 parts of n-butyl acrylates, 100 parts of n-BMAs, 150 parts of hydroxyethyl methylacrylates, 25 part third
Olefin(e) acid, 40 parts of hydrophilic acrylate's derivants ACX (m=70, n=20)) and 10 parts of peroxidating acetic acid tert-pentyl esters after protected
Temperature 1 hour, continues 5 parts of peroxidating acetic acid tert-pentyl esters of Deca, is incubated 1 hour, removes unnecessary molten after being then cooled to uniform temperature
Agent, is incubated 1 hour after adding 20 parts of dimethylethanolamines, and 1000 parts of deionized waters of last Deca, insulation were filtered out after 1 hour
Material, obtains the hydroxyl polyacrylate aqueous dispersion of the excellent in stability.
Embodiment 1～9 is as shown in table 1 with the performance test results of comparative example 1～3：
Table 1
Note：Zero represents outstanding, and △ represents general, × represent poor.
From embodiment 1 and the result of comparative example 1, comparative example 1 is very big by the resin viscosity that one-step polymerization is obtained, breast
Change process is difficult, and heat storage is layered after one week quickly.
From embodiment 1 and the result of comparative example 2, comparative example 2 is without hydrophilic acrylate's derivant ACX
In the case of, the neutralization emulsion process of resin is relatively easy, but the stability for obtaining resin is not good enough, and after heat is stored up two weeks, acid value rises
Substantially, while particle diameter is also significantly raised, resin sedimentation after four weeks.
From embodiment 1 and the result of comparative example 3, excessive alkoxyl chain link in hydrophilic acrylate's derivant ACX
Presence cause emulsifying difficult, dispersion viscosity is very big, needs dilute just with considerable mobility.
The hydroxyl polyacrylate aqueous dispersion of the excellent in stability prepared by the present invention, due to having imported hydrophilic third
Olefin(e) acid ester derivant, on the one hand the presence of non-ionic segments can reduce anion is easily affected by strong electrolyte and soda acid,
On the other hand play a part of again to protect the ester bond of polymer lateral chain and then suppress its hydrolysis, so that the storage of dispersion is steady
It is qualitative very excellent, more than one month is stored under the conditions of 50 DEG C without any layering, sedimentation change, particle diameter, acid value, pH are protected substantially
Hold constant.
The hydroxyl polyacrylate aqueous dispersion of the excellent in stability prepared by the present invention and traditional polyacrylate
Secondary breakup body phase ratio, the presence of nucleocapsid structure make resin viscosity lower and admittedly containing higher, while the decline of acid number causes tree
The resistance to water of fat is significantly improved.
The hydroxyl polyacrylate aqueous dispersion of excellent in stability obtained in of the invention and water-compatible amino resin or aqueouss
The film that diisocyanate curing agent is prepared have gloss it is high, it is water-fast it is good, the characteristics of weatherability is excellent.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not right
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, the embodiment enumerated by the present invention cannot give to all of embodiment thoroughly
To the greatest extent, it is every belong to technical scheme it is extended obvious change or change still in protection model of the invention
The row for enclosing.The all documents for referring in the present invention all in this application be incorporated as reference, as same piece document it is independent
It is cited as with reference to such.
Claims (10)
1. a kind of hydroxyl polyacrylate aqueous dispersion, it is characterised in that：Including the component of following weight portion：
400～1000 parts of solvent；
Part I monomer mixture, including：
50～200 parts of hydroxyl monomer,
200～450 parts of acrylate monomer,
0～150 part of vinyl monomer；
Part II monomer mixture, including：
2. hydroxyl polyacrylate aqueous dispersion according to claim 1, it is characterised in that：The hydroxyl monomer choosing
At least one from (methyl) 2-(Acryloyloxy)ethanol, (methyl) Hydroxypropyl acrylate, (methyl) hy-droxybutyl.
3. hydroxyl polyacrylate aqueous dispersion according to claim 1, it is characterised in that：The carboxyl group-containing monomer choosing
At least one from acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid.
4. hydroxyl polyacrylate aqueous dispersion according to claim 1, it is characterised in that：The acrylate monomer
Selected from (methyl) acrylic acid methyl ester., (methyl) sec-butyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate,
(methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) lauryl base
Ester, (methyl) acrylic acid cocinin, (methyl) octadecyl acrylate, (methyl) dimethylaminoethyl acrylate, (first
Base) diethylaminoethyl acrylate, (methyl) dimethylaminoethyl methacrylate, (methyl) glycidyl acrylate, ethylene glycol
Two (methyl) acrylate, Propylene Glycol two (methyl) acrylate, BDO two (methyl) acrylate, Polyethylene Glycol two
In (methyl) acrylate, polypropylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate at least
It is a kind of.
5. hydroxyl polyacrylate aqueous dispersion according to claim 1, it is characterised in that：The vinyl monomer choosing
From vinyl acetate, vinyl chloride, dichloro- ethylene, styrene, acrylonitrile, (methyl) acrylamide, N- (1,1- dimethyl -3- oxygen
For butyl) (methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, N- methylols (methyl) acrylamide, the positive fourths of N-
At least one in epoxide (methyl) acrylamide, N- isobutoxies (methyl) acrylamide, divinylbenzene.
6. hydroxyl polyacrylate aqueous dispersion according to claim 1, it is characterised in that：The hydrophilic acrylic
Ester derivant be and meanwhile have can addition polymerization double bond and multiple-CH2-CH2- O- and/or-CH (CH3)-CH2One class of-O- chain links
Compound ACX, shown in structural formula such as formula (1)：
CH2=C (CH3)-CH2-CH2-O-(CH2-CH2-O)m-(CH(CH3)-CH2-O)n- H formulas (1)
Wherein：M, n are chain number, m=10～60, n=0～10.
7. hydroxyl polyacrylate aqueous dispersion according to claim 1, it is characterised in that：The initiator is azo
Bis-isobutyronitrile, dibenzoyl peroxide, dilauroyl peroxide, cumyl peroxide, peroxidating tert-butyl acetate, peroxidating
Acetic acid tert-pentyl ester, peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, peroxide -2-ethyl hexanoic acid tert-butyl, peroxide
In change -2 ethyl hexanoic acid tert-pentyl ester, the peroxidating trimethylacetic acid tert-butyl ester, di-tert-butyl peroxide, two t-amyl peroxy compounds
It is at least one.
8. hydroxyl polyacrylate aqueous dispersion according to claim 1, it is characterised in that：The nertralizer is selected from ammonia
Water, triethylamine, triethanolamine, dimethylethanolamine, 2- methyl-2-amino propanol, dimethylisopro panolamine, methyl diethanol
At least one in amine, ethyl diisopropylamine, diethyl ethylene diamine；Degree of neutralization is 50-100%；
The solvent is butyl acetate, diethylene glycol dimethyl ether, No. 100 solvent naphthas, No. 200 solvent naphthas, toluene, dimethylbenzene, second
Alcohol, isopropanol, n-butyl alcohol, acetone, butanone, methyl iso-butyl ketone (MIBK), Ketohexamethylene, isophorone, DAA, ethylene glycol ethyl ethers
Ether, butyl glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propandiol butyl ether, ethylene glycol ether acetate, second
Glycol monobutyl ether acetate, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetate, diethylene glycol dimethyl ether, butyl, two
At least one in propylene glycol monomethyl ether, dipropylene glycol ethyl ether, dipropylene, dimethyl ether.
9. the preparation method of the arbitrary described hydroxyl polyacrylate aqueous dispersion of a kind of claim 1 to 8, its feature exist
In：Comprise the following steps：
400-1000 part solvents are added, reaction temperature, the mixing of Deca Part I monomer are heated under the protection of nitrogen
Thing and Part I initiator, the Part I monomer mixture include that 200-450 part acrylate monomers, 50-200 parts contain
Carboxylic monomer, 0～150 part of vinyl monomer, are incubated for the first time, continue Deca Part II monomer mixture and Part II draws
Second insulation is carried out after sending out agent, the Part II monomer mixture includes 50-150 part acrylate monomers, 50-150 parts
Hydroxyl monomer, 0～150 part of vinyl monomer, 15～30 parts of carboxyl group-containing monomers, 10～80 parts of hydrophilic acrylates derive
Thing, continues Deca Part III initiator, and third time is incubated, then cooling removing excess of solvent, after adding 18-25 part nertralizers
4th insulation, last Deca 800-1200 part deionized water, filtering and discharging after the 5th insulation obtain the hydroxyl poly- third
Olefin(e) acid ester aqueous dispersion, wherein：The total number of Part I, Part II and Part III initiator is 20-40 parts.
10. the preparation method of hydroxyl polyacrylate aqueous dispersion according to claim 9, it is characterised in that：It is described
Insulation for the first time, second insulation, third time insulation, the 4th insulation, the time of the 5th insulation are 0.5-2 hours.
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