CN107513124A - A kind of polyester acrylic ester aqueous dispersion and preparation method thereof - Google Patents
A kind of polyester acrylic ester aqueous dispersion and preparation method 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
The present invention relates to a kind of polyester acrylic ester aqueous dispersion, it is made up of water-based saturated polyester resin and polyacrylate two parts, described water-based saturated polyester resin coats polyacrylate wherein as macromole emulsifying agent；The mass ratio of described water-based saturated polyester resin and polyacrylate is 1:0.6‑1.5；Its preparation process is：Step 1：Water-based saturated polyester resin, step 2 is made：With hydroxyl (methyl) acrylic monomer, (methyl) alkyl-acrylates monomer, initiator azodiisobutyronitrile and/or benzoyl peroxide, the mixed liquor of chain-transferring agent mercaptoethanol, it is added dropwise in water-based saturated polyester resin, Raolical polymerizable is carried out, obtains polyester acrylic ester aqueous dispersion；The polyester acrylic ester aqueous dispersion incorporates the weatherability of the excellent richness of polyester resin and acrylic resin, can be widely applied to prepare the coating such as coating varnish, solid color enamel and metal flash paint, has good versatility.
Description
Technical field
The present invention relates to a kind of preparation method of coating resin, and in particular to a kind of waterborne polyester acrylate moisture dissipates
Body and preparation method thereof.
Background technology
Coating using acrylic resin as matrix has excellent weatherability and protects light colour retention, but its richness is not enough managed
Think；Coating using polyester resin as matrix has excellent richness, but its weatherability, acid and alkali-resistance and water resistance are not ideal enough.
The advantages of integrating two kinds of resins, at utmost meets high request of the industry for the outward appearance of coating, dryness and durability, is current
One of hot issue of industry research.
In order to obtain acrylic acid modified polyester resin, general scheme can be divided into three classes：1) cold spelling, i.e., by acrylic acid tree
Fat and polyester resin physical blending, such as patent CN200680030088, CN200810233331；2) first condensation methods, i.e., it is sharp first
Unsaturated polyester (UP) is prepared with unsaturated monomers such as cis-butenedioic anhydride, fumaric acid, itaconic acids, then by (methyl) acrylic ester monomer and not
Saturated polyester reacts, and realizes both grafting, such as CN200680052504；3) first pre-polymerization aftercondensated method, i.e., prepare end first
Acrylic resin with carboxyl or/and hydroxyl, itself and polyacid and polyalcohol are then subjected to condensation reaction, acrylic acid is made
Modified polyester resin, such as CN200610024367.
Cold spelling is higher to the compatibility requirements of resin, and use range is limited, and effect is also not ideal enough；First condensation methods need
Unsaturated polyester (UP) is first prepared, but because unsaturated polyester (UP) viscosity is big, functional group's steric hindrance is larger, position of double bond, and number and activity are low
The problems such as cause the later stage carry out (methyl) acrylic ester monomer graft polymerization rate it is low, can even not be grafted successfully；It is first pre-
Poly- aftercondensated method technique, it is very high to the structural requirement of acrylic resin, and easily occur by high-temperature polycondensation acrylic resin
Cracking, coking, this method technique is difficult to control, easy gelation.
Patent CN201210329381.9 provides a kind of preparation method of the hybrid aqueous dispersion of polyester acrylate.This method is first
After first mixing synthetic polyester resin and acrylic ester monomer, then using the feed way being added dropwise, acrylic acid is carried out
Polymerisation in solution, make to form inierpeneirating network structure between two kinds of resin segments by this method, improve the compatible of two kinds of resins
Property, its essence is " cold spelling ", but is to carry out at a certain temperature, and its formed interpenetrating networks another " line " be by
Gradually formed, can so improve the compatibility of two kinds of resins.
The content of the invention
The technical problems to be solved by the invention are, for conventional polyester and polyacrylate resin physical mixed compatibility
A kind of difference, the shortcomings of chemical mode modified technique difficulty, there is provided polyester acrylic ester aqueous dispersion.
In order to solve the above technical problems, the technical scheme used for：A kind of polyester acrylic ester aqueous dispersion, by water-based full
Formed with polyester resin and polyacrylate two parts, described water-based saturated polyester resin, will be poly- as macromole emulsifying agent
Acrylate coats wherein；The mass ratio of described water-based saturated polyester resin and polyacrylate is 1:0.6~1.5；
Described water-based saturated polyester resin, its hydroxyl value are 80~160mgKOH/g, and acid number is 60~100mgKOH/g, Gu
Body content is 50~60 weight %, viscosity be 1000~3000mPa.s (25 ± 1 DEG C of temperature during test, during viscosity test at a temperature of
Together), number-average molecular weight is 2000~4000, and glass transition temperature is -10 DEG C~20 DEG C；
Described polyester acrylic ester aqueous dispersion, its average grain diameter are 100~150nm, and particle diameter distribution is narrow, and hydroxyl value is
100~160mgKOH/g, acid number are 40~60mgKOH/g, and solids content is 60~70 weight %, viscosity is 1500~
4000mPa.s, number-average molecular weight are 4000~7000, and glass transition temperature is -10 DEG C~30 DEG C；Its preparation method：First
Step first be made water-based saturated polyester resin, the water-based saturated polyester resin that second step is synthesized using the first step as macromole emulsifying agent,
By the way that hydroxyl (methyl) acrylic monomer, (methyl) alkyl-acrylates monomer, initiator azo are gradually added dropwise thereto
Bis-isobutyronitrile and/or benzoyl peroxide, the mixed liquor of chain-transferring agent composition, in macromole emulsifying agent (aqueous polyester resin)
Portion carries out radical polymerization.
Second technical problem to be solved by this invention be：A kind of preparation side of polyester acrylic ester aqueous dispersion is provided
Method；This method polymerization technique is simple, the problem of can solve two kinds of resin compatible differences, fully integrates two kinds of resins each
Excellent specific property.
To solve second technical problem, the technical solution adopted by the present invention is：A kind of polyester acrylic ester aqueous dispersion
Preparation method, its step is：Step 1：Water-based saturated polyester resin, step 2 is made：The water-based saturation synthesized to step 1
Gradually it is added dropwise containing hydroxyl (methyl) acrylic monomer, (methyl) alkyl-acrylates monomer, initiator in polyester resin
Azodiisobutyronitrile and/or benzoyl peroxide, the mixed liquor of chain-transferring agent mercaptoethanol, are carried out inside saturated polyester resin
Radical polymerization, obtain polyester acrylic ester aqueous dispersion；
By weight, the parts by weight of described hydroxyl (methyl) acrylic monomer 30~70, (methyl) acrylic acid alkyl
The parts by weight of esters monomer 30~80, initiator azodiisobutyronitrile and/or the parts by weight of benzoyl peroxide 1~5, chain-transferring agent mercapto
The parts by weight of base ethanol 1~5；Water-based saturated polyester resin described in step 1 and the monomer described in step 2, initiator and
The weight ratio that chain-transferring agent three amounts to is 1：0.6~1.5；
The preparation of water-based saturated polyester resin described in step 1, its step include：Described water-based saturated polyester tree
Include organic solvent and dimethylethanolamine in fat, the content of organic solvent is figured as 10~50 parts by mass parts, dimethyl second
The content of hydramine is figured as 10~40 parts by mass parts, and its preparation method is as follows：
a：In a kettle, phthalic anhydride, M-phthalic acid, adipic acid, HHPA, ethylene glycol, diethylene glycol, new penta are added
Glycol, trimethylolpropane and Mono-n-butyltin, and logical nitrogen protection；
b：150~160 DEG C are warming up to, melts most of solid matter, starts stirring；
c：170 ± 5 DEG C and 1 ± 0.1h of constant temperature are warming up to, are warming up to 190 ± 5 DEG C, 2~3h of reaction to water yield reaches >=
90% Theoretical Mass；Then 220~230 DEG C are gradually warming up to, is incubated 2~3h；
d：Sampling detecting acid number, when acid number is 5~10mgKOH/g, 170~180 DEG C are cooled to, adds the inclined benzene of formula ratio
Three acid anhydrides；
e：Sampling detecting acid number again, when acid number is 60~100mgKOH/g, add the organic solvent of formula ratio；
f：50~80 DEG C are cooled to, adds dimethylethanolamine 0.5 ± 0.1h of neutralization reaction, adds deionized water, adjustment
Solid content is 50~60%, and agitation and filtration produces water-based saturated polyester resin；Described water-based saturated polyester resin, hydroxyl value 80
~160mgKOH/g, acid number are 60~100mgKOH/g, and solids content is 50~60 weight %, viscosity is 1000~
3000mPa.s, number-average molecular weight are 2000~4000, and glass transition temperature is -10 DEG C~20 DEG C.
By mass fraction, the mass fraction of reaction raw materials is：Phthalic anhydride：15-30 parts, M-phthalic acid：20-30 parts, oneself two
Acid：20-30 parts, HHPA：25-30 parts, trimellitic anhydride：15-40 parts, ethylene glycol：25-30 parts, diethylene glycol：15-20
Part, neopentyl glycol：25-30 parts, trimethylolpropane：5-25 parts, Mono-n-butyltin：0.1-0.5 parts；Organic solvent：10-50
Part, dimethylethanolamine 10-40 parts.
In the preparation process of water-based saturated polyester resin described in step 1, organic solvent used is propylene glycol monomethyl ether
One or more in acetate, glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether；
The specific preparation method of described step two includes：
a：The water-based saturated polyester tree of the gained of the step of mass fraction is 100 parts (solid gauge) one is added in the reactor
Fat, and logical nitrogen deoxygenation；
b：Stirring is warming up to 60~90 DEG C, is added dropwise at this temperature by the hydroxyl (methyl) that mass fraction is 60~150 parts
Acrylic monomer, (methyl) alkyl-acrylates monomer, initiator azodiisobutyronitrile and/or benzoyl peroxide, chain
The mixed liquor of transfer agent mercaptoethanol, time for adding are 2~3h；
c：2~3h of insulation reaction again is dripped, reaction terminates, and is cooled to≤50 DEG C, filtering, discharging is polyester acrylic
Ester aqueous dispersion, its average grain diameter is small, is 100~150nm, and particle diameter distribution is narrow, and hydroxyl value is 100~160mgKOH/g, and acid number is
40~60mgKOH/g, solids content are 60~70 weight %, and viscosity is 1500~4000mPa.s, number-average molecular weight is 4000~
7000, glass transition temperature is -10 DEG C~30 DEG C.
Described hydroxyl (methyl) acrylic monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid hydroxyl fourth
One or more in ester, hydroxyethyl methacrylate, hydroxy propyl methacrylate, methacrylate.
Described (methyl) alkyl-acrylates monomer is methyl methacrylate, EMA, methyl-prop
Olefin(e) acid N-butyl, Isobutyl methacrylate, Tert-butyl Methacrylate, methacrylic acid -2- ethylhexyls, methacrylic acid
Cyclohexyl, phenyl methacrylate, methacrylic acid 3-methyl cyclohexanol ester, t-butyl cyclohexyl ester, metering system
Sour isobornyl thiocyanoacetate, lauryl methacrylate, octadecyl methacrylate, methyl acrylate, ethyl acrylate, acrylic acid
One or more in propyl ester, butyl acrylate, acrylic acid-2-ethyl caproite, lauryl acrylate.
Beneficial effect：Polyester acrylic aqueous dispersion disclosed in the present application, overcomes conventional polyester and polyacrylate tree
The shortcomings that fat physical mixed poor compatibility, the polyester acrylic ester aqueous dispersion average grain diameter being prepared are 100~150nm,
Particle diameter distribution is narrow, overcomes the shortcomings that chemical mode modified technique difficulty, and this preparation process only needs two steps, and second step polymerization temperature
Spend it is low, 60~90 DEG C.
Brief description of the drawings
Fig. 1：Polyester acrylic ester aqueous dispersion structural formula；
1 is polyacrylate in figure；
Fig. 2：Water-based saturated polyester resin GPC (molecular weight) collection of illustrative plates of embodiment 1；
Fig. 3：Water-based saturated polyester resin DSC (Tg) collection of illustrative plates of embodiment 1；
Fig. 4：Embodiment 1 polyester acrylic ester aqueous dispersion GPC (molecular weight) collection of illustrative plates；
Fig. 5：Embodiment 1 polyester acrylic ester aqueous dispersion DSC (Tg) collection of illustrative plates；
Fig. 6：Embodiment 1 polyester acrylic ester aqueous dispersion DLS (particle diameter) collection of illustrative plates；
Fig. 7：Embodiment 2 polyester acrylic ester aqueous dispersion GPC (molecular weight) collection of illustrative plates；
Fig. 8：Embodiment 2 polyester acrylic ester aqueous dispersion DSC (Tg) collection of illustrative plates；
Fig. 9：Embodiment 2 polyester acrylic ester aqueous dispersion DLS (particle diameter) collection of illustrative plates；
Figure 10：The application reaction mechanism schematic diagram.
Embodiment
In order to preferably understand the present invention, the present invention is further described with reference to comparative example and embodiment, but the present invention
Claimed scope is not limited to the scope of embodiment statement.
Embodiment 1
1) step 1：The preparation of water-based saturated polyester resin：By 80g phthalic anhydrides (PA), 100g M-phthalic acids (IPA),
100g adipic acids (AA), 100g HHPAs (HHPA), 112g ethylene glycol (EG), 60g diethylene glycols (DEG), 112g new penta 2
Alcohol (NPG), 20g trimethylolpropanes (TMP) and 1.2g Mono-n-butyltins are added to condenser pipe, water knockout drum, puddler
And have logical nitrogen device four round flask in, heated up when being passed through nitrogen.150~160 DEG C are warming up to, makes most of solid
Matter melts, start stirring；170 DEG C and constant temperature 1h are warming up to, is warming up to 190 DEG C, 2~3h of reaction to water yield reaches theoretical amount
More than 90%；Then 220~230 DEG C are gradually warming up to, is incubated 2~3h；Sampling detecting acid number, when acid number is 5~10mgKOH/g
When, 170~180 DEG C are cooled to, adds 120g trimellitic anhydrides (TMA)；Sampling detecting acid number, when acid number is 95 ± 2mgKOH/g
When, add 110g ethylene glycol monobutyl ethers；50~80 DEG C are cooled to, adds 100g dimethylethanolamines (DMEA) neutralization reaction
0.5h, 392g deionized waters are added, adjustment solid content is 55%, and agitation and filtration produces water-based saturated polyester resin.Described water
The hydroxyl value of property saturated polyester resin (PE) is 142mgKOH/g, acid number 95mgKOH/g, solid content 55%, and viscosity is
1500mPa.s, number-average molecular weight are that 2500 (water-based saturated polyester resin GPC (molecular weight) collection of illustrative plates is shown in Fig. 2；), glass transition
Temperature is -7.6 DEG C (water-based saturated polyester resin DSC (Tg) collection of illustrative plates is shown in Fig. 3), and the aqueous solution pH of polyester 1% is 8.5；
Water-based saturated polyester resin GPC (molecular weight) result：
GPC results
Obtained water-based saturated polyester resin carries out performance characterization using following methods：
Molecular weight is tested：Determined using the Waters515 gel permeation chrommatographs of Waters, US；
Solid content is tested：With reference to determination of solid content GB/T1725-2007；
Acid value measuring：With reference to the measure HG/T2708-1995 of acid number
Hydroxy value measuring：With reference to the measure HG/T2709-1995 of hydroxyl value
Viscosity is tested：Determined using NDJ-1 types rotary viscosimeter
PH value is tested：Use pHS-2C type precision acidity meters
Step 2：The preparation of polyester acrylic ester aqueous dispersion：By the water-based saturated polyester tree prepared by 250g step 1
Fat is added in the reactor with condensing unit and puddler, and 80 DEG C are warming up to when being passed through nitrogen；After constant temperature, start to be added dropwise
20g methyl methacrylates, 30g butyl acrylates, 30g hydroxyethyl methacrylates, 3g azodiisobutyronitriles, 2g mercaptoethanols
The mixed solution of composition.Control rate of addition, time for adding 3h；Insulation reaction 2h again is dripped, stops reaction, be cooled to≤
50 DEG C, polyester acrylic ester aqueous dispersion (PEA) is made in filtering, discharging.Outward appearance is white emulsion, and hydroxyl value is
145.8mgKOH/g, acid number 58.7mgKOH/g, solid content 66.4%, viscosity 2000mPa.s, number-average molecular weight are
5100 (polyester acrylic ester aqueous dispersion GPC (molecular weight) collection of illustrative plates is shown in Fig. 4), glass transition temperature has two, waterborne polyester
Part is -8.1 DEG C, and polyacrylic acid ester moiety is 23.8 DEG C, and it is 5.2 DEG C of (polyester to convert total glass transition temperature by weight
Acrylate aqueous dispersion DSC (Tg) collection of illustrative plates is shown in Fig. 5), the aqueous solution pH of polyester acrylic ester aqueous dispersion 1% is 7.9, and particle diameter is
108nm (polyester acrylic ester aqueous dispersion DLS (particle diameter) collection of illustrative plates is shown in Fig. 6).
Polyester acrylic ester aqueous dispersion GPC (molecular weight) result
GPC results
Obtained polyester acrylic ester aqueous dispersion carries out performance characterization using following methods：
Particle size distribution test：Using ZetasizerNanoZS90 laser fineness gages.
Embodiment 2
1) step 1：The preparation of water-based saturated polyester resin：It is identical with step 1 in embodiment 1.
2) step 2：The preparation of polyester acrylic ester aqueous dispersion：Water-based saturation prepared by the step 1 of 125g embodiments 1
Polyester resin and 21.5g deionized waters are added in the reactor with condensing unit and puddler, are heated up when being passed through nitrogen
To 80 DEG C；After constant temperature, start that 20g methyl methacrylates, 30g butyl acrylates, 30g hydroxyethyl methacrylates, 3g is added dropwise
The mixed solution of azodiisobutyronitrile, 2g mercaptoethanols composition.Control rate of addition, time for adding 3h；Drip and be incubated again
2h is reacted, stops reaction, is cooled to≤50 DEG C, polyester acrylic ester aqueous dispersion is made in filtering, discharging.Outward appearance is white breast
Liquid, hydroxyl value 147.6mgKOH/g, acid number 42.5mgKOH/g, solid content 66.4%, viscosity 2500mPa.s, number are divided equally
Son amount is 5300 (polyester acrylic ester aqueous dispersion GPC (molecular weight) collection of illustrative plates is shown in Fig. 7), and glass transition temperature has two, water
Property polyester portion be -8.8 DEG C, polyacrylic acid ester moiety is 24.9 DEG C, converts total glass transition temperature by weight as 12.3
DEG C (polyester acrylic ester aqueous dispersion DSC (Tg) collection of illustrative plates is shown in Fig. 8), the aqueous solution pH of polyester acrylic ester aqueous dispersion 1% is
7.8, particle diameter is 150nm (polyester acrylic ester aqueous dispersion DLS (particle diameter) collection of illustrative plates is shown in Fig. 9).
Obtained water-based saturated polyester resin carries out the method for performance characterization with embodiment 1.
Polyester acrylic ester aqueous dispersion GPC (molecular weight) result
GPC results
As a result and discuss
The application uses two-step method synthesizing polyester polyacrylate aqueous dispersion, i.e. water-based saturated polyester is first made in step 1
Resin, its hydroxyl value are 80~160mgKOH/g, and acid number is 60~100mgKOH/g, and solids content is 50~60 weight %, viscosity
For 1000~3000mPa.s, number-average molecular weight is 2000~4000, and glass transition temperature is -10 DEG C~20 DEG C；Because it has
Compared with polyhydroxy and neutralized carboxyl functional group, therefore it has excellent water solubility.Because water is as continuous in step 1 product
Phase, therefore its state in water similar to the surfactant of small molecule is hydrophilic radical assembles towards water, the aggregation of hydrophobic grouping backwater；Step
Rapid two, by the use of the product of step 1 as macromole emulsifying agent, are added dropwise monomer, initiator and chain-transferring agent carry out emulsion polymerization, most
Polyester acrylic ester aqueous dispersion is obtained eventually；Its hydroxyl value is 100~160mgKOH/g, and acid number is 40~60mgKOH/g, and solid contains
It is 1500~4000mPa.s to measure as 60~70 weight %, viscosity, and number-average molecular weight is 4000~7000, glass transition temperature
For 0 DEG C~25 DEG C；Its average grain diameter is small, is 100~150nm, and particle diameter distribution is narrow.Specific reaction mechanism as shown in Figure 10, this method
Polymerization technique is simple, solves the problems, such as two kinds of resin compatible differences well, incorporate the excellent richness of polyester resin and
It the weatherability of acrylic resin, can be widely applied to prepare the coating such as coating varnish, solid color enamel and metal flash paint, have fine
Versatility.
Comparing embodiment 1 and 2 we have found that itself main difference is that, embodiment 2 reduces water-based saturated polyester resin
The dosage of dosage, i.e. macromole emulsifying agent reduces, from the result of particle diameter we can see that particle diameter is from the 108nm of embodiment 1
Become for the 150nm of embodiment 2, this is also to explain, with the reduction of emulsifying agent, the micellar phase of formation, which should be reduced, gathers
Place is closed to tail off, and amount of monomer is unchanged, its particle diameter becomes big naturally.What macromole emulsifying agent dosage can not be unlimited certainly tails off,
After diminishing to a certain extent, monomer can so cause the failure of polymerisation just without enough locus of polymerization, therefore water-based saturation
Polyester resin (macromole emulsifying agent) and the parts by weight for carrying out monomer used in radical polymerization, initiator and chain-transferring agent wherein
Than being calculated as 1 by solid masses：0.6~1.5；The structure of macromole emulsifying agent also has special requirement, i.e., its hydroxyl value be 80~
160mgKOH/g, acid number are 60~100mgKOH/g, and solids content is 50~60 weight %, and viscosity is 1000~3000mPa.s,
Number-average molecular weight is 2000~4000, and glass transition temperature is -10 DEG C~20 DEG C, not so will also result in the mistake of polymerisation
Lose.
Claims (9)
1. a kind of polyester acrylic ester aqueous dispersion, is made up of water-based saturated polyester resin and polyacrylate two parts, described
Water-based saturated polyester resin as macromole emulsifying agent, by polyacrylate cladding wherein；Described water-based saturated polyester tree
The mass ratio of fat and polyacrylate is 1:0.6~1.5；
Described water-based saturated polyester resin, its hydroxyl value are 80~160mgKOH/g, and acid number is 60~100mgKOH/g, and solid contains
It is 1000~3000mPa.s to measure as 50~60 weight %, viscosity, and number-average molecular weight is 2000~4000, glass transition temperature
For -10 DEG C~20 DEG C；
Described polyester acrylic ester aqueous dispersion, its average grain diameter are 100~150nm, and hydroxyl value is 100~160mgKOH/g,
Acid number is 40~60mgKOH/g, and solids content is 60~70 weight %, and viscosity is 1500~4000mPa.s, and number-average molecular weight is
4000~7000, glass transition temperature is -10 DEG C~30 DEG C.
2. a kind of preparation method of polyester acrylic ester aqueous dispersion described in claim 1, its preparation process include：Step
One：Water-based saturated polyester resin, step 2 is made：Gradually it is added dropwise in the water-based saturated polyester resin synthesized to step 1 and contains hydroxyl
Base (methyl) acrylic monomer, (methyl) alkyl-acrylates monomer, initiator azodiisobutyronitrile and/or benzoyl peroxide
The mixed liquor of formyl, chain-transferring agent mercaptoethanol, radical polymerization is carried out inside saturated polyester resin, obtains polyester acrylate
Aqueous dispersion.
A kind of 3. preparation method of polyester acrylic ester aqueous dispersion according to claim 2, it is characterised in that：By weight
Part meter, the parts by weight of hydroxyl (methyl) acrylic monomer 30~70 described in step 2, (methyl) alkyl-acrylates
The parts by weight of monomer 30~80, initiator azodiisobutyronitrile and/or the parts by weight of benzoyl peroxide 1~5, chain-transferring agent sulfydryl second
The parts by weight of alcohol 1~5；
Water-based saturated polyester resin and the monomer described in step 2, initiator and chain-transferring agent three described in step 1 is total
The weight ratio of meter is 1：0.6~1.5.
A kind of 4. preparation method of polyester acrylic ester aqueous dispersion according to claim 2, it is characterised in that：Step 1
Described in water-based saturated polyester resin, its preparation process includes：
a：In a kettle, phthalic anhydride, M-phthalic acid, adipic acid, HHPA, ethylene glycol, diethylene glycol, new penta 2 are added
Alcohol, trimethylolpropane and Mono-n-butyltin, and logical nitrogen protection；
b：150~160 DEG C are warming up to, starts stirring；
c：170 ± 5 DEG C and 1 ± 0.1h of constant temperature are warming up to, is warming up to 190 ± 5 DEG C, 2~3h of reaction to water yield reaches >=90%
Theoretical Mass；Then 220~230 DEG C are warming up to, is incubated 2~3h；
d：Sampling detecting acid number, when acid number is 5~10mgKOH/g, 170~180 DEG C are cooled to, adds the trimellitic acid of formula ratio
Acid anhydride；
e：Sampling detecting acid number again, when acid number is 60~100mgKOH/g, add the organic solvent of formula ratio；
f：50~80 DEG C are cooled to, adds dimethylethanolamine 0.5 ± 0.1h of neutralization reaction, adds deionized water, adjustment contains admittedly
Measure as 50~60%, agitation and filtration produces water-based saturated polyester resin.
A kind of 5. preparation method of polyester acrylic ester aqueous dispersion according to claim 4, it is characterised in that：By quality
Number, the mass fraction of described reaction raw materials are respectively：Phthalic anhydride：15-30 parts, M-phthalic acid：20-30 parts, adipic acid：
20-30 parts, HHPA：25-30 parts, trimellitic anhydride：15-40 parts, ethylene glycol：25-30 parts, diethylene glycol：15-20 parts,
Neopentyl glycol：25-30 parts, trimethylolpropane：5-25 parts, Mono-n-butyltin：0.1-0.5 parts；Organic solvent：10-50 parts,
Dimethylethanolamine 10-40 parts.
A kind of 6. preparation method of polyester acrylic ester aqueous dispersion according to claim 4 or 5, it is characterised in that：Step
In the preparation process of water-based saturated polyester resin described in rapid one, described organic solvent is propylene glycol methyl ether acetate, second
One or more in glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether.
A kind of 7. preparation method of polyester acrylic ester aqueous dispersion according to claim 2, it is characterised in that：Described
The specific preparation process of step 2 includes：
a：The water-based saturated polyester resin of the gained of the step of adding in the reactor using solid gauge mass fraction as 100 parts one, and
Logical nitrogen deoxygenation；
b：Stirring is warming up to 60~90 DEG C, and hydroxyl (methyl) propylene that mass fraction is 60~150 parts is added dropwise at this temperature
Acrylic monomer, (methyl) alkyl-acrylates monomer, the mixed liquor of initiator and chain-transferring agent, time for adding is 2~3h；
c：2~3h of insulation reaction again is dripped, reaction terminates, and is cooled to≤50 DEG C, filtering, discharging is polyester acrylate water
Dispersion.
A kind of 8. preparation method of polyester acrylic ester aqueous dispersion according to claim 2 or 7, it is characterised in that：Institute
Hydroxyl (methyl) acrylic monomer stated is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, metering system
One or more in sour hydroxyl ethyl ester, hydroxy propyl methacrylate, methacrylate.
A kind of 9. preparation method of polyester acrylic ester aqueous dispersion according to claim 2 or 7, it is characterised in that：Institute
(methyl) the alkyl-acrylates monomer stated be methyl methacrylate, EMA, n-BMA,
Isobutyl methacrylate, Tert-butyl Methacrylate, methacrylic acid -2- ethylhexyls, cyclohexyl methacrylate, methyl
Phenyl acrylate, methacrylic acid 3-methyl cyclohexanol ester, t-butyl cyclohexyl ester, isobornyl methacrylate,
Lauryl methacrylate, octadecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid
One or more in butyl ester, acrylic acid-2-ethyl caproite, lauryl acrylate.
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| CN108690172A (en) * | 2018-06-01 | 2018-10-23 | 浙江枧洋高分子科技有限公司 | A kind of acrylic polymer polyether polyol and preparation method thereof |
| CN109467638A (en) * | 2018-10-25 | 2019-03-15 | 无锡洪汇新材料科技股份有限公司 | Diamond Search, hydroxyl acrylic aqueous dispersion of polyester modification and preparation method thereof |
| CN110746587A (en) * | 2019-06-11 | 2020-02-04 | 扬州工业职业技术学院 | Preparation method of macromolecular emulsifier capable of undergoing free radical copolymerization |
| CN112011258A (en) * | 2020-08-24 | 2020-12-01 | 江苏华夏制漆科技有限公司 | Quick-drying water-based modified polyester wood coating |
| CN113603835A (en) * | 2021-07-01 | 2021-11-05 | 清远慧谷新材料技术有限公司 | High-branching-degree water-based saturated polyester modified acrylic resin, preparation method thereof and water-based gloss oil for metals |
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| CN112011258A (en) * | 2020-08-24 | 2020-12-01 | 江苏华夏制漆科技有限公司 | Quick-drying water-based modified polyester wood coating |
| CN113603835A (en) * | 2021-07-01 | 2021-11-05 | 清远慧谷新材料技术有限公司 | High-branching-degree water-based saturated polyester modified acrylic resin, preparation method thereof and water-based gloss oil for metals |
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