CN107513124B - 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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- CN107513124B CN107513124B CN201710741970.0A CN201710741970A CN107513124B CN 107513124 B CN107513124 B CN 107513124B CN 201710741970 A CN201710741970 A CN 201710741970A CN 107513124 B CN107513124 B CN 107513124B
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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
-
- 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
-
- 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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- 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
- 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
-
- 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
Abstract
The present invention relates to a kind of polyester acrylic ester aqueous dispersions, are made of aqueous saturated polyester resin and polyacrylate two parts, and the aqueous saturated polyester resin is as macromole emulsifying agent, wherein by polyacrylate cladding；The mass ratio of the aqueous saturated polyester resin and polyacrylate is 1:0.6-1.5；Its preparation step are as follows: step 1: aqueous saturated polyester resin is made, step 2: with the mixed liquor of hydroxyl (methyl) acrylic monomer, (methyl) alkyl-acrylates monomer, initiator azodiisobutyronitrile and/or benzoyl peroxide, chain-transferring agent mercaptoethanol, it is added dropwise in aqueous saturated polyester resin, Raolical polymerizable is carried out, polyester acrylic ester aqueous dispersion is obtained；The polyester acrylic ester aqueous dispersion incorporates the weatherability of polyester resin excellent richness 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 methods of coating resin, and in particular to a kind of waterborne polyester acrylate water dispersion
Body and preparation method thereof.
Background technique
There is excellent weatherability as the coating of matrix using acrylic resin and protect light colour retention, but its richness is not enough managed
Think；There is excellent richness by the coating of matrix of polyester resin, but its weatherability, acid and alkali-resistance and water resistance are not ideal enough.
The advantages of integrating two kinds of resins utmostly meets industry for the high request of the appearance of coating, stemness and durability, is current
One of hot issue of industry research.
Acrylic acid modified polyester resin in order to obtain, general scheme can be divided into three classes: 1) cold spelling, i.e., by acrylic acid tree
Rouge 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 reaction, realizes the grafting of the two, such as CN200680052504；3) first pre-polymerization aftercondensated method, i.e., prepare end first
Then it is carried out condensation reaction with polyacid and polyalcohol, acrylic acid is made by the acrylic resin with carboxyl or/and hydroxyl
Modified polyester resin, such as CN200610024367.
Cold spelling is higher to the compatibility requirements of resin, and use scope is limited, and effect is also not ideal enough；First condensation methods need
Unsaturated polyester (UP) is first prepared, but since unsaturated polyester (UP) viscosity is big, functional group's steric hindrance is larger, position of double bond, number and activity are low
The problems such as cause the later period to carry out (methyl) acrylic ester monomer graft polymerization rate it is low, or even can not successfully be grafted；It is first pre-
Poly- aftercondensated method technique, it is very high to the structural requirement of acrylic resin, and be easy to happen by high-temperature polycondensation acrylic resin
Cracking, coking, this method technique are difficult to control, are easy gelation.
Patent CN201210329381.9 provides a kind of preparation method of 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 is made to form inierpeneirating network structure between two kinds of resin segments by this method, improves the compatible of two kinds of resins
Property, essence is " cold spelling ", but be carry out at a certain temperature, and its formed interpenetrating networks another " line " be by
It is gradually formed, the compatibility of two kinds of resins can be improved in this way.
Summary of the invention
The technical problem to be solved by the present invention is to for conventional polyester and polyacrylate resin physical mixed compatibility
The disadvantages of difference, chemical mode modified technique is difficult, provides a kind of polyester acrylic ester aqueous dispersion.
In order to solve the above technical problems, the technical solution used are as follows: a kind of polyester acrylic ester aqueous dispersion, by aqueous full
It is formed with polyester resin and polyacrylate two parts, the aqueous saturated polyester resin will gather as macromole emulsifying agent
Acrylate coats wherein；The mass ratio of the aqueous saturated polyester resin and polyacrylate is 1:0.6~1.5；
The aqueous saturated polyester resin, hydroxyl value are 80~160mgKOH/g, and acid value is 60~100mgKOH/g, Gu
Body content is 50~60 weight %, viscosity be 1000~3000mPa.s (25 ± 1 DEG C of temperature when test, when 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；
The polyester acrylic ester aqueous dispersion, average grain diameter are 100~150nm, and particle diameter distribution is narrow, and hydroxyl value is
100~160mgKOH/g, acid value be 40~60mgKOH/g, solid content be 60~70 weight %, viscosity be 1500~
4000mPa.s, number-average molecular weight are 4000~7000, and glass transition temperature is -10 DEG C~30 DEG C；Preparation method: first
Step aqueous saturated polyester resin is first made, the aqueous 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
The mixed liquor of bis-isobutyronitrile and/or benzoyl peroxide, chain-transferring agent composition, in macromole emulsifying agent (aqueous polyester resin)
Portion carries out free radical polymerization.
Second technical problem to be solved by this invention is: providing a kind of preparation side of polyester acrylic ester aqueous dispersion
Method；This method polymerization technique is simple, can solve the problem of two kinds of resin compatible differences, sufficiently integrates two kinds of resins respectively
Excellent characteristics.
To solve second technical problem, the technical solution adopted by the present invention is that: a kind of polyester acrylic ester aqueous dispersion
Preparation method, the steps include: step 1: aqueous saturated polyester resin be made, step 2: to step 1 synthesize aqueous saturation
It is gradually added dropwise in polyester resin and contains hydroxyl (methyl) acrylic monomer, (methyl) alkyl-acrylates monomer, initiator
The mixed liquor of azodiisobutyronitrile and/or benzoyl peroxide, chain-transferring agent mercaptoethanol carries out inside saturated polyester resin
Free radical polymerization obtains polyester acrylic ester aqueous dispersion；
By weight, 30~70 parts by weight of the hydroxyl (methyl) acrylic monomer, (methyl) acrylic acid alkyl
1~5 parts by weight of 30~80 parts by weight of esters monomer, initiator azodiisobutyronitrile and/or benzoyl peroxide, chain-transferring agent mercapto
1~5 parts by weight of base ethyl alcohol；Monomer described in aqueous saturated polyester resin described in step 1 and step 2, initiator and
The weight ratio that chain-transferring agent three amounts to is 1:0.6~1.5；
The preparation of aqueous saturated polyester resin described in step 1, step include: the aqueous saturated polyester tree
It include organic solvent and dimethylethanolamine in rouge, it is 10~50 parts that the content of organic solvent is figured by mass parts, dimethyl second
It is 10~40 parts that the content of hydramine is figured by mass parts, and preparation method is as follows:
A: in a kettle, phthalic anhydride, M-phthalic acid, adipic acid, hexahydrophthalic anhydride, ethylene glycol, diethylene glycol, new penta is added
Glycol, trimethylolpropane and Mono-n-butyltin, and logical nitrogen protection；
B: being warming up to 150~160 DEG C, melts most of solid matter, starts stirring；
C: being warming up to 170 ± 5 DEG C and 1 ± 0.1h of constant temperature, is warming up to 190 ± 5 DEG C, and 2~3h of reaction to water yield reaches >=
90% Theoretical Mass；Then it is gradually warmed up to 220~230 DEG C, keeps the temperature 2~3h；
D: sampling detecting acid number is cooled to 170~180 DEG C, the inclined benzene of formula ratio is added when acid value is 5~10mgKOH/g
Three acid anhydrides；
E: the organic solvent of formula ratio is added when acid value is 60~100mgKOH/g in sampling detecting acid number again；
F: being cooled to 50~80 DEG C, and 0.5 ± 0.1h of dimethylethanolamine neutralization reaction is added, and deionized water, adjustment is added
Solid content is 50~60%, and agitation and filtration is up to aqueous saturated polyester resin；The aqueous saturated polyester resin, hydroxyl value 80
~160mgKOH/g, acid value be 60~100mgKOH/g, solid content be 50~60 weight %, viscosity be 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 are as follows: phthalic anhydride: 15-30 parts, M-phthalic acid: 20-30 parts, oneself two
Acid: 20-30 parts, hexahydrophthalic anhydride: 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, 10-40 parts of dimethylethanolamine.
In the preparation process of aqueous saturated polyester resin described in step 1, organic solvent used is propylene glycol monomethyl ether
One or more of acetate, glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether；
The specific preparation method of the step two includes:
A: the one aqueous saturated polyester tree of gained of the step of mass fraction is 100 parts (solid meter) is added in the reactor
Rouge, and logical nitrogen deoxygenation；
B: stirring is warming up to 60~90 DEG C, and the hydroxyl (methyl) for being 60~150 parts by mass fraction is added dropwise at this temperature
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: dripping 2~3h of insulation reaction again, and reaction terminates, and is cooled to≤50 DEG C, filtering, discharging is polyester acrylic
Ester aqueous dispersion, average grain diameter is small, is 100~150nm, and particle diameter distribution is narrow, and hydroxyl value is 100~160mgKOH/g, and acid value is
40~60mgKOH/g, solid content be 60~70 weight %, viscosity be 1500~4000mPa.s, number-average molecular weight be 4000~
7000, glass transition temperature is -10 DEG C~30 DEG C.
Hydroxyl (methyl) acrylic monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid hydroxyl fourth
One or more of ester, hydroxyethyl methacrylate, hydroxy propyl methacrylate, methacrylate.
Described (methyl) the alkyl-acrylates monomer is methyl methacrylate, ethyl methacrylate, methyl-prop
Olefin(e) acid N-butyl, Isobutyl methacrylate, Tert-butyl Methacrylate, methacrylic acid -2- ethylhexyl, 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 of propyl ester, butyl acrylate, acrylic acid-2-ethyl caproite, lauryl acrylate.
The utility model has the advantages that polyester acrylic aqueous dispersion disclosed in the present application, overcomes conventional polyester and polyacrylate tree
The shortcomings that rouge 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 disadvantage of chemical mode modified technique difficulty, this preparation process only needs two steps, and second step polymerization temperature
Spend it is low, 60~90 DEG C.
Detailed description of the invention
Fig. 1: polyester acrylic ester aqueous dispersion structural formula；
1 is polyacrylate in figure；
Fig. 2: aqueous saturated polyester resin GPC (molecular weight) map of embodiment 1；
Fig. 3: aqueous saturated polyester resin DSC (Tg) map of embodiment 1；
Fig. 4: embodiment 1 polyester acrylic ester aqueous dispersion GPC (molecular weight) map；
Fig. 5: embodiment 1 polyester acrylic ester aqueous dispersion DSC (Tg) map；
Fig. 6: embodiment 1 polyester acrylic ester aqueous dispersion DLS (partial size) map；
Fig. 7: embodiment 2 polyester acrylic ester aqueous dispersion GPC (molecular weight) map；
Fig. 8: embodiment 2 polyester acrylic ester aqueous dispersion DSC (Tg) map；
Fig. 9: embodiment 2 polyester acrylic ester aqueous dispersion DLS (partial size) map；
Figure 10: the application reaction mechanism schematic diagram.
Specific embodiment
In order to preferably understand the present invention, the present invention is further described below with reference to comparative example and embodiment, but the present invention
Claimed range is not limited to the scope of the embodiments.
Embodiment 1
1) step 1: the preparation of aqueous saturated polyester resin: by 80g phthalic anhydride (PA), 100g M-phthalic acid (IPA),
100g adipic acid (AA), 100g hexahydrophthalic anhydride (HHPA), 112g ethylene glycol (EG), 60g diethylene glycol (DEG), 112g new penta 2
Alcohol (NPG), 20g trimethylolpropane (TMP) and 1.2g Mono-n-butyltin are added to condenser pipe, water segregator, stirring rod
And have logical nitrogen device four round flask in, heat up when being passed through nitrogen.150~160 DEG C are warming up to, most of solid is made
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
90% or more；Then it is gradually warmed up to 220~230 DEG C, keeps the temperature 2~3h；Sampling detecting acid number, when acid value is 5~10mgKOH/g
When, 170~180 DEG C are cooled to, is added 120g trimellitic anhydride (TMA)；Sampling detecting acid number, when acid value is 95 ± 2mgKOH/g
When, 110g ethylene glycol monobutyl ether is added；50~80 DEG C are cooled to, 100g dimethylethanolamine (DMEA) neutralization reaction is added
392g deionized water is added in 0.5h, and adjustment solid content is 55%, and agitation and filtration is up to aqueous saturated polyester resin.The water
Property saturated polyester resin (PE) hydroxyl value be 142mgKOH/g, acid value 95mgKOH/g, solid content 55%, viscosity is
1500mPa.s, number-average molecular weight are that 2500 (aqueous saturated polyester resin GPC (molecular weight) map is shown in Fig. 2；), glass transition
Temperature is -7.6 DEG C (aqueous saturated polyester resin DSC (Tg) map is shown in Fig. 3), and 1% aqueous solution pH of polyester is 8.5；
Aqueous saturated polyester resin GPC (molecular weight) result:
GPC result
Aqueous saturated polyester resin obtained carries out performance characterization using following methods:
Molecular weight test: it is measured using the Waters515 gel permeation chrommatograph of Waters, US；
Solid content test: referring to determination of solid content GB/T1725-2007；
Acid value measuring: referring to the measurement HG/T2708-1995 of acid value
Hydroxy value measuring: referring to the measurement HG/T2709-1995 of hydroxyl value
Viscosity test: it is measured using NDJ-1 type rotary viscosimeter
PH value test: pHS-2C type precision acidity meter is used
Step 2: the preparation of polyester acrylic ester aqueous dispersion: by aqueous saturated polyester tree prepared by 250g step 1
Rouge is added in the reaction kettle with condensing unit and stirring rod, and 80 DEG C are warming up to when being passed through nitrogen；After constant temperature, start to be added dropwise
20g methyl methacrylate, 30g butyl acrylate, 30g hydroxyethyl methacrylate, 3g azodiisobutyronitrile, 2g mercaptoethanol
The mixed solution of composition.Control rate of addition, time for adding 3h；Insulation reaction 2h again is dripped, reaction is stopped, being cooled to≤
50 DEG C, filtering, discharging obtains polyester acrylic ester aqueous dispersion (PEA).Appearance is white emulsion, and hydroxyl value is
145.8mgKOH/g, acid value 58.7mgKOH/g, solid content 66.4%, viscosity 2000mPa.s, number-average molecular weight are
5100 (polyester acrylic ester aqueous dispersion GPC (molecular weight) map is shown in Fig. 4), there are two glass transition temperatures, waterborne polyester
Part is -8.1 DEG C, and polyacrylic acid ester moiety is 23.8 DEG C, and converting total glass transition temperature by weight is 5.2 DEG C of (polyester
Acrylate aqueous dispersion DSC (Tg) map is shown in Fig. 5), 1% aqueous solution pH of polyester acrylic ester aqueous dispersion is 7.9, and partial size is
108nm (polyester acrylic ester aqueous dispersion DLS (partial size) map is shown in Fig. 6).
Polyester acrylic ester aqueous dispersion GPC (molecular weight) result
GPC result
Polyester acrylic ester aqueous dispersion obtained carries out performance characterization using following methods:
Particle size distribution test: ZetasizerNanoZS90 laser fineness gage is used.
Embodiment 2
1) step 1: the preparation of aqueous saturated polyester resin: identical with step 1 in embodiment 1.
2) step 2: the preparation of polyester acrylic ester aqueous dispersion: aqueous saturation prepared by 1 step 1 of 125g embodiment
Polyester resin and 21.5g deionized water are added in the reaction kettle with condensing unit and stirring rod, are heated up when being passed through nitrogen
To 80 DEG C；After constant temperature, start that 20g methyl methacrylate, 30g butyl acrylate, 30g hydroxyethyl methacrylate, 3g is added dropwise
The mixed solution of azodiisobutyronitrile, 2g mercaptoethanol composition.Control rate of addition, time for adding 3h；It drips and keeps the temperature again
2h is reacted, reaction is stopped, being cooled to≤50 DEG C, filtering, discharging obtains polyester acrylic ester aqueous dispersion.Appearance is white cream
Liquid, hydroxyl value 147.6mgKOH/g, acid value 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) map is shown in Fig. 7), and there are two glass transition temperatures, water
Property polyester portion be -8.8 DEG C, polyacrylic acid ester moiety be 24.9 DEG C, convert by weight total glass transition temperature be 12.3
DEG C (polyester acrylic ester aqueous dispersion DSC (Tg) map is shown in Fig. 8), 1% aqueous solution pH of polyester acrylic ester aqueous dispersion is
7.8, partial size is 150nm (polyester acrylic ester aqueous dispersion DLS (partial size) map is shown in Fig. 9).
Aqueous saturated polyester resin obtained carries out the method for performance characterization with embodiment 1.
Polyester acrylic ester aqueous dispersion GPC (molecular weight) result
GPC result
As a result it and discusses
The application synthesizes polyester polyacrylate aqueous dispersion using two-step method, i.e. aqueous saturated polyester is first made in step 1
Resin, hydroxyl value are 80~160mgKOH/g, and acid value is 60~100mgKOH/g, and solid 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 is with excellent water solubility.Because water is as continuous in step 1 product
Phase, thus its in water state similar to small molecule surfactant, that is, hydrophilic radical towards water assemble, hydrophobic grouping backwater aggregation；Step
Rapid two, using the product of step 1 as macromole emulsifying agent, are added dropwise monomer, and 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 value is 40~60mgKOH/g, and solid contains
Amount is 60~70 weight %, and viscosity is 1500~4000mPa.s, and number-average molecular weight is 4000~7000, glass transition temperature
It is 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, the very good solution problem of two kinds of resin compatible differences, incorporate the excellent richness of polyester resin and
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 aqueous saturated polyester resin
The dosage of dosage, i.e. macromole emulsifying agent reduces, from the result of partial size we can see that partial size is from the 108nm of embodiment 1
The 150nm of embodiment 2 is become, this is also that can explain, with the reduction of emulsifier, the micellar phase of formation should reduce i.e. poly-
Place is closed to tail off, and amount of monomer is unchanged, partial size becomes larger naturally.What macromole emulsifying agent dosage cannot be unlimited certainly tails off,
After becoming smaller to a certain extent, monomer will cause the failure of polymerization reaction just without enough locus of polymerization in this way, therefore aqueous saturation
Polyester resin (macromole emulsifying agent) and monomer used in progress free radical polymerization wherein, the parts by weight of initiator and chain-transferring agent
Than being calculated as 1:0.6~1.5 by solid masses；The structure of macromole emulsifying agent also has a special requirement, i.e., its hydroxyl value be 80~
160mgKOH/g, acid value are 60~100mgKOH/g, and solid 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 polymerization reaction
It loses.
Claims (9)
1. a kind of polyester acrylic ester aqueous dispersion, is made of aqueous saturated polyester resin and polyacrylate two parts, described
Aqueous saturated polyester resin as macromole emulsifying agent, wherein by polyacrylate cladding；The aqueous saturated polyester tree
The mass ratio of rouge and polyacrylate is 1:0.6 ~ 1.5；
The aqueous saturated polyester resin, hydroxyl value are 80~160mgKOH/g, and acid value is 60~100mgKOH/g, and solid contains
Amount is 50~60 weight %, and viscosity is 1000~3000mPa.s, and number-average molecular weight is 2000~4000, glass transition temperature
It is -10 DEG C~20 DEG C；
The polyester acrylic ester aqueous dispersion, average grain diameter are 100~150nm, and hydroxyl value is 100~160mgKOH/g,
Acid value is 40~60mgKOH/g, and solid 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, preparation step includes: step
One: aqueous saturated polyester resin is made, step 2: being gradually added dropwise in the aqueous saturated polyester resin synthesized to step 1 and contain hydroxyl
Base (methyl) acrylic monomer, (methyl) alkyl-acrylates monomer, initiator azodiisobutyronitrile and/or benzoyl peroxide
The mixed liquor of formyl, chain-transferring agent mercaptoethanol carries out free radical polymerization inside saturated polyester resin, obtains polyester acrylate
Aqueous dispersion.
3. a kind of preparation method of polyester acrylic ester aqueous dispersion according to claim 2, it is characterised in that: by weight
Part meter, 30~70 parts by weight of hydroxyl described in step 2 (methyl) acrylic monomer, (methyl) alkyl-acrylates
1~5 parts by weight of 30~80 parts by weight of monomer, initiator azodiisobutyronitrile and/or benzoyl peroxide, chain-transferring agent sulfydryl second
1~5 parts by weight of alcohol；
Aqueous saturated polyester resin described in step 1 and monomer described in step 2, initiator and chain-transferring agent three are total
The weight ratio of meter is 1:0.6~1.5.
4. a kind of preparation method of polyester acrylic ester aqueous dispersion according to claim 2, it is characterised in that: step 1
Described in aqueous saturated polyester resin, preparation step includes:
A: in a kettle, phthalic anhydride, M-phthalic acid, adipic acid, hexahydrophthalic anhydride, ethylene glycol, diethylene glycol, new penta 2 is added
Alcohol, trimethylolpropane and Mono-n-butyltin, and logical nitrogen protection；
B: being warming up to 150~160 DEG C, starts stirring；
C: being warming up to 170 ± 5 DEG C and 1 ± 0.1h of constant temperature, 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, 2~3h is kept the temperature；
D: sampling detecting acid number is cooled to 170~180 DEG C, the trimellitic acid of formula ratio is added when acid value is 5~10mgKOH/g
Acid anhydride；
E: the organic solvent of formula ratio is added when acid value is 60~100mgKOH/g in sampling detecting acid number again；
F: being cooled to 50~80 DEG C, and 0.5 ± 0.1h of dimethylethanolamine neutralization reaction is added, and deionized water is added, and adjustment contains admittedly
Amount is 50~60%, and agitation and filtration is up to aqueous saturated polyester resin.
5. a kind of preparation method of polyester acrylic ester aqueous dispersion according to claim 4, it is characterised in that: press quality
The mass fraction of number, the reaction raw materials is respectively as follows: phthalic anhydride: 15-30 parts, M-phthalic acid: 20-30 parts, adipic acid:
20-30 parts, hexahydrophthalic anhydride: 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,
10-40 parts of dimethylethanolamine.
6. a kind of 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 aqueous saturated polyester resin described in rapid one, the organic solvent is propylene glycol methyl ether acetate, second
One or more of glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether.
7. a kind of preparation method of polyester acrylic ester aqueous dispersion according to claim 2, it is characterised in that: described
The specific preparation step of step 2 includes:
A: being added in the reactor with solid meter mass fraction the one aqueous saturated polyester resin of gained of the step of being 100 parts, 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, initiator and chain-transferring agent mixed liquor, time for adding be 2~3h；
C: dripping 2~3h of insulation reaction again, and reaction terminates, and is cooled to≤50 DEG C, filtering, discharging is polyester acrylate water
Dispersion.
8. a kind of 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 of sour hydroxyl ethyl ester, hydroxy propyl methacrylate, methacrylate.
9. a kind of 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, ethyl methacrylate, n-BMA,
Isobutyl methacrylate, Tert-butyl Methacrylate, methacrylic acid -2- ethylhexyl, cyclohexyl methacrylate, methyl
Acrylic acid 3-methyl cyclohexanol ester, t-butyl cyclohexyl ester, lauryl methacrylate, methacrylic acid octadecyl
Ester, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid-2-ethyl caproite, lauryl acrylate
One or more of.
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| CN109467638B (en) * | 2018-10-25 | 2020-10-16 | 无锡洪汇新材料科技股份有限公司 | zero-VOC, polyester-modified hydroxyacrylic acid dispersions and process for their preparation |
| CN110746587B (en) * | 2019-06-11 | 2022-02-15 | 扬州工业职业技术学院 | Preparation method of macromolecular emulsifier capable of undergoing free radical copolymerization |
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| 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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Effective date of registration: 20191113 Address after: 31 Haibin 4th Road, Rudong Coastal Economic Development Zone, Nantong, Jiangsu Patentee after: Nantong Boyi Chemical Co., Ltd. Address before: 215026 Changyang street, Suzhou Park, Suzhou, Jiangsu Province, No. 425, song and blue resin Mstar Technology Ltd Patentee before: Suzhou blue resin Mstar Technology Ltd |