CN110408013A - A kind of polyester resin for powder coating and preparation method thereof - Google Patents
A kind of polyester resin for powder coating and preparation method thereof Download PDFInfo
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- CN110408013A CN110408013A CN201910816624.3A CN201910816624A CN110408013A CN 110408013 A CN110408013 A CN 110408013A CN 201910816624 A CN201910816624 A CN 201910816624A CN 110408013 A CN110408013 A CN 110408013A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
- C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
- C08G63/195—Bisphenol A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to technical field of coatings more particularly to a kind of polyester resin for powder coating and preparation method thereof.The invention discloses a kind of polyester resin for powder coating, formaldehyde, nontoxic health environment-friendly are not contained in the polyester resin feed stock.Wherein, bisphenols monomer is heat-resist, rigidity is strong, and price is low compared with neopentyl glycol.In the case where other base stocks are constant, the glass transition temperature of polyester resin for powder coating is can be improved in the use of bisphenols monomer, improves its storge quality, additionally it is possible to improve the impact resistance of its weather resistance and film；The addition of a small amount of trimethylolpropane, can be improved the degree of branching of polyester resin；The antioxygenic property of more effectively reinforced polyester resin is capable of in the use of antioxidant, and then improves the weather resistance of powdery paints.
Description
Technical field
The present invention relates to technical field of coatings more particularly to a kind of polyester resin for powder coating and preparation method thereof.
Background technique
Powdery paints is widely used in door and window aluminium due to having the advantages such as economic, environmentally friendly, efficient, excellent performance
The fields such as the coating of extrusion type material, household electrical appliances furniture, frame.Powdery paints have solvent-free, excellent mechanical property and
Mechanical performance can meet the needs of market well.Limitation with national governments to VOC emission, powdery paints will be by
Traditional solvent based coating is gradually substituted, the pillar industry in coating industry is become.
Polyester resin powder coating has preferable weather resistance and heat resistance, and its compared to other powdery paints
His performance indicator substantially meets requirement, has obtained faster development in recent years.Polyester powder coating be mainly used in building coating,
The fields such as road equipment, automotive lacquer it requires that its coating should have excellent weatherability, heat resistance and preferably watch
Property, higher storage temperature and good comprehensive performance.It is poly- that Chinese patent CN 105482663A discloses a kind of Heat-resistant anti-static
Ester powdery paints and preparation method thereof, this method remove modified polyester resin with novolac epoxy resin, and novolac epoxy resin is a kind of
Heat-resistance epoxy resin, it is known that the resin of patent synthesis has preferable heat resistance, and novolac epoxy resin is in acid medium
Phenol and formaldehyde carry out polycondensation reaction and obtain linear phenol-aldehyde resin, then polycondensation is anti-in the presence of sodium hydroxide with excess propylene oxide
Novolac epoxy resin should be obtained, contains formaldehyde in the novolac epoxy resin synthesis material, formaldehyde is carcinogenic, does not meet environmentally protective want
It asks.
Summary of the invention
The present invention provides a kind of polyester resin for powder coating and preparation method thereof, solve existing polyester resin powder
The problem of last coating contains formaldehyde, does not meet environment protection requirement.
Its specific technical solution is as follows:
The present invention provides a kind of polyester resin for powder coating, comprising: polyalcohol, polyacid, esterification catalyst, acidolysis
Agent, antioxidant and curing accelerator；
The polyalcohol includes one of neopentyl glycol, 1,4-CHDM or trimethylpentanediol, preferably
One of neopentyl glycol and trimethylolpropane, pentaerythrite or ethoxylated pentaerythritol, preferably trimethylolpropane with
And bisphenols monomer.Bisphenols monomer is heat-resist, rigidity is strong, and price is low compared with neopentyl glycol.
Preferably, the molar ratio of the polyalcohol and the polyacid is (1.05~1.15): 1；The polyacid and institute
The ratio for stating the moles total number of acidolysis agent and the mole of the polyalcohol is (1.0~1.1): 1, two kinds of molar ratios are more excellent respectively
It is selected as 1.1:1,1.0476:1；1.13:1 1.0502:1；1.15:1 1.0475:1；1.05:1 1.0116:1.
The suitable acid-alcohol ratio of the present invention, available suitable molecular size range (molecular weight is 2000~10000) and divides
Son amount distribution (molecular weight distribution is about 1.0), and there is suitable melting viscosity (viscosity is 1000~10000mPas),
It ensure that the good flow leveling of polyester resin.
Preferably, the bisphenols monomer includes one of bisphenol-A, tetrabromobisphenol A, hexafluoro bisphenol-a and bisphenol S or more
Kind, the more preferably mixture of bisphenol-A or bisphenol-A and bisphenol S.
In the present invention, bisphenols monomer substitutes part neopentyl glycol, in the case where guaranteeing that other raw materials are basically unchanged, mentions
The high glass transition temperature of polyester resin for powder coating of the present invention, improves its storge quality.A small amount of trihydroxy methyl third
The degree of branching of polyester resin can be improved in the addition of alkane.If polyalcohol is only bisphenols monomer, the monomer meeting of a large amount of bisphenols
It causes system steric hindrance bigger, is difficult to synthesize polyester resin.
Preferably, the polyacid is selected from: terephthalic acid (TPA), adipic acid, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic or phthalic acid
Acid anhydride, more preferably terephthalic acid (TPA) and adipic acid；
The impact property of polyester resin powder coating can be improved in adipic acid flexible group in the present invention.
The esterification catalyst is Mono-n-butyltin, dibutyl tin dilaurate or dihydroxy dibutyl tin oxide；
The antioxidant be selected from antioxidant 1076, antioxidant 1010, antioxidant 168, antioxidant 1076 with
168 composite antioxidant of 168 composite antioxidant of antioxidant, antioxidant 1010 and antioxidant, more preferably antioxidant
1076 with 168 composite antioxidant of antioxidant, and antioxidant 1076 and the quality of 168 composite antioxidant of antioxidant are
(1~2): (1~2), preferably 2:1；Or more preferably antioxidant 1076 and 168 composite antioxidant of antioxidant, and it is anti-
Oxidant 1076 and 168 composite antioxidant of antioxidant (1~2): (1~2), preferably 2:1.
In the present invention, composite antioxidant is more preferable than single antioxidant effect, being capable of more effectively reinforced polyester tree
The antioxygenic property of rouge, and then improve the weather resistance of powdery paints.
The curing accelerator includes: ammonium salt or microcosmic salt, more preferably microcosmic salt, further preferably triphenyl ethyl phosphonium bromide
Phosphorus.
Preferably, the esterification catalyst accounts for the polyalcohol, the polyacid and the acidolysis agent gross mass
0.1wt%~0.5wt%, more preferably 0.1wt%, 0.2wt%, 0.3wt% or 0.5wt%；
The antioxidant account for the 0.1wt% of the polyalcohol, the polyacid and the acidolysis agent gross mass~
0.7wt%, more preferably 0.5wt%.
The curing accelerator be the polyalcohol, the polyacid and the acidolysis agent gross mass 0.01wt%~
0.1wt%, more preferably 0.01wt%, 0.05wt%, 0.08wt% or 0.1wt%.
Preferably, the bisphenols monomer accounts for 1wt%~10wt% of the polyalcohol gross mass, more preferably 5wt%,
7wt% or 10wt%, further preferably 5wt%；
The trimethylolpropane accounts for 1wt%~7wt% of the polyalcohol gross mass, more preferably 1wt%,
3wt%, 5wt% or 7wt%, further preferably 5wt%.
The present invention also provides the preparation methods of above-mentioned polyester resin for powder coating, comprising the following steps:
Step 1: after polyalcohol is heated to melting, polyacid mixing is added, adds esterification catalyst and carries out first instead
It answers, obtains the first product；
Step 2: acidolysis agent being added into the first product and carries out the second reaction, obtains the second product；
Step 3: the second product being carried out to vacuumize reaction, obtains third product；
Step 4: third product being mixed with antioxidant and curing accelerator, obtains polyester resin for powder coating.
In the present invention, polyalcohol, polyacid, esterification catalyst is added in step 1, by polycondensation reaction, synthesizes the first product
Hydroxyl telechelic polyester resin；Acidolysis agent is added in step 2, and opposite end hydroxy polyester resin is blocked, and the second product carboxyl end group of synthesis is poly-
Ester resin；Step 3 vacuumizes reaction, is to improve its degree of polymerization, polycondensation reaction is a reversible process, by constantly taking out
Vacuum belt goes out product water, to accelerate its reaction.The polyester resin that is incorporated as of bisphenols monomer of the present invention introduces benzene ring structure,
So as to increase the glass transition temperature and heat resistance of polyester resin, due to this stable structure, also in certain journey
Weather resistance is improved on degree, there are also the impact resistances of film.
It should be noted that the addition of organic siliconresin or hydroxyl silicone resin intermediate can be improved with modified poly ester resin
Its heat-resisting and weather resistance, but will lead to it due to containing silicon oxygen bond in the structure of organic siliconresin and hydroxyl silicone resin intermediate
Melting extrusion temperature and solidification temperature are high, and hydroxyl silicon intermediate is easy to happen autohemagglutination.The present invention is by being added bisphenols list
Body improves the heat-resisting and weather resistance of polyester resin, and is free of silicon oxygen bond.
In step 1 of the present invention, the temperature of the heating is 120~135 DEG C, preferably 125 DEG C, 130 DEG C or 136 DEG C；The
One reaction carries out in a kettle；It being added after polyacid and is preferably mixed using stirring, the revolving speed of stirring is preferably 150~
180r/min, preferably 160r/min, 170r/min or 180r/min；Before esterification catalyst is added, it is preferably pressed into nitrogen or lazy
Property gas；After esterification catalyst is added, 190 DEG C are preferably warming up to, then carry out the first reaction.
Preferably, with 5~15 DEG C/h, the heating rate of more preferably 10 DEG C/h is warming up to 230~245 for first reaction
DEG C, more preferably 235 DEG C, 240 DEG C or 245 DEG C keep the temperature 1~4h, more preferably 4h, 3.5h or 3h.
It is described second reaction temperature be 230~245 DEG C, soaking time be 2~5h, more preferably 235 DEG C, 4h；240
DEG C, 3.5h；245 DEG C, 4h；240 DEG C, 4h；245 DEG C, 3h.
In step 2 of the present invention, be added acidolysis agent before, be preferably cooled to 190~215 DEG C, preferably 200 DEG C, 210 DEG C or
215℃。
It is described vacuumize reaction before need to be cooled to 215~230 DEG C, more preferably 220 DEG C, 230 DEG C.
The vacuum degree that reaction is vacuumized described in this is -0.09~-0.098MPa, preferably -0.095MPa, and soaking time is
1~4h, more preferably 4h, 3.5h or 2h；
The vacuum degree of mixing described in step 4 is -0.09~-0.098MPa, more preferably -0.095MPa.
In step 4 of the present invention, vacuumizing reaction also needs to stir, and the revolving speed of stirring is identical as step 1 speed of agitator, and the time is
10~40min, preferably 20min, 30min or 40min.
Preferably, the acidolysis agent includes: M-phthalic acid, Isosorbide-5-Nitrae-one of cyclohexane cyclohexanedimethanodibasic and adipic acid or several
Kind, more preferably M-phthalic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, and M-phthalic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic mole
Than for 2:1.M-phthalic acid and both monomers of Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic have excellent yellowing resistance and weather resistance.
As can be seen from the above technical solutions, the invention has the following advantages that
The present invention provides a kind of polyester resin for powder coating, comprising: polyalcohol, polyacid, esterification catalyst, antioxygen
Agent and curing accelerator；Polyalcohol includes one of neopentyl glycol, 1,4-CHDM or trimethylpentanediol, and
One of trimethylolpropane, pentaerythrite or ethoxylated pentaerythritol and bisphenols monomer.
Formaldehyde, nontoxic health environment-friendly are not contained in polyester resin for powder coating raw material of the present invention.Bisphenols list of the present invention
Body is heat-resist, rigidity is strong, and price is low compared with neopentyl glycol.In the case where other base stocks are constant, bisphenols monomer draws
Enter benzene ring structure, the glass transition temperature of polyester resin for powder coating can be improved, improves its storge quality, due to
This stable structure, also improves weather resistance to a certain extent, and there are also the impact resistances of film.A small amount of trihydroxy methyl
The degree of branching of polyester resin can be improved in the addition of propane.The use of antioxidant being capable of more effectively reinforced polyester resin
Antioxygenic property, and then improve the weather resistance of powdery paints.By experimental data it is found that using the polyester resin powdery paints
There is preferable levelability, hardness is high, and glossiness is high, and impact resistance is excellent, and has good heat resistance and weatherability.
Specific embodiment
The embodiment of the invention provides a kind of polyester resin for powder coating and preparation method thereof, existing poly- for solving
The problem of ester toner coating contains formaldehyde, does not meet environment protection requirement.
It in order to make the invention's purpose, features and advantages of the invention more obvious and easy to understand, below will be to of the invention real
The technical solution applied in example is clearly and completely described, it is clear that the embodiments described below are only present invention a part
Embodiment, and not all embodiment.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creation
Property labour under the premise of all other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
The present embodiment is the preparation of polyester resin for powder coating
Polyester resin for powder coating raw material are as follows: polyalcohol, polyacid, acidolysis agent, esterification catalyst, antioxidant and solid
Change promotor, wherein polyalcohol includes neopentyl glycol, bisphenol-A, bisphenol S and trimethylolpropane；Polyacid is terephthalic acid (TPA)
And adipic acid；Polyacid is terephthalic acid (TPA) and adipic acid；Esterification catalyst is Mono-n-butyltin；Acidolysis agent is isophthalic diformazan
Acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, and molar ratio is 2:1；Antioxidant is antioxidant 1076 and antioxidant 168, mass ratio
For 1:1；Curing accelerator is triphenyl ethyl phosphonium bromide phosphorus；Wherein, the molar ratio of polyalcohol and polyacid is 1.1:1, polyacid
It is 1.0476:1 with the ratio of the mole of the integral molar quantity and polyalcohol of acidolysis agent, the dosage of bisphenol-A and bisphenol S accounts for polyalcohol
The 5wt% of gross mass, trimethylolpropane account for the 5wt% of polyalcohol gross mass, and esterification catalyst accounts for polyalcohol, polyacid and acid
The 0.2wt% of agent gross mass is solved, curing accelerator accounts for the 0.05wt% of polyalcohol, polyacid and acidolysis agent gross mass, anti-oxidant
Agent accounts for the 0.5wt% of polyalcohol, polyacid and acidolysis agent gross mass.
The polyalcohol of 228g is added in a kettle, is heated to 125 DEG C, after alcohol melting clarification, adds the more members of 330g
Acid is stirred with the revolving speed of 170r/min, after leading to nitrogen reaction a period of time, 0.61g esterification catalyst is added, is warming up to 190 DEG C,
Then 235 DEG C are warming up to the heating rate of 10 DEG C/h, insulation reaction 4h；200 DEG C are cooled to, 51g acidolysis agent is added, is warming up to
235 DEG C, insulation reaction 4h；It is cooled to 220 DEG C to vacuumize, vacuum degree is -0.095MPa, insulation reaction 4h；Antioxidant is added
And curing accelerator, after 20min is stirred in the revolving speed stirring in the case where vacuum degree is -0.095MPa with 170r/min, cooling discharge.Mark
It is denoted as polyester resin for powder coating A.
Embodiment 2
The present embodiment is the preparation of polyester resin for powder coating
Polyester resin for powder coating raw material are as follows: polyalcohol, polyacid, acidolysis agent, esterification catalyst, antioxidant and solid
Change promotor, wherein polyalcohol includes neopentyl glycol, bisphenol-A and trimethylolpropane；Polyacid be terephthalic acid (TPA) and oneself two
Acid；Polyacid is terephthalic acid (TPA) and adipic acid；Esterification catalyst is Mono-n-butyltin；Acidolysis agent be M-phthalic acid and 1,
4- cyclohexane cyclohexanedimethanodibasic, and molar ratio is 2:1；Antioxidant is antioxidant 1076 and antioxidant 168, mass ratio 2:1；
Curing accelerator is triphenyl ethyl phosphonium bromide phosphorus；Wherein, polyalcohol/polyacid molar ratio is 1.13:1, polyacid and acidolysis
The ratio of the mole of the integral molar quantity and polyalcohol of agent is 1.0502:1, and the dosage of bisphenol-A accounts for polyalcohol gross mass
7wt%, trimethylolpropane account for the 7wt% of polyalcohol gross mass, and esterification catalyst accounts for polyalcohol, polyacid and the total matter of acidolysis agent
The 0.5wt% of amount, curing accelerator account for the 0.1wt% of polyalcohol, polyacid and acidolysis agent gross mass, and antioxidant accounts for polynary
The 0.5wt% of alcohol, polyacid and acidolysis agent gross mass.
237g polyalcohol is added in a kettle, is heated to 130 DEG C, after alcohol melting clarification, adds 335g polyacid,
It is stirred with the revolving speed of 160r/min, after leading to nitrogen reaction a period of time, 0.63g esterification catalyst is added, is warming up to 190 DEG C, so
240 DEG C are warming up to the heating rate of 10 DEG C/h afterwards, insulation reaction 3.5h；210 DEG C are cooled to, 62g acidolysis agent is added, is warming up to
240 DEG C, insulation reaction 3.5h；It is cooled to 230 DEG C to vacuumize, vacuum degree is -0.095MPa, insulation reaction 2.5h；Antioxygen is added
Agent and curing accelerator cool down out after 30min is stirred in the revolving speed stirring in the case where vacuum degree is -0.095MPa with 160r/min
Material.Labeled as polyester resin for powder coating B.
Embodiment 3
The present embodiment is the preparation of polyester resin for powder coating
Polyester resin for powder coating raw material are as follows: polyalcohol, polyacid, acidolysis agent, esterification catalyst, antioxidant and solid
Change promotor, wherein polyalcohol includes neopentyl glycol, bisphenol-A and trimethylolpropane；Polyacid be terephthalic acid (TPA) and oneself two
Acid；Polyacid is terephthalic acid (TPA) and adipic acid；Esterification catalyst is Mono-n-butyltin；Acidolysis agent be M-phthalic acid and 1,
4- cyclohexane cyclohexanedimethanodibasic, and molar ratio is 2:1；Antioxidant is antioxidant 1010 and antioxidant 168, mass ratio 2:1；
Curing accelerator is triphenyl ethyl phosphonium bromide phosphorus；Wherein, polyalcohol/polyacid molar ratio is 1.15, polyacid and acidolysis agent
The ratio of the mole of integral molar quantity and polyalcohol is 1.0475:1, and the dosage of bisphenol-A accounts for the 10wt% of polyalcohol gross mass, three
Hydroxymethyl-propane accounts for the 3wt% of polyalcohol gross mass, and esterification catalyst accounts for polyalcohol, polyacid and acidolysis agent gross mass
0.3wt%, curing accelerator account for the 0.08wt% of polyalcohol, polyacid and acidolysis agent gross mass, and antioxidant accounts for polyalcohol, more
The 0.5wt% of first acid and acidolysis agent gross mass.
240g polyalcohol is added in a kettle, is heated to 135 DEG C, after alcohol melting clarification, adds 332g polyacid,
It is stirred with the revolving speed of 180r/min, after leading to nitrogen reaction a period of time, 0.64g esterification catalyst is added, is warming up to 190 DEG C, so
245 DEG C are warming up to the heating rate of 10 DEG C/h afterwards, insulation reaction 4h；215 DEG C are cooled to, 69g acidolysis agent is added, is warming up to
245 DEG C, insulation reaction 4h；It is cooled to 230 DEG C to vacuumize, vacuum degree is -0.098MPa, insulation reaction 2h；Antioxidant is added
And curing accelerator, after 40min is stirred in the revolving speed stirring in the case where vacuum degree is 0.098MPa with 180r/min, cooling discharge.Mark
It is denoted as polyester resin for powder coating C.
Embodiment 4
The present embodiment is the preparation of polyester resin for powder coating
Polyester resin for powder coating raw material are as follows: polyalcohol, polyacid, acidolysis agent, esterification catalyst, antioxidant and solid
Change promotor, wherein polyalcohol includes neopentyl glycol, bisphenol S and trimethylolpropane；Polyacid be terephthalic acid (TPA) and oneself two
Acid；Polyacid is terephthalic acid (TPA) and adipic acid；Esterification catalyst is Mono-n-butyltin；Acidolysis agent be M-phthalic acid and 1,
4- cyclohexane cyclohexanedimethanodibasic, and molar ratio is 2:1；Antioxidant is antioxidant 1010 and antioxidant 168, mass ratio 1:1；
Curing accelerator is triphenyl ethyl phosphonium bromide phosphorus；Wherein, polyalcohol/polyacid molar ratio is 1.05:1, polyacid and acidolysis
The ratio of the mole of agent integral molar quantity and polyalcohol is 1.0116:1, and the dosage of bisphenol S accounts for the 5wt% of polyalcohol gross mass,
Trimethylolpropane accounts for the 5wt% of polyalcohol gross mass, and esterification catalyst accounts for polyalcohol, polyacid and acidolysis agent gross mass
0.1wt%, curing accelerator account for the 0.01wt% of polyalcohol, polyacid and acidolysis agent gross mass, and antioxidant accounts for polyalcohol, more
The 0.5wt% of first acid and acidolysis agent gross mass.
220g polyalcohol is added in a kettle, is heated to 130 DEG C, after alcohol melting clarification, adds 320g polyacid,
It is stirred with the revolving speed of 160r/min, after leading to nitrogen reaction a period of time, 0.55g esterification catalyst is added, is warming up to 190 DEG C, so
240 DEG C are warming up to the heating rate of 10 DEG C/h afterwards, insulation reaction 3.5h；210 DEG C are cooled to, 35g acidolysis agent is added, is warming up to
240 DEG C, insulation reaction 4h；It is cooled to 230 DEG C to vacuumize, vacuum degree is -0.095MPa, insulation reaction 2.5h；It is added anti-oxidant
Agent and curing accelerator, after 20min is stirred in the revolving speed stirring in the case where vacuum degree is -0.095MPa with 160r/min, cooling discharge.
Labeled as polyester resin for powder coating D.
Embodiment 5
The present embodiment is the preparation of polyester resin for powder coating
Polyester resin for powder coating raw material are as follows: polyalcohol, polyacid, acidolysis agent, esterification catalyst, antioxidant and solid
Change promotor, wherein polyalcohol includes neopentyl glycol, bisphenol-A, bisphenol S and trimethylolpropane；Polyacid is terephthalic acid (TPA)
And adipic acid；Polyacid is terephthalic acid (TPA) and adipic acid；Esterification catalyst is Mono-n-butyltin；Acidolysis agent is isophthalic diformazan
Acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, and molar ratio is 1:1；Antioxidant is antioxidant 1010 and antioxidant 168, mass ratio
For 2:1；Curing accelerator is triphenyl ethyl phosphonium bromide phosphorus；Wherein, polyalcohol/polyacid molar ratio be 1.1:1, polyacid and
The ratio of acidolysis agent moles total number and the mole of polyalcohol is 1.0476:1, and the dosage of bisphenol-A and bisphenol S accounts for the total matter of polyalcohol
The 5wt% of amount, trimethylolpropane account for the 5wt% of polyalcohol gross mass, and esterification catalyst accounts for polyalcohol, polyacid and acidolysis agent
The 0.5wt% of gross mass, curing accelerator account for the 0.1wt% of polyalcohol, polyacid and acidolysis agent gross mass, and antioxidant accounts for more
The 0.5wt% of first alcohol, polyacid and acidolysis agent gross mass.
228g polyalcohol is added in a kettle, is heated to 130 DEG C, after alcohol melting clarification, adds 330g polyacid,
It is stirred with the revolving speed of 180r/min, after leading to nitrogen reaction a period of time, 0.61g esterification catalyst is added, is warming up to 190 DEG C, so
245 DEG C are warming up to the heating rate of 10 DEG C/h afterwards, insulation reaction 3h；210 DEG C are cooled to, 51g acidolysis agent is added, is warming up to
245 DEG C, insulation reaction 3h；It is cooled to 215~230 DEG C to vacuumize, vacuum degree is -0.09MPa, insulation reaction 4h；Antioxygen is added
Agent and curing accelerator cool down out after 40min is stirred in the revolving speed stirring in the case where vacuum degree is -0.09MPa with 180r/min
Material.Labeled as polyester resin for powder coating E.
Comparative example 1
The present embodiment is the preparation of polyester resin for powder coating
Polyester resin for powder coating raw material are as follows: polyalcohol, polyacid, acidolysis agent, esterification catalyst, antioxidant and solid
Change promotor, wherein polyacid is terephthalic acid (TPA) and adipic acid；Polyalcohol is neopentyl glycol and trimethylolpropane；Esterification
Catalyst is Mono-n-butyltin；Acidolysis agent is M-phthalic acid and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, molar ratio 2:1；It is anti-oxidant
Agent is antioxidant 1076 and antioxidant 168, mass ratio 2:1；Curing accelerator is triphenyl ethyl phosphonium bromide phosphorus；Wherein,
The molar ratio of polyalcohol and polyacid is that the mole ratio of 1.05:1, polyacid and acidolysis agent integral molar quantity and polyalcohol is
1.0116:1, trimethylolpropane account for the 1wt% of polyalcohol gross mass；Esterification catalyst accounts for polyalcohol, polyacid and acidolysis agent
The 0.1wt% of gross mass；Curing accelerator accounts for the 0.01wt% of polyalcohol, polyacid and acidolysis agent gross mass.Antioxidant accounts for
The 0.5wt% of polyalcohol, polyacid and acidolysis agent gross mass.
220g polyalcohol is added in a kettle, is heated to 120 DEG C, after alcohol melting clarification, adds 320g polyacid,
It is stirred with the revolving speed of 150r/min, after leading to nitrogen reaction a period of time, the esterification catalyst of 0.55g is added, is warming up to 190 DEG C,
Then 230 DEG C are warming up to the heating rate of 10 DEG C/h, insulation reaction 3h；190 DEG C are cooled to, the acidolysis agent of 35g is added, is heated up
To 230 DEG C, insulation reaction 3h；It is cooled to 215 DEG C to vacuumize, vacuum degree is -0.09MPa, insulation reaction 2h；Antioxidant is added
And curing accelerator, after 10min is stirred in the revolving speed stirring in the case where vacuum degree is -0.09MPa with 150r/min, cooling discharge.Mark
It is denoted as polyester resin for powder coating F.
Embodiment 7
The physicochemical property for the polyester resin for powder coating that Examples 1 to 5 and comparative example 1 are prepared is detected,
The results are shown in Table 1.
From table 1 it follows that the polyester resin that Examples 1 to 5 joined biphenol monomer has the viscosity properly closed, number
The glass transition of the polyester resin of biphenol monomer is not added compared with comparative example 1 in average molecular weight and molecular weight distribution, Examples 1 to 5
Temperature and initial decomposition temperature increase.
Table 1 is polyester resin for powder coating physicochemical property
Embodiment 8
Examples 1 to 5 and comparative example 1 are prepared into polyester resin powdery paints by each component that table 2 provides, and detect its painting
Film properties, the results are shown in Table 2.
From table 2 it can be seen that Examples 1 to 5 joined the hardness of the polyester resin powder coating of biphenol monomer, gloss
Degree, levelability, impact resistance, heat resistance and weatherability are superior to the polyester resin powder that biphenol monomer is not added for comparative example 1
Coating.
Table 2 is polyester resin powder coating formula and film performance
The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although referring to before
Stating embodiment, invention is explained in detail, those skilled in the art should understand that: it still can be to preceding
Technical solution documented by each embodiment is stated to modify or equivalent replacement of some of the technical features；And these
It modifies or replaces, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of polyester resin for powder coating characterized by comprising polyalcohol, polyacid, esterification catalyst, acidolysis agent,
Antioxidant and curing accelerator；
The polyalcohol includes one of neopentyl glycol, 1,4-CHDM or trimethylpentanediol and trihydroxy methyl
One of propane, pentaerythrite or ethoxylated pentaerythritol and bisphenols monomer.
2. polyester resin for powder coating according to claim 1, which is characterized in that the polyalcohol and the polyacid
Molar ratio is (1.05~1.15): 1；
The ratio of the mole of the moles total number and the polyalcohol of the polyacid and the acidolysis agent is (1.0~1.1): 1.
3. polyester resin for powder coating according to claim 1, which is characterized in that the bisphenols monomer includes bis-phenol
A, one of tetrabromobisphenol A, hexafluoro bisphenol-a and bisphenol S or a variety of.
4. polyester resin for powder coating according to claim 1, which is characterized in that the polyacid is selected from: to benzene two
Formic acid, adipic acid, 1,4 cyclohexanedicarboxylic acid or phthalic anhydride；
The esterification catalyst is Mono-n-butyltin, dibutyl tin dilaurate or dihydroxy dibutyl tin oxide；
The antioxidant is selected from antioxidant 1076, antioxidant 1010, antioxidant 168, antioxidant 1076 and antioxygen
168 composite antioxidant of agent or antioxidant 1010 and 168 composite antioxidant of antioxidant；
The curing accelerator includes: ammonium salt or microcosmic salt；
The acidolysis agent includes: one or more of M-phthalic acid, 1,4 cyclohexanedicarboxylic acid and adipic acid.
5. polyester resin for powder coating according to claim 1, which is characterized in that the esterification catalyst accounts for described more
0.1wt%~0.5wt% of first alcohol, the polyacid and the acidolysis agent gross mass.
6. polyester resin for powder coating according to claim 1, which is characterized in that the antioxidant accounts for described polynary
0.1wt%~0.7wt% of alcohol, the polyacid and the acidolysis agent gross mass.
7. polyester resin for powder coating according to claim 3, which is characterized in that the curing accelerator is described more
0.01wt%~0.1wt% of first alcohol, the polyacid and the acidolysis agent gross mass.
8. polyester resin for powder coating according to claim 3, which is characterized in that the bisphenols monomer accounts for described more
1wt%~10wt% of first alcohol gross mass；
The trimethylolpropane accounts for 1wt%~7wt% of the polyalcohol gross mass.
9. the preparation method of polyester resin for powder coating described in claim 1 to 8 any one, which is characterized in that including
Following steps:
Step 1: after polyalcohol is heated to melting, polyacid mixing is added, adds esterification catalyst and carries out the first reaction, obtain
To the first product；
Step 2: acidolysis agent being added into the first product and carries out the second reaction, obtains the second product；
Step 3: the second product being carried out to vacuumize reaction, obtains third product；
Step 4: third product being mixed with antioxidant and curing accelerator, obtains polyester resin for powder coating.
10. preparation method according to claim 9, which is characterized in that first reaction is with the heating speed of 5~15 DEG C/h
Rate is warming up to 230~245 DEG C, keeps the temperature 1~4h；
The temperature of second reaction is 230~245 DEG C, and soaking time is 2~5h；
The vacuum degree for vacuumizing reaction is -0.09~-0.098MPa, and soaking time is 1~4h；
The vacuum degree of mixing described in step 4 is -0.09~-0.098MPa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111440295A (en) * | 2020-03-25 | 2020-07-24 | 广东工业大学 | Polyester resin for boiling-resistant high-leveling powder coating and preparation method and application thereof |
| CN114316233A (en) * | 2022-01-11 | 2022-04-12 | 安徽智成实业有限公司 | Polyester resin with excellent ozone oxidation resistance and high and low temperature performance and preparation method thereof |
| CN115449246A (en) * | 2022-09-21 | 2022-12-09 | 无锡新而奇化工科技有限公司 | Preparation method of super-weather-resistant powder coating |
| WO2024082179A1 (en) * | 2022-10-19 | 2024-04-25 | 擎天材料科技有限公司 | Polyester resin for metal powder coating, preparation method therefor, and application thereof |
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| CN102492125A (en) * | 2011-11-30 | 2012-06-13 | 上海天洋热熔胶有限公司 | Preparation method of copolyester for metal powder coating |
| CN103724603A (en) * | 2013-12-20 | 2014-04-16 | 黄山永佳三利科技有限公司 | Polyester resin for anticorrosive powder paint and preparation method thereof |
| CN104356369A (en) * | 2014-10-10 | 2015-02-18 | 广州擎天材料科技有限公司 | Polyester resin for weather-proof and impact-resisting powder coating and preparation method of polyester resin |
| CN105601892A (en) * | 2015-11-17 | 2016-05-25 | 广东伊诗德新材料科技有限公司 | Polyester resin for powdery coating and with low volatile component content and preparation method thereof |
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| CN102492125A (en) * | 2011-11-30 | 2012-06-13 | 上海天洋热熔胶有限公司 | Preparation method of copolyester for metal powder coating |
| CN103724603A (en) * | 2013-12-20 | 2014-04-16 | 黄山永佳三利科技有限公司 | Polyester resin for anticorrosive powder paint and preparation method thereof |
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|---|---|---|---|---|
| CN111440295A (en) * | 2020-03-25 | 2020-07-24 | 广东工业大学 | Polyester resin for boiling-resistant high-leveling powder coating and preparation method and application thereof |
| CN111440295B (en) * | 2020-03-25 | 2023-04-18 | 广东工业大学 | Polyester resin for boiling-resistant high-leveling powder coating and preparation method and application thereof |
| CN114316233A (en) * | 2022-01-11 | 2022-04-12 | 安徽智成实业有限公司 | Polyester resin with excellent ozone oxidation resistance and high and low temperature performance and preparation method thereof |
| CN115449246A (en) * | 2022-09-21 | 2022-12-09 | 无锡新而奇化工科技有限公司 | Preparation method of super-weather-resistant powder coating |
| WO2024082179A1 (en) * | 2022-10-19 | 2024-04-25 | 擎天材料科技有限公司 | Polyester resin for metal powder coating, preparation method therefor, and application thereof |
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