CN106634476B - A kind of curable epoxide high-flexibility polyester resin for powder coating and preparation method thereof - Google Patents
A kind of curable epoxide high-flexibility polyester resin for powder coating and preparation method thereof Download PDFInfo
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- CN106634476B CN106634476B CN201610864925.XA CN201610864925A CN106634476B CN 106634476 B CN106634476 B CN 106634476B CN 201610864925 A CN201610864925 A CN 201610864925A CN 106634476 B CN106634476 B CN 106634476B
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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
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
The present invention relates to a kind of curable epoxide high-flexibility polyester resin for powder coating and preparation method thereof.The polyester resin that purpose is to provide should have the characteristics that high-flexibility；The method of offer has the characteristics that process is succinct.Technical solution is: a kind of curable epoxide high-flexibility polyester resin for powder coating, including component be: neopentyl glycol, 2- methyl propanediol etc..Preparation method sequentially includes the following steps: and neopentyl glycol, 2- methyl propanediol, 3- methyl-1 .5- pentanediol 1) is added in a kettle, heating, then puts into terephthalic acid (TPA), adipic acid and catalyst；Warming while stirring；2) esterification water is generated and is steamed；Heating rate regulation, carries out insulation reaction；Esterification water water yield reaches 95% or more of theoretical water yield, and heat preservation terminates；3) triphenyl phosphite is added, gradually vacuumizes, the reaction was continued；4) trimellitic anhydride is added；Insulation reaction；5) antioxidant is added and curing accelerator is stirred to react, discharge.
Description
Technical field
The present invention relates to chemical powder paint fields, and in particular to curable epoxide high-flexibility powdery paints with polyester tree
Rouge and preparation method thereof, polyester resin obtained can prepare powdery paints in the ratio of 60:40 or 50:50 with epoxy resin.
Background technique
High-flexibility powdery paints can satisfy the requirement of workpiece elder generation coating reshaping, such as vehicle filter core device, spring, anti-
Steal the workpiece such as door.Wherein security door polyester resin for powder coating mainly has TGIC solidification and two kinds of curable epoxide, indoor antitheft
Door mainly uses curable epoxide powdery paints.Existing deficiency is when the powdery paints of normal polyester preparation is on security door:
When film is 50-90 μ m thick, workpiece carries out will appear cracking when the machine-shapings such as die mould, flanging, roll-in, bound edge sealing again
Or it falls off.Chinese patent CN103265874A reports the dedicated high-flexibility powdery paints of security door, the composition of the powdery paints
In be added to a kind of polyester resin that the diethyl oxalate with 3%-10% is modified, while needing to add one in formulation for coating material
The plasticizer of polyvinyl butyral is planted to increase the toughness of film, addition ethyltriphenylphosphonium bromide promotes as a kind of solidification
Agent accelerates the solidification of film.
Improvement epoxy resin is mainly concentrated in the research of high-flexibility powdery paints at present；Patent
CN103467912A discloses " one kind has high-flexibility composition epoxy resin ", and in particular to arrives pure epoxy resin composition
The material of preparation has inierpeneirating network structure, to have excellent flexibility, can be used for electronic package material and powdery paints
Field.Patent CN104817677A discloses " a kind of epoxy curing agent of high-flexibility ", primarily directed to epoxy resin
The improvement of powdery paints curing agent reduces its toxicity, and is meeting heat distortion temperature and increasing the feelings of elongation characteristics requirement
Under condition, the appropriate toughness for enhancing curing system.Chinese patent CN 105367767A " high-flexibility powdery paints saturation in hydroxyl
Base polyester and preparation method thereof ", it is related to high-flexibility polyester resin for powder coating and preparation method thereof, the powder coating systems
For by the cured polyurethane powder coating system of blocked isocyanate, the formula design and craft control of the polyester resin is not
Polyester/epoxy systems suitable for curable epoxide.
The polyester of curable epoxide/epoxy systems powdery paints, because of a large amount of presence of epoxy resin, thus the powder prepared applies
Material is general more crisp, generally requires the flexibility that polyester resin is improved by addition special auxiliary agent, Lai Zengjia powdery paints it is flexible
Property；But improve in this way it is flexible simultaneously, it tends to be difficult to take into account polyester resin storage stability.
Currently, not needing addition special auxiliary agent, that is, has polyester/epoxy systems Gao Rou of the curable epoxide of excellent flexibility
Toughness powdery paints, there is not yet open report.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of above-mentioned background technique, a kind of curable epoxide powder is provided
Coating polyester resin, the polyester resin should have the characteristics that high-flexibility, while molecular weight with higher and molecular weight point
The narrow feature of cloth；The a certain proportion of epoxy resin of polyester resin collocation, the powdery paints being prepared have excellent decoration
Performance (flow leveling, surface richness, clarity) and protective performance especially have shock resistance outstanding, bending
It can be with cupping performance.
The present invention also provides the preparation method of the polyester resin, this method answers process succinct, and production efficiency is higher.
Present invention provide the technical scheme that a kind of curable epoxide high-flexibility polyester resin for powder coating, including
Component and corresponding parts by weight are: neopentyl glycol 280-450,2- methyl propanediol 100-200,3- methyl-1 .5- pentanediol 82-
100, terephthalic acid (TPA) 850-900, adipic acid 25-100, trimellitic anhydride 100-165, triphenyl phosphite 1.5-2.5, catalysis
Agent 1.5-2.5, antioxidant 3.5-4.5, curing accelerator 9-12.
The 1.4- cyclohexanedimethanol of 50-100 parts by weight can also be added.
The ethylene glycol of 20-70 parts by weight can also be added.
The antioxidant is the antioxidant 1010 and irgasfos 168 that the mass ratio of 1:2 mixes.
The catalyst is environmental protection inorganic tin catalyst stannous oxalate.
The curing accelerator is the octadecyldimethyl tertiary amine and etradecyldimethylamine mixed with the mass ratio of 3:7
Base tertiary amine.
Preparation method (polyester resin and asphalt mixtures modified by epoxy resin obtained of the high-flexibility polyester resin for powder coating of curable epoxide
Rouge prepares coating with the weight ratio of 60:40), it sequentially includes the following steps:
1) in the reaction kettle for having heating device, blender and distillation column, be added neopentyl glycol, 2- methyl propanediol,
3- methyl-1 .5- pentanediol, triphenyl phosphite, normal pressure are warming up to 110-130 DEG C, then put into terephthalic acid (TPA), adipic acid and
Catalyst；Side stirring, while being heated up with 2-3 DEG C per minute of speed；
2) temperature of charge rises to 170-180 DEG C, and esterification water starts to generate and steam by distillation column；It will heat up rate at this time
Regulation every 30 minutes 2-3 DEG C；When material temperature rises to 195 DEG C ± 2 DEG C, will heat up at this time rate regulation every 30 minutes 5-6 DEG C, material
When temperature rise is to 240 DEG C ± 2 DEG C, carry out insulation reaction 1-1.5 hours；When distillation column top gas temperature drop to less than 70 DEG C, while ester
Change water water yield and reach 95% or more of theoretical water yield, heat preservation terminates；
3) temperature of charge is down to 230-235 DEG C, and trimellitic anhydride is added；Insulation reaction 40-60 points under the conditions of 235 DEG C
Clock；
4) under conditions of 220~225 DEG C, it is gradually evacuated to -0.090~-0.085MPa, the reaction was continued 90 minutes；
5) 200 DEG C are finally cooled to, antioxidant is added and curing accelerator is stirred to react 15-30 minutes, discharges.
Preparation method (polyester resin and asphalt mixtures modified by epoxy resin obtained of the high-flexibility polyester resin for powder coating of curable epoxide
Rouge prepares coating with the weight ratio of 50:50), it sequentially includes the following steps:
1) in the reaction kettle for having heating device, blender and distillation column, be added neopentyl glycol, 2- methyl propanediol,
3- methyl-1 .5- pentanediol, normal pressure is warming up to 110-130 DEG C, then puts into terephthalic acid (TPA), adipic acid and catalyst；Side stirring
While being heated up with 2-3 DEG C per minute of speed；
2) temperature of charge rises to 170-180 DEG C, and esterification water starts to generate and steam by distillation column；It will heat up rate at this time
Regulation every 30 minutes 2-3 DEG C；When material temperature rises to 195 DEG C ± 2 DEG C, will heat up at this time rate regulation system every 30 minutes 5-6 DEG C, material
When temperature rise is to 240 DEG C ± 2 DEG C, carry out insulation reaction 1-1.5 hours；When distillation column top gas temperature drop to less than 70 DEG C, while ester
Change water water yield and reach 95% or more of theoretical water yield, heat preservation terminates；
3) material is added triphenyl phosphite, is gradually evacuated to -0.099--0.098MPa, the reaction was continued at 240 DEG C
60-80 minutes；
4) temperature of charge is down to 185-190 DEG C, and trimellitic anhydride is added；The insulation reaction 60 minutes under the conditions of 185 DEG C；
5) finally under the conditions of 185 DEG C, antioxidant is added and curing accelerator is stirred to react 15-30 minutes, discharges.
Compared with prior art, the present invention the beneficial effect having is:
1. not only realizing that polyester and epoxy 60:40 cured powder paint are prepared into the high-flexibility of film, realize simultaneously
Polyester and epoxy 50:50 cured powder paint are prepared into the high-flexibility of film.
2. introducing 3- methyl-1 .5- pentanediol on the basis of being conventionally synthesized monomer；3- methyl-1 .5- pentanediol is compared
Main body dihydric alcohol -- neopentyl glycol has longer main chain, while the side-chain structure having in molecule can destroy molecule segment
Regularity is not easy to crystallize, more flexible.There is main chain flexible in 3- methyl-1 .5- pentanediol molecular structure, while having again
The structure of one side chain.In the motion process of molecule, the molecule of side-chain structure can try hard to the main chain of repulsion polyester, increase molecule
The distance of interchain, thus the locomitivity of segment is increased, play the role of reactive plasticizer.3- methyl-1 .5- penta is used using containing
The powdery paints of the polyester resin preparation of glycol, film have excellent shock resistance and bending ability.
3. the present invention controls synthesis technology according to different formula features compared with conventional synthesis technology.It is poly- in synthesis
When ester and cured in the 60:40 ratio high-flexibility polyester resin for powder coating of epoxy, synthesis step 1), 2) after, first
Trimellitic anhydride is added, then carries out vacuumizing reaction.The temperature of material when strict control vacuumizes, at 220-225 DEG C, vacuum
Degree control guarantees to vacuumize the ample time of reaction between -0.090--0.085MPa, thus preferably control molecular weight and
Molecular weight distribution guarantees that polyester has biggish molecular weight, relatively narrow molecular weight distribution on the basis of same recipe.It is synthesizing
When polyester and the cured high-flexibility polyester resin for powder coating of epoxy 50:50 ratio, synthesis step 1), 2) after, then
It first carries out vacuumizing polycondensation reaction, obtains the hydroxy polyester resin of certain molecular weight, add TMA and carry out functional group's conversion instead
It answers, the strategic point of the technique is vacuumizing the stage of reaction, and needing relatively high material reaction temperature, (present invention control exists
240 DEG C), relatively high vacuum degree, the purpose of the reachable -0.099MPa~-0.098MPa. technology controlling and process of vacuum condition of the present invention
It is under identical formula system, to be obtained relatively using high vacuum degree in order to which polyester resin is before functional group's conversion reaction
Molecular weight is high, the polyester resin of narrow molecular weight distribution.In terms of showing physical and chemical index: relatively high glass transition temperature is glued with low
Degree.Meanwhile relative to small-molecular-weight polyester, the polyester of high molecular weight under equal conditions has better mechanical strength, performance
There is better shock resistance, bend-resistance performance and cupping performance for film.
Product of the present invention and existing product compare, and the polyester resin and suitable curing agent, pigments and fillers, auxiliary agent etc. are by common
The powdery paints that is prepared of heat curable powder coating formula have excellent decorative performance (flow leveling, surface richness,
Clarity) and protective performance, especially have shock resistance, buckling performance and cupping performance outstanding.
Detailed description of the invention
Fig. 1 is the mechanical strength and molecular weight relational graph of polymer.
Specific embodiment
The present invention is further described combined with specific embodiments below.
1 polyester resin of table is with when resin property index
The acid value of resin tests the standard detection according to GB/T 6743-2008
The viscosity test of resin according to GB/T 9751.1-2008 standard detection
The glass transition temperature of resin measures the standard detection according to GB/T 19466.2-2004
The softening point measurement of resin according to GB/T27808-2011 standard detection
The molecular weight and molecular weight distribution of resin are measured using gel permeation chromatography.
Corresponding instance description of the process:
Embodiment A.B.C technique are as follows: the preparation method of curable epoxide high-flexibility polyester resin for powder coating is (obtained
Polyester resin and epoxy resin prepare coating with the weight ratio of 60:40), it sequentially includes the following steps:
1) in the reaction kettle for having heating device, blender and distillation column, be added neopentyl glycol, 2- methyl propanediol,
3- methyl-1 .5- pentanediol, triphenyl phosphite, normal pressure are warming up to 110-130 DEG C, then put into terephthalic acid (TPA), adipic acid and
Catalyst；Side stirring, while being heated up with 2-3 DEG C per minute of speed；
2) temperature of charge rises to 170-180 DEG C, and esterification water starts to generate and steam by distillation column；It will heat up rate at this time
Regulation every 30 minutes 2-3 DEG C；When material temperature rises to 195 DEG C ± 2 DEG C, will heat up at this time rate regulation every 30 minutes 5-6 DEG C, material
When temperature rise is to 240 DEG C ± 2 DEG C, carry out insulation reaction 1-1.5 hours；When distillation column top gas temperature drop to less than 70 DEG C, while ester
Change water water yield and reach 95% or more of theoretical water yield, heat preservation terminates；
3) temperature of charge is down to 230-235 DEG C, and trimellitic anhydride is added；Insulation reaction 40-60 points under the conditions of 235 DEG C
Clock；
4) under conditions of 220~225 DEG C, it is gradually evacuated to -0.090~-0.085MPa, the reaction was continued 90 minutes；
5) 200 DEG C are finally cooled to, antioxidant is added and (is mixed by antioxidant 1010 and irgasfos 168 with the mass ratio of 1:2
Close) and curing accelerator be stirred to react 15-30 minutes, discharge.
Embodiment E.F.G technique are as follows: the preparation method of curable epoxide high-flexibility polyester resin for powder coating is (obtained
Polyester resin and epoxy resin prepare coating with the weight ratio of 50:50), it sequentially includes the following steps:
1) in the reaction kettle for having heating device, blender and distillation column, be added neopentyl glycol, 2- methyl propanediol,
3- methyl-1 .5- pentanediol, normal pressure is warming up to 110-130 DEG C, then puts into terephthalic acid (TPA), adipic acid and catalyst；Side stirring
While being heated up with 2-3 DEG C per minute of speed；
2) temperature of charge rises to 170-180 DEG C, and esterification water starts to generate and steam by distillation column；It will heat up rate at this time
Regulation every 30 minutes 2-3 DEG C；When material temperature rises to 195 DEG C ± 2 DEG C, will heat up at this time rate regulation system every 30 minutes 5-6 DEG C, material
When temperature rise is to 240 DEG C ± 2 DEG C, carry out insulation reaction 1-1.5 hours；When distillation column top gas temperature drop to less than 70 DEG C, while ester
Change water water yield and reach 95% or more of theoretical water yield, heat preservation terminates；
3) material is added triphenyl phosphite, is gradually evacuated to -0.099--0.098MPa, the reaction was continued at 240 DEG C
60-80 minutes.
4) temperature of charge is down to 185-190 DEG C, and trimellitic anhydride is added；The insulation reaction 60 minutes under the conditions of 185 DEG C；
5) finally under the conditions of 185 DEG C, antioxidant is added and curing accelerator is stirred to react 15-30 minutes, discharges.
The 6 kinds of polyester resin that will be synthesized with above-described embodiment, mix a certain proportion of epoxy resin E-12, barium sulfate, titanium
White powder (or other pigment such as carbon black), levelling agent, styrax, 701 etc., uniformly mixed merga pass extruder dispersion, mill screen
Divide, after electrostatic spraying, taken out after 180 DEG C/15min solidification, powdery paints is obtained after cooling (for conventional powdery paints preparation work
Skill).Table 2 shows the performance of the coating and film.
2 powder coating component of table is with when film performance
In table 2:
1.E-12 is epoxy resin, epoxide equivalent: 833g/mol
2. levelling agent: the dedicated levelling agent of powdery paints (such as polyacrylate of Ningbo South-sea Chemical Co., Ltd.'s production
Levelling agent, GLP588)
3.701: the powdery paints wetting enhancer (acrylate copolymer that such as Ningbo South-sea Chemical Co., Ltd. produces
Based on powdery paints additive, BLC701)
4. Resin A, resin B ... resin F in table are successively embodiment A, embodiment B ... embodiment F in table 1
Resin obtained.Example is using above-mentioned resin plus coating made from auxiliary material.
5. powdery paints film performance testing standard
The thickness of film tests the standard detection according to GB/T 13452.2-2008；
The measurement of luster of film according to GB/T1743-1979 standard detection；
The solvent resistant rubbing test of film according to GB 23989-2009 standard detection；
The adhesive force of film tests the standard detection according to GB/T 9286-1998；
The impact property of film tests the standard detection according to GB-T1732-1993；
The bend-resistance performance test of film according to GB/T30791-2014 standard detection；
The cupping performance test of film according to GB/T9753-2007 standard testing；
The gel time of powdery paints tests the standard detection according to GB/T 16995-1997.
From table 2: embodiment B embodiment A compared with embodiment C just has better cupping performance, more excellent low
Warm shock resistance, while buckling performance is promoted to 0T by 1T.Same embodiment E embodiment D compared with embodiment F also has more
Good cupping performance, more excellent low-temperature impact resistance, buckling performance are promoted to 0T by 2T.Illustrate in polyester resin system
The middle 3- methyl-1 .5- pentanediol monomer that introduces helps to promote buckling performance, cupping performance and the low-temperature impact resistance of film,
Facilitate the flexibility of promotion film.All embodiments of the present invention compared to common process synthesis polyester resin all have compared with
High molecular weight, relatively narrow molecular weight distribution.Illustrate preferably control polyester resin using technology controlling and process of the invention
Molecular weight and molecular weight distribution.
The present invention optimizes the collocation of monomer, obtains high-flexibility by introducing functional monomer 3- methyl-1 .5- pentanediol
Polyester resin；Meanwhile by optimum synthesis technique, the polyester resin being prepared has relative molecular weight height, molecular weight point
The narrow feature of cloth.Using the series polyester resin, a certain proportion of epoxy resin of arranging in pairs or groups, the powdery paints being prepared has excellent
Different decorative performance (flow leveling, surface richness, clarity) and protective performance, especially have impact resistance outstanding
Energy, buckling performance and cupping performance, can be used for the higher field of the flexibility requirements such as security door.
Claims (3)
1. a kind of curable epoxide high-flexibility polyester resin for powder coating, including component and corresponding parts by weight be: new penta
Glycol 280-450,2- methyl propanediol 100-200,3- methyl-1 .5- pentanediol 82-100, terephthalic acid (TPA) 850-900, oneself
Diacid 25-100, trimellitic anhydride 100-165, triphenyl phosphite 1.5-2.5, catalyst 1.5-2.5, antioxidant 3.5-4.5,
Curing accelerator 9-12；
The 1.4- cyclohexanedimethanol of 50-100 parts by weight is additionally added in the polyester resin；
The ethylene glycol of 20-70 parts by weight is additionally added in the polyester resin；
Antioxidant described in the polyester resin is the antioxidant 1010 and irgasfos 168 that the mass ratio of 1:2 mixes；
Catalyst described in the polyester resin is environmental protection inorganic tin catalyst stannous oxalate；
Curing accelerator described in the polyester resin is the octadecyldimethyl tertiary amine and 16 mixed with the mass ratio of 3:7
Alkyl dimethyl tertiary amide.
2. the preparation method of curable epoxide high-flexibility polyester resin for powder coating described in claim 1, according to the following steps
It carries out:
1) in the reaction kettle for having heating device, blender and distillation column, neopentyl glycol, 2- methyl propanediol, 3- first is added
Base -1.5- pentanediol, triphenyl phosphite, normal pressure are warming up to 110-130 DEG C, then put into terephthalic acid (TPA), adipic acid and catalysis
Agent；Side stirring, while being heated up with 2-3 DEG C per minute of speed；
2) temperature of charge rises to 170-180 DEG C, and esterification water starts to generate and steam by distillation column；It will heat up rate regulation at this time
Every 30 minutes 2-3 DEG C；When material temperature rises to 195 DEG C ± 2 DEG C, will heat up at this time rate regulation every 30 minutes 5-6 DEG C, material temperature liter
When to 240 DEG C ± 2 DEG C, carry out insulation reaction 1-1.5 hours；When distillation column top gas temperature drop to less than 70 DEG C, while esterification water
Water yield reaches 95% or more of theoretical water yield, and heat preservation terminates；
3) temperature of charge is down to 230-235 DEG C, and trimellitic anhydride is added；Insulation reaction 40-60 minutes under the conditions of 235 DEG C；
4) under conditions of 220~225 DEG C, it is gradually evacuated to -0.090~-0.085MPa, the reaction was continued 90 minutes；
5) be finally cooled to 200 DEG C, be added antioxidant (by antioxidant 1010 and irgasfos 168 with the mass ratio of 1:2 mixes and
At) and curing accelerator be stirred to react 15-30 minutes, discharge.
3. the preparation method of curable epoxide high-flexibility polyester resin for powder coating described in claim 1, according to the following steps
It carries out:
1) in the reaction kettle for having heating device, blender and distillation column, neopentyl glycol, 2- methyl propanediol, 3- first is added
Base -1.5- pentanediol, normal pressure are warming up to 110-130 DEG C, then put into terephthalic acid (TPA), adipic acid and catalyst；While stirring with
2-3 DEG C of speed heating per minute；
2) temperature of charge rises to 170-180 DEG C, and esterification water starts to generate and steam by distillation column；It will heat up rate regulation at this time
Every 30 minutes 2-3 DEG C；When material temperature rises to 195 DEG C ± 2 DEG C, will heat up at this time rate regulation system every 30 minutes 5-6 DEG C, material temperature liter
When to 240 DEG C ± 2 DEG C, carry out insulation reaction 1-1.5 hours；When distillation column top gas temperature drop to less than 70 DEG C, while esterification water
Water yield reaches 95% or more of theoretical water yield, and heat preservation terminates；
3) material is at 240 DEG C, and triphenyl phosphite is added, is gradually evacuated to -0.099--0.098MPa, the reaction was continued 60-80
Minute；
4) temperature of charge is down to 185-190 DEG C, and trimellitic anhydride is added；The insulation reaction 60 minutes under the conditions of 185 DEG C；
5) finally under the conditions of 185 DEG C, antioxidant is added and curing accelerator is stirred to react 15-30 minutes, discharges.
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| CN111205731A (en) * | 2020-02-14 | 2020-05-29 | 广东涂亿科技有限公司 | High-toughness bending-delaying powder coating and preparation method thereof |
| CN111234196B (en) * | 2020-03-20 | 2022-07-05 | 东莞市左镕工实业有限公司 | Polycarbonate resin for elastic hand feeling paint, preparation method thereof and elastic hand feeling paint |
| CN112062941A (en) * | 2020-09-16 | 2020-12-11 | 浙江中法新材料有限公司 | 6040 type polyester resin and preparation method thereof |
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