CN106634476A - Epoxy cured high-flexibility polyester resin used for powdery paint and a preparing method thereof - Google Patents
Epoxy cured high-flexibility polyester resin used for powdery paint and a preparing method thereof Download PDFInfo
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- CN106634476A CN106634476A CN201610864925.XA CN201610864925A CN106634476A CN 106634476 A CN106634476 A CN 106634476A CN 201610864925 A CN201610864925 A CN 201610864925A CN 106634476 A CN106634476 A CN 106634476A
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to epoxy cured high-flexibility polyester resin used for powdery paint and a preparing method thereof. The provided polyester resin has a characteristic of high flexibility. The provided method has characteristics of simple and concise steps. According to a technical scheme, the polyester resin includes neopentyl glycol, 2-methyl propanediol, and the like. The method includes steps of 1) adding the neopentyl glycol, the 2-methyl propanediol and 3-methyl-1,5-pentanediol into a reaction kettle, raising the temperature, then adding terephthalic acid, adipic acid and a catalyst and raising the temperature under stirring; 2) generating esterification water and evaporating the water to remove the water, controlling and regulating the temperature raising rate, reacting under a maintained temperature, and finishing temperature maintaining when the amount of the esterification water is 95% or above of the theoretical water discharge amount; 3) adding triphenyl phosphite, gradually vacuumizing and reacting continuously; 4) adding trimellitic anhydride and reacting under a maintained temperature; and 5) adding an antioxidant and a curing promoter, reacting under stirring and discharging a material.
Description
Technical field
The present invention relates to chemical powder paint field, and in particular to curable epoxide high-flexibility polyester tree used for powder coating
Fat and preparation method thereof, obtained polyester resin can press 60 with epoxy resin:40 or 50:50 ratio prepares powdery paints.
Background technology
High-flexibility powdery paints can meet the requirement of workpiece elder generation application reshaping, for example vehicle filter core device, spring, anti-
Steal the workpiece such as door.Wherein antitheft door polyester resin for powder coating mainly has two kinds of TGIC solidifications and curable epoxide, indoor antitheft
Door mainly adopts curable epoxide powdery paints.The deficiency that exists is when powdery paints prepared by normal polyester is used on antitheft door：
When film is 50-90 μ m thicks, workpiece carries out that cracking occurs during the machine-shapings such as die mould, flanging, roll-in, bound edge sealing again
Or come off.Chinese patent CN103265874A reports the special high-flexibility powdery paints of antitheft door, the composition of the powdery paints
In with the addition of a kind of modified polyester resin of diethyl oxalate of use 3%-10%, while needing addition one in formulation for coating material
Increasing the toughness of film, addition ethyltriphenylphosphonium bromide promotes the plasticizer of kind of polyvinyl butyral resin as a kind of solidification
Agent, accelerates the solidification of film.
The research of high-flexibility powdery paints is mainly concentrated at present improve epoxy resin；Patent
CN103467912A is disclosed《One kind has high-flexibility composition epoxy resin》, and in particular to pure epoxy resin composition
The material of preparation has inierpeneirating network structure, so as to excellent pliability, can be used for electronic package material and powdery paints
Field.Patent CN104817677A is disclosed《A kind of epoxy curing agent of high-flexibility》, it is primarily directed to epoxy resin
The improvement of curing agent used for powder coating, reduces its toxicity, and is meeting heat distortion temperature and increasing the feelings that elongation characteristics are required
Under condition, the appropriate toughness for strengthening curing system.Chinese patent CN 105367767A《Hydroxyl in high-flexibility saturation used for powder coating
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
It is the polyurethane powder coating system solidified by blocked isocyanate, the formula design and craft of the polyester resin is controlled not
Suitable for the polyester/epoxy systems of curable epoxide.
The polyester of curable epoxide/epoxy systems powdery paints, because of a large amount of presence of epoxy resin, thus the powder for preparing is applied
Material is general more crisp, generally requires to increase the flexible of powdery paints by adding the pliability of special auxiliary agent improvement polyester resin
Property；But by this mode improve it is flexible simultaneously, it tends to be difficult to take into account polyester resin storage stability.
At present, it is not necessary to add special auxiliary agent, that is, possesses the polyester/epoxy systems Gao Rou of the curable epoxide of excellent flexibility
Toughness powdery paints, there is not yet open report.
The content of the invention
The technical problem to be solved is to overcome the shortcomings of above-mentioned background technology, there is provided a kind of curable epoxide powder
Coating polyester resin, the characteristics of the polyester resin should have high-flexibility, while with higher molecular weight and molecular weight point
The characteristics of cloth is narrow；The a certain proportion of epoxy resin of polyester resin collocation, the powdery paints for preparing has excellent decoration
Performance (flow leveling, surface richness, definition) and barrier propterty, especially possess prominent shock resistance, bending
Can be with cupping performance.
Present invention also offers the preparation method of the polyester resin, the method answers operation succinct, and production efficiency is higher.
The present invention provide technical scheme be：A kind of curable epoxide high-flexibility polyester resin for powder coating, including
Component and corresponding weight portion are：Neopentyl glycol 280-450,2- methyl propanediol 100-200,3- methyl isophthalic acid .5- pentanediol 82-
100th, 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- cyclohexanedimethanols of 50-100 weight portions can also be added.
The ethylene glycol of 20-70 weight portions can also be added.
The antioxidant is 1:Antioxidant 1010 and irgasfos 168 that 2 mass ratio is mixed.
The catalyst is environmental protection inorganic tin catalyst stannous oxalate.
The curing accelerator is with 3:The octadecyldimethyl tertiary amine and etradecyldimethylamine of 7 mass ratio mixing
Base tertiary amine.
Preparation method (obtained polyester resin and the asphalt mixtures modified by epoxy resin of the high-flexibility polyester resin for powder coating of curable epoxide
Fat is with 60:40 part by weight prepares coating), carry out according to the following steps：
1) in the reactor of heater, agitator and distillation column is had, add neopentyl glycol, 2- methyl propanediols,
3- methyl isophthalic acid .5- pentanediols, triphenyl phosphite, normal pressure is warming up to 110-130 DEG C, then put into terephthalic acid (TPA), adipic acid and
Catalyst；Side is stirred, 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 is started to generate and steamed by distillation column；Now will heat up speed
Regulation and control per 30 minutes 2-3 DEG C；When material temperature rises to 195 DEG C ± 2 DEG C, now will heat up speed regulation and control per 30 minutes 5-6 DEG C, material
When temperature rise is to 240 DEG C ± 2 DEG C, insulation reaction 1-1.5 hour is carried out；When distillation column top gas temperature is decreased to less than 70 DEG C, while ester
Change water water yield reach theoretical water yield 95% and more than, insulation terminates；
3) temperature of charge is down to 230-235 DEG C, adds trimellitic anhydride；Insulation reaction 40-60 point under the conditions of 235 DEG C
Clock；
4) under conditions of 220～225 DEG C, -0.090～-0.085MPa is progressively evacuated to, continues to react 90 minutes；
5) 200 DEG C are finally cooled to, antioxidant and curing accelerator stirring reaction 15-30 minute, discharging is added.
Preparation method (obtained polyester resin and the asphalt mixtures modified by epoxy resin of the high-flexibility polyester resin for powder coating of curable epoxide
Fat is with 50:50 part by weight prepares coating), carry out according to the following steps：
1) in the reactor of heater, agitator and distillation column is had, add neopentyl glycol, 2- methyl propanediols,
3- methyl isophthalic acid .5- pentanediols, normal pressure is warming up to 110-130 DEG C, then puts into terephthalic acid (TPA), adipic acid and catalyst；Stir on side
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 is started to generate and steamed by distillation column；Now will heat up speed
Regulation and control per 30 minutes 2-3 DEG C；When material temperature rises to 195 DEG C ± 2 DEG C, now will heat up speed regulation and control system per 30 minutes 5-6 DEG C, material
When temperature rise is to 240 DEG C ± 2 DEG C, insulation reaction 1-1.5 hour is carried out；When distillation column top gas temperature is decreased to less than 70 DEG C, while ester
Change water water yield reach theoretical water yield 95% and more than, insulation terminates；
3) material adds triphenyl phosphite at 240 DEG C, is progressively evacuated to -0.099--0.098MPa, continues to react
60-80 minutes；
4) temperature of charge is down to 185-190 DEG C, adds trimellitic anhydride；Insulation reaction 60 minutes under the conditions of 185 DEG C；
5) it is last under the conditions of 185 DEG C, add antioxidant and curing accelerator stirring reaction 15-30 minute, discharging.
Compared with prior art, the beneficial effect for possessing is the present invention：
1. polyester and epoxy 60 are not only realized:40 cured powder paints are prepared into the high-flexibility of film, while realizing
Polyester and epoxy 50:50 cured powder paints are prepared into the high-flexibility of film.
2. on the basis of monomer is conventionally synthesized, 3- methyl isophthalic acid .5- pentanediols are introduced；3- methyl isophthalic acid .5- pentanediols are compared
Main body dihydroxylic alcohols -- neopentyl glycol, with longer main chain, while the side-chain structure energy saboteur's segment having in molecule
Regularity, is difficult crystallization, more flexible.There is flexible main chain, while and carrying in 3- methyl isophthalic acid .5- pentanediol molecular structures
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 a part of reactive plasticizer.3- methyl isophthalic acids .5- penta is used using containing
Powdery paints prepared by the polyester resin of glycol, film has excellent shock resistance and bending ability.
3. compared with conventional synthesis technique, the present invention is according to different formula feature control synthesis techniques.It is poly- in synthesis
Ester presses 60 with epoxy:During the high-flexibility polyester resin for powder coating of 40 ratios solidification, synthesis step 1), 2) terminate after, first
Trimellitic anhydride is added, then carries out vacuumizing reaction.The temperature of material when strict control is vacuumized, at 220-225 DEG C, vacuum
Degree control between -0.090--0.085MPa, it is ensured that vacuumize the ample time of reaction, so as to preferably control molecular weight and
Molecular weight distribution, ensures that polyester has larger molecular weight, the molecular weight distribution of opposite, narrow on the basis of same recipe.In synthesis
Polyester and epoxy 50:50 ratios solidification high-flexibility polyester resin for powder coating when, synthesis step 1), 2) terminate after, then
First carry out vacuumizing polycondensation reaction, obtain the hydroxy polyester resin of certain molecular weight, adding TMA carries out functional group's conversion instead
Should, the strategic point of the technique is vacuumizing the stage of reaction, and (present invention control exists to need relatively high material reaction temperature
240 DEG C), relatively high vacuum, the purpose of the reachable -0.099MPa～-0.098MPa. technology controlling and process of vacuum condition of the present invention
It is, in order to polyester resin is before functional group's conversion reaction, under identical formula system, to be obtained relatively using high vacuum
Molecular weight is high, the polyester resin of narrow molecular weight distribution.Show physical and chemical index aspect：Relatively high vitrification point is glued with low
Degree.Meanwhile, relative to small-molecular-weight polyester, the polyester of HMW under equal conditions has more preferable mechanical strength, performance
There is more preferable shock resistance, bend-resistance performance and cupping performance for film.
Product of the present invention and existing product are contrasted, and the polyester resin and suitable curing agent, color stuffing, auxiliary agent etc. are by conventional
The powdery paints for preparing of heat curable powder coating formula have excellent decoration performance (flow leveling, surface richness,
Definition) and barrier propterty, especially possess prominent shock resistance, buckling performance and cupping performance.
Description of the drawings
Fig. 1 is the mechanical strength and molecular weight graph of a relation of polymer.
Specific embodiment
With reference to specific embodiment, the present invention is further described.
The polyester resin of table 1 is with when resin property index
The acid number of resin is tested according to the standard detection of GB/T 6743-2008
The viscosity test of resin according to GB/T 9751.1-2008 standard detection
The vitrification point of resin is determined according to the standard detection of 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 is determined using gel permeation chromatography.
Corresponding instance description of the process：
Embodiment A.B.C technique is：The preparation method of curable epoxide high-flexibility polyester resin for powder coating is (obtained
Polyester resin is with epoxy resin with 60:40 part by weight prepares coating), carry out according to the following steps：
1) in the reactor of heater, agitator and distillation column is had, add neopentyl glycol, 2- methyl propanediols,
3- methyl isophthalic acid .5- pentanediols, triphenyl phosphite, normal pressure is warming up to 110-130 DEG C, then put into terephthalic acid (TPA), adipic acid and
Catalyst；Side is stirred, 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 is started to generate and steamed by distillation column；Now will heat up speed
Regulation and control per 30 minutes 2-3 DEG C；When material temperature rises to 195 DEG C ± 2 DEG C, now will heat up speed regulation and control per 30 minutes 5-6 DEG C, material
When temperature rise is to 240 DEG C ± 2 DEG C, insulation reaction 1-1.5 hour is carried out；When distillation column top gas temperature is decreased to less than 70 DEG C, while ester
Change water water yield reach theoretical water yield 95% and more than, insulation terminates；
3) temperature of charge is down to 230-235 DEG C, adds trimellitic anhydride；Insulation reaction 40-60 point under the conditions of 235 DEG C
Clock；
4) under conditions of 220～225 DEG C, -0.090～-0.085MPa is progressively evacuated to, continues to react 90 minutes；
5) 200 DEG C are finally cooled to, antioxidant is added (by antioxidant 1010 and irgasfos 168 with 1:2 mass ratio is mixed
Conjunction is formed) and curing accelerator stirring reaction 15-30 minute, discharging.
Embodiment E.F.G technique is：The preparation method of curable epoxide high-flexibility polyester resin for powder coating is (obtained
Polyester resin is with epoxy resin with 50:50 part by weight prepares coating), carry out according to the following steps：
1) in the reactor of heater, agitator and distillation column is had, add neopentyl glycol, 2- methyl propanediols,
3- methyl isophthalic acid .5- pentanediols, normal pressure is warming up to 110-130 DEG C, then puts into terephthalic acid (TPA), adipic acid and catalyst；Stir on side
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 is started to generate and steamed by distillation column；Now will heat up speed
Regulation and control per 30 minutes 2-3 DEG C；When material temperature rises to 195 DEG C ± 2 DEG C, now will heat up speed regulation and control system per 30 minutes 5-6 DEG C, material
When temperature rise is to 240 DEG C ± 2 DEG C, insulation reaction 1-1.5 hour is carried out；When distillation column top gas temperature is decreased to less than 70 DEG C, while ester
Change water water yield reach theoretical water yield 95% and more than, insulation terminates；
3) material adds triphenyl phosphite at 240 DEG C, is progressively evacuated to -0.099--0.098MPa, continues to react
60-80 minutes.
4) temperature of charge is down to 185-190 DEG C, adds trimellitic anhydride；Insulation reaction 60 minutes under the conditions of 185 DEG C；
5) it is last under the conditions of 185 DEG C, add antioxidant and curing accelerator stirring reaction 15-30 minute, discharging.
By the 6 kinds of polyester resin synthesized with above-described embodiment, a certain proportion of epoxy resin E-12, barium sulfate, titanium are mixed
White powder other pigment such as (or) carbon blacks, levelling agent, styrax, 701 etc., uniformly mixed merga pass extruder dispersion, mill screen
Point, after electrostatic spraying, take out after 180 DEG C/15min solidifications, powdery paints is obtained after cooling and (prepares work for conventional powdery paints
Skill).Table 2 shows the performance of the coating and film.
The powder coating component of table 2 is with when film performance
In table 2：
1.E-12 for epoxy resin, epoxide equivalent：833g/mol
2. levelling agent：The special levelling agent of powdery paints is (such as the polyacrylate of Ningbo South-sea Chemical Co., Ltd.'s production
Levelling agent, GLP588)
3.701：Wetting enhancer used for powder coating is (such as the acrylate copolymer of Ningbo South-sea Chemical Co., Ltd.'s production
For the powdery paints additive of main body, BLC701)
4. Resin A in table, resin B ... resin F, are successively embodiment A, embodiment B ... embodiments F in table 1
Obtained resin.Example is to add coating obtained in auxiliary material using above-mentioned resin.
5. powdery paints film performance testing standard
The thickness measuring of film according to GB/T 13452.2-2008 standard detection；
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 is tested according to the standard detection of GB/T 9286-1998；
The impact property of film is tested according to the standard detection of 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 is tested according to the standard detection of GB/T 16995-1997.
From table 2：Embodiment B embodiment A compared with embodiment C just has more preferable cupping performance, and more excellent is 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 is promoted to 0T by 2T.Illustrate in polyester resin system
Middle introducing 3- methyl isophthalic acid .5- pentanediol monomers contribute to lifting buckling performance, cupping performance and the low-temperature impact resistance of film,
Contribute to lifting the pliability of film.The all of embodiment of the present invention compare the polyester resin of common process synthesis all have compared with
High molecular weight, the molecular weight distribution of opposite, narrow.The technology controlling and process using the present invention is illustrated, polyester resin can be preferably controlled
Molecular weight and molecular weight distribution.
The present invention optimizes the collocation of monomer by introducing functional monomer 3- methyl isophthalic acid .5- pentanediols, obtains high-flexibility
Polyester resin；Meanwhile, by optimum synthesis technique, the polyester resin for preparing has relative molecular weight height, molecular weight point
The characteristics of cloth is narrow.Using the serial polyester resin, a certain proportion of epoxy resin of arranging in pairs or groups, the powdery paints for preparing has excellent
Different decoration performance (flow leveling, surface richness, definition) and barrier propterty, especially possess prominent impact resistance
Energy, buckling performance and cupping performance, can be used for the higher field of the flexibility requirements such as antitheft door.
Claims (8)
1. a kind of curable epoxide high-flexibility polyester resin for powder coating, including component and corresponding weight portion be：New penta
Glycol 280-450,2- methyl propanediol 100-200,3- methyl isophthalic acid .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.
2. curable epoxide high-flexibility polyester resin for powder coating according to claim 1, it is characterised in that：The polyester
The 1.4- cyclohexanedimethanols of 50-100 weight portions are additionally added in resin.
3. curable epoxide high-flexibility polyester resin for powder coating according to claim 2, it is characterised in that：The polyester
The ethylene glycol of 20-70 weight portions is additionally added in resin.
4. curable epoxide high-flexibility polyester resin for powder coating according to claim 3, it is characterised in that：The polyester
Antioxidant described in resin is 1:Antioxidant 1010 and irgasfos 168 that 2 mass ratio is mixed.
5. curable epoxide high-flexibility polyester resin for powder coating according to claim 4, it is characterised in that：The polyester
Catalyst described in resin is environmental protection inorganic tin catalyst stannous oxalate.
6. curable epoxide high-flexibility polyester resin for powder coating according to claim 5, it is characterised in that：The polyester
Curing accelerator described in resin is with 3:The octadecyldimethyl tertiary amine and hexadecyldimethyl benzyl ammonium of 7 mass ratio mixing
Tertiary amine.
7. the preparation method of the curable epoxide high-flexibility polyester resin for powder coating described in claim 1, according to the following steps
Carry out：
1) in the reactor of heater, agitator and distillation column is had, neopentyl glycol, 2- methyl propanediols, 3- first are added
Base -1.5- pentanediols, triphenyl phosphite, normal pressure is warming up to 110-130 DEG C, then puts into terephthalic acid (TPA), adipic acid and catalysis
Agent；Side is stirred, 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 is started to generate and steamed by distillation column；Now will heat up speed regulation and control
Per 30 minutes 2-3 DEG C；When material temperature rises to 195 DEG C ± 2 DEG C, now will heat up speed regulation and control per 30 minutes 5-6 DEG C, material temperature liter
During to 240 DEG C ± 2 DEG C, insulation reaction 1-1.5 hour is carried out；When distillation column top gas temperature is decreased to less than 70 DEG C, while esterification water
Water yield reach the 95% of theoretical water yield and more than, insulation terminates；
3) temperature of charge is down to 230-235 DEG C, adds trimellitic anhydride；The insulation reaction 40-60 minute under the conditions of 235 DEG C；
4) under conditions of 220～225 DEG C, -0.090～-0.085MPa is progressively evacuated to, continues to react 90 minutes；
5) 200 DEG C are finally cooled to, antioxidant is added (by antioxidant 1010 and irgasfos 168 with 1:2 mass ratio mixing and
Into) and curing accelerator stirring reaction 15-30 minute, discharging.
8. the preparation method of the curable epoxide high-flexibility polyester resin for powder coating described in claim 1, according to the following steps
Carry out：
1) in the reactor of heater, agitator and distillation column is had, neopentyl glycol, 2- methyl propanediols, 3- first are added
Base -1.5- pentanediols, normal pressure is warming up to 110-130 DEG C, then puts into terephthalic acid (TPA), adipic acid and catalyst；While stirring with
2-3 DEG C per minute of speed heats up；
2) temperature of charge rises to 170-180 DEG C, and esterification water is started to generate and steamed by distillation column；Now will heat up speed regulation and control
Per 30 minutes 2-3 DEG C；When material temperature rises to 195 DEG C ± 2 DEG C, now will heat up speed regulation and control system per 30 minutes 5-6 DEG C, material temperature liter
During to 240 DEG C ± 2 DEG C, insulation reaction 1-1.5 hour is carried out；When distillation column top gas temperature is decreased to less than 70 DEG C, while esterification water
Water yield reach the 95% of theoretical water yield and more than, insulation terminates；
3) material adds triphenyl phosphite at 240 DEG C, is progressively evacuated to -0.099--0.098MPa, continues to react 60-80
Minute；
4) temperature of charge is down to 185-190 DEG C, adds trimellitic anhydride；Insulation reaction 60 minutes under the conditions of 185 DEG C；
5) it is last under the conditions of 185 DEG C, add antioxidant and curing accelerator stirring reaction 15-30 minute, discharging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250419A (en) * | 2018-01-16 | 2018-07-06 | 浙江光华科技股份有限公司 | A kind of mixed powder coating strong bending polyester resin and preparation method thereof |
| CN109824879A (en) * | 2019-03-06 | 2019-05-31 | 安徽永利新材料科技有限公司 | Levelability and the excellent curable epoxide 70:30 polyester resin and preparation method of solvent resistant |
| CN109880494A (en) * | 2019-03-06 | 2019-06-14 | 安徽永利新材料科技有限公司 | A kind of indoor high rigidity, high glaze powder 50:50 polyester resin and preparation method thereof |
| 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 |
| CN111234196A (en) * | 2020-03-20 | 2020-06-05 | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1244544A (en) * | 1999-08-26 | 2000-02-16 | 南亚塑胶工业股份有限公司 | Copolymerized polyester suitable for extrusion |
| CN1708530A (en) * | 2002-11-08 | 2005-12-14 | 旭电化工业株式会社 | Polyester plasticizer and chlorine-containing resin compositions |
| CN103642014A (en) * | 2013-12-11 | 2014-03-19 | 浙江天松新材料股份有限公司 | Polyester resin for epoxy-cured powder coating with high glossiness and high leveling property and preparation method thereof |
| CN105367765A (en) * | 2015-12-07 | 2016-03-02 | 浙江传化天松新材料有限公司 | Polyester resin used for TGIC curing high-toughness thermal transfer printing powder paints, and preparation method thereof |
-
2016
- 2016-09-30 CN CN201610864925.XA patent/CN106634476B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1244544A (en) * | 1999-08-26 | 2000-02-16 | 南亚塑胶工业股份有限公司 | Copolymerized polyester suitable for extrusion |
| CN1708530A (en) * | 2002-11-08 | 2005-12-14 | 旭电化工业株式会社 | Polyester plasticizer and chlorine-containing resin compositions |
| CN103642014A (en) * | 2013-12-11 | 2014-03-19 | 浙江天松新材料股份有限公司 | Polyester resin for epoxy-cured powder coating with high glossiness and high leveling property and preparation method thereof |
| CN105367765A (en) * | 2015-12-07 | 2016-03-02 | 浙江传化天松新材料有限公司 | Polyester resin used for TGIC curing high-toughness thermal transfer printing powder paints, and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250419A (en) * | 2018-01-16 | 2018-07-06 | 浙江光华科技股份有限公司 | A kind of mixed powder coating strong bending polyester resin and preparation method thereof |
| CN109824879A (en) * | 2019-03-06 | 2019-05-31 | 安徽永利新材料科技有限公司 | Levelability and the excellent curable epoxide 70:30 polyester resin and preparation method of solvent resistant |
| CN109880494A (en) * | 2019-03-06 | 2019-06-14 | 安徽永利新材料科技有限公司 | A kind of indoor high rigidity, high glaze powder 50:50 polyester resin and preparation method thereof |
| 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 |
| CN111234196A (en) * | 2020-03-20 | 2020-06-05 | 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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