CN106085157B - A kind of method for preparing cryogenic curing resin - Google Patents
A kind of method for preparing cryogenic curing resin Download PDFInfo
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- CN106085157B CN106085157B CN201610510625.1A CN201610510625A CN106085157B CN 106085157 B CN106085157 B CN 106085157B CN 201610510625 A CN201610510625 A CN 201610510625A CN 106085157 B CN106085157 B CN 106085157B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- 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
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
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- 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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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
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- 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
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- 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
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention discloses a kind of methods for preparing cryogenic curing resin.The method includes five esterification, polycondensation, modification, compounding and blowing steps.Preparation method of the present invention is simple, easy to implement, mild condition, raw material are easy to get and therefore can carry out big batch preparation.In addition, not only solidification temperature is low and also has following advantages below for the cryogenic curing toner coating obtained by preparation method of the present invention：Good leveling property, hardness height, glossiness height, good mechanical property, excellent corrosion resistance, weatherability and storage stability are good, and therefore have widely applicability.
Description
Technical field
The invention belongs to art of powder coatings, and in particular to a kind of preparation method and purposes of cryogenic curing resin, and
Further relate to a kind of method that ultra-low-temperature solidity powder coating is prepared by prepared cryogenic curing resin.
Background technology
In recent years, due to having many advantages, such as that energy-saving and environmental protection, efficient, performance is remarkable, economical, powdery paints becomes coating row
Important development direction in industry is just applied to household electrical appliance, auto industry, office accommodation, metal material, family more and more widely
The application of the shells such as External building, and gradually substitute organic solvent type coatings.But powdery paints conventional at present is equal in curing
Higher temperature is needed, usually 180-220 DEG C, excessively high solidification temperature can not only limit it in engineering plastics, timber and gold
Belong to the application in field of alloy material, can also increase energy consumption.Therefore, research center of gravity is concentrated on exploitation and existed by many researchers
It also can fully cured low temperature cured powder coating under low temperature.Wherein thermosetting polyester powdery paints because its good weatherability,
Anticorrosive property, electrical property and mechanical performance and have and have been widely used, be current dosage greatly a kind of powdery paints.Polyester
Type powdery paints is generally divided into two classes:Indoor polyester type powder paint and outdoor polyester type powder paint, indoor polyester-type powder
Coating is cured using epoxy resin compounding, and outdoor polyester type powder paint uses triglycidyl isocyanurate (TGIC)
As curing agent.The research of polyester powder coating low-temperature setting is made some progress in the recent period.
101735432 A of CN disclose a kind of low-temperature cured terminal carboxyl polyester resin for mixed powder coating, by with
The component of lower weight content is obtained through melt polycondensation reaction：Polyalcohol 25-45%, aromatic polycarboxylic acid 35-65%, aliphatic polyol acid
0-10%, branching agent 0-2%, acidolysis agent 6-15% and esterification catalyst 0.01-0.15%, powdery paints obtained can be
Cure at 160 DEG C.102010501 A of CN disclose a kind of beta-hydroxy alkylamide low-temperature setting Weather-resisting powder coating polyester
Resin is obtained by the component of following weight content through melt polycondensation reaction：Polyalcohol 25-45%, aromatic polycarboxylic acid 40-
55%th, aliphatic polyol acid 0-8%, branching agent 0-5%, acidolysis agent 5-15% and esterification catalyst 0.01-0.15%, made from
Powdery paints has many advantages, such as excellent flow leveling, mechanical performance and good anti-thick film pin hole.
However, although these low-temperature setting powder have curability at low temperatures but other performances do not protrude, limiting it should
There is limitation with, application field, it is therefore desirable to develop that a kind of solidification temperature is low and other performances such as physical mechanical property, resistance to
The low temperature cured powder coating of time property and excellent chemical resistance.
Invention content
Present invention seek to address that the problems of the prior art, provide a kind of ultra-low-temperature solidity powder coating and its preparation side
Method.For this purpose, the present inventor has found after testing repeatedly, by with ethylene glycol, diethylene glycol, 2- methyl-1s, 3-propanediol, 1,6- oneself
Glycol, neopentyl glycol, 1,4 cyclohexanedimethanols, 2- ethyl -2- butyl -1,3- propylene glycol, glycerine, trimethylolpropane, 1,
6- adipic acids, terephthalic acid (TPA), M-phthalic acid, 1,4 cyclohexanedicarboxylic acid, ethylenediamine, hexamethylene diamine, triethanolamine and to benzene
The cryogenic curing that diamines is prepared for the cryogenic curing resin that raw material is combined to obtain by condensation polymerization and chemical modification
Powdery paints cures at 130-145 DEG C and with prominent levelability, hardness, glossiness, mechanical performance, corrosion resistance, resistance to
Time property and storage stability.
Therefore, in the first aspect of the present invention, a kind of method for preparing cryogenic curing resin is provided, including following step
Suddenly：
(1) it is esterified：By raw material monomer, catalyst and polymerization inhibitor be placed in equipped with blender, thermometer, reflux condensing tube and
In the reactor of nitrogen inlet, then under the protection of nitrogen, 190-250 DEG C is warming up to, carries out esterification, until reactant
The acid value of system is 20-66mgKOH/g；
(2) polycondensation：The temperature of reaction system after esterification is remained at 190-250 DEG C, and vacuumizes and carries out vacuum contracting
It is poly-, until the acid value of reaction system is 6-55mgKOH/g and viscosity is 1500-5500mPas；
(3) it is modified：The temperature of reaction system after polycondensation is down to 170-220 DEG C, terminal groups modification agent is then added in and carries out
It is modified, until the acid value of reaction system is 35-60mgKOH/g and viscosity is 1000-5500mPas；
(4) it compounds：The temperature of modified reaction system is down to 150-190 DEG C, antioxidant is then added in and curing promotees
Into agent and keep the temperature mixing 0.5-2 hours；
(5) blowing：The temperature of reaction system after compounding is down to room temperature, discharging can obtain cryogenic curing resin,
Wherein, raw material monomer used in the step (1) includes 0-5 parts by weight ethylene glycol, 0-10 parts by weight diethyl two
Alcohol, 0-10 parts by weight 2- methyl-1,3-propanediols, 0-10 parts by weight 1,6-HD, 5-15 parts by weight neopentyl glycol, 5-20 weights
Measure 1,4 cyclohexanedimethanol of part, 0-10 parts by weight 2- ethyl -2- butyl -1,3- propylene glycol, 0-3 parts by weight glycerine, 0-3 weights
Measure part trimethylolpropane, 0-5 parts by weight 1,6- adipic acids, 0-15 parts by weight terephthalic acid (TPA), 0-15 parts by weight isophthalic diformazans
Acid, 10-40 parts by weight 1,4 cyclohexanedicarboxylic acid, 0-3 parts by weight ethylenediamine, 0-3 parts by weight hexamethylene diamine, three second of 0-3 parts by weight
Hydramine and 0-3 parts by weight p-phenylenediamine, and the temperature of the reaction system in step (2) is more than the reaction system in step (3)
Temperature, and the temperature of the reaction system in step (3) is more than the temperature in the reaction system in step (4).
Preferably, in the method for preparing cryogenic curing resin, until the acid of reaction system in the step (1)
It is worth and just carries out step (2) for 20-55mgKOH/g.
Preferably, in the method for preparing cryogenic curing resin, catalyst used in the step (1) is second
Sour zinc, antimony oxide, stannous chloride, stannous octoate, Mono-n-butyltin, Dibutyltin oxide, dibutyl tin laurate, list
One or more of n-butyl tin chloride dihydroxide, butyl titanate.
Preferably, in the method for preparing cryogenic curing resin, the weight of catalyst used in the step (1)
The percentage for measuring the weight based on raw material monomer is 0.05-0.2%.
Preferably, in the method for preparing cryogenic curing resin, polymerization inhibitor used in the step (1) is 2,
6- di-tert-butyl hydroquinones, hydroquinone, p-hydroxyanisole, methylnaphthohydroquinone, one kind in NO free radical piperidine alcohols or
It is a variety of.
Preferably, in the method for preparing cryogenic curing resin, the weight of polymerization inhibitor used in the step (1)
The percentage for measuring the weight based on raw material monomer is 0.05-0.5%, makes system viscosity mistake to prevent reaction system overreaction
Cause gelation greatly.
Preferably, in the method for preparing cryogenic curing resin, in the vacuum polycondensation process in the step (2)
The vacuum degree of reaction system is-(0.090-0.098) MPa.
Preferably, in the method for preparing cryogenic curing resin, terminal groups modification agent used in the step (3)
It is one or more in trimellitic anhydride, phthalic anhydride, maleic anhydride, fumaric acid.
Preferably, in the method for preparing cryogenic curing resin, terminal groups modification agent used in the step (3)
Weight of the weight based on raw material monomer percentage be 1-12%.
Preferably, in the method for preparing cryogenic curing resin, antioxidant used in the step (4) is three
(2,4- di-tert-butyl-phenyls) phosphite ester, triphenyl phosphite, DBPC 2,6 ditertiary butyl p cresol, 1010 antioxidant, 1076 resist
It is one or more in oxygen agent, 1098 antioxidant.
Preferably, in the method for preparing cryogenic curing resin, the weight of antioxidant used in the step (4)
The percentage for measuring the weight based on raw material monomer is 0.1-0.5%.
Preferably, in the method for preparing cryogenic curing resin, curing accelerator used in the step (4)
For 2- phenylimidazoles, dodecyl tertiary amine, triphenyl phosphorus, triphenyl ethyl phosphonium bromide phosphorus, triphenyl ethyl phosphorus chloride, tribenzyl second
It is one or more in base phosphonium bromide, tribenzyl ethylmercury chloride phosphorus.
Preferably, in the method for preparing cryogenic curing resin, curing accelerator used in the step (4)
Weight of the weight based on raw material monomer percentage be 0.1-1%.
In the second aspect of the present invention, provide it is a kind of obtained by the above-mentioned method for preparing cryogenic curing resin it is super
Low temperature curing resin.
Curing accelerator and antioxidant are distributed evenly in ultralow temperature in the cryogenic curing resin obtained in the present invention
In solidified resin, cause the performance of the cryogenic curing resin more excellent and stablize.
In the third aspect of the present invention, a kind of cryogenic curing powder prepared by the cryogenic curing resin is provided and is applied
Material, it includes above-mentioned cryogenic curing resin, pigment, filler, curing agent and auxiliary agents.
Preferably, in the ultra-low-temperature solidity powder coating, the weight of the cryogenic curing resin is based on described surpass
The percentage of the weight of low temperature cured powder coating is 25-60%.
Preferably, in the ultra-low-temperature solidity powder coating, the pigment be this field in convention pigment, including but
It is not limited to azo pigments, anthraquinone pigment, benzimidazole pigment, dihydro quinoline bifurcation pyridine pigment, quinoline phthalein ketone pigment, diketone pyrrolo- pyrrole
Cough up pigment, isoindoline pigment, isoindolenone pigments, metal complex pigments, perylene pigment, phthalocyanine color, aniline
Black, titanium dioxide, zinc white, carbon black, ferrimanganic are black, chromate pigment (such as chrome green hydrate), iron oxide brown, iron oxide yellow
Or pucherite.These pigment can be used alone or use as a mixture.
Preferably, in the ultra-low-temperature solidity powder coating, the weight of the pigment is based on the cryogenic curing powder
The percentage of the weight of last coating is 0.5-45%.
Preferably, in the ultra-low-temperature solidity powder coating, the filler include but not limited to diatomite, talcum powder,
Calcium carbonate, kaolin, barium sulfate, magnesium silicate, crystalline silica, amorphous silica, aluminium oxide etc..These fillers can be single
Solely use or use as a mixture.
Preferably, in the ultra-low-temperature solidity powder coating, the weight of the filler is based on the cryogenic curing powder
The percentage of the weight of last coating is 0.1-45%.
Preferably, in the ultra-low-temperature solidity powder coating, the curing agent is epoxy resin E12 and/or isocyanide urea
Sour three-glycidyl ester (TGIC).
Preferably, in the ultra-low-temperature solidity powder coating, the weight of the curing agent is consolidated based on the ultralow temperature
The percentage for changing the weight of powdery paints is 1-30%.
Preferably, in the ultra-low-temperature solidity powder coating, the auxiliary agent can be stabilizer, rheology control agent, dispersion
It is one or more in agent, tackifier, brightener, antifoaming agent etc..These auxiliary agents are well known, and can be to be typically used in
The dosage of powdery paints is used in ultra-low-temperature solidity powder coating of the present invention.
Preferably, in the ultra-low-temperature solidity powder coating, the weight of the auxiliary agent is based on the cryogenic curing powder
The percentage of the weight of last coating is 1-4%.
Due to containing curing accelerator in cryogenic curing resin used in the ultra-low-temperature solidity powder coating and resisting
Oxygen agent, distribution situation ratio just mix resin more uniformly with curing accelerator and antioxidant during coating is prepared, and
Ultra-low-temperature solidity powder coating of the present invention is made more to have excellent performance.
In the fourth aspect of the present invention, a kind of method for preparing above-mentioned ultra-low-temperature solidity powder coating is also provided, including
Following steps：
(1) the cryogenic curing resin, curing agent, pigment, filler and auxiliary agent are uniformly mixed in the desired amount；
(2) mixture for being obtained step (1) is squeezed out at 80-120 DEG C by extruder；
(3) material that step (2) is obtained is crushed, then crushes and be sieved, that is, obtain cryogenic curing powder of the present invention
Last coating.
Compared with prior art, preparation method of the present invention is simple, easy to implement, mild condition, raw material are easy to get and therefore
It can carry out big batch preparation.In addition, the cryogenic curing toner coating obtained by preparation method of the present invention not only cures
Temperature is low and also has following advantages below：Good leveling property, hardness height, glossiness height, good mechanical property, excellent corrosion resistance,
Weatherability and storage stability are good, and therefore have widely applicability.
Specific embodiment
In order to make objects and advantages of the present invention more concise, the present invention will be explained with specific examples below
It is bright, but the present invention is only limitted to absolutely not these embodiments.Following embodiment is only more preferably embodiment, and be only used for explaining of the invention
State the present invention, it is impossible to be interpreted as limiting the scope of the present invention.It should be pointed out that it is all the present invention essence and principle it
Interior done all any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention.Therefore, it is of the invention
The protection domain of patent should be determined by the appended claims.
In the present invention, acid value means the resulting value measured by the acid-base titration by means of KOH standard solution, viscosity
It is measured according to GB/T 7193-2008 unsaturated polyester resin test methods.
The synthesis of cryogenic curing resin
Synthetic example 1
Added in into the reactor equipped with blender, thermometer, reflux condensing tube and nitrogen inlet duct 10g ethylene glycol,
100g diethylene glycols, 90g 2- methyl-1,3-propanediols, 200g 1,4 cyclohexane dimethanols, 150g terephthalic acid (TPA)s, 150g
M-phthalic acid, 100g 1,4 cyclohexanedicarboxylic acids, 30g ethylenediamines, 0.8g Mono-n-butyltins, 0.5g 2,6- di-t-butyls
Hydroquinone, 1g methylnaphthohydroquinones, 0.5g NO free radical piperidine alcohols.Then nitrogen is filled with into reactor and carries out nitrogen protection,
And reaction mixture is heated to 200 DEG C under nitrogen protection.It maintains to carry out esterification at this temperature later, in the esterification
In reaction process, the acid value of primary sample detection reaction system is carried out every half an hour, until the acid value of reaction system is
22mgKOH/g.The vacuum degree for being subsequently vacuumed out making reaction system is -0.098MPa, and vacuum polycondensation is carried out under the vacuum degree,
And the acid value and viscosity of primary sample detection reaction system are carried out every half an hour in the vacuum polycondensation process, until reactant
The acid value of system is 12mgKOH/g and viscosity is 4500mPas.Then the temperature of reaction mixture is reduced to 180 DEG C, later
80g trimellitic anhydrides are added in into reactor and are modified reaction, and still carried out during the modified-reaction every half an hour
Primary sample detects the acid value and viscosity of reaction system, until the acid value of reaction system is 55mgKOH/g and viscosity is
2500mPa·s.The temperature in reactor is then down to 150 DEG C and 1g triphenyl phosphites, 1g are added in into reactor
1010 antioxidant and 5g 2- phenylimidazoles carry out heat preservation mixing 1 hour, then by the temperature of reactor at such a temperature later
It is reduced to room temperature and takes out product, you can obtain cryogenic curing resin of the present invention, be denoted as A1.
Synthetic example 2
Added in into the reactor equipped with blender, thermometer, reflux condensing tube and nitrogen inlet duct 50g ethylene glycol,
50g diethylene glycols, 50g neopentyl glycols, 150g 1,4 cyclohexane dimethanols, 50g 2- ethyl -2- butyl -1,3- propylene glycol,
100g terephthalic acid (TPA)s, 100g M-phthalic acids, 200g 1,4 cyclohexanedicarboxylic acids, 30g hexamethylene diamines, the oxidation of 0.8g dibutyl
Tin, 0.2g 2,6- di-tert-butyl hydroquinones, 0.8g methylnaphthohydroquinones, 0.5g NO free radical piperidine alcohols.Then into reactor
It is filled with nitrogen and carries out nitrogen protection, and reaction mixture is heated to 210 DEG C under nitrogen protection.It maintains later at this temperature
Esterification is carried out, in the esterification reaction process, the acid value of primary sample detection reaction system is carried out every half an hour, until
The acid value of reaction system is 20mgKOH/g.The vacuum degree for being subsequently vacuumed out making reaction system is -0.098MPa, and in the vacuum
Degree is lower to carry out vacuum polycondensation, and carry out the acid value of primary sample detection reaction system every half an hour in the vacuum polycondensation process
And viscosity, until the acid value of reaction system is 8mgKOH/g and viscosity is 5400mPas.Then by the temperature of reaction mixture
Be reduced to 190 DEG C, backward reactor in add in 80g trimellitic anhydrides be modified reaction, and during the modified-reaction
The acid value and viscosity of primary sample detection reaction system are still carried out every half an hour, until the acid value of reaction system is 58mgKOH/
G and viscosity are 5000mPas.The temperature in reactor is then down to 170 DEG C and bis- uncles of 1g 2,6- are added in into reactor
Butyl paracresol, 1076 antioxidant of 1g and 7g dodecyl tertiary amines carry out heat preservation mixing 1 hour, then at such a temperature later
The temperature of reactor is reduced to room temperature and takes out product, you can obtains cryogenic curing resin of the present invention, is denoted as A2.
Synthetic example 3
50g diethyls two are added in into the reactor equipped with blender, thermometer, reflux condensing tube and nitrogen inlet duct
Alcohol, 40g 2- methyl-1,3-propanediols, 50g 1,6-HDs, 100g neopentyl glycols, 100g 1,4 cyclohexane dimethanols,
50g 2- ethyl -2- butyl -1,3- propylene glycol, 50g terephthalic acid (TPA)s, 50g M-phthalic acids, 300g 1,4- hexamethylene diformazans
Acid, 30g triethanolamines, 1g stannous octoates, 1g 2,6- di-tert-butyl hydroquinones, 1g methylnaphthohydroquinones, 2g NO free radical piperidines
Alcohol.Then nitrogen is filled with into reactor and carries out nitrogen protection, and reaction mixture is heated to 220 DEG C under nitrogen protection.
It maintains to carry out esterification at this temperature later, in the esterification reaction process, primary sample detection is carried out every half an hour
The acid value of reaction system, until the acid value of reaction system is 26mgKOH/g.Be subsequently vacuumed out making the vacuum degree of reaction system for-
0.095MPa, and vacuum polycondensation is carried out under the vacuum degree, and once taken every half an hour in the vacuum polycondensation process
Sample detects the acid value and viscosity of reaction system, until the acid value of reaction system is 14mgKOH/g and viscosity is 3400mPas.So
The temperature of reaction mixture is reduced to 200 DEG C afterwards, backward reactor in add in 40g trimellitic anhydrides, 20g phthalic anhydrides and 30g
Fumaric acid is modified reaction, and still carries out primary sample detection reaction system every half an hour during the modified-reaction
Acid value and viscosity, until the acid value of reaction system is 55mgKOH/g and viscosity is 1500mPas.Then by the temperature in reactor
Degree is down to 180 DEG C and 1g tri- (2,4- di-tert-butyl-phenyls) phosphite ester, 1098 antioxidant of 1g and 1g tri- is added in into reactor
Phenyl phosphorus carries out heat preservation mixing 1.5 hours, the temperature of reactor then is reduced to room temperature and takes out production at such a temperature later
Object, you can obtain cryogenic curing resin of the present invention, be denoted as A3.
Synthetic example 4
50g diethyls two are added in into the reactor equipped with blender, thermometer, reflux condensing tube and nitrogen inlet duct
Alcohol, 40g 1,6-HDs, 150g neopentyl glycols, 50g 1,4 cyclohexane dimethanols, 100g 2- ethyl -2- butyl -1,3- third
Glycol, 400g 1,4 cyclohexanedicarboxylic acids, 40g triethanolamines, 40g p-phenylenediamine, 1.5g dibutyl tin dilaurates, 0.4g
Methylnaphthohydroquinone, 0.4g NO free radical piperidine alcohols.Then nitrogen is filled with into reactor and carries out nitrogen protection, and protect in nitrogen
It is lower that reaction mixture is heated to 230 DEG C.It maintains to carry out esterification at this temperature later, in the esterification reaction process,
The acid value of primary sample detection reaction system is carried out every half an hour, until the acid value of reaction system is 22mgKOH/g.Then take out
Vacuum makes the vacuum degree of reaction system be -0.096MPa, and carry out vacuum polycondensation under the vacuum degree, and in the vacuum polycondensation
The acid value and viscosity of primary sample detection reaction system are carried out in journey every half an hour, until the acid value of reaction system is
6mgKOH/g and viscosity are 4500mPas.Then the temperature of reaction mixture is reduced to 190 DEG C, backward reactor in plus
Enter 30g trimellitic anhydrides, 30g phthalic anhydrides and 30g maleic anhydrides and be modified reaction, and still every half during the modified-reaction
Hour carries out the acid value and viscosity of primary sample detection reaction system, until the acid value of reaction system is 55mgKOH/g and viscosity
For 1100mPas.The temperature in reactor is then down to 150 DEG C and (the 2,4- di-tert-butyls of 1g tri- are added in into reactor
Base) phosphite ester, 1098 antioxidant of 1g and 2g triphenyl ethyl phosphonium bromide phosphorus, it is small to carry out heat preservation mixing 1 at such a temperature later
When, the temperature of reactor is then reduced to room temperature and takes out product, you can obtains cryogenic curing resin of the present invention, is denoted as
A4。
Synthetic example 5
Added in into the reactor equipped with blender, thermometer, reflux condensing tube and nitrogen inlet duct 90g 2- methyl-
1,3- propylene glycol, 100g 1,6-HDs, 200g 1,4 cyclohexane dimethanols, 20g glycerine, 150g terephthalic acid (TPA)s,
150g M-phthalic acids, 250g 1,4 cyclohexanedicarboxylic acids, 20g ethylenediamines, 0.8g Dibutyltin oxides, bis- uncles of 0.2g 2,6-
Butylhydroquinone, 0.8g methylnaphthohydroquinones, 0.5g NO free radical piperidine alcohols.Then nitrogen is filled with into reactor and carries out nitrogen
Protection, and reaction mixture is heated to 230 DEG C under nitrogen protection.It maintains to carry out esterification at this temperature later,
In the esterification reaction process, the acid value of primary sample detection reaction system is carried out every half an hour, until the acid value of reaction system
For 50mgKOH/g.The vacuum degree for being subsequently vacuumed out making reaction system is -0.090MPa, and vacuum contracting is carried out under the vacuum degree
It is poly-, and every the acid value and viscosity of half an hour progress primary sample detection reaction system in the vacuum polycondensation process, until anti-
The acid value for answering system is 30mgKOH/g and viscosity is 4500mPas.Then the temperature of reaction mixture is reduced to 170 DEG C,
Backward reactor in add in 10g maleic anhydrides and be modified reaction, and during the modified-reaction still every half an hour into
Row primary sample detects the acid value and viscosity of reaction system, until the acid value of reaction system is 35mgKOH/g and viscosity is
4500mPa·s.The temperature in reactor is then down to 150 DEG C and 1g 2,6- di-t-butyls are added in into reactor to first
Phenol, 1076 antioxidant of 1g and 1g triphenyl ethyl phosphorus chloride carry out heat preservation mixing 2 hours at such a temperature later, then will be anti-
The temperature of device is answered to be reduced to room temperature and takes out product, you can obtains cryogenic curing resin of the present invention, is denoted as A5.
Synthetic example 6
Added in into the reactor equipped with blender, thermometer, reflux condensing tube and nitrogen inlet duct 50g 2- methyl-
1,3- propylene glycol, 60g 1,6-HDs, 50g neopentyl glycols, 150g 1,4 cyclohexane dimethanols, 50g 2- ethyl -2- fourths
Base -1,3- propylene glycol, 120g terephthalic acid (TPA)s, 150g M-phthalic acids, 350g 1,4 cyclohexanedicarboxylic acids, 20g hexamethylene diamines,
1g stannous octoates, 1g 2,6- di-tert-butyl hydroquinones, 1g methylnaphthohydroquinones, 2g NO free radical piperidine alcohols.Then to reactor
In be filled with nitrogen and carry out nitrogen protection, and reaction mixture is heated to 240 DEG C under nitrogen protection.It is maintained later in this temperature
Lower carry out esterification in the esterification reaction process, the acid value of primary sample detection reaction system is carried out every half an hour, directly
Acid value to reaction system is 46mgKOH/g.The vacuum degree for being subsequently vacuumed out making reaction system is -0.096MPa, and true at this
Vacuum polycondensation is carried out under reciprocal of duty cycle, and carries out the acid of primary sample detection reaction system every half an hour in the vacuum polycondensation process
Value and viscosity, until the acid value of reaction system is 32mgKOH/g and viscosity is 5100mPas.Then by the temperature of reaction mixture
Degree be reduced to 210 DEG C, backward reactor in addition 40g trimellitic anhydrides be modified reaction, and in the modified-reaction process
In still carry out the acid value and viscosity of primary sample detection reaction system every half an hour, until the acid value of reaction system is
38mgKOH/g and viscosity are 4600mPas.The temperature in reactor is then down to 190 DEG C and 1g tri- is added in into reactor
(2,4- di-tert-butyl-phenyl) phosphite ester, 1098 antioxidant of 1g and 1g tribenzyl ethyl phosphonium bromide phosphorus, later at such a temperature into
Row heat preservation mixing 1.5 hours, is then reduced to room temperature by the temperature of reactor and takes out product, you can obtain ultralow temperature of the present invention
Solidified resin is denoted as A6.
Synthetic example 7
Added in into the reactor equipped with blender, thermometer, reflux condensing tube and nitrogen inlet duct 30g 2- methyl-
1,3- propylene glycol, 80g 1,6-HDs, 100g neopentyl glycols, 120g 1,4 cyclohexane dimethanols, 50g 2- ethyl -2- fourths
Base -1,3- propylene glycol, 10g glycerine, 10g trimethylolpropanes, 50g terephthalic acid (TPA)s, 100g M-phthalic acids, 400g 1,
4- cyclohexane cyclohexanedimethanodibasics, 10g triethanolamines, 2g dibutyl tin dilaurates, 0.4g methylnaphthohydroquinones, 0.4g NO free radical piperidines
Alcohol.Then nitrogen is filled with into reactor and carries out nitrogen protection, and reaction mixture is heated to 230 DEG C under nitrogen protection.
It maintains to carry out esterification at this temperature later, in the esterification reaction process, primary sample detection is carried out every half an hour
The acid value of reaction system, until the acid value of reaction system is 53mgKOH/g.Be subsequently vacuumed out making the vacuum degree of reaction system for-
0.095MPa, and vacuum polycondensation is carried out under the vacuum degree, and once taken every half an hour in the vacuum polycondensation process
Sample detects the acid value and viscosity of reaction system, until the acid value of reaction system is 33mgKOH/g and viscosity is 3600mPas.So
The temperature of reaction mixture is reduced to 200 DEG C afterwards, backward reactor in add in 40g trimellitic anhydrides be modified reaction,
And the acid value and viscosity of primary sample detection reaction system still are carried out every half an hour during the modified-reaction, until reaction
The acid value of system is 38mgKOH/g and viscosity is 3200mPas.The temperature in reactor is then down to 170 DEG C and to reaction
1g tri- (2,4- di-tert-butyl-phenyl) phosphite ester, 1098 antioxidant of 1g and 1g tribenzyl ethylmercury chloride phosphorus are added in device, later
Heat preservation mixing 0.5 hour is carried out at such a temperature, the temperature of reactor is then reduced to room temperature and takes out product, you can is obtained
Cryogenic curing resin of the present invention, is denoted as A7.
Synthetic example 8
Added in into the reactor equipped with blender, thermometer, reflux condensing tube and nitrogen inlet duct 100g 1,6- oneself
Glycol, 150g neopentyl glycols, 50g 1,4 cyclohexane dimethanols, 100g 2- ethyl -2- butyl -1,3- propylene glycol, tri- hydroxyls of 20g
Methylpropane, 50g terephthalic acid (TPA)s, 80g M-phthalic acids, 400g 1,4 cyclohexanedicarboxylic acids, 10g p-phenylenediamine, 0.8g are mono-
Butyl tin oxide, 0.5g 2,6- di-tert-butyl hydroquinones, 1g methylnaphthohydroquinones, 0.5g NO free radical piperidine alcohols.Then to anti-
It answers and nitrogen progress nitrogen protection is filled in device, and reaction mixture is heated to 220 DEG C under nitrogen protection.It maintains later herein
At a temperature of carry out esterification, in the esterification reaction process, every half an hour carry out primary sample detection reaction system acid
Value, until the acid value of reaction system is 53mgKOH/g.The vacuum degree for being subsequently vacuumed out making reaction system is -0.095MPa, and
Vacuum polycondensation is carried out under the vacuum degree, and primary sample detection reaction system is carried out every half an hour in the vacuum polycondensation process
Acid value and viscosity, until the acid value of reaction system is 30mgKOH/g and viscosity is 5300mPas.Then by reaction mixture
Temperature be reduced to 180 DEG C, backward reactor in add in 10g fumaric acid be modified reaction, and in the modified-reaction process
In still carry out the acid value and viscosity of primary sample detection reaction system every half an hour, until the acid value of reaction system is
35mgKOH/g and viscosity are 4600mPas.The temperature in reactor is then down to 160 DEG C and 1g Asias are added in into reactor
Triphenyl phosphate, 1010 antioxidant of 1g, 1g tribenzyl ethyl phosphonium bromide phosphorus and 2g tribenzyl ethylmercury chloride phosphorus, later in the temperature
Under carry out heat preservation mixing 1 hour, the temperature of reactor is then reduced to room temperature and takes out product, you can obtain the present invention it is ultralow
Warm solidified resin, is denoted as A8.
Synthetic example 9
Synthetic example 1 is repeated, the difference lies in will be reacted after adding in trimellitic anhydride and being modified reaction
The temperature of device is reduced to room temperature and takes out product, without the temperature in reactor is down to 150 DEG C and is added in into reactor
1g triphenyl phosphites, 1010 antioxidant of 1g and 5g 2- phenylimidazoles, and carry out heat preservation mixing 1 at such a temperature after this
Hour.Obtained product is denoted as A9.
Synthetic example 10
236g new penta 2 is added in into the reactor equipped with blender, thermometer, reflux condensing tube and nitrogen inlet duct
Then alcohol, 40g ethylene glycol and 60g trimethylolpropanes are heated to the mixture melting.Later again into reactor according to
Secondary addition 470g terephthalic acid (TPA)s, 50g adipic acids and 70g butyl tin oxide.Nitrogen is carried out then to nitrogen is filled in reactor
Protection, and reaction mixture is heated to 250 DEG C under nitrogen protection, wherein starting esterification at 185 DEG C, have aquatic
Into.Esterification is carried out at a temperature of 250 DEG C later, in the esterification reaction process, primary sample is carried out every half an hour
The acid value of reaction system is detected, until the acid value of reaction system is 15mgKOH/g.It is subsequently vacuumed out the vacuum degree for making reaction system
For -0.096MPa, and vacuum polycondensation is carried out under the vacuum degree, and carried out every half an hour in the vacuum polycondensation process primary
The acid value of sampling detection reaction system, until the acid value of reaction system is 10mgKOH/g.Then the temperature of reaction mixture is dropped
Down to 180 DEG C, backward reactor in add in 28g pyromellitic dianhydrides and blocked, and still every during the end capping reaction
The acid value of primary sample detection reaction system is carried out within 20 minutes, until the acid value of reaction system is 65mgKOH/g.It then will reaction
The temperature of device is reduced to room temperature and takes out product, you can obtains product, is denoted as A10.
Use embodiment 1-8 and comparative example 1-2
Use the preparation of the powder curing coating of the ultralow temperature powder curing coating and comparative example 1-2 of embodiment 1-8：
The formula shown in cryogenic curing resin according to the form below 1 that above-mentioned synthetic example 1-10 is obtained is uniformly mixed with other components,
Then it is squeezed out, crush, crush after cooling and is sieved by double screw extruder under 100 DEG C of extrusion temperature respectively, obtain grain
Ultra-low-temperature solidity powder coating of the diameter between 50-110 μm.
Table 1 uses the component of the cured powder paint of embodiment 1-8 and comparative example 1-2
Testing example
Prepare test sample plate：Embodiment 1-8 and the powdery paints of comparative example 1-2 will be used to pass through electrostatic precipitation respectively
Using 1 spray guns of GEMA-Volstatic PCG by the powder paint of acquisition in the surface treated (phosphorus that thickness is 0.8mm
Change) set-iron on, set-iron is transferred to ventilated drying oven later and is cured, then carries out various performance tests.
It is shown in the following table 2 using the condition of cure and the performance test results of embodiment 1-8 and comparative example 1-2.Wherein,
Each performance test standard is as follows：
Coating thickness is detected by the standard of GB/T 13452.2；
Glossiness is detected by the standard of GB/T 9754；
Levelling is PCI grades, and 1-10 grades, 1=is poor, and 10=is excellent；
Adhesive force (cross-hatching) is detected by the standard of GB/T 9286；
Pencil hardness is detected by the standard of GB/T 6739；
Impact resistance is detected by the standard of GB/T 1732；
Neutral salt spray is detected by the standard of GB/T 1771；
Weatherability is detected by the standard of GB/T 1865.
Table 2 is tied using condition of cure and the properties test of the powdery paints of embodiment 1-8 and comparative example 1-2
Fruit
As shown in Table 2, since the present invention using the polymerization inhibitor of special raw material monomer formula and specific quantity and passes through end group
Modifying agent, which is modified and carries out compounding using curing accelerator and antioxidant, prepares low temperature curing resin, it is achieved thereby that made
Standby powdery paints can cure at lower temperature, that is, 135-150 DEG C, the powder prepared especially with embodiment 1,2,5 and 6
Coating can cure at 135 DEG C in 15 minutes, realize cryogenic curing, and coating gloss and hardness are higher simultaneously, levelling
It has excellent performance, satisfactory mechanical property, good chemical resistance, weatherability is good, and adhesion strength is big, therefore powdery paints of the present invention has
There is preferable performance, and realize cryogenic curing, application prospect is very wide.
Claims (8)
- A kind of 1. method for preparing cryogenic curing resin, which is characterized in that it includes the following steps：(1) it is esterified：Raw material monomer, catalyst and polymerization inhibitor are placed in equipped with blender, thermometer, reflux condensing tube and nitrogen In the reactor of entrance, then under the protection of nitrogen, 190-250 DEG C is warming up to, carries out esterification, until reaction system Acid value is 20-66mgKOH/g；(2) polycondensation：The temperature of reaction system after esterification is remained at 190-250 DEG C, and vacuumizes and carries out vacuum polycondensation, directly Acid value to reaction system is 6-55mgKOH/g and viscosity is 1500-5500mPas；(3) it is modified：The temperature of reaction system after polycondensation is down to 170-220 DEG C, terminal groups modification agent is then added in and is modified, Until the acid value of reaction system is 35-60mgKOH/g and viscosity is 1000-5500mPas；(4) it compounds：The temperature of modified reaction system is down to 150-190 DEG C, then adds in antioxidant and curing accelerator And keep the temperature mixing 0.5-2 hours；(5) blowing：The temperature of reaction system after compounding is down to room temperature, discharging can obtain cryogenic curing resin,The percentage of weight of the catalyst weight based on raw material monomer is 0.05-0.2%, and the polymerization inhibitor weight is based on single The percentage of the weight of body raw material is 0.05-0.5%, and the percentage of the weight of the antioxidant weight based on raw material monomer is 0.1-0.5%, the percentage of the weight of the curing accelerator weight based on raw material monomer is 0.1-1%；Wherein, raw material monomer used in the step (1) be 5 parts by weight ethylene glycol, 5 parts by weight diethylene glycols, 5 parts by weight it is new Pentanediol, 15 parts by weight 1,4 cyclohexane dimethanols, 5 parts by weight 2- ethyl -2- butyl -1,3- propylene glycol, 10 parts by weight are to benzene Dioctyl phthalate, 10 parts by weight M-phthalic acids, 20 parts by weight 1,4 cyclohexanedicarboxylic acids, 3 parts by weight hexamethylene diamines, and in step (2) The temperature of reaction system be more than the temperature of the reaction system in step (3), and the temperature of the reaction system in step (3) is more than The temperature in reaction system in step (4).
- 2. the method according to claim 1 for preparing cryogenic curing resin, which is characterized in that institute in the step (1) Catalyst is zinc acetate, antimony oxide, stannous chloride, stannous octoate, Mono-n-butyltin, Dibutyltin oxide, two One or more of butyl tin laurate, monobutyl dihydroxy stannic chloride, butyl titanate.
- 3. the method according to claim 1 for preparing cryogenic curing resin, which is characterized in that institute in the step (1) Polymerization inhibitor is 2,6- di-tert-butyl hydroquinones, hydroquinone, p-hydroxyanisole, methylnaphthohydroquinone, NO free radical piperazine It is one or more in pyridine alcohol.
- 4. the method according to claim 1 for preparing cryogenic curing resin, which is characterized in that institute in the step (4) Antioxidant is three (2,4- di-tert-butyl-phenyls) phosphite esters, triphenyl phosphite, DBPC 2,6 ditertiary butyl p cresol, 1010 It is one or more in antioxidant, 1076 antioxidant, 1098 antioxidant.
- 5. the method according to claim 1 for preparing cryogenic curing resin, which is characterized in that institute in the step (4) Curing accelerator is 2- phenylimidazoles, dodecyl tertiary amine, triphenylphosphine, triphenyl ethyl phosphonium bromide phosphine, triphenyl ethyl It is one or more in phosphonium chloride, tribenzyl ethyl phosphonium bromide phosphine, tribenzyl ethylmercury chloride phosphine.
- 6. a kind of cryogenic curing obtained by the method for preparing cryogenic curing resin of any one of claim 1-5 Resin.
- 7. ultra-low-temperature solidity powder coating prepared by a kind of cryogenic curing resin by claim 6, which is characterized in that described Ultra-low-temperature solidity powder coating includes cryogenic curing resin, pigment, filler, curing agent and the auxiliary agent of claim 6；The face The percentage of weight of the weight of material based on the ultra-low-temperature solidity powder coating is 0.5-45%, and the weight of the filler is based on The percentage of the weight of the ultra-low-temperature solidity powder coating is 0.1-45%, and the weight of the curing agent is based on described ultralow The percentage of the weight of warm cured powder paint is 1-30%, and the weight of the auxiliary agent is based on the ultra-low-temperature solidity powder coating Weight percentage for 1-4%, the weight of the weight of cryogenic curing resin based on the ultra-low-temperature solidity powder coating The percentage of amount is 25-60%.
- A kind of 8. method for preparing the ultra-low-temperature solidity powder coating described in claim 7, which is characterized in that it includes following step Suddenly：(1) the cryogenic curing resin, curing agent, pigment, filler and auxiliary agent are uniformly mixed in the desired amount；(2) mixture for being obtained step (1) is squeezed out at 80-120 DEG C by extruder；(3) material that step (2) is obtained is crushed, then crushes and be sieved, that is, obtain ultra-low-temperature solidity powder coating.
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| CN111234185A (en) * | 2020-01-15 | 2020-06-05 | 浙江光华科技股份有限公司 | High-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating and synthesis method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3340327A (en) * | 1961-03-13 | 1967-09-05 | Desoto Inc | Fumaric acid-polyoxyalkylene glycoldicyclopentadiene polyesters curable with vinyl monomer and mixtures thereof |
| CN101735432A (en) * | 2009-12-25 | 2010-06-16 | 广州擎天实业有限公司 | Low-temperature cured terminal carboxyl polyester resin for mixed powder coating and preparation method thereof |
| CN104356892A (en) * | 2014-10-25 | 2015-02-18 | 重庆市金渝管道设备有限公司 | Synthetic method of outdoor low-temperature curing powder coating |
| CN104448265A (en) * | 2014-11-19 | 2015-03-25 | 广州擎天材料科技有限公司 | Polyester resin for low-temperature-cured and energy-saving thermal-transfer-printing powdery coating material and preparation method thereof |
| CN105254860A (en) * | 2015-11-09 | 2016-01-20 | 广州擎天材料科技有限公司 | Polyester resin for powder coating for structural member of engineering machine and preparation method of polyester resin |
-
2016
- 2016-06-30 CN CN201610510625.1A patent/CN106085157B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3340327A (en) * | 1961-03-13 | 1967-09-05 | Desoto Inc | Fumaric acid-polyoxyalkylene glycoldicyclopentadiene polyesters curable with vinyl monomer and mixtures thereof |
| CN101735432A (en) * | 2009-12-25 | 2010-06-16 | 广州擎天实业有限公司 | Low-temperature cured terminal carboxyl polyester resin for mixed powder coating and preparation method thereof |
| CN104356892A (en) * | 2014-10-25 | 2015-02-18 | 重庆市金渝管道设备有限公司 | Synthetic method of outdoor low-temperature curing powder coating |
| CN104448265A (en) * | 2014-11-19 | 2015-03-25 | 广州擎天材料科技有限公司 | Polyester resin for low-temperature-cured and energy-saving thermal-transfer-printing powdery coating material and preparation method thereof |
| CN105254860A (en) * | 2015-11-09 | 2016-01-20 | 广州擎天材料科技有限公司 | Polyester resin for powder coating for structural member of engineering machine and preparation method of polyester resin |
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