CN110156973A - The excellent PU cured powder paint polyester resin of cold resistance and preparation method - Google Patents
The excellent PU cured powder paint polyester resin of cold resistance and preparation method Download PDFInfo
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- CN110156973A CN110156973A CN201910507481.8A CN201910507481A CN110156973A CN 110156973 A CN110156973 A CN 110156973A CN 201910507481 A CN201910507481 A CN 201910507481A CN 110156973 A CN110156973 A CN 110156973A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—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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- 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
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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
- 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
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Abstract
The invention belongs to polyester resin fields, are related to the excellent PU cured powder paint polyester resin and preparation method thereof of above-mentioned cold resistance.The polyester resin is formed by copolymerization such as terephthalic acid (TPA), 3,3- tetramethylene glutaric acid, resorcinol-O, O'- oxalic acid, hydrogenated castor oleic acid, N butyl diethanol amine, 1,4- bis- (methylol) hexamethylene, catechins.The present invention by cold resistance it is excellent 3,3- tetramethylene glutaric acid, resorcinol-O, O'- oxalic acid, hydrogenated castor oleic acid and N butyl diethanol amine make the segment softness of polyester resin and resistance to low temperature is outstanding, reduce the black brittleness of final film, the polyester resin that the present invention obtains can solidify with polyurethane curing agent, film cold resistance is excellent, 0 DEG C, -5 DEG C respectively freeze 6h after on impact almost without influence, the requirement of powdery paints is fully achieved in final film performance.
Description
Technical field
The invention belongs to polyester resin fields, are related to the excellent PU cured powder paint of above-mentioned cold resistance with polyester tree
Rouge, the preparation method for further relating to above-mentioned polyester resin and the application in B1530 curing system.
Background technique
The advantages that polyester powder coating is because of its excellent comprehensive performance, weather resistance and relatively low cost, is widely used in
In the outdoor facilities such as building, automobile, traffic.As the weatherability of polyester powder coating also has its shortcoming, for example, its hardness
Height, brittleness is big, causes cold resistance poor, and impact property decline is obvious under low temperature, and many low-temperature region applications have biggish in winter
Defect.
PU is the abbreviation of polyurethane, and PU generally refers to polyurethane curing agent in powdery paints, and most common polyurethane is solid
Agent is exactly B1530 curing agent, this is a kind of powdery paints polyurethane curing agent of goldschmidt chemical corporation (Degussa), is
A kind of closed isocyanate curing agent, is mainly solidified with hydroxy polyester resin.Since B1530 curing agent rigidity is stronger,
The matching film that can just obtain better performances of special polyester resin is needed, B1530 system powdery paints common at present
It is primarily present coating hardness height, brittleness is big, causes cold resistance poor, and impact property decline is obvious under low temperature, especially 0 DEG C freezing 6h
Afterwards, 50cm impact is more difficult passes through, and many low-temperature region applications have biggish defect in winter.
CN105482641A discloses a kind of low temperature resistant cracking resistance water pump powdery paints, which is characterized in that it is by following
The raw material of parts by weight is made:
Bisphenol A type epoxy resin 40-50, acetylbutyrylcellulose 3-5, tributyl 2-acetylcitrate 1-2, bentonite 20-
30, talcum powder 5-10, styrene-acrylic emulsion 3-5, zirconium colloidal sol 1.5-2.5, Aluminum sol 4-6, aqueous polyurethane emulsion 3-5, phenolic cure
Agent 3-5, coalescing agent 3-5；
The zirconium colloidal sol solid content is 20-30%, and Aluminum sol solid content is 20-30%, aqueous polyurethane emulsion solid content
For 40-50%, styrene-acrylic emulsion solid content is 50-60%；
The coalescing agent is made from the following raw materials in parts by weight: rosin 2-4, epoxidized soybean oil 5-10, acrylic acid 3-5,
Glycerin monostearate 0.5-1, silane coupling agent KH-5600.3-0.5；The preparation method of coalescing agent is first by rosin, epoxy
Soybean oil and glycerin monostearate are uniform in 160-180 DEG C of melt blending, then adjust the temperature to 110-120 DEG C and it is added
Remaining raw material stirring 2-4h to get.
CN104212214A discloses a kind of low temperature resistant polyvinyl-chloride powder paint, which is characterized in that including according to quality
The following raw material of number meter: 89-95 parts of Corvic, 5-10 parts of epoxy resin, 1-3 parts of barium zinc compound stabilizer, suitable fourth
5-7 parts of enedioic acid acid anhydride, 4-6 parts of talcum powder, 1-3 parts of pentaerythrite four-(2,2- diethyl acrylic acid).
In above patent application, using bisphenol A type epoxy resin and Corvic and epoxy resin；
And above-mentioned raw material its defect is that weatherability is poor, is easy to degrade with exposing to the weather is passed through outdoors, to lose painting
The performance of film coating system can not use outdoors.
Therefore, it is necessary to be improved further to above-mentioned material system, invent it is a kind of can be used for for a long time it is outdoor weather-proof
The product of property system, can be used for outdoor cold district, had little influence under low-temperature condition impact property polyester resin in order to
The resin makes coating have preferable cold resistance and impact resistance after being applied to coating.
Summary of the invention
In order to solve the above technical problems, the present invention provides one kind can be used for outdoor cold district, low-temperature condition
Under have little influence on the polyester resin of impact property；
The present invention also provides the preparation method of above-mentioned polyester resin and the applications in B1530 curing system；
The present invention provides a kind of preferable B1530 curing system polyester resin of cold resistance, by cold resistance monomer and
Functional monomer is copolymerized, and be can be used for outdoor cold district, is had little influence on impact property under low-temperature condition.
The excellent PU cured powder paint polyester resin of cold resistance provided by the present invention, which is to pass through master
Want raw material terephthalic acid (TPA), 3,3- tetramethylene glutaric acid, resorcinol-O, O'- oxalic acid, hydrogenated castor oleic acid, N- butyl
Diethanol amine, 1,4- bis- (methylol) hexamethylene, neopentyl glycol, catechin are copolymerized to be formed.
The excellent PU cured powder paint polyester resin of cold resistance provided by the present invention, primary raw material are as follows:
Terephthalic acid (TPA) 10-20mol
3,3- tetramethylene glutaric acid 8-20mol
Resorcinol-O, O'- oxalic acid 5-15mol
Hydrogenated castor oleic acid 8-15mol
N butyl diethanol amine 8-18mol
(methylol) hexamethylene of 1,4- bis- 9-22mol
Neopentyl glycol 10-25mol
Catechin 7-15mol.
Above-mentioned polyester resin further include: catalyst 2- octyl succinic acid two (tributyl tin), dosage 0.03-
0.15mol。
Above-mentioned polyester resin further include: antioxidant four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] Ji Wusi
Alcohol ester, dosage 0.1-0.3mol.
The excellent PU cured powder paint polyester resin of cold resistance, primary raw material are as follows:
Terephthalic acid (TPA) 15mol
3,3- tetramethylene glutaric acid 15mol
Resorcinol-O, O'- oxalic acid 10mol
Hydrogenated castor oleic acid 10mol
N butyl diethanol amine 15mol
(methylol) hexamethylene of 1,4- bis- 15mol
Neopentyl glycol 12mol
Catechin 8mol.
The preparation method of the excellent PU cured powder paint polyester resin of cold resistance, comprising the following steps:
(1) by terephthalic acid (TPA), 3,3- tetramethylene glutaric acid, N butyl diethanol amine, 1,4- bis- (methylol) hexamethylene
Alkane and catalyst are added in reaction kettle, sufficiently melting and after mixing evenly, then slowly heating simultaneously insulation reaction；
(2) it is reduced to acid value, resorcinol-O, O'- oxalic acid, the hydrogenation castor of formula ratio is added in Xiang Shangshu mixed material
Sesame oil acid and neopentyl glycol, gradually temperature reaction again under nitrogen protection, sufficiently reaction are added anti-to steaming without obvious distillate
The formation of polyester resin is facilitated in oxygen agent under vacuum condition, stops pulling vacuum；
(3) cool down, catechin is added, and heats up, insulation reaction stops after reaction high temperature discharging while hot, cooling polyester tree
Rouge is crushed and is granulated, and obtains the polyester resin of the excellent PU cured powder paint of cold resistance.
Preferably, the preparation method of the excellent PU cured powder paint polyester resin of above-mentioned cold resistance, including it is following
Step:
(1) polymerization reaction: by 10~20mol terephthalic acid (TPA), 8~20mol 3,3- tetramethylene glutaric acid, 8~
18molN- butyl diethanolamine, 9-22mol1, (methylol) hexamethylene of 4- bis- and catalyst are added in reaction kettle, first 110~
130 DEG C sufficiently melting and after mixing evenly, then with the heating rate of 3~7 DEG C/h be to slowly warm up to 170~190 DEG C and keep the temperature instead
2~4h is answered, mixed material is obtained；Catalyst is that polymerisation catalysts are 2- octyl succinic acid two (tributyl tin), and dosage is
0.03-0.15mol；
(2) when acid value is reduced to 75~90mgKOH/g or less, the isophthalic two of formula ratio is added in Xiang Shangshu mixed material
Phenol-O, O'- oxalic acid, hydrogenated castor oleic acid and neopentyl glycol are gradually heated up instead with 8~12 DEG C/h rate again under nitrogen protection
Should be to 220~250 DEG C, [β-(3,5- bis- uncles of antioxidant four are added to steaming without obvious distillate in sufficiently 4~8h of reaction, reaction
Butyl -4- hydroxy phenyl) propionic acid] pentaerythritol ester, dosage 0.1-0.3mol, 2~5h of vacuum degree of 50~80mmHg of holding,
Facilitate the formation of polyester resin, object acid value to be polymerized be 15~25mgKOH/g hereinafter, and viscosity reach 3000~3800mPa
Stop pulling vacuum at s/200 DEG C；
(3) when being cooled to 190~210 DEG C, the catechin of formula ratio is added, and it is warming up in 0.8~1.2h 210~
240 DEG C of 2~4h of insulation reaction, the hydroxyl value of object to be polymerized reach 80~100mgKOH/g, 4000~5800mPas/200 of viscosity
DEG C when stop reaction, then high temperature discharging while hot, and with the cooling polyester resin of the steel band with condensed water is crushed and is granulated, obtains resistance to
The polyester resin of cold excellent PU cured powder paint.
It is furthermore preferred that the preparation method of the excellent PU cured powder paint polyester resin of above-mentioned cold resistance, including with
Lower step:
(1) by 15mol terephthalic acid (TPA), 15mol3,3- tetramethylene glutaric acid, 15molN- butyl diethanolamine,
(methylol) hexamethylene of 15mol1,4- bis- and catalyst are added in reaction kettle, first in 120 DEG C of sufficiently meltings and after mixing evenly,
185 DEG C and insulation reaction 3h are to slowly warm up to the heating rate of 5 DEG C/h again, obtains mixed material；
Polymerisation catalysts are 2- octyl succinic acid two (tributyl tin), dosage 0.12mol；
(2) when acid value is reduced to 85mgKOH/g, 10mol resorcinol-O, O'- bis- is added in Xiang Shangshu mixed material
Acetic acid, 10mol hydrogenated castor oleic acid and neopentyl glycol 12mol, under nitrogen protection again with the gradually temperature reaction of 10 DEG C/h rate
To 235 DEG C, [β-(3, the 5- di-t-butyl -4- hydroxyls of antioxidant four are added to steaming without obvious distillate in sufficiently reaction 6h, reaction
Phenyl) propionic acid] pentaerythritol ester, dosage 0.15mol keeps the vacuum degree 4h of 70mmHg, facilitates the formation of polyester resin,
When object acid value to be polymerized is 20mgKOH/g, and when viscosity reaches 3000-3800mPas/200 DEG C, stops pulling vacuum；
(3) when being cooled to 200 DEG C, the catechin of 8mol is added, and is warming up to 225 DEG C of insulation reaction 3h in 1h, to poly-
The hydroxyl value of conjunction object stops reaction when reaching 80~100mgKOH/g, 4000-5800mPas/200 DEG C of viscosity, and high temperature goes out while hot
Material, and with the cooling polyester resin of the steel band with condensed water, it is then crushed and is granulated, obtain the excellent PU cured powder paint of cold resistance
Polyester resin.
The resin that the preparation method of the excellent PU cured powder paint polyester resin of cold resistance obtains, appearance colorless or
Light yellow clear particle；Hydroxyl value 85-95mgKOH/g, viscosity: 4800-5500mPas/200 DEG C.
The resin that the preparation method of the excellent PU cured powder paint polyester resin of above-mentioned cold resistance obtains is in B1530
Application in curing system also obtains invention which is intended to be protected.
Polyester resin in the present invention be first using terephthalic acid (TPA), 3,3- tetramethylene glutaric acid, resorcinol-O,
O'- oxalic acid, hydrogenated castor oleic acid, N butyl diethanol amine, 1,4- bis- (methylol) hexamethylene, neopentyl glycol are gathered
It closes, after obtaining the polymer that viscosity is 3500-4000mPas/200 DEG C, finally adds catechin progress end capping reaction and obtain hydroxyl
The polyester resin of base sealing end；
By the excellent 3,3- tetramethylene glutaric acid of cold resistance, resorcinol-O, O'- oxalic acid, hydrogenated castor oleic acid
And N butyl diethanol amine can make the segment softness of polyester resin and resistance to low temperature is outstanding, the low temperature for reducing final film is crisp
Property；The use of terephthalic acid (TPA), (methylol) hexamethylene of Isosorbide-5-Nitrae-two and neopentyl glycol ensure that final film by enough hardness,
And the water resistance and weatherability of film can be improved；
The catechin of big steric hindrance, which carries out sealing end, can suitably reduce curing rate, guarantee flow time, to obtain levelling
The excellent appearance of film of property.The hydroxyl value of finally obtained polyester resin is 80-100mgKOH/g, viscosity 4000-5800mPas/
200 DEG C, can be solidified with polyurethane curing agent B1530, film cold resistance is excellent, 0 DEG C, -5 DEG C respectively freeze 6h after liquidate
The requirement of powdery paints is fully achieved almost without influence, final film performance in hitting property.
Specific embodiment
Embodiment 1
The preparation method of the excellent PU cured powder paint polyester resin of cold resistance, comprising the following steps:
(1) by 15mol terephthalic acid (TPA), 15mol3,3- tetramethylene glutaric acid, 15molN- butyl diethanolamine,
(methylol) hexamethylene of 15mol1,4- bis- and catalyst are added in reaction kettle, first in 120 DEG C of sufficiently meltings and after mixing evenly,
185 DEG C and insulation reaction 3h are to slowly warm up to the heating rate of 5 DEG C/h again, obtains mixed material；
Polymerisation catalysts are 2- octyl succinic acid two (tributyl tin), dosage 0.12mol；
(2) when acid value is reduced to 85mgKOH/g, 10mol resorcinol-O, O'- bis- is added in Xiang Shangshu mixed material
Acetic acid, 10mol hydrogenated castor oleic acid and neopentyl glycol 12mol, under nitrogen protection again with the gradually temperature reaction of 10 DEG C/h rate
To 235 DEG C, [β-(3, the 5- di-t-butyl -4- hydroxyls of antioxidant four are added to steaming without obvious distillate in sufficiently reaction 6h, reaction
Phenyl) propionic acid] pentaerythritol ester, dosage 0.15mol keeps the vacuum degree 4h of 70mmHg, facilitates the formation of polyester resin,
When object acid value to be polymerized is 20mgKOH/g, and when viscosity reaches 3200mPas/200 DEG C or so, stops pulling vacuum；
(3) when being cooled to 200 DEG C, the catechin of 8mol is added, and is warming up to 225 DEG C of insulation reaction 3h in 1h, to poly-
The hydroxyl value of conjunction object stops reaction when reaching 90mgKOH/g, 5400mPas/200 DEG C of viscosity, while hot high temperature discharging, and with cold
The cooling polyester resin of the steel band of condensate, is then crushed and is granulated, obtain the polyester tree of the excellent PU cured powder paint of cold resistance
Rouge.
Prepared polyester resin hydroxyl value: 5415mPas/200 DEG C of 90mgKOH/g, viscosity.
Embodiment 2
The preparation method of the excellent PU cured powder paint polyester resin of cold resistance, comprising the following steps:
(1) by 12mol terephthalic acid (TPA), 18mol3,3- tetramethylene glutaric acid, 12molN- butyl diethanolamine,
(methylol) hexamethylene of 16mol1,4- bis- and catalyst are added in reaction kettle, first in 120 DEG C of sufficiently meltings and after mixing evenly,
185 DEG C and insulation reaction 3h are to slowly warm up to the heating rate of 5 DEG C/h again, obtains mixed material；
Polymerisation catalysts are 2- octyl succinic acid two (tributyl tin), dosage 0.12mol；
(2) when acid value is reduced to 85mgKOH/g, 10mol resorcinol-O, O'- bis- is added in Xiang Shangshu mixed material
Acetic acid, 12mol hydrogenated castor oleic acid and 12mol neopentyl glycol, under nitrogen protection again with the gradually temperature reaction of 10 DEG C/h rate
To 235 DEG C, [β-(3, the 5- di-t-butyl -4- hydroxyls of antioxidant four are added to steaming without obvious distillate in sufficiently reaction 6h, reaction
Phenyl) propionic acid] pentaerythritol ester, dosage 0.2mol keeps the vacuum degree 4h of 60mmHg, facilitates the formation of polyester resin,
When object acid value to be polymerized is 20mgKOH/g, and when viscosity reaches 3500mPas/200 DEG C, stops pulling vacuum；
(3) when being cooled to 200 DEG C, the catechin of 8mol is added, and is warming up to 225 DEG C of insulation reaction 3h in 1h, to poly-
The hydroxyl value of conjunction object stops reaction when reaching 86mgKOH/g, 5480mPas/200 DEG C of viscosity, while hot high temperature discharging, and with cold
The cooling polyester resin of the steel band of condensate, is then crushed and is granulated, obtain the polyester tree of the excellent PU cured powder paint of cold resistance
Rouge.
Prepared polyester resin hydroxyl value: 5480mPas/200 DEG C of 86mgKOH/g, viscosity.
Embodiment 3
The preparation method of the excellent PU cured powder paint polyester resin of cold resistance, comprising the following steps:
(1) by 10mol terephthalic acid (TPA), 20mol3,3- tetramethylene glutaric acid, 15molN- butyl diethanolamine,
(methylol) hexamethylene of 15mol1,4- bis- and catalyst are added in reaction kettle, first in 120 DEG C of sufficiently meltings and after mixing evenly,
180 DEG C and insulation reaction 3h are to slowly warm up to the heating rate of 6 DEG C/h again, obtains mixed material；
Polymerisation catalysts are 2- octyl succinic acid two (tributyl tin), dosage 0.1mol；
(2) when acid value is reduced to 85mgKOH/g, 10mol resorcinol-O, O'- bis- is added in Xiang Shangshu mixed material
Acetic acid, 10mol hydrogenated castor oleic acid and neopentyl glycol 10mol, under nitrogen protection again with the gradually temperature reaction of 10 DEG C/h rate
To 235 DEG C, [β-(3, the 5- di-t-butyl -4- hydroxyls of antioxidant four are added to steaming without obvious distillate in sufficiently reaction 6h, reaction
Phenyl) propionic acid] pentaerythritol ester, dosage 0.2mol keeps the vacuum degree 4h of 70mmHg, facilitates the formation of polyester resin,
When object acid value to be polymerized is 20mgKOH/g, and when viscosity reaches 3400mPas/200 DEG C or so, stops pulling vacuum；
(3) when being cooled to 200 DEG C, the catechin of 10mol is added, and is warming up to 225 DEG C of insulation reaction 3h in 1h, to poly-
The hydroxyl value of conjunction object stops reaction when reaching 90mgKOH/g, 5400mPas/200 DEG C of viscosity, while hot high temperature discharging, and with cold
The cooling polyester resin of the steel band of condensate, is then crushed and is granulated, obtain the polyester tree of the excellent PU cured powder paint of cold resistance
Rouge.
Prepared polyester resin hydroxyl value: 4834mPas/200 DEG C of 95mgKOH/g, viscosity.
Embodiment 4
The preparation method of the excellent PU cured powder paint polyester resin of cold resistance, comprising the following steps:
(1) by 20mol terephthalic acid (TPA), 10mol3,3- tetramethylene glutaric acid, 18molN- butyl diethanolamine,
(methylol) hexamethylene of 10mol1,4- bis- and catalyst are added in reaction kettle, first in 120 DEG C of sufficiently meltings and after mixing evenly,
185 DEG C and insulation reaction 3h are to slowly warm up to the heating rate of 5 DEG C/h again, obtains mixed material；
Polymerisation catalysts are 2- octyl succinic acid two (tributyl tin), dosage 0.12mol；
(2) when acid value is reduced to 85mgKOH/g, 10mol resorcinol-O, O'- bis- is added in Xiang Shangshu mixed material
Acetic acid, 12mol hydrogenated castor oleic acid and neopentyl glycol 10mol, under nitrogen protection again with the gradually temperature reaction of 10 DEG C/h rate
To 235 DEG C, [β-(3, the 5- di-t-butyl -4- hydroxyls of antioxidant four are added to steaming without obvious distillate in sufficiently reaction 6h, reaction
Phenyl) propionic acid] pentaerythritol ester, dosage 0.1mol keeps the vacuum degree 4h of 70mmHg, facilitates the formation of polyester resin,
When object acid value to be polymerized is 20mgKOH/g, and when viscosity reaches 3000mPas/200 DEG C, stops pulling vacuum；
(3) when being cooled to 200 DEG C, the catechin of 10mol is added, and is warming up to 225 DEG C of insulation reaction 3h in 1h, to poly-
The hydroxyl value of conjunction object stops reaction when reaching 90mgKOH/g, 5400mPas/200 DEG C of viscosity, while hot high temperature discharging, and with cold
The cooling polyester resin of the steel band of condensate, is then crushed and is granulated, obtain the polyester tree of the excellent PU cured powder paint of cold resistance
Rouge.
Prepared polyester resin hydroxyl value: 5169mPas/200 DEG C of 92mgKOH/g, viscosity.
Embodiment 5
The preparation method of the excellent PU cured powder paint polyester resin of cold resistance, comprising the following steps:
(1) by 18mol terephthalic acid (TPA), 12mol3,3- tetramethylene glutaric acid, 10molN- butyl diethanolamine,
(methylol) hexamethylene of 20mol1,4- bis- and catalyst are added in reaction kettle, first in 120 DEG C of sufficiently meltings and after mixing evenly,
185 DEG C and insulation reaction 3h are to slowly warm up to the heating rate of 5 DEG C/h again, obtains mixed material；
Polymerisation catalysts are 2- octyl succinic acid two (tributyl tin), dosage 0.1mol；
(2) when acid value is reduced to 85mgKOH/g, 12mol resorcinol-O, O'- bis- is added in Xiang Shangshu mixed material
Acetic acid, 10mol hydrogenated castor oleic acid and neopentyl glycol 10mol, under nitrogen protection again with the gradually temperature reaction of 10 DEG C/h rate
To 235 DEG C, [β-(3, the 5- di-t-butyl -4- hydroxyls of antioxidant four are added to steaming without obvious distillate in sufficiently reaction 6h, reaction
Phenyl) propionic acid] pentaerythritol ester, dosage 0.3mol keeps the vacuum degree 4h of 70mmHg, facilitates the formation of polyester resin,
When object acid value to be polymerized is 20mgKOH/g, and when viscosity reaches 3600mPas/200 DEG C, stops pulling vacuum；
(3) when being cooled to 200 DEG C, the catechin of 8mol is added, and is warming up to 225 DEG C of insulation reaction 3h in 1h, to poly-
The hydroxyl value of conjunction object stops reaction when reaching 90mgKOH/g, 5400mPas/200 DEG C of viscosity, while hot high temperature discharging, and with cold
The cooling polyester resin of the steel band of condensate, is then crushed and is granulated, obtain the polyester tree of the excellent PU cured powder paint of cold resistance
Rouge.
Prepared polyester resin hydroxyl value: 5383mPas/200 DEG C of 88mgKOH/g, viscosity.
Comparative example 1
The other the same as in Example 1, in addition to not using terephthalic acid (TPA)；
Prepared polyester resin hydroxyl value: 4330mPas/200 DEG C of 98mgKOH/g, viscosity.
Comparative example 2
The other the same as in Example 1, in addition to not using 3,3- tetramethylene glutaric acid；
Prepared polyester resin hydroxyl value: 5820mPas/200 DEG C of 101mgKOH/g, viscosity.
Comparative example 3
The other the same as in Example 1, in addition to not using resorcinol-O, O'- oxalic acid；
Prepared polyester resin hydroxyl value: 5740mPas/200 DEG C of 78mgKOH/g, viscosity.
Comparative example 4
The other the same as in Example 1, in addition to not using hydrogenated castor oleic acid；
Prepared polyester resin hydroxyl value: 6135mPas/200 DEG C of 86mgKOH/g, viscosity.
Comparative example 5
The other the same as in Example 1, in addition to not using N butyl diethanol amine；
Prepared polyester resin hydroxyl value: 5780mPas/200 DEG C of 75mgKOH/g, viscosity.
Comparative example 6
The other the same as in Example 1, in addition to not using Isosorbide-5-Nitrae-two (methylol) hexamethylene；
Prepared polyester resin hydroxyl value: 4060mPas/200 DEG C of 71mgKOH/g, viscosity.
Comparative example 7
The other the same as in Example 1, in addition to not using neopentyl glycol；
Prepared polyester resin hydroxyl value: 4335mPas/200 DEG C of 70mgKOH/g, viscosity.
Comparative example 8
The other the same as in Example 1, in addition to not using catechin；
Prepared polyester resin hydroxyl value: 4640mPas/200 DEG C of 56mgKOH/g, viscosity.
Comparative example 9
Common commercially available hydroxy polyester resin (hydroxyl value: 105mgKOH/g, 6050mPas/200 DEG C of viscosity) :) conduct pair
Ratio 9 is illustrated.
The product hydroxyl value and viscosity comparison sheet of 1 embodiment of table and comparative example
As can be seen from the table above, 85~95mgKOH/g of its hydroxyl value of product, the viscosity 4800- in embodiment 1-5
5500mPas/200 DEG C or so；And in comparative example 1-9, the hydroxyl value of portioned product be in 70mgKOH/g or so, or even
50mgKOH/g or so, the hydroxyl value of portioned product are relatively high in 100 or so mgKOH/g；Product viscosity value in comparative example 1~9
Distribution is also relatively wide, and stability is poor, minimum 4060mPas/200 DEG C or so, up to 6135mPas/200 DEG C or so.
Embodiment 6
The resin concrete application effect of embodiment and comparative example, is shown in the present embodiment；
PU curing agent is purchased from goldschmidt chemical corporation, trade mark B1530.
PU cured powder paint formula, formula is generally as follows in parts by weight:
Paint coatings preparation: mixing each material according to PU cured powder paint formula, is squeezed out with double screw extruder, pressure
Piece is crushed, and then sheet stock pulverizes and sieves, powdery paints is made.After powdery paints is sprayed on surface treated using electrostatic gun
Tinplate substrate on, through 200 DEG C/15min solidify to get paint coatings.
Coating Indexs measure is according to GB/T 21776-2008 " the examination criteria guide of powdery paints and its coating "
2 the embodiment of the present invention of table and comparative example products application are in coating testing result
From the data and description in above table it can be seen that
Product in embodiment 1-5, appearance is all smooth or substantially smooth, gloss angle (60 ° of angles) 92% with
On, and impact resistance is preferable, positive recoil passes through, and boiling water boiling (2h) is unchanged, 0 DEG C of cold resistance (impact, 50cm after freezing)
Lower holding 6h, which is just recoiling, to be passed through, and is just being recoiled under -5 DEG C/6h and is being passed through；This illustrate product of the invention by cold resistance monomer and
Functional monomer is copolymerized, and be can be used for outdoor cold district, is had little influence on impact property under low-temperature condition.
From the point of view of appearance, comparative example 2,3,4,5,8 is poor, surface or has obvious pin hole or coarse, or has obvious tangerine
Skin, appearance are mostly undesirable；From the point of view of gloss angle (60 ° of angles), minimum is 78%, and highest is 90%, impact (50cm)
In investigation, most of square impacts pass through, and recoil slight cracking, illustrate that its impact resistance is generally poor；Cold resistance (is impacted after freezing
Property, 50cm) investigate, 0 DEG C/6h, the phenomenon that having serious cracking generation；0 DEG C/6h, which is just recoiling, to crack.
The effect for analyzing comparative example 1-9 and embodiment 1-5, is nothing like embodiment 1-5, this is because adopting in the present invention
With by the excellent 3,3- tetramethylene glutaric acid of cold resistance, resorcinol-O, O'- oxalic acid, hydrogenated castor oleic acid and N-
Butyl diethanolamine can make the segment softness of polyester resin and resistance to low temperature is outstanding, reduce the black brittleness of final film；
The use of terephthalic acid (TPA), (methylol) hexamethylene of 1,4- bis- and neopentyl glycol ensure that final film have enough water resistances and
Weatherability；
The catechin of big steric hindrance, which carries out sealing end, can suitably reduce curing rate, guarantee flow time, to obtain levelling
The excellent appearance of film of property.The hydroxyl value of finally obtained polyester resin is 85-95mgKOH/g, viscosity 4800-5500mPas/
200 DEG C, can be solidified with polyurethane curing agent B1530, film cold resistance is excellent, 0 DEG C, -5 DEG C respectively freeze 6h after liquidate
The requirement of powdery paints is fully achieved almost without influence, final film performance in hitting property.
Formula of the invention is as a whole, common to act synergistically, several under low-temperature condition in cold district to product
Its impact resistance is not interfered with.
In order to further verify the cold resistance of product of the present invention, as a result specially progress long-time limit cold resistance test is shown in
Table 3.
3 the embodiment of the present invention of table and comparative example products application are in (the freezing backlash of coating testing result-limit cold resistance
Hitting property, 50cm)
As can be seen from the table above, product of the invention (embodiment 1- embodiment 5) is applied to after coating, coating
Hardness is preferable, and under cryogenic can its impact resistance is all preferable at -15 DEG C in 90 days.Since comparative example 1 is at -10 DEG C
Its impact resistance is poor, thus to it under further cryogenic conditions and the low-temperature impact resistance of longer time not
It investigates again.
Claims (10)
1. the excellent PU cured powder paint polyester resin of cold resistance, which is characterized in that the polyester resin is by main former
Expect terephthalic acid (TPA), 3,3- tetramethylene glutaric acid, resorcinol-O, O'- oxalic acid, hydrogenated castor oleic acid, N- butyl diethyl
Hydramine, 1,4- bis- (methylol) hexamethylene, neopentyl glycol, catechin are copolymerized to be formed.
2. the excellent PU cured powder paint polyester resin of cold resistance as described in claim 1, primary raw material are as follows:
Terephthalic acid (TPA) 10-20mol
3,3- tetramethylene glutaric acid 8-20mol
Resorcinol-O, O'- oxalic acid 5-15mol
Hydrogenated castor oleic acid 8-15mol
N butyl diethanol amine 8-18mol
(methylol) hexamethylene of 1,4- bis- 9-22mol
Neopentyl glycol 10-25mol
Catechin 7-15mol.
3. the excellent PU cured powder paint polyester resin of cold resistance as described in claim 1, which is characterized in that also wrap
It includes: catalyst 2- octyl succinic acid two (tributyl tin), dosage 0.03-0.15mol.
4. the excellent PU cured powder paint polyester resin of cold resistance as described in claim 1, which is characterized in that also wrap
Include: antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, dosage 0.1-0.3mol.
5. the excellent PU cured powder paint polyester resin of cold resistance as described in claim 1, which is characterized in that it is main
Raw material is as follows:
Terephthalic acid (TPA) 15mol
3,3- tetramethylene glutaric acid 15mol
Resorcinol-O, O'- oxalic acid 10mol
Hydrogenated castor oleic acid 10mol
N butyl diethanol amine 15mol
(methylol) hexamethylene of 1,4- bis- 15mol
Neopentyl glycol 12mol
Catechin 8mol.
6. the preparation method of the excellent PU cured powder paint polyester resin of cold resistance as described in claim 1, including with
Lower step:
(1) by terephthalic acid (TPA), 3,3- tetramethylene glutaric acid, N butyl diethanol amine, (methylol) hexamethylene of 1,4- bis- and
Catalyst be added reaction kettle in, sufficiently melting and after mixing evenly, then slowly heating simultaneously insulation reaction；
(2) it is reduced to acid value, resorcinol-O, O'- oxalic acid, the rilanit special of formula ratio is added in Xiang Shangshu mixed material
Antioxygen is added to steaming without obvious distillate in acid and neopentyl glycol, gradually temperature reaction again under nitrogen protection, sufficiently reaction
The formation of polyester resin is facilitated in agent under vacuum condition, stops pulling vacuum；
(3) cool down, catechin is added, heating, insulation reaction, high temperature discharging, cooling polyester resin are crushed while hot after stopping reaction
It is granulated, obtains the polyester resin of the excellent PU cured powder paint of cold resistance.
7. the preparation method of the excellent PU cured powder paint polyester resin of cold resistance as claimed in claim 6, including with
Lower step:
(1) by 10~20mol terephthalic acid (TPA), 8~20mol3,3- tetramethylene glutaric acid, 8~18molN- butyl diethanol
Amine, 9-22mol1, (methylol) hexamethylene of 4- bis- and catalyst are added in reaction kettle, first sufficiently melt and stir at 110~130 DEG C
After mixing uniformly, then 170~190 DEG C and 2~4h of insulation reaction are to slowly warm up to the heating rate of 3~7 DEG C/h, obtain mixture
Material；Catalyst is that polymerisation catalysts are 2- octyl succinic acid two (tributyl tin), dosage 0.03-0.15mol；
(2) when acid value is reduced to 75~90mgKOH/g or less, the resorcinol-of 5-15mol is added in Xiang Shangshu mixed material
The neopentyl glycol of O, O'- oxalic acid, 8-15mol hydrogenated castor oleic acid and 10-25mol, under nitrogen protection again with 8~12 DEG C/h
Gradually to 220~250 DEG C, antioxidant is added to steaming without obvious distillate in sufficiently 4~8h of reaction, reaction to rate for temperature reaction
Four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, dosage 0.1-0.3mol keep 50~80mmHg
2~5h of vacuum degree, facilitate the formation of polyester resin, when object acid value to be polymerized is 15~25mgKOH/g, and viscosity reaches 3000
~3800mPas/200 DEG C when stop pulling vacuum；
(3) when being cooled to 190~210 DEG C, the catechin of formula ratio is added, and is warming up to 210~240 DEG C in 0.8~1.2h
2~4h of insulation reaction, the hydroxyl value of object to be polymerized are stopped when reaching 80~100mgKOH/g, 4000~5800mPas/200 DEG C of viscosity
It only reacts, while hot high temperature discharging, and cools down polyester resin with the steel band with condensed water, be then crushed and be granulated, it is excellent to obtain cold resistance
The polyester resin of good PU cured powder paint.
8. the preparation method of the excellent PU cured powder paint polyester resin of cold resistance as claimed in claim 6, including with
Lower step:
(1) polymerization reaction: by 15mol terephthalic acid (TPA), 15mol3,3- tetramethylene glutaric acid, 15molN- butyl diethanol
Amine, 15mol1, (methylol) hexamethylene of 4- bis- and catalyst are added in reaction kettle, first sufficiently melt and stir evenly at 120 DEG C
Afterwards, then with the heating rate of 5 DEG C/h 185 DEG C and insulation reaction 3h are to slowly warm up to, obtain mixed material；
Polymerisation catalysts are 2- octyl succinic acid two (tributyl tin), dosage 0.12mol；
(2) when acid value is reduced to 85mgKOH/g, in Xiang Shangshu mixed material be added 10mol resorcinol-O, O'- oxalic acid,
10mol hydrogenated castor oleic acid and neopentyl glycol 12mol, under nitrogen protection again with 10 DEG C/h rate gradually temperature reaction to 235
DEG C, [the β-(3,5- di-tert-butyl-hydroxy phenyl) of antioxidant four is added to steaming without obvious distillate in sufficiently reaction 6h, reaction
Propionic acid] pentaerythritol ester, dosage 0.15mol keeps the vacuum degree 4h of 70mmHg, facilitates the formation of polyester resin, to poly-
When to close object acid value be 20mgKOH/g, and when viscosity reaches 3000-3800mPas/200 DEG C, stops pulling vacuum；
(3) when being cooled to 200 DEG C, the catechin of 8mol is added, and is warming up to 225 DEG C of insulation reaction 3h, object to be polymerized in 1h
Hydroxyl value stop reaction when reaching 80~100mgKOH/g, 4000-5800mPas/200 DEG C of viscosity, high temperature discharging while hot, and
It with the cooling polyester resin of the steel band with condensed water, is then crushed and is granulated, obtain the excellent PU cured powder paint of cold resistance
Polyester resin.
9. being obtained by the preparation method of the excellent PU cured powder paint polyester resin of cold resistance according to any one of claims 8
Resin, appearance colorless or light yellow clear particle；Hydroxyl value 85-95mgKOH/g, viscosity: 4800-5500mPas/200 DEG C.
10. the preparation method by the excellent PU cured powder paint polyester resin of cold resistance according to any one of claims 8 obtains
Application of the resin in B1530 curing system.
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| CN109180925A (en) * | 2018-09-07 | 2019-01-11 | 安徽恒隆新材料有限公司 | A kind of high glaze powdery paints hydroxy polyester resin and the preparation method and application thereof |
| CN110804164A (en) * | 2019-11-26 | 2020-02-18 | 黄山市徽州康佳化工有限责任公司 | Polyester resin with excellent boiling resistance and salt fog resistance for low-temperature curing type powder and preparation method thereof |
| CN111978527A (en) * | 2020-09-11 | 2020-11-24 | 安徽鑫友高分子新材料科技有限公司 | High-hardness powder coating with excellent fluorescence performance, preparation method and polyester resin used in preparation method |
| CN112029081A (en) * | 2020-09-11 | 2020-12-04 | 安徽鑫友高分子新材料科技有限公司 | Low-temperature curing type metal powder coating, preparation method and polyester resin used in low-temperature curing type metal powder coating |
| CN115073955A (en) * | 2022-08-02 | 2022-09-20 | 黄山学院 | Curing agent for low-temperature curing type powder with thick coating pinhole resistance and preparation method thereof |
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| CN109438688A (en) * | 2018-11-14 | 2019-03-08 | 黄山学院 | A kind of N, N, (2- hydroxypropyl) the adipamide system polyester resin of N`, N`- tetra- and preparation method |
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| CN109438688A (en) * | 2018-11-14 | 2019-03-08 | 黄山学院 | A kind of N, N, (2- hydroxypropyl) the adipamide system polyester resin of N`, N`- tetra- and preparation method |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109180925A (en) * | 2018-09-07 | 2019-01-11 | 安徽恒隆新材料有限公司 | A kind of high glaze powdery paints hydroxy polyester resin and the preparation method and application thereof |
| CN109180925B (en) * | 2018-09-07 | 2020-12-18 | 安徽恒隆新材料有限公司 | Hydroxyl polyester resin for high-gloss powder coating and preparation method and application thereof |
| CN110804164A (en) * | 2019-11-26 | 2020-02-18 | 黄山市徽州康佳化工有限责任公司 | Polyester resin with excellent boiling resistance and salt fog resistance for low-temperature curing type powder and preparation method thereof |
| CN111978527A (en) * | 2020-09-11 | 2020-11-24 | 安徽鑫友高分子新材料科技有限公司 | High-hardness powder coating with excellent fluorescence performance, preparation method and polyester resin used in preparation method |
| CN112029081A (en) * | 2020-09-11 | 2020-12-04 | 安徽鑫友高分子新材料科技有限公司 | Low-temperature curing type metal powder coating, preparation method and polyester resin used in low-temperature curing type metal powder coating |
| CN111978527B (en) * | 2020-09-11 | 2022-08-12 | 安徽鑫友高分子新材料科技有限公司 | High-hardness powder coating with excellent fluorescence performance, preparation method and polyester resin used in preparation method |
| CN112029081B (en) * | 2020-09-11 | 2022-09-30 | 安徽鑫友高分子新材料科技有限公司 | Low-temperature curing type metal powder coating, preparation method and polyester resin used in low-temperature curing type metal powder coating |
| CN115073955A (en) * | 2022-08-02 | 2022-09-20 | 黄山学院 | Curing agent for low-temperature curing type powder with thick coating pinhole resistance and preparation method thereof |
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