CN105601892B - A kind of low volatile content polyester resin for powder coating and preparation method thereof - Google Patents
A kind of low volatile content polyester resin for powder coating and preparation method thereof Download PDFInfo
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- CN105601892B CN105601892B CN201510789529.0A CN201510789529A CN105601892B CN 105601892 B CN105601892 B CN 105601892B CN 201510789529 A CN201510789529 A CN 201510789529A CN 105601892 B CN105601892 B CN 105601892B
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Abstract
The present invention provides a kind of low volatile content polyester resin for powder coating, and the polyester resin for powder coating has following characteristics：The mole ratio of polyacid and polyalcohol is 1.04~1.08:1, acid number is 28mgKOH/g~45mgKOH/g, and the polyester resin also includes following components：By percentage to the quality, esterification catalyst 0.08%~0.15%, auxiliary antioxidant 0.04%~0.2%, main anti-oxidant 0.2%~1%, curing accelerator 0%~0.1% also provides a kind of method for preparing low volatile content polyester resin for powder coating.The maximum feature of polyester resin for powder coating of the present invention is that volatile matter content is low, also with good mechanical performance, water boiling resistance, the characteristics of weatherability is good.
Description
Technical field
The present invention relates to a kind of low volatile content polyester resin for powder coating and preparation method thereof, specifically refer to one
Planting is used to prepare powdery paints and has extremely low volatile polyester resin and preparation method thereof in its baking process, belongs to
Industrial coating field.
Background technology
Powdery paints has the remarkable feature of efficient, economic, environmental protection, performance, is one of important directions of coatings industry development.
With the development of powder coating technology, its kind becomes increasingly abundant, and performance is more perfect.Current polyester resin for powder coating is opened
That sends out more focuses on its application effect, and such as levelling, surface definition, impact less focus on it and powdery paints produced
The influence of journey.
Because the solidification temperature of powdery paints is high, more cigarette is produced in its baking process can cause air pollution, make
The feature of environmental protection reduction of spraying process；Meanwhile, the cigarette of generation condenses in drying tunnel forms the black dirt that can not be re-used, it is necessary to periodically
Cleaning, reduces the service efficiency and production efficiency of powdery paints.The main volatile materials by powdery paints of black dirt is produced.
A variety of side reactions such as ester exchange, thermal degradation, oxidative degradation can occur in polyester resin for powder coating building-up process,
Produce volatile materials --- the volatile matter of small molecule.One of main component as powdery paints, the volatile matter of polyester resin
It is also one of main source of cigarette ash.
But it is low for volatile matter content, and only produce in powdery paints baking-curing powder that is a small amount of or not producing black dirt
The research of coating polyester resin is less.
The content of the invention
In view of the above-mentioned problems, the present invention provides a kind of low volatile polyester resin for powder coating, including it is polyalcohol, polynary
Acid, auxiliary antioxidant and main anti-oxidant；The polyalcohol include 1,4 cyclohexane dimethanol, 2- methyl-1,3-propanediols,
One or more in 2-butyl-2-ethyl-1,3-propanediol and 1,6-HD.
1,4-CHDM in the percentages of total polyalcohol molal quantity, the polyalcohol is accounted for each component molal quantity
For 0%~20%；2- methyl-1,3-propanediols are 0%~15%；2- butyl -2- ethyls -1,3-PD is 0%-20%,
1,6-HD is 0%~20%.
Other polyalcohols, including neopentyl glycol, 2 are also added into during the polyester resin is synthesized, 2,4- trimethyl -1,
3 ,-pentanediol, trimethylolpropane；The percentages of total polyalcohol molal quantity are accounted for each component：Neopentyl glycol be 60%~
100%；2,2,4- trimethyl -1,3,-pentanediol is 0%~10%；Trimethylolpropane is 0%~4%.
The polyacid is terephthalic acid (TPA), M-phthalic acid, 1,4 cyclohexanedicarboxylic acid, 1,6- adipic acids, hexahydrobenzene
Acid anhydride；The percentages of total polyacid molal quantity are accounted for each component：Terephthalic acid (TPA) is 40%~89%；M-phthalic acid is 8%
~60%；1,4 cyclohexanedicarboxylic acid is 0%~50%；1,6- adipic acid is 0%~6%, and HHPA is 0%~20%.
The mol ratio of the polyacid/polyalcohol is 1.04~1.30:1, the acid value of final gained resin is
28mgKOH/g~45mgKOH/g.
The amount of the antioxidant added, is accounted in terms of the mass percent of polyacid and polyalcohol total amount by component, and auxiliary is anti-
Oxidant is 0.04%~0.2%, and main anti-oxidant is 0.2%~1%.
Described is triphenyl phosphite, three (2,4- di-tert-butyl-phenyls) phosphite esters, double (2,4- bis- containing cooxidant
Tert-butyl-phenyl) pentaerythritol diphosphites, 3,5- di-t-butyl -4- hydroxyl benzyl groups diethyl phosphonate, double (tertiary fourths of 3,5- bis-
Base -4- hydroxyl benzyl group phosphonic acids mono ethyl ester) one or more in calcium；The main anti-oxidant be four [β-(3,5- di-t-butyls-
4- hydroxy phenyls) propionic acid] pentaerythritol ester, N, N '-bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine,
One or more in β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid octadecyl ester.
Auxiliary antioxidant described above can be in decomposition reaction system hydroperoxides, the main anti-oxidant can
Free radical is caught, in this polyester resin building-up process, this two classes antioxidant can slow down the reaction that free radical be combined with each other
Speed, it is to avoid free radical generation is excessive and causes macromolecular cleavage, so as to reduce the generation of small molecule by-product, makes reaction completeer
Entirely, polyalcohol and polyacid are made with the participation synthesizing polyester resin of maximal efficiency.
Also include esterification catalyst and curing accelerator, in terms of the mass percent of polyacid and polyalcohol total amount, esterification
Catalyst is 0.08%~0.15%, and curing accelerator is 0%~0.1%；
The esterification catalyst is tin catalyst or titanium class catalyst；
The tin catalyst is one kind of Mono-n-butyltin, monobutyl dihydroxy stannic chloride or stannous oxalate；
The titanate ester catalyst is one kind of alkoxy organic titanium or organic titanium compound；
The curing accelerator be triphenylphosphine, ethyltriphenylphosphonium bromide, tetraethylammonium bromide, TBAB or
One kind of benzyl group triethyl ammonium chloride.
The present invention also provides a kind of method for preparing low volatile polyester resin for powder coating, comprises the following steps：
(1) polyalcohol, polyacid and esterification catalyst are put into reactor, carries out esterification；
(2) polyacid is continuously added to be reacted；
(3) auxiliary antioxidant and main anti-oxidant are added, occurs polycondensation reaction；
(4) add main anti-oxidant and curing accelerator reacts and low volatile polyester resin for powder coating is made；
The main anti-oxidant used in the step (3) accounts for the 10%-40% of main anti-oxidant usage amount.
It is preferred that, polyalcohol is put into reactor in the step (1), (110~130) DEG C is heated to, is passed through nitrogen
Gas, stirring, then polyacid, catalyst are put into, it is warming up to (170~180) DEG C and carries out esterification, is gradually heating to (245 ± 5)
DEG C, and remaining limpid to reaction system, control system acid number is (9~18) mg KOH/g；
(2) polyacid is put into again, and keeping temperature is that (230~245) DEG C reaction to system acid number is (42~62) mg
KOH/g；
(3) input phosphorus antioxidant and main anti-oxidant, be in (220~240) DEG C and vacuum (- 0.093MPa)~(-
Under 0.098MPa), reaction to system acid number is (28~45) mg KOH/g；
(4) it is cooled to (200~220) DEG C, input curing accelerator and main anti-oxidant are stirred, discharging；
The mol ratio of the polyacid and the polyacid used in step (2) that are used in the step (1) is：(3~10)：
1。
In this method, antioxidant is to put into two steps in reactor, auxiliary is added first in step 2 anti-
Oxidant and main anti-oxidant, after reaction a period of time, add main anti-oxidant, substep plus antioxidant can make raw material anti-
The combined coefficient of target product polyester resin more completely, should be improved, the generation of accessory substance is reduced, so as to reduce volatile part, closed
Into polyester resin structure it is more stable, apply in powdery paints, not volatile, properties of product more stablize, economical, produce
Powder that is a small amount of or not producing black dirt is only produced in journey during powdery paints baking-curing, the process is more environmentally friendly.
The beneficial effects of the invention are as follows：
1st, from 1,4-CHDM, 2- methyl isophthalic acids, ammediol, 2- butyl -2- ethyls -1,3-PD, 1,
6- hexylene glycols participate in the synthesis of polyester resin, and these new alcohols esterification speed are fast, and can prevent small molecule oligomer
Generation, neopentyl glycol, 2,2,4- trimethyls -1,3,-pentanediol and trihydroxy methyl with being traditionally used for synthesizing polyester resin
Propane participates in polycondensation reaction jointly, and the degree of polymerization is higher, reacts more complete；
2nd, using auxiliary antioxidant and main anti-oxidant, the utilization rate of raw material is improved, the life of small molecule by-product is reduced
Into so as to reduce volatile point during for powdery paints；
3rd, antioxidant is added in two steps, makes reaction more complete, and reducing accessory substance must generate, and reduces volatile part, synthesis
Polyester resin structure it is more stable, apply in powdery paints, not volatile, properties of product are more stablized, economic, production process
Powder that is a small amount of or not producing black dirt is only produced during middle powdery paints baking-curing, the process is more environmentally friendly.
Powdery paints low volatile content polyester resin prepared by the present invention has volatile matter content low, glass transition
Temperature is appropriate, the characteristics of mechanical performance, weatherability and water boiling resistance function admirable.
Embodiment
The embodiment to the present invention is described further below：
Embodiment 1：Polyester resin A synthesis
By 23.63kg neopentyl glycols, 10.77kg 1,4-CHDMs, 11.97kg 2- butyl -2- ethyls -1,3
In propane diols input reactor, 110 DEG C are heated to, after alcohol is completely melt, leads to nitrogen, stirring is opened, 57.95kg is to benzene for input
Dioctyl phthalate, 89.2g Mono-n-butyltins are warming up to 190 DEG C and start to generate esterification water, and it is 99 DEG C to control to evaporate temperature, is gradually heating to
250 DEG C, insulation is limpid to reaction solution, and sampling measures acid number for 18.4mg KOH/g, and viscosity is 1100cP/200 DEG C.
Reaction temperature is adjusted to 245 DEG C, 5.21k g M-phthalic acids are put into, 3.75k g Isosorbide-5-Nitraes-cyclohexane cyclohexanedimethanodibasic,
1.72kg1,6- adipic acid, remain limpid to reaction solution, and sampling measures acid number for 43.1mg KOH/g, and viscosity is 1240cP/200
℃。
Reaction temperature is adjusted to 220 DEG C, input 44.6g triphenyl phosphites and 112g tetra- [β-(3,5- di-t-butyls-
4- hydroxy phenyls) propionic acid] pentaerythritol ester, -0.093MPa is gradually evacuated to, 1h is maintained, sampling measures acid number for 32.8mg
KOH/g, viscosity is 4650cP/200 DEG C.
Reaction temperature is adjusted to 220 DEG C, [β-(3, the 5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons of 1.01kg tetra- are put into
Doutrate, stirring 0.5h dischargings.
Embodiment 2：Polyester resin B synthesis
By 36.98kg neopentyl glycols, 1.96kg trimethylolpropanes enter in reactor, are heated to 130 DEG C, treat that alcohol melts completely
After change, lead to nitrogen, open stirring, put into 26.05kg terephthalic acid (TPA)s, 27.36kg M-phthalic acids, 157g monobutyl dihydroxy
Stannic chloride, is warming up to 170 DEG C, and it is 96~104 DEG C to control to evaporate temperature, is gradually heating to 240 DEG C, is incubated, sampling limpid to reaction solution
Acid number is measured for 9.1mg KOH/g, viscosity is 875cP/200 DEG C.
Reaction temperature is adjusted to 230 DEG C, 7.81kg M-phthalic acids are put into, 3.44kg 1,6- adipic acids are maintained to anti-
Answer liquid limpid, sampling measures acid number for 42.0mg KOH/g, viscosity is 970cP/200 DEG C.
Reaction temperature is adjusted to 240 DEG C, input (2, the 4- di-tert-butyl-phenyl) phosphite esters of 209g tri- and 418g β-(3,
5- di-tert-butyl-hydroxy phenyls) propionic acid octadecyl ester, -0.098MPa is gradually evacuated to, 1h is maintained, sampling measures acid number and is
28.0mg KOH/g, viscosity is 5940cP/200 DEG C.
Reaction temperature is adjusted to 200 DEG C, input 628g β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester and
111g ethyltriphenylphosphonium bromides, stirring 0.5h dischargings.
Embodiment 3：Polyester resin C synthesis
By 31.42kg neopentyl glycols, 10.77kg 1,4-CHDMs put into reactor, are heated to 120 DEG C, treat
After alcohol is completely melt, lead to nitrogen, open and stir, input 31.26kg terephthalic acid (TPA)s, 27kg Isosorbide-5-Nitraes-cyclohexane cyclohexanedimethanodibasic,
0.1kg stannous oxalates, are warming up to 170 DEG C, and it is 96~104 DEG C to control to evaporate temperature, is gradually heating to 245 DEG C, is incubated clear to reaction solution
Clear, sampling measures acid number for 13.7mg KOH/g, and viscosity is 875cP/200 DEG C.
Reaction temperature is adjusted to 235 DEG C, 6.75kg M-phthalic acids are put into, 1.15kg 1,6- adipic acids are maintained to anti-
Answer liquid limpid, sampling measures acid number for 44.5mg KOH/g, viscosity is 970cP/200 DEG C.
Reaction temperature is adjusted to 240 DEG C, double (2, the 4- di-tert-butyl-phenyl) pentaerythritol diphosphites of input 65g and
300g N, N '-bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, are gradually evacuated to -0.097MPa,
1h is maintained, sampling measures acid number for 31.6mg KOH/g, and viscosity is 5285cP/200 DEG C.
Reaction temperature is adjusted to 210 DEG C, input 700g N, N '-bis--(3- (3,5- di-tert-butyl-hydroxy phenyl) third
Acyl group) hexamethylene diamine and 50g triphenylphosphines, stirring 1h dischargings.
Embodiment 4：Polyester resin D synthesis
By 34.17kg neopentyl glycols, 1.0kg trimethylolpropanes, 5.4kg 2,2,4- trimethyls -1,3- pentanediol input
In reactor, 110 DEG C are heated to, after alcohol is completely melt, leads to nitrogen, opens stirring, put into 57.95kg PTA, 0.1kg alcoxyls
Base organic titanium, is warming up to 190 DEG C, and it is 96~104 DEG C to control to evaporate temperature, is gradually heating to 250 DEG C, insulation is limpid to reaction solution, takes
Sample measures acid number for 13.3mg KOH/g, and viscosity is 950cP/200 DEG C.
Reaction temperature is adjusted to 235 DEG C, 7.16kg M-phthalic acids are put into, remains limpid to reaction solution, sampling is measured
Acid number is 44.1mg KOH/g, and viscosity is 950cP/200 DEG C.
Reaction temperature is adjusted to 240 DEG C, 100g 3 is put into, 5- di-t-butyl -4- hydroxyl benzyl group diethyl phosphonates and
350g tetra- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, is gradually evacuated to -0.097MPa, maintains
1h, sampling measures acid number for 32.1mg KOH/g, and viscosity is 4710cP/200 DEG C.
Reaction temperature is adjusted to 210 DEG C, [β-(3, the 5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons penta of 650g tetra- are put into
Four alcohol ester esters and 50g benzyltriethylammoinium chlorides, stirring 0.5h dischargings.
Embodiment 5：Polyester resin E synthesis
By 31.3kg neopentyl glycols, 1.5kg trimethylolpropanes, 4.95kg2- methyl isophthalic acids, ammediol input reactor
In, 110 DEG C are heated to, after alcohol is completely melt, leads to nitrogen, opens stirring, put into 26.49kg M-phthalic acids, 27.45kg
Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, 0.1kg stannous oxalates are warming up to 170 DEG C, and it is 96~104 DEG C to control to evaporate temperature, is gradually heating to 250
DEG C, insulation is limpid to reaction solution, and sampling measures acid number for 11.4mg KOH/g, and viscosity is 1050cP/200 DEG C.
Reaction temperature is adjusted to 235 DEG C, 13.84kg M-phthalic acids are put into, remains limpid to reaction solution, sampling is measured
Acid number is 62.0mg KOH/g, and viscosity is 1145cP/200 DEG C.
Reaction temperature is adjusted to 240 DEG C, double (3, the 5- di-t-butyl -4- hydroxyl benzyl group phosphonic acids mono ethyl ester) calcium of input 90g
And 400g β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, -0.097MPa is gradually evacuated to, 1h is maintained, takes
Sample measures acid number for 45.0mg KOH/g, and viscosity is 2150cP/200 DEG C.
Reaction temperature is adjusted to 210 DEG C, input 600g β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester and
97g TBABs, stirring 0.5h dischargings.
Embodiment 6：Polyester resin F synthesis
By 31.3kg neopentyl glycols, 1.5kg trimethylolpropanes, 6.4kg 1,6- hexylene glycols are put into reactor, heating
To 110 DEG C, after alcohol is completely melt, lead to nitrogen, open stirring, put into 26.49kg M-phthalic acids, 22.23kg Isosorbide-5-Nitraes-hexamethylene
Alkane dioctyl phthalate, 4.67kg HHPAs, 0.1kg stannous oxalates are warming up to 170 DEG C, and it is 96~104 DEG C to control to evaporate temperature, is gradually risen
Temperature is to 250 DEG C, and insulation is limpid to reaction solution, and sampling measures acid number for 11.4mg KOH/g, and viscosity is 1090cP/200 DEG C.
Reaction temperature is adjusted to 235 DEG C, 13.84kg M-phthalic acids are put into, remains limpid to reaction solution, sampling is measured
Acid number is 62.0mg KOH/g, and viscosity is 1115cP/200 DEG C.
Reaction temperature is adjusted to 240 DEG C, double (3, the 5- di-t-butyl -4- hydroxyl benzyl group phosphonic acids mono ethyl ester) calcium of input 90g
And 400g β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, -0.097MPa is gradually evacuated to, 1h, sampling is maintained
Acid number is measured for 42.8mg KOH/g, viscosity is 2450cP/200 DEG C.
Reaction temperature is adjusted to 210 DEG C, input 600g β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester and
97g TBABs, stirring 0.5h dischargings.
Comparative example 1：Polyester resin A ' synthesis
Comparative example 1 is the contrast experiment done for embodiment 1, without using three kinds of alcohol to be protected in the present invention, uses equivalent
The neopentyl glycol of tradition is replaced, and polyester resin A ' is prepared, for contrasting polyester resin A and polyester resin A ' in powdery paints
Effect.
39.19kg neopentyl glycols are put into reactor, 110 DEG C are heated to, after alcohol is completely melt, leads to nitrogen, opens
Stirring, puts into 57.95kg terephthalic acid (TPA)s, and 89.2g Mono-n-butyltins are warming up to 190 DEG C and start to generate esterification water, control evaporates
Temperature is 99 DEG C, is gradually heating to 250 DEG C, insulation is limpid to reaction solution, and sampling measures acid number for 18.1mg KOH/g, and viscosity is
1130cP/200℃。
Reaction temperature is adjusted to 245 DEG C, 5.21k g M-phthalic acids are put into, 3.75k g1,4- cyclohexane cyclohexanedimethanodibasics,
1.72kg1,6- adipic acid, remain limpid to reaction solution, and sampling measures acid number for 42.5mg KOH/g, and viscosity is 1345cP/200
℃。
Reaction temperature is adjusted to 220 DEG C, 44.6g triphenyl phosphites is put into, is gradually evacuated to -0.093MPa, is tieed up
1h is held, sampling measures acid number for 32.8mg KOH/g, and viscosity is 4650cP/200 DEG C.
Reaction temperature is adjusted to 220 DEG C, [β-(3, the 5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons of 1.01kg tetra- are put into
Doutrate, stirring 0.5h dischargings.
Embodiment 6-10 is the powdery paints prepared according to 1-5 of the embodiment of the present invention, the polyester resin prepared with comparative example 1
Contrast experiments of the A ' with comparative example 2 to be carried out with the commercially available conventional outdoor polyester resin N of certain offshore company.According to the form below 1 is by all originals
Material premix, is extruded by double screw extruder, and the extruded material after cooling carries out powder and crosses 200 mesh sieves, then using electrostatic
Spraying process is sprayed on aluminium sheet, and properties test is carried out after the condition solidification through 200 DEG C × 10min.Test condition is according to GB/
T 5237.4-2008《The part of aluminum alloy building section the 4th：Powder spray section bar》Some adjustment, wherein impact resistance are carried out
For 8mm drifts test result (kg.cm), boiling water resistance is that III level water boils the light-protection rate after 4h, and hardness is Chinese pencil test
Hardness is abraded, salt fog resistance is test 1000h unilateral Erosion Width (mm), and it is guarantor's light after test 1000h to accelerate weatherability
Rate.Volatile matter test condition is：The powdery paints sieved is placed in surface plate, 200 DEG C × 10min solidifications, then 240 DEG C of perseverances
Temperature baking 30min, quality m1 and m2, volatile matter %=(m1-m2)/m1 × 100% before and after record baking.
The Application Example formula table of table 1
The Application Example result of table 2
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 1 | Comparative example 2 | |
| Outward appearance | Flat smooth | Flat smooth | Flat smooth | Flat smooth | Flat smooth | Flat smooth | Flat smooth |
| Gloss/60 ° | 94% | 95% | 94% | 96% | 96% | 955 | 95% |
| Impact resistance | Positive and negative 50 | Positive and negative 50 | Positive and negative 50 | Positive and negative 50 | Positive and negative 50 | Positive and negative 50 | Positive and negative 50 |
| Adhesive force | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Salt fog resistance | 3.1 | 2.7 | 2.5 | 2.7 | 2.6 | 2.7 | 2.6 |
| Boiling water resistance | 92% | 95% | 97% | 96% | 92% | 90% | 92% |
| Hardness | H | H | H | H | H | H | H |
| Weatherability | 68% | 75% | 78% | 67% | 62% | 62% | 67% |
| Volatile matter | 0.2% | 0.2% | 0.1% | 0.1% | 0.1% | 0.4% | 0.4% |
From table 2 it can be seen that the powdery paints prepared by the low volatility polyester resin of the present invention meets industrial powder
The Essential Performance Requirements of coating, and the present invention low volatility polyester resin prepared by powdery paints volatile matter compared with Resin A '
It is low with resin N, and with good weatherability and water boiling resistance.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and changed.Therefore, the invention is not limited in embodiment disclosed and described above, to the one of invention
A little modifications and changes should also be as falling into the scope of the claims of the present invention.Although in addition, being used in this specification
Some specific terms, but these terms are merely for convenience of description, do not constitute any limitation to invention.
Claims (4)
1. a kind of low volatile polyester resin for powder coating, it is characterised in that anti-oxidant including polyalcohol, polyacid, auxiliary
Agent and main anti-oxidant；The polyalcohol includes 1,4 cyclohexane dimethanol, 2- methyl-1,3-propanediols, 2- butyl -2- second
Base -1,3-PD, the one or more of 1,6- hexylene glycol；
1,4-CHDM 0% in the percentages of total polyalcohol molal quantity, the polyalcohol is accounted for each component molal quantity
~20%；2- methyl-1,3-propanediols are 0%~15%；2-butyl-2-ethyl-1,3-propanediol is 0%-20%；1,6- oneself
Glycol is 0%~20%；
The polyalcohol also includes neopentyl glycol, 2,2,4- trimethyl -1,3,-pentanediol, trimethylolpropane；Accounted for each component
The percentages of total polyalcohol molal quantity：Neopentyl glycol is 60%~100%；2,2,4- trimethyl -1,3,-pentanediol is 0%
~10%；Trimethylolpropane is 0%~4%；
The auxiliary antioxidant is triphenyl phosphite, three (2,4- di-tert-butyl-phenyls) phosphite esters, double (tertiary fourths of 2,4- bis-
Base phenyl) pentaerythritol diphosphites, 3,5- di-t-butyl -4- hydroxyl benzyl groups diethyl phosphonate, it is double (3,5- di-t-butyls -
4- hydroxyl benzyl group phosphonic acids mono ethyl ester) one or more in calcium；The main anti-oxidant is four [β-(3,5- di-t-butyl -4- hydroxyls
Base phenyl) propionic acid] pentaerythritol ester, N, N '-bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine, β-
One or more in (3,5- di-tert-butyl-hydroxy phenyls) propionic acid octadecyl ester；
The preparation method of the low volatile polyester resin for powder coating is as follows：
Comprise the following steps：
(1) polyalcohol, polyacid and esterification catalyst are put into reactor, carries out esterification；
(2) polyacid is continuously added to be reacted；
(3) auxiliary antioxidant and main anti-oxidant are added, occurs polycondensation reaction；
(4) add main anti-oxidant and curing accelerator reacts and low volatile polyester resin for powder coating is made；
The main anti-oxidant used in the step (3) accounts for the 10%-40% of main anti-oxidant usage amount；
The mol ratio of the polyacid/polyalcohol is 1.04~1.30:1, the acid number of polyester resin for 28mgKOH/g~
45mgKOH/g；
Also include esterification catalyst and curing accelerator, in terms of the mass percent of polyacid and polyalcohol total amount, catalyzing esterification
Agent is 0.08%~0.15%, and curing accelerator is 0%~0.1%；
The esterification catalyst is tin catalyst or titanium class catalyst；
The tin catalyst be Mono-n-butyltin, monobutyl dihydroxy stannic chloride, three-(2 ethyl hexanoic acid) Monobutyltin or
One kind of stannous oxalate；
The titanate ester catalyst is one kind of alkoxy organic titanium or organic titanium compound；
The curing accelerator is triphenylphosphine, ethyltriphenylphosphonium bromide, tetraethylammonium bromide, TBAB or benzyl group
One kind of triethyl ammonium chloride.
2. a kind of low volatile polyester resin for powder coating according to claim 1, it is characterised in that the polyacid
For terephthalic acid (TPA), M-phthalic acid, 1,4 cyclohexanedicarboxylic acid, 1,6- adipic acids；Total polyacid molal quantity is accounted for each component
Percentages：Terephthalic acid (TPA) is 40%~89%；M-phthalic acid is 8%~60%；1,4 cyclohexanedicarboxylic acid is 0%
~50%；1,6- adipic acids are 0%~6%.
3. a kind of low volatile polyester resin for powder coating according to claim 1, it is characterised in that account for many with component
The mass percent meter of first acid and polyalcohol total amount, is 0.04%~0.2% containing auxiliary antioxidant, and main anti-oxidant is
0.2%~1%.
4. a kind of low volatile polyester resin for powder coating according to claim 1, it is characterised in that the step
(1) polyalcohol is put into reactor in, (110~130) DEG C are heated to, nitrogen, stirring is passed through, then put into polyacid, esterification
Catalyst, is warming up to (170~180) DEG C and carries out esterification, be gradually heating to (245 ± 5) DEG C, and maintain clear to reaction system
Clear, control system acid number is (9~18) mg KOH/g；
(2) polyacid is put into again, and keeping temperature is that (230~245) DEG C reaction to system acid number is (42~62) mg KOH/g；
(3) input auxiliary antioxidant and main anti-oxidant, be in (220~240) DEG C and vacuum (- 0.093MPa)~(-
Under 0.098MPa), reaction to system acid number is (28~45) mg KOH/g；
(4) it is cooled to (200~220) DEG C, input curing accelerator and main anti-oxidant are stirred, discharging.
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| CN106543420A (en) * | 2016-10-24 | 2017-03-29 | 广州擎天材料科技有限公司 | High TGIC type polyester resin for powder coating of a kind of water boiling resistance color fastness and preparation method thereof |
| CN106496532A (en) * | 2016-12-12 | 2017-03-15 | 衡阳山泰化工有限公司 | A kind of extra-weather-proof polyester resin for powder coating |
| CN107118337A (en) * | 2017-06-14 | 2017-09-01 | 陈丽 | A kind of preparation method of polyester resin for powder coating |
| CN109054004B (en) * | 2018-08-31 | 2021-04-13 | 擎天材料科技有限公司 | High-humidity-heat-resistant high-irradiance polyester resin and preparation method and application thereof |
| CN109517149A (en) * | 2018-11-23 | 2019-03-26 | 浙江中法新材料有限公司 | A kind of formula and preparation method thereof of hydrolysis dry mixed powders coating polyester resin |
| CN109734883B (en) * | 2018-12-28 | 2022-03-29 | 安徽神剑新材料股份有限公司 | Fast curing polyester resin and preparation method thereof |
| CN110408013A (en) * | 2019-08-30 | 2019-11-05 | 广东工业大学 | A kind of polyester resin for powder coating and preparation method thereof |
| CN111205446B (en) * | 2020-02-28 | 2022-08-19 | 衡阳山泰化工有限公司 | High-temperature-resistant organic amine modified polyester resin and preparation method and application thereof |
| CN111440295B (en) * | 2020-03-25 | 2023-04-18 | 广东工业大学 | Polyester resin for boiling-resistant high-leveling powder coating and preparation method and application thereof |
| CN111440296B (en) * | 2020-04-13 | 2022-10-18 | 广东伊诗德新材料科技有限公司 | Water-boiling-resistant outdoor polyester resin and preparation method thereof |
| CN111748082A (en) * | 2020-05-18 | 2020-10-09 | 安徽美佳新材料股份有限公司 | Special high-performance carboxyl-terminated polyester resin for powder coating and synthesis method thereof |
| CN111690140A (en) * | 2020-07-14 | 2020-09-22 | 重庆三峡油漆股份有限公司 | Solvent-free polyester siloxane resin and preparation method and application thereof |
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| CN102977346B (en) * | 2012-11-20 | 2014-12-10 | 广州擎天材料科技有限公司 | Polyester resin for triglycidyl isocyanurate (TGIC)-cured weather-resistant heat transfer printing powdery paint and preparation method thereof |
| CN103304789A (en) * | 2013-06-06 | 2013-09-18 | 广东伊诗德新材料科技有限公司 | 6:4 type polyester resin with good water boiling resistance and preparation method thereof |
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