CN105601892A - Polyester resin for powdery coating and with low volatile component content and preparation method thereof - Google Patents
Polyester resin for powdery coating and with low volatile component content and preparation method thereof Download PDFInfo
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Abstract
The invention provides polyester resin for a powdery coating and with low volatile component content. The polyester resin for the powdery coating is characterized in that the ratio of the mole number of polybasic acids to the mole number of polyols is (1.04-1.08) to 1, and the acid value is 28 mg KOH/g to 45 mg KOH/g; and the polyester resin also includes the following components by the mass percentage: 0.08%-0.15% of an esterification catalyst, 0.04%-0.2% of an auxiliary antioxidant, 0.2%-1% of a main antioxidant, and 0%-0.1% of a curing accelerant; and the invention also provides a method for preparation of the polyester resin for the powdery coating and with low volatile component content. The polyester resin for the powdery coating has the main characteristic of low volatile component content, and also has the characteristics of excellent mechanical property, good water boiling resistance and good weather resistance.
Description
Technical field
The present invention relates to a kind of low volatile content polyester resin for powder coating and preparation method thereof, concrete refers to onePlant for the preparation of powdery paints and in its bake process, there is mylar of utmost point low volatility and preparation method thereof, belonging toIndustrial coating field.
Background technology
Powdery paints has efficiently, the remarkable feature of economy, environmental protection, performance, is one of important directions of coatings industry development.Along with the development of powdery paints technology, its kind becomes increasingly abundant, and performance is more perfect. Current polyester resin for powder coating is openedSend out more and pay close attention to its effect, as levelling, surperficial definition, impact etc., it produced less concern powdery paintsThe impact of journey.
Because the solidification temperature of powdery paints is high, in its bake process, produce more cigarette and can cause air pollution, makeThe feature of environmental protection of spraying process reduces; Meanwhile, the cigarette of generation condenses and forms the black dirt that cannot re-use in drying tunnel, needs regularlyClear up, reduced service efficiency and the production efficiency of powdery paints. Black dirt is mainly produced by the volatile materials in powdery paints.
In polyester resin for powder coating building-up process, can there is the multiple side reactions such as ester exchange, thermal degradation, oxidative degradation,Produce micromolecular volatile materials---volatile matter. As one of main component of powdery paints, the volatile matter of mylarAlso be one of main source of cigarette ash.
But low for volatile matter content, and in the time of powdery paints baking-curing, only produce on a small quantity or do not produce the powder of black dirtCoating is less with the research of mylar.
Summary of the invention
For the problems referred to above, the invention provides a kind of low volatile polyester resin for powder coating, comprise polyalcohol, polynaryAcid, auxiliary antioxidant and main anti-oxidant; Described polyalcohol comprises 1,4-CHDM, 2-methyl isophthalic acid, ammediol,One or more in 2-butyl-2-ethyl-1,3-PD and 1,6-hexylene glycol.
Account for the percentage of total polyalcohol molal quantity in each component molal quantity, 1,4-CHDM in described polyalcoholBe 0%～20%; 2-methyl isophthalic acid, ammediol is 0%～15%; 2-butyl-2-ethyl-1,3-PD is 0%-20%,1,6-hexylene glycol is 0%～20%.
In synthetic this mylar process, also add other polyalcohols, comprised neopentyl glycol, 2,2,4-trimethyl-1,3 ,-pentanediol, trimethylolpropane; Account for the percentage of total polyalcohol molal quantity taking each component: neopentyl glycol as 60%～100%; 2,2,4-trimethyl-1,3 ,-pentanediol is 0%～10%; Trimethylolpropane is 0%～4%.
Described polyacid is terephthalic acid (TPA), M-phthalic acid, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, 1,6-adipic acid, hexahydrobenzeneAcid anhydride; Account for the percentage of total polyacid molal quantity taking each component: terephthalic acid (TPA) is 40%～89%; M-phthalic acid is 8%～60%; Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic is 0%～50%; 1,6-adipic acid is 0%～6%, and HHPA is 0%～20%.
The mol ratio of described polyacid/polyalcohol is 1.04～1.30:1, and the acid number scope of final gained resin is28mgKOH/g～45mgKOH/g。
The amount of the antioxidant adding, accounts for the mass percent of polyacid and polyalcohol total amount in component, auxiliary 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-phenyl) phosphite ester, two (2,4-bis-containing cooxidantTert-butyl-phenyl) pentaerythritol diphosphites, 3,5-di-t-butyl-4-hydroxyl Bian Ji diethyl phosphonate, two (tertiary fourth of 3,5-bis-Base-4-hydroxyl Bian Ji phosphonic acids mono ethyl ester) one or more in calcium; Described main anti-oxidant be four [β-(3,5-di-t-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester, N, N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine,One or more in β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester.
The hydroperoxides of the above auxiliary antioxidant in can decomposition reaction system, described main anti-oxidant canMulberry Extract, in this mylar building-up process, this two classes antioxidant can slow down the reaction that free radical mutually combinesSpeed, avoids free radical to generate and too much causes macromolecular cleavage, thereby reduce the generation of small molecule by-product, makes reaction completeerEntirely, make polyalcohol and the polyacid participation synthesizing polyester resin with maximal efficiency.
Also comprise esterification catalyst and curing accelerator, in the mass percent of polyacid and polyalcohol total amount, esterificationCatalyst is 0.08%～0.15%, and curing accelerator is 0%～0.1%;
Described esterification catalyst is tin class catalyst or titanium class catalyst;
Described tin class catalyst is the one of Mono-n-butyltin, monobutyl dihydroxy stannic chloride or stannous oxalate;
Described titanate ester catalyst is the one of alkoxyl organic titanium or organic titanium compound;
Described curing accelerator be triphenylphosphine, ethyltriphenylphosphonium bromide, tetraethylammonium bromide, TBAB orThe one of Bian TEBA.
The present invention also provides a kind of method of preparing low volatile polyester resin for powder coating, comprises the steps:
(1) polyalcohol, polyacid and esterification catalyst are dropped in reactor, carry out esterification;
(2) continue to add polyacid to react;
(3) add auxiliary antioxidant and main anti-oxidant, polycondensation reaction occurs;
(4) add again main anti-oxidant and curing accelerator to react and make low volatile polyester resin for powder coating;
The main anti-oxidant using in described step (3) accounts for the 10%-40% of main anti-oxidant use amount.
Preferably, in described step (1), polyalcohol is dropped in reactor, be heated to (110～130) DEG C, pass into nitrogenGas, stirring, then drop into polyacid, catalyst, be warming up to (170～180) DEG C and carry out esterification, be warming up to gradually (245 ± 5)DEG C, and it is limpid to be maintained until reaction system, hierarchy of control acid number is (9～18) mgKOH/g;
(2) again drop into polyacid, keep temperature for (230～245) DEG C react to system acid number be (42～62) mgKOH/g；
(3) drop into phosphorus antioxidant and main anti-oxidant, (220～240) DEG C and vacuum be (0.093MPa)～(0.098MPa), react to system acid number be (28～45) mgKOH/g;
(4) be cooled to (200～220) DEG C, drop into curing accelerator and main anti-oxidant, stir discharging;
The mol ratio of the polyacid using in the polyacid using in described step (1) and step (2) is: (3～10):1。
In the method, antioxidant is to put in two steps in reactor, first in step 2, adds auxiliary anti-Oxidant and main anti-oxidant, after reaction a period of time, then add main anti-oxidant, and substep adds antioxidant can make raw material anti-Should be more complete, improve the combined coefficient of target product mylar, reduce the generation of accessory substance, thereby reduce volatile part, closeThe mylar structure becoming is more stable, is applied in powdery paints, not volatile, and properties of product are more stable, economical, produceIn journey, only produce on a small quantity or do not produce the powder of black dirt when powdery paints baking-curing, the more environmental protection of this process.
The invention has the beneficial effects as follows:
1, select 1,4-CHDM, 2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1,3-PD, 1,6-hexylene glycol participates in the synthetic of mylar, these novel alcohols esterification speed are fast, and can stop little molecule oligomerGenerate, with traditional neopentyl glycol for the synthesis of mylar, 2,2,4-trimethyl-1,3 ,-pentanediol and trihydroxy methylPropane participates in polycondensation reaction jointly, and the degree of polymerization is higher, reacts more complete;
2, use auxiliary antioxidant and main anti-oxidant, improve the utilization rate of raw material, reduce the life of small molecule by-productBecome, thereby reduce volatile point while being used for powdery paints;
3, antioxidant adds in two steps, makes reaction more complete, and reducing accessory substance must generate, and reduces volatile part, syntheticMylar structure more stable, be applied in powdery paints, not volatile, properties of product are more stable, economical, production processWhen middle powdery paints baking-curing, only produce on a small quantity or do not produce the powder of black dirt, the more environmental protection of this process.
It is low that low volatile content mylar used for powder coating prepared by the present invention has volatile matter content, glass transitionTemperature is suitable, the feature of mechanical performance, weatherability and water boiling resistance function admirable.
Detailed description of the invention
Below the specific embodiment of the present invention is described further:
Embodiment 1: mylar A's is synthetic
By 23.63kg neopentyl glycol, 10.77kg1,4-cyclohexanedimethanol, 11.97kg2-butyl-2-ethyl-1,3Propane diols drops in reactor, is heated to 110 DEG C, and after alcohol melts completely, logical nitrogen, opens stirring, drops into 57.95kg to benzeneDioctyl phthalate, 89.2g Mono-n-butyltin, is warming up to 190 DEG C and starts to generate esterification water, and it is 99 DEG C that temperature is heated up in a steamer in control, is warming up to gradually250 DEG C, be incubated to reactant liquor limpidly, to record acid number be 18.4mgKOH/g in sampling, viscosity is 1100cP/200 DEG C.
Reaction temperature is adjusted into 245 DEG C, drops into 5.21kg M-phthalic acid, 3.75kg1,4-cyclohexane cyclohexanedimethanodibasic,1.72kg1,6-adipic acid, is maintained until reactant liquor limpid, and it is 43.1mgKOH/g that sampling records acid number, and viscosity is 1240cP/200℃。
Reaction temperature is adjusted into 220 DEG C, input 44.6g triphenyl phosphite and 112g tetra-[β-(3,5-di-t-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester, be evacuated to gradually-0.093MPa, maintain 1h, it is 32.8mg that sampling records acid numberKOH/g, viscosity is 4650cP/200 DEG C.
Reaction temperature is adjusted into 220 DEG C, drops into 1.01kg tetra-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] seasonDoutrate, stirs 0.5h discharging.
Embodiment 2: mylar B's is synthetic
By 36.98kg neopentyl glycol, 1.96kg trimethylolpropane enters in reactor, is heated to 130 DEG C, treats that alcohol is completely moltenAfter change, logical nitrogen, opens stirring, drops into 26.05kg terephthalic acid (TPA), 27.36kg M-phthalic acid, 157g monobutyl dihydroxyStannic chloride, is warming up to 170 DEG C, controls that to heat up in a steamer temperature be 96～104 DEG C, is warming up to gradually 240 DEG C, be incubated to reactant liquor limpid, samplingRecording acid number is 9.1mgKOH/g, and viscosity is 875cP/200 DEG C.
Reaction temperature is adjusted into 230 DEG C, drops into 7.81kg M-phthalic acid, 3.44kg1,6-adipic acid, is maintained until anti-Answer liquid limpid, it is 42.0mgKOH/g that sampling records acid number, and viscosity is 970cP/200 DEG C.
Reaction temperature is adjusted into 240 DEG C, input 209g tri-(2,4-di-tert-butyl-phenyl) phosphite ester and 418g β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, be evacuated to gradually-0.098MPa, maintain 1h, sampling records acid number and is28.0mgKOH/g, viscosity is 5940cP/200 DEG C.
Reaction temperature is adjusted into 200 DEG C, drop into 628g β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester and111g ethyltriphenylphosphonium bromide, stirs 0.5h discharging.
Embodiment 3: mylar C's is synthetic
By 31.42kg neopentyl glycol, 10.77kg1,4-cyclohexanedimethanol drops in reactor, is heated to 120 DEG C, treatsAfter alcohol melts completely, logical nitrogen, opens stirring, drops into 31.26kg terephthalic acid (TPA), 27kg1, and 4-cyclohexane cyclohexanedimethanodibasic,0.1kg stannous oxalate, is warming up to 170 DEG C, and it is 96～104 DEG C that temperature is heated up in a steamer in control, is warming up to gradually 245 DEG C, is incubated to reactant liquor clearClear, it is 13.7mgKOH/g that sampling records acid number, and viscosity is 875cP/200 DEG C.
Reaction temperature is adjusted into 235 DEG C, drops into 6.75kg M-phthalic acid, 1.15kg1,6-adipic acid, is maintained until anti-Answer liquid limpid, it is 44.5mgKOH/g that sampling records acid number, and viscosity is 970cP/200 DEG C.
Reaction temperature is adjusted into 240 DEG C, drop into two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites of 65g and300gN, N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, is evacuated to-0.097MPa gradually,Maintain 1h, it is 31.6mgKOH/g that sampling records acid number, and viscosity is 5285cP/200 DEG C.
Reaction temperature is adjusted into 210 DEG C, drops into 700gN, N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) thirdAcyl group) hexamethylene diamine and 50g triphenylphosphine, stir 1h discharging.
Embodiment 4: mylar D's is synthetic
By 34.17kg neopentyl glycol, 1.0kg trimethylolpropane, 5.4kg2,2,4-trimethyl-1,3-pentanediol drops intoIn reactor, be heated to 110 DEG C, after alcohol melts completely, logical nitrogen, opens stirring, drops into 57.95kgPTA, 0.1kg alcoxylBase organic titanium, is warming up to 190 DEG C, controls that to heat up in a steamer temperature be 96～104 DEG C, is warming up to gradually 250 DEG C, is incubated to reactant liquor limpidly, getsIt is 13.3mgKOH/g that sample records acid number, and viscosity is 950cP/200 DEG C.
Reaction temperature is adjusted into 235 DEG C, drops into 7.16kg M-phthalic acid, be maintained until reactant liquor limpid, sampling recordsAcid number is 44.1mgKOH/g, and viscosity is 950cP/200 DEG C.
Reaction temperature is adjusted into 240 DEG C, drop into 100g3,5-di-t-butyl-4-hydroxyl Bian Ji diethyl phosphonate and350g tetra-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, is evacuated to-0.097MPa gradually, maintains1h, it is 32.1mgKOH/g that sampling records acid number, viscosity is 4710cP/200 DEG C.
Reaction temperature is adjusted into 210 DEG C, drops into 650g tetra-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] season pentaTetrol ester ester and 50g benzyltriethylammoinium chloride, stir 0.5h discharging.
Embodiment 5: mylar E's is synthetic
By 31.3kg neopentyl glycol, 1.5kg trimethylolpropane, 4.95kg2-methyl isophthalic acid, ammediol drops into reactorIn, be heated to 110 DEG C, after alcohol melts completely, logical nitrogen, opens stirring, drops into 26.49kg M-phthalic acid, 27.45kgIsosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, 0.1kg stannous oxalate, is warming up to 170 DEG C, and it is 96～104 DEG C that temperature is heated up in a steamer in control, is warming up to gradually 250DEG C, be incubated to reactant liquor limpidly, to record acid number be 11.4mgKOH/g in sampling, viscosity is 1050cP/200 DEG C.
Reaction temperature is adjusted into 235 DEG C, drops into 13.84kg M-phthalic acid, be maintained until reactant liquor limpid, sampling recordsAcid number is 62.0mgKOH/g, and viscosity is 1145cP/200 DEG C.
Reaction temperature is adjusted into 240 DEG C, drops into two (3, the 5-di-t-butyl-4-hydroxyl Bian Ji phosphonic acids mono ethyl ester) calcium of 90gAnd 400g β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, be evacuated to gradually-0.097MPa, maintain 1h, getIt is 45.0mgKOH/g that sample records acid number, and viscosity is 2150cP/200 DEG C.
Reaction temperature is adjusted into 210 DEG C, drop into 600g β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester and97g TBAB, stirs 0.5h discharging.
Embodiment 6: mylar F's is synthetic
By 31.3kg neopentyl glycol, 1.5kg trimethylolpropane, 6.4kg1,6-hexylene glycol drops in reactor, heatingTo 110 DEG C, after alcohol melts completely, logical nitrogen, opens stirring, drops into 26.49kg M-phthalic acid, 22.23kg1,4-hexamethyleneAlkane dioctyl phthalate, 4.67kg HHPA, 0.1kg stannous oxalate, is warming up to 170 DEG C, and it is 96～104 DEG C that temperature is heated up in a steamer in control, rises graduallyTemperature is to 250 DEG C, is incubated to reactant liquor limpidly, and to record acid number be 11.4mgKOH/g in sampling, and viscosity is 1090cP/200 DEG C.
Reaction temperature is adjusted into 235 DEG C, drops into 13.84kg M-phthalic acid, be maintained until reactant liquor limpid, sampling recordsAcid number is 62.0mgKOH/g, and viscosity is 1115cP/200 DEG C.
Reaction temperature is adjusted into 240 DEG C, drops into two (3, the 5-di-t-butyl-4-hydroxyl Bian Ji phosphonic acids mono ethyl ester) calcium of 90gAnd 400g β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, be evacuated to gradually-0.097MPa, maintain 1h, samplingRecording acid number is 42.8mgKOH/g, and viscosity is 2450cP/200 DEG C.
Reaction temperature is adjusted into 210 DEG C, drop into 600g β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester and97g TBAB, stirs 0.5h discharging.
Comparative example 1: mylar A's ' is synthetic
Comparative example 1 is the contrast experiment who does for embodiment 1, does not use three kinds of alcohol will protecting in the present invention, uses equivalentThe neopentyl glycol of tradition use replaces, and prepares mylar A ', for contrasting mylar A and mylar A ' at powdery paintsEffect.
39.19kg neopentyl glycol is dropped in reactor, be heated to 110 DEG C, after alcohol melts completely, logical nitrogen, opensStir, drop into 57.95kg terephthalic acid (TPA), 89.2g Mono-n-butyltin, is warming up to 190 DEG C and starts to generate esterification water, and control is heated up in a steamerTemperature is 99 DEG C, is warming up to gradually 250 DEG C, is incubated to reactant liquor limpidly, and to record acid number be 18.1mgKOH/g in sampling, and viscosity is1130cP/200℃。
Reaction temperature is adjusted into 245 DEG C, drops into 5.21kg M-phthalic acid, 3.75kg1,4-cyclohexane cyclohexanedimethanodibasic,1.72kg1,6-adipic acid, is maintained until reactant liquor limpid, and it is 42.5mgKOH/g that sampling records acid number, and viscosity is 1345cP/200℃。
Reaction temperature is adjusted into 220 DEG C, drops into 44.6g triphenyl phosphite, be evacuated to gradually-0.093MPa, dimensionHold 1h, it is 32.8mgKOH/g that sampling records acid number, and viscosity is 4650cP/200 DEG C.
Reaction temperature is adjusted into 220 DEG C, drops into 1.01kg tetra-[β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] seasonDoutrate, stirs 0.5h discharging.
Embodiment 6-10 is the powdery paints of preparing according to embodiment of the present invention 1-5, the mylar of preparing with comparative example 1A ' and the contrast experiment of comparative example 2 for carrying out with the commercially available conventional outdoor mylar N of certain offshore company. According to the form below 1 is by all formerMaterial premix, extrudes by double screw extruder, and cooled extruded material carries out powder and crosses 200 mesh sieves, adopts subsequently staticSpraying process is sprayed on aluminium sheet, after the condition of 200 DEG C × 10min is solidified, carries out properties test. Test condition is according to GB/T5237.4-2008 " aluminum alloy building section the 4th part: powder spray section bar " has carried out some and has adjusted, wherein resistance to impactFor 8mm drift test result (kg.cm), boiling water resistance is the guarantor's light rate after III level poach 4h, and hardness is that Chinese pencil is testedScratch hardness, salt fog resistance is the monolateral corrosion width (mm) of test 1000h, accelerating weatherability is the guarantor's light after test 1000hRate. Volatile matter test condition is: the powdery paints having sieved is placed in to surface plate, and 200 DEG C × 10min solidifies, then 240 DEG C of perseverancesTemperature baking 30min, quality m1 and m2 before and after record baking, volatile matter %=(m1-m2)/m1 × 100%.
Table 1 Application Example formula table
Table 2 Application Example result
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 1 | Comparative example 2 | |
| Outward appearance | Smooth smooth | Smooth smooth | Smooth smooth | Smooth smooth | Smooth smooth | Smooth smooth | Smooth smooth |
| Gloss/60 ° | 94％ | 95％ | 94％ | 96％ | 96％ | 955 | 95％ |
| Resistance to impact | 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％ |
As can be seen from Table 2, the prepared powdery paints of low volatility mylar of the present invention meets industrial powderThe Essential Performance Requirements of coating, and the volatile matter of the prepared powdery paints of low volatility mylar of the present invention is compared with Resin A 'N is low with resin, and has good weatherability and water boiling resistance.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also be to above-mentioned enforcement sideFormula changes and revises. Therefore, the present invention is not limited to detailed description of the invention disclosed and described above, to invent oneA little modifications and changes also should fall in the protection domain of claim of the present invention. In addition, although used in this descriptionSome specific terms, but these terms are just for convenience of description, invention do not formed to any restriction.
Claims (10)
1. a low volatile polyester resin for powder coating, is characterized in that, comprises polyalcohol, polyacid, auxiliary anti-oxidantAgent and main anti-oxidant; Described polyalcohol comprises 1,4-CHDM, 2-methyl isophthalic acid, ammediol, 2-butyl-2-secondBase-1,3-PD, one or more of 1,6-hexylene glycol.
2. a kind of low volatile polyester resin for powder coating according to claim 1, is characterized in that, rubs with each componentYour number accounts for the percentage meter of total polyalcohol molal quantity, and in described polyalcohol, 1,4-CHDM is 0%～20%; 2-firstBase-1,3-PD is 0%～15%; 2-butyl-2-ethyl-1,3-PD is 0%-20%; 1,6-hexylene glycol is 0%～20％。
3. a kind of low volatile polyester resin for powder coating according to claim 1, is characterized in that described polyalcoholAlso comprise neopentyl glycol, 2,2,4-trimethyl-1,3 ,-pentanediol, trimethylolpropane; Account for total polyalcohol molal quantity with each componentPercentage meter: neopentyl glycol is 60%～100%; 2,2,4-trimethyl-1,3 ,-pentanediol is 0%～10%; Trihydroxy methylPropane is 0%～4%.
4. according to a kind of low volatile polyester resin for powder coating described in claim 1 or 3, it is characterized in that, described manyUnit's acid is terephthalic acid (TPA), M-phthalic acid, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, 1,6-adipic acid, HHPA; Account for always with each componentThe percentage meter of polyacid molal quantity: terephthalic acid (TPA) is 40%～89%; M-phthalic acid is 8%～60%; Isosorbide-5-Nitrae-hexamethyleneAlkane dioctyl phthalate is 0%～50%; 1,6-adipic acid is 0%～6%, and HHPA is 0%～20%.
5. according to a kind of low volatile polyester resin for powder coating described in claim 1 or 3, it is characterized in that, described manyThe mol ratio of unit's acid/polyalcohol is 1.04～1.30:1, and acid number is 28mgKOH/g～45mgKOH/g.
6. according to a kind of low volatile polyester resin for powder coating described in claim 1 or 3, it is characterized in that, with componentAccounting for the mass percent meter of polyacid and polyalcohol total amount, is 0.04%～0.2% containing auxiliary antioxidant, and main anti-oxidant is0.2％～1％。
7. a kind of low volatile polyester resin for powder coating according to claim 6, is characterized in that, described auxiliary anti-Oxidant is triphenyl phosphite, three (2,4-di-tert-butyl-phenyl) phosphite ester, two (2,4-di-tert-butyl-phenyl) Ji WusiAlcohol diphosphites, 3,5-di-t-butyl-4-hydroxyl Bian Ji diethyl phosphonate, two (3,5-di-t-butyl-4-hydroxyl Bian Ji phosphonic acidsMono ethyl ester) one or more in calcium; Described main anti-oxidant was four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] seasonsDoutrate, N, N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine, β-(3,5-di-t-butyl-4-Hydroxy phenyl) one or more in propionic acid octadecyl ester.
8. according to a kind of low volatile polyester resin for powder coating described in claim 1 or 3, it is characterized in that, also compriseEsterification catalyst and curing accelerator, in the mass percent of polyacid and polyalcohol total amount, esterification catalyst is 0.08%～0.15%, curing accelerator is 0%～0.1%;
Described esterification catalyst is tin class catalyst or titanium class catalyst;
Described tin class catalyst be Mono-n-butyltin, monobutyl dihydroxy stannic chloride, three-(2 ethyl hexanoic acid) Monobutyltin orThe one of stannous oxalate;
Described titanate ester catalyst is the one of alkoxyl organic titanium or organic titanium compound;
Described curing accelerator is triphenylphosphine, ethyltriphenylphosphonium bromide, tetraethylammonium bromide, TBAB or Bian JiThe one of triethyl ammonium chloride.
9. a method of preparing the low volatile polyester resin for powder coating described in claim 1 or 3, is characterized in that,Comprise the steps:
(1) polyalcohol, polyacid and esterification catalyst are dropped in reactor, carry out esterification;
(2) continue to add polyacid to react;
(3) add auxiliary antioxidant and main anti-oxidant, polycondensation reaction occurs;
(4) add again main anti-oxidant and curing accelerator to react and make low volatile polyester resin for powder coating;
The main anti-oxidant using in described step (3) accounts for the 10%-40% of main anti-oxidant use amount.
10. the method for preparing low volatile polyester resin for powder coating according to claim 9, is characterized in that, instituteState in step (1) polyalcohol is dropped in reactor, be heated to (110～130) DEG C, pass into nitrogen, stirring, then drop into polynaryAcid, catalyst, be warming up to (170～180) DEG C and carry out esterification, is warming up to gradually (245 ± 5) DEG C, and is maintained until reaction bodyBe limpid, hierarchy of control acid number is (9～18) mgKOH/g;
(2) again drop into polyacid, keep temperature for (230～245) DEG C react to system acid number be (42～62) mgKOH/g;
(3) drop into phosphorus antioxidant and main anti-oxidant, (220～240) DEG C and vacuum be (0.093MPa)～(0.098MPa), react to system acid number be (28～45) mgKOH/g;
(4) be cooled to (200～220) DEG C, drop into curing accelerator and main anti-oxidant, stir discharging.
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