CN109988491A - A kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin - Google Patents
A kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin Download PDFInfo
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- CN109988491A CN109988491A CN201811456037.XA CN201811456037A CN109988491A CN 109988491 A CN109988491 A CN 109988491A CN 201811456037 A CN201811456037 A CN 201811456037A CN 109988491 A CN109988491 A CN 109988491A
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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
- 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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- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention discloses a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin, includes the raw material of following weight percent: polyalcohol: 34-44%wt；Aromatic polycarboxylic acid 43-58%wt；Branching agent: 0.0-2%wt；Containing silicon material: 3-12%；Acidolysis agent: 0-5%wt；Esterification catalyst 0.03-0.15%wt；Alcoholysis agent 0-3%；Antioxidant 0.01-2%wt；Curing accelerator 0-1%wt；And also disclose the preparation method of the Silicon-containing Polyester resin.The resin number average molecular weight is in 2500-5000 g/mol, glass transition temperature (Tg) >=54 DEG C.The powdery paints that the resin is prepared into after solidification coating have gloss height, mechanical performance is excellent, 280/2h light-protection rate can achieve 50% or more and adhesive force be 1 grade or more.
Description
Technical field
The present invention relates to technical field of coatings more particularly to a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resins.
Background technique
Powdery paints obtains in coating metal surfaces widely answer at present as a kind of environmental type powdery paints
With.For powdery paints mainly with epoxy resin, polyester resin, polyurethane and acrylic acid etc. for matrix, main chain is generally carbon-at present
Carbon or carbon-oxide structure, are limited to its molecular structure, and heat resistance is very poor such as 280 DEG C of baking 1h dusting.
Compared with common organic resin, due to the presence of silicon-oxygen key in organic siliconresin, so that its heat resistance is very
The outstanding 3 hours light-protection rates that can such as be on active service at 400 DEG C are greater than 50%.Therefore powdery paints industry is passed through frequently with polyester tree at present
The mode that rouge and organic siliconresin are total to agent realizes the promotion of heat resistance.However due to the compatibility of organic siliconresin and polyester resin
It is poor, be directly total under conditions of agent there is spillover, to the hardness on surface, gloss, mechanical performance adhesive force all
Have a significant impact, the performance for eventually leading to film can not be readily accepted by customers.
CN200810053803.8 discloses a kind of organosilicon modified polyester electronic packaging material, mainly passes through organic
Silicone resin and alcohol realized in resin backbone by way of alcoholysis there is silicon oxygen bond, at present commercialized organosilicon tree in industry
Rouge there is it is a large amount of three replace and quaternary silicon atom, after alcoholysis equally be easy autohemagglutination, therefore cause production not
It is easy to control.CN201110058635.3 discloses a kind of heat-resisting hydroxy resin, and composition principle is equally using organosilicon
Resin and polyalcohol are realized in resin backbone by way of alcoholysis.CN201210351864.9, CN201210579587.7 and
CN201711291536.3- discloses the preparation method of polyester resin containing organosilicon, be equally using silicone intermediate and
Polyalcohol realizes the synthesis of containing silicone resin by way of alcoholysis to realize the high temperature resistance of matrix.Therefore it is equally existed
The possibility of autohemagglutination and cause production difficult in synthesis process.CN201510486238.4 discloses a kind of conjunction of organic siliconresin
At being mainly equal to hydrolysis in the mixed solution of water and toluene by using phenyl trichlorosilane and prepare intermediate, there is
The presence of water and solvent, which causes production technology to need to remove solvent, leads to complex process, easy shape after the hydrolysis of the monomers such as trichlorosilane
At monomer have 3 degrees of functionality be easy autohemagglutination, in this way control it is more difficult.Therefore being badly in need of one kind will not occur in process of production
The Heat Resistant Powder Coatings of autohemagglutination Silicon-containing Polyester process for preparing resins, and simple production process is easy to control.
Summary of the invention
To solve the above problems, the present invention provides a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin, including polyalcohol,
Aromatic polycarboxylic acid, branching agent, containing silicon material, acidolysis agent, esterification catalyst, alcoholysis agent, antioxidant is good and curing accelerator, and
And there are also the preparation method of the resin, the number average molecular weight of the resin is in 2500-5000 g/mol, glass transition temperature (Tg)
>=54 DEG C, coating has gloss height to the powdery paints being prepared into after solidification, and mechanical performance is excellent, 280/2h light-protection rate can be with
Reach 50% or more and adhesive force be 1 grade or more, solve the problems in the background art.
The object of the present invention is to provide a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resins, include following weight percent
The raw material of ratio: polyalcohol: 34-44%wt；Aromatic polycarboxylic acid 43-58%wt；Branching agent: 0.0-2%wt；Containing silicon material: 3-12%；
Acidolysis agent: 0-5%wt；Esterification catalyst 0.03-0.15%wt；Alcoholysis agent 0-3%；Antioxidant 0.01-2%wt；Curing accelerator 0-
1%wt。
Further improvement lies in that: the polyalcohol is neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), first
Base propylene glycol (MPDI), one of ethyl butyl propanediol (BEPD) and cyclohexanedimethanol (CHDM) or numerous compositions.
Further improvement lies in that: the branching agent is one in trimethylolpropane (TMP) and trimethylolethane (TME)
Kind or two kinds of mixing.
Further improvement lies in that: the aromatic polycarboxylic acid is one of phthalic acid (PTA) and M-phthalic acid (IPA)
Or both mixture.
Further improvement lies in that: the antioxidant is phosphite ester (three [2.4- di-tert-butyl-phenyl] phosphite esters, antioxygen
Agent 626) and Hinered phenols antioxidant (four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, antioxidant
1010) mode compounded synthesizes, and the gross mass based on resin, usage amount is 0.01-2%wt.
Further improvement lies in that: the alcoholysis agent is one of neopentyl glycol or trimethylolpropane or combination
Object.
Further improvement lies in that: the antioxidant is tetraethylammonium bromide, 4 bromide, benzyl triethyl ammonium chlorination
Ammonium, in triphenyl ethyl phosphonium bromide phosphine, the one or several kinds of dibutyl tin dilaurate, the gross mass based on resin is used
Amount is 0.01-1%wt.
Further improvement lies in that: the esterification catalyst is tin catalyst, is Dibutyltin oxide, tributyl oxidation
Tin, dihydroxy dibutyl tin oxide, stannous oxalate, one of Mono-n-butyltin or several, the gross mass based on resin,
Usage amount is 0.03-0.15%wt.
Further improvement lies in that: the acidolysis agent is M-phthalic acid (IPA), adipic acid (ADA), Isosorbide-5-Nitrae hexamethylene diformazan
The mixing of one or more of sour (CHDA) and fumaric acid (FCC).
Further improvement lies in that: the resin is the difunctional of terminal carboxyl polyester resin or hydroxyl telechelic polyester resin or both
Polyester resin.
Further improvement lies in that: the resin is two substitution silicone oil or dichlorosilane or disubstituted alkyl silicon containing silicon material
Alkane.
Further improvement lies in that: the resin is two substitution silicone oil containing silicon material, is dimethicone or diethyl silicone oil
Or diphenyl silicone oil.
Further improvement lies in that: the resin is dichlorosilane containing silicon material, is dimethyldichlorosilane or diethyl two
Chlorosilane or diphenyl silane.
Further improvement lies in that: the resin is disubstituted alkyl silane or is dimethylformamide dimethyl oxygroup silicon containing silicon material
Alkane or dimethyl diethoxysilane or diethyldimethoxysilane or diethyldiethoxysilane or diphenyl dimethoxy
Base silane or diphenyl diethoxy silane.
Further improvement lies in that: the resin is terminal carboxyl polyester resin, acid value 25-55 mgKOH/g；The resin
For hydroxyl telechelic polyester resin, hydroxyl value range 25-120 mgKOH/g；The resin is difunctional polyester resin, acid value
For 15-55 mgKOH/g, hydroxyl value range is 15-55 mgKOH/g.
Further improvement lies in that: the resin be terminal carboxyl polyester resin, synthetic method are as follows: by the polyalcohol of formula ratio,
Branching agent and containing silicon material investment reaction kettle in heating and melting, 195 DEG C are then to slowly warm up in nitrogen atmosphere to no liquid
Production is then cooled to 140-185 DEG C and by aromatic acid and suitable catalyst while putting into reaction kettle, slow in nitrogen atmosphere
Slowly it is warming up to 235-255 DEG C and maintains, be added two when sample detection acid value (AV) reaches 5-20 mgKOH/g after system clarification
Secondary acidolysis agent IPA, ADA, CHDA and FCC etc. simultaneously maintain to carry out acidolysis sealing end at 235-250 DEG C of temperature；Acid value 35- to polyester
230-240 DEG C and vacuum (- 0.1MPA) polycondensation are cooled at 70 DEG C for a period of time, so that the acid value of polyester reaches 25-55；Therewith
After be cooled to 180-230 DEG C of throwing antioxidant and curing accelerator and maintain blowing after 5-30min.
Further improvement lies in that: the resin be hydroxyl telechelic polyester resin, synthetic method are as follows: by the polyalcohol of formula ratio,
Branching agent and containing silicon material investment reaction kettle in heating and melting, 195 DEG C are then being to slowly warm up in nitrogen atmosphere to aneroid
Body production, is then cooled to 140-185 DEG C and by aromatic acid and suitable catalyst while putting into reaction kettle, in nitrogen atmosphere
It is to slowly warm up to 235-255 DEG C and maintains, cooling when sample detection acid value (AV) reaches 5-20 mgKOH/g after system clarification
To 230-240 DEG C and vacuum (- 0.1MPA) polycondensation for a period of time so that the acid value < 2 of polyester；With being cooled to 180-230 later
It DEG C throws antioxidant and curing accelerator and maintains blowing after 5-30min.
Further improvement lies in that: the resin is carboxyl end group and hydroxyl difunctional polyester resin, synthetic method are as follows: will match
The polyalcohol just measured, branching agent and containing heating and melting in silicon material investment reaction kettle, then slowly heat up in nitrogen atmosphere
It is produced to 195 DEG C to no liquid, is then cooled to 140-185 DEG C and by aromatic acid and suitable catalyst while putting into reaction kettle
In, it is to slowly warm up to 235-255 DEG C in nitrogen atmosphere and maintains, sample detection acid value (AV) reaches 5-20 after system clarification
Secondary acidolysis agent IPA, ADA, CHDA and FCC etc. are added when mgKOH/g and maintains to carry out acidolysis sealing end at 235-250 DEG C of temperature；
230-240 DEG C and vacuum (- 0.1MPA) polycondensation are cooled to when the acid value 30-70mgKOH/g of polyester for a period of time, so that polyester
Acid value reach 25-55；It is then cooled at 210-230 DEG C and throws alcoholysis agent and maintain to be cooled to 180-225 DEG C of throwing after 20min
Antioxidant and curing accelerator simultaneously maintain blowing after 5-30min.
Further improvement lies in that: the resin number average molecular weight is in 2500-5000 g/mol, glass transition temperature Tg >=54
℃。
Further improvement lies in that: 60 DEG C of > of plexiglas transition temperature Tg.
Further improvement lies in that: the resin adds curing agent (isocyanuric acid three-glycidyl ester (TGIC), hydroxyalkyl amide
(HAA) and blocked isocyanate), curing accelerator, pigment, filler, levelling agent and degasser be prepared into powder resistant to high temperature
Coating.
Further improvement lies in that: the powdery paints resistant to high temperature that the resin is prepared into obtains gloss after being solidified and does machine
The good coating of tool performance, the coating 280/2h light-protection rate can achieve 50% or more and adhesive force be 1 grade or more.
Beneficial effects of the present invention: resin raw material of the invention uses polyalcohol, aromatic polycarboxylic acid, branching agent, siliceous original
Material, acidolysis agent, esterification catalyst, alcoholysis agent, antioxidant is good and curing accelerator, and there are also the preparation method of the resin,
The number average molecular weight of the resin is in 2500-5000 g/mol, glass transition temperature (Tg) >=54 DEG C, the powdery paints being prepared into
After solidification coating have gloss height, mechanical performance is excellent, 280/2h light-protection rate can achieve 50% or more and adhesive force be 1
Grade or more.
Specific embodiment
In order to deepen the understanding of the present invention, the present invention will be described in further detail with reference to the examples below, the embodiment
For explaining only the invention, it is not intended to limit the scope of the present invention..
Embodiment one:
The resin is terminal carboxyl polyester resin, synthetic method are as follows: is thrown by the polyalcohol of formula ratio, branching agent and containing silicon material
Enter heating and melting in reaction kettle, 195 DEG C are then to slowly warm up in nitrogen atmosphere and is produced to no liquid, is then cooled to 140 DEG C
And put into aromatic acid and suitable catalyst in reaction kettle simultaneously, it is to slowly warm up to 235 DEG C in nitrogen atmosphere and maintains, to body
Secondary acidolysis agent IPA, ADA, CHDA and FCC etc. is added and ties up when sample detection acid value (AV) reaches 5 mgKOH/g after system's clarification
Hold progress acidolysis sealing end at 235 DEG C of temperature；230 DEG C and vacuum (- 0.1MPA) polycondensation are cooled to when 35-70 DEG C of acid value of polyester
For a period of time, so that the acid value of polyester reaches 25；With being cooled to 180 DEG C of throwing antioxidant and curing accelerator later and maintain 5min
Blowing later.
Embodiment two:
The resin is hydroxyl telechelic polyester resin, synthetic method are as follows: is thrown by the polyalcohol of formula ratio, branching agent and containing silicon material
Enter heating and melting in reaction kettle, is then being to slowly warm up to 195 DEG C in nitrogen atmosphere to no liquid production, is then being cooled to 140
DEG C and aromatic acid and suitable catalyst are put into reaction kettle simultaneously, 235 DEG C are to slowly warm up in nitrogen atmosphere and is maintained, to
When being cooled to 230 DEG C and one section of vacuum (- 0.1MPA) polycondensation when sample detection acid value (AV) reaches 5 mgKOH/g after system clarification
Between, so that the acid value of polyester is 1；With being cooled to 180 DEG C of throwing antioxidant and curing accelerator later and maintain blowing after 5min.
Embodiment three:
The resin is terminal carboxyl polyester resin, synthetic method are as follows: is thrown by the polyalcohol of formula ratio, branching agent and containing silicon material
Enter heating and melting in reaction kettle, 195 DEG C are then to slowly warm up in nitrogen atmosphere and is produced to no liquid, is then cooled to 165 DEG C
And put into aromatic acid and suitable catalyst in reaction kettle simultaneously, it is to slowly warm up to 245 DEG C in nitrogen atmosphere and maintains, to body
Secondary acidolysis agent IPA, ADA, CHDA and FCC etc. is added and ties up when sample detection acid value (AV) reaches 12 mgKOH/g after system's clarification
Hold progress acidolysis sealing end at 242 DEG C of temperature；235 DEG C and vacuum (- 0.1MPA) polycondensation are cooled to when 35-70 DEG C of acid value of polyester
For a period of time, so that the acid value of polyester reaches 40；With being cooled to 200 DEG C of throwing antioxidant and curing accelerator later and maintain
Blowing after 18min.
Example IV:
The resin is hydroxyl telechelic polyester resin, synthetic method are as follows: is thrown by the polyalcohol of formula ratio, branching agent and containing silicon material
Enter heating and melting in reaction kettle, is then being to slowly warm up to 195 DEG C in nitrogen atmosphere to no liquid production, is then being cooled to 185
DEG C and aromatic acid and suitable catalyst are put into reaction kettle simultaneously, 255 DEG C are to slowly warm up in nitrogen atmosphere and is maintained, to
240 DEG C and one section of vacuum (- 0.1MPA) polycondensation are cooled to when sample detection acid value (AV) reaches 20 mgKOH/g after system clarification
Time, so that the acid value 1 of polyester；With being cooled to 230 DEG C of throwing antioxidant and curing accelerator later and maintain to put after 30min
Material.
Embodiment five:
The resin is terminal carboxyl polyester resin, synthetic method are as follows: is thrown by the polyalcohol of formula ratio, branching agent and containing silicon material
Enter heating and melting in reaction kettle, 195 DEG C are then to slowly warm up in nitrogen atmosphere and is produced to no liquid, is then cooled to 185 DEG C
And put into aromatic acid and suitable catalyst in reaction kettle simultaneously, it is to slowly warm up to 255 DEG C in nitrogen atmosphere and maintains, to body
Secondary acidolysis agent IPA, ADA, CHDA and FCC etc. is added and ties up when sample detection acid value (AV) reaches 20 mgKOH/g after system's clarification
Hold progress acidolysis sealing end at 250 DEG C of temperature；240 DEG C and vacuum (- 0.1MPA) polycondensation one are cooled to when 70 DEG C of acid value of polyester
The section time, so that the acid value of polyester reaches 55；With being cooled to 230 DEG C of throwing antioxidant and curing accelerator later and maintain 30min
Blowing later.
Embodiment six: the resin is carboxyl end group and hydroxyl difunctional polyester resin, synthetic method are as follows: by formula ratio
Polyalcohol, branching agent and containing silicon material investment reaction kettle in heating and melting, 195 DEG C are then being to slowly warm up in nitrogen atmosphere
It produces to no liquid, be then cooled to 160 DEG C and by aromatic acid and suitable catalyst while putting into reaction kettle, in nitrogen atmosphere
In be to slowly warm up to 245 DEG C and maintain, be added when sample detection acid value (AV) reaches 15 mgKOH/g after system clarification secondary
Acidolysis agent IPA, ADA, CHDA and FCC etc. simultaneously maintain to carry out acidolysis sealing end at 242 DEG C of temperature；It is cooled to when the acid value 50 of polyester
235 DEG C and vacuum (- 0.1MPA) polycondensation for a period of time so that the acid value of polyester reaches 35；It is then cooled at 220 DEG C and throws alcoholysis
Agent simultaneously maintains to be cooled to 200 DEG C of throwing antioxidant and curing accelerator after 20min and maintain blowing after 20min.
Table 1 is polyester resin component, the control acid value in production process and performance (each component list of embodiment one to six
Position is g)
Continuous table above
Embodiment seven: the performance of the saturated polyester resin synthesized with above embodiments can pass through manufactured powder
The performance of last coating embodies.
The saturated polyester resin that above embodiments 1-6 is synthesized, respectively at curing agent (three-glycidyl chlorinated isocyanurates
(TGIC), blocked isocyanate (B1530)), levelling agent, titanium dioxide, barium sulfate, styrax and 701B etc. be according in table 2
Ratio mixes after weighing up, and powdery paints is made after melting extrusion, tabletting, broken and sieving respectively with screw extruder.Then will
Powder paint is on the metal plate after surface granosealing, and test system is each after solidifying under suitable condition of cure
Kind performance, is then placed on 280 DEG C/2h overbaking for the painting after solidification, tests its heat resistance and adhesive force, as a result as follows.
The composition and coating performance of 2. powdery paints of table
It is excellent to can be seen that coating of the polyester resin of embodiment 1-6 after being prepared into powder coating solidification has from table 2
Different heat resistance, the light-protection rate > 50% of coating after 280 DEG C/2h overbaking, and adhesive force are 1 grade, show to have excellent
Heat resistance more.
The present invention can be described with others without prejudice to the concrete form of spirit or essential characteristics of the invention.The present invention
The embodiment above can only all be considered the description to invention rather than limit, it is full to be such as not limited to carboxyl end group of the present invention
With the one-step method preparation method of polyester resin.Using one-step method preparation method, i.e., by polyalcohol, aromatic polycarboxylic acid, aliphatic polyol
The mode that acid, branching agent, acidolysis agent and esterification catalyst carry out esterification condensation reaction after mixing is prepared into saturated resin,
It is available polyester resin of the present invention.Therefore all substantial technologicals according to the present invention are made to the above embodiment
Any trickle amendment, equivalent variations modification, belong in the range of technical solution of the present invention.
Claims (22)
1. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin, it is characterised in that: include the raw material of following weight percent:
Polyalcohol: 34-44%wt；Aromatic polycarboxylic acid 43-58%wt；Branching agent: 0.0-2%wt；Containing silicon material: 3-12%；Acidolysis agent: 0-
5%wt；Esterification catalyst 0.03-0.15%wt；Alcoholysis agent 0-3%；Antioxidant 0.01-2%wt；Curing accelerator 0-1%wt.
2. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as described in claim 1, it is characterised in that: the polyalcohol
For neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), methyl propanediol (MPDI), ethyl butyl propanediol
(BEPD) and one of cyclohexanedimethanol (CHDM) or numerous compositions.
3. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as described in claim 1, it is characterised in that: the branching agent
It is mixed for one of trimethylolpropane (TMP) and trimethylolethane (TME) or two kinds.
4. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as described in claim 1, it is characterised in that: the fragrance is more
First acid is the mixture of one of phthalic acid (PTA) and M-phthalic acid (IPA) or both.
5. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as described in claim 1, it is characterised in that: the antioxidant
For phosphite ester (three [2.4- di-tert-butyl-phenyl] phosphite esters, antioxidant 626) and Hinered phenols antioxidant (four [β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, antioxidant 1010) compounding mode synthesize, total matter based on resin
Amount, usage amount is 0.01-2%wt.
6. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as described in claim 1, it is characterised in that: the alcoholysis agent
For one of neopentyl glycol or trimethylolpropane or composition.
7. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as described in claim 1, it is characterised in that: the antioxidant
For tetraethylammonium bromide, 4 bromide, benzyltriethylammoinium chloride, in triphenyl ethyl phosphonium bromide phosphine, two fourth of tin dilaurate
The one or several kinds of base tin, the gross mass based on resin, usage amount are 0.01-1%wt.
8. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as described in claim 1, it is characterised in that: the esterification is urged
Agent is tin catalyst, is Dibutyltin oxide, tributyltin oxide, dihydroxy dibutyl tin oxide, stannous oxalate, monobutyl
One of tin oxide is several, and the gross mass based on resin, usage amount is 0.03-0.15%wt.
9. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as described in claim 1, it is characterised in that: the acidolysis agent
For one of M-phthalic acid (IPA), adipic acid (ADA), Isosorbide-5-Nitrae cyclohexane cyclohexanedimethanodibasic (CHDA) and fumaric acid (FCC) or
A variety of mixing.
10. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as described in claim 1, it is characterised in that: the resin is
The difunctional polyester resin of terminal carboxyl polyester resin or hydroxyl telechelic polyester resin or both.
11. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as described in claim 1 or 10, it is characterised in that: the tree
Rouge is two substitution silicone oil or dichlorosilane or disubstituted alkyl silane containing silicon material.
12. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as claimed in claim 11, it is characterised in that: the resin
It is two substitution silicone oil containing silicon material, is dimethicone or diethyl silicone oil or diphenyl silicone oil.
13. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as claimed in claim 11, it is characterised in that: the resin contains
Silicon material is dichlorosilane, is dimethyldichlorosilane or diethyl dichlorosilane or diphenyl silane.
14. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as claimed in claim 11, it is characterised in that: the resin contains
Silicon material is disubstituted alkyl silane or is dimethyldimethoxysil,ne or dimethyl diethoxysilane or diethyl
Dimethoxysilane or diethyldiethoxysilane or dimethoxydiphenylsilane or diphenyl diethoxy silane.
15. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as claimed in claim 10, it is characterised in that: the resin is
Terminal carboxyl polyester resin, acid value 25-55 mgKOH/g；The resin is hydroxyl telechelic polyester resin, hydroxyl value range 25-
120 mgKOH/g；The resin is difunctional polyester resin, and acid value is 15-55 mgKOH/g, and hydroxyl value range is 15-
55 mgKOH/g。
16. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as described in claim 10 or 15, it is characterised in that: the tree
Rouge is terminal carboxyl polyester resin, synthetic method are as follows: puts into reaction kettle by the polyalcohol of formula ratio, branching agent and containing silicon material
Middle heating and melting is then to slowly warm up to 195 DEG C in nitrogen atmosphere and produces to no liquid, is then cooled to 140-185 DEG C and incites somebody to action
Aromatic acid and suitable catalyst are put into reaction kettle simultaneously, and 235-255 DEG C is to slowly warm up in nitrogen atmosphere and is maintained, to body
Secondary acidolysis agent IPA, ADA, CHDA and FCC etc. is added simultaneously when sample detection acid value (AV) reaches 5-20 mgKOH/g after system's clarification
It maintains to carry out acidolysis sealing end at 235-250 DEG C of temperature；Be cooled to when 35-70 DEG C of acid value of polyester 230-240 DEG C and vacuum (-
0.1MPA) polycondensation for a period of time so that the acid value of polyester reaches 25-55；With being cooled to 180-230 DEG C of throwing antioxidant and solid later
Change promotor and maintains blowing after 5-30min.
17. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as described in claim 10 or 15, it is characterised in that: the tree
Rouge is hydroxyl telechelic polyester resin, synthetic method are as follows: puts into reaction kettle by the polyalcohol of formula ratio, branching agent and containing silicon material
Middle heating and melting is then being to slowly warm up to 195 DEG C to no liquid production in nitrogen atmosphere, is then being cooled to 140-185 DEG C simultaneously
Aromatic acid and suitable catalyst are put into reaction kettle simultaneously, 235-255 DEG C is to slowly warm up in nitrogen atmosphere and is maintained, to
230-240 DEG C and vacuum (- 0.1MPA) contracting are cooled to when sample detection acid value (AV) reaches 5-20 mgKOH/g after system clarification
Poly- a period of time, so that the acid value < 2 of polyester；With being cooled to 180-230 DEG C of throwing antioxidant and curing accelerator later and maintain
Blowing after 5-30min.
18. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as described in claim 10 or 15, it is characterised in that: the tree
Rouge is carboxyl end group and hydroxyl difunctional polyester resin, synthetic method are as follows: by the polyalcohol of formula ratio, branching agent and siliceous original
Material puts into heating and melting in reaction kettle, is then being to slowly warm up to 195 DEG C in nitrogen atmosphere to no liquid production, is then cooling down
It is put into reaction kettle simultaneously to 140-185 DEG C and by aromatic acid and suitable catalyst, 235- is to slowly warm up in nitrogen atmosphere
255 DEG C and maintain, be added when sample detection acid value (AV) reaches 5-20 mgKOH/g after system clarification secondary acidolysis agent IPA,
ADA, CHDA and FCC etc. simultaneously maintain to carry out acidolysis sealing end at 235-250 DEG C of temperature；It is dropped when the acid value 30-70mgKOH/g of polyester
Temperature to 230-240 DEG C and vacuum (- 0.1MPA) polycondensation for a period of time so that the acid value of polyester reaches 25-55；Then it is cooled to
Alcoholysis agent is thrown at 210-230 DEG C and maintains to be cooled to 180-225 DEG C of throwing antioxidant and curing accelerator after 20min and maintain 5-
Blowing after 30min.
19. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as described in claim 1, it is characterised in that: the resin number
According to molecular weight in 2500-5000 g/mol, glass transition temperature Tg >=54 DEG C.
20. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as claimed in claim 19, it is characterised in that: the resin glass
60 DEG C of > of glass transition temperature Tg.
21. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as described in claim 1, it is characterised in that: the resin adds
Curing agent (isocyanuric acid three-glycidyl ester (TGIC), hydroxyalkyl amide (HAA) and blocked isocyanate), solidification is added to promote
Agent, pigment, filler, levelling agent and degasser are prepared into powdery paints resistant to high temperature.
22. a kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin as claimed in claim 21, it is characterised in that: the resin system
It is standby at powdery paints resistant to high temperature solidified after obtain the coating that gloss does good mechanical property, the coating is in 280/2h guarantor
Light rate can achieve 50% or more and adhesive force be 1 grade or more.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811456037.XA CN109988491A (en) | 2018-11-30 | 2018-11-30 | A kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin |
| PCT/CN2019/116152 WO2020108263A1 (en) | 2018-11-30 | 2019-11-07 | Silicon-containing polyester resin used for high temperature-resistant powder coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811456037.XA CN109988491A (en) | 2018-11-30 | 2018-11-30 | A kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin |
Publications (1)
| Publication Number | Publication Date |
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| CN109988491A true CN109988491A (en) | 2019-07-09 |
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| CN201811456037.XA Pending CN109988491A (en) | 2018-11-30 | 2018-11-30 | A kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin |
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| WO (1) | WO2020108263A1 (en) |
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| CN110511367A (en) * | 2019-08-20 | 2019-11-29 | 安徽神剑新材料股份有限公司 | A kind of polyester resin for powder coating of containing graphene |
| CN110511365A (en) * | 2019-08-15 | 2019-11-29 | 安徽神剑新材料股份有限公司 | A kind of engineering machinery polyester resin |
| CN110527073A (en) * | 2019-09-05 | 2019-12-03 | 安徽神剑新材料股份有限公司 | A kind of high temperature resistant and extra-weather-proof powdery paints Silicon-containing Polyester resin |
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| CN112142965A (en) * | 2020-10-22 | 2020-12-29 | 安徽神剑新材料股份有限公司 | Silicon-containing polyester resin, preparation method thereof and low-surface-tension powder coating |
| CN112341610A (en) * | 2020-10-11 | 2021-02-09 | 芜湖市森沐知识产权科技服务有限公司 | Mixed polyester resin and synthetic method thereof |
| CN112625560A (en) * | 2020-12-28 | 2021-04-09 | 常州市碳索新材料科技有限公司 | Antistatic graphene modified polyester resin powder coating and preparation method thereof |
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| CN112142965A (en) * | 2020-10-22 | 2020-12-29 | 安徽神剑新材料股份有限公司 | Silicon-containing polyester resin, preparation method thereof and low-surface-tension powder coating |
| CN112625560A (en) * | 2020-12-28 | 2021-04-09 | 常州市碳索新材料科技有限公司 | Antistatic graphene modified polyester resin powder coating and preparation method thereof |
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| WO2020108263A1 (en) | 2020-06-04 |
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Application publication date: 20190709 |