CN106750222A - A kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating and preparation method thereof - Google Patents
A kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating and preparation method thereof Download PDFInfo
- Publication number
- CN106750222A CN106750222A CN201611082633.7A CN201611082633A CN106750222A CN 106750222 A CN106750222 A CN 106750222A CN 201611082633 A CN201611082633 A CN 201611082633A CN 106750222 A CN106750222 A CN 106750222A
- Authority
- CN
- China
- Prior art keywords
- polyester resin
- fluorine
- weather
- extra
- powder coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6828—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating and preparation method thereof, fluorine-containing polyester resin acid number prepared by the inventive method is 23 35mgKOH/g resins, hydroxyl value is less than 10mgKOH/g resins, glass transition temperature is 55 75 DEG C, melt viscosity is 2000 22000mPa.s/200 DEG C, it is 2,500 8000 that number divides equally quality, and Oil repellent is 1% to 5% continuously adjustabe.It has suitable glass transition temperature, synthetic technology of resins simple and the low advantage of cost, has the advantages such as super extra-weather-proof, glossiness is high, levelling is excellent and impact property is excellent with isocyanuric acid three-glycidyl ester or the hydroxyalkyl amide powder coating that is made of solidification.
Description
Technical field
The invention belongs to coating resin field, and in particular to a kind of extra-weather-proof fluorine-containing polyester of end carboxyl used for powder coating
Resin and preparation method thereof.
Background technology
Outdoor polyester powder coating is a kind of widely used thermohardening lacquer, and powdery paints total yield is already taken up at present
About the 70% of amount, it has energy saving, environment-friendly, the advantage such as long service life and excellent performance, is widely used in family
The application of outer various component surfaces.
With the expansion in powdery paints market, weatherability more and more higher of the people to it.Such as skyscraper aluminium section bar and
Secondary application is extremely difficult in the life-span under arms for bridge spanning the sea etc., therefore general all selects super super-weathering resistance powdery paints to avoid
Frequently secondary application.Therefore its polyester resin for powder coating weatherability into the head of PET industry at the moment is further expanded
Want task.
FEVE fluorocarbon resins (F-C) are mainly and are obtained by CTFE and alkyl vinyl ether free radical block polymerization
Arrive.Alkyl vinyl ether deposits hydroxyl (OH) functional group of activity so that it can be prepared into powder with the reaction of curing agent isocyanates
Last coating.Because C-F keys are extremely short in fluorocarbon resin, bond energy is big, polarizability is low, therefore fluorine atom is arranged closely in polymer carbon
Around, resin matrix is played a very good protection so that FEVE fluorocarbon resins possess excellent weatherability.But pure FEVE
The cost of fluorocarbon resin is very high, and mechanical performance and poor heat resistance, limits its application in certain fields.
The super-weathering resistance polyester resin for powder coating that current industrial quarters is typically used be by conventional material such as NPG, EG,
DEG, MPD, BEPD, TMP, PTA, IPA, ADA and FCC are prepared from by suitable formula, and its conventional formulation determines it very
Hardly possible prepares super extra-weather-proof polyester resin for powder coating.Such as Chinese patent CN201110360033.3, " a kind of extra-weather-proof powder is applied
Material terminal carboxyl polyester resin and preparation method thereof " etc..
The mode of polyester resin addition fluorine element extends its weatherability also has part to study, but always there is part and lack
Fall into.As Chinese patent CN201510009803.8 " extra-weather-proof polyester resin for powder coating, the powdery paints using the resin and
Its preparation method " by add in building-up process tetrafluoro M-phthalic acid, hexafluoro glutaric acid and 1H, 1H, 10H, 10H- perfluor-
The mode of 1,10- certain herbaceous plants with big flowers glycol improves weatherability, but tetrafluoro M-phthalic acid, hexafluoro glutaric acid and 1H, 1H, 10H, 10H- are complete
Fluoro- 1,10- certain herbaceous plants with big flowers glycol price is very high, it is impossible to realize that it is industrialized.
Chinese patent CN200910184341.8 " a kind of powdery paints with super-weathering resistance and preparation method thereof and should
With " disclose preparing extra-weather-proof powder by way of blending is extruded using conventional weatherability polyester resin and FEVE fluorocarbon resins
Last coating, but the mixed system prepared by the way of extrusion causes the glossiness of system low due to poor compatibility, rushes
The defects such as poor performance are hit, is equally unfavorable for the popularization in market.
Therefore a kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating, other traditional performances and pure polyester tree are developed
Fat is close and price is properly extremely important and urgent to current industrial quarters.
The content of the invention
It is an object of the invention to provide a kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating, with suitable
Glass transition temperature, possess super-weathering resistance while its traditional performance of the powdery paints of preparation and close pure polyester resin
Advantage, it is adaptable to polyester/isocyanuric acid three-glycidyl ester (TGIC) and polyester/hydroxyalkyl amide curing system.
Another object of the present invention is to provide a kind of system of the extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating
Preparation Method.
A kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating that the present invention is provided, including following weight percent
The raw material of ratio：
Polyalcohol 28-40wt%, aromatic polycarboxylic acid 40-55wt%, branching agent 0.05-2wt%, acidolysis agent 5-15wt%,
Esterification catalyst 0.03-0.15wt%, epoxychloropropane 0.1-4%, fluorine-containing alcohol 1-8% and NaOH 0.1-2%.
The fluorine-containing alcohol using tetrafluoropropanol, octafluoropentanol, ten difluoro enanthol, 2- perfluorobutylethyl alcohols, 2- perfluors oneself
One kind or several mixtures in base ethyl alcohol, 2- perfluorooctylethyl groups alcohol or 2- perfluor certain herbaceous plants with big flowers base ethyl alcohols.
Described polyalcohol use neopentyl glycol NPG, 2- methyl isophthalic acid, 3 propane diols MPD, methyl butyl propane diols BEPD, 1,
One kind or several various mixtures in 4 cyclohexanedimethanol CHDM or ethylene glycol EG.
The branching agent is using the one or two kinds of mixing in trimethylolpropane TMP and trimethylolethane TME.
The aromatic polycarboxylic acid is using the one kind in terephthalic acid (TPA) PTA and M-phthalic acid IPA or two kinds.
The acidolysis agent uses M-phthalic acid IPA, adipic acid ADA, Isosorbide-5-Nitrae cyclohexane cyclohexanedimethanodibasic CHDA, trimellitic anhydride
One kind or various mixing in TMA and fumaric acid FCC.It is preferred that M-phthalic acid IPA and Isosorbide-5-Nitrae cyclohexane cyclohexanedimethanodibasic CHDA
In one or two kinds of mixture.
The esterification catalyst uses organic tin or titanium class catalyst, including but not limited to Mono-n-butyltin, grass
Sour stannous and tetrabutyl titanate.Gross mass based on resin, its usage amount is 0.03-0.15wt%.
A kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating that the present invention is provided, including it is following by step：
1) during the fluorine-containing alcohol of formula ratio, NaOH and epoxychloropropane, put into reactor, after reaction, then steaming of depressurizing
Evaporate, fluoro epoxide is obtained；
2), the polyalcohol of formula ratio, aromatic polycarboxylic acid and branching agent are placed in another reactor, catalyzing esterification is added
Agent, carries out esterifying polycondensation reaction；
3) to step 2) prepared by system in add acidolysis agent carry out polycondensation and end-blocking, then vacuum is polycondensed into polyester tree
Fat intermediate；
4) in fluoro epoxide being put into polyester resin intermediate, extra-weather-proof end used for powder coating is prepared
The fluorine-containing polyester resin of carboxyl.
Further, step 1) described in reaction be to react 1-6h at 30-110 DEG C；
Further, step 2) in esterifying polycondensation reaction condition be：System is warming up to 230-255 DEG C and ties up in blanket of nitrogen
Hold, 5-15mgKOH/g resins are reached after detection acid number AV is sampled after system clarification, that is, stop.
Further, step 3) it is specially：Add acidolysis agent and control the temperature polycondensation and envelope are carried out at 230-250 DEG C
End, is cooled to 225-240 DEG C and vacuum polycondensation 1-3h so that polyester when the acid number of polyester reaches 40-60mgKOH/g resins
Acid number maintains 25-38mgKOH/g resins, prepares polyester resin intermediate；
Further, step 4) it is specially：At 200-240 DEG C, fluoro epoxide is put into the middle of polyester resin
In body, maintenance reaction 0.5-2h, afterwards blowing obtain final product the extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating.
Or, a kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating that the present invention is provided, including it is following by step
Suddenly：
A, prepare fluoro epoxide：The fluorine-containing alcohol of formula ratio, NaOH and epoxychloropropane are put into reactor
In, 1-6h, then vacuum distillation are reacted at 30-110 DEG C, fluoro epoxide is obtained；
B, the polyalcohol of formula ratio, aromatic polycarboxylic acid, aliphatic polyol acid, branching agent, acidolysis agent and esterification catalyst are mixed
230-255 DEG C is warming up to after closing uniformly and maintains to after clarifying to be cooled to again 225-240 DEG C and vacuum polycondensation 1-3h so that polyester
Acid number maintain 25-38mgKOH/g resins, be prepared obtaining polyester resin intermediate；
C, fluoro epoxide is put into intermediate polyester resin at 200-240 DEG C after maintain 0.5-2h, then put
Material so obtains the extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating.
The preparation process of powdery paints is：By the fluorine-containing polyester resin of the end carboxyl (558g) prepared by the present invention respectively with it is solid
Agent TGIC (42g), filler barium sulfate (250g), pigment titanium white (150g), levelling agent (10g), styrax (3g) and add lustre to
Agent 701B (3g) mixing, melting extrusion, cooling are broken, sieving is made powdery paints.
Compared with prior art, the fluorine-containing polyester resin acid number that prepared by the inventive method is 23-35mgKOH/g resins, hydroxyl
Value is less than 10mgKOH/g resins, and glass transition temperature is 55-75 DEG C, and melt viscosity is 2000-22000mPa.s/200 DEG C,
It is 2500-8000 that number divides equally quality, and Oil repellent is 1% to 5% continuously adjustabe.The fluorine-containing polyester resin of end carboxyl of present invention synthesis
Possess the advantages such as low cost, excellent performance compared with polyester resin described in Chinese patent CN201510009803.8.The present invention is closed
Into the fluorine-containing polyester resin of end carboxyl prepare into powdery paints after applied with powder described in Chinese patent CN200910184341.8
Material is compared to possessing the advantages such as levelling is excellent, glossiness is high and impact property is excellent.Fluorine-containing polyester resin of the present invention has suitable
Glass transition temperature, synthetic technology of resins be simple and the low advantage of cost, and fluorine-containing polyester resin of the present invention is urinated with isocyanide
Sour three-glycidyl ester or the hydroxyalkyl amide powder coating that is made of solidification have that super extra-weather-proof, glossiness is high, levelling is excellent and
The advantage such as impact property is excellent.
Specific embodiment
A part of specific embodiment is set forth below, and the present invention will be described.
Embodiment 1
A kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating, formula such as table 1：
A kind of extra-weather-proof fluorine-containing preparation method of polyester resin of end carboxyl used for powder coating, comprises the following steps：
1) by the NaOH of formula ratio and epoxychloropropane proportioning input reactor, system is then warming up to 70
DEG C, the 2- perfluoro hexyl ethyl alcohols of formula ratio in table 1 are added dropwise in reactor using the rate of addition of 40ml/h then, maintain
5h, then taking the mode of vacuum distillation, to prepare fluorine-containing epoxide (F-C-EP) standby as what is tested below；
2) polyalcohol and branching agent the heat temperature raising fusing at 100-140 DEG C of proportional quantity listed by table 1 are added, then successively
The aromatic dibasic acid of formula ratio in table 1 is added, esterification catalyst stannous oxalate is added, leads to nitrogen and with the speed liter of 10 DEG C/h
Esterification and water outlet take place from 185~194 DEG C for temperature, system, are then warming up to system with the programming rate of 5 DEG C/h
240 DEG C, 1-2h is then maintained to be clarified to system at 240 DEG C, now the acid number of system is 7-12mgKOH/g resins；
3) the acidolysis agent ADA and IPA of formula ratio and 1-3h is maintained at 240 DEG C in addition table 1 so that the acid number of system reaches
To 40-50mgKOH/g resins；Then vacuum polycondensation 1-3h causes that the acid number of system reaches 35-38mgKOH/ at 230-240 DEG C
G resins, are successfully prepared intermediate polyester resin；
4) 220 DEG C are cooled to, then the F-C-EP of input formula ratio and blowing obtains extra-weather-proof after maintaining 0.5-2h
The fluorine-containing polyester resin of end carboxyl used for powder coating.
The parameter of the fluorine-containing polyester resin of prepared end carboxyl is：Acid number 34-36mgKOH/g resins；Viscosity 3800-
4300mPa.s/200℃；Number average molecular weight 4000-8000；64-66 DEG C of glass transition temperature.
The compositing formula of the extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating of embodiment 1~8 is given in table 1
And performance, wherein embodiment 1 and 4 is pure polyester resin intermediate, and remaining is fluorine-containing polyester resin.Wherein in embodiment 1~8
Polyalcohol uses NPG, MPD, CHDM or BEPD, and branching agent uses TMP or TME, and aromatic polycarboxylic acid uses PTA
With the mixture of IPA, esterification catalyst uses stannous oxalate, and acidolysis agent uses the mixture of IPA and ADA, fluorine-containing
Alcohol uses 2- perfluoro hexyl ethyl alcohols.
The compositing formula and performance of the extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating of table 1.
With the present invention synthesis the fluorine-containing polyester resin of end carboxyl performance can by the performance of the powdery paints being made come
Embody.By embodiment of the present invention 1-8 synthesize the fluorine-containing polyester resin of end carboxyl respectively with TGIC, levelling agent, titanium dioxide, sulfuric acid
Barium, styrax and 701B etc. are mixed after being weighed up according to the ratio in table 2, with screw extruder melt respectively extrusion, compressing tablet, crush
With powdery paints is made after sieving.Then on the metal plate by powder paint after through surface granosealing, through 200
DEG C/10min solidifications after test system various performances, the performance test results are shown in Table 2.
The composition and coating performance of the powdery paints of table 2.
Weatherability testing standard in table 2 is GSB AL 631-2012, and specific parameter is：Illumination temperature：50±3℃；
Condensation temperature：40℃±3℃；Intensity of illumination：0.75w/(m2·nm)；UVB illumination 300h；Illumination and condensation cycle：4h illumination,
4h is condensed.A 1-4 is applied for one group of control experiment, embodiment 5-8 is another set control experiment.Wherein it can be found that real in table 1
Only NaOH, epoxychloropropane, 2- perfluoro hexyls ethyl alcohol is different with the amount of acidolysis agent IPA in applying the formula of a 1-4.Hydrogen
Sodium oxide molybdena, epoxychloropropane and 2- perfluoro hexyl ethyl alcohols show ratio change, the amount of fluorine-containing epoxy in main influence resin
And finally it is embodied in the change of the effective Oil repellent of resin.And the addition of fluorine-containing epoxy can reduce the acid number of resin intermediate, therefore
The appropriate amount for adding acidolysis agent IPA is needed to balance the acid number of final resin.The formula difference of embodiment 5-8 is produced in table 1
Reason is similar to embodiment 1-4 in table 1.By table 1 and 2 it is recognised that fluorine resin of the present invention is pure relative to intermediate poly-
For ester (embodiment 1 and 5), weatherability is obviously improved, while other performances of system such as lustrous surface, impact, levelling, attached
Put forth effort close with pure polyester with hardness etc..Show that the fluorine-containing polyester that we prepare possesses extra-weather-proof advantage, contained by adjustment
The formula of fluorine polyester can so prepare the super extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating.It is real that the present invention does powder plate-making
It is that, using conventional inorganic raw material and auxiliary agent, the data of table 2 are only for reference to test, and is such as contained by adjusting end carboxyl in actual applications
The performance powder coating that fluorine polyester formulation and power formulations finally give will have preferably performance.Present invention synthesis
The excellent fluorine-containing polyester resin of end carboxyl extra-weather-proof used for powder coating of high glaze, impact property has suitable glass transition temperature
Degree and storage stability, the powdery paints being made possess excellent mechanical performance and weatherability.
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 to invent description rather than limitation, be such as not limited to end carboxyl of the present invention and contain
The four step rule of fluorine polyester resin prepares scheme.Scheme is prepared using three-step approach, i.e., prepares fluorine-containing epoxy first, then will be polynary
Carry out esterification condensation reaction after alcohol, aromatic polycarboxylic acid, branching agent, acidolysis agent and esterification catalyst are well mixed and prepare intermediate gathering
Ester resin, finally reacts intermediate polyester resin and fluoro epoxide, also can be to obtain end carboxylic of the present invention
The fluorine-containing polyester resin of base.Therefore it is every according to substantial technological of the invention to any trickle amendment made for any of the above embodiments, etc.
Same modifications, belong in the range of technical solution of the present invention.
Claims (10)
1. a kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating, it is characterised in that the extra-weather-proof powder is applied
Material includes the raw material of following percentage by weight with the fluorine-containing polyester resin of end carboxyl：
Polyalcohol 28-40wt%, aromatic polycarboxylic acid 40-55wt%, branching agent 0.05-2wt%, acidolysis agent 5-15wt%, esterification
Catalyst 0.03-0.15wt%, epoxychloropropane 0.1-4%, fluorine-containing alcohol 1-8% and NaOH 0.1-2%.
2. the extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating according to claim 1, it is characterised in that described
Fluorine-containing alcohol is complete using tetrafluoropropanol, octafluoropentanol, ten difluoro enanthol, 2- perfluorobutylethyl alcohols, 2- perfluoro hexyls ethyl alcohol, 2-
One kind or several mixtures in fluorine octyl group ethyl alcohol or 2- perfluor certain herbaceous plants with big flowers base ethyl alcohols.
3. the extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating according to claim 1 and 2, it is characterised in that
Described polyalcohol uses neopentyl glycol NPG, 2- methyl isophthalic acid, 3 propane diols MPD, methyl butyl propane diols BEPD, Isosorbide-5-Nitrae hexamethylene
One kind or several various mixtures in dimethanol CHDM or ethylene glycol EG.
4. the extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating according to claim 1 and 2, it is characterised in that
The branching agent is using the one or two kinds of mixing in trimethylolpropane TMP and trimethylolethane TME.
5. the extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating according to claim 1 and 2, it is characterised in that
The aromatic polycarboxylic acid is using the one kind in terephthalic acid (TPA) PTA and M-phthalic acid IPA or two kinds.
6. the extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating according to claim 1 and 2, it is characterised in that
The acidolysis agent uses M-phthalic acid IPA, adipic acid ADA, Isosorbide-5-Nitrae cyclohexane cyclohexanedimethanodibasic CHDA, trimellitic anhydride TMA and Fu Ma
One kind or various mixing in sour FCC；The esterification catalyst uses organic tin or titanium class catalyst.
7. the preparation side of the extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating described in a kind of any one of claim 1-6
Method, it is characterised in that the preparation method includes following by step：
1) during the fluorine-containing alcohol of formula ratio, NaOH and epoxychloropropane, put into reactor, after reaction, then vacuum distillation, system
Obtain fluoro epoxide；
2), the polyalcohol of formula ratio, aromatic polycarboxylic acid and branching agent are placed in another reactor, esterification catalyst is added,
Carry out esterifying polycondensation reaction；
3) to step 2) prepared by system in add acidolysis agent carry out polycondensation and end-blocking, then vacuum is polycondensed into polyester resin
Mesosome；
4) in fluoro epoxide being put into polyester resin intermediate, extra-weather-proof end carboxyl used for powder coating is prepared
Fluorine-containing polyester resin.
8. the preparation method of the extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating according to claim 7, it is special
Levy and be, step 2) in esterifying polycondensation reaction condition be：System is warming up to 230-255 DEG C and maintains in blanket of nitrogen, treats system
Detection acid number AV is sampled after clarification and reaches 5-15mgKOH/g resins, that is, stopped.
9. the preparation method of the extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating according to claim 7 or 8, its
It is characterised by, step 3) it is specially：Add acidolysis agent and control the temperature polycondensation and end-blocking are carried out at 230-250 DEG C, treat polyester
Acid number 225-240 DEG C and vacuum polycondensation 1-3h is cooled to when reaching 40-60mgKOH/g resins so that the acid number of polyester is maintained
In 25-38mgKOH/g resins, polyester resin intermediate is prepared.
10. the preparation method of the extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating according to claim 7 or 8,
Characterized in that, step 4) it is specially：At 200-240 DEG C, by fluoro epoxide input polyester resin intermediate, tie up
Reaction 0.5-2h is held, blowing obtains final product the extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating afterwards.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611082633.7A CN106750222A (en) | 2016-11-30 | 2016-11-30 | A kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611082633.7A CN106750222A (en) | 2016-11-30 | 2016-11-30 | A kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106750222A true CN106750222A (en) | 2017-05-31 |
Family
ID=58901492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611082633.7A Pending CN106750222A (en) | 2016-11-30 | 2016-11-30 | A kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106750222A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047900A (en) * | 2017-12-29 | 2018-05-18 | 安徽鑫发铝业有限公司 | A kind of preparation method of weatherability aluminium alloy transfer printing wood grain section bar |
| CN110804164A (en) * | 2019-11-26 | 2020-02-18 | 黄山市徽州康佳化工有限责任公司 | Polyester resin with excellent boiling resistance and salt fog resistance for low-temperature curing type powder and preparation method thereof |
| CN111100279A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Fluorine-containing copolyester for powder coating and preparation method thereof |
| CN111944137A (en) * | 2020-08-25 | 2020-11-17 | 黄山嘉恒科技有限公司 | Epoxidized polyester resin for weather-resistant high-impact powder coating and preparation method thereof |
| CN114106304A (en) * | 2021-12-23 | 2022-03-01 | 安徽神剑新材料股份有限公司 | Low-temperature curing weather-resistant polyester resin, low-temperature curing weather-resistant powder coating and preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199280A (en) * | 2011-04-08 | 2011-09-28 | 浙江大学 | Fluoro-polyester resin and preparation method and application thereof |
| CN102408550A (en) * | 2011-11-14 | 2012-04-11 | 广州擎天实业有限公司 | Carboxyl-terminated polyester resin for super weather-proof powder coating and preparation method thereof |
| CN105062330A (en) * | 2015-07-22 | 2015-11-18 | 安徽圣德建材科技有限公司 | High-performance thermosetting polyester powder coating |
-
2016
- 2016-11-30 CN CN201611082633.7A patent/CN106750222A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199280A (en) * | 2011-04-08 | 2011-09-28 | 浙江大学 | Fluoro-polyester resin and preparation method and application thereof |
| CN102408550A (en) * | 2011-11-14 | 2012-04-11 | 广州擎天实业有限公司 | Carboxyl-terminated polyester resin for super weather-proof powder coating and preparation method thereof |
| CN105062330A (en) * | 2015-07-22 | 2015-11-18 | 安徽圣德建材科技有限公司 | High-performance thermosetting polyester powder coating |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047900A (en) * | 2017-12-29 | 2018-05-18 | 安徽鑫发铝业有限公司 | A kind of preparation method of weatherability aluminium alloy transfer printing wood grain section bar |
| CN111100279A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Fluorine-containing copolyester for powder coating and preparation method thereof |
| CN110804164A (en) * | 2019-11-26 | 2020-02-18 | 黄山市徽州康佳化工有限责任公司 | Polyester resin with excellent boiling resistance and salt fog resistance for low-temperature curing type powder and preparation method thereof |
| CN111944137A (en) * | 2020-08-25 | 2020-11-17 | 黄山嘉恒科技有限公司 | Epoxidized polyester resin for weather-resistant high-impact powder coating and preparation method thereof |
| CN111944137B (en) * | 2020-08-25 | 2022-08-19 | 黄山嘉恒科技有限公司 | Epoxidized polyester resin for weather-resistant high-impact-resistance powder coating and preparation method thereof |
| CN114106304A (en) * | 2021-12-23 | 2022-03-01 | 安徽神剑新材料股份有限公司 | Low-temperature curing weather-resistant polyester resin, low-temperature curing weather-resistant powder coating and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106750222A (en) | A kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating and preparation method thereof | |
| CN106752940B (en) | A kind of high glaze, impact resistance and extra-weather-proof fluorine-containing polyester resin of powdery paints carboxyl end group and preparation method thereof | |
| CN102127212B (en) | Terminal carboxyl group polyester resin for weather-resistance high-gloss powder coating and preparation method thereof | |
| CN103131308B (en) | A kind of be superly weather-proofly dry mixed extinction powder coating just acid number bicomponent terminal carboxyl polyester resin composition and application thereof | |
| CN102408550A (en) | Carboxyl-terminated polyester resin for super weather-proof powder coating and preparation method thereof | |
| CN101735432B (en) | Low-temperature cured terminal carboxyl polyester resin for mixed powder coating and preparation method thereof | |
| CN101735431B (en) | Weather resistant polyester resin with excellent water-boiling resisting performance and method for preparing same | |
| CN102010501B (en) | Polyester resin for beta-hydroxyalkylamide low temperature curing weather-resistant powder paint and preparation method thereof | |
| EP3835379A1 (en) | Polyester resin composition, powder coating and workpiece | |
| KR100592607B1 (en) | Powder thermosetting compositions for preparing coatings with low gloss finish | |
| US5439988A (en) | Carboxyl-terminated polyesters for the preparation of powder coating compositions | |
| CN109280468B (en) | Organic silicon modified polyester resin for super-weather-resistant powder coating and preparation method thereof | |
| CN103739830B (en) | Polyester resin for TGIC cured high-toughness powder coating and preparation method thereof | |
| KR101729798B1 (en) | Low temperature cure powder coating compositions | |
| CN101205293A (en) | Mixed polyester resin for matte powder coatings and preparation thereof | |
| WO2021031377A1 (en) | Polyester resin used for graphene-containing powder coating | |
| CN102443148A (en) | Polyester resin for rapid curing of weather-durable powdery paint by beta-hydroxyalkylamide and preparation method thereof | |
| CN103483565B (en) | A kind of TGIC solidifies high levelling semi-crystalline polyester resin used for powder coating and synthetic method thereof | |
| CN107868235A (en) | A kind of powdery paints difunctional polyester resin and preparation method thereof | |
| CN101445591A (en) | Polyester resin with high acid value and low acid value for environment-friendly dry blended low-gloss powder coating and preparation method thereof | |
| RU2436809C2 (en) | Powder coating and its application | |
| WO2021016731A1 (en) | Polyester resin and preparation method therefor, coating, and workpiece | |
| CN107603427A (en) | A kind of PEN modified epoxies polyester mixed type powder paint polyester resin and preparation method thereof | |
| CN103755932A (en) | Preparation method of crystalline polyester resin and application of crystalline polyester resin to powder coating | |
| CN104356370A (en) | Terminal polyester resin for high filler filling quantity mixed type powder coating and preparation method of terminal polyester resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170531 |
|
| RJ01 | Rejection of invention patent application after publication |