CN106244000A - Heat Resistant Powder Coatings polyester and preparation method thereof - Google Patents
Heat Resistant Powder Coatings polyester and preparation method thereof Download PDFInfo
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- CN106244000A CN106244000A CN201610625455.1A CN201610625455A CN106244000A CN 106244000 A CN106244000 A CN 106244000A CN 201610625455 A CN201610625455 A CN 201610625455A CN 106244000 A CN106244000 A CN 106244000A
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- polyester
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- heat resistant
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- 229920000728 polyester Polymers 0.000 title claims abstract description 61
- 238000000576 coating method Methods 0.000 title claims abstract description 45
- 239000000843 powder Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 22
- 239000010703 silicon Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims description 31
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 16
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 9
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 9
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 9
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 8
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 239000005054 phenyltrichlorosilane Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 238000012423 maintenance Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 239000005046 Chlorosilane Substances 0.000 claims 1
- -1 benzenetricarboxylic anhydride Chemical class 0.000 claims 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims 1
- 239000006193 liquid solution Substances 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 8
- 229920001225 polyester resin Polymers 0.000 description 8
- 239000004645 polyester resin Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002454 metastable transfer emission spectrometry Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a kind of Heat Resistant Powder Coatings polyester and preparation method thereof, comprise the following steps: A) prepare intermediate polyester solution；B) silicon midbody solution is prepared；C) described intermediate polyester solution reacts with described silicon midbody solution and obtains Heat Resistant Powder Coatings polyester.The Heat Resistant Powder Coatings polyester of the present invention can reach the temperature tolerance requirement of more than 300 DEG C；Adhesive force and the glossiness of baking 1h and 3h all changes without obvious at such a temperature, is better than prior art at equal conditions.
Description
Technical field
The invention belongs to high molecular polymer field；Relate to a kind of polyester resin and preparation method thereof, be specifically related to one
Plant Heat Resistant Powder Coatings polyester and preparation method thereof.
Background technology
Powdery paints is one of coating variety most with prospects in the range of the world today, belongs to one and develops rapidly
Coating branch.Compared with traditional solvent-borne coating, there is the saving energy and resource, minimizing environmental pollution, simple process, coating heavily fortified point
Gu the features such as durable, powder recoverable, application are extensive.Conventional powder coatings mainly include film forming matter, firming agent,
Levelling agent and pigment etc..Wherein, modal film forming matter is polyester resin.
The temperature tolerance of existing powdery paints generally only 200 DEG C, it is difficult to reach the temperature tolerance requirement of more than 300 DEG C.At height
Under temperature, there is the breakoff phenomenon such as loss of gloss, loss of adhesion, coating is brittle, the obvious xanthochromia of film, reduction of pliability, efflorescence in coating,
Coating is made to lose the protective effect to ground.It has been investigated that, determine that the durothermic key factor of powdery paints is film forming
The material i.e. temperature tolerance of polyester resin.Therefore, people are devoted to polyester to be carried out physical modification and chemical modification and enters one always
Step improves the durothermic research of powdery paints.
But, for physical modification, most prior aries use organic siliconresin blending polyester resin to make powder and are coated with
Material, temperature tolerance can improve to 500 DEG C, but polyester resin viscosity is higher, poor with inorganic color stuffing and organic siliconresin compatibility,
Coating levelling is poor, it is impossible to meet higher cosmetic requirement.Therefore, for disadvantages mentioned above, people begin one's study by chemistry
Modified method improves the temperature tolerance of polyester resin, i.e. reasonable selection polyester resin and silica modifier, in conjunction with specific production technology,
Obtain Heat Resistant Powder Coatings polyester.But existing silicon-modified polyester resin there is also various shortcoming, no in preparation and application
Above-mentioned application request can be met；Its adhesive force and glossiness are unsatisfactory simultaneously.
For disadvantages mentioned above, in the urgent need to finding a kind of Heat Resistant Powder Coatings that disclosure satisfy that above-mentioned application request
With polyester and preparation method thereof.
Summary of the invention
Inventor finds, uses specific silicon intermediate and intermediate polyester, carries out chemistry under specific process conditions
Modification, can be met the Heat Resistant Powder Coatings polyester of above-mentioned application request.
One of the object of the invention is to overcome the deficiencies in the prior art, it is provided that a kind of temperature tolerance is good, adhesive force is high, glossiness good
Heat Resistant Powder Coatings polyester.
The two of the object of the invention are to provide a kind of method preparing above-mentioned Heat Resistant Powder Coatings polyester.Method is simple,
Easily operated, equipment cost is low and pollution-free.
For achieving the above object, on the one hand, the invention provides the preparation method of a kind of Heat Resistant Powder Coatings polyester,
The method comprises the following steps: A) prepare intermediate polyester solution；B) silicon midbody solution is prepared；C) described intermediate polyester is molten
Liquid reacts with described silicon midbody solution and obtains Heat Resistant Powder Coatings polyester.
Step A) farther include following steps:
1) in reaction vessel, p-phthalic acid, M-phthalic acid, trimellitic anhydride, neopentyl glycol and metatitanic acid four isopropyl are added
Ester, its parts by weight are respectively 14-18 part, 6-9 part, 2-5 part, 10-15 part and 0.1 part, are simultaneously introduced dimethylbenzene as solvent；
2) being heated to 170 DEG C makes material all melt, and is subsequently adding 0.3 portion of triphenyl phosphite, is to slowly warm up to 220 DEG C, rises
Temperature speed is 10-20 DEG C/h；
3) after temperature is higher than 220 DEG C, the temperature of control reactant mixture is between 220-240 DEG C, and the response time is 3-12h；
4) it is cooled to 180 DEG C, adds 0.5-2.5 part trimethylolpropane, be to slowly warm up to 220 DEG C and continue reaction so that it is acid number
Less than 10mgKOH/g；It is subsequently added dimethylbenzene and is made into the intermediate polyester solution that solid content is 50-70%.
Step B) farther include following steps:
5) in another reaction vessel, VTES, phenyl trichlorosilane and diphenyl dichlorosilane are added, its
Parts by weight are respectively 2.5-3.5 part, 0.5-1 part and 0.5-1 part, are simultaneously introduced the toluene of volume ratio 3:1 and acetone as molten
Agent；
6) dropping distilled water is hydrolyzed reaction, and maintenance temperature is at 60 DEG C；Standing separation, obtains organic layer, is washed to neutrality, subtracts
Pressure is distilled off toluene, and reduce pressure at 160 DEG C condensation reaction 2-4h, obtains silicon midbody solution.
Step C) farther include following steps:
7) in reaction vessel add step 4) intermediate polyester solution, step 6) silicon midbody solution, phosphorous acid triphen
Ester and tetraisopropyl titanate, its parts by weight are respectively 40-50 part, 12-16 part, 0.3 part and 0.1 part, are simultaneously introduced dimethylbenzene
As solvent；
8) being to slowly warm up to 220 DEG C, heating rate is 10-20 DEG C/h, insulation reaction 4-8h, after separating solvent, obtains high temperature resistant
Polyester used for powder coating.
In step A) in, p-phthalic acid, M-phthalic acid, trimellitic anhydride, neopentyl glycol and trimethylolpropane
Parts by weight are respectively 14-18 part, 6-9 part, 2-5 part, 10-15 part and 0.5-2.5 part.Preferably, p-phthalic acid, isophthalic two
The parts by weight of formic acid, trimellitic anhydride, neopentyl glycol and trimethylolpropane are respectively 15-17 part, 7-8 part, 3-4 part, 11-
14 parts and 1-2 part.Most preferably, p-phthalic acid, M-phthalic acid, trimellitic anhydride, neopentyl glycol and trimethylolpropane
Parts by weight be respectively 16 parts, 7.5 parts, 3.5 parts, 12 parts and 1.5 parts.
In step A) in, the solid content of intermediate polyester solution is 50-70%.Preferably, the consolidating of intermediate polyester solution
Content is 55-65%.Most preferably, the solid content of intermediate polyester solution is 60%.
In step B) in, the parts by weight of VTES, phenyl trichlorosilane and diphenyl dichlorosilane
It is respectively 2.5-3.5 part, 0.5-1 part and 0.5-1 part.Preferably, VTES, phenyl trichlorosilane and hexichol
The parts by weight of base dichlorosilane are respectively 2.8-3.2 part, 0.7-0.9 part and 0.6-0.8 part.Most preferably, vinyl three second
The parts by weight of TMOS, phenyl trichlorosilane and diphenyl dichlorosilane are respectively 3.0 parts, 0.8 part and 0.7 part.
In step C) in, step 4) intermediate polyester solution and step 6) silicon midbody solution parts by weight respectively
For 40-50 part and 12-16 part.Preferably, step 4) intermediate polyester solution and step 6) the weight of silicon midbody solution
Number is respectively 42-48 part and 13-15 part.Most preferably, step 4) intermediate polyester solution and step 6) silicon intermediate
The parts by weight of solution are respectively 45 parts and 14 parts.
On the other hand, the invention provides a kind of resistance to height obtained by above-mentioned Heat Resistant Powder Coatings preparation process of polyester
Temperature polyester used for powder coating.
Inventor finds, with specific silicon intermediate and intermediate polyester, carries out chemistry and change under specific process conditions
Property, the Heat Resistant Powder Coatings polyester of above-mentioned application request can be met.
Compared with prior art, the present invention has a following advantage:
1) the Heat Resistant Powder Coatings polyester of the present invention can reach the temperature tolerance requirement of more than 300 DEG C；Simultaneously adhesive force and
Glossiness is better than prior art at equal conditions；
2) the Heat Resistant Powder Coatings preparation process of polyester of the present invention is simple, easily operated, equipment cost is low and pollution-free；Can
It has a tremendous social and economic benefits, be suitable for popularity and use.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate this
Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read present disclosure, those skilled in the art
Can make various changes or modifications the present invention, these equivalent form of values fall within what the application appended claims was limited equally
Scope.
Embodiment 1:
Preparing the Heat Resistant Powder Coatings polyester of the present invention in following manner, the method comprises the following steps: 1)
Reaction vessel adds p-phthalic acid, M-phthalic acid, trimellitic anhydride, neopentyl glycol and tetraisopropyl titanate, its weight
Number is respectively 15 parts, 7 parts, 3 parts, 11 parts and 0.1 part, is simultaneously introduced dimethylbenzene as solvent；
2) being heated to 170 DEG C makes material all melt, and is subsequently adding 0.3 portion of triphenyl phosphite, is to slowly warm up to 220 DEG C, rises
Temperature speed is 10-20 DEG C/h；
3) after temperature is higher than 220 DEG C, the temperature of control reactant mixture is between 220-240 DEG C, and the response time is 3-12h；
4) it is cooled to 180 DEG C, adds 1 part of trimethylolpropane, be to slowly warm up to 220 DEG C and continue reaction so that it is acid number is less than
10mgKOH/g；It is subsequently added dimethylbenzene and is made into the intermediate polyester solution that solid content is 50%；
5) in another reaction vessel, VTES, phenyl trichlorosilane and diphenyl dichlorosilane are added, its
Parts by weight are respectively 2.8 parts, 0.7 part and 0.6 part, are simultaneously introduced the toluene of volume ratio 3:1 and acetone as solvent；
6) dropping distilled water is hydrolyzed reaction, and maintenance temperature is at 60 DEG C；Standing separation, obtains organic layer, is washed to neutrality, subtracts
Pressure is distilled off toluene, and reduce pressure at 160 DEG C condensation reaction 2-4h, obtains silicon midbody solution；
7) in reaction vessel add step 4) intermediate polyester solution, step 6) silicon midbody solution, phosphorous acid triphen
Ester and tetraisopropyl titanate, its parts by weight are respectively 42 parts, 13 parts, 0.3 part and 0.1 part, are simultaneously introduced dimethylbenzene as molten
Agent；
8) being to slowly warm up to 220 DEG C, heating rate is 10-20 DEG C/h, insulation reaction 4-8h, after separating solvent, obtains embodiment 1
Heat Resistant Powder Coatings polyester.
Embodiment 2:
Preparing the Heat Resistant Powder Coatings polyester of the present invention in following manner, the method comprises the following steps: 1)
Reaction vessel adds p-phthalic acid, M-phthalic acid, trimellitic anhydride, neopentyl glycol and tetraisopropyl titanate, its weight
Number is respectively 16 parts, 7.5 parts, 3.5 parts, 12 parts and 0.1 part, is simultaneously introduced dimethylbenzene as solvent；
2) being heated to 170 DEG C makes material all melt, and is subsequently adding 0.3 portion of triphenyl phosphite, is to slowly warm up to 220 DEG C, rises
Temperature speed is 10-20 DEG C/h；
3) after temperature is higher than 220 DEG C, the temperature of control reactant mixture is between 220-240 DEG C, and the response time is 3-12h；
4) it is cooled to 180 DEG C, adds 1.5 parts of trimethylolpropanes, be to slowly warm up to 220 DEG C and continue reaction so that it is acid number is less than
10mgKOH/g；It is subsequently added dimethylbenzene and is made into the intermediate polyester solution that solid content is 70%；
5) in another reaction vessel, VTES, phenyl trichlorosilane and diphenyl dichlorosilane are added, its
Parts by weight are respectively 3.2 parts, 0.9 part and 0.8 part, are simultaneously introduced the toluene of volume ratio 3:1 and acetone as solvent；
6) dropping distilled water is hydrolyzed reaction, and maintenance temperature is at 60 DEG C；Standing separation, obtains organic layer, is washed to neutrality, subtracts
Pressure is distilled off toluene, and reduce pressure at 160 DEG C condensation reaction 2-4h, obtains silicon midbody solution；
7) in reaction vessel add step 4) intermediate polyester solution, step 6) silicon midbody solution, phosphorous acid triphen
Ester and tetraisopropyl titanate, its parts by weight are respectively 48 parts, 15 parts, 0.3 part and 0.1 part, are simultaneously introduced dimethylbenzene as molten
Agent；
8) being to slowly warm up to 220 DEG C, heating rate is 10-20 DEG C/h, insulation reaction 4-8h, after separating solvent, obtains embodiment 2
Heat Resistant Powder Coatings polyester.
Embodiment 3:
Preparing the Heat Resistant Powder Coatings polyester of the present invention in following manner, the method comprises the following steps: 1)
Reaction vessel adds p-phthalic acid, M-phthalic acid, trimellitic anhydride, neopentyl glycol and tetraisopropyl titanate, its weight
Number is respectively 17 parts, 8 parts, 4 parts, 14 parts and 0.1 part, is simultaneously introduced dimethylbenzene as solvent；
2) being heated to 170 DEG C makes material all melt, and is subsequently adding 0.3 portion of triphenyl phosphite, is to slowly warm up to 220 DEG C, rises
Temperature speed is 10-20 DEG C/h；
3) after temperature is higher than 220 DEG C, the temperature of control reactant mixture is between 220-240 DEG C, and the response time is 3-12h；
4) it is cooled to 180 DEG C, adds 2 parts of trimethylolpropanes, be to slowly warm up to 220 DEG C and continue reaction so that it is acid number is less than
10mgKOH/g；It is subsequently added dimethylbenzene and is made into the intermediate polyester solution that solid content is 60%；
5) in another reaction vessel, VTES, phenyl trichlorosilane and diphenyl dichlorosilane are added, its
Parts by weight are respectively 3.0 parts, 0.8 part and 0.7 part, are simultaneously introduced the toluene of volume ratio 3:1 and acetone as solvent；
6) dropping distilled water is hydrolyzed reaction, and maintenance temperature is at 60 DEG C；Standing separation, obtains organic layer, is washed to neutrality, subtracts
Pressure is distilled off toluene, and reduce pressure at 160 DEG C condensation reaction 2-4h, obtains silicon midbody solution；
7) in reaction vessel add step 4) intermediate polyester solution, step 6) silicon midbody solution, phosphorous acid triphen
Ester and tetraisopropyl titanate, its parts by weight are respectively 45 parts, 14 parts, 0.3 part and 0.1 part, are simultaneously introduced dimethylbenzene as molten
Agent；
8) being to slowly warm up to 220 DEG C, heating rate is 10-20 DEG C/h, insulation reaction 4-8h, after separating solvent, obtains embodiment 3
Heat Resistant Powder Coatings polyester.
Comparative example 1:
Using the trimellitic anhydride of the adipic acid alternate embodiment 3 of 4.6 parts, remaining condition, with embodiment 3, obtains comparative example
The Heat Resistant Powder Coatings polyester of 1.
Comparative example 2:
Using the MTES of the adipic acid alternate embodiment 3 of 2.8 parts, remaining condition, with embodiment 3, obtains
The Heat Resistant Powder Coatings polyester of comparative example 2.
Respectively according to concerned countries standard GB/T9286-1998 and GB/T1735-1979 testing example 1-3 and comparative example
The Heat Resistant Powder Coatings of 1-2 polyester film toasts adhesive force and the glossiness of 1h and 3h at 300 DEG C, and record is in Table 1.
Table 1 embodiment 1-3 and the technical specification of comparative example 1-2 Heat Resistant Powder Coatings polyester
As it can be seen from table 1 compared with comparative example 1-2, the Heat Resistant Powder Coatings polyester of embodiment of the present invention 1-3 can
To reach the temperature tolerance requirement of more than 300 DEG C；Adhesive force and the glossiness of baking 1h and 3h all changes without obvious at such a temperature,
It is better than comparative example 1-2 at equal conditions.As can be seen here, the Heat Resistant Powder Coatings polyester of embodiment of the present invention 1-3 is more applicable
In preparing Heat Resistant Powder Coatings.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, that is made any repaiies
Change, equivalent, improvement etc., within being all contained in protection scope of the present invention.
Claims (9)
1. a preparation method for Heat Resistant Powder Coatings polyester, the method comprises the following steps:
A) intermediate polyester solution is prepared；B) silicon midbody solution is prepared；C) in the middle of described intermediate polyester solution and described silicon
Liquid solution reaction obtains Heat Resistant Powder Coatings polyester.
Preparation method the most according to claim 1, wherein, described step A) farther include following steps:
1) in reaction vessel, p-phthalic acid, M-phthalic acid, trimellitic anhydride, neopentyl glycol and metatitanic acid four isopropyl are added
Ester, its parts by weight are respectively 14-18 part, 6-9 part, 2-5 part, 10-15 part and 0.1 part, are simultaneously introduced dimethylbenzene as solvent；
2) being heated to 170 DEG C makes material all melt, and is subsequently adding 0.3 portion of triphenyl phosphite, is to slowly warm up to 220 DEG C, rises
Temperature speed is 10-20 DEG C/h；
3) after temperature is higher than 220 DEG C, the temperature of control reactant mixture is between 220-240 DEG C, and the response time is 3-12h；
4) it is cooled to 180 DEG C, adds 0.5-2.5 part trimethylolpropane, be to slowly warm up to 220 DEG C and continue reaction so that it is acid number
Less than 10mgKOH/g；It is subsequently added dimethylbenzene and is made into the intermediate polyester solution that solid content is 50-70%.
Preparation method the most according to claim 2, wherein, described step A) in, p-phthalic acid, M-phthalic acid, partially
The parts by weight of benzenetricarboxylic anhydride, neopentyl glycol and trimethylolpropane are respectively 16 parts, 7.5 parts, 3.5 parts, 12 parts and 1.5 parts.
Preparation method the most according to claim 2, wherein, described step A) in, the solid content of intermediate polyester solution is
60%.
Preparation method the most according to claim 1, wherein, described step B) farther include following steps: 5) at another
Adding VTES, phenyl trichlorosilane and diphenyl dichlorosilane in reaction vessel, its parts by weight are respectively
For 2.5-3.5 part, 0.5-1 part and 0.5-1 part, it is simultaneously introduced the toluene of volume ratio 3:1 and acetone as solvent；
6) dropping distilled water is hydrolyzed reaction, and maintenance temperature is at 60 DEG C；Standing separation, obtains organic layer, is washed to neutrality, subtracts
Pressure is distilled off toluene, and reduce pressure at 160 DEG C condensation reaction 2-4h, obtains silicon midbody solution.
Preparation method the most according to claim 5, wherein, described step B) in, VTES, phenyl three
The parts by weight of chlorosilane and diphenyl dichlorosilane are respectively 3.0 parts, 0.8 part and 0.7 part.
Preparation method the most according to claim 1, wherein, described step C) farther include following steps:
7) in reaction vessel add step 4) intermediate polyester solution, step 6) silicon midbody solution, phosphorous acid triphen
Ester and tetraisopropyl titanate, its parts by weight are respectively 40-50 part, 12-16 part, 0.3 part and 0.1 part, are simultaneously introduced dimethylbenzene
As solvent；
8) being to slowly warm up to 220 DEG C, heating rate is 10-20 DEG C/h, insulation reaction 4-8h, after separating solvent, obtains high temperature resistant
Polyester used for powder coating.
Preparation method the most according to claim 7, wherein, described step C) in, step 4) intermediate polyester solution and
Step 6) the parts by weight of silicon midbody solution be respectively 45 parts and 14 parts.
9. a Heat Resistant Powder Coatings polyester, it is characterised in that use the method system described in any one of claim 1-8
Standby.
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| CN107254050A (en) * | 2017-06-16 | 2017-10-17 | 江苏三木化工股份有限公司 | Solid polyester modified silicone resin for Heat Resistant Powder Coatings and preparation method thereof |
| CN108409952A (en) * | 2018-03-19 | 2018-08-17 | 江苏大力士投资有限公司 | A kind of silane-modified unsaturated polyester resin and preparation method thereof |
| CN109306232A (en) * | 2018-09-03 | 2019-02-05 | 浙江光华科技股份有限公司 | A kind of effective powder coating polyester resin of automobile exhausting and preparation method thereof |
| CN109988491A (en) * | 2018-11-30 | 2019-07-09 | 安徽神剑新材料股份有限公司 | A kind of Heat Resistant Powder Coatings Silicon-containing Polyester resin |
| CN111234192A (en) * | 2020-03-26 | 2020-06-05 | 山东福司特新材料科技有限公司 | Preparation method of organic silicon modified saturated polyester resin with high weather resistance |
| CN113683941A (en) * | 2021-09-18 | 2021-11-23 | 航佳彩新材料(广东)有限公司 | Open fire-resistant high-temperature powder coating special for fireplace and preparation method thereof |
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| CN113683941A (en) * | 2021-09-18 | 2021-11-23 | 航佳彩新材料(广东)有限公司 | Open fire-resistant high-temperature powder coating special for fireplace and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN106244000B (en) | 2018-05-29 |
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Denomination of invention: High-temperature-resistant polyester for powder coating and preparation method of high-temperature-resistant polyester Effective date of registration: 20191227 Granted publication date: 20180529 Pledgee: China Postal Savings Bank Limited by Share Ltd. Shexian branch Pledgor: HUANGSHAN ZHENGJIE NEW MATERIALS Co.,Ltd. Registration number: Y2019980001356 |
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Denomination of invention: Polyester for high temperature resistant powder coatings and its preparation Effective date of registration: 20201026 Granted publication date: 20180529 Pledgee: China Postal Savings Bank Limited by Share Ltd. Shexian branch Pledgor: HUANGSHAN ZHENGJIE NEW MATERIALS Co.,Ltd. Registration number: Y2020990001254 |
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Denomination of invention: Polyester for high temperature resistant powder coating and its preparation method Effective date of registration: 20221101 Granted publication date: 20180529 Pledgee: China Co. truction Bank Corp Shexian branch Pledgor: HUANGSHAN ZHENGJIE NEW MATERIALS Co.,Ltd. Registration number: Y2022980020424 |
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