CN106244000B - Heat Resistant Powder Coatings polyester and preparation method thereof - Google Patents
Heat Resistant Powder Coatings polyester and preparation method thereof Download PDFInfo
- Publication number
- CN106244000B CN106244000B CN201610625455.1A CN201610625455A CN106244000B CN 106244000 B CN106244000 B CN 106244000B CN 201610625455 A CN201610625455 A CN 201610625455A CN 106244000 B CN106244000 B CN 106244000B
- Authority
- CN
- China
- Prior art keywords
- parts
- polyester
- solution
- reaction
- heat resistant
- 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.)
- Active
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 61
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 239000000843 powder Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 19
- 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
- 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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 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
- 239000007787 solid Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- -1 benzenetricarboxylic anhydride Chemical class 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 150000002148 esters Chemical class 0.000 claims 2
- 239000005046 Chlorosilane Substances 0.000 claims 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims 1
- 239000005052 trichlorosilane Substances 0.000 claims 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229920001225 polyester resin Polymers 0.000 description 8
- 239000004645 polyester resin Substances 0.000 description 8
- 239000005054 phenyltrichlorosilane Substances 0.000 description 7
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 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 description 4
- PTVDYMGQGCNETM-UHFFFAOYSA-N trityl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OC(=O)C(=C)C)C1=CC=CC=C1 PTVDYMGQGCNETM-UHFFFAOYSA-N 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
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 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
- 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
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000010410 dusting 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
- 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
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 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
Abstract
The invention discloses a kind of Heat Resistant Powder Coatings polyester and preparation method thereof, comprise the following steps：A intermediate polyester solution) is prepared；B silicon midbody solution) is prepared；C) Heat Resistant Powder Coatings polyester is obtained by the reaction with the silicon midbody solution in the intermediate polyester solution.The Heat Resistant Powder Coatings polyester of the present invention can reach 300 DEG C or more of temperature tolerance requirement；The adhesive force and glossiness nothing for toasting 1h and 3h at such a temperature are substantially change, and are better than the prior art in equal conditions.
Description
Technical field
The invention belongs to high molecular polymer fields；It is related to a kind of polyester resin and preparation method thereof, and in particular to one
Kind 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, belong to one rapid development
Coating branch.Compared with traditional solvent-borne coating, have save the energy and resource, reduce environmental pollution, simple process, coating it is hard
Gu durable, powder recoverable, the features such as application field is extensive.Conventional powder coatings mainly include film forming matter, curing agent,
Levelling agent and pigment etc..Wherein, most common film forming matter is polyester resin.
Usually only 200 DEG C of the temperature tolerance of existing powdery paints, it is difficult to reach 300 DEG C or more of temperature tolerance requirement.In height
Under temperature, there are the breakoff phenomenons such as loss of gloss, adhesive force decline, coating embrittlement, the apparent xanthochromia of film, reduction of pliability, dusting in coating,
So that coating loses the protective effect to ground.It has been investigated that determine that the durothermic key factor of powdery paints is to form a film
The temperature tolerance of substance, that is, polyester resin.Therefore, people have been devoted to carry out polyester physical modification and chemical modification and into one
Step improves the durothermic research of powdery paints.
However, for physical modification, most prior arts are made powder using organic siliconresin blending polyester resin and are applied
Material, temperature tolerance can be improved to 500 DEG C, but polyester resin viscosity is higher, poor with inorganic color stuffing and organic siliconresin compatibility,
Coating levelling is poor, can not meet higher cosmetic requirement.Therefore, for disadvantages mentioned above, people, which begin one's study, passes through chemistry
Modified method improves the temperature tolerance of polyester resin, i.e. reasonable selection polyester resin and silica modifier, with reference to specific production technology,
Obtain Heat Resistant Powder Coatings polyester.But existing silicon-modified polyester resin in preparation and application also there are various shortcoming, no
Above-mentioned application request can be met；Its adhesive force and glossiness are unsatisfactory simultaneously.
For disadvantages mentioned above, there is an urgent need to find a kind of Heat Resistant Powder Coatings that disclosure satisfy that above-mentioned application request
With polyester and preparation method thereof.
The content of the invention
Inventor has found, using specific silicon intermediate and intermediate polyester, chemistry is carried out under specific process conditions
It is modified, the Heat Resistant Powder Coatings polyester for meeting above-mentioned application request can be obtained.
One of the object of the invention is to overcome the deficiencies of the prior art and provide that a kind of temperature tolerance is good, adhesive force is high, glossiness is good
Heat Resistant Powder Coatings polyester.
The two of the object of the invention are to provide a kind of method for preparing above-mentioned Heat Resistant Powder Coatings polyester.Method is simple,
It is easily operated, equipment cost is low and pollution-free.
To achieve the above object, on the one hand, the present invention provides a kind of preparation method of Heat Resistant Powder Coatings polyester,
This method comprises the following steps：A intermediate polyester solution) is prepared；B silicon midbody solution) is prepared；C) intermediate polyester is molten
Heat Resistant Powder Coatings polyester is obtained by the reaction with the silicon midbody solution in liquid.
Step A) further comprise following steps：
1) it is different that terephthalic acid (TPA), M-phthalic acid, trimellitic anhydride, neopentyl glycol and metatitanic acid four are added in reaction vessel
Propyl ester, parts by weight are respectively 14-18 parts, 6-9 parts, 2-5 parts, 10-15 parts and 0.1 part, while add in dimethylbenzene as molten
Agent；
2) being heated to 170 DEG C makes material all melt, and then adds in 0.3 portion of triphenyl phosphite, is to slowly warm up to 220
DEG C, heating rate is 10-20 DEG C/h；
3) after temperature is higher than 220 DEG C, the temperature of reaction mixture is controlled between 220-240 DEG C, reaction time 3-
12h；
4) 180 DEG C are cooled to, adds in 0.5-2.5 parts of trimethylolpropanes, being to slowly warm up to 220 DEG C, the reaction was continued, makes it
Acid value is less than 10mgKOH/g；It then adds in dimethylbenzene and is made into the intermediate polyester solution that solid content is 50-70%.
Step B) further comprise following steps：
5) vinyltriethoxysilane, phenyl trichlorosilane and diphenyl dichloro silicon are added in another reaction vessel
Alkane, parts by weight are respectively 2.5-3.5 parts, 0.5-1 parts and 0.5-1 parts, while add in volume ratio 3：1 toluene and acetone is made
For solvent；
6) distilled water is added dropwise and reaction is hydrolyzed, maintain temperature at 60 DEG C；Standing separation obtains organic layer, in being washed to
Property, it is evaporated under reduced pressure and removes toluene, condensation reaction 2-4h is depressurized at 160 DEG C, obtain silicon midbody solution.
Step C) further comprise following steps：
7) intermediate polyester solution, silicon midbody solution, the phosphorous acid of step 6) of step 4) are added in reaction vessel
Triphenylmethyl methacrylate and tetraisopropyl titanate, parts by weight are respectively 40-50 parts, 12-16 parts, 0.3 part and 0.1 part, while add in two
Toluene is as solvent；
8) 220 DEG C are to slowly warm up to, heating rate is 10-20 DEG C/h, insulation reaction 4-8h, after separating solvent, is obtained resistance to
High temperature powder coating polyester.
In step A) in, terephthalic acid (TPA), M-phthalic acid, trimellitic anhydride, neopentyl glycol and trimethylolpropane
Parts by weight are respectively 14-18 parts, 6-9 parts, 2-5 parts, 10-15 parts and 0.5-2.5 parts.Preferably, terephthalic acid (TPA), isophthalic two
Formic acid, trimellitic anhydride, the parts by weight of neopentyl glycol and trimethylolpropane are respectively 15-17 parts, 7-8 parts, 3-4 parts, 11-
14 parts and 1-2 parts.Most preferably, terephthalic acid (TPA), 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, intermediate polyester solution is consolidated
Content is 55-65%.Most preferably, the solid content of intermediate polyester solution is 60%.
In step B) in, the parts by weight of vinyltriethoxysilane, phenyl trichlorosilane and diphenyl dichlorosilane
Respectively 2.5-3.5 parts, 0.5-1 parts and 0.5-1 parts.Preferably, vinyltriethoxysilane, phenyl trichlorosilane and hexichol
The parts by weight of base dichlorosilane are respectively 2.8-3.2 parts, 0.7-0.9 parts and 0.6-0.8 parts.Most preferably, three second of vinyl
The parts by weight of oxysilane, phenyl trichlorosilane and diphenyl dichlorosilane are respectively 3.0 parts, 0.8 part and 0.7 part.
In step C) in, the parts by weight difference of the intermediate polyester solution of step 4) and the silicon midbody solution of step 6)
For 40-50 parts and 12-16 parts.Preferably, the weight of the silicon midbody solution of the intermediate polyester solution and step 6) of step 4)
Number is respectively 42-48 parts and 13-15 parts.Most preferably, the intermediate polyester solution of step 4) and the silicon intermediate of step 6)
The parts by weight of solution are respectively 45 parts and 14 parts.
On the other hand, the present invention provides a kind of resistance to height obtained by above-mentioned Heat Resistant Powder Coatings with preparation process of polyester
Warm powdery paints polyester.
Inventor has found that, with specific silicon intermediate and intermediate polyester, progress chemistry changes under specific process conditions
Property, the Heat Resistant Powder Coatings polyester for meeting above-mentioned application request can be obtained.
Compared with prior art, the present invention has following advantage：
1) Heat Resistant Powder Coatings polyester of the invention can reach 300 DEG C or more of temperature tolerance requirement；Adhere to simultaneously
Power and glossiness are better than the prior art in equal conditions；
2) Heat Resistant Powder Coatings preparation process of polyester of the invention is simple, easily operated, equipment cost is low and without dirt
Dye；It can have a tremendous social and economic benefits, popularity is suitble to use.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It is to be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after present disclosure has been read, those skilled in the art
The present invention can be made various changes or modifications, such equivalent forms equally fall within what the application the appended claims were limited
Scope.
Embodiment 1：
The Heat Resistant Powder Coatings polyester of the present invention is prepared in following manner, and this method comprises the following steps：1) exist
Terephthalic acid (TPA), M-phthalic acid, trimellitic anhydride, neopentyl glycol and tetraisopropyl titanate, weight are added in reaction vessel
Number is respectively 15 parts, 7 parts, 3 parts, 11 parts and 0.1 part, while adds in dimethylbenzene as solvent；
2) being heated to 170 DEG C makes material all melt, and then adds in 0.3 portion of triphenyl phosphite, is to slowly warm up to 220
DEG C, heating rate is 10-20 DEG C/h；
3) after temperature is higher than 220 DEG C, the temperature of reaction mixture is controlled between 220-240 DEG C, reaction time 3-
12h；
4) 180 DEG C are cooled to, adds in 1 part of trimethylolpropane, being to slowly warm up to 220 DEG C, the reaction was continued, makes its acid value small
In 10mgKOH/g；It then adds in dimethylbenzene and is made into the intermediate polyester solution that solid content is 50%；
5) vinyltriethoxysilane, phenyl trichlorosilane and diphenyl dichloro silicon are added in another reaction vessel
Alkane, parts by weight are respectively 2.8 parts, 0.7 part and 0.6 part, while add in volume ratio 3：1 toluene and acetone is as solvent；
6) distilled water is added dropwise and reaction is hydrolyzed, maintain temperature at 60 DEG C；Standing separation obtains organic layer, in being washed to
Property, it is evaporated under reduced pressure and removes toluene, condensation reaction 2-4h is depressurized at 160 DEG C, obtain silicon midbody solution；
7) intermediate polyester solution, silicon midbody solution, the phosphorous acid of step 6) of step 4) are added in reaction vessel
Triphenylmethyl methacrylate and tetraisopropyl titanate, parts by weight are respectively 42 parts, 13 parts, 0.3 part and 0.1 part, while add in dimethylbenzene work
For solvent；
8) 220 DEG C are to slowly warm up to, heating rate is 10-20 DEG C/h, insulation reaction 4-8h, after separating solvent, obtains reality
Apply the Heat Resistant Powder Coatings polyester of example 1.
Embodiment 2：
The Heat Resistant Powder Coatings polyester of the present invention is prepared in following manner, and this method comprises the following steps：1) exist
Terephthalic acid (TPA), M-phthalic acid, trimellitic anhydride, neopentyl glycol and tetraisopropyl titanate, weight are added in reaction vessel
Number is respectively 16 parts, 7.5 parts, 3.5 parts, 12 parts and 0.1 part, while adds in dimethylbenzene as solvent；
2) being heated to 170 DEG C makes material all melt, and then adds in 0.3 portion of triphenyl phosphite, is to slowly warm up to 220
DEG C, heating rate is 10-20 DEG C/h；
3) after temperature is higher than 220 DEG C, the temperature of reaction mixture is controlled between 220-240 DEG C, reaction time 3-
12h；
4) 180 DEG C are cooled to, adds in 1.5 parts of trimethylolpropanes, being to slowly warm up to 220 DEG C, the reaction was continued, makes its acid value
Less than 10mgKOH/g；It then adds in dimethylbenzene and is made into the intermediate polyester solution that solid content is 70%；
5) vinyltriethoxysilane, phenyl trichlorosilane and diphenyl dichloro silicon are added in another reaction vessel
Alkane, parts by weight are respectively 3.2 parts, 0.9 part and 0.8 part, while add in volume ratio 3：1 toluene and acetone is as solvent；
6) distilled water is added dropwise and reaction is hydrolyzed, maintain temperature at 60 DEG C；Standing separation obtains organic layer, in being washed to
Property, it is evaporated under reduced pressure and removes toluene, condensation reaction 2-4h is depressurized at 160 DEG C, obtain silicon midbody solution；
7) intermediate polyester solution, silicon midbody solution, the phosphorous acid of step 6) of step 4) are added in reaction vessel
Triphenylmethyl methacrylate and tetraisopropyl titanate, parts by weight are respectively 48 parts, 15 parts, 0.3 part and 0.1 part, while add in dimethylbenzene work
For solvent；
8) 220 DEG C are to slowly warm up to, heating rate is 10-20 DEG C/h, insulation reaction 4-8h, after separating solvent, obtains reality
Apply the Heat Resistant Powder Coatings polyester of example 2.
Embodiment 3：
The Heat Resistant Powder Coatings polyester of the present invention is prepared in following manner, and this method comprises the following steps：1) exist
Terephthalic acid (TPA), M-phthalic acid, trimellitic anhydride, neopentyl glycol and tetraisopropyl titanate, weight are added in reaction vessel
Number is respectively 17 parts, 8 parts, 4 parts, 14 parts and 0.1 part, while adds in dimethylbenzene as solvent；
2) being heated to 170 DEG C makes material all melt, and then adds in 0.3 portion of triphenyl phosphite, is to slowly warm up to 220
DEG C, heating rate is 10-20 DEG C/h；
3) after temperature is higher than 220 DEG C, the temperature of reaction mixture is controlled between 220-240 DEG C, reaction time 3-
12h；
4) 180 DEG C are cooled to, adds in 2 parts of trimethylolpropanes, being to slowly warm up to 220 DEG C, the reaction was continued, makes its acid value small
In 10mgKOH/g；It then adds in dimethylbenzene and is made into the intermediate polyester solution that solid content is 60%；
5) vinyltriethoxysilane, phenyl trichlorosilane and diphenyl dichloro silicon are added in another reaction vessel
Alkane, parts by weight are respectively 3.0 parts, 0.8 part and 0.7 part, while add in volume ratio 3：1 toluene and acetone is as solvent；
6) distilled water is added dropwise and reaction is hydrolyzed, maintain temperature at 60 DEG C；Standing separation obtains organic layer, in being washed to
Property, it is evaporated under reduced pressure and removes toluene, condensation reaction 2-4h is depressurized at 160 DEG C, obtain silicon midbody solution；
7) intermediate polyester solution, silicon midbody solution, the phosphorous acid of step 6) of step 4) are added in reaction vessel
Triphenylmethyl methacrylate and tetraisopropyl titanate, parts by weight are respectively 45 parts, 14 parts, 0.3 part and 0.1 part, while add in dimethylbenzene work
For solvent；
8) 220 DEG C are to slowly warm up to, heating rate is 10-20 DEG C/h, insulation reaction 4-8h, after separating solvent, obtains reality
Apply the Heat Resistant Powder Coatings polyester of example 3.
Comparative example 1：
Using the trimellitic anhydride of 4.6 parts of adipic acid alternate embodiment 3, remaining condition obtains comparative example with embodiment 3
1 Heat Resistant Powder Coatings polyester.
Comparative example 2：
Using the methyltriethoxysilane of 2.8 parts of adipic acid alternate embodiment 3, remaining condition is obtained with embodiment 3
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 toast the adhesive force and glossiness of 1h and 3h with polyester film at 300 DEG C, are recorded in table 1.
The technical indicator of 1 embodiment 1-3 of table and 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 1-3 of the embodiment of the present invention can
To reach 300 DEG C or more of temperature tolerance requirement；The adhesive force and glossiness nothing for toasting 1h and 3h at such a temperature are substantially change,
It is better than comparative example 1-2 in equal conditions.It can be seen that the Heat Resistant Powder Coatings of 1-3 of the embodiment of the present invention are more applicable with polyester
In preparing Heat Resistant Powder Coatings.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., be all contained within protection scope of the present invention.
Claims (6)
1. a kind of preparation method of Heat Resistant Powder Coatings polyester, this method comprise the following steps：
A intermediate polyester solution) is prepared；B silicon midbody solution) is prepared；C) among the intermediate polyester solution and the silicon
Heat Resistant Powder Coatings polyester is obtained by the reaction in liquid solution；
Wherein, the step A) further comprise following steps：
1) terephthalic acid (TPA), M-phthalic acid, four isopropyl of trimellitic anhydride, neopentyl glycol and metatitanic acid are added in reaction vessel
Ester, parts by weight are respectively 14-18 parts, 6-9 parts, 2-5 parts, 10-15 parts and 0.1 part, while add in dimethylbenzene as solvent；
2) being heated to 170 DEG C makes material all melt, and then adds in 0.3 portion of triphenyl phosphite, is to slowly warm up to 220 DEG C, rises
Warm rate is 10-20 DEG C/h；
3) after temperature is higher than 220 DEG C, the temperature of reaction mixture is controlled between 220-240 DEG C, reaction time 3-12h；
4) 180 DEG C are cooled to, adds in 0.5-2.5 parts of trimethylolpropanes, being to slowly warm up to 220 DEG C, the reaction was continued, makes its acid value
Less than 10mgKOH/g；It then adds in dimethylbenzene and is made into the intermediate polyester solution that solid content is 50-70%；
The step B) further comprise following steps：5) vinyltriethoxysilane, benzene are added in another reaction vessel
Base trichlorosilane and diphenyl dichlorosilane, parts by weight are respectively 2.5-3.5 parts, 0.5-1 parts and 0.5-1 parts, are added simultaneously
Enter volume ratio 3：1 toluene and acetone is as solvent；
6) distilled water is added dropwise and reaction is hydrolyzed, maintain temperature at 60 DEG C；Standing separation obtains organic layer, is washed to neutrality, subtracts
Toluene is distilled off in pressure, depressurizes condensation reaction 2-4h at 160 DEG C, obtains silicon midbody solution；
The step C) further comprise following steps：
7) the intermediate polyester solution of step 4), the silicon midbody solution of step 6), phosphorous triphenyl phosphate are added in reaction vessel
Ester and tetraisopropyl titanate, parts by weight are respectively 40-50 parts, 12-16 parts, 0.3 part and 0.1 part, while add in dimethylbenzene
As solvent；
8) 220 DEG C are to slowly warm up to, heating rate is 10-20 DEG C/h, insulation reaction 4-8h, after separating solvent, obtains high temperature resistant
Powdery paints polyester.
2. preparation method according to claim 1, wherein, the step A) in, terephthalic acid (TPA), 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.
3. preparation method according to claim 1, wherein, the step A) in, the solid content of intermediate polyester solution is
60%.
4. preparation method according to claim 1, wherein, the step B) in, vinyltriethoxysilane, phenyl three
The parts by weight of chlorosilane and diphenyl dichlorosilane are respectively 3.0 parts, 0.8 part and 0.7 part.
5. preparation method according to claim 4, wherein, the step C) in, the intermediate polyester solution of step 4) and
The parts by weight of the silicon midbody solution of step 6) are respectively 45 parts and 14 parts.
6. a kind of Heat Resistant Powder Coatings polyester, which is characterized in that usage right requires 1-5 any one of them method systems
It is standby.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610625455.1A CN106244000B (en) | 2016-08-02 | 2016-08-02 | Heat Resistant Powder Coatings polyester and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610625455.1A CN106244000B (en) | 2016-08-02 | 2016-08-02 | Heat Resistant Powder Coatings polyester and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106244000A CN106244000A (en) | 2016-12-21 |
| CN106244000B true CN106244000B (en) | 2018-05-29 |
Family
ID=57606916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610625455.1A Active CN106244000B (en) | 2016-08-02 | 2016-08-02 | Heat Resistant Powder Coatings polyester and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106244000B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109306232B (en) * | 2018-09-03 | 2020-09-15 | 浙江光华科技股份有限公司 | Powder coating polyester resin for motor vehicle exhaust pipe 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 |
| CN111234192B (en) * | 2020-03-26 | 2023-04-07 | 邦弗特(山东)新材料有限公司 | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962728A (en) * | 2006-11-01 | 2007-05-16 | 金小凤 | Thermostable organosilicon resin preparation method |
| CN102838740A (en) * | 2012-09-21 | 2012-12-26 | 广东大盈化工有限公司 | Powder coating polyester containing organic silicon and preparation method thereof |
| CN103450465A (en) * | 2012-06-05 | 2013-12-18 | 慧智科技（中国）有限公司 | Organosilicone-modified polyester and low-VOC (Volatile Organic Compounds) heat-resistant water-based paint |
| CN105482089A (en) * | 2015-12-26 | 2016-04-13 | 杭州吉华高分子材料股份有限公司 | Water-soluble organic silicone modified polyester resin as well as preparation method and application thereof |
-
2016
- 2016-08-02 CN CN201610625455.1A patent/CN106244000B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962728A (en) * | 2006-11-01 | 2007-05-16 | 金小凤 | Thermostable organosilicon resin preparation method |
| CN103450465A (en) * | 2012-06-05 | 2013-12-18 | 慧智科技（中国）有限公司 | Organosilicone-modified polyester and low-VOC (Volatile Organic Compounds) heat-resistant water-based paint |
| CN102838740A (en) * | 2012-09-21 | 2012-12-26 | 广东大盈化工有限公司 | Powder coating polyester containing organic silicon and preparation method thereof |
| CN105482089A (en) * | 2015-12-26 | 2016-04-13 | 杭州吉华高分子材料股份有限公司 | Water-soluble organic silicone modified polyester resin as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106244000A (en) | 2016-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106244000B (en) | Heat Resistant Powder Coatings polyester and preparation method thereof | |
| CN101913280B (en) | Crackle paint and preparation method and construction process thereof | |
| CN109867991A (en) | One kind is exempted to cure high-performance ceramic sealing wax and preparation method thereof | |
| CN106243838B (en) | A kind of electrosilvering coating composition, preparation method and applications | |
| CN103755940B (en) | A kind of preparation method and application being applied to heat-sensitive substrate material powder coating polyester resin | |
| CN102653628A (en) | Preparation method and application of nano sol modified waterborne polyurethane emulsion | |
| CN102690584A (en) | Epoxy resin powder paint and application thereof | |
| CN105860833B (en) | A kind of preparation method of alcohol radical aluminium alloy wheel hub coating | |
| CN105368150B (en) | A kind of water-based weather-proof glass ink | |
| CN104119470B (en) | Anticorrosive paint is by acrylic resin modified, the preparation method of copper surface anticorrosion coating | |
| CN102277024A (en) | Construction powdery paint | |
| CN106317969A (en) | Method for preparing coated aluminum powder pigment | |
| CN101928516A (en) | Thermostable powder paint with glazed surface and preparation method and application thereof | |
| CN102492102A (en) | Silicon-containing acrylic-acid-modified epoxy ester resin and paint thereof | |
| CN107033296A (en) | Extra-weather-proof polysiloxane-modified acrylic resin and finish paint preparation method | |
| CN105968325B (en) | A kind of organosilicon modified polyester epoxy resin with resisting high-temperature yellowing performance | |
| CN105295720A (en) | Preparation method for organic silicon impregnating varnish | |
| CN105567058A (en) | Coil coating bonded with PVC film and preparation method thereof | |
| CN101747827B (en) | Environment-friendly alkyd coating | |
| CN109942801A (en) | A kind of MDF material high-leveling 50:50 polyester resin and the preparation method and application thereof | |
| CN109265667A (en) | A kind of volume aluminum ceiling polyester resin and preparation method thereof | |
| CN113861840A (en) | Environment-friendly spray quick-drying chromium-free fingerprint-resistant liquid and preparation method thereof | |
| CN106317764B (en) | A kind of method of modifying improving phenolic resin toughness and anti-flammability | |
| CN102732072B (en) | Preparation method and product of high-adhesion polishing-free PE (Poly Ethylene) top-coat | |
| CN116285470B (en) | High-temperature reflective heat-insulating composite coating, preparation method thereof and application thereof in high-temperature-resistant motor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
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 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 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: Y2019980001356 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
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 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20211018 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 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
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 |