CN115368543B - Polyester resin for powder coating and preparation method thereof - Google Patents
Polyester resin for powder coating and preparation method thereof Download PDFInfo
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- CN115368543B CN115368543B CN202211168024.9A CN202211168024A CN115368543B CN 115368543 B CN115368543 B CN 115368543B CN 202211168024 A CN202211168024 A CN 202211168024A CN 115368543 B CN115368543 B CN 115368543B
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 70
- 239000004645 polyester resin Substances 0.000 title claims abstract description 70
- 238000000576 coating method Methods 0.000 title claims abstract description 53
- 239000011248 coating agent Substances 0.000 title claims abstract description 47
- 239000000843 powder Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002699 waste material Substances 0.000 claims abstract description 44
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 28
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims abstract description 27
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 24
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- ROFZMKDROVBLNY-UHFFFAOYSA-N 4-nitro-2-benzofuran-1,3-dione Chemical compound [O-][N+](=O)C1=CC=CC2=C1C(=O)OC2=O ROFZMKDROVBLNY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 12
- 239000001361 adipic acid Substances 0.000 claims abstract description 12
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 isooctyl Chemical group 0.000 claims abstract description 10
- 125000004185 ester group Chemical group 0.000 claims abstract description 7
- WDRCVXGINNJWPH-UHFFFAOYSA-N tris(6-methylheptyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCOC(=O)C1=CC=C(C(=O)OCCCCCC(C)C)C(C(=O)OCCCCCC(C)C)=C1 WDRCVXGINNJWPH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 6
- 239000003822 epoxy resin Substances 0.000 claims abstract description 6
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000003963 antioxidant agent Substances 0.000 claims description 18
- 230000003078 antioxidant effect Effects 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000005809 transesterification reaction Methods 0.000 claims description 16
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 239000004927 clay Substances 0.000 claims description 9
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 8
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 125000005590 trimellitic acid group Chemical group 0.000 claims description 5
- 244000028419 Styrax benzoin Species 0.000 claims description 3
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 3
- 229960002130 benzoin Drugs 0.000 claims description 3
- 238000005282 brightening Methods 0.000 claims description 3
- 235000019382 gum benzoic Nutrition 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- 239000005028 tinplate Substances 0.000 claims description 3
- 239000001038 titanium pigment Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000003921 oil Substances 0.000 abstract description 40
- 239000002199 base oil Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000155 melt Substances 0.000 abstract description 2
- 238000013035 low temperature curing Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000004042 decolorization Methods 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005034 decoration Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 1
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
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
- C07C29/1285—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis of esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- 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
- C08G63/78—Preparation processes
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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 relates to a polyester resin for powder coating and a preparation method thereof, the polyester resin is obtained by using waste high-temperature chain oil, diethylene glycol, neopentyl glycol, terephthalic acid, adipic acid and 3-nitrophthalic anhydride to carry out step polymerization under the action of a catalyst, wherein the waste high-temperature chain oil is a variety taking triisooctyl trimellitate as base oil, the synthesis of the polyester resin not only comprehensively utilizes the waste high-temperature chain oil, but also recovers isooctyl alcohol with high purity for sale, the raw material cost of the polyester resin is reduced, a certain amount of isooctyl ester groups are contained in a chain segment of the obtained polyester resin, the softening point of the polyester resin is lower, the melt fluidity is good, the low-temperature curing speed of the polyester resin and E-12 epoxy resin is relatively slow under the action of end capping of large steric hindrance 3-nitrophthalic anhydride, the leveling property of the cured film is very excellent, and the market application prospect is wide.
Description
Technical Field
The invention relates to the technical field of powder coatings, in particular to a polyester resin for powder, a preparation method thereof and application thereof in high-leveling 50/50 powder coatings.
Background
The powder coating is a novel 100% solid coating without solvent, has the advantages of no solvent, no pollution, energy and resource saving, labor intensity reduction, high mechanical strength of coating film and the like, and has relatively rapid development in recent years; the requirements on the leveling performance are generally higher in the field with higher decoration requirements, and along with the gradual sensitivity of downstream to price, the requirements on the cost of customers are also higher and higher, so that the cost of the polyester resin is reduced, and meanwhile, the high-leveling coating with excellent decoration is difficult to achieve.
The high-temperature chain oil of the synthetic esters is mainly prepared by blending trioctyl trimellitate variety base oil with a small amount of lubricating oil additive components such as antioxidants, antiwear agents, viscosity index regulators and the like; the waste high-temperature chain oil is difficult to recycle after being recycled, and how to improve the added value and comprehensive utilization of the waste high-temperature chain oil is also a difficulty in the industry.
Aiming at the problems, the invention uses waste high-temperature chain oil, diethylene glycol, neopentyl glycol, terephthalic acid, adipic acid and 3-nitrophthalic anhydride to carry out step polymerization reaction under the action of a catalyst to obtain the polyester resin. The synthesis of the polyester resin not only comprehensively utilizes waste high-temperature chain oil, but also recovers and obtains isooctanol which can be sold with high purity, thereby not only reducing the raw material cost of the polyester resin, but also having lower softening point, good melt fluidity, relatively slower curing speed with E-12 epoxy resin at 180 ℃, long leveling time, excellent leveling property of the cured coating film and wider market application prospect.
Disclosure of Invention
The invention relates to a polyester resin for powder coating, which is prepared by using waste high-temperature chain oil, diethylene glycol, neopentyl glycol, terephthalic acid, adipic acid and 3-nitrophthalic anhydride to carry out stepwise polymerization under the action of a catalyst.
A polyester resin for powder coating, the raw materials comprising the components:
wherein the triisooctyl trimellitate in the waste high-temperature chain oil accounts for more than 92 weight percent of the waste high-temperature chain oil; the rest components are antioxidant, antiwear agent, viscosity index improver, etc.
The components can also contain a certain amount of catalyst 1, catalyst 2, antioxidant and activated clay.
The polyester resin for the powder coating, further, the catalyst 1 is sodium methoxide, and the dosage is 0.5-0.8% of the mass of the waste high-temperature chain oil; the catalyst 2 is monobutyl tin oxide, and the dosage is 0.1-0.2% of the total mass of the raw materials; the antioxidant is antioxidant 1076, and the dosage is 0.3-0.5% of the total mass of the raw materials; the usage amount of the activated clay is 0.5-3% of the mass of the waste high-temperature chain oil, and more preferably 1%.
The preparation method of the polyester resin for the powder coating comprises the following steps:
A. decolorizing the waste high-temperature chain oil;
B. waste high-temperature chain oil, diethylene glycol and neopentyl glycol after the decolorization treatment are subjected to transesterification reaction by a catalyst 1;
C. adding terephthalic acid, adipic acid and a catalyst 2, and heating to perform polymerization reaction;
D. adding an antioxidant to perform vacuum polycondensation reaction;
E. adding 3-nitrophthalic anhydride, performing carboxyl end-capping reaction on the polyester resin, discharging at a high temperature after the reaction is finished, and performing post-treatment to obtain the polyester resin.
Further, the preparation method of the polyester resin for powder coating as described above may comprise the steps of:
A. adding the formula amount of waste high-temperature chain oil into a reaction kettle, adding activated clay, heating to 80-90 ℃, fully stirring for 2-3 hours, and after the decoloration is finished, obtaining decolored high-temperature chain oil through centrifugal separation of a centrifugal machine;
B. adding the waste high-temperature chain oil, diethylene glycol and neopentyl glycol after the decolorization treatment into a reaction kettle, heating to 195-200 ℃ to perform transesterification, and collecting isooctanol byproducts after transesterification through rectification, wherein the gas chromatographic purity of the collected isooctanol reaches more than 95%;
C. stopping the reaction when the dosage of the collected isooctanol reaches more than 85% of the theoretical dosage, and stopping the transesterification of the isooctanol with the rest of about 15% to ensure that the isooctyl octanol is remained on a trimellitic acid chain segment in an isooctyl ester group mode to participate in the subsequent polymerization reaction, adding the terephthalic acid, adipic acid and a catalyst 2 with the formula dosage at the moment, and heating to 230-235 ℃ to perform the polymerization reaction;
D. sampling and detecting the acid value of the reaction mixture, adding antioxidant with the formula amount when the acid value of the reaction mixture reaches 30-35mgKOH/g, starting a vacuum system, and maintaining the vacuum degree of-0.097 to-0.99 Mpa for vacuum polycondensation reaction;
E. stopping pulling vacuum when the acid value is reduced to 12-18mgKOH/g, then adding 3-nitrophthalic anhydride with the formula amount, continuously carrying out carboxyl end-capping reaction on the polyester resin at 230-235 ℃, stopping the reaction when the acid value reaches the expected value (67-74 mgKOH/g), discharging at high temperature while the polyester resin is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin.
The polyester resin for powder coating, which is obtained by the preparation method, has an acid value of 67-74mgKOH/g and a softening point of 102-115 ℃.
The polyester resin for the powder coating or the polyester resin obtained by the preparation method is used in the high-leveling 50/50 powder coating, and the powder coating formula can comprise polyester resin, epoxy resin, titanium pigment, barium sulfate, leveling agent, brightening agent, benzoin and the like.
The polyester resin is applied to the powder coating, firstly, the materials are uniformly mixed, respectively extruded, pressed into slices and crushed by a double-screw extruder, and then the slices are crushed and sieved to prepare the powder coating; and spraying the powder coating on the tinplate substrate subjected to surface treatment by adopting an electrostatic spray gun, and curing to obtain the coating.
For example, a polyester resin for a low raw material cost, high leveling 50/50 powder coating, the raw materials comprising:
the catalyst 1 is sodium methoxide, and the dosage is 0.5-0.8% of the mass of the waste high-temperature chain oil;
the catalyst 2 is monobutyl tin oxide, and the dosage is 0.1-0.2% of the total mass of the raw materials;
the antioxidant is antioxidant 1076, and the dosage is 0.3-0.5% of the total mass of the raw materials.
Waste high-temperature chain oil, wherein the triisooctyl trimellitate accounts for more than 92wt% of the waste high-temperature chain oil, and the balance of 3-4wt% of antioxidant, 1-2wt% of antiwear agent and 3-4wt% of viscosity index improver (available from Huangshan city long system lubricating oil selling Co., ltd.);
the preparation method of the polyester resin for the powder coating comprises the following steps:
A. adding the formula amount of waste high-temperature chain oil into a reaction kettle, adding activated clay accounting for 1% of the mass of the waste high-temperature chain oil, heating to 80-90 ℃, fully stirring for 2-3 hours, and after the decoloration is finished, obtaining decolored high-temperature chain oil through centrifugal separation of a centrifugal machine;
B. adding the waste high-temperature chain oil, diethylene glycol and neopentyl glycol after the decolorization treatment into a reaction kettle, heating to 195-200 ℃ to perform transesterification, and collecting isooctanol byproducts after transesterification through rectification, wherein the gas chromatographic purity of the collected isooctanol reaches more than 95%;
C. stopping the reaction when the dosage of the collected isooctanol reaches more than 85% of the theoretical dosage, and stopping the transesterification of the isooctanol with the rest of about 15% to ensure that the isooctyl octanol is remained on a trimellitic acid chain segment in an isooctyl ester group mode to participate in the subsequent polymerization reaction, adding the terephthalic acid, adipic acid and a catalyst 2 with the formula dosage at the moment, and heating to 230-235 ℃ to perform the polymerization reaction;
D. sampling and detecting the acid value of the reaction mixture, adding antioxidant 1076 with the formula amount when the acid value of the reaction mixture reaches 30-35mgKOH/g, starting a vacuum system, and maintaining the vacuum degree of-0.097 to-0.99 Mpa for vacuum polycondensation reaction;
G. stopping pulling vacuum when the acid value is reduced to 12-18mgKOH/g, then adding 3-nitrophthalic anhydride with the formula amount, continuously carrying out carboxyl end-capping reaction on the polyester resin at 230-235 ℃, stopping the reaction when the acid value reaches 67-74mgKOH/g, discharging at a high temperature, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin.
The obtained product has the appearance of pale yellow transparent particles, the acid value of 67-74mgKOH/g and the softening point of 102-115 ℃.
The invention has the beneficial effects that:
the invention uses waste high temperature chain oil, diethylene glycol, neopentyl glycol, terephthalic acid, adipic acid and 3-nitrophthalic anhydride to carry out step polymerization reaction under the action of catalyst to obtain polyester resin, wherein the waste high temperature chain oil is a variety taking triisooctyl trimellitate as base oil, the triisooctyl trimellitate accounts for more than 92wt% of the waste high temperature chain oil, the synthesis of the polyester resin not only comprehensively utilizes the waste high temperature chain oil, but also recovers and obtains isooctanol which can be sold in high purity, the raw material cost of the polyester resin is reduced, a certain amount of isooctyl ester groups are contained in the chain segment of the obtained polyester resin, the softening point of the polyester resin is lower, the melt fluidity is good, the curing speed with E-12 epoxy resin is relatively slow at 180 ℃ under the end-capped effect of large steric hindrance 3-nitrophthalic anhydride, the leveling time is long, and the cured coating film has excellent performance and wide market application prospect.
Detailed Description
For the purposes of promoting an understanding of the invention, reference will now be made in detail to various exemplary embodiments of the invention, which should not be considered as limiting the invention in any way, but rather as describing in more detail certain aspects, features and embodiments of the invention.
Example 1
A polyester resin for a low raw material cost, high leveling 50/50 powder coating, the raw materials comprising:
the catalyst 1 is sodium methoxide, and the dosage is 0.5% of the mass of the waste high-temperature chain oil;
the catalyst 2 is monobutyl tin oxide, and the dosage is 0.1% of the total mass of the raw materials;
the antioxidant is antioxidant 1076, and the dosage is 0.3% of the total mass of the raw materials.
The waste high-temperature chain oil contains more than 92wt% of triisooctyl trimellitate, and the balance of 3-4wt% of antioxidant, 1-2wt% of antiwear agent and 3-4wt% of viscosity index improver; the product was purchased from Huangshan city long systems oil marketing Co., ltd (hereinafter the same).
The preparation method of the polyester resin for the powder coating comprises the following steps:
A. adding the formula amount of waste high-temperature chain oil into a reaction kettle, adding activated clay accounting for 1% of the mass of the waste high-temperature chain oil, heating to 90 ℃, fully stirring for 2.5 hours, and after the decoloration is finished, obtaining decolored high-temperature chain oil through centrifugal separation of a centrifugal machine;
B. adding the waste high-temperature chain oil, diethylene glycol and neopentyl glycol after the decolorization treatment into a reaction kettle, heating to 200 ℃ to perform transesterification, and collecting isooctanol byproducts after transesterification through rectification, wherein the gas chromatographic purity of the collected isooctanol reaches more than 95%;
C. stopping the reaction when the dosage of the collected isooctanol reaches more than 85% of the theoretical dosage, and stopping the transesterification of the isooctanol with the rest of about 15% to ensure that the isooctyl octanol is remained on a trimellitic acid chain segment in an isooctyl ester group mode to participate in the subsequent polymerization reaction, adding the terephthalic acid, adipic acid and the catalyst 2 with the formula dosage at the moment, and heating to 230 ℃ to perform the polymerization reaction;
D. sampling and detecting the acid value of the reaction mixture, adding antioxidant with the formula amount when the acid value of the reaction mixture reaches 30mgKOH/g, starting a vacuum system, and maintaining the vacuum degree of-0.99 Mpa for vacuum polycondensation reaction;
G. stopping pulling vacuum when the acid value is reduced to 15mgKOH/g, then adding 3-nitrophthalic anhydride with the formula amount, continuously carrying out carboxyl end-capping reaction on the polyester resin at 235 ℃, stopping the reaction when the acid value reaches the expected value, discharging at high temperature while the acid value is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin.
Finally, the acid value of the polyester resin prepared was 69mgKOH/g, and the softening point was 107 ℃.
Example 2
A polyester resin for a low raw material cost, high leveling 50/50 powder coating, the raw materials comprising:
the catalyst 1 is sodium methoxide, and the dosage is 0.8% of the mass of the waste high-temperature chain oil;
the catalyst 2 is monobutyl tin oxide, and the dosage is 0.2% of the total mass of the raw materials;
the antioxidant is antioxidant 1076, and the dosage is 0.5% of the total mass of the raw materials.
The preparation method is the same as in example 1.
Finally, the acid value of the polyester resin thus prepared was 72mgKOH/g, and the softening point was 111 ℃.
Example 3
A polyester resin for a low raw material cost, high leveling 50/50 powder coating, the raw materials comprising:
the catalyst 1 is sodium methoxide, and the dosage is 0.6% of the mass of the waste high-temperature chain oil;
the catalyst 2 is monobutyl tin oxide, and the dosage is 0.15% of the total mass of the raw materials;
the antioxidant is antioxidant 1076, and the dosage is 0.4% of the total mass of the raw materials.
The preparation method is the same as in example 1.
Finally, the acid value of the polyester resin thus prepared was 70mgKOH/g, and the softening point was 108 ℃.
Example 4
A polyester resin for a low raw material cost, high leveling 50/50 powder coating, the raw materials comprising:
the catalyst 1 is sodium methoxide, and the dosage is 0.8% of the mass of the waste high-temperature chain oil;
the catalyst 2 is monobutyl tin oxide, and the dosage is 0.15% of the total mass of the raw materials;
the antioxidant is antioxidant 1076, and the dosage is 0.5% of the total mass of the raw materials.
The preparation method is the same as in example 1.
Finally, the acid value of the polyester resin thus prepared was 68mgKOH/g, and the softening point was 109 ℃.
Comparative example 1
A commercially available 50/50 polyester resin, available from Anhui Yongli New Material technology Co., ltd., model YL9050A, acid value 71mgKOH/g, was used.
Application example
The formula of the powder coating comprises the following steps: 300g of polyester resin, 300g of E-12 epoxy resin, 180g of titanium pigment, 180g of barium sulfate, 8 parts of flatting agent, 8 parts of brightening agent and 3 parts of benzoin, which are obtained in the corresponding examples or comparative examples.
From examples 1 to 4 and corresponding comparative example 1, application examples 1 to 4 and corresponding comparative application example 1 were obtained, respectively, and performance test was performed thereon.
Preparing a paint coating:
mixing the materials according to the powder coating formula, extruding, tabletting and crushing the materials by a double-screw extruder respectively, and crushing and sieving the tablets to obtain the powder coating. The powder coating is sprayed on the tinplate base material after surface treatment by adopting an electrostatic spray gun, and is solidified by 180 ℃/15min, thus obtaining the coating.
Performance comparison:
coating index detection basis: GB/T21776-2008, inspection Standard guidelines for powder coatings and coatings thereof; the leveling grade is according to JB/T3998-1999 coating leveling scratch determination method.
Polyester resins prepared in the above examples and comparative examples the coating formulations provided in accordance with the present invention were tested for coating properties and the results are shown in table 1 below.
TABLE 1 film coating Properties
As can be seen from Table 1, the coating film prepared by the product of the invention has a flat and smooth surface, a gloss of about 93%, good forward and reverse impact, good adhesion, a leveling grade of 6 grade or more, almost no change in boiling water for 2 hours, and good performance, and the leveling grade of the coating film is higher than that of the coating film prepared by the common commercial 50/50 powder coating (comparative application example 1), and other performance differences are not great. The invention also comprehensively utilizes the waste high-temperature chain oil, changes waste into valuable, obtains high-purity isooctyl alcohol, and further improves the added value of the isooctyl alcohol.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (5)
1. The polyester resin for the powder coating is characterized in that the polyester resin is obtained by step polymerization reaction of waste high-temperature chain oil, diethylene glycol, neopentyl glycol, terephthalic acid, adipic acid and 3-nitrophthalic anhydride under the action of a catalyst;
comprises the following components:
55-75kg of waste high-temperature chain oil;
diethylene glycol 18-24 kg;
33-45kg of neopentyl glycol;
8-13kg of terephthalic acid;
adipic acid 5-8 kg;
10-15kg of 3-nitrophthalic anhydride;
wherein the triisooctyl trimellitate in the waste high-temperature chain oil accounts for more than 92 weight percent of the waste high-temperature chain oil;
the components also comprise a certain amount of catalyst 1, catalyst 2, antioxidant and activated clay; the catalyst 1 is sodium methoxide, and the dosage is 0.5-0.8% of the mass of the waste high-temperature chain oil; the catalyst 2 is monobutyl tin oxide, and the dosage is 0.1-0.2% of the total mass of the raw materials;
the preparation method of the polyester resin for the powder coating comprises the following steps:
A. adding the formula amount of waste high-temperature chain oil into a reaction kettle, adding the formula amount of activated clay, heating to 80-90 ℃, fully stirring for 2-3 hours, and after the decoloration is finished, obtaining decolored high-temperature chain oil through centrifugal separation of a centrifugal machine;
B. adding the decolored high-temperature chain oil, diethylene glycol and neopentyl glycol into a reaction kettle, heating to 195-200 ℃ to perform transesterification, and collecting isooctanol byproducts after transesterification through rectification, wherein the gas chromatographic purity of the collected isooctanol reaches more than 95%;
C. stopping the reaction when the dosage of the collected isooctyl alcohol reaches more than 85% of the theoretical dosage, and stopping the rest isooctyl alcohol from undergoing transesterification reaction, so that the isooctyl alcohol is remained on a trimellitic acid chain segment in a mode of isooctyl ester group to participate in subsequent polymerization reaction, and adding the formula amount of terephthalic acid, adipic acid and a catalyst 2 at the moment, and heating to 230-235 ℃ to carry out polymerization reaction;
D. sampling and detecting the acid value of the reaction mixture, adding antioxidant with the formula amount when the acid value of the reaction mixture reaches 30-35mgKOH/g, starting a vacuum system, and maintaining the vacuum degree of-0.097 to-0.99 Mpa for vacuum polycondensation reaction;
E. stopping vacuum when the acid value is reduced to 12-18mgKOH/g, then adding 3-nitrophthalic anhydride with the formula amount, continuously carrying out carboxyl end-capping reaction on the polyester resin at 230-235 ℃, stopping the reaction when the acid value reaches the expected value, discharging at a high temperature while the acid value is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin; the acid value of the obtained polyester resin is 67-74mgKOH/g, and the softening point is 102-115 ℃.
2. The polyester resin for powder coating according to claim 1, wherein the antioxidant is antioxidant 1076 in an amount of 0.3 to 0.5% based on the total mass of the raw materials; the usage amount of the activated clay is 0.5-3% of the mass of the waste high-temperature chain oil.
3. The method for preparing a polyester resin for powder coating according to claim 1, comprising the steps of:
A. adding the formula amount of waste high-temperature chain oil into a reaction kettle, adding the formula amount of activated clay, heating to 80-90 ℃, fully stirring for 2-3 hours, and after the decoloration is finished, obtaining decolored high-temperature chain oil through centrifugal separation of a centrifugal machine;
B. adding the decolored high-temperature chain oil, diethylene glycol and neopentyl glycol into a reaction kettle, heating to 195-200 ℃ to perform transesterification, and collecting isooctanol byproducts after transesterification through rectification, wherein the gas chromatographic purity of the collected isooctanol reaches more than 95%;
C. stopping the reaction when the dosage of the collected isooctyl alcohol reaches more than 85% of the theoretical dosage, and stopping the rest isooctyl alcohol from undergoing transesterification reaction, so that the isooctyl alcohol is remained on a trimellitic acid chain segment in a mode of isooctyl ester group to participate in subsequent polymerization reaction, and adding the formula amount of terephthalic acid, adipic acid and a catalyst 2 at the moment, and heating to 230-235 ℃ to carry out polymerization reaction;
D. sampling and detecting the acid value of the reaction mixture, adding antioxidant with the formula amount when the acid value of the reaction mixture reaches 30-35mgKOH/g, starting a vacuum system, and maintaining the vacuum degree of-0.097 to-0.99 Mpa for vacuum polycondensation reaction;
E. stopping vacuum when the acid value is reduced to 12-18mgKOH/g, then adding 3-nitrophthalic anhydride with the formula amount, continuously carrying out carboxyl end-capping reaction on the polyester resin at 230-235 ℃, stopping the reaction when the acid value reaches the expected value, discharging at high temperature while the acid value is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin.
4. Use of a polyester resin for powder coatings according to claim 1 or 2 or a polyester resin obtained by the preparation process according to claim 3 in high-leveling 50/50 powder coatings.
5. The use according to claim 4, wherein the polyester resin, the epoxy resin, the titanium pigment, the barium sulfate, the flatting agent, the brightening agent and the benzoin are firstly mixed uniformly, extruded, pressed and crushed respectively by a double-screw extruder, and then the tablet is crushed and sieved to prepare the powder coating; and spraying the powder coating on the tinplate substrate subjected to surface treatment by adopting an electrostatic spray gun, and curing to obtain the coating.
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