CN115368541B - Preparation and application of bio-based copolyester based on 4-hydroxybenzaldehyde - Google Patents
Preparation and application of bio-based copolyester based on 4-hydroxybenzaldehyde Download PDFInfo
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- CN115368541B CN115368541B CN202210869857.1A CN202210869857A CN115368541B CN 115368541 B CN115368541 B CN 115368541B CN 202210869857 A CN202210869857 A CN 202210869857A CN 115368541 B CN115368541 B CN 115368541B
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- hydroxybenzaldehyde
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- diphenol
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- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 96
- 239000000843 powder Substances 0.000 claims abstract description 81
- 239000011248 coating agent Substances 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims abstract description 14
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims abstract description 12
- 229960002479 isosorbide Drugs 0.000 claims abstract description 12
- 239000000123 paper Substances 0.000 claims abstract description 6
- 229920003023 plastic Polymers 0.000 claims abstract description 6
- 239000004033 plastic Substances 0.000 claims abstract description 6
- 239000002023 wood Substances 0.000 claims abstract description 5
- 239000007921 spray Substances 0.000 claims description 51
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000012153 distilled water Substances 0.000 claims description 27
- 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 26
- 238000001816 cooling Methods 0.000 claims description 25
- -1 decane-3, 9-diyl Chemical group 0.000 claims description 24
- 239000012043 crude product Substances 0.000 claims description 22
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- 150000002009 diols Chemical class 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 18
- 238000005282 brightening Methods 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 244000028419 Styrax benzoin Species 0.000 claims description 13
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 13
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 13
- 229960002130 benzoin Drugs 0.000 claims description 13
- 235000019382 gum benzoic Nutrition 0.000 claims description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 9
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 abstract description 26
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000002028 Biomass Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 230000032050 esterification Effects 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 239000013256 coordination polymer Substances 0.000 description 36
- 238000012360 testing method Methods 0.000 description 35
- 238000002156 mixing Methods 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- 238000007873 sieving Methods 0.000 description 14
- 230000032683 aging Effects 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 12
- 229920002961 polybutylene succinate Polymers 0.000 description 11
- 239000004631 polybutylene succinate Substances 0.000 description 11
- 229920001225 polyester resin Polymers 0.000 description 10
- 239000004645 polyester resin Substances 0.000 description 10
- 238000005507 spraying Methods 0.000 description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- KRFFWELOYNJROH-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1.C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 KRFFWELOYNJROH-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 101100518501 Mus musculus Spp1 gene Proteins 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 241001669696 Butis Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241001326934 Triarrhena Species 0.000 description 1
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical compound [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-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
- C08G63/02—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
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
-
- 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
- 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)
- 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)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses preparation and application of bio-based copolyester based on 4-hydroxybenzaldehyde, and belongs to the field of preparation of novel coating materials. Biomass 4-hydroxybenzaldehyde is taken as a raw material, a biomass dihydric alcohol monomer M is obtained through further chemical reaction, and then the biomass dihydric alcohol monomer M, isosorbide, 1, 4-cyclohexanedicarboxylic acid and a catalyst are subjected to esterification and polycondensation reaction to obtain the polyester product. The weight average molecular weight of the copolyester obtained by the method is 20000-29000 g/mol, the tensile breaking strength of the copolyester is 67.9-90.1 MPa, and the impact strength of the copolyester is 18.1-20.1 KJ/m 2 Has better mechanical property, stronger impact resistance and no harm to environment. The copolyester prepared by the invention can be used for preparing super weather-resistant polyester powder coating and coating, can be applied to the coating aspect of automobiles, motorcycles, paper, plastics, wood, advanced furniture and engineering pipelines, and is used for protecting materials from being corroded by external environment.
Description
Technical Field
The invention belongs to the field of preparation of novel coating materials. In particular to a preparation method and application of copolyester based on 4-hydroxybenzaldehyde, which takes 4-hydroxybenzaldehyde and 1, 4-cyclohexanedicarboxylic acid as raw materials and synthesizes the copolyester based on 4-hydroxybenzaldehyde by adopting a melt polymerization method, and can be used for preparing powder coatings and coatings.
Background
The powder coating is a solid powder synthetic resin coating formed by taking solid resin, various pigments, fillers, other auxiliary agents and the like as raw materials. The 100% solids content of the powder coating makes it different from traditional solvent-borne or water-borne coatings, and the powder coating is produced without any solvent for dispersion, and the production process and the product itself have less environmental pollution. Since the first 60 s of the last century had been used in the industry in italy, global powder coatings have grown rapidly in the last decades, and China has become one of the fastest growing countries for powder coatings.
The largest growing fields of the powder coating application market in China are mainly the ship industry, the pipeline engineering and the automobile industry. With the continuous refinement of industry technology, in addition to the application, powder coatings are involved in the fields of color steel plate coating, fluorocarbon coating, containers, medium density fiber boards, plastic parts and the like. Although the industry application prospect is wide, it must be acknowledged that the quality of the powder coating in China is different from that of the foreign high-quality product. Such as powder impact resistance and weather resistance, which are applied to the ship industry, are to be enhanced. More than half of the thermosetting powder coatings are currently important components based on polyester resins. However, with the expansion of the application field, the weather resistance of the polyester powder coating still cannot well meet the market demand, and the key problem is mainly that the weather resistance of the polyester resin is insufficient.
QUALICOAT (QUALICOAT is a european union quality marking organization, working on maintaining and improving the quality of architectural aluminum and aluminum alloy spray products) categorizes powder coatings according to their differences in gloss retention after accelerated aging tests (1 000 h xenon lamp aging test or 300 h manual accelerated aging test) (except for type 3 powder coatings): a class 1 powder coating (general weathering grade) having a light retention of 50% or more, a class 1.5 powder coating having a light retention of 75% or more, and a class 2 powder coating (super weathering grade) having a light retention of 90% or more.
Conventional class 1.5 weatherable polyester resins for powder coatings meet the QUALICOAT standard butIs poor in mechanical properties. At present, super weather-resistant polyester powder coating is widely used, but the mechanical property and weather resistance of the super weather-resistant polyester powder coating are difficult to obtain satisfactory results [1] ([1] Jiang Y,Pan M, Yuan J, et al. Fabrication and structural characterization of poly (vinylidene fluoride)/polyacrylate composite waterborne coatings with excellentweather resistance and room-temperature curing[J]Colloids and Surfaces A: physicochemical and Engineering Aspects, 2020, 598: 124851.). The resins used for weather-resistant powder coatings are of a wide variety, but generally have poor durability. The fluorine-containing resin has a fluorine-carbon bond structure with shorter bond length and bond energy far higher than that of carbon-carbon and carbon-oxygen bonds, and can be closely arranged around a polymer, so that the fluorocarbon powder coating has excellent weather resistance, is widely applied to the fields of high-end building aluminum profiles, electric and electronic fields, aerospace and the like, has mature production and construction processes, is a super weather-resistant coating variety accepted in the current world, but has low impact resistance, uneven coating appearance and poor adhesive force.
To advance the application of powder coatings, solving these problems is also a research hotspot within the industry. The mass fraction of polyester in the polyester powder coating is more than 50%, so that the key for improving the comprehensive performance of the super weather-resistant powder coating is polyester resin. The existing super weather-resistant polyester resin is basically synthesized by weather-resistant monomers such as isophthalic acid (the light retention rate is 80% -90% in an aging test 308 h), but because the isophthalic acid has high rigidity, a paint film is very brittle, the impact resistance is less than 50cm in all tests, and the impact resistance is very poor [2] （[2]Qian Renjun, yang Dong, liao Ping, shao Fei, wang Huili Synthesis and application research of polyester resins for powder coatings with excellent weather resistance [ J]Chinese paint, 2021,36 (12): 34-39.).
The development of super weather-resistant polyester powder coating in the current market is still at a low level, the light retention rate of an aging test 308h is lower than 87%, and the impact resistance of the fluorine-containing polyester powder coating is poorer and the impact resistance test is lower than 50cm although the weather resistance of the fluorine-containing polyester powder coating is better (the aging test 308h can reach 90%). The general problem of poor impact resistance of super weather-resistant polyester resins on the market is that the super weather-resistant polyester resins are not suitable for preparing powder products with high weather resistance and mechanical property requirements, so that development of weather-resistant powder coatings with excellent weather resistance and good mechanical property is very necessary.
Disclosure of Invention
Aiming at the problems in the prior art, the invention adopts 4-hydroxybenzaldehyde derived from biomass as a raw material, prepares a novel dihydric alcohol monomer M through further reaction on the raw material, and then synthesizes a novel polyester material by using a melt polymerization method. The powder coating and the coating prepared by the invention have good weather resistance and mechanical property and are harmless to the environment.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
in order to better realize the technical scheme of the invention, the invention discloses preparation and application of bio-based copolyester based on 4-hydroxybenzaldehyde. The preparation method of the polyester comprises the following steps:
1) Synthesis of diol monomer M: adding 4-hydroxybenzaldehyde and pentaerythritol into a single-neck flask according to the mass ratio of (1-1.2), adding 20-50 ml of DMF, adding 0.24-0.5% of p-toluenesulfonic acid by mass of 4-hydroxybenzaldehyde, reacting for 2-3 hours at 85-100 ℃, cooling to room temperature, pouring into 80-100 ml of distilled water to precipitate, filtering, washing filter residues with distilled water until precipitation is complete, and drying to obtain 4,4'- (2, 4,8, 10-tetraoxaaspiro [5,5] decane-3, 9-diyl) diphenol with the Chinese name of 4,4' - (2, 4,8, 10-tetraoxapyridine [5,5] undecane-3, 9-diyl) diphenol, wherein the structure is shown as formula a;
a, a
4-5 g of 4,4' - (2, 4,8,10-tetraoxaspiro [5,5]]undecane-3,9-diyl diphenol Chinese name 4,4' - (2, 4,8, 10-tetraoxapyridine [5,5]]Undecane-3, 9-diyl) diphenol is dissolved in 30 to 50ml DMFAdding ethylene carbonate, wherein the mass ratio of the substance A to the ethylene carbonate is 1:2-2.3, and adding K accounting for 1% -5% of the mass of the substance A 2 CO 3 Reacting for 2-3 hours at 150-160 ℃ as a catalyst, cooling to room temperature after the reaction, transferring to distilled water, precipitating white solid, filtering, collecting precipitate, washing with water for 2-3 times, and drying to obtain a diol monomer M with a structure shown as formula b;
b
2) Synthesis of polycondensation crude products: adding (5.3-6.1) a proper amount of catalyst into a reaction container, introducing nitrogen for protection, stirring at 180-200 ℃ for 3-4 hours, heating to 240-260 ℃, controlling the absolute pressure in a reaction system to 80-150 Pa, and carrying out polycondensation reaction for 2-4 hours under full stirring to obtain a polycondensation crude product, wherein the diol monomer M is used as a first alcohol source, the isosorbide is used as a second alcohol source, and the ratio of the 1, 4-cyclohexanedicarboxylic acid to the first alcohol source is 10 (3.8-4.4);
3) Purifying a polycondensation crude product: dissolving the polycondensation crude product with chloroform, filtering, taking clear liquid, adding enough methanol into the clear liquid until precipitation is not increased, centrifugally separating, filtering, washing the obtained solid with ethanol, and drying the filtered solid at 60-80 ℃ for 1-2 hours to obtain the bio-based copolyester based on 4-hydroxybenzaldehyde.
As a further preferred aspect, the catalyst in the step 2) is one of cerium acetate-tetrabutyl titanate catalyst, zinc acetate, potassium fluotitanate and niobic acid, the catalyst is used in an amount of 0.06% -0.19% of the amount of 1, 4-cyclohexane dicarboxylic acid substances, and the molar ratio of cerium acetate to tetrabutyl titanate in the cerium acetate-tetrabutyl titanate catalyst is 1.0:0.0009-0.3.
The use of the bio-based copolyester based on 4-hydroxybenzaldehyde as claimed in claims 1 to 3, which is characterized by being used as a coating for automobiles, motorcycles, paper, plastics, wood, advanced furniture, engineering pipelines, for protecting materials from the external environment, and the preparation method is as follows: 100g of bio-based copolyester based on 4-hydroxybenzaldehyde, 30 g-40 g of triglycidyl isocyanurate, 100 g-120 g of barium sulfate, 6 g-10 g of flatting agent GLP588, 3 g-4 g of benzoin and 4 g-6 g of brightening agent 701B are added into an internal mixer to be fully and uniformly mixed, then the mixture is transferred into a double screw extruder to be extruded, cooled and tableted, crushed, screened by a 180-mesh screen, the lower layer is poured into a spray can with a spray gun, the spray gun voltage is set to be 50-70 kV, and the spray gun is sprayed on a degreased base material to obtain the ultra-resistant Hou Juzhi powder coating with the thickness of 70-120 mu m, and the ultra-high-strength Hou Juzhi powder coating is used for protecting materials from the corrosion of external environment.
The beneficial effects are that:
1. careful selection of raw materials: the raw materials adopted in the experiment are all from biomass, and are harmless to the environment after being discarded, so that the requirements of environmental protection and sustainable development are met. The 4-hydroxybenzaldehyde can be extracted from triarrhena longifolia which is widely distributed in the downstream river basin in the Yangtze river of China, and has wide sources, low cost and easy obtainment. Therefore, the synthetic polyester has the characteristics of low cost of raw materials, reproducibility and the like.
2. The mechanical properties of the synthesized polyester are excellent: the invention introduces diester and diol monomers with aromatic ring structures and aliphatic ring structures, which greatly improves the mechanical properties (including tensile strength, hardness and impact resistance) of the polyester, and the number average molecular weight of the polyester material is 20000-29000 g/mol, and the tensile breaking strength is 67-98 MPa.
3. The powder coating and the coating prepared by the invention have good weather resistance and impact resistance, and are prepared from isophthalic acid/terephthalic acid, adipic acid and polyol synthetic polyester [2] ([2]Qian Renjun, yang Dong, liao Ping, shao Fei, wang Huili Synthesis and application research of polyester resins for powder coatings with excellent weather resistance [ J]Compared with the Chinese paint (2021,36 (12): 34-39.) (the light retention rate of the artificial aging test is 83% -87%, the impact resistance is about 50 cm), the light retention rate of the powder paint and the coating prepared by the invention can reach 90% -93% in the artificial accelerated aging performance, and the minimum impact resistance can reach 60cm. The annular rigid aromatic ring structure and the aliphatic ring structure are matched for use, the chemical structures are tightly packed, the acting force between molecular chains is enhanced, and the performances caused by incomplete curing and poor flow under the low-temperature curing condition can be compensatedDefects.
Detailed description of the preferred embodiments
The present invention is further illustrated by the following examples, but the present invention is not limited by the examples. The raw materials in the invention are all conventional and commercially available.
The polyesters prepared in the examples were each characterized by 1H NMR using a Bruker Avance DMX NMR apparatus with TMS as an internal standard and CDCl 3 Is a solvent.
Molecular weight testing: intrinsic viscosity was measured with reference to GB/T1632.5-2008 at 25℃with phenol/tetrachloroethane (50/50, wt/wt) as solvent and polyester concentration of 0.5g/dL, measured with an Ubbelohde viscometer.
Mechanical property test: tensile breaking strength test is carried out according to GB/T1040.1-2006 standard; breaking strength is carried out according to GB/T31967.2-2015 standard; elongation at break is carried out according to GB/T2567-2008 standard; impact properties are carried out according to GB/T1843-2008 standard;
artificial accelerated ageing test
The accelerated ageing test was carried out in a manual accelerated ageing oven QUV-II (Kedi instrument: weathering test oven) using a wavelength peak at 313nm. According to national standard GBT-14522-2008, exposing the sample plate to ultraviolet light for 360 hours, setting the temperature of a blackboard to 50 ℃, setting the temperature of a dry bulb to 60 ℃, setting the temperature of a wet bulb to 50 ℃, and carrying out 4-hour condensation and 4-hour illumination on one cycle period.
The coating thickness was measured with reference to GB/T20220-2006.
The impact resistance of the coating is obtained by an impact instrument of a national Tianjin instrument testing machine factory;
yield = 100% x actual yield of target product/theoretical yield of target product.
Example 1:
4g of 4-hydroxybenzaldehyde and 2.218g of pentaerythritol were placed in a one-necked flask, and 20ml of DMF and 0.112g of p-toluenesulfonic acid were added. The reaction was carried out at 85℃for 3 hours, after the completion of the reaction, the reaction mixture was cooled, and the reaction mixture was added dropwise to 100ml of distilled water to precipitate a white precipitate. After the precipitation is completed, the mixture is filtered, washed by 100ml of distilled water and dried to obtain 4.231g of 4,4'- (2, 4,8, 10-tetraoxapipro [5,5] undecane-3, 9-diyl) diphenol (4, 4' - (2, 4,8, 10-tetraoxapyridine [5,5] undecane-3, 9-diyl) diphenol). The yield was 76.9%.
4.231g (12.3 mmol) of 4,4' - (2, 4,8, 10-tetraoxapiporo [5, 5)]undecane-3, 9-diyl) diphenol (4, 4' - (2, 4,8, 10-tetraoxapyridine [5, 5)]Undecane-3, 9-diyl) diphenol) was dissolved in 30ml DMF, 2.273g (24.6 mmol) of ethylene carbonate were added, 0.211g K was added 2 CO 3 And (3) reacting for 2 hours at 150-160 ℃ as a catalyst, cooling to room temperature after the reaction, transferring to 100ml of distilled water, precipitating white solid, filtering, collecting precipitate, washing with water for 2-3 times, and drying to obtain 4.516g of diol monomer M with the yield of 85.1%.
3.444g (20 mmol) of 1, 4-cyclohexanedicarboxylic acid, 3.024g (7.0 mmol) of diol monomer M and 1.606g (11 mmol) of isosorbide are added into a reaction vessel, 0.0021g of cerium acetate-tetrabutyl titanate is added, nitrogen is introduced for protection, stirring reaction is carried out for 4 hours at 180 ℃, the temperature is continuously increased to 240 ℃, the absolute pressure in the reaction system is controlled to be about 80 Pa, and polycondensation reaction is carried out under full stirring for 2h, thus obtaining a polycondensation crude product; dissolving the polycondensation crude product with 30ml chloroform, filtering, collecting clear liquid, adding enough methanol into clear liquid until precipitation is not increased, centrifuging, filtering, washing the obtained solid with 50ml ethanol, and drying the filtered solid at 60deg.C for 2h to obtain 7.088g copolyester CP 1 Copolyester CP 1 Molecular weight of 2.05X10 4 g/mol, yield 88.2%. For copolyester CP 1 The test results are shown in Table 1.
Collection of 100g of copolyester CP 1 Adding 34g of triglycidyl isocyanurate, 104g of barium sulfate, 8g of flatting agent (GLP 588), 3.2g of Benzoin (Benzoin) and 4.8g of brightening agent (701B) into a premixing machine, fully and uniformly mixing, pouring into a double-screw extruder, extruding, cooling, tabletting, crushing, sieving by using a 180-mesh screen, pouring the lower layer into a spray can with a spray gun, setting the spray gun voltage to be 60 kV, and spraying on a degreased substrate to obtain the ultra-resistant Hou Juzhi powder coating with the thickness of 90-100 mu m.
Super-resistant Hou Juzhi powder coatings are used for automotive hubs. Collection of 100g of copolyester CP 1 With 34g of isocyanuric acidAdding triglycidyl acid, 104g of barium sulfate, 8g of a leveling agent (GLP 588), 3.2g of Benzoin (Benzon) and 4.8g of a brightening agent (701B) into a premixing machine, fully and uniformly mixing, pouring into a double-screw extruder, extruding, cooling, tabletting, crushing, sieving by using a 180-mesh screen, pouring the lower layer into a spray can with a spray gun, setting the spray gun voltage to be 60 kV, spraying on an automobile hub, and baking and thermosetting in a high-temperature oven to form a film. The results of the ultra-high Hou Juzhi powder coating test are shown in table 2.
Example 2:
4g of 4-hydroxybenzaldehyde and 2.218g of pentaerythritol were placed in a one-necked flask, and 20ml of DMF and 0.112g of p-toluenesulfonic acid were added. The reaction was carried out at 85℃for 8 hours, after the completion of the reaction, the reaction mixture was cooled, and the reaction mixture was added dropwise to 100ml of distilled water to precipitate a white precipitate. After the precipitation is complete, the mixture is filtered, washed by 100ml of distilled water and dried to obtain 4.328g of 4,4'- (2, 4,8, 10-tetraoxapipro [5,5] undecan-3, 9-diyl) diphenol (4, 4' - (2, 4,8, 10-tetraoxapyridine [5,5] undecane-3, 9-diyl) diphenol). The yield was 78.7%.
4.328g (12.6 mmol) of 4,4' - (2, 4,8, 10-tetraoxapiporo [5, 5)]undecane-3, 9-diyl) diphenol (4, 4' - (2, 4,8, 10-tetraoxapyridine [5, 5)]Undecane-3, 9-diyl) diphenol) was dissolved in 30ml DMF, 2.218g (25.2 mmol) of ethylene carbonate were added, 0.216g K was added 2 CO 3 And (3) reacting for 2 hours at 150-160 ℃ as a catalyst, cooling to room temperature after the reaction, transferring to 100ml of distilled water, precipitating white solid, filtering, collecting precipitate, washing with water for 2-3 times, and drying to obtain 4.540g of diol monomer M with the yield of 83.4%.
3.444g (20 mmol) of 1, 4-cyclohexanedicarboxylic acid, 3.456g (8.0 mmol) of diol monomer M and 1.606g (11 mmol) of isosorbide are added into a reaction vessel, 0.0021g of cerium acetate-tetrabutyl titanate is added, nitrogen is introduced for protection, stirring reaction is carried out for 4 hours at 180 ℃, the temperature is continuously increased to 240 ℃, the absolute pressure in the reaction system is controlled to be about 80 Pa, and polycondensation reaction is carried out under full stirring for 2h, thus obtaining a polycondensation crude product; dissolving the polycondensation crude product with 30ml chloroform, filtering, collecting clear solution, adding enough methanol into the clear solution until precipitation is not increased, centrifuging, and filteringThe solid was washed with 50ml ethanol and the re-filtered solid was dried at 60℃for 2h to give 7.664g of copolyester CP 2 Copolyester CP 2 Molecular weight of 2.18×10 4 g/mol, yield 90.1%, for copolyester CP 2 The test results are shown in Table 1.
Collection of 100g of copolyester CP 2 Adding 34g of triglycidyl isocyanurate, 104g of barium sulfate, 8g of flatting agent (GLP 588), 3.2g of Benzoin (Benzoin) and 4.8g of brightening agent (701B) into a premixing machine, fully and uniformly mixing, pouring into a double-screw extruder, extruding, cooling, tabletting, crushing, sieving by using a 180-mesh screen, pouring the lower layer into a spray can with a spray gun, setting the spray gun voltage to be 60 kV, and spraying on a degreased substrate to obtain the ultra-resistant Hou Juzhi powder coating with the thickness of 90-100 mu m.
Super-resistant Hou Juzhi powder coatings are used as motorcycle topcoats. Collection of 100g of copolyester CP 2 Adding 34g of triglycidyl isocyanurate, 104g of barium sulfate, 8g of flatting agent (GLP 588), 3.2g of Benzoin (Benzon) and 4.8g of brightening agent (701B) into a premixing machine, fully and uniformly mixing, pouring into a double-screw extruder, extruding, cooling, tabletting, crushing, sieving by using a 180-mesh screen, pouring the lower layer into a spray can with a spray gun, setting the voltage of the spray gun to be 60 kV, spraying on the surface of a motorcycle body, and baking and thermally curing in a high-temperature oven to form a film. The results of the ultra-high Hou Juzhi powder coating test are shown in table 2.
Example 3:
4g of 4-hydroxybenzaldehyde and 2.218g of pentaerythritol were placed in a one-necked flask, and 20ml of DMF and 0.112g of p-toluenesulfonic acid were added. The reaction was carried out at 85℃for 8 hours, after the completion of the reaction, the reaction mixture was cooled, and the reaction mixture was added dropwise to 100ml of distilled water to precipitate a white precipitate. After the precipitation is completed, the mixture is filtered, washed by 100ml of distilled water and dried to obtain 4.4573 g of 4,4'- (2, 4,8, 10-tetraoxapiporo [5,5] undecane-3, 9-diyl) diphenol (4, 4' - (2, 4,8, 10-tetraoxapyridine [5,5] undecane-3, 9-diyl) diphenol) with the yield of 81.0 percent.
4.453g (12.9 mmol) of 4,4' - (2, 4,8, 10-tetraoxapiporo [5, 5)]undecane-3,9-diyl)diphenol(4,4'-(2, 4,8, 10-tetraoxapyridine [5,5]]Undecane-3, 9-diyl) diphenol) was dissolved in 30ml DMF, 2.218g (25.8 mmol) of ethylene carbonate were added, 0.223g K was added 2 CO 3 As a catalyst, reacting for 2 hours at 150-160 ℃, cooling to room temperature after the reaction, transferring to 100ml of distilled water, precipitating white solid, filtering, collecting precipitate, washing with water for 2-3 times, and drying to obtain 4.631g of glycol monomer M with the yield of 83.1%.
3.444g (20 mmol) of 1, 4-cyclohexanedicarboxylic acid, 3.802g (8.8 mmol) of diol monomer M and 1.606g (11 mmol) of isosorbide are added into a reaction vessel, 0.0021g of cerium acetate-tetrabutyl titanate is added, nitrogen is introduced for protection, stirring reaction is carried out for 4 hours at 180 ℃, the temperature is continuously increased to 240 ℃, the absolute pressure in the reaction system is controlled to be about 80 Pa, and polycondensation reaction is carried out under full stirring for 2h, thus obtaining a polycondensation crude product; dissolving the polycondensation crude product with 30ml chloroform, filtering, collecting clear liquid, adding enough methanol into clear liquid until precipitation is not increased, centrifuging, filtering, washing the obtained solid with 50ml ethanol, and drying the filtered solid at 60deg.C for 2h to obtain 7.896g copolyester CP 3 Copolyester CP 3 Molecular weight of 2.36×10 4 g/mol, yield 89.2%, for copolyester CP 3 The test results are shown in Table 1.
Collection of 100g of copolyester CP 3 Adding 34g of Triglycidyl Isocyanurate (TIGC), 104g of barium sulfate, 8g of flatting agent (GLP 588), 3.2g of Benzoin (Benzonin) and 4.8g of brightening agent (701B) into a premixing machine, fully and uniformly mixing, pouring into a double-screw extruder, extruding, cooling, tabletting, crushing, sieving by using a 180-mesh screen, pouring the lower layer into a spray can with a spray gun, setting the spray gun voltage to be 60 kV, and spraying on a degreased base material to obtain the super-resistant Hou Juzhi powder coating with the thickness of 90-100 mu m.
Super-resistant Hou Juzhi powder coatings are used on paper used for important document materials in archives, museums, etc. Collection of 100g of copolyester CP 3 Adding 34g triglycidyl isocyanurate, 104g barium sulfate, 8g leveling agent (GLP 588), 3.2g Benzoin (Benzon) and 4.8g brightening agent (701B) into a premixing machine for fillingUniformly mixing, pouring into a double-screw extruder, extruding, cooling, tabletting, crushing, sieving with a 180-mesh screen, pouring the lower layer into a spray can with a spray gun, setting the voltage of the spray gun to be 60 kV, directly adsorbing powder coating on the surface of paper under the action of an electric field, and fixing on the surface of the paper through thermo-mechanical calendaring treatment to form the ultra-resistant Hou Juzhi powder coating. The results of the ultra-high Hou Juzhi powder coating test are shown in table 2.
Example 4:
4g of 4-hydroxybenzaldehyde and 2.218g of pentaerythritol were placed in a one-necked flask, and 20ml of DMF and 0.112g of p-toluenesulfonic acid were added. The reaction was carried out at 85℃for 8 hours, after the completion of the reaction, the reaction mixture was cooled, and the reaction mixture was added dropwise to 100ml of distilled water to precipitate a white precipitate. After the precipitation is completed, the mixture is filtered, washed by 100ml of distilled water and dried to obtain 4.252g of 4,4'- (2, 4,8, 10-tetraoxapipro [5,5] undecane-3, 9-diyl) diphenol (4, 4' - (2, 4,8, 10-tetraoxapyridine [5,5] undecane-3, 9-diyl) diphenol). The yield was 77.3%.
4.252g (12.4 mmol) of 4,4' - (2, 4,8, 10-tetraoxapiporo [5, 5)]undecane-3, 9-diyl) diphenol (4, 4' - (2, 4,8, 10-tetraoxapyridine [5, 5)]Undecane-3, 9-diyl) diphenol) was dissolved in 30ml DMF, 2.182g (24.8 mmol) of ethylene carbonate were added, 0.213g K was added 2 CO 3 And (3) reacting for 2 hours at 150-160 ℃ as a catalyst, cooling to room temperature after the reaction, transferring to 100ml of distilled water, precipitating white solid, filtering, collecting precipitate, washing with water for 2-3 times, and drying to obtain 4.569g of diol monomer M with the yield of 85.3%.
3.444g (20 mmol) of 1, 4-cyclohexanedicarboxylic acid, 3.802g (8.8 mmol) of diol monomer M and 1.548g (10.6 mmol) of isosorbide are added into a reaction vessel, 0.0021g of cerium acetate-tetrabutyl titanate is added, nitrogen is introduced for protection, stirring reaction is carried out for 4 hours at 180 ℃, the temperature is continuously increased to 240 ℃, the absolute pressure in a reaction system is controlled to be about 80 Pa, and polycondensation reaction is carried out under full stirring for 2h, thus obtaining a polycondensation crude product; dissolving the polycondensation crude product with 30ml chloroform, filtering, collecting clear solution, adding methanol into clear solution until precipitation is not increased, centrifuging, filtering, washing the obtained solid with 50ml ethanol, and filtering again to obtain solid at 60deg.CDrying 2h to give 8.029g of copolyester CP 4 Copolyester CP 4 Molecular weight of 2.21×10 4 g/mol, yield 91.3%, for copolyester CP 4 The test results are shown in Table 1.
Collection of 100g of copolyester CP 4 Adding 34g of Triglycidyl Isocyanurate (TIGC), 104g of barium sulfate, 8g of flatting agent (GLP 588), 3.2g of Benzoin (Benzonin) and 4.8g of brightening agent (701B) into a premixing machine, fully and uniformly mixing, pouring into a double-screw extruder, extruding, cooling, tabletting, crushing, sieving by using a 180-mesh screen, pouring the lower layer into a spray can with a spray gun, setting the spray gun voltage to be 60 kV, and spraying on a degreased base material to obtain the super-resistant Hou Juzhi powder coating with the thickness of 90-100 mu m.
Super-resistant Hou Juzhi powder coatings are used for plastic surfaces. Collection of 100g of copolyester CP 4 Adding 34g of triglycidyl isocyanurate, 104g of barium sulfate, 8g of flatting agent (GLP 588), 3.2g of Benzoin (Benzon) and 4.8g of brightening agent (701B) into a premixing machine, fully and uniformly mixing, pouring into a double-screw extruder, extruding, cooling, tabletting, crushing, sieving by using a 180-mesh screen, pouring the lower layer into a spray can with a spray gun, setting the voltage of the spray gun to be 60 kV, and adsorbing the powder coating on the surface of plastic under the action of an electric field to form the super-resistant Hou Juzhi powder coating. The results of the ultra-high Hou Juzhi powder coating test are shown in table 2.
Example 5:
4g of 4-hydroxybenzaldehyde and 2.218g of pentaerythritol were placed in a one-necked flask, and 20ml of DMF and 0.112g of p-toluenesulfonic acid were added. The reaction was carried out at 85℃for 8 hours, after the completion of the reaction, the reaction mixture was cooled, and the reaction mixture was added dropwise to 100ml of distilled water to precipitate a white precipitate. After the precipitation is completed, the mixture is filtered, washed by 100ml of distilled water and dried to obtain 4.153g of 4,4'- (2, 4,8, 10-tetraoxapiporo [5,5] undecane-3, 9-diyl) diphenol (4, 4' - (2, 4,8, 10-tetraoxapyridine [5,5] undecane-3, 9-diyl) diphenol) with the yield of 75.5 percent.
4.153g (12.1 mmol) of 4,4' - (2, 4,8, 10-tetraoxapiporo [5, 5)]undecane-3, 9-diyl) diphenol (4, 4' - (2, 4,8, 10-tetraoxapyridine [5, 5)]Undecane-3, 9-diyl) diphenol) was dissolved in 30ml DMF, 2.130g (24.2 mmol) of ethylene carbonate were added, 0.208g K was added 2 CO 3 And (3) reacting for 2 hours at 150-160 ℃ as a catalyst, cooling to room temperature after the reaction, transferring to 100ml of distilled water, precipitating white solid, filtering, collecting precipitate, washing with water for 2-3 times, and drying to obtain 4.427g of glycol monomer M with the yield of 84.7%.
3.444g (20 mmol) of 1, 4-cyclohexanedicarboxylic acid, 3.802g (8.8 mmol) of diol monomer M and 1.664g (11.4 mmol) of isosorbide are added into a reaction vessel, 0.0021g of cerium acetate-tetrabutyl titanate is added, nitrogen is introduced for protection, stirring reaction is carried out for 4 hours at 180 ℃, the temperature is continuously increased to 240 ℃, the absolute pressure in a reaction system is controlled to be about 80 Pa, and polycondensation reaction is carried out under full stirring for 2h, thus obtaining a polycondensation crude product; dissolving the polycondensation crude product with 30ml chloroform, filtering, collecting clear liquid, adding enough methanol into clear liquid until precipitation is not increased, centrifuging, filtering, washing the obtained solid with 50ml ethanol, and drying the filtered solid at 60deg.C for 2h to obtain 7.903g copolyester CP 5 Copolyester CP 5 Molecular weight of 2.57×10 4 g/mol, yield 88.7%, for copolyester CP 5 The test results are shown in Table 1.
Collection of 100g of copolyester CP 5 Adding 34g of Triglycidyl Isocyanurate (TIGC), 104g of barium sulfate, 8g of flatting agent (GLP 588), 3.2g of Benzoin (Benzonin) and 4.8g of brightening agent (701B) into a premixing machine, fully and uniformly mixing, pouring into a double-screw extruder, extruding, cooling, tabletting, crushing, sieving by using a 180-mesh screen, pouring the lower layer into a spray can with a spray gun, setting the spray gun voltage to be 60 kV, and spraying on a degreased base material to obtain the super-resistant Hou Juzhi powder coating with the thickness of 90-100 mu m.
Super-resistant Hou Juzhi powder coatings are used on wood surfaces. Collection of 100g of copolyester CP 5 Adding 34g triglycidyl isocyanurate, 104g barium sulfate, 8g flatting agent (GLP 588), 3.2g Benzoin and 4.8g brightening agent (701B) into a premixing machine, fully and uniformly mixing, pouring into a double screw extruder, extruding, cooling, tabletting, crushing and powderingAfter crushing, sieving with a 180-mesh screen, pouring the lower layer into a spray can with a spray gun, setting the voltage of the spray gun to be 60 kV, adsorbing the powder coating on the surface of wood under the action of an electric field, and infrared heating to cure the surface to form the ultra-resistant Hou Juzhi powder coating. The results of the ultra-high Hou Juzhi powder coating test are shown in table 2.
Example 6:
4g of 4-hydroxybenzaldehyde and 2.218g of pentaerythritol were placed in a one-necked flask, and 20ml of DMF and 0.112g of p-toluenesulfonic acid were added. The reaction was carried out at 85℃for 8 hours, after the completion of the reaction, the reaction mixture was cooled, and the reaction mixture was added dropwise to 100ml of distilled water to precipitate a white precipitate. After the precipitation is completed, the mixture is filtered, washed by 100ml of distilled water and dried to obtain 4.421g of 4,4'- (2, 4,8, 10-tetraoxapipro [5,5] undecane-3, 9-diyl) diphenol (4, 4' - (2, 4,8, 10-tetraoxapyridine [5,5] undecane-3, 9-diyl) diphenol) with the yield of 80.4 percent.
4.421g (12.9 mmol) of 4,4' - (2, 4,8, 10-tetraoxapiporo [5, 5)]undecane-3, 9-diyl) diphenol (4, 4' - (2, 4,8, 10-tetraoxapyridine [5, 5)]Undecane-3, 9-diyl) diphenol) was dissolved in 30ml DMF, 2.270g (25.8 mmol) of ethylene carbonate were added, 0.221g K was added 2 CO 3 And (3) reacting for 2 hours at 150-160 ℃ as a catalyst, cooling to room temperature after the reaction, transferring to 100ml of distilled water, precipitating white solid, filtering, collecting precipitate, washing with water for 2-3 times, and drying to obtain 4.620g of diol monomer M with the yield of 82.9%.
3.444g (20 mmol) of 1, 4-cyclohexanedicarboxylic acid, 3.802g (8.8 mmol) of diol monomer M and 1.781g (12.2 mmol) of isosorbide are added into a reaction vessel, 0.0021g of cerium acetate-tetrabutyl titanate is added, nitrogen is introduced for protection, stirring reaction is carried out for 4 hours at 180 ℃, the temperature is continuously increased to 240 ℃, the absolute pressure in a reaction system is controlled to be about 80 Pa, and polycondensation reaction is carried out for 2h under full stirring, thus obtaining a polycondensation crude product; dissolving the polycondensation crude product with 30ml chloroform, filtering, collecting clear liquid, adding enough methanol into clear liquid until precipitation is not increased, centrifuging, filtering, washing the obtained solid with 50ml ethanol, and drying the filtered solid at 60deg.C for 2h to obtain 7.935g copolyester CP 6 Copolyester CP 6 Molecular weight of 2.83×10 4 g/mol, yield87.9% for copolyester CP 6 The test results are shown in Table 1.
Collection of 100g of copolyester CP 6 Adding 34g of Triglycidyl Isocyanurate (TIGC), 104g of barium sulfate, 8g of flatting agent (GLP 588), 3.2g of Benzoin (Benzonin) and 4.8g of brightening agent (701B) into a premixing machine, fully and uniformly mixing, pouring into a double-screw extruder, extruding, cooling, tabletting, crushing, sieving by using a 180-mesh screen, pouring the lower layer into a spray can with a spray gun, setting the spray gun voltage to be 60 kV, and spraying on a degreased base material to obtain the super-resistant Hou Juzhi powder coating with the thickness of 90-100 mu m.
Super-resistant Hou Juzhi powder coatings are used on furniture surfaces. Collection of 100g of copolyester CP 6 Adding 34g of triglycidyl isocyanurate, 104g of barium sulfate, 8g of flatting agent (GLP 588), 3.2g of Benzoin (Benzon) and 4.8g of brightening agent (701B) into a premixing machine, fully and uniformly mixing, pouring into a double-screw extruder, extruding, cooling, tabletting, crushing, sieving by using a 180-mesh screen, pouring the lower layer into a spray can with a spray gun, setting the voltage of the spray gun to be 60 kV, adsorbing the powder coating on the surface of a household appliance under the action of an electric field, and forming an ultra-high Hou Juzhi powder coating on the infrared heat-cured surface. The results of the ultra-high Hou Juzhi powder coating test are shown in table 2.
Example 7:
4g of 4-hydroxybenzaldehyde and 2.218g of pentaerythritol were placed in a one-necked flask, and 20ml of DMF and 0.112g of p-toluenesulfonic acid were added. The reaction was carried out at 85℃for 8 hours, after the completion of the reaction, the reaction mixture was cooled, and the reaction mixture was added dropwise to 100ml of distilled water to precipitate a white precipitate. After the precipitation is completed, the mixture is filtered, washed by 100ml of distilled water and dried to obtain 4.208g of 4,4'- (2, 4,8, 10-tetraoxapipro [5,5] undecane-3, 9-diyl) diphenol (4, 4' - (2, 4,8, 10-tetraoxapyridine [5,5] undecane-3, 9-diyl) diphenol) with the yield of 76.5 percent.
4.208g (12.2 mmol) of 4,4' - (2, 4,8,10-tetraoxaspiro [5, 5)]undecane-3, 9-diyl) diphenol (4, 4' - (2, 4,8, 10-tetraoxapyridine [5, 5)]Undecane-3, 9-diyl) diphenol) was dissolved in 30ml DMF, 2.147g (24.4 mmol) of ethylene carbonate were added0.210gK 2 CO 3 And (3) reacting for 2 hours at 150-160 ℃ as a catalyst, cooling to room temperature after the reaction, transferring to 100ml of distilled water, precipitating white solid, filtering, collecting precipitate, washing with water for 2-3 times, and drying to obtain 4.448g of glycol monomer M with the yield of 84.4%.
3.444g (20 mmol) of 1, 4-cyclohexanedicarboxylic acid, 3.802g (8.8 mmol) of diol monomer M and 1.781g (12.2 mmol) of isosorbide are added into a reaction vessel, 0.0021g of niobic acid is added, nitrogen is introduced for protection, stirring reaction is carried out for 4 hours at 180 ℃, heating is continued to 240 ℃, absolute pressure in a reaction system is controlled to be about 80 Pa, and polycondensation reaction is carried out under full stirring for 2h, thus obtaining a polycondensation crude product; dissolving the polycondensation crude product with 30ml chloroform, filtering, collecting clear liquid, adding enough methanol into clear liquid until precipitation is not increased, centrifuging, filtering, washing the obtained solid with 50ml ethanol, and drying the filtered solid at 60deg.C for 2h to obtain 7.709g copolyester CP 7 Copolyester CP 7 Molecular weight of 2.52×10 4 g/mol, yield of 85.4%, for copolyester CP 7 The test results are shown in Table 1.
Collection of 100g of copolyester CP 7 Adding 34g of Triglycidyl Isocyanurate (TIGC), 104g of barium sulfate, 8g of flatting agent (GLP 588), 3.2g of Benzoin (Benzonin) and 4.8g of brightening agent (701B) into a premixing machine, fully and uniformly mixing, pouring into a double-screw extruder, extruding, cooling, tabletting, crushing, sieving by using a 180-mesh screen, pouring the lower layer into a spray can with a spray gun, setting the spray gun voltage to be 60 kV, and spraying on a degreased base material to obtain the super-resistant Hou Juzhi powder coating with the thickness of 90-100 mu m.
The super-resistant Hou Juzhi powder coating is used for engineering pipelines. Collection of 100g of copolyester CP 7 Adding 34g triglycidyl isocyanurate, 104g barium sulfate, 8g flatting agent (GLP 588), 3.2g Benzoin (Benzoin) and 4.8g brightening agent (701B) into a premixing machine, fully and uniformly mixing, pouring into a double-screw extruder, extruding, cooling, tabletting, crushing, sieving with a 180-mesh screen, pouring the lower layer into a spray can with a spray gun, and setting the voltage of the spray gun to 60 kAnd V, spraying the powder coating on the surface of the pipeline under the action of an electric field, and curing the surface at high temperature to form the super-resistant Hou Juzhi powder coating. The results of the ultra-high Hou Juzhi powder coating test are shown in table 2.
TABLE 1 copolyester CP in examples 1-7 1 ～CP 7 Test results of samples
[ eta 1] is the initial intrinsic viscosity of the sample, and [ eta 2] is the intrinsic viscosity of the sample after 3 years of degradation in a natural soil environment.
[3] Tang Zhuohua research on biodegradable polyester elastomer particle modified PBS [ D ]. Qingdao university of science and technology, 2019.
Table 2: powder coating test results
| Project | CP 1 | CP 2 | CP 3 | CP 4 | CP 5 | CP 6 | CP 7 |
| Film thickness/. Mu.m | 90~100 | 90~100 | 90~100 | 90~100 | 90~100 | 90~100 | 90~100 |
| Gloss retention (%) | 90 | 92 | 91 | 93 | 90 | 91 | 92 |
| Impact test (1)/cm | 60 | 62 | 61 | 60 | 63 | 64 | 62 |
| Impact test (2)/cm | 60 | 62 | 60 | 61 | 63 | 63 | 62 |
(1) Test after 0d (2) test after 30d
As can be seen from the comparison of the data in the table 1, the invention takes 1, 4-cyclohexane dicarboxylic acid, a dihydric alcohol monomer M and isosorbide as monomers, the number average molecular weight of the synthesized polyester is higher than that of polybutylene succinate (PBS), and the tensile breaking strength is 35.1-57.3 MPa higher than that of polybutylene succinate (PBS); polybutylene succinate (PBS) has an elongation at break of 265.0%, while the copolyester CP synthesized by the invention 1 ～CP 7 The elongation at break of (2) is slightly lower than that of polybutylene succinate (PBS). From Table 1 [ eta 1]]And [ eta 2]Compared with the prior art, the bio-based copolyester based on the 4-hydroxybenzaldehyde synthesized by the invention is degraded in natural soil environment, and the intrinsic viscosity of the polyester is reduced by more than half after 3 years, which proves that the molecular weight of the polyester is greatly reduced from the other aspect. Copolyester CP synthesized by the invention 1 ～CP 7 The impact strength of the polymer is about 4-5 times of that of polybutylene succinate (PBS). As can be seen from Table 2, the results of the artificial accelerated aging properties of the powder coating show that the light retention after 360-h light irradiation can still be kept at 90% -93%, and the powder coating prepared from the synthetic polyester of isophthalic acid/terephthalic acid, adipic acid and polyalcohol [2] ([2]Qian Renjun, yang Dong, liao Ping, shao Fei,wang Huili Synthesis and application research of polyester resin for powder coating with Excellent weather resistance [ J]Compared with the Chinese paint (2021,36 (12): 34-39 ") (the light retention rate of the artificial aging test is 83% -87%, and the impact resistance is about 50 cm), the light retention rate of the powder paint and the coating prepared by the invention can reach 90% -93% in the artificial accelerated aging performance, the minimum impact resistance can reach 60cm, and the impact resistance after 30 days can still be basically unchanged, so that the powder paint and the coating have substantial improvement compared with the prior art.
In conclusion, the impact resistance and weather resistance of the super weather-resistant polyester powder coating reported in the prior literature are difficult to meet the requirements of various industries, the paint film is too brittle in the use process, the front and back impact resistance is poor, and the requirements of various aspects of material properties in practical application are difficult to meet. Aiming at the problems in the prior art, the main purpose of the invention is to provide a preparation method and application of a bio-based copolyester based on 4-hydroxybenzaldehyde, in particular to a bio-based copolyester based on 4-hydroxybenzaldehyde prepared by using 4-hydroxybenzaldehyde and isosorbide as raw materials. The degradable copolyester based on biomass as a monomer can be used for preparing a super weather-resistant polyester powder coating, and compared with the existing super weather-resistant polyester powder coating, the degradable copolyester has good weather resistance and mechanical properties and is harmless to the environment. Therefore, the invention patent of the invention 'preparation of bio-based copolyester based on 4-hydroxybenzaldehyde and application thereof' has good market prospect.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (4)
1. A bio-based copolyester based on 4-hydroxybenzaldehyde, which is characterized by the following structure as shown in formula 1:
in formula 1, x is 23 to 37, and y is 46 to 67.
2. The preparation method of the bio-based copolyester based on 4-hydroxybenzaldehyde is characterized by comprising the following three steps:
1) Synthesis of diol monomer M: adding 4-hydroxybenzaldehyde and pentaerythritol into a single-neck flask according to the mass ratio of (1-1.2), adding 20-50 ml of DMF, adding 0.24-0.5% of p-toluenesulfonic acid by mass of 4-hydroxybenzaldehyde, reacting for 2-3 hours at 85-100 ℃, cooling to room temperature, pouring into 80-100 ml of distilled water to precipitate, filtering, washing filter residues with distilled water until precipitation is complete, and drying to obtain 4,4'- (2, 4,8, 10-tetraoxaaspiro [5,5] decane-3, 9-diyl) diphenol with the Chinese name of 4,4' - (2, 4,8, 10-tetraoxapyridine [5,5] undecane-3, 9-diyl) diphenol, wherein the structure is shown as formula a;
4-5 g of 4,4' - (2, 4,8,10-tetraoxaspiro [5,5]]undecane-3,9-diyl diphenol Chinese name 4,4' - (2, 4,8, 10-tetraoxapyridine [5,5]]Undecane-3, 9-diyl) diphenol is dissolved in 30-50 ml DMF, ethylene carbonate is added, the mass ratio of substance A to ethylene carbonate is 1:2-2.3, K is added in an amount of 1-5% by mass of substance A 2 CO 3 Reacting for 2-3 h at 150-160 ℃ as a catalyst, cooling to room temperature after the reaction, transferring to distilled water, precipitating white solid, filtering, collecting precipitate, washing with water for 2-3 times, and drying to obtain a diol monomer M with a structure shown as formula b;
2) Synthesis of polycondensation crude products: adding (5.3-6.1) a proper amount of catalyst into a reaction container, introducing nitrogen for protection, stirring at 180-200 ℃ for 3-4 hours, heating to 240-260 ℃, controlling the absolute pressure in a reaction system to 80-150 Pa, and carrying out polycondensation reaction for 2-4 hours under full stirring to obtain a polycondensation crude product, wherein the diol monomer M is used as a first alcohol source, the isosorbide is used as a second alcohol source, and the ratio of 1, 4-cyclohexanedicarboxylic acid to the first alcohol source is 10 (3.8-4.4);
3) Purifying a polycondensation crude product: dissolving the polycondensation crude product with chloroform, filtering, taking clear liquid, adding enough methanol into the clear liquid until precipitation is not increased, centrifugally separating, filtering, washing the obtained solid with ethanol, and drying the filtered solid at 60-80 ℃ for 1-2 h to obtain the bio-based copolyester based on 4-hydroxybenzaldehyde.
3. The preparation method of the bio-based copolyester based on 4-hydroxybenzaldehyde according to claim 2, wherein the catalyst in the step 2) is one of cerium acetate-tetrabutyl titanate catalyst, zinc acetate, potassium fluotitanate and niobic acid, the dosage of the catalyst is 0.06% -0.19% of the dosage of 1, 4-cyclohexane dicarboxylic acid substances, and the molar ratio of cerium acetate to tetrabutyl titanate in the cerium acetate-tetrabutyl titanate catalyst is 1.0:0.0009-0.3.
4. Use of a bio-based copolyester based on 4-hydroxybenzaldehyde as claimed in claim 1, in the coating of automobiles, motorcycles, paper, plastics, wood, advanced furniture, engineering pipes, for protecting materials from the external environment, in the preparation method: 100g of bio-based copolyester based on 4-hydroxybenzaldehyde, 30 g-40 g of triglycidyl isocyanurate, 100 g-120 g of barium sulfate, 6 g-10 g of flatting agent GLP588, 3 g-4 g of benzoin and 4 g-6 g of brightening agent 701B are added into an internal mixer to be fully and uniformly mixed, then the mixture is transferred into a double screw extruder to be extruded, cooled and tableted, crushed, screened by a 180-mesh screen, the lower layer is poured into a spray can with a spray gun, the spray gun voltage is set to be 50-70 kV, and the spray gun is sprayed on a degreased base material to obtain the super-resistant Hou Juzhi powder coating with the thickness of 70-120 mu m, and the super-resistant Hou Juzhi powder coating is used for protecting materials from the corrosion of external environment.
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