CN110396182B - Polyester resin prepared from bio-based raw materials and preparation method and application thereof - Google Patents
Polyester resin prepared from bio-based raw materials and preparation method and application thereof Download PDFInfo
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- CN110396182B CN110396182B CN201910807180.7A CN201910807180A CN110396182B CN 110396182 B CN110396182 B CN 110396182B CN 201910807180 A CN201910807180 A CN 201910807180A CN 110396182 B CN110396182 B CN 110396182B
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- polyester resin
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- oxabicyclo
- heptane
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 25
- 239000004645 polyester resin Substances 0.000 title claims abstract description 25
- 239000002994 raw material Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 21
- JAABVEXCGCXWRR-UHFFFAOYSA-N norcantharidin Chemical compound C1CC2C3C(=O)OC(=O)C3C1O2 JAABVEXCGCXWRR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 14
- 229960002479 isosorbide Drugs 0.000 claims abstract description 14
- 229920005862 polyol Polymers 0.000 claims abstract description 7
- 150000003077 polyols Chemical class 0.000 claims abstract description 7
- 150000001298 alcohols Chemical class 0.000 claims abstract description 6
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 230000009477 glass transition Effects 0.000 claims abstract description 4
- 150000007513 acids Chemical class 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 7
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 5
- 229940035437 1,3-propanediol Drugs 0.000 claims description 5
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 229960004063 propylene glycol Drugs 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 abstract description 7
- 230000003335 steric effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Substances OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 229940119177 germanium dioxide Drugs 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 229920013724 bio-based polymer Polymers 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920003270 Cymel® Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-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
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/56—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds other than from esters thereof
- C08G63/58—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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/863—Germanium or compounds thereof
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a polyester resin prepared from bio-based raw materials and a preparation method thereof, wherein the polyester resin is prepared by polymerizing 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride, isosorbide, 1, 3-propylene glycol, polyol and polybasic acid from bio-based, the 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride accounts for 50-100% of the molar content of all acids, the isosorbide accounts for 20-60% of the molar content of all alcohols, and the 1, 3-propylene glycol accounts for 10-30% of the molar content of all alcohols. The polyester resin of the invention completely uses bio-based materials, and is environment-friendly and energy-saving. Meanwhile, the combination of 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride, which is a polycyclic dibasic acid with strong rigidity, and polycyclic isosorbide is adopted, so that the product has high glass transition temperature. Due to the existence of the polycyclic structure, the steric effect of the product is high, ester bonds which are easy to attack can be well protected, and the product has good resistance.
Description
Technical Field
The invention belongs to the technical field of high polymer polymerization, and particularly relates to polyester resin prepared from bio-based raw materials, and a preparation method and application thereof.
Background
The bio-based polymer is a green environment-friendly polymer synthesized by biological monomers. The bio-based polymer generally has the characteristics of green source, low price, easy obtainment, easy degradation and the like. In addition, in view of saving petroleum resources, protecting environment, developing recycling economy, etc., the production of polymer materials by using renewable biological resources instead of petrochemicals has become a hotspot of people's research, and the synthesis and application of bio-based polymers are more and more paid attention by people.
The bio-based polyester resin is also in the rapid development process at present, but most products only use the bio-based material partially, and can be replaced completely rarely, otherwise, the use performance is greatly reduced. The can coating has high requirements on the mechanical property, resistance and safety performance of resin due to direct contact with food, and the synthetic raw materials of the can coating are mainly petroleum-based raw materials at present.
Disclosure of Invention
The invention provides a polyester resin prepared from bio-based raw materials, and a preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme:
a method for preparing polyester resin from bio-based raw materials by polymerizing 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride, isosorbide, 1, 3-propanediol, and bio-based polyol and polybasic acid, wherein the 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride accounts for 50-100% of the molar content of all acids, the isosorbide accounts for 20-60% of the molar content of all alcohols, and the 1, 3-propanediol accounts for 10-30% of the molar content of all alcohols.
Preferably, a method for preparing a polyester resin from bio-based raw materials as described above, comprises the steps of,
s1, adding 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride, isosorbide, 1, 3-propylene glycol, polyol from a biological group and polybasic acid into a reaction kettle, stirring and heating for three times under the protection of nitrogen until the amount of byproducts reaches a theoretical value;
and S2, adding a catalyst and a stabilizer into the reaction kettle, continuously heating to 275-295 ℃, reducing the pressure to be below 100Pa to perform polycondensation reaction, sampling and analyzing until the viscosity of the polymer reaches an expected value, and discharging.
Preferably, in the S1, under the protection of nitrogen, the temperature is raised to 60-100 ℃ for the first time, the temperature is raised to 220 ℃ for the second time, and the temperature is raised to 230-270 ℃ for the third time.
Preferably, the 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride is derived from the bio-based material furfural preparation. Specifically, furfural reacts with sodium perchlorate to be oxidized into maleic acid, maleic anhydride is produced through dehydration, and the 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride is prepared through hydrogenation after the maleic anhydride reacts with furan.
Preferably, the polyol from the bio-based group is selected from 1, 6-hexanediol, 1, 4-butanediol, 1, 2-propanediol, glycerol, or any combination of two or more thereof.
Preferably, the polybasic acid from the bio-based group is selected from 1, 4-succinic acid, adipic acid and furan dicarboxylic acid, or any combination of two of the two.
Preferably, a polyester resin produced by a method of producing a polyester resin produced from bio-based raw materials as described in any of the above.
Preferably, the number average molecular weight of the polyester resin is 15000-45000, and the glass transition temperature is 80-120 ℃.
The invention has the beneficial effects that: the polyester resin of the invention completely uses bio-based materials, and is environment-friendly and energy-saving. Meanwhile, the combination of 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride, which is a polycyclic dibasic acid with strong rigidity, and polycyclic isosorbide is adopted, so that the product has high glass transition temperature. Due to the existence of the polycyclic structure, the steric effect of the product is high, ester bonds which are easy to attack can be well protected, and the product has good resistance. The polycyclic structure of the 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride can improve the rigidity of the product and also provide certain flexibility, so that the processability of the product is improved better.
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1
9.3kg of 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride, 7kg of furandicarboxylic acid, 1.5kg of 1, 3-propylene glycol, 8kg of isosorbide and 3.5kg of 1, 6-hexanediol are put into a 100L stainless steel reaction kettle, stirred at the rotating speed of 55-80 rpm under the protection of nitrogen, quickly heated to 60-100 ℃ for reaction for 0.3 hour, gradually heated to 220 ℃ for heat preservation for reaction for 1 hour, heated to 230-270 ℃ for reaction for about 2.2 hours, and the reaction is finished when the amount of the byproduct reaches a theoretical value. Adding 21g of ethylene glycol antimony, 10g of germanium dioxide and 16g of triphenyl phosphate, continuously heating and slowly reducing pressure, adjusting the rotating speed to 30-50 rpm, controlling the temperature to 275-295 ℃, and gradually reducing the pressure to below 100Pa to perform polycondensation reaction. Sampling and analyzing, stopping stirring when the viscosity of the polymer reaches a desired value, eliminating vacuum, and discharging a product.
Example 2
11.8kg of 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride, 3.5kg of 1, 4-succinic acid, 1.6kg of 1, 3-propylene glycol, 7.3kg of isosorbide and 2.8kg of 1, 4-butanediol are put into a 100L stainless steel reaction kettle, stirred at the rotating speed of 55-80 rpm under the protection of nitrogen, quickly heated to 60-100 ℃ for reaction for 0.3 hour, gradually heated to 220 ℃ for heat preservation for reaction for 1 hour, then heated to 230-270 ℃ for reaction for about 2.2 hours, and the reaction is finished when the amount of the byproduct reaches the theoretical value. Adding 21g of ethylene glycol antimony, 10g of germanium dioxide and 16g of triphenyl phosphate, continuously heating and slowly reducing pressure, adjusting the rotating speed to 30-50 rpm, controlling the temperature to 275-295 ℃, and gradually reducing the pressure to below 100Pa to perform polycondensation reaction. Sampling and analyzing, stopping stirring when the viscosity of the polymer reaches a desired value, eliminating vacuum, and discharging a product.
Example 3
14.3kg of 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride, 1.8kg of 1, 4-succinic acid, 2.1kg of 1, 3-propylene glycol, 9.2kg of isosorbide, 1.4kg of 1, 4-butanediol and 0.2kg of glycerol are put into a 100L stainless steel reaction kettle, stirred at the rotating speed of 55-80 rpm under the protection of nitrogen, quickly heated to 60-100 ℃ for reaction for 0.3 hour, gradually heated to 220 ℃ for heat preservation for reaction for 1 hour, and then heated to 230-270 ℃ for reaction for about 2.2 hours, and the reaction is finished when the amount of the byproduct reaches the theoretical value. Adding 21g of ethylene glycol antimony, 10g of germanium dioxide and 16g of triphenyl phosphate, continuously heating and slowly reducing pressure, adjusting the rotating speed to 30-50 rpm, controlling the temperature to 275-295 ℃, and gradually reducing the pressure to below 100Pa to perform polycondensation reaction. Sampling and analyzing, stopping stirring when the viscosity of the polymer reaches a desired value, eliminating vacuum, and discharging a product.
Example 4
16.8kg of 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride, 1.4kg of 1, 3-propylene glycol, 4.6kg of isosorbide, 4.5kg of 1, 2-propylene glycol and 0.3kg of glycerol are put into a 100L stainless steel reaction kettle, stirred at the rotating speed of 55-80 rpm under the protection of nitrogen, quickly heated to 60-100 ℃ for reaction for 0.3 hour, gradually heated to 220 ℃ for reaction for 1 hour under heat preservation, heated to 230-270 ℃ for reaction for 2.2 hours, and the reaction is finished when the amount of byproducts reaches the theoretical value. Adding 21g of ethylene glycol antimony, 10g of germanium dioxide and 16g of triphenyl phosphate, continuously heating and slowly reducing pressure, adjusting the rotating speed to 30-50 rpm, controlling the temperature to 275-295 ℃, and gradually reducing the pressure to below 100Pa to perform polycondensation reaction. Sampling and analyzing, stopping stirring when the viscosity of the polymer reaches a desired value, eliminating vacuum, and discharging a product.
Comparative example
Putting 8.3kg of terephthalic acid, 8.3kg of isophthalic acid, 1.4kg of 1, 3-propanediol, 4.6kg of ethylene glycol and 4.5kg of neopentyl glycol into a 100L stainless steel reaction kettle, stirring at the rotating speed of 55-80 rpm under the protection of nitrogen, quickly heating to 60-100 ℃ for reaction for 0.3 hour, gradually heating to 220 ℃ for reaction for 1 hour, heating to 230-270 ℃ for reaction for about 2.2 hours, and finishing the reaction when the amount of the byproducts reaches a theoretical value. Adding 21g of ethylene glycol antimony and 16g of triphenyl phosphate, continuously heating and slowly reducing pressure, adjusting the rotating speed to 30-50 rpm, controlling the temperature to 275-295 ℃, and gradually reducing the pressure to below 100Pa to perform polycondensation reaction. Sampling and analyzing, stopping stirring when the viscosity of the polymer reaches a desired value, eliminating vacuum, and discharging a product.
Preparing a coating:
adding 40kg of mixed solvent of propylene glycol methyl ether acetate, ethylene glycol monobutyl ether and Solvesso100 (mass ratio is 1:1: 4) into a mixing kettle, respectively adding 18kg of the resins of examples 1-4 and comparative example into the mixing kettle under the stirring state, and uniformly stirring to obtain a transparent coating; then adding 1.5kg of catalyst (NACURE 4046), 1.1kg of flatting agent (BKY 016) and 2.4kg of curing agent amino resin (cymel 303) into the mixture, and uniformly stirring the mixture at a high speed for 1 hour to obtain the coating on the inner wall of the food can cover.
Preparing a coating:
the prepared example paint and comparative paint were coated on tin plate with 20# wire bar, baked at 200 ℃ for 12min, and cooled for testing.
And (3) performance testing:
solvent-resistant wiping:
the surface of the coating is linearly wiped back and forth with absorbent cotton occupying butanone and pressed with a force of one kilogram, one is counted as 1 time, and the number of times of wiping until the substrate is exposed is counted, and is counted as more than 100 times higher than 100 times.
Anti-citric acid test:
cutting the plate with the cured coating into long strips, bending the strips for several times, putting the strips into 2% citric acid solution, boiling the strips at 121 ℃/30min, observing the surface gloss and smoothness after boiling, and grading according to the gloss and smoothness, wherein if the surface is smooth and has no light loss, the surface gloss and smoothness are 10; if the surface is matt, the coating is 0 when peeled off and a score below 7 is unacceptable.
Acetic acid resistance test
Cutting the plate with the cured coating into strips, bending the strips for several times, putting the strips into a 2% acetic acid solution, boiling the strips at 121 ℃/30min, observing the surface gloss and smoothness after boiling, and grading according to the gloss and smoothness, wherein if the surface is smooth and has no light loss, the surface gloss and smoothness are 10; if the surface is subjected to light loss, the coating is 0 when the coating falls off, and the fraction is less than 7, the coating is unqualified;
and (3) steaming resistance test:
cutting the plate with the cured coating into long strips, bending the strips for several times, putting the strips into distilled water at a temperature of 85 ℃/30min, observing the surface gloss and the smoothness after boiling, and grading according to the gloss and the smoothness, wherein the surface gloss and the smoothness are 10 if the surface is smooth and has no light loss; if the surface is subjected to light loss, the coating is 0 when the coating falls off, and the fraction is less than 7, the coating is unqualified;
and (3) deep drawing resistance test:
the coated sheet was punched using a punch press to form 206 a base cap and the punched and stretched area was observed for cracking, preferably no cracking, one good cracking and one poor cracking.
And (3) testing the adhesive force:
on the coating layer of the sample surface, a checkerboard-like grid pattern with eleven cuts in each direction was cut with a cutter and cut all the way to the base, a scotch tape was attached to the grid and then peeled off, and the adhesion of the coating layer was evaluated by the peeled area of the coating layer in the manner shown in table 1:
table 1: adhesion test evaluation table
| Grade | Degree of coating peeling |
| 0 | The edge of the cut is completely smooth, and no square lattice falls off |
| 1 | Small flaky coatings fall off at the crossing points, and the area of the fallen coatings accounts for no more than 5 percent of the area of the cross grid |
| 2 | Small pieces of the coating come off along the edges and intersections of the cuts, the area of the coating that comes off accounts for 6-50% of the area of the cross-cut |
| 3 | The coating is seriously peeled off, and the area of the peeled coating accounts for more than 50 percent of the area of the grid |
. Test results the performance pairs are shown in table 2.
Table 2: the test results of each example are shown in the table.
| Numbering | Solvent resistant wipe | Anti-citric acid | Anti-acetic acid | Steaming-resistant cooking utensil | Deep drawing resistance | Adhesion force |
| Example 1 | >100 | 10 | 9 | 9 | Superior food | 0 |
| Example 2 | >100 | 10 | 10 | 10 | Superior food | 0 |
| Example 3 | >100 | 9 | 9 | 10 | Superior food | 0 |
| Example 4 | >100 | 10 | 10 | 9 | Superior food | 0 |
| Comparative example | >100 | 6 | 7 | 8 | Good wine | 0 |
Through comparison of the data, the raw materials provided by the invention are completely from polyester resin synthesized by a bio-based method, have good resistance and processability, and can meet the use requirement of the coating in a can.
There are numerous specific embodiments of the invention. All technical solutions formed by using equivalent substitutions or equivalent transformations fall within the scope of the claimed invention.
Claims (7)
1. A method for preparing polyester resin from bio-based raw materials is characterized in that: prepared by polymerizing 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride, isosorbide, 1, 3-propanediol, and polyols and polyacids from a bio-based group, wherein the 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride accounts for 50-100% of the molar content of all acids, the isosorbide accounts for 20-60% of the molar content of all alcohols, and the 1, 3-propanediol accounts for 10-30% of the molar content of all alcohols; the polyol from the bio-based is selected from one or any combination of more than two of 1, 6-hexanediol, 1, 4-butanediol, 1, 2-propanediol and glycerol;
the polybasic acid from the biological group is selected from one or any combination of more than two of 1, 4-succinic acid, adipic acid and furandicarboxylic acid.
2. The method of claim 1, wherein the polyester resin is prepared from bio-based raw materials, and the method comprises the steps of: comprises the following steps of (a) carrying out,
s1, adding 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride, isosorbide, 1, 3-propylene glycol, polyol from a biological group and polybasic acid into a reaction kettle, stirring and heating for three times under the protection of nitrogen until the amount of byproducts reaches a theoretical value;
and S2, adding a catalyst and a stabilizer into the reaction kettle, continuously heating to 275-295 ℃, reducing the pressure to be below 100Pa to perform polycondensation reaction, sampling and analyzing until the viscosity of the polymer reaches an expected value, and discharging.
3. The method of claim 2, wherein the polyester resin is prepared from bio-based raw materials, and the method comprises the steps of: in the S1, under the protection of nitrogen, the temperature is raised to 60-100 ℃ for heat preservation reaction for the first time, the temperature is raised to 220 ℃ for heat preservation reaction for the second time, and the temperature is raised to 230-270 ℃ for heat preservation reaction for the third time.
4. The method of claim 1, wherein the polyester resin is prepared from bio-based raw materials, and the method comprises the steps of: the 7-oxabicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride is prepared from bio-based material furfural.
5. A polyester resin produced by the method for producing a polyester resin produced from a bio-based raw material according to any one of claims 1 to 4.
6. The polyester resin according to claim 5, wherein: the number average molecular weight of the polyester resin is 15000-45000, and the glass transition temperature is 80-120 ℃.
7. The polyester resin according to claim 5, wherein: the polyester resin is applied to the inner coating of a can.
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| CN102190782A (en) * | 2010-03-17 | 2011-09-21 | 东丽纤维研究所（中国）有限公司 | Copolyester compound and method for preparing same |
| JP6407600B2 (en) * | 2014-07-23 | 2018-10-17 | 国立大学法人群馬大学 | Biodegradable polyester |
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| CN102190782A (en) * | 2010-03-17 | 2011-09-21 | 东丽纤维研究所（中国）有限公司 | Copolyester compound and method for preparing same |
| JP6407600B2 (en) * | 2014-07-23 | 2018-10-17 | 国立大学法人群馬大学 | Biodegradable polyester |
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