CN116836375A - Ultraviolet-resistant polyester resin - Google Patents
Ultraviolet-resistant polyester resin Download PDFInfo
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- CN116836375A CN116836375A CN202310783101.XA CN202310783101A CN116836375A CN 116836375 A CN116836375 A CN 116836375A CN 202310783101 A CN202310783101 A CN 202310783101A CN 116836375 A CN116836375 A CN 116836375A
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 48
- 239000004645 polyester resin Substances 0.000 title claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 238000010438 heat treatment Methods 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 12
- NGCFMKFMMGSXJO-UHFFFAOYSA-N n,n,n',n'-tetrapropylmethanediamine Chemical compound CCCN(CCC)CN(CCC)CCC NGCFMKFMMGSXJO-UHFFFAOYSA-N 0.000 claims description 11
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- PZYHLENTJZMOQC-UHFFFAOYSA-N 1-bromohexan-1-ol Chemical compound CCCCCC(O)Br PZYHLENTJZMOQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- JUGRTVJQTFZHOM-UHFFFAOYSA-N 1,1,1-tribromo-2-methylpropan-2-ol Chemical compound CC(C)(O)C(Br)(Br)Br JUGRTVJQTFZHOM-UHFFFAOYSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- KITZQTGXRDWCKG-UHFFFAOYSA-N 1-bromopentan-1-ol Chemical compound CCCCC(O)Br KITZQTGXRDWCKG-UHFFFAOYSA-N 0.000 claims description 2
- JCERKCRUSDOWLT-UHFFFAOYSA-N 1-bromopropan-1-ol Chemical compound CCC(O)Br JCERKCRUSDOWLT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 2
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- ZMCZWKGAWRLZNP-UHFFFAOYSA-N methyl-oxo-phenyltin Chemical compound C[Sn](=O)C1=CC=CC=C1 ZMCZWKGAWRLZNP-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims 1
- 239000012964 benzotriazole Substances 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 16
- FJGQBLRYBUAASW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)phenol Chemical compound OC1=CC=CC=C1N1N=C2C=CC=CC2=N1 FJGQBLRYBUAASW-UHFFFAOYSA-N 0.000 description 5
- 150000001565 benzotriazoles Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000006750 UV protection Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides an anti-ultraviolet polyester resin, which comprises the following steps: 1) Adding an ultraviolet-resistant monomer, dihydric alcohol and dibasic acid into a reaction kettle, introducing nitrogen, heating to melt raw materials, and uniformly stirring; 2) Adding a catalyst, heating to 95-105 ℃ to react for 2-6 hours, and removing water generated in the reaction; 3) Starting a vacuum pump, heating to 140-145 ℃ to react for 1.5-2.5 hours, heating to 160-165 ℃ to react for 1.5-2.5 hours, heating to 180-185 ℃ to react for 1.5-2.5 hours, heating to 200-205 ℃ to react for 1.5-2.5 hours, heating to 220-225 ℃ to react for 1.5-2.5 hours, and discharging at a high temperature after the reaction is completed to obtain the ultraviolet-resistant polyester resin. The benzotriazole group with the anti-ultraviolet function is connected to the main chain of the polyester, so that the anti-ultraviolet characteristic of the whole polyester material is effectively improved.
Description
Technical Field
The invention relates to the technical field of polyester resins, in particular to an ultraviolet-resistant polyester resin.
Background
The polyester resin is a high molecular polymer which is formed by taking polybasic acid (or derivative thereof) and polyalcohol as synthetic monomers, carrying out catalytic esterification and carrying out vacuum polycondensation reaction. As the name suggests, the repeating units contained in the polyester resin backbone are-COOH groups, and the pendant groups are also ester pendant groups. The types of polyester resins are classified into aliphatic and aromatic types, saturated and unsaturated polyesters, linear and branched types, according to the classification mode. Different polyester varieties are applied to different products, and the polyester resin has wide application in engineering plastics and daily life fields, such as polyester fibers, polyester bottle flakes, polyester films, polyester powder coatings and the like. With the expansion of the productivity of polyester resin in recent years, the excess productivity makes the polyester industry develop to a high concentration, and meanwhile, environment-friendly, technical and functional polyester becomes a new target for industry development.
For outdoor polyester resins, the aging problem is one of the important difficulties faced by them due to the limitations of their composition and structure. Such as outdoor polyester powder coating, advertisement lamp box cloth, waterproof material, tarpaulin, industrial cloth and other polyester products, can undergo irreversible aging reaction such as wet hydrolysis, thermal oxygen degradation, ultraviolet light oxygen degradation and the like during service, thereby greatly reducing the durability. The shortening of the service life brings new resource and energy consumption, and increases the environmental load. Therefore, the durability of the polyester resin is improved, the ultraviolet aging time is delayed, and the polyester can be endowed with higher environmental protection value and additional value, and has important academic significance and engineering application value.
Patent CN107698954B discloses a preparation method of ultraviolet-resistant and anti-aging unsaturated polyester resin, which comprises the steps of mixing unsaturated polyester resin with gel coat resin, adding cobalt naphthenate and N, N-dimethylaniline, adding a curing agent, and curing and forming in one step under vacuum condition.
Therefore, it is necessary to provide a polyester resin with strong ultraviolet resistance and lasting effect to meet the requirements of practical application.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide the polyester resin with strong ultraviolet resistance and lasting effect.
To achieve the purpose, the technical scheme of the invention is as follows:
the invention provides an anti-ultraviolet polyester resin, which comprises the following steps:
(1) Adding an ultraviolet-resistant monomer, dihydric alcohol and dibasic acid into a reaction kettle, introducing nitrogen, heating to melt raw materials, and uniformly stirring;
(2) Adding a catalyst, heating to 95-105 ℃ to react for 2-6 hours, and removing water generated in the reaction;
(3) Starting a vacuum pump, heating to 140-145 ℃ to react for 1.5-2.5 hours, heating to 160-165 ℃ to react for 1.5-2.5 hours, heating to 180-185 ℃ to react for 1.5-2.5 hours, heating to 200-205 ℃ to react for 1.5-2.5 hours, heating to 220-225 ℃ to react for 1.5-2.5 hours, and discharging at a high temperature after the reaction is completed to obtain the ultraviolet-resistant polyester resin.
In some embodiments of the invention, the mole ratio of the uv-blocking monomer, glycol, diacid in step (1) is 1:5-10:5-10; the temperature rise is 70-80 ℃.
In some embodiments of the invention, the glycol in step (1) is selected from one or more combinations of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-octanediol, 1, 10-decanediol.
In some embodiments of the invention, the diacid in step (1) is selected from one or more combinations of oxalic acid, 1, 3-malonic acid, 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 1, 9-suberic acid, 1, 10-sebacic acid.
In some embodiments of the invention, the catalyst in step (2) is selected from dibutyltin oxide or methylphenyltin oxide.
In some embodiments of the invention, the vacuum in step (3) is from-0.1 to-0.08 MPa.
In some embodiments of the invention, the structure of the uv-resistant monomer is as shown in formula a:
wherein R is any one of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl; n is an integer of 2 to 6.
In some embodiments of the invention, the method of preparing the uv resistant monomer comprises the steps of:
1) Uniformly mixing benzotriazole derivatives, sodium hydroxide and bis (di-n-propylamino) methane, heating to 115-125 ℃ to melt all materials, then increasing the reaction temperature to 135-145 ℃, reacting for 1-2 hours, distilling off n-propylamine under reduced pressure, then increasing the reaction temperature to 155-165 ℃, reacting for 2-3 hours under vacuum, stopping heating and removing vacuum, reducing the temperature to 105-115 ℃, adding toluene to completely dissolve the materials, reducing the temperature to 85-95 ℃, adding hydrochloric acid solution with the concentration of 10-15%, stirring to completely turn the materials into neutrality, crystallizing and cooling for 4-5 hours with ice water, filtering and collecting precipitated substances, washing a filter cake with deionized water for 2-3 times, washing with methanol for 2-3 times, and drying to obtain an intermediate; the structural formula of the benzotriazole derivative is shown as a formula B:
wherein R is any one of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, and the structural formula of the intermediate is shown as formula C:
2) Adding intermediate, sodium carbonate and hydroxyl-containing bromohydrocarbon into N, N-dimethylformamide, stirring at 20-40 ℃ for reaction for 18-24 hours, distilling to remove unreacted hydroxyl-containing bromohydrocarbon, distilling to remove most of N, N-dimethylformamide, adding water, filtering to collect precipitate, flushing with N-heptane for 2-3 times, and drying to obtain the anti-ultraviolet monomer.
In the preparation method of the anti-ultraviolet monomer, the molar ratio of the benzotriazole derivative to the bis (di-n-propylamino) methane in the step (1) is 1:1-2; the mass of the sodium hydroxide is 0.5-1.5% of the total mass of the benzotriazole derivatives and the bis (di-n-propylamino) methane; the vacuum degree is-0.1 to-0.05 MPa.
In the preparation method of the ultraviolet resistant monomer, the molar ratio of the intermediate to the hydroxyl-containing brominated hydrocarbon in the step (2) is 1:1-2; the hydroxyl-containing brominated hydrocarbon is selected from any one of bromoethanol, bromopropanol, bromobutanol, bromopentanol and bromohexanol.
Compared with the prior art, the invention has the following beneficial effects:
the ultraviolet-resistant polyester resin provided by the invention is prepared from the substances such as dihydric alcohol and dibasic acid as raw materials, and the benzotriazole group with the ultraviolet-resistant function is connected to the main chain of the polyester by adding the ultraviolet-resistant monomer, so that the ultraviolet-resistant monomer can be well combined with the polyester resin, has very low volatility, can more effectively improve the ultraviolet-resistant characteristic of the whole polyester material, and can prevent the polyester resin from being degraded and deteriorated due to the degradation of the polymer caused by the automatic oxidation reaction generated by the ultraviolet effect, and compared with the conventional mode of adding the ultraviolet-resistant additive, the ultraviolet-resistant polyester resin has the advantages of simple preparation method, contribution to improving the production efficiency and reducing the cost.
Detailed Description
The invention will be described below in connection with specific embodiments. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention. The starting materials used in the examples were all commercially available, wherein 2- (2H-benzotriazol-2-yl) -phenol was purchased from Anzier technologies, inc., bis (di-n-propylamino) methane was purchased from Tianjin An Long New Material Co., ltd, and nano titanium dioxide was purchased from Jiangsu Mifeng Nano materials technologies Co., ltd.
Example 1
An anti-ultraviolet polyester resin, the preparation method of the anti-ultraviolet polyester resin comprises the following steps:
(1) Adding 0.1mol of ultraviolet-resistant monomer, 0.9mol of 1, 5-pentanediol and 0.9mol of oxalic acid into a reaction kettle, introducing nitrogen, heating to 80 ℃, and uniformly stirring after the raw materials are melted;
(2) Adding 0.3g of dibutyl tin oxide, heating to 100 ℃ for reaction for 6 hours, and removing water generated in the reaction;
(3) Starting a vacuum pump, controlling the vacuum degree to be minus 0.1MPa, heating to 140 ℃ for reaction for 2 hours, heating to 160 ℃ for reaction for 2 hours, heating to 180 ℃ for reaction for 2 hours, heating to 200 ℃ for reaction for 2 hours, heating to 220 ℃ for reaction for 2 hours, and discharging at a high temperature after the reaction is completed, thus obtaining the ultraviolet-resistant polyester resin.
The preparation method of the ultraviolet resistant monomer comprises the following steps:
1) 1mol of 2- (2H-benzotriazole-2-yl) -phenol, 3g of sodium hydroxide and 1mol of bis (di-n-propylamino) methane are uniformly mixed, heated to 120 ℃ to melt all materials, then the reaction temperature is increased to 140 ℃, the reaction is carried out for 2 hours, n-propylamine is distilled off under reduced pressure, then the reaction temperature is increased to 160 ℃, the reaction is carried out for 3 hours under vacuum (the vacuum degree is minus 0.1 MPa), heating is stopped, the vacuum is removed, the temperature is reduced to 110 ℃, 500g of toluene is added to dissolve the materials completely, the temperature is reduced to 90 ℃, hydrochloric acid solution with the concentration of 10% is added, stirring is carried out to make the materials completely neutral, ice water crystallization is carried out for 5 hours, precipitated substances are collected by filtration, filter cakes are washed 2 times by deionized water, and then methanol is used for washing 2 times, and drying is carried out to obtain an intermediate;
2) Adding 1mol of intermediate, 3mol of sodium carbonate and 1mol of bromoethanol into 2000ml of N, N-dimethylformamide, stirring and reacting for 24 hours at 40 ℃, distilling to remove unreacted bromoethanol after the reaction is completed, distilling off most of N, N-dimethylformamide, adding 1000ml of water, filtering and collecting precipitate, flushing with N-heptane for 2 times, and drying to obtain the ultraviolet-resistant monomer.
Example 2
An anti-ultraviolet polyester resin, the preparation method of the anti-ultraviolet polyester resin comprises the following steps:
(1) Adding 0.2mol of ultraviolet-resistant monomer, 1.5mol of 1, 5-pentanediol and 1.5mol of oxalic acid into a reaction kettle, introducing nitrogen, heating to 80 ℃, and uniformly stirring after the raw materials are melted;
(2) Adding 0.3g of dibutyl tin oxide, heating to 100 ℃ for reaction for 6 hours, and removing water generated in the reaction;
(3) Starting a vacuum pump, controlling the vacuum degree to be minus 0.1MPa, heating to 140 ℃ for reaction for 2 hours, heating to 160 ℃ for reaction for 2 hours, heating to 180 ℃ for reaction for 2 hours, heating to 200 ℃ for reaction for 2 hours, heating to 220 ℃ for reaction for 2 hours, and discharging at a high temperature after the reaction is completed, thus obtaining the ultraviolet-resistant polyester resin.
The preparation method of the ultraviolet resistant monomer comprises the following steps:
1) 1mol of 2- (2H-benzotriazole-2-yl) -phenol, 3g of sodium hydroxide and 1mol of bis (di-n-propylamino) methane are uniformly mixed, heated to 120 ℃ to melt all materials, then the reaction temperature is increased to 140 ℃, the reaction is carried out for 2 hours, n-propylamine is distilled off under reduced pressure, then the reaction temperature is increased to 160 ℃, the reaction is carried out for 3 hours under vacuum (the vacuum degree is minus 0.1 MPa), heating is stopped, the vacuum is removed, the temperature is reduced to 110 ℃, 500g of toluene is added to dissolve the materials completely, the temperature is reduced to 90 ℃, hydrochloric acid solution with the concentration of 10% is added, stirring is carried out to make the materials completely neutral, ice water crystallization is carried out for 5 hours, precipitated substances are collected by filtration, filter cakes are washed 2 times by deionized water, and then methanol is used for washing 2 times, and drying is carried out to obtain an intermediate;
2) Adding 1mol of intermediate, 3mol of sodium carbonate and 1mol of bromoethanol into 2000ml of N, N-dimethylformamide, stirring and reacting for 24 hours at 40 ℃, distilling to remove unreacted bromoethanol after the reaction is completed, distilling off most of N, N-dimethylformamide, adding 1000ml of water, filtering and collecting precipitate, flushing with N-heptane for 2 times, and drying to obtain the ultraviolet-resistant monomer.
Example 3
An anti-ultraviolet polyester resin, the preparation method of the anti-ultraviolet polyester resin comprises the following steps:
(1) Adding 0.2mol of ultraviolet-resistant monomer, 1.5mol of 1, 5-pentanediol and 1.5mol of oxalic acid into a reaction kettle, introducing nitrogen, heating to 80 ℃, and uniformly stirring after the raw materials are melted;
(2) Adding 0.3g of dibutyl tin oxide, heating to 100 ℃ for reaction for 6 hours, and removing water generated in the reaction;
(3) Starting a vacuum pump, controlling the vacuum degree to be minus 0.1MPa, heating to 140 ℃ for reaction for 2 hours, heating to 160 ℃ for reaction for 2 hours, heating to 180 ℃ for reaction for 2 hours, heating to 200 ℃ for reaction for 2 hours, heating to 220 ℃ for reaction for 2 hours, and discharging at a high temperature after the reaction is completed, thus obtaining the ultraviolet-resistant polyester resin.
The preparation method of the ultraviolet resistant monomer comprises the following steps:
1) 1mol of 2- (2H-benzotriazole-2-yl) -phenol, 3g of sodium hydroxide and 2mol of bis (di-n-propylamino) methane are uniformly mixed, heated to 120 ℃ to melt all materials, then the reaction temperature is increased to 140 ℃, the reaction is carried out for 2 hours, n-propylamine is distilled off under reduced pressure, then the reaction temperature is increased to 160 ℃, the reaction is carried out for 3 hours under vacuum (the vacuum degree is minus 0.1 MPa), heating is stopped, the vacuum is removed, the temperature is reduced to 110 ℃, 500g of toluene is added to dissolve the materials completely, the temperature is reduced to 90 ℃, hydrochloric acid solution with the concentration of 10% is added, stirring is carried out to make the materials completely neutral, ice water crystallization is carried out for 5 hours, precipitated substances are collected by filtration, filter cakes are washed 2 times by deionized water, and then methanol is used for washing 2 times, and drying is carried out to obtain an intermediate;
2) Adding 1mol of intermediate, 3mol of sodium carbonate and 1mol of bromoethanol into 2000ml of N, N-dimethylformamide, stirring and reacting for 24 hours at 40 ℃, distilling to remove unreacted bromoethanol after the reaction is completed, distilling off most of N, N-dimethylformamide, adding 1000ml of water, filtering and collecting precipitate, flushing with N-heptane for 2 times, and drying to obtain the ultraviolet-resistant monomer.
Example 4
An anti-ultraviolet polyester resin, the preparation method of the anti-ultraviolet polyester resin comprises the following steps:
(1) Adding 0.2mol of ultraviolet-resistant monomer, 1.5mol of 1, 5-pentanediol and 1.5mol of oxalic acid into a reaction kettle, introducing nitrogen, heating to 80 ℃, and uniformly stirring after the raw materials are melted;
(2) Adding 0.3g of dibutyl tin oxide, heating to 100 ℃ for reaction for 6 hours, and removing water generated in the reaction;
(3) Starting a vacuum pump, controlling the vacuum degree to be minus 0.1MPa, heating to 140 ℃ for reaction for 2 hours, heating to 160 ℃ for reaction for 2 hours, heating to 180 ℃ for reaction for 2 hours, heating to 200 ℃ for reaction for 2 hours, heating to 220 ℃ for reaction for 2 hours, and discharging at a high temperature after the reaction is completed, thus obtaining the ultraviolet-resistant polyester resin.
The preparation method of the ultraviolet resistant monomer comprises the following steps:
1) 1mol of 2- (2H-benzotriazole-2-yl) -phenol, 3g of sodium hydroxide and 2mol of bis (di-n-propylamino) methane are uniformly mixed, heated to 120 ℃ to melt all materials, then the reaction temperature is increased to 140 ℃, the reaction is carried out for 2 hours, n-propylamine is distilled off under reduced pressure, then the reaction temperature is increased to 160 ℃, the reaction is carried out for 3 hours under vacuum (the vacuum degree is minus 0.1 MPa), heating is stopped, the vacuum is removed, the temperature is reduced to 110 ℃, 500g of toluene is added to dissolve the materials completely, the temperature is reduced to 90 ℃, hydrochloric acid solution with the concentration of 10% is added, stirring is carried out to make the materials completely neutral, ice water crystallization is carried out for 5 hours, precipitated substances are collected by filtration, filter cakes are washed 2 times by deionized water, and then methanol is used for washing 2 times, and drying is carried out to obtain an intermediate;
2) Adding 1mol of intermediate, 4mol of sodium carbonate and 2mol of bromohexanol into 2000ml of N, N-dimethylformamide, stirring and reacting for 24 hours at 40 ℃, distilling to remove unreacted bromohexanol after the reaction is completed, distilling off most of N, N-dimethylformamide, adding 1000ml of water, filtering and collecting precipitate, flushing with N-heptane for 2 times, and drying to obtain the ultraviolet-resistant monomer.
Comparative example 1
The difference from example 1 is that: no anti-uv monomer was added.
Comparative example 2
The difference from example 1 is that: the substitution of the uv-resistant monomer with an inorganic uv-resistant additive: nano titanium dioxide.
The ultraviolet resistant polyester resins prepared in the same amount of examples and comparative examples were melt extruded into a polyester raw material resin in a sheet form, and were cooled and molded on a casting drum to prepare a polyester resin film, which was subjected to ultraviolet resistant performance test by referring to ASTM D4329-13, the test method was performed, and the measurement results are shown in table 1:
TABLE 1
As can be seen from comparison of the test results of each example and the comparative example in Table 1, the ultraviolet resistant polyester resin provided by the invention can effectively improve the ultraviolet resistance of the material by using the ultraviolet resistant monomer, and the benzotriazole group with the ultraviolet resistant function is connected to the main chain of the polyester, so that the ultraviolet resistant characteristic of the whole polyester material is effectively improved, the current increasing practical requirements can be effectively met, and the ultraviolet resistant polyester resin has good application prospect.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement it, but not limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the ultraviolet resistant polyester resin is characterized by comprising the following steps of:
(1) Adding an ultraviolet-resistant monomer, dihydric alcohol and dibasic acid into a reaction kettle, introducing nitrogen, heating to melt raw materials, and uniformly stirring;
(2) Adding a catalyst, heating to 95-105 ℃ to react for 2-6 hours, and removing water generated in the reaction;
(3) Starting a vacuum pump, heating to 140-145 ℃ to react for 1.5-2.5 hours, heating to 160-165 ℃ to react for 1.5-2.5 hours, heating to 180-185 ℃ to react for 1.5-2.5 hours, heating to 200-205 ℃ to react for 1.5-2.5 hours, heating to 220-225 ℃ to react for 1.5-2.5 hours, and discharging at a high temperature after the reaction is completed to obtain the ultraviolet-resistant polyester resin.
2. The uv resistant polyester resin according to claim 1, wherein the molar ratio of the uv resistant monomer, glycol, diacid in step (1) is 1:5-10:5-10; the temperature rise is 70-80 ℃.
3. The uv resistant polyester resin according to claim 1, wherein the glycol in step (1) is selected from one or more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-octanediol, 1, 10-decanediol.
4. The uv resistant polyester resin according to claim 1, wherein the dibasic acid in step (1) is selected from one or more of oxalic acid, 1, 3-malonic acid, 1, 4-succinic acid, 1, 5-glutaric acid, 1, 6-adipic acid, 1, 7-pimelic acid, 1, 8-suberic acid, 1, 9-suberic acid, 1, 10-sebacic acid.
5. The uv resistant polyester resin according to claim 1, wherein the catalyst in step (2) is selected from dibutyltin oxide or methylphenyltin oxide.
6. The ultraviolet-resistant polyester resin according to claim 1, wherein the vacuum degree in the step (3) is-0.1 to-0.08 MPa.
7. The uv resistant polyester resin according to claim 1, wherein the uv resistant monomer in step (1) has a structure represented by formula a:
A
wherein R is any one of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl; n is an integer of 2 to 6.
8. The ultraviolet-resistant polyester resin according to claim 7, wherein the preparation method of the ultraviolet-resistant monomer comprises the steps of:
1) Uniformly mixing benzotriazole derivatives, sodium hydroxide and bis (di-n-propylamino) methane, heating to 115-125 ℃ to melt all materials, then increasing the reaction temperature to 135-145 ℃, reacting for 1-2 hours, distilling off n-propylamine under reduced pressure, then increasing the reaction temperature to 155-165 ℃, reacting for 2-3 hours under vacuum, stopping heating and removing vacuum, reducing the temperature to 105-115 ℃, adding toluene to completely dissolve the materials, reducing the temperature to 85-95 ℃, adding hydrochloric acid solution with the concentration of 10-15%, stirring to completely turn the materials into neutrality, crystallizing and cooling for 4-5 hours by using ice water, filtering and collecting precipitated substances, washing a filter cake by using deionized water for 2-3 times, washing by using methanol for 2-3 times, and drying to obtain an intermediate, wherein the structural formula of the benzotriazole derivatives is shown in a formula B:
b, wherein R is any one of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, and the structural formula of the intermediate is shown as formula C:
C；
2) Adding intermediate, sodium carbonate and hydroxyl-containing bromohydrocarbon into N, N-dimethylformamide, stirring at 20-40 ℃ for reaction for 18-24 hours, distilling to remove unreacted hydroxyl-containing bromohydrocarbon, distilling to remove most of N, N-dimethylformamide, adding water, filtering to collect precipitate, flushing with N-heptane for 2-3 times, and drying to obtain the anti-ultraviolet monomer.
9. The uv resistant polyester resin according to claim 8, wherein the molar ratio of benzotriazole-based derivative to bis (di-n-propylamino) methane in step (1) is 1:1-2; the mass of the sodium hydroxide is 0.5-1.5% of the total mass of the benzotriazole derivatives and the bis (di-n-propylamino) methane; the vacuum degree is-0.1 to-0.05 MPa.
10. The uv resistant polyester resin according to claim 8, wherein the molar ratio of the intermediate to hydroxyl-containing brominated hydrocarbon in step (2) is 1:1-2; the hydroxyl-containing brominated hydrocarbon is selected from any one of bromoethanol, bromopropanol, bromobutanol, bromopentanol and bromohexanol.
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