CN117736424B - Synthesis method of isosorbide modified PET copolyester - Google Patents
Synthesis method of isosorbide modified PET copolyester Download PDFInfo
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- CN117736424B CN117736424B CN202410185782.4A CN202410185782A CN117736424B CN 117736424 B CN117736424 B CN 117736424B CN 202410185782 A CN202410185782 A CN 202410185782A CN 117736424 B CN117736424 B CN 117736424B
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 33
- 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 title claims abstract description 30
- 229960002479 isosorbide Drugs 0.000 title claims abstract description 30
- 238000001308 synthesis method Methods 0.000 title claims description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 239000011347 resin Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000005886 esterification reaction Methods 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 18
- 238000006068 polycondensation reaction Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 230000032050 esterification Effects 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- YLGRTLMDMVAFNI-UHFFFAOYSA-N tributyl(prop-2-enyl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)CC=C YLGRTLMDMVAFNI-UHFFFAOYSA-N 0.000 claims description 8
- SEIGKYBFMXSLAH-IJIVKGSJSA-N 2-[(1e,3e)-4-thiophen-2-ylbuta-1,3-dienyl]thiophene Chemical compound C=1C=CSC=1\C=C\C=C\C1=CC=CS1 SEIGKYBFMXSLAH-IJIVKGSJSA-N 0.000 claims description 7
- OOXOBWDOWJBZHX-UHFFFAOYSA-N n-(dimethylaminosilyl)-n-methylmethanamine Chemical compound CN(C)[SiH2]N(C)C OOXOBWDOWJBZHX-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 4
- 229920000728 polyester Polymers 0.000 abstract description 13
- 230000004888 barrier function Effects 0.000 abstract description 6
- 230000009477 glass transition Effects 0.000 abstract description 3
- 125000001544 thienyl group Chemical group 0.000 abstract description 3
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 abstract description 3
- 230000021615 conjugation Effects 0.000 abstract description 2
- 239000011968 lewis acid catalyst Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 32
- 239000005020 polyethylene terephthalate Substances 0.000 description 32
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- -1 Polyethylene terephthalate Polymers 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- GIYJWSOHUZOJBM-UHFFFAOYSA-N 2-buta-1,3-dienylthiophene Chemical compound C=CC=CC1=CC=CS1 GIYJWSOHUZOJBM-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000007524 organic acids Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to the technical field of polyester preparation, in particular to a synthetic method of isosorbide modified PET copolyester. The tin-doped resin catalyst prepared by the method can improve the conversion rate of the esterification reaction, and tributyltin can be used as a Lewis acid catalyst to promote the esterification reaction; thienyl groups may participate in hydrogen bonding or conjugation between the catalyst and the substrate, thereby affecting the progress of the reaction; the components are synergistic in the catalyst, so that the conversion rate of the esterification reaction of the isosorbide modified PET copolyester is improved; meanwhile, the separation is easy; the isosorbide disclosed by the invention can effectively improve the glass transition temperature, so that the heat resistance of PET polyester is improved, and the barrier property of the polyester material is improved.
Description
Technical Field
The invention relates to the technical field of polyester preparation, in particular to a synthetic method of isosorbide modified PET copolyester.
Background
Polyethylene terephthalate (PET) is a thermoplastic resin with excellent comprehensive performance, has the advantages of low cost, high melting point, excellent mechanical property, good formability and the like, and is widely applied to the fields of fibers, packaging bottles, films and the like.
Chinese patent publication No. CN103665788B discloses a modified PET copolyester with high viscosity and low carboxyl end, and a preparation method and application thereof. The copolyester comprises the following components in parts by weight: 100 parts of low-viscosity PET copolyester; 0.8 to 2.0 portions of oxazoline compound; 0.6 to 2.0 portions of hydroxyl chain extender. The invention prepares the high-viscosity modified PET copolyester by adding the oxazoline compound and the hydroxyl chain extender. The oxazoline compound is added to react with carboxyl end groups in the resin, so that the carboxyl end groups content of the resin is reduced, and the hot water resistance of the resin is improved. And a hydroxyl chain extender is added to improve the molecular weight of the resin, so that the balance of physical properties and processing properties is achieved.
The Chinese patent with the publication number of CN112724378B discloses a quick-crystallization modified PET copolyester and a preparation method thereof, wherein terephthalic acid, glycol, a nucleating agent, a crystallization promoter, a catalyst, an ether inhibitor and an auxiliary agent are adopted as raw materials to synthesize a monomer, and then a polymer ionomer is added for blending modification, wherein the quick-crystallization modified PET copolyester is prepared by 62.8-70.4 wt% of terephthalic acid, 26.3-29.4 wt% of glycol, 0.1-2.0 wt% of the nucleating agent, 0.1-5.0 wt% of the crystallization promoter, 4-20 ppm of the catalyst, 1-100 ppm of the ether inhibitor, 0.01-0.2 wt% of the auxiliary agent and 0.1-5.0 wt% of the polymer ionomer, the nucleating agent is an organic acid metal salt, the crystallization promoter is polyether alcohol, and the auxiliary agent is a thermo-oxygen stabilizer.
Chinese patent with bulletin number CN112851919B, discloses a1, 4;3, 6-diglycidyl hexaol modified PET polyester and a semi-continuous preparation method thereof, wherein the monomers of the modified PET polyester comprise: (a) terephthalic acid (b) ethylene glycol (c) 1,4;3, 6-diglycidyl hexaol or mixtures thereof (d) aliphatic and/or cycloaliphatic diols. The method comprises the steps of preparing a certain amount of ethylene glycol terephthalate in a first esterification kettle, continuously adding mixed terephthalic acid and ethylene glycol slurry into the first esterification kettle at a certain flow rate to react, intermittently discharging the reaction product into a second esterification kettle, adding a modified monomer/transesterification catalyst into the second esterification kettle to perform esterification/transesterification reaction to obtain a prepolymer, and then discharging all the prepolymer into a polycondensation kettle and adding a polycondensation catalyst to perform melt polycondensation to obtain the final polymer.
However, the modified PET polyester prepared by the above patent and the prior art has poor heat resistance and unsatisfactory barrier property.
Disclosure of Invention
The invention provides a synthesis method of isosorbide modified PET copolyester, which effectively solves the technical problems of poor heat resistance and poor barrier property of the existing PET polyester.
The invention discloses a synthesis method of isosorbide modified PET copolyester, which comprises the following steps:
S1: weighing 0.5-2 parts of isosorbide, 10-20 parts of phthalic acid, 5-10 parts of ethylene glycol and 0.01-0.05 part of catalyst according to parts by weight, adding into a polymerization kettle, and heating while stirring;
S2: firstly, replacing air in a polymerization kettle with nitrogen, then boosting the pressure by using the nitrogen, slowly heating, starting the esterification reaction, and slowly decompressing to normal pressure when the esterification distillate appears;
s3: heating and slowly vacuumizing, starting polycondensation reaction, and granulating and drying after the reaction is finished to obtain the isosorbide modified PET copolyester.
Preferably, the temperature in the step S1 is raised to 70-90 ℃ and the stirring time is 20-40min.
Preferably, the reaction pressure of S2 is 2-3kpa, and the reaction temperature is 230-250 ℃.
Preferably, the vacuum pressure of S3 is 80-100kpa.
Preferably, the reaction temperature of the S3 is 260-280 ℃, and the polycondensation reaction time is 2-5h.
Preferably, the catalyst is a tin-doped resin catalyst, and the preparation method comprises the following steps:
H1: putting 120-150 parts of resin catalyst into a plasma reactor, introducing di (dimethylamino) silane steam as a modified gas, wherein the input voltage of the plasma reactor is 20-30V, and the gas flow is 10-22ml/min; performing plasma modification in the atmosphere for 30-50min to obtain a resin catalyst with silicon-hydrogen bonds;
H2: according to the mass parts, introducing nitrogen to replace air in a closed reaction kettle, adding 2-5 parts of allyl tributyltin, 0.05-0.5 part of 1, 4-di (2-thienyl) -1, 3-butadiene, 50-80 parts of resin catalyst with silicon-hydrogen bond, 0.01-0.1 part of Caster catalyst and 300-400 parts of ethanol, introducing nitrogen, heating, and stirring at 60-70 ℃ for reaction for 50-100 minutes; filtering and drying to obtain the tin-doped resin catalyst.
Preferably, the resin catalyst is selected from the group consisting of a D001 resin catalyst, a D006 resin catalyst, and an A15 resin catalyst.
Reaction mechanism: a resin catalyst with a silicon hydrogen bond; and respectively carrying out hydrosilylation reaction with allyl tributyltin and 1, 4-di (2-thienyl) -1, 3-butadiene to obtain a catalyst containing tributyltin, sulfonic acid and thienyl, which can improve the conversion rate of the esterification reaction of the isosorbide modified PET copolyester.
The beneficial effects are that: 1. the isosorbide disclosed by the invention is used for modifying PET copolyester due to the characteristics of excellent rigidity, chiral structure, no toxicity and the like, and can effectively improve the glass transition temperature, so that the heat resistance of the PET polyester is improved;
2. according to the invention, isosorbide is introduced into PET polyester molecular chains, so that the rigidity of the molecular chains can be improved, and the free volume of a matrix can be reduced, thereby reducing gaps among the molecular chains, preventing permeation of small molecules, and improving the barrier property of the polyester material;
3. The tin-doped resin catalyst prepared by the method can improve the conversion rate of the esterification reaction, and tributyltin can be used as a Lewis acid catalyst to promote the esterification reaction; thienyl groups may participate in hydrogen bonding or conjugation between the catalyst and the substrate, thereby affecting the progress of the reaction; the components are synergistic in the catalyst, so that the conversion rate of the esterification reaction of the isosorbide modified PET copolyester is improved; and at the same time, the separation is easy, and the product can not be brought into the product.
Detailed Description
The following embodiments are merely exemplary embodiments employed to illustrate the principles of the present invention, however, the present invention is not limited thereto. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the invention, and are also considered to be within the scope of the invention.
Example test method:
1. Intrinsic viscosity: analyzing by referring to a GB/T14190-2018 fiber grade polyester chip test method;
2. Thermal performance analysis: testing by using a differential scanning calorimeter, and under the nitrogen atmosphere, raising the temperature from 25 ℃ to 260 ℃ at a speed of 10 ℃/min and keeping for 5min; then the temperature is reduced to 25 ℃ at the speed of 400 ℃/min and is kept for 5min; raising the temperature to 220 ℃ at the speed of 10 ℃/min and keeping the temperature for 5min; finally, the temperature is reduced to 100 ℃ at a rate of 10 ℃;
3. Barrier performance test: the blow-molded modified PET polyester bottle is subjected to the test of the oxygen resistance of a container on a differential pressure type oxygen permeation tester, wherein the wall thickness of the bottle is (0.3+/-0.05) mm, the oxygen permeability of the bottle is tested, and 99.99% of high-purity N 2 is used as carrier gas.
Example 1: the synthesis method of the isosorbide modified PET copolyester comprises the following steps:
s1: weighing 0.5g of isosorbide, 10g of phthalic acid, 5g of ethylene glycol and 0.01g of catalyst, adding into a polymerization kettle, and heating while stirring;
S2: firstly, replacing air in a polymerization kettle with nitrogen, then boosting the pressure by using the nitrogen, slowly heating, starting the esterification reaction, and slowly decompressing to normal pressure when the esterification distillate appears;
s3: heating and slowly vacuumizing, starting polycondensation reaction, and granulating and drying after the reaction is finished to obtain the isosorbide modified PET copolyester.
And in the step S1, the temperature is raised to 70 ℃, and the stirring time is 20min.
The reaction pressure of S2 is 2kpa, and the reaction temperature is 230 ℃.
The vacuum pressure of S3 is 80kpa.
The reaction temperature of the S3 is 260 ℃, and the polycondensation reaction time is 2h.
The catalyst is a tin-doped resin catalyst, and the preparation method comprises the following steps:
h1: 120g of resin catalyst is put into a plasma reactor, di (dimethylamino) silane steam is introduced as modified gas, the input voltage of the plasma reactor is 20V, and the gas flow is 10ml/min; performing plasma modification in the atmosphere for 30min to obtain a resin catalyst with a silicon-hydrogen bond;
h2: introducing nitrogen to replace air in a closed reaction kettle, adding 2g of allyl tributyltin, 0.05g of 1, 4-di (2-thienyl) -1, 3-butadiene, 50g of resin catalyst with silicon-hydrogen bond, 0.01g of Kanst catalyst and 300g of ethanol, introducing nitrogen, heating, and stirring at 60 ℃ for reaction for 50 minutes; filtering and drying to obtain the tin-doped resin catalyst.
The resin catalyst is a D001 resin catalyst.
Example 2: the synthesis method of the isosorbide modified PET copolyester comprises the following steps:
S1: 1g of isosorbide, 13g of phthalic acid, 6g of ethylene glycol and 0.02g of catalyst are weighed and added into a polymerization kettle, and the temperature is raised while stirring;
S2: firstly, replacing air in a polymerization kettle with nitrogen, then boosting the pressure by using the nitrogen, slowly heating, starting the esterification reaction, and slowly decompressing to normal pressure when the esterification distillate appears;
s3: heating and slowly vacuumizing, starting polycondensation reaction, and granulating and drying after the reaction is finished to obtain the isosorbide modified PET copolyester.
And in the step S1, the temperature is raised to 75 ℃, and the stirring time is 25min.
The reaction pressure of S2 is 2kpa, and the reaction temperature is 235 ℃.
The vacuum pressure of S3 is 85kpa.
The reaction temperature of the S3 is 265 ℃, and the polycondensation reaction time is 3h.
The catalyst is a tin-doped resin catalyst, and the preparation method comprises the following steps:
H1: 130g of resin catalyst is put into a plasma reactor, di (dimethylamino) silane steam is introduced as modified gas, the input voltage of the plasma reactor is 25V, and the gas flow is 15ml/min; carrying out plasma modification in the atmosphere for 35min to obtain a resin catalyst with a silicon-hydrogen bond;
h2: introducing nitrogen to replace air in a closed reaction kettle, adding 3g of allyl tributyltin, 0.2g of 1, 4-di (2-thienyl) -1, 3-butadiene, 60g of resin catalyst with silicon-hydrogen bond, 0.05g of Kanst catalyst and 330g of ethanol, introducing nitrogen, heating, and stirring at 65 ℃ for reaction for 60 minutes; filtering and drying to obtain the tin-doped resin catalyst.
The resin catalyst is a D006 resin catalyst.
Example 3: the synthesis method of the isosorbide modified PET copolyester comprises the following steps:
S1: 1.5g of isosorbide, 18g of phthalic acid, 9g of ethylene glycol and 0.04g of catalyst are weighed and added into a polymerization kettle, and the temperature is raised while stirring;
S2: firstly, replacing air in a polymerization kettle with nitrogen, then boosting the pressure by using the nitrogen, slowly heating, starting the esterification reaction, and slowly decompressing to normal pressure when the esterification distillate appears;
s3: heating and slowly vacuumizing, starting polycondensation reaction, and granulating and drying after the reaction is finished to obtain the isosorbide modified PET copolyester.
And in the step S1, the temperature is raised to 85 ℃, and the stirring time is 35min.
The reaction pressure of S2 is 3kpa, and the reaction temperature is 245 ℃.
The vacuum pressure of S3 is 90kpa.
The reaction temperature of the S3 is 275 ℃, and the polycondensation reaction time is 4 hours.
The catalyst is a tin-doped resin catalyst, and the preparation method comprises the following steps:
h1: 140g of resin catalyst is put into a plasma reactor, di (dimethylamino) silane steam is introduced as modified gas, the input voltage of the plasma reactor is 25V, and the gas flow is 20ml/min; carrying out plasma modification in the atmosphere for 45min to obtain a resin catalyst with a silicon-hydrogen bond;
H2: introducing nitrogen to replace air in a closed reaction kettle, adding 4g of allyl tributyltin, 0.4g of 1, 4-di (2-thienyl) -1, 3-butadiene, 70g of resin catalyst with silicon-hydrogen bond, 0.08g of Kanst catalyst and 380g of ethanol, introducing nitrogen, heating, and stirring at 65 ℃ for reaction for 80 minutes; filtering and drying to obtain the tin-doped resin catalyst.
The resin catalyst is a D006 resin catalyst.
Example 4: the synthesis method of the isosorbide modified PET copolyester comprises the following steps:
s1: 2g of isosorbide, 20g of phthalic acid, 10g of ethylene glycol and 0.05g of catalyst are weighed and added into a polymerization kettle, and the temperature is raised while stirring;
S2: firstly, replacing air in a polymerization kettle with nitrogen, then boosting the pressure by using the nitrogen, slowly heating, starting the esterification reaction, and slowly decompressing to normal pressure when the esterification distillate appears;
s3: heating and slowly vacuumizing, starting polycondensation reaction, and granulating and drying after the reaction is finished to obtain the isosorbide modified PET copolyester.
And (2) heating to 90 ℃ in the step (S1), and stirring for 40min.
The reaction pressure of S2 was 3kpa and the reaction temperature was 250 ℃.
The vacuum pressure of S3 is 100kpa.
The reaction temperature of the S3 is 280 ℃, and the polycondensation reaction time is 5h.
The catalyst is a tin-doped resin catalyst, and the preparation method comprises the following steps:
H1: 150g of resin catalyst is put into a plasma reactor, di (dimethylamino) silane steam is introduced as modified gas, the input voltage of the plasma reactor is 30V, and the gas flow is 22ml/min; carrying out plasma modification in the atmosphere for 50min to obtain a resin catalyst with a silicon-hydrogen bond;
H2: introducing nitrogen to replace air in a closed reaction kettle, adding 5g of allyl tributyltin, 0.5g of 1, 4-di (2-thienyl) -1, 3-butadiene, 80g of resin catalyst with silicon-hydrogen bond, 0.1g of Kanst catalyst, 400g of ethanol, introducing nitrogen, heating, and stirring at 70 ℃ for reacting for 100 minutes; filtering and drying to obtain the tin-doped resin catalyst.
The resin catalyst is an A15 resin catalyst.
Comparative example 1: di (dimethylamino) silane was not added, otherwise as in example 1.
Comparative example 2: allyl tributyltin was not added, otherwise as in example 1.
Comparative example 3:1, 4-bis (2-thienyl) -1, 3-butadiene was not added, otherwise the same as in example 1.
Table 1: test results for examples and comparative examples
Through the data analysis of Table 1, the modified PET copolyester prepared by the invention has higher glass transition temperature and excellent heat resistance and barrier property; meanwhile, the tin-doped resin catalyst prepared by the invention effectively improves the conversion rate of the esterification reaction of the isosorbide modified PET copolyester.
The many features and advantages of the embodiments are apparent from the detailed specification, and thus, it is intended by the appended claims to cover all such features and advantages of the embodiments which fall within the true spirit and scope thereof. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the embodiments of the invention to the exact construction and operation illustrated and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope thereof.
Claims (5)
1. The synthesis method of the isosorbide modified PET copolyester is characterized by comprising the following steps of: the method comprises the following steps:
S1: weighing 0.5-2 parts of isosorbide, 10-20 parts of phthalic acid, 5-10 parts of ethylene glycol and 0.01-0.05 part of catalyst according to parts by weight, adding into a polymerization kettle, and heating while stirring;
S2: firstly, replacing air in a polymerization kettle with nitrogen, then boosting the pressure by using the nitrogen, slowly heating, starting the esterification reaction, and slowly decompressing to normal pressure when the esterification distillate appears;
S3: heating and slowly vacuumizing, starting polycondensation reaction, and granulating and drying after the reaction is finished to obtain isosorbide modified PET copolyester;
the catalyst is a tin-doped resin catalyst, and the preparation method comprises the following steps:
h1: putting 120-150 parts of resin catalyst into a plasma reactor, introducing di (dimethylamino) silane steam as a modified gas, wherein the input voltage of the plasma reactor is 20-30V, and the gas flow is 10-22ml/min; performing plasma modification in the atmosphere for 30-50min to obtain a resin catalyst with silicon-hydrogen bonds;
H2: according to the mass parts, introducing nitrogen to replace air in a closed reaction kettle, adding 2-5 parts of allyl tributyltin, 0.05-0.5 part of 1, 4-di (2-thienyl) -1, 3-butadiene, 50-80 parts of resin catalyst with silicon-hydrogen bond, 0.01-0.1 part of Caster catalyst and 300-400 parts of ethanol, introducing nitrogen, heating, and stirring at 60-70 ℃ for reaction for 50-100 minutes; filtering and drying to obtain a tin-doped resin catalyst;
The resin catalyst is selected from the group consisting of a D001 resin catalyst, a D006 resin catalyst and an A15 resin catalyst.
2. The method for synthesizing the isosorbide-modified PET copolyester according to claim 1, which is characterized in that: heating to 70-90 ℃ in the step S1, and stirring for 20-40min.
3. The method for synthesizing the isosorbide-modified PET copolyester according to claim 1, which is characterized in that: the reaction pressure of the S2 is 2-3kpa, and the reaction temperature is 230-250 ℃.
4. The method for synthesizing the isosorbide-modified PET copolyester according to claim 1, which is characterized in that: the vacuum pressure of the S3 is 80-100kpa.
5. The method for synthesizing the isosorbide-modified PET copolyester according to claim 1, which is characterized in that: the reaction temperature of the S3 is 260-280 ℃, and the polycondensation reaction time is 2-5h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410185782.4A CN117736424B (en) | 2024-02-20 | 2024-02-20 | Synthesis method of isosorbide modified PET copolyester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410185782.4A CN117736424B (en) | 2024-02-20 | 2024-02-20 | Synthesis method of isosorbide modified PET copolyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117736424A CN117736424A (en) | 2024-03-22 |
| CN117736424B true CN117736424B (en) | 2024-04-16 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105658606A (en) * | 2013-10-29 | 2016-06-08 | 捷恩智株式会社 | Anthracene compound; light-emitting-layer material; and organic electroluminescent element, display device, and illumination device using same |
| CN114591496A (en) * | 2022-01-11 | 2022-06-07 | 浙江恒逸石化研究院有限公司 | Preparation method of rigid copolyester |
| CN116284712A (en) * | 2023-04-26 | 2023-06-23 | 绍兴翔宇绿色包装有限公司 | Environment-friendly polyester film and preparation method thereof |
| WO2023165112A1 (en) * | 2022-03-01 | 2023-09-07 | 杭州和顺科技股份有限公司 | Polyester film having high light transmittance and method for manufacturing same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105658606A (en) * | 2013-10-29 | 2016-06-08 | 捷恩智株式会社 | Anthracene compound; light-emitting-layer material; and organic electroluminescent element, display device, and illumination device using same |
| CN114591496A (en) * | 2022-01-11 | 2022-06-07 | 浙江恒逸石化研究院有限公司 | Preparation method of rigid copolyester |
| WO2023165112A1 (en) * | 2022-03-01 | 2023-09-07 | 杭州和顺科技股份有限公司 | Polyester film having high light transmittance and method for manufacturing same |
| CN116284712A (en) * | 2023-04-26 | 2023-06-23 | 绍兴翔宇绿色包装有限公司 | Environment-friendly polyester film and preparation method thereof |
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| CN117736424A (en) | 2024-03-22 |
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