CN111303394A - Preparation method of modified high-temperature-resistant polyester and modified high-temperature-resistant polyester - Google Patents
Preparation method of modified high-temperature-resistant polyester and modified high-temperature-resistant polyester Download PDFInfo
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- CN111303394A CN111303394A CN202010313489.3A CN202010313489A CN111303394A CN 111303394 A CN111303394 A CN 111303394A CN 202010313489 A CN202010313489 A CN 202010313489A CN 111303394 A CN111303394 A CN 111303394A
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- resistant polyester
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- dihydric alcohol
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- 229920000728 polyester Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000032050 esterification Effects 0.000 claims abstract description 22
- 238000005886 esterification reaction Methods 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 21
- 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 19
- 229960002479 isosorbide Drugs 0.000 claims abstract description 19
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 19
- BNNBECJSDDMHFF-UHFFFAOYSA-N 2,2,3,3-tetramethylcyclobutane-1,1-diol Chemical compound CC1(C)CC(O)(O)C1(C)C BNNBECJSDDMHFF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 5
- 239000004014 plasticizer Substances 0.000 claims abstract description 5
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical group CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 16
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical group O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 6
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 6
- 229910006113 GeCl4 Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- QYCSNMDOZNUZIT-UHFFFAOYSA-N benzhydrylidenehydrazine Chemical compound C=1C=CC=CC=1C(=NN)C1=CC=CC=C1 QYCSNMDOZNUZIT-UHFFFAOYSA-N 0.000 claims description 4
- XCLKKWIIZMHQIV-UHFFFAOYSA-N isobutylgermane Chemical compound CC(C)C[Ge] XCLKKWIIZMHQIV-UHFFFAOYSA-N 0.000 claims description 4
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical group CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 11
- 230000009477 glass transition Effects 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 238000005266 casting Methods 0.000 description 8
- 235000013339 cereals Nutrition 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- SHRAEISUGISTAR-UHFFFAOYSA-L dibutyltin(2+);6-methylheptanoate Chemical compound CCCC[Sn+2]CCCC.CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O SHRAEISUGISTAR-UHFFFAOYSA-L 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Inorganic materials [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000000318 high-performance liquid chromatography-electrospray ionisation tandem mass spectrometry Methods 0.000 description 1
- 229910052739 hydrogen Chemical group 0.000 description 1
- 239000001257 hydrogen Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004885 tandem mass spectrometry Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000004580 weight loss Effects 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
-
- 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
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 discloses a preparation method of modified high-temperature-resistant polyester, which comprises the following steps: the method comprises the following steps: mixing terephthalic acid, dihydric alcohol, a catalyst and an additive uniformly to obtain slurry; the dihydric alcohol is a mixture of tetramethyl cyclobutanediol, isosorbide and ethylene glycol, and the molar ratio of the terephthalic acid to the dihydric alcohol is 1: 1.2-1.5; the catalyst is a germanium-based catalyst and/or a titanium-based catalyst which is 0.1-0.5 per mill of the total mass of reactants; the additive is a mixture of 0.1-5 per mill of antioxidant, 0.1-5 per mill of heat stabilizer and 0.1-5% of plasticizer, wherein the total mass of reactants is taken as a base number; esterification: esterifying the slurry at 230-270 ℃ and under the relative pressure of 0.01-0.20 MPa; polycondensation: and polycondensing the obtained esterification product at 260-280 ℃ under the absolute pressure of 0-150 Pa. The modified high-temperature-resistant polyester prepared by the invention has higher polymerization degree, higher glass transition temperature and good hydrolytic resistance, is not easy to yellow and does not contain bisphenol A.
Description
Technical Field
The invention belongs to the field of synthesis of high-molecular polyester materials, and particularly relates to a preparation method of modified high-temperature-resistant polyester and modified high-temperature-resistant resin.
Background
The polyester yield in China reaches 4500W tons, which is the top of the world. The traditional PET polyester has the characteristics of large yield and large dosage, but has the problems of poor heat resistance, catalyst toxicity and the like. The introduction of the environment-friendly green catalyst through modification and the improvement of the heat resistance and the mechanical property of the catalyst become a development direction of PET. At present, in the aspect of modification, rigid structure comonomer is introduced to improve corresponding performance.
Isosorbide is a bio-based diol monomer obtained by dehydrating starch in cereals. Because of having a rigid structure and being chiral molecules, the compound is an ideal raw material for synthesizing polyester with high glass transition temperature or excellent mechanical properties. However, two hydroxyl groups of isosorbide are secondary hydroxyl groups, and hydrogen bonds exist in the internal terminal hydroxyl groups of the ring, so that the isosorbide has low reactivity, the polymerization degree of the polymer is easy to be insufficient, and the generated polyester has poor hydrolysis resistance and is easy to yellow. In addition, the modified polyester in the prior art is easy to release toxic substance bisphenol A in the using process, so that the using range of the modified polyester is limited.
Disclosure of Invention
The purpose of the invention is as follows: the preparation method of the modified high-temperature-resistant polyester is provided, and the modified high-temperature-resistant polyester prepared by the method does not release bisphenol A in use and has good hydrolysis resistance.
The technical scheme of the invention is as follows:
a preparation method of modified high-temperature-resistant polyester comprises the following steps:
the method comprises the following steps: mixing materials: mixing terephthalic acid, dihydric alcohol, a catalyst and an additive uniformly to obtain slurry; the dihydric alcohol is a mixture of tetramethyl cyclobutanediol, isosorbide and glycol; wherein the molar ratio of the terephthalic acid to the dihydric alcohol is 1: 1.2-1.5; the catalyst is a germanium-based catalyst and/or a titanium-based catalyst which is 0.1-0.5 per mill of the total mass of reactants; the additive is a mixture of 0.1-5 per mill of antioxidant, 0.1-5 per mill of heat stabilizer and 0.1-5 percent of plasticizer, wherein the total mass of the reactants is taken as a base number;
step two: esterification: esterifying the slurry at 230-270 ℃ and under the relative pressure of 0.01-0.20 MPa;
step three: polycondensation: and polycondensing the obtained esterification product at 260-280 ℃ under the absolute pressure of 0-150 Pa.
According to the method for preparing the modified high-temperature-resistant polyester, the tetramethyl cyclobutanediol, the isosorbide and the ethylene glycol copolyester are added, the reaction activity of isosorbide can be improved due to the addition of the tetramethyl cyclobutanediol, and the generated polyester has high polymerization degree, so that the modified high-temperature-resistant polyester has high glass transition temperature and good hydrolysis resistance and is not easy to yellow. In addition, the modified high temperature resistant polyester prepared by the method does not contain bisphenol A and is nontoxic.
Preferably, the molar ratio of the tetramethylcyclobutanediol to the ethylene glycol is 1: 3 to 5.
Preferably, the molar ratio of isosorbide to ethylene glycol is 1: 3 to 5.
Preferably, the germanium-based catalyst is GeO2、GeCl4Or isobutylgermane. The germanium-based catalyst is non-toxic and environment-friendly, so that the prepared modified high-temperature-resistant polyester is more environment-friendly.
Preferably, the titanium-based catalyst is TiO2、TiCl4Or Ti (NO)3)4. The titanium-based catalyst is non-toxic and environment-friendly, so that the prepared modified high-temperature-resistant polyester is more environment-friendly.
Preferably, the antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite. The antioxidant is added, so that the modified high-temperature resistant polyester prepared in the invention is not included due to oxidation in the preparation process, and meanwhile, the antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite ester, so that the modified high-temperature resistant polyester is more stable in performance in the use process and is not easy to oxidize and denature.
Preferably, the heat stabilizer is dibutyl tin diisooctoate or zinc acetylacetonate. The thermal stabilizer of dibutyltin diisooctoate or zinc acetylacetonate is added, so that the occurrence of side reaction caused by high temperature in the reaction process can be reduced, and the generated modified high-temperature resistant polyester has no inclusion.
Preferably, the plasticizer is dibutyl phthalate or dioctyl phthalate. The addition of dibutyl phthalate or dioctyl phthalate can better improve the plasticity of each substance in the reaction process, so that each substance is mixed more uniformly and reacts more fully in the reaction process.
Preferably, the additive is also mixed with 0.1 percent of ultraviolet resistant agent based on the total mass of reactants, and the ultraviolet resistant agent is zinc oxide, benzophenone hydrazone or Ni (pi-C)3H5)2. The addition of 0.1 percent of the ultraviolet resistant agent can make the modified high temperature resistant polyester more resistant to ultraviolet rays in the using process and be not easily denatured by the influence of the ultraviolet rays in the using process under the condition of not influencing other properties of the modified high temperature resistant polyester.
The invention also provides the modified high-temperature resistant polyester prepared by the preparation method of the modified high-temperature resistant polyester.
The invention has the beneficial effects that:
according to the preparation method of the modified high-temperature-resistant polyester, the reaction activity of isosorbide is improved by adding the tetramethyl cyclobutanediol, so that the prepared modified high-temperature-resistant polyester has higher polymerization degree, and the modified high-temperature-resistant polyester has higher glass transition temperature and good hydrolytic resistance and is not easy to yellow. The modified high temperature resistant polyester prepared by the method does not contain bisphenol A, is nontoxic and can be widely applied to the fields of food packaging and the like.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Preparing a modified high-temperature-resistant polyester:
the method comprises the following steps: mixing material
16.6Kg of terephthalic acid, 4.33Kg of tetramethyl cyclobutanediol, 4.38Kg of isosorbide, 5.58Kg of ethylene glycol and catalyst GeO23.09g、TiO23.09g of tris (2.4-di-tert-butylphenyl) phosphite, 7.0g of dibutyltin diisooctanoate and 70.0g of dibutyl phthalate were mixed, and the mixture was made into slurry and stirred.
Step two: esterification: the slurry was esterified at 230 ℃ under a relative pressure of 0.01MPa for 2 hours.
Step three: polycondensation: and (3) carrying out polycondensation on the obtained esterification product at the temperature of 280 ℃ and the absolute pressure of 80Pa, reacting for 4 hours, and carrying out casting belt and grain cutting on the obtained product.
Example 2
Preparing a modified high-temperature-resistant polyester:
the method comprises the following steps: mixing material
16.6Kg of terephthalic acid, 3.61Kg of tetramethyl cyclobutanediol, 3.65Kg of isosorbide, 6.2Kg of ethylene glycol and catalyst GeCl47.5g、TiCl47.5g, tris (2.4-di-tert-butylphenyl) phosphite 8.0g, zinc acetylacetonate 80.0g and dioctyl phthalate 80.0g were mixed, and the mixture was slurried and stirred.
Step two: esterification: the slurry was esterified at 270 ℃ under a relative pressure of 0.05MPa for 1 hour.
Step three: polycondensation: and (3) carrying out polycondensation on the obtained esterification product at the temperature of 260 ℃ and under the absolute pressure of 100Pa, reacting for 5 hours, and carrying out casting belt and grain cutting on the obtained product.
Example 3
Preparing a modified high-temperature-resistant polyester:
the method comprises the following steps: mixing material
16.6Kg of terephthalic acid, 2.88Kg of tetramethyl cyclobutanediol, 2.92Kg of isosorbide, 6.2Kg of ethylene glycol, 8.6g of catalyst isobutyl germane and Ti (NO)3)45.7g, tris (2.4-di-tert-butylphenyl) phosphite 9.0g, zinc acetylacetonate 20.0g, dibutyl phthalate 90.0g and anti-ultraviolet agent zinc oxide 28.6g, after mixing, the mixture was made into slurry and stirred.
Step two: esterification: the slurry was esterified at a temperature of 250 ℃ and a relative pressure of 0.10MPa for 2 hours.
Step three: polycondensation: and (3) carrying out polycondensation on the obtained esterification product at the temperature of 265 ℃ and the absolute pressure of 120Pa, reacting for 5 hours, and carrying out casting belt and grain cutting on the obtained product.
Example 4
Preparing a modified high-temperature-resistant polyester:
the method comprises the following steps: mixing material
41.5Kg of terephthalic acid, 8.65Kg of tetramethyl cyclobutanediol, 8.76Kg of isosorbide, 11.16Kg of ethylene glycol and catalyst GeO27.1g、Ti(NO3)421.02g, 15.0g of tris (2.4-di-tert-butylphenyl) phosphite, 20.0g of dibutyltin diisooctanoate, 100.0g of dioctyl phthalate and 70.0g of benzophenone hydrazone as an anti-ultraviolet agent are mixed, and then the mixture is made into slurry and stirred uniformly.
Step two: esterification: the slurry was esterified at 240 ℃ under a relative pressure of 0.20MPa for 2 hours.
Step three: polycondensation: and (3) carrying out polycondensation on the obtained esterification product at the temperature of 275 ℃ and under the absolute pressure of 0Pa, reacting for 6 hours, and carrying out casting and pelletizing on the obtained product.
Example 5
Preparing a modified high-temperature-resistant polyester:
the method comprises the following steps: mixing material
33.2Kg of terephthalic acid, 7.21Kg of tetramethyl cyclobutanediol, 7.3Kg of isosorbide, 12.4Kg of ethylene glycol and catalyst GeCl46.1g、Ti(NO3)46.1g of tris (2.4-di-tert-butylphenyl) phosphite, 15.0g of dibutyltin diisooctanoate, 10.0g of dioctylphthalate, 60.0g of anti-ultraviolet Ni (. pi. -C)3H5)261.0g of the mixture is made into slurry and stirred evenly.
Step two: esterification: the slurry was esterified at a temperature of 250 ℃ and a relative pressure of 0.15MPa for 2 hours.
Step three: polycondensation: and (3) carrying out polycondensation on the obtained esterification product at the temperature of 270 ℃ and under the absolute pressure of 50Pa, reacting for 5 hours, and carrying out casting belt and grain cutting on the obtained product.
Example 6
Preparing a modified high-temperature-resistant polyester:
the method comprises the following steps: mixing material
16.6Kg of terephthalic acid, 4.33Kg of tetramethyl cyclobutanediol, 4.38Kg of isosorbide, 5.58Kg of ethylene glycol, 5g of catalyst isobutyl germane and TiO23g of tris (2, 4-di-tert-butylphenyl) phosphite, 10g of zinc acetylacetonate, 80g of dibutyl phthalate and 30.8g of benzophenone hydrazone as an anti-ultraviolet agent are mixed, and then the mixture is made into slurry and stirred uniformly.
Step two: esterification: the slurry is esterified at the temperature of 260 ℃ and the relative pressure of 0.03MPa, and the reaction lasts for 2 hours.
Step three: polycondensation: and (3) carrying out polycondensation on the obtained esterification product at the temperature of 260 ℃ and under the absolute pressure of 0Pa, reacting for 6 hours, and carrying out casting belt and grain cutting on the obtained product.
Example 7
Preparing a modified high-temperature-resistant polyester:
the method comprises the following steps: mixing material
16.6Kg of terephthalic acid, 3.61Kg of tetramethyl cyclobutanediol, 3.65Kg of isosorbide, 6.2Kg of ethylene glycol and catalyst GeCl43g of tris (2, 4-di-tert-butylphenyl) phosphite, 150g of dibutyltin diisooctanoate, 1.5kg of dibutyl phthalate and an anti-UV agent Ni (. pi. -C)3H5)230g of the mixture is made into slurry and stirred evenly.
Step two: esterification: the slurry was esterified at 270 ℃ under a relative pressure of 0.04MPa for 2 hours.
Step three: polycondensation: and (3) carrying out polycondensation on the obtained esterification product at the temperature of 280 ℃ and under the absolute pressure of 150Pa, reacting for 6 hours, and carrying out casting belt and grain cutting on the obtained product.
Example 8
Preparing a modified high-temperature-resistant polyester:
the method comprises the following steps: mixing material
16.6Kg of terephthalic acid, 3.61Kg of tetramethyl cyclobutanediol, 3.65Kg of isosorbide, 6.2Kg of ethylene glycol and a catalyst TiO23.0g of tris (2.4-di-tert-butylphenyl) phosphite, 150g of dibutyltin diisooctanoate, 1.5kg of dibutyl phthalate and an anti-ultraviolet agent Ni (. pi. -C)3H5)2Mixing 30g, and beatingForming into slurry, and stirring.
Step two: esterification: the slurry was esterified at 270 ℃ under a relative pressure of 0.04MPa for 2 hours.
Step three: polycondensation: and (3) carrying out polycondensation on the obtained esterification product at the temperature of 280 ℃ and under the absolute pressure of 100Pa, reacting for 6 hours, and carrying out casting belt and grain cutting on the obtained product.
And (3) performance detection:
the glass transition temperature of the modified high temperature resistant polyesters prepared in examples 1 to 7 and comparative example was measured by Differential Scanning Calorimeter (DSC), and the amount of bisphenol A detected was measured by high performance liquid chromatography-electrospray tandem mass spectrometry (HPLC-ESI-MS/MS), and the results are shown in Table 1.
And (3) detecting hydrolysis resistance: 100g of the prepared modified high-temperature resistant polyester is sampled and respectively placed in the solutions of pH1.0 solution and pH13.0 solution to be soaked for 200 days at the temperature of 80 ℃, the weight loss quality of the modified high-temperature resistant polyester before and after soaking is tested, and the results are shown in Table 1.
TABLE 1
The results show that the prepared modified high-temperature-resistant polyester has higher polymerization degree by adding the tetramethyl cyclobutanediol, so that the modified high-temperature-resistant polyester has higher glass transition temperature and good hydrolysis resistance, and is not easy to yellow.
It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features related to the embodiments of the present invention described above may be combined with each other as long as they do not conflict with each other. In addition, the above embodiments are only some embodiments, not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention belong to the protection scope of the present invention.
Claims (10)
1. The preparation method of the modified high-temperature-resistant polyester is characterized by comprising the following steps of:
the method comprises the following steps: mixing material
Mixing terephthalic acid, dihydric alcohol, a catalyst and an additive uniformly to obtain slurry; the dihydric alcohol is a mixture of tetramethyl cyclobutanediol, isosorbide and glycol; wherein the molar ratio of the terephthalic acid to the dihydric alcohol is 1: 1.2-1.5;
the catalyst is a germanium-based catalyst and/or a titanium-based catalyst which is 0.1-0.5 per mill of the total mass of reactants; the additive is a mixture of 0.1-5 per mill of antioxidant, 0.1-5 per mill of heat stabilizer and 0.1-5 percent of plasticizer, wherein the total mass of the reactants is taken as a base number;
step two: esterification: esterifying the slurry at 230-270 ℃ and under the relative pressure of 0.01-0.20 MPa;
step three: polycondensation: and polycondensing the obtained esterification product at 260-280 ℃ under the absolute pressure of 0-150 Pa.
2. The method of claim 1, wherein the mole ratio of the tetramethylcyclobutanediol to the ethylene glycol is from 1: 3 to 5.
3. The method of claim 2, wherein the molar ratio of isosorbide to ethylene glycol is 1: 3 to 5.
4. The method of claim 3, wherein the germanium-based catalyst is GeO2、GeCl4Or isobutylgermane.
5. The method of claim 3, wherein the titanium-based catalyst is TiO2、TiCl4Or Ti (NO)3)4。
6. The process for preparing modified high temperature resistant polyester according to claim 3, wherein the antioxidant is tris (2, 4-di-t-butylphenyl) phosphite.
7. The method for preparing the modified high temperature resistant polyester according to claim 3, wherein the heat stabilizer is dibutyl tin diisooctoate or zinc acetylacetonate.
8. The method of claim 3, wherein the plasticizer is dibutyl phthalate or dioctyl phthalate.
9. The process for preparing modified high temperature resistant polyester according to any of claims 1 to 8, wherein 0.1% by mass of the total mass of reactants of an anti-UV agent selected from zinc oxide, benzophenone hydrazone or Ni (π -C) is further mixed in the additive3H5)2。
10. A modified high temperature resistant polyester, characterized in that it is produced by the process for the preparation of a modified high temperature resistant polyester according to one of claims 1 to 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090306313A1 (en) * | 2008-06-06 | 2009-12-10 | Wellman, Inc. | Titanium-Nitride Catalyzed Polyester |
| CN102666681A (en) * | 2009-11-13 | 2012-09-12 | Sk化学株式会社 | Copolymerized polyester heat shrinkable film |
| CN108431078A (en) * | 2015-12-02 | 2018-08-21 | 罗盖特公司 | Containing 1,4:The aromatic thermoplastic copolyesters of the bis- dewatering hexitols of 3,6- and various cyclic diols |
| CN109563249A (en) * | 2016-08-18 | 2019-04-02 | 伊士曼化工公司 | The polymer blend comprising tetramethylcyclobutanediol and ethylene glycol for calendering |
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2020
- 2020-04-20 CN CN202010313489.3A patent/CN111303394A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090306313A1 (en) * | 2008-06-06 | 2009-12-10 | Wellman, Inc. | Titanium-Nitride Catalyzed Polyester |
| CN102666681A (en) * | 2009-11-13 | 2012-09-12 | Sk化学株式会社 | Copolymerized polyester heat shrinkable film |
| CN108431078A (en) * | 2015-12-02 | 2018-08-21 | 罗盖特公司 | Containing 1,4:The aromatic thermoplastic copolyesters of the bis- dewatering hexitols of 3,6- and various cyclic diols |
| CN109563249A (en) * | 2016-08-18 | 2019-04-02 | 伊士曼化工公司 | The polymer blend comprising tetramethylcyclobutanediol and ethylene glycol for calendering |
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Application publication date: 20200619 |