CN110606941B - Low-end carboxyl hydrolysis-resistant polyester and preparation method and application thereof - Google Patents
Low-end carboxyl hydrolysis-resistant polyester and preparation method and application thereof Download PDFInfo
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- CN110606941B CN110606941B CN201810531122.1A CN201810531122A CN110606941B CN 110606941 B CN110606941 B CN 110606941B CN 201810531122 A CN201810531122 A CN 201810531122A CN 110606941 B CN110606941 B CN 110606941B
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- 229920000728 polyester Polymers 0.000 title claims abstract description 88
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 42
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 35
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 33
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 29
- 239000010936 titanium Substances 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- 238000005886 esterification reaction Methods 0.000 claims description 32
- 238000006068 polycondensation reaction Methods 0.000 claims description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 18
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 10
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 9
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- -1 titanium carboxylate Chemical class 0.000 claims description 4
- 229940083957 1,2-butanediol Drugs 0.000 claims description 3
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 3
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 3
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 3
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 claims description 3
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 claims description 3
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 3
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- JDQXDRTXTZSRLY-UHFFFAOYSA-L C(C(=O)[O-])(=O)[O-].[O-2].[Ti+4].[Li+] Chemical compound C(C(=O)[O-])(=O)[O-].[O-2].[Ti+4].[Li+] JDQXDRTXTZSRLY-UHFFFAOYSA-L 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 4
- 238000010248 power generation Methods 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 229920006267 polyester film Polymers 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 229940035437 1,3-propanediol Drugs 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRXBVZUTZPDWQI-UHFFFAOYSA-N ethane-1,2-diol;titanium Chemical compound [Ti].OCCO KRXBVZUTZPDWQI-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 229940093476 ethylene glycol Drugs 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- QKKWJYSVXDGOOJ-UHFFFAOYSA-N oxalic acid;oxotitanium Chemical compound [Ti]=O.OC(=O)C(O)=O QKKWJYSVXDGOOJ-UHFFFAOYSA-N 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SLWIPPZWFZGHEU-UHFFFAOYSA-N 2-[4-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=C(CC(O)=O)C=C1 SLWIPPZWFZGHEU-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
- C08G63/87—Non-metals or inter-compounds thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a low-end carboxyl hydrolysis-resistant polyester, a preparation method and application thereof. The low-end carboxyl hydrolysis-resistant polyester is prepared by adding an environment-friendly high-efficiency titanium polyester catalyst and controlling the feeding ratio of dibasic acid and a dibasic alcohol monomer under the condition of not introducing new reagents and groups. The polyester prepared by the invention is not subjected to end capping and/or chain extension treatment, has good hydrolysis resistance, and is simple in preparation method and easy for industrial production. The polyester has the intrinsic viscosity of 0.5-1.2 dL/g, the terminal carboxyl group content of 2-10 mmol/kg and excellent comprehensive performance, can meet the performance requirements of photovoltaic modules on polyester films, is expected to be applied to photovoltaic power generation modules, and has important effects on prolonging the service life of Chinese photovoltaic products and promoting the healthy and stable development of the Chinese photovoltaic industry.
Description
Technical Field
The invention belongs to the technical field of polyester and preparation thereof, and particularly relates to low-end carboxyl hydrolysis-resistant polyester and a preparation method and application thereof.
Background
Under the great trend of global low-carbon economy and new energy revolution, compared with hydroelectric power, wind power, nuclear power and the like, the solar power generation has the obvious advantages of zero emission, no noise and mature application technology. Photovoltaic power generation without any fuel except sunshine is one of strategic emerging industries and is expected to become the leading energy with the largest future share in China.
Polyester, one of the five engineering plastics, has the characteristics of low price, excellent wear resistance, heat resistance, chemical resistance, electrical insulation, high mechanical strength and the like, and can be widely applied to photovoltaic back plates in photovoltaic modules. Because the photovoltaic module needs to be used outdoors for a long time, although the dry heat aging performance of the conventional polyester film is good, the hydrolysis resistance is poor, and the photovoltaic module is easy to degrade and lose efficiency under the damp and hot conditions, so that the requirement on the service life of the photovoltaic module cannot be met. Therefore, the development of a novel hydrolysis-resistant polyester material is an urgent need for the application of the polyester material in the fields of photovoltaic modules and the like.
Chinese patent document CN103665788B discloses the preparation of high viscosity modified PET copolyester by adding oxazoline compound and hydroxyl chain extender. The method can improve the viscosity and the melt strength of the PET copolyester, reduce the content of terminal carboxyl groups and improve the hot water resistance. However, the introduction of new substances destroys the ordered long-chain structure of PET, so that the structural performance of the film is unstable.
Chinese patent document CN101215730A discloses a method of adding a hydrolysis resistant agent, namely carbodiimide, to modify polyester. Although the hydrolysis resistance of the modified polyester obtained by the method is improved, the production cost is high, and a large amount of harmful volatile matters are generated in the production process, so that the influence on the environment and the health of personnel is caused.
Chinese patent document CN102344654B provides a hydrolysis-resistant PET composite material and a preparation method thereof, in the method, a mixed raw material obtained by uniformly mixing PET resin, a hydrolysis-resistant agent, a chain extender, a heat stabilizer, a nucleating agent and an auxiliary agent is placed in a double-screw extruder to be blended with glass fiber, and the hydrolysis-resistant PET composite material is obtained through melt extrusion and granulation. Although the composite material obtained by the method has better hydrolysis resistance, the complicated production procedure can cause the increase of the industrial production cost.
The improvement of the performance parameters of the polyester disclosed above is mainly realized by introducing other additives such as hydrolysis resistance agents, chain extenders, heat stabilizers, nucleating agents and the like or compounding various additives, and the polyester does not have a low-end carboxyl group in the structure; it would be of great research interest to develop a polyester with low carboxyl end group properties by itself, without end capping and without the introduction of other adjuvants.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a novel low-end carboxyl hydrolysis-resistant polyester, and a preparation method and application thereof. Under a certain reaction condition, a novel low-end carboxyl hydrolysis-resistant polyester is prepared by directly polymerizing by using an environment-friendly high-efficiency titanium polyester catalyst and controlling the feeding proportion of dibasic acid and a dibasic alcohol monomer, wherein the polyester has no end capping and/or chain extension treatment, and the structure of the polyester has the characteristic of low-end carboxyl.
The low-end carboxyl group in the invention means that the content of the low-end carboxyl group in the polyester is 2-10 mmol/kg.
The purpose of the invention is realized by the following technical scheme:
a low-end carboxyl hydrolysis-resistant polyester is prepared by using a titanium polyester catalyst and controlling the feeding ratio of dibasic acid and a dihydric alcohol monomer to carry out esterification and polycondensation, wherein the feeding molar ratio of the dibasic acid to the dihydric alcohol is 1 (1.3-10); the content of the terminal carboxyl groups in the polyester is 2-10 mmol/kg.
In the present invention, the polyester is not subjected to end capping and/or chain extension treatment.
According to the invention, the molar ratio of the dibasic acid to the dihydric alcohol is controlled, and the environment-friendly and efficient titanium polyester catalyst is matched, so that the amount of the terminal carboxyl is effectively reduced, and the low-end carboxyl hydrolysis-resistant polyester is obtained.
Preferably, the feeding molar ratio of the dibasic acid to the dihydric alcohol is 1 (1.4-8), still preferably 1 (1.5-5), and further preferably 1 (1.6-3).
According to an embodiment of the present invention, the intrinsic viscosity of the polyester is 0.5 to 1.2 dL/g.
According to an embodiment of the present invention, the dibasic acid is an aromatic dibasic acid, for example, at least one selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid, terephthallic acid, isophthalic acid, orthophthalic acid, 2, 6-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 4 '-biphenyldicarboxylic acid, and 2, 2' -biphenyldicarboxylic acid; at least one of terephthalic acid, isophthalic acid and phthalic acid is preferable.
According to an embodiment of the present invention, the diol is a short-chain aliphatic diol, for example, at least one selected from the group consisting of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-dimethyl-1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, and 2, 3-butanediol; at least one of ethylene glycol, 1, 3-propanediol and 1, 4-butanediol is preferred.
According to the embodiment of the invention, the titanium polyester catalyst is selected from at least one of organic compounds, oxides or complexes of titanium; at least one of titanium dioxide, a silica/titanium dioxide composite, ethylene glycol titanium, tetrabutyl titanate, tetraisopropyl titanate, titanium carboxylate, and lithium titanyl oxalate is preferable.
The invention also provides a preparation method of the low-end carboxyl hydrolysis-resistant polyester, which comprises an esterification reaction step and a polycondensation reaction step of dibasic acid and dibasic alcohol, wherein a titanium polyester catalyst is added before and/or after the esterification reaction, and the feeding molar ratio of the dibasic acid to the dibasic alcohol is 1 (1.3-10); the process does not include an end-capping step and/or a chain extension step.
According to the invention, the method comprises the following steps:
1) mixing dibasic acid and dihydric alcohol, and carrying out esterification reaction to prepare a polyester esterified substance; wherein the feeding molar ratio of the dibasic acid to the dihydric alcohol is 1 (1.3-10);
2) performing polycondensation reaction on the polyester esterified substance in the step 1) to prepare low-end carboxyl hydrolysis-resistant polyester;
adding a titanium polyester catalyst into a mixed system of dibasic acid and dihydric alcohol before esterification reaction, and/or adding the titanium polyester catalyst into the mixed system of polyester esterified in the step 1) after esterification reaction;
the process does not include an end-capping step and/or a chain extension step.
According to the embodiment of the invention, the feeding molar ratio of the dibasic acid to the dihydric alcohol is 1 (1.4-8), preferably 1 (1.5-5), and further preferably 1 (1.6-3).
According to an embodiment of the present invention, the dibasic acid is an aromatic dibasic acid, for example, at least one selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid, terephthallic acid, isophthalic acid, orthophthalic acid, 2, 6-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 4 '-biphenyldicarboxylic acid, and 2, 2' -biphenyldicarboxylic acid; at least one of terephthalic acid, isophthalic acid and phthalic acid is preferable.
According to an embodiment of the present invention, the diol is a short-chain aliphatic diol, for example, at least one selected from the group consisting of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-dimethyl-1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, and 2, 3-butanediol; at least one of ethylene glycol, 1, 3-propanediol and 1, 4-butanediol is preferred.
According to the embodiment of the invention, the addition amount of the titanium polyester catalyst is 10 of the mass of the polyester-7wt% -0.1 wt%; preferably 10-4wt％～0.1wt％。
According to the embodiment of the invention, the titanium polyester catalyst is selected from at least one of organic compounds, oxides or complexes of titanium; at least one of titanium dioxide, a silica/titanium dioxide composite, ethylene glycol titanium, tetrabutyl titanate, tetraisopropyl titanate, titanium carboxylate, and lithium titanyl oxalate is preferable.
According to an embodiment of the present invention, the esterification reaction of step 1) is carried out under pressure.
According to the embodiment of the invention, the pressure of the esterification reaction in the step 1) is 10-500 KPa, the temperature of the esterification reaction is 150-260 ℃, and the time of the esterification reaction is 0.5-4 hours.
Preferably, the pressure of the esterification reaction in the step 1) is 250 to 500KPa, the temperature of the esterification reaction is 200 to 250 ℃, and the time of the esterification reaction is 1.5 to 3.5 hours.
According to an embodiment of the present invention, the polycondensation reaction of step 2) is performed under a certain degree of vacuum.
According to the embodiment of the invention, the vacuum degree of the polycondensation reaction in the step 2) is 10-200 Pa, the temperature of the polycondensation reaction is 250-290 ℃, and the time of the polycondensation reaction is 0.5-4 hours.
According to an embodiment of the invention, the method comprises the steps of:
a) mixing dibasic acid and dihydric alcohol, and carrying out esterification reaction under certain pressure to prepare a polyester esterified substance; wherein the feeding molar ratio of the dibasic acid to the dihydric alcohol is 1 (1.3-10); mixing a titanium polyester catalyst and a polyester ester, and carrying out polycondensation reaction under certain vacuum to prepare low-end carboxyl hydrolysis-resistant polyester; alternatively, the first and second electrodes may be,
b) mixing dibasic acid, dihydric alcohol and a titanium polyester catalyst, and carrying out esterification reaction under certain pressure to prepare a polyester esterified substance; wherein the feeding molar ratio of the dibasic acid to the dihydric alcohol is 1 (1.3-10); under a certain vacuum, performing polycondensation reaction on polyester esterification to prepare low-end carboxyl hydrolysis-resistant polyester; alternatively, the first and second electrodes may be,
c) mixing dibasic acid, dihydric alcohol and a titanium polyester catalyst, and carrying out esterification reaction under certain pressure to prepare a polyester esterified substance; wherein the feeding molar ratio of the dibasic acid to the dihydric alcohol is 1 (1.3-10); mixing a titanium polyester catalyst and a polyester ester, and carrying out polycondensation reaction under certain vacuum to prepare the low-end carboxyl hydrolysis-resistant polyester.
The low-end carboxyl hydrolysis-resistant polyester is prepared by the method for preparing the low-end carboxyl hydrolysis-resistant polyester.
The invention also provides application of the low-end carboxyl hydrolysis-resistant polyester, which is applied to the fields of photovoltaic modules and the like.
Preferably, the polyester is applied to the fields of photovoltaic modules and the like in the form of films or other products.
The invention has the beneficial effects that:
the invention provides a low-end carboxyl hydrolysis-resistant polyester, a preparation method and application thereof. The low-end carboxyl hydrolysis-resistant polyester is prepared by controlling the feeding ratio of dibasic acid and dihydric alcohol monomer (the research finds that the feeding ratio can be controlled within the range of 1 (1.3-10)) and adding an environment-friendly and efficient titanium polyester catalyst under the condition of not introducing new reagents and groups. The polyester prepared by the invention is not subjected to end capping and/or chain extension treatment, has good hydrolysis resistance, and is simple in preparation method and easy for industrial production. The polyester has the intrinsic viscosity of 0.5-1.2 dL/g, the terminal carboxyl group content of 2-10 mmol/kg and excellent comprehensive performance, can meet the performance requirements of photovoltaic modules on polyester films, is expected to be applied to photovoltaic power generation modules, and has important effects on prolonging the service life of Chinese photovoltaic products and promoting the healthy and stable development of the Chinese photovoltaic industry.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The terminal carboxyl group content and intrinsic viscosity in the following examples were measured in accordance with GB/T14190-20085.4.2 method B and GB/T14190-20085.1.1 method A (solvent 5.1.1.3.1), respectively.
Example 1
3000g (18.0mol) of terephthalic acid, 1786g (28.8mol) of ethylene glycol and 0.02g of silicon dioxide/titanium dioxide composite are added into a reactor, the temperature is raised to 230 ℃ under a certain stirring rate, the reaction is carried out for 2 hours, and the pressure of the reactor is controlled at 400 KPa. And after the esterification reaction is finished, heating to 275 ℃, controlling the vacuum degree of the system to be 10-200 Pa, and carrying out polycondensation reaction for 3 hours and 6 minutes to obtain the polymer.
The intrinsic viscosity of the polymer was measured to be 0.61dL/g and the carboxyl end group content was 10mmol/kg according to the above-mentioned national standard.
Example 2
3000g (18.0mol) of terephthalic acid, 2009g (32.4mol) of ethylene glycol and 3.0g of tetrabutyl titanate are added into a reactor, the temperature is increased to 230 ℃ under a certain stirring rate, the reaction is carried out for 2 hours, and the pressure of the reactor is controlled at 410 KPa. And after the esterification reaction is finished, heating to 275 ℃, controlling the vacuum degree of the system to be 10-200 Pa, and carrying out polycondensation reaction for 3 hours to obtain the polymer.
The intrinsic viscosity of the polymer was measured to be 0.81dL/g and the carboxyl end group content was 8mmol/kg according to the above-mentioned national standard.
Example 3
2905g (17.5mol) of terephthalic acid, 90g (0.5mol) of isophthalic acid, 2232g (36.0mol) of ethylene glycol and 2.4g of tetraisopropyl titanate were charged into a reactor, and the temperature was raised to 230 ℃ at a constant stirring rate to react for 2 hours, with the reactor pressure being controlled at 410 KPa. And after the esterification reaction is finished, heating to 275 ℃, controlling the vacuum degree of the system to be 10-200 Pa, and carrying out polycondensation reaction for 2 hours and 48 minutes to obtain the polymer.
The intrinsic viscosity of the polymer was 1.1dL/g and the carboxyl end group content was 5.8mmol/kg, as determined according to the above-mentioned national standard.
Example 4
3000g (18.0mol) of terephthalic acid, 1550g (25.0mol) of ethylene glycol, 836g (11.0mol) of 1, 3-propanediol and 3.2g of tetrabutyl titanate are added into a reactor, the temperature is raised to 230 ℃ under a certain stirring rate, the reaction is carried out for 2 hours, and the pressure of the reactor is controlled at 400 KPa. And after the esterification reaction is finished, heating to 275 ℃, controlling the vacuum degree of the system to be 10-200 Pa, and carrying out polycondensation reaction for 3 hours and 6 minutes to obtain the polymer.
The intrinsic viscosity of the polymer was 1.0dL/g and the carboxyl end group content was 7.9mmol/kg, as determined according to the above-mentioned national standard.
Example 5
2905g (17.5mol) of terephthalic acid, 90g (0.5mol) of phthalic acid and 2232g (36.0mol) of ethylene glycol are added into a reactor, the temperature is raised to 230 ℃ at a certain stirring rate, the reaction is carried out for 2 hours, and the pressure of the reactor is controlled at 400 KPa. And (3) adding 0.01g of titanium dioxide after the esterification reaction is finished, heating to 275 ℃, controlling the vacuum degree of the system at 10-200 Pa, and carrying out polycondensation reaction for 3.5 hours to obtain the polymer.
The intrinsic viscosity of the polymer was measured to be 0.85dL/g and the carboxyl end group content was 8.6mmol/kg according to the above-mentioned national standard.
Example 6
3456g (18.0mol) of p-phenylenediacetic acid and 2480g (40.0mol) of ethylene glycol are added into a reaction vessel, the temperature is raised to 230 ℃ under a certain stirring rate, the reaction is carried out for 2 hours, and the pressure of the reactor is controlled at 400 KPa. And (3) adding 0.3g of ethylene glycol titanium after the esterification reaction is finished, heating to 275 ℃, controlling the vacuum degree of the system at 10-200 Pa, and carrying out polycondensation reaction for 3 hours to obtain the polymer.
The intrinsic viscosity of the polymer was measured to be 0.79dL/g and the carboxyl end group content was 9mmol/kg according to the above-mentioned national standard.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of low-end carboxyl hydrolysis-resistant polyester is characterized by comprising the following steps:
1) mixing dibasic acid and dihydric alcohol, and carrying out esterification reaction to prepare a polyester esterified substance; wherein the feeding molar ratio of the dibasic acid to the dihydric alcohol is 1 (1.6-3);
2) performing polycondensation reaction on the polyester esterified substance in the step 1) to prepare low-end carboxyl hydrolysis-resistant polyester;
adding a titanium polyester catalyst into a mixed system of dibasic acid and dihydric alcohol before esterification reaction, and/or adding the titanium polyester catalyst into the mixed system of polyester esterified in the step 1) after esterification reaction; the titanium polyester catalyst is selected from at least one of tetrabutyl titanate, tetraisopropyl titanate, titanium carboxylate and lithium titanium oxide oxalate;
the method does not comprise an end-capping step and/or a chain extension step;
the pressure of the esterification reaction in the step 1) is 400-410 KPa, the temperature of the esterification reaction is 200-250 ℃, and the time of the esterification reaction is 1.5-3.5 hours;
the vacuum degree of the polycondensation reaction in the step 2) is 10-200 Pa, the temperature of the polycondensation reaction is 250-290 ℃, and the time of the polycondensation reaction is 0.5-4 hours;
the content of terminal carboxyl groups in the polyester is 5.8-7.9 mmol/kg;
the dihydric alcohol is at least one of ethylene glycol, 1, 3-propylene glycol, 2-dimethyl-1, 3-propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol and 2, 3-butanediol.
2. The method according to claim 1, wherein the intrinsic viscosity of the polyester is 0.5 to 1.2 dL/g.
3. The method according to claim 1, wherein the titanium-based polyester catalyst is at least one selected from the group consisting of tetrabutyl titanate and tetraisopropyl titanate.
4. The method according to claim 1, wherein the dibasic acid is at least one selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid, 2, 6-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 4 '-biphenyldicarboxylic acid and 2, 2' -biphenyldicarboxylic acid.
5. The process according to claim 4, wherein the dibasic acid is at least one member selected from the group consisting of terephthalic acid, isophthalic acid and phthalic acid.
6. The method according to claim 1, wherein the titanium-based polyester catalyst is addedIn an amount of 10 parts by mass of the polyester-7 wt %～0.1wt%。
7. The method for preparing according to claim 1, characterized in that it comprises the steps of:
a) mixing dibasic acid and dihydric alcohol, and carrying out esterification reaction to prepare a polyester esterified substance; mixing a titanium polyester catalyst with a polyester ester, and carrying out polycondensation reaction to prepare low-end carboxyl hydrolysis-resistant polyester; alternatively, the first and second electrodes may be,
b) mixing dibasic acid, dihydric alcohol and a titanium polyester catalyst, and performing esterification reaction to prepare a polyester esterified substance; performing polycondensation reaction on the polyester ester to prepare low-end carboxyl hydrolysis-resistant polyester; alternatively, the first and second electrodes may be,
c) mixing dibasic acid, dihydric alcohol and a titanium polyester catalyst, and performing esterification reaction to prepare a polyester esterified substance; mixing a titanium polyester catalyst and a polyester ester, and carrying out polycondensation reaction to prepare the low-end carboxyl hydrolysis-resistant polyester.
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| CN111154127A (en) * | 2020-01-16 | 2020-05-15 | 陈志威 | Method for preparing hydrolysis-resistant polyester film |
| CN113461925B (en) * | 2021-07-01 | 2022-12-13 | 杭州鑫富科技有限公司 | Flame-retardant biodegradable polyester and preparation method thereof |
| CN113930178A (en) * | 2021-12-08 | 2022-01-14 | 太仓金煜电子材料有限公司 | High-temperature-resistant silicon-free transfer process protective adhesive tape and preparation method and application thereof |
| CN115386074B (en) * | 2022-08-18 | 2024-04-12 | 中国科学院大连化学物理研究所 | Functional nano composite polyester, preparation method and application |
| CN115286777B (en) * | 2022-09-30 | 2023-03-07 | 北京致聆科技有限公司 | Low-end carboxyl biodegradable polyester and preparation method of special material thereof |
| CN115625870A (en) * | 2022-11-30 | 2023-01-20 | 江苏康辉新材料科技有限公司 | Super-weather-resistant white polyester film and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1753930A (en) * | 2002-12-27 | 2006-03-29 | 三菱化学株式会社 | Polybutylene terephthalate and method for production thereof, and composition comprising the same and film |
| WO2007140925A1 (en) * | 2006-06-02 | 2007-12-13 | Uhde Inventa-Fischer Gmbh | Process for continuous preparation of high molecular weight polyesters by esterification of dicarboxylic acids and/or transesterification of dicarboxylic acids with diols and/or mixtures thereof and an apparatus therefor |
| CN101314637A (en) * | 2007-05-31 | 2008-12-03 | 中国科学院化学研究所 | Poly-p-benzene dicarboxylic acid 1,2-propylene glycol ester and copolyester, and preparation thereof |
| CN101891884A (en) * | 2009-05-22 | 2010-11-24 | 中国科学院化学研究所 | Polyester polycondensation catalyst and preparation method and application thereof |
| CN102286192A (en) * | 2010-06-11 | 2011-12-21 | 富士胶片株式会社 | Polyester film and method for producing same, backsheet for solar cell, and solar cell module |
| CN102850534A (en) * | 2012-08-20 | 2013-01-02 | 江苏和时利新材料股份有限公司 | Method for preparing high-quality polybutylene terephthalate (PBT) by TiO2/SiO2 composite nano-catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2394312A1 (en) * | 2000-01-19 | 2001-07-26 | Shunichi Matsumura | Wholly aromatic polyester and process for producing the same |
-
2018
- 2018-05-29 CN CN201810531122.1A patent/CN110606941B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1753930A (en) * | 2002-12-27 | 2006-03-29 | 三菱化学株式会社 | Polybutylene terephthalate and method for production thereof, and composition comprising the same and film |
| WO2007140925A1 (en) * | 2006-06-02 | 2007-12-13 | Uhde Inventa-Fischer Gmbh | Process for continuous preparation of high molecular weight polyesters by esterification of dicarboxylic acids and/or transesterification of dicarboxylic acids with diols and/or mixtures thereof and an apparatus therefor |
| CN101314637A (en) * | 2007-05-31 | 2008-12-03 | 中国科学院化学研究所 | Poly-p-benzene dicarboxylic acid 1,2-propylene glycol ester and copolyester, and preparation thereof |
| CN101891884A (en) * | 2009-05-22 | 2010-11-24 | 中国科学院化学研究所 | Polyester polycondensation catalyst and preparation method and application thereof |
| CN102286192A (en) * | 2010-06-11 | 2011-12-21 | 富士胶片株式会社 | Polyester film and method for producing same, backsheet for solar cell, and solar cell module |
| CN102850534A (en) * | 2012-08-20 | 2013-01-02 | 江苏和时利新材料股份有限公司 | Method for preparing high-quality polybutylene terephthalate (PBT) by TiO2/SiO2 composite nano-catalyst |
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