CN110563937A - High-barrier thiophene polyester and preparation method and application thereof - Google Patents
High-barrier thiophene polyester and preparation method and application thereof Download PDFInfo
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- CN110563937A CN110563937A CN201911018618.XA CN201911018618A CN110563937A CN 110563937 A CN110563937 A CN 110563937A CN 201911018618 A CN201911018618 A CN 201911018618A CN 110563937 A CN110563937 A CN 110563937A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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Abstract
The invention discloses high-barrier thiophene polyester and a preparation method and application thereof. The preparation method comprises the following steps: in a protective atmosphere, reacting thiophenedicarboxylic acid and/or thiophenedicarboxylic acid ester, dihydric alcohol, an esterification catalyst, a compound catalyst, a phosphorus stabilizer, an oxygen stabilizer, an ultraviolet-resistant auxiliary agent and a crystallization nucleating agent to obtain the thiophenic polyester. The high-barrier thiophene polyester prepared by the invention has excellent light transmittance, heat resistance, mechanical property and gas barrier property, and can be widely applied to the fields of packaging materials, barrier films, barrier bottles, fibers or engineering plastics.
Description
Technical Field
the invention belongs to the technical field of macromolecules, and particularly relates to high-barrier thiophene polyester and a preparation method and application thereof.
background
At present, the bio-based polymer materials widely used mainly include polylactic acid (PLA), Polyhydroxyalkanoate (PHA), polyglycolic acid (PGA), polybutylene succinate (PBS), and the like. They all belong to aliphatic polymers, and because of lack of rigid aromatic ring structure in the molecular structure, the mechanical properties (such as strength, modulus, creep resistance and the like) and heat resistance (such as thermal mechanical properties, thermal deformation temperature and the like) of the aliphatic polymers are obviously lower than petroleum-based high polymer materials such as polyethylene terephthalate (PET), Polycarbonate (PC), aromatic nylon (PA), bisphenol A type Epoxy resin (Epoxy) and the like, and the application range of the aliphatic polymers is severely limited. Poly-ethylene-2, 5-furandicarboxylate (PEF) prepared from bio-based 2, 5-furandicarboxylic acid and ethylene glycol has excellent mechanical properties, heat resistance and gas barrier properties, but the problem of yellowing of the polyester has been difficult to solve.
Disclosure of Invention
the invention mainly aims to provide a colorless high-molecular-weight high-barrier thiophene polyester and a preparation method and application thereof, so as to overcome the defects of the prior art.
in order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of colorless high-molecular-weight high-barrier thiophene polyester, which comprises the following steps: in a protective atmosphere, reacting thiophenedicarboxylic acid and/or thiophenedicarboxylic acid ester, dihydric alcohol, an esterification catalyst, a compound catalyst, a phosphorus stabilizer, an oxygen stabilizer, an ultraviolet-resistant auxiliary agent and a crystallization nucleating agent to obtain the thiophenic polyester.
The embodiment of the invention provides high-barrier thiophene polyester prepared by the method, the visible light transmittance of the thiophene polyester is more than 86%, and the initial thermal decomposition temperature T is5％380-410 deg.c, tensile strength of 50-80MPa and tensile modulus of 1.4-2.0 GPa.
Further, the L value of the thiophene polyester is more than 85, and the b value is less than 10.
Further, the relative number average molecular mass of the thiophene polyester is 30000-60000 g/mol.
Further, the thiophene polyester has oxygen barrier properties of 0.6 x 10-12cm3·cm/cm2·s·cmHg～2.1×10-12cm3·cm/cm2s.cmHg, carbon dioxide barrier properties of 0.5X 10-12cm3·cm/cm2·s·cmHg～2.0×10-12cm3·cm/cm2·s·cmHg。
The embodiment of the invention provides application of the high-barrier thiophene polyester in the field of preparation of packaging materials, barrier films, barrier bottles, fibers or engineering plastics.
compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, thiophene dicarboxylic acid or an esterified product thereof is copolymerized with dihydric alcohol, a high-efficiency antimony-system and tin-system compound catalyst is adopted to catalyze the polycondensation reaction, meanwhile, a phosphorus-system stabilizer and an oxygen stabilizer are added to prevent the oxidation and decomposition reaction in the polymerization process, and a crystallization nucleating agent is added to improve the crystallization capacity of polyester, so that thiophene polyester with high molecular weight, high visible light transmittance and high gas barrier property is prepared;
(2) The thiophene polyester prepared by the invention has the advantages of high molecular weight, high crystallization speed, high modulus and strength, good oxygen and carbon dioxide barrier property and light color, and can meet the application requirements in the fields of packaging materials, films, fibers, engineering plastics and the like;
(3) The preparation method provided by the invention can promote the bio-based high polymer material industry to get rid of high dependence on petroleum resources.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a drawing of poly (ethylene 2, 5-thiophenedicarboxylate) prepared in example 11An H-NMR spectrum;
FIG. 2 is a DSC spectrum of poly (ethylene 2, 5-thiophenedicarboxylate) prepared in example 1;
FIG. 3 is a TGA spectrum of poly (ethylene 2, 5-thiophenecarboxylate) prepared in example 1;
FIG. 4 is a photograph of a sample of the polyethylene 2, 5-thiophenedicarboxylate film prepared in example 1;
FIG. 5 is a drawing of poly (trimethylene 2, 5-thiophenedicarboxylate) prepared in example 21an H-NMR spectrum;
FIG. 6 is a drawing of poly (butylene 2, 5-thiophenedicarboxylate) prepared in example 31an H-NMR spectrum;
FIG. 7 is a photograph of a sample of the polyethylene 2, 5-thiophenedicarboxylate film prepared in comparative example 1.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
one aspect of the embodiment of the present invention provides a preparation method of a colorless high molecular weight high-barrier thiophene polyester, which includes:
In a protective atmosphere, reacting thiophenedicarboxylic acid and/or thiophenedicarboxylic acid ester, dihydric alcohol, an esterification catalyst, a compound catalyst, a phosphorus stabilizer, an oxygen stabilizer, an ultraviolet-resistant auxiliary agent and a crystallization nucleating agent to obtain the thiophenic polyester.
in some more specific embodiments, the preparation method of the thiophene polyester specifically includes: reacting a mixed reaction system containing thiophenedicarboxylic acid and/or thiophenedicarboxylic acid ester, dihydric alcohol, an esterification catalyst, a compound catalyst, a phosphorus stabilizer, an oxygen stabilizer, an ultraviolet-resistant auxiliary agent and a crystallization nucleating agent at 160-190 ℃ for 2-6h in a protective atmosphere, then heating to 190-240 ℃, pre-polycondensing for 0.5-2h under the condition of vacuum degree of 1000-2000Pa, and finally reacting for 2-6h under the vacuum degree of 45Pa to obtain the thiophenic polyester.
In some embodiments, the molar ratio of the diol to the thiophenedicarboxylic acid and/or thiophenedicarboxylic acid ester is 160-220: 100.
Furthermore, the molar ratio of the esterification catalyst to the thiophene dicarboxylic acid and/or thiophene dicarboxylic acid ester is 0.05-0.3: 100.
Furthermore, the molar ratio of the compound catalyst to the thiophene dicarboxylic acid and/or thiophene dicarboxylic acid ester is 0.05-0.3: 100.
furthermore, the molar ratio of the phosphorus stabilizer to the thiophenedicarboxylic acid and/or the thiophenedicarboxylic acid ester is 0.1-0.4: 100.
furthermore, the molar ratio of the oxygen stabilizer to the thiophenedicarboxylic acid and/or the thiophenedicarboxylic acid ester is 0.03-0.3: 100.
furthermore, the molar ratio of the ultraviolet-resistant auxiliary agent to the thiophenedicarboxylic acid and/or the thiophenedicarboxylic acid ester is 0.1-1.0: 100.
furthermore, the molar ratio of the crystallization nucleating agent to the thiophenedicarboxylic acid and/or the thiophenedicarboxylic acid ester is 0.1-1.0: 100.
In some embodiments, the thiophenedicarboxylic acid includes 2, 5-thiophenedicarboxylic acid, 2, 4-thiophenedicarboxylic acid, and is not limited thereto.
Further, the thiophene dicarboxylate includes any one or a combination of two or more of dimethyl 2, 5-thiophene dicarboxylate, diethyl 2, 5-thiophene dicarboxylate, dipropyl 2, 5-thiophene dicarboxylate, and dibutyl 2, 5-thiophene dicarboxylate, and is not limited thereto.
Further, the diol includes any one or a combination of two or more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 2, 3-butanediol, and 2-methyl-1, 3-propanediol, without being limited thereto.
Further, the esterification catalyst includes anhydrous zinc acetate, and is not limited thereto.
In some embodiments, the compound catalyst comprises a tin-based catalyst and an antimony-based catalyst, wherein the compound catalyst comprises 10-90 mol% of the tin-based catalyst and 10-90 mol% of the antimony-based catalyst.
Further, the compound catalyst is prepared by directly mixing and loading the mixture on an organic matter.
Further, the tin-based catalyst includes any one or a combination of two or more of dibutyltin oxide, stannous isooctanoate, monobutyl triisooctanoate, and dioctyltin oxide, but is not limited thereto.
Further, the antimony-based catalyst includes any one or a combination of two or more of antimony trioxide, ethylene glycol antimony, antimony acetate, and polyethylene glycol antimony, but is not limited thereto.
In some embodiments, the phosphorus-based stabilizer and the oxygen stabilizer may inhibit oxidation and crosslinking reactions that occur during polymerization.
Further, the phosphorus-based stabilizer includes any one or a combination of two or more of phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite, and ammonium dihydrogen phosphate, but is not limited thereto.
Further, the oxygen stabilizer includes any one or a combination of two or more of pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], n-octadecyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, phenyl tris (2, 4-di-t-butyl) phosphite, 2, 6-di-t-butyl-p-cresol, 3, 5-di-t-butyl-4-hydroxybenzyldiethylphosphonate, and 2,2' -methylenebis- (4-methyl-6-t-butylphenol), and is not limited thereto.
Further, the anti-ultraviolet auxiliary agent includes any one or a combination of two or more of 2-hydroxybenzophenone, hydroxyphenyl benzotriazole, cinnamate, oxanilide, and is not limited thereto.
Further, the crystallization nucleating agent includes any one or a combination of two or more of sodium 2-thiophenecarboxylate, benzoic acid, sodium benzoate, talc, and dimethyl- (4, 4-terephthaloyl dioxy) dibenzoate, and is not limited thereto.
Further, the protective atmosphere includes a nitrogen atmosphere, an inert gas atmosphere, and is not limited thereto.
One aspect of an embodiment of the present invention provides a colorless, high molecular weight, high barrier thiophene polyester prepared by the foregoing method.
In some embodiments, the thiophene polyesters have an L value above 85 and a b value below 10.
Further, the relative number average molecular mass of the thiophene polyester is 30000-60000 g/mol.
Further, the thiophene polyester has oxygen barrier properties of 0.6 x 10-12cm3·cm/cm2·s·cmHg～2.1×10-12cm3·cm/cm2s.cmHg, carbon dioxide barrier properties of 0.5X 10-12cm3·cm/cm2·s·cmHg～2.0×10-12cm3·cm/cm2·s·cmHg。
One aspect of the embodiments of the present invention provides an application of the colorless high molecular weight high-barrier thiophene polyester in the field of preparing packaging materials, barrier films, barrier bottles, fibers or engineering plastics.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
in the examples, NMR spectra1H-NMR was measured on a Bruker 400AVANCE III Spectrometer type instrument at 400MHz, CF3COOD。
In the examples, GPC, model Agilent PL-GPC220, column PLgel 5. mu. m Mixed-D (300X 7.5mm), test temperature 40 ℃, mobile phase of chloroform, flow rate of 1ml/min, dissolved polymer solvent of o-chlorophenol and chloroform in a volume ratio of 1:9, and standard polystyrene 3070-258000g/mol were used for the relative molecular mass test.
In the examples, thermal analysis was carried out using differential scanning calorimetry (Mettler Toledo DSC) at a temperature rise rate of 10 ℃/minIn N at2The atmosphere is carried out, and the temperature range is-50-300 ℃. Thermogravimetric analysis (TGA) was performed on a Perkin-Elmer Diamond TG/DTA with a heating rate of 20 ℃/min and a temperature range of 50-800 ℃.
In the examples, the barrier properties against oxygen and carbon dioxide were measured by permeability testing using Labthink VAC-V2, each in CO2and O2As an air source, under the conditions of temperature and humidity of 30 ℃ and 50% RH respectively, the sample size phi of 97mm and the transmission area of 38.5cm are selected2。
Example 1
0.25mol of dimethyl 2, 5-thiophenedicarboxylate, 0.40mol of ethylene glycol, 0.00025mol of anhydrous zinc acetate, 0.00025mol of antimony trioxide, 0.000125mol of dibutyltin oxide, 0.0004mol of triphenyl phosphate and 0.00025mol of tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid]Pentaerythritol ester, 0.0001mol of 2-hydroxybenzophenone and 0.0002mol of 2-thiophenecarboxylic acid sodium are added into a 1000mL reactor, vacuum-pumping and nitrogen-filled for replacement are carried out for three times, stirring is started, the temperature is gradually increased to 180 ℃, reaction is carried out for 3h, then vacuum-pumping is slowly carried out to 1000-2000Pa, the temperature is gradually increased to 230 ℃, pre-polycondensation is carried out for 0.5h, then reaction is carried out for 3h under the condition that the vacuum degree is controlled to be below 45Pa, and poly-2, 5-thiophenedicarboxylic acid ethylene glycol ester is obtained,1H-NMR is shown in FIG. 1; the relative number average molecular mass is 39000 g/mol; glass transition temperature 64.0 ℃, melting point 192 ℃, and crystallization melting enthalpy DeltaHmIs 1.4J/g, and the DSC spectrum is shown in figure 2; t in nitrogen5％The thermal weight loss temperature is 409 ℃, and a TGA spectrum is shown in figure 3; the film L value is 88, the b value is 8, and the sample photograph is shown in FIG. 4. The tensile strength of the sample strip is 72MPa, the tensile modulus is 2.0GPa, and the breaking elongation is 300%. The gas permeability coefficient of carbon dioxide is 0.75X 10-12cm3·cm/cm2s.cmHg, gas permeability coefficient of oxygen 0.9X 10-12cm3·cm/cm2·s·cmHg。
Example 2
0.25mol of 2, 5-thiophenedicarboxylic acid dimethyl ester, 0.40mol of 1, 3-propanediol, 0.0004mol of anhydrous zinc acetate, 0.0003mol of antimony acetate, 0.00015mol of stannous isooctanoate, 0.0006mol of trimethyl phosphate and 0.00020mol of beta- (3, 5-di-tert-butyl) phthalateAdding n-octadecyl butyl-4-hydroxyphenyl) propionate, 0.0001mol of hydroxyphenyl benzotriazole and 0.0001mol of sodium benzoate into a 1000mL reactor, vacuumizing, charging nitrogen for three times, starting stirring, gradually heating to 170 ℃, reacting for 4h, slowly vacuumizing to 1000-2000Pa, gradually heating to 220 ℃, pre-condensing for 1.0h, controlling the vacuum degree to 40Pa, reacting for 3.5h to obtain poly (2, 5-thiofuran dicarboxylic acid trimethylene glycol ester),1H-NMR is shown in FIG. 5; the relative number average molecular mass is 33000 g/mol; glass transition temperature 35.0 ℃, melting point 187 ℃, and crystallization melting enthalpy Δ HmIs 48J/g; t in nitrogen5％the thermal weight loss temperature is 383 ℃; film L value 89, b value 7. The tensile strength of a sample strip is 53MPa, the tensile modulus is 1.5GPa, and the breaking elongation is 390 percent. The gas permeability coefficient of carbon dioxide is 1.2X 10-12cm3·cm/cm2s.cmHg, gas permeability coefficient of oxygen 1.1X 10-12cm3·cm/cm2·s·cmHg。
Example 3
adding 0.25mol of dimethyl 2, 5-thiophenedicarboxylate, 0.40mol of 1, 4-butanediol, 0.00045mol of anhydrous zinc acetate, 0.00035mol of antimony acetate, 0.00012mol of monobutyl triisooctanoic acid tin, 0.0005mol of diphenyl phosphite, 0.00010mol of tris (2, 4-di-tert-butyl) phenyl phosphite, 0.0001mol of cinnamate and 0.0001mol of dimethyl- (4, 4-terephthaloyl dioxy) dibenzoate into a 1000mL reactor, vacuumizing, filling nitrogen for replacement for three times, starting stirring, gradually heating to 160 ℃, reacting for 4.5h, slowly vacuumizing to between 1000 and 2000Pa, gradually heating to 220 ℃, pre-condensing for 1.0h, controlling the vacuum degree to 30Pa, reacting for 4.5h to obtain poly (butylene 2, 5-thiophenedicarboxylate),1H-NMR is shown in FIG. 6; the relative number average molecular mass is 53500 g/mol; glass transition temperature 22.0 ℃, melting point 154 ℃, and crystallization melting enthalpy Δ HmIs 37J/g; t in nitrogen5％The thermal weight loss temperature is 381 ℃; film L value 86, b value 9. The tensile strength of the sample strip is 50MPa, the tensile modulus is 1.4GPa, and the breaking elongation is 590 percent. The gas permeability coefficient of carbon dioxide is 1.6X 10-12cm3·cm/cm2s.cmHg, gas permeability coefficient of oxygen 1.6X 10-12cm3·cm/cm2·s·cmHg。
Example 4
Adding 0.25mol of 2, 5-thiophenedicarboxylic acid dimethyl ester, 0.40mol of 2, 3-butanediol, 0.0005mol of anhydrous zinc acetate, 0.0006mol of antimony trioxide, 0.00015mol of monobutyl triisooctanoic acid tin, 0.0008mol of diphenyl phosphite, 0.00015mol of tris (2, 4-di-tert-butyl) phenyl phosphite, 0.0001mol of oxanilide and 0.0001mol of 2-thiophenecarboxylic acid sodium into a 1000mL reactor, vacuumizing, filling nitrogen for replacement three times, starting stirring, gradually heating to 180 ℃, reacting for 4.0h, slowly vacuumizing to 1000-2000Pa, gradually heating to 220 ℃, pre-condensing for 1.0h, controlling the vacuum degree to 30Pa, reacting for 6.0h, and obtaining 2, 5-thiophenedicarboxylic acid 2, 3-butanediol ester, wherein the relative number average molecular mass is 43000 g/mol; glass transition temperature 26.0 ℃, melting point 164 ℃, and crystallization melting enthalpy Δ HmIs 17J/g; t in nitrogen5％The thermal weight loss temperature is 383 ℃; film L value 87, b value 9. The tensile strength of a sample strip is 53MPa, the tensile modulus is 1.4GPa, and the breaking elongation is 290%. The gas permeability coefficient of carbon dioxide is 1.5X 10-12cm3·cm/cm2s.cmHg, gas permeability coefficient of oxygen 1.4X 10-12cm3·cm/cm2·s·cmHg。
Example 5
Adding 0.25mol of dimethyl 2, 5-thiophenedicarboxylate, 0.40mol of 2-methyl-1, 3-propanediol, 0.00045mol of anhydrous zinc acetate, 0.0003mol of antimony polyethylene glycol, 0.00015mol of stannous isooctanoate, 0.0006mol of trimethyl phosphate, 0.00020mol of 2, 6-di-tert-butyl-p-cresol, 0.0001mol of 5mol of 2-hydroxybenzophenone and 0.0001mol of sodium benzoate into a 1000mL reactor, vacuumizing, filling nitrogen for replacement for three times, starting stirring, gradually heating to 180 ℃, reacting for 3.0h, slowly vacuumizing to 1000-2000Pa, gradually heating to 210 ℃, pre-shrinking for 1.0h, then controlling the vacuum degree to 20Pa, and reacting for 3.0h to obtain 2, 5-thiophenedicarboxylate-2-methyl-1, 3-propanediol ester, wherein the relative number average molecular mass is 00 g/mol; glass transition temperature 36.0 ℃, melting point 181 ℃, and crystallization melting enthalpy DeltaHm1.4J/g; t in nitrogen5％The thermal weight loss temperature is387 ℃; film L value 87, b value 7. The tensile strength of the sample strip is 51MPa, the tensile modulus is 1.3GPa, and the breaking elongation is 450%. The gas permeability coefficient of carbon dioxide is 1.3X 10-12cm3·cm/cm2s.cmHg, gas permeability coefficient of oxygen 1.3X 10-12cm3·cm/cm2·s·cmHg。
Comparative example 1
0.25mol of dimethyl 2, 5-thiophenedicarboxylate, 0.40mol of ethylene glycol, 0.00025mol of anhydrous zinc acetate, 0.00025mol of antimony trioxide, 0.000125mol of dibutyltin oxide and 0.00025mol of tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate]Adding pentaerythritol ester, 0.0001mol of 2-hydroxybenzophenone and 0.0002mol of 2-thiophenecarboxylic acid sodium into a 1000mL reactor, vacuumizing, filling nitrogen for three times, starting stirring, gradually heating to 180 ℃, reacting for 3 hours, slowly vacuumizing to 1000-2000Pa, gradually heating to 230 ℃, pre-condensing for 0.5 hour, controlling the vacuum degree to be below 45Pa, reacting for 3 hours, and obtaining poly-2, 5-thiophenedicarboxylic acid ethylene glycol ester, wherein the relative number average molecular weight is 31000 g/mol; glass transition temperature of 62.0 ℃, melting point of 190 ℃, and crystallization melting enthalpy Δ Hm1.4J/g, T in nitrogen5％The temperature of the thermal weight loss is 406 ℃, the color of the film is yellow, the L value is 78, the b value is 15, and the color of the film is light yellow as shown in a sample photo in figure 7. The tensile strength of the sample strip is 61MPa, the tensile modulus is 1.5GPa, and the breaking elongation is 180 percent. The gas permeability coefficient of carbon dioxide is 0.93X 10-12cm3·cm/cm2s.cmHg, gas permeability coefficient of oxygen 1.2X 10-12cm3·cm/cm2·s·cmHg。
Comparative example 2
adding 0.25mol of 2, 5-thiophenedicarboxylic acid dimethyl ester, 0.40mol of ethylene glycol, 0.00025mol of anhydrous zinc acetate, 0.00025mol of antimony trioxide, 0.000125mol of dibutyltin oxide, 0.0004mol of triphenyl phosphate, 0.0001mol of 2-hydroxybenzophenone and 0.0002mol of 2-thiophenecarboxylic acid sodium into a 1000mL reactor, vacuumizing, filling nitrogen for replacing three times, starting stirring, gradually heating to 180 ℃, reacting for 3 hours, slowly vacuumizing to 1000-2000Pa, gradually heating to 230 ℃, and pre-condensing and polymerizingControlling the vacuum degree to be below 45Pa for reaction for 3h after 0.5h to obtain poly (ethylene 2, 5-thiophene dicarboxylate), wherein the relative number average molecular mass is 35000 g/mol; glass transition temperature 65.0 ℃, melting point 192 ℃, and crystallization melting enthalpy DeltaHm1.3J/g, T in nitrogen5％The temperature of thermal weight loss is 400 ℃, the color of the film is light yellow, the L value is 85, and the b value is 10. The tensile strength of the sample strip is 63MPa, the tensile modulus is 1.7GPa, and the elongation at break is 270%. The gas permeability coefficient of carbon dioxide is 0.90X 10-12cm3·cm/cm2s.cmHg, gas permeability coefficient of oxygen 1.1X 10-12cm3·cm/cm2·s·cmHg。
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A preparation method of high-barrier thiophene polyester is characterized by comprising the following steps:
under the protective atmosphere, the thiophene dicarboxylic acid and/or thiophene dicarboxylic acid ester, dihydric alcohol, an esterification catalyst, a compound catalyst, a phosphorus stabilizer, an oxygen stabilizer, an ultraviolet-resistant auxiliary agent and a crystallization nucleating agent are uniformly mixed and react to generate the thiophene polyester.
2. The method according to claim 1, characterized in that the method comprises in particular:
Reacting a mixed reaction system containing thiophenedicarboxylic acid and/or thiophenedicarboxylic acid ester, dihydric alcohol, an esterification catalyst, a compound catalyst, a phosphorus stabilizer, an oxygen stabilizer, an ultraviolet-resistant auxiliary agent and a crystallization nucleating agent at 160-190 ℃ for 2-6h in a protective atmosphere, heating to 190-240 ℃, pre-polycondensing for 0.5-2h under the condition of vacuum degree of 1000-2000Pa, and then reducing the vacuum degree to below 45Pa for polycondensing for 2-6h to obtain the thiophenic polyester.
3. The preparation method according to claim 1, wherein the molar ratio of the diol to the thiophenedicarboxylic acid and/or thiophenedicarboxylic acid ester is 160-220: 100;
And/or the molar ratio of the esterification catalyst to the thiophene dicarboxylic acid and/or thiophene dicarboxylic acid esterified substance is 0.05-0.3: 100;
And/or the molar ratio of the compound catalyst to the thiophene dicarboxylic acid and/or the thiophene dicarboxylic acid ester is 0.05-0.3: 100;
and/or the molar ratio of the phosphorus stabilizer to the thiophenedicarboxylic acid and/or the thiophenedicarboxylic acid ester is 0.1-0.4: 100;
And/or the molar ratio of the oxygen stabilizer to the thiophenedicarboxylic acid and/or the thiophenedicarboxylic acid ester is 0.03-0.3: 100;
and/or the molar ratio of the ultraviolet-resistant auxiliary agent to the thiophenedicarboxylic acid and/or the thiophenedicarboxylic acid ester is 0.1-1.0: 100;
And/or the molar ratio of the crystallization nucleating agent to the thiophenedicarboxylic acid and/or the thiophenedicarboxylic acid ester is 0.1-1.0: 100.
4. The production method according to claim 1, wherein the thiophenedicarboxylic acid comprises 2, 5-thiophenedicarboxylic acid;
and/or the thiophene dicarboxylate comprises any one or the combination of more than two of 2, 5-thiophene dicarboxylic acid dimethyl ester, 2, 5-thiophene dicarboxylic acid diethyl ester, 2, 5-thiophene dicarboxylic acid dipropyl ester and 2, 5-thiophene dicarboxylic acid dibutyl ester;
And/or the dihydric alcohol comprises any one or the combination of more than two of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 2, 3-butanediol and 2-methyl-1, 3-propylene glycol;
And/or, the esterification catalyst comprises anhydrous zinc acetate.
5. The preparation method according to claim 1, wherein the compound catalyst comprises a tin catalyst and an antimony catalyst, wherein the mole percentage of the tin catalyst in the compound catalyst is 10-90%, and the mole percentage of the antimony catalyst is 10-90%;
Preferably, the tin catalyst comprises any one or a combination of more than two of dibutyltin oxide, stannous isooctanoate, monobutyl triisooctanoate tin and dioctyltin oxide;
Preferably, the antimony-based catalyst comprises any one or a combination of two or more of antimony trioxide, ethylene glycol antimony, antimony acetate and polyethylene glycol antimony.
6. The method according to claim 1, wherein the phosphorus-based stabilizer and the oxygen stabilizer are capable of preventing oxidation and crosslinking reactions occurring during polymerization;
and/or the phosphorus stabilizer comprises any one or the combination of more than two of phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite and ammonium dihydrogen phosphate;
And/or the oxygen stabilizer comprises one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, phenyl tris (2, 4-di-tert-butyl) phosphite, 2, 6-di-tert-butyl-p-cresol, 3, 5-di-tert-butyl-4-hydroxybenzyl diethylphosphonate and 2,2' -methylenebis- (4-methyl-6-tert-butylphenol).
7. The preparation method according to claim 1, wherein the anti-ultraviolet auxiliary agent comprises any one or a combination of two or more of 2-hydroxybenzophenone, hydroxyphenyl benzotriazole, cinnamate, oxanilide;
And/or the crystallization nucleating agent comprises any one or the combination of more than two of 2-thiophenecarboxylic acid sodium salt, benzoic acid, sodium benzoate, talcum powder and dimethyl- (4, 4-terephthaloyl dioxy) dibenzoate;
and/or the protective atmosphere comprises a nitrogen atmosphere and/or an inert gas atmosphere.
8. The high-barrier thiophene polyester prepared according to any one of claims 1-7, wherein the thiophene polyester has a high visible light transmittanceAt 86%, the initial thermal decomposition temperature T5％380-410 deg.c, tensile strength of 50-80MPa and tensile modulus of 1.4-2.0 GPa.
9. The high barrier thiophene polyester of claim 8, wherein said thiophene polyester has an L value of 85 or more and a b value of 10 or less;
And/or the relative number average molecular mass of the thiophene polyester is 30000-60000 g/mol;
And/or the oxygen barrier property of the thiophene polyester is 0.6 multiplied by 10-12cm3·cm/cm2·s·cmHg～2.1×10- 12cm3·cm/cm2s.cmHg, carbon dioxide barrier properties of 0.5X 10-12cm3·cm/cm2·s·cmHg～2.0×10-12cm3·cm/cm2·s·cmHg。
10. Use of the high-barrier thiophene polyester of any one of claims 8-9 in the preparation of packaging materials, barrier films, barrier bottles, fibers, or engineering plastics.
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Application publication date: 20191213 |