CN116675842A - Bio-based thermoplastic polyether ester elastomer and preparation method and application thereof - Google Patents
Bio-based thermoplastic polyether ester elastomer and preparation method and application thereof Download PDFInfo
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- CN116675842A CN116675842A CN202310609779.6A CN202310609779A CN116675842A CN 116675842 A CN116675842 A CN 116675842A CN 202310609779 A CN202310609779 A CN 202310609779A CN 116675842 A CN116675842 A CN 116675842A
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 87
- 229920000570 polyether Polymers 0.000 title claims abstract description 87
- 229920001971 elastomer Polymers 0.000 title claims abstract description 84
- 239000000806 elastomer Substances 0.000 title claims abstract description 84
- 229920006392 biobased thermoplastic Polymers 0.000 title claims abstract description 83
- 150000002148 esters Chemical class 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000005809 transesterification reaction Methods 0.000 claims description 19
- 238000006068 polycondensation reaction Methods 0.000 claims description 17
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 claims description 17
- 230000032050 esterification Effects 0.000 claims description 15
- 238000005886 esterification reaction Methods 0.000 claims description 15
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 15
- 150000005690 diesters Chemical class 0.000 claims description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- -1 alicyclic diol Chemical class 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 150000002009 diols Chemical class 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 7
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 7
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 claims description 7
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 7
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 7
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- XZPSVGIICNVIID-UHFFFAOYSA-N 3,4-diethylthiophene-2,5-dicarboxylic acid Chemical compound CCc1c(sc(C(O)=O)c1CC)C(O)=O XZPSVGIICNVIID-UHFFFAOYSA-N 0.000 claims 1
- OOXLBCRRSIYSPI-UHFFFAOYSA-N 3,4-dimethylthiophene-2,5-dicarboxylic acid Chemical compound CC=1C(C)=C(C(O)=O)SC=1C(O)=O OOXLBCRRSIYSPI-UHFFFAOYSA-N 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 8
- 238000002834 transmittance Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 238000011084 recovery Methods 0.000 description 13
- 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 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- CYUGNCLRGFKPAE-UHFFFAOYSA-N dimethyl thiophene-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)S1 CYUGNCLRGFKPAE-UHFFFAOYSA-N 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- KWZUUCHRIBVBJW-UHFFFAOYSA-N dibutyl thiophene-2,5-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=C(C(=O)OCCCC)S1 KWZUUCHRIBVBJW-UHFFFAOYSA-N 0.000 description 2
- FOLYMTHZDUYMGS-UHFFFAOYSA-N diethyl thiophene-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)S1 FOLYMTHZDUYMGS-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- TZTOBOROVOKWCM-UHFFFAOYSA-N dipropyl thiophene-2,5-dicarboxylate Chemical compound CCCOC(=O)C1=CC=C(C(=O)OCCC)S1 TZTOBOROVOKWCM-UHFFFAOYSA-N 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- DSLZVSRJTYRBFB-LLEIAEIESA-N D-glucaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O DSLZVSRJTYRBFB-LLEIAEIESA-N 0.000 description 1
- TXXHDPDFNKHHGW-CCAGOZQPSA-N Muconic acid Natural products OC(=O)\C=C/C=C\C(O)=O TXXHDPDFNKHHGW-CCAGOZQPSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-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
- C08G63/68—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a bio-based thermoplastic polyether ester elastomer, a preparation method and application thereof. The bio-based thermoplastic polyether ester elastomer has a structure shown in a formula (1), wherein X, y and m are integers, X is more than or equal to 1 and less than or equal to 10, y is more than or equal to 1 and less than or equal to 10, m is more than or equal to 2 and less than or equal to 60, R is selected from structural units of aliphatic or alicyclic dihydric alcohol with carbon atoms of 4-10, and X is selected from structural units of polyether dihydric alcohol with the number average molecular weight of 250-5000 g/mol. The bio-based thermoplastic polyether ester elastomer has high rebound, high toughness and excellent optical performance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a bio-based thermoplastic polyether ester elastomer and a preparation method and application thereof.
Background
The application of the bio-based thermoplastic polyether ester elastomer gradually expands along with the enrichment of the variety of the bio-based monomer, and the bio-based thermoplastic polyether ester elastomer can be applied to oil-resistant materials and degradable materials at the present stage, but the bio-based thermoplastic polyether ester elastomer has the defects, and the mechanical property and the optical property of the bio-based thermoplastic polyether ester elastomer are still to be improved.
In the prior art, the 2, 5-thiophene dicarboxylic acid based bio-ester has high rigidity and high modulus, so the bio-based thermoplastic polyether ester has potential as a hard segment of a bio-based thermoplastic polyether ester elastomer, but has poor toughness, and the maximum elongation at break is only 600 percent, and can not meet the requirements of fields such as films, plastics, sports products, medical implant materials and the like on high resilience, high toughness and excellent optical properties.
Disclosure of Invention
Based on this, it is necessary to provide a bio-based thermoplastic polyetherester elastomer having high rebound, high toughness and excellent optical properties, and a method for preparing the same and application thereof.
A bio-based thermoplastic polyetherester elastomer having a structure represented by formula (1):
wherein X, y and m are integers, X is more than or equal to 1 and less than or equal to 10, y is more than or equal to 1 and less than or equal to 10, m is more than or equal to 2 and less than or equal to 60, R is selected from structural units of aliphatic or alicyclic dihydric alcohol with 4-10 carbon atoms, and X is selected from structural units of polyether dihydric alcohol with the number average molecular weight of 250g/mol-5000 g/mol.
In one embodiment, the mass fraction of soft segments in the bio-based thermoplastic polyetherester elastomer is 70% -80%;
the number average molecular weight of the polyether glycol is 1000g/mol-3000g/mol.
In one embodiment, the polyether glycol is selected from at least one of polyethylene glycol and polytetrahydrofuran;
the aliphatic or alicyclic diol with 4-10 carbon atoms is selected from at least one of 1, 4-butanediol, pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 4-cyclohexanedimethanol and 2, 4-tetramethyl-1, 3-cyclobutanediol.
The preparation method of the bio-based thermoplastic polyether ester elastomer comprises the following steps:
mixing 2, 5-thiophene dicarboxylic acid or diester thereof, aliphatic or alicyclic dihydric alcohol with 4-10 carbon atoms, polyether dihydric alcohol with the number average molecular weight of 250-5000 g/mol and an esterification or transesterification catalyst under a protective atmosphere, and carrying out esterification or transesterification reaction to obtain a prepolymer;
and (3) under the vacuum condition, carrying out polycondensation reaction on the prepolymer under the action of a polycondensation catalyst to obtain the bio-based thermoplastic polyether ester elastomer.
In one embodiment, the polyether glycol has a number average molecular weight of 1000g/mol to 3000g/mol.
In one embodiment, the molar ratio of the aliphatic or cycloaliphatic diol having 4 to 10 carbon atoms to the polyether diol is 1:99 to 99:1;
and/or the molar ratio of the sum of the molar amounts of the aliphatic or alicyclic diol with the carbon number of 4-10 and the polyether diol to the 2, 5-thiophene dicarboxylic acid or diester thereof is 1.2:1-2:1.
In one embodiment, the 2, 5-thiophenedicarboxylic acid or diester thereof is selected from at least one of 2, 5-thiophenedicarboxylic acid, dimethyl 2, 5-thiophenedicarboxylate, diethyl 2, 5-thiophenedicarboxylate, dipropyl 2, 5-thiophenedicarboxylate, dibutyl 2, 5-thiophenedicarboxylate;
the polyether glycol is at least one selected from polyethylene glycol and polytetrahydrofuran;
the aliphatic or alicyclic diol with 4-10 carbon atoms is selected from at least one of 1, 4-butanediol, pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 4-cyclohexanedimethanol and 2, 4-tetramethyl-1, 3-cyclobutanediol.
In one embodiment, the esterification or transesterification reaction is carried out at a temperature of 150℃to 220℃and for a time of 2 hours to 6 hours.
In one embodiment, in the step of polycondensation, the vacuum degree is less than or equal to 30Pa, the reaction temperature is 220 ℃ to 260 ℃, and the reaction time is 3 hours to 7 hours.
The use of a bio-based thermoplastic polyetherester elastomer as described above in plastic articles.
In the bio-based thermoplastic polyether ester elastomer provided by the invention, the hard segment part has good crystallization capability through the mutual coordination of specific molecular structures, the hard segment part belongs to a semi-crystalline type in an aggregation state, and a crystal region generated by the hard segment part serves as a physical crosslinking point in the whole aggregation state to provide mechanical property support for the bio-based thermoplastic polyether ester elastomer; the soft segment part is an amorphous structure, can form certain microphase separation with the hard segment, and provides elastic performance for the thermoplastic polyether ester elastomer, so that the bio-based thermoplastic polyether ester elastomer has high rebound, high toughness and excellent optical performance.
Drawings
FIG. 1 is a one-dimensional nuclear magnetic resonance hydrogen spectrum of the bio-based thermoplastic polyetherester elastomer obtained in example 1;
FIG. 2 is a graph of visible light transmittance of the bio-based thermoplastic polyetherester elastomer obtained in example 1;
FIG. 3 is a stress-strain curve of the bio-based thermoplastic polyetherester elastomer obtained in example 1;
FIG. 4 is a one-dimensional nuclear magnetic resonance hydrogen spectrum of the bio-based thermoplastic polyetherester elastomer obtained in example 10;
FIG. 5 is a graph of visible light transmittance of the bio-based thermoplastic polyetherester elastomer obtained in example 10;
FIG. 6 is a stress-strain curve of the bio-based thermoplastic polyetherester elastomer obtained in example 10.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The bio-based thermoplastic polyether ester elastomer provided by the invention has a structure shown in a formula (1):
wherein X, y and m are integers, X is more than or equal to 1 and less than or equal to 10, y is more than or equal to 1 and less than or equal to 10, m is more than or equal to 2 and less than or equal to 60, R is selected from structural units of aliphatic or alicyclic dihydric alcohol with 4-10 carbon atoms, and X is selected from structural units of polyether dihydric alcohol with the number average molecular weight of 250g/mol-5000 g/mol.
In the bio-based thermoplastic polyether ester elastomer provided by the invention, the hard segment part has good crystallization capability through the mutual coordination of specific molecular structures, the hard segment part belongs to a semi-crystalline type in an aggregation state, and a crystal region generated by the hard segment part serves as a physical crosslinking point in the whole aggregation state to provide mechanical property support for the bio-based thermoplastic polyether ester elastomer; the soft section part is an amorphous structure, can form certain microphase separation with the hard section, and provides elastic performance for the thermoplastic polyether ester elastomer, so that the bio-based thermoplastic polyether ester elastomer has high rebound, high toughness and excellent optical performance, specifically, the refractive index can reach more than 0.56, the transmittance can reach more than 80%, the primary deformation recovery rate can reach more than 62%, and the elongation at break can reach more than 623%.
Further, in the formula (1), x is not less than 1 and not more than 8, y is not less than 1 and not more than 8, and m is not less than 10 and not more than 40.
In order to better enable the bio-based thermoplastic polyether ester elastomer to have high rebound resilience, high toughness and excellent optical performance, in an embodiment, the mass fraction of a soft segment in the bio-based thermoplastic polyether ester elastomer is 70% -80%, the number average molecular weight of the polyether glycol is preferably 1000g/mol-3000g/mol, at the moment, the refractive index of the bio-based thermoplastic polyether ester elastomer can reach more than 0.6, the transmittance can reach more than 93%, the initial deformation recovery rate can reach more than 77%, and the elongation at break can reach more than 1180%.
The R structural unit is obtained by removing hydrogen from aliphatic or alicyclic diol with 4-10 carbon atoms in esterification or transesterification reaction; the X structural unit is obtained by removing hydrogen from polyether glycol with the number average molecular weight of 250g/mol-5000g/mol in esterification or transesterification reaction.
In one embodiment, the polyether glycol is selected from at least one of polyethylene glycol and polytetrahydrofuran, and the corresponding X structural unit is selected from at least one of formulas (2) - (3):
where n is an integer, n=5-114.
In one embodiment, the aliphatic or cycloaliphatic diol having 4 to 10 carbon atoms is selected from at least one of 1, 4-butanediol, pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 4-cyclohexanedimethanol, 2, 4-tetramethyl-1, 3-cyclobutanediol.
The invention also provides a preparation method of the bio-based thermoplastic polyether ester elastomer, which comprises the following steps:
s1, mixing 2, 5-thiophene dicarboxylic acid or diester thereof, aliphatic or alicyclic dihydric alcohol with the carbon number of 4-10, polyether dihydric alcohol with the number average molecular weight of 250-5000 g/mol and an esterification or transesterification catalyst under a protective atmosphere, and carrying out esterification or transesterification reaction to obtain a prepolymer;
s2, under the vacuum condition, carrying out polycondensation reaction on the prepolymer under the action of a polycondensation catalyst to obtain the bio-based thermoplastic polyether ester elastomer.
In the step S1, 2, 5-thiophene dicarboxylic acid or diester thereof can be obtained by reacting adipic acid with thionyl chloride, and adipic acid can be synthesized by biological resources of glucaric acid or muconic acid, so that the 2, 5-thiophene dicarboxylic acid or diester thereof is a monomer derived from biomass resources, the dependence of traditional polyester on fossil resources can be reduced, and the double effects of saving petroleum resources and protecting environment are achieved. In one embodiment, the 2, 5-thiophenedicarboxylic acid or diester thereof is selected from at least one of 2, 5-thiophenedicarboxylic acid, dimethyl 2, 5-thiophenedicarboxylate, diethyl 2, 5-thiophenedicarboxylate, dipropyl 2, 5-thiophenedicarboxylate, dibutyl 2, 5-thiophenedicarboxylate.
In one embodiment, the polyether glycol is at least one selected from polyethylene glycol and polytetrahydrofuran, and the number average molecular weight of the polyether glycol is preferably 1000g/mol to 3000g/mol.
In one embodiment, the aliphatic or cycloaliphatic diol having 4 to 10 carbon atoms is selected from at least one of 1, 4-butanediol, pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 4-cyclohexanedimethanol, 2, 4-tetramethyl-1, 3-cyclobutanediol.
In order to better regulate the structure of the bio-based thermoplastic polyether ester elastomer, in an embodiment, the molar ratio of the aliphatic or alicyclic diol with the carbon number of 4-10 to the polyether diol is 1:99-99:1, preferably 50:1-99:1, and more preferably 1.3:1-5.5:1, and the refractive index of the prepared bio-based thermoplastic polyether ester elastomer can reach more than 0.6, the transmittance can reach more than 86%, the initial deformation recovery rate can reach more than 70%, and the elongation at break can reach more than 1029%. In particular, when the polyether diol is selected from polytetrahydrofuran, the molar ratio is preferably 1.9:1 to 4.2:1; when the polyether glycol is selected from polyethylene glycols, the molar ratio is preferably 1.3:1 to 5.5:1.
In an embodiment, the molar ratio of the sum of the molar amounts of the aliphatic or alicyclic diol having 4 to 10 carbon atoms and the polyether diol to the 2, 5-thiophenedicarboxylic acid or diester thereof is 1.2:1 to 2:1, preferably 1.3:1 to 1.5:1, and the refractive index of the bio-based thermoplastic polyether ester elastomer prepared at this time may reach 0.6 or more, the transmittance may reach 86% or more, the initial deformation recovery may reach 70% or more, and the elongation at break may reach 1029% or more.
In order to increase the rate of the esterification or transesterification reaction, a catalyst is added in the reaction process, and the esterification or transesterification catalyst is at least one selected from tetrabutyl titanate or isopropyl titanate.
In one embodiment, the molar ratio of the esterification or transesterification catalyst to 2, 5-thiophenedicarboxylic acid or diester thereof is from 0.01:100 to 0.3:100.
In one embodiment, the esterification or transesterification reaction step is carried out at a temperature of 150 ℃ to 220 ℃, preferably 180 ℃ to 220 ℃, for a reaction time of 2 hours to 6 hours, preferably 5 hours to 6 hours.
The esterification or transesterification reaction is carried out under a protective atmosphere, and the kind of the protective atmosphere is not limited in the present invention, but is preferably nitrogen, helium, neon, argon, krypton or xenon.
In step S2, in order to increase the rate of the polycondensation reaction, a polycondensation catalyst is added during the reaction, and the polycondensation catalyst is at least one selected from tetrabutyl titanate and isopropyl titanate.
In one embodiment, the molar ratio of the polycondensation catalyst to 2, 5-thiophenedicarboxylic acid or diester thereof is from 0.01:100 to 0.3:100.
In one embodiment, in the polycondensation reaction stage, the vacuum degree is 30Pa or less, the reaction temperature is 220℃to 260℃and preferably 230℃to 250℃and the reaction time is 3 hours to 7 hours and preferably 5 hours to 7 hours.
The invention also provides application of the bio-based thermoplastic polyether ester elastomer in plastic products, and the bio-based thermoplastic polyether ester elastomer has high rebound, high toughness and excellent optical performance, and can be widely applied to the fields of films, plastic toughening modification, sports products, medical implants and the like.
Hereinafter, the bio-based thermoplastic polyetherester elastomer, and the preparation method and application thereof will be further described by the following specific examples.
In the examples, nuclear magnetic resonance hydrogen spectrum 1 H-NMR was performed using a Bruker AVANCENEO600 Specter meter instrument at 600MHz with trifluoroacetic acid (CF) 3 COOD)。
In the examples, the refractive index was measured using an Abbe refractometer at room temperature.
In the examples, the visible light transmittance was measured in the wavelength range of 200nm to 800nm using an ultraviolet-visible near infrared spectrophotometer (Perkin-Elmer Lambda 950) at room temperature.
In the examples, the mechanical properties were measured on a Zwick Z1.0 Universal materials tester 1KN instrument at a test speed of 50mm/min.
Example 1
200g of dimethyl 2, 5-thiophenedicarboxylate, 115g of 1, 4-butanediol, 230g of polytetrahydrofuran with the molecular weight of 1000g/mol and 0.7g of tetrabutyl titanate are added into a reaction kettle, and the transesterification reaction is carried out under the protection of nitrogen, wherein the reaction temperature is 170 ℃ and the reaction time is 4 hours, so that the prepolymer is obtained.
And vacuumizing the reaction kettle until the vacuum degree is 29Pa, and heating to 220 ℃ to perform polycondensation reaction for 7 hours. Taking out the product under the protection of nitrogen after the reaction is stopped to obtain the bio-based thermoplastic polyether ester elastomer with the mass fraction of the soft segment of 60 percent, the structure of the bio-based thermoplastic polyether ester elastomer is shown as a formula (1-1),
wherein x, y, m, n are integers, x=4, y=1, m=20-50, n=10-12.
The one-dimensional nuclear magnetic resonance hydrogen spectrogram of the bio-based thermoplastic polyether ester elastomer prepared by the embodiment is shown in figure 1, and the structure of the bio-based thermoplastic polyether ester elastomer is clear; the transmittance graph is shown in FIG. 2, the cut-off is 700nm, and the visible light transmittance is 90%; the stress-strain curve is shown in FIG. 3, the tensile strength is 28MPa, and the elongation at break is 1066%.
The initial deformation recovery of the bio-based thermoplastic polyetherester elastomer obtained in this example was 71% and the refractive index was 0.62, as tested.
Examples 2 to 3
Examples 2-3 were carried out with reference to example 1, except that the mass of each raw material was different, in which:
the mass of the 2, 5-thiophene dimethyl dicarboxylate is 120.00g and 100.00g respectively;
the mass of the 1, 4-butanediol is 53.14g and 38.60g respectively;
the mass of the polytetrahydrofuran with the molecular weight of 1000g/mol is 190.38g and 221.75g respectively;
the mass of tetrabutyl titanate is respectively 0.42g and 0.35g.
Examples 2-3 biobased thermoplastic elastomers with soft segments at mass fractions of 70% and 80%, respectively, were synthesized.
The test shows that the initial deformation recovery rates of the bio-based thermoplastic polyether ester elastomers obtained in the examples 2-3 are 82% and 77% respectively, the elongation at break is 1180% and 1289% respectively, the tensile strengths are 24MPa and 19MPa respectively, the refractive indexes are 0.61 and 0.60 respectively, the visible light transmittance is 93% and 94% respectively at the cut-off of 700 nm.
In examples 2-3, the resulting biobased thermoplastic polyetherester elastomer has a structural formula represented by formula (1-2),
in example 2, x, y, m, n is an integer, x=2, y=1, m=20 to 50, and n=10 to 12;
in example 3, x, y, m, n are integers, x=3, y=2, m=20 to 50, and n=10 to 12.
Examples 4 to 9
Examples 4-9 were carried out with reference to example 1, except that the mass of each raw material was different, in which:
the mass of the 2, 5-thiophene dimethyl dicarboxylate is 200g;
the mass of the pentanediol, the 1, 6-hexanediol, the 1, 7-heptanediol, the 1, 8-octanediol, the 1, 9-nonanediol and the 1, 10-decanediol is 110.24g, 123.90g, 137.28g, 150.38g, 163.20g and 175.74g in sequence;
the masses of the polytetrahydrofuran with the molecular weight of 1000g/mol are 240.00g, 250.00g, 260.00g, 270.00g, 280.00g and 290.00g respectively;
the mass of each tetrabutyl titanate was 0.70g.
Examples 4-9 respectively synthesize a 60% soft segment mass fraction bio-based thermoplastic elastomer.
The initial strain recovery rates of the bio-based thermoplastic polyether ester elastomers obtained in examples 4 to 9 were 70%, 68%, 66%, 65%, 63%, 62%, elongation at break was 1198%, 1147%, 1029%, 986%, 874%, 859%, tensile strengths were 19MPa, 18MPa, 17MPa, 16MPa, 15MPa, respectively, refractive indexes were 0.61, 0.60, 0.59, 0.58, 0.57, 0.56, and visible light transmittance was 91%, 89%, 88%, 86%, 87%, 89%, respectively, by testing.
In the bio-based thermoplastic polyether ester elastomer obtained in examples 4 to 9, the structural formula of R is shown as formula (1-3) -formula (1-8), respectively:
example 10
200g of dimethyl 2, 5-thiophenedicarboxylate, 149g of 1, 4-cyclohexanedimethanol, 270g of polytetrahydrofuran with a molecular weight of 1000g/mol and 0.7g of tetrabutyl titanate are added into a reaction kettle, and the transesterification reaction is carried out under the protection of nitrogen, wherein the reaction temperature is 220 ℃ and the reaction time is 3 hours, so as to obtain the prepolymer.
And vacuumizing the reaction kettle until the vacuum degree is 29Pa, and heating to 240 ℃ to perform polycondensation reaction for 7 hours. Taking out the product under the protection of nitrogen after the reaction is stopped to obtain the bio-based thermoplastic polyether ester elastomer with the mass fraction of the soft segment of 60 percent, the structure of the bio-based thermoplastic polyether ester elastomer is shown as the formula (1-9),
wherein x, y, m, n are integers, x=3, y=1, m=20-50, n=10-12.
The one-dimensional nuclear magnetic resonance hydrogen spectrum of the bio-based thermoplastic polyether ester elastomer prepared in the embodiment is shown in figure 4, and the structure of the bio-based thermoplastic polyether ester elastomer is clear; the transmittance graph is shown in FIG. 5, the visible light transmittance is 89% when the light is cut off at 700 nm; the stress-strain curve is shown in FIG. 6, and the tensile strength is 11MPa and the elongation at break is 804%.
The initial deformation recovery of the bio-based thermoplastic polyetherester elastomer obtained in this example was 79% and the refractive index was 0.58, as tested.
Example 11
Example 11 was performed with reference to example 1, except that: 80g of dimethyl 2, 5-thiophenedicarboxylate, 59.6g of 2, 4-tetramethyl-1, 3-cyclobutanediol, 108g of polytetrahydrofuran having a molecular weight of 1000g/mol and 0.28g of tetrabutyl titanate are introduced into a reaction vessel.
The obtained bio-based thermoplastic polyether ester elastomer with the mass fraction of the soft segment of 60 percent has the structure shown in the formula (1-10),
wherein x, y, m, n are integers, x=3, y=1, m=20-50, n=10-12.
The test shows that the initial deformation recovery rate of the bio-based thermoplastic polyether ester elastomer with the mass fraction of the soft segment of 60% obtained in the embodiment is 66%, the elongation at break is 623%, the tensile strength is 15MPa, the refractive index is 0.56, the cut-off is 700nm, and the visible light transmittance is 85%.
Examples 12 to 13
Examples 12-13 were carried out with reference to example 1, except that the mass of each raw material was different, in which:
the mass of the 2, 5-thiophene dimethyl dicarboxylate is 100.00g and 120.00g respectively;
the mass of the 1, 4-butanediol is 52.40g and 65.04g respectively;
the mass of polytetrahydrofuran with the molecular weight of 2000g/mol and 3000g/mol is 137.15g and 175.80g in sequence;
the mass of the tetrabutyl titanate is 0.35g and 0.42g.
Examples 12-13 each synthesized a 60% soft segment mass fraction bio-based thermoplastic elastomer.
In examples 12 to 13, the resulting biobased thermoplastic polyetherester elastomer has a structural formula represented by the following formula (1 to 11),
in example 12, x, y, m, n is an integer, x=6, y=1, m=20 to 50, and n=26 to 28;
in example 13, x, y, m, n are integers, x=10, y=1, m=20 to 50, and n=40 to 42.
The test shows that the initial deformation recovery rates of the bio-based thermoplastic polyether ester elastomers obtained in examples 12-13 are 82% and 74% respectively, the elongation at break is 1273% and 1136% respectively, the tensile strengths are 22MPa and 19MPa respectively, the refractive indexes are 0.61 and 0.59 respectively, the cut-off is 700nm, and the visible light transmittance is 80% and 82% respectively.
Examples 14 to 16
Examples 14-16 were carried out with reference to example 1, except that the mass of each raw material was different, in which:
the mass of the 2, 5-thiophene dimethyl dicarboxylate is 200.00g, 100.00g and 120.00g respectively;
the mass of the 1, 4-butanediol is 115.00g, 52.40g and 65.04g respectively;
the mass of polyethylene glycol with the molecular weight of 1000g/mol, 2000g/mol and 3000g/mol is 230.00g, 137.15g and 175.80g in sequence;
the mass of the tetrabutyl titanate is 0.70g, 0.35g and 0.42g.
Examples 14-16 each synthesized a 60% soft segment mass fraction of a bio-based thermoplastic elastomer.
The bio-based thermoplastic polyether ester elastomers obtained in examples 14 to 16 have the structures shown in the formulas (1 to 12),
in example 14, x, y, m, n is an integer, x=4, y=1, m=10 to 30, and n=21 to 23;
in example 15, x, y, m, n are integers, x=6, y=1, m=10 to 30, n=44 to 46;
in example 16, x, y, m, n are integers, x=10, y=1, m=10-30, and n=66-68.
The test shows that the initial deformation recovery rates of the bio-based thermoplastic polyether ester elastomers obtained in examples 14-16 are respectively 70%, 75% and 73%, the elongation at break is respectively 1083%, 1125% and 1147%, the tensile strengths are respectively 17MPa, 19MPa and 20MPa, the refractive indexes are respectively 0.62, 0.60 and 0.59, and the visible light transmittance is respectively 87%, 86% and 84% when the bio-based thermoplastic polyether ester elastomers are cut off at 700 nm.
Comparative example 1
184.15g of dimethyl 2, 5-furandicarboxylate, 98.1g of 1, 4-butanediol, 210g of polytetrahydrofuran with the molecular weight of 1000g/mol and 0.7g of tetrabutyl titanate are added into a reaction kettle, and the transesterification reaction is carried out under the protection of nitrogen, wherein the reaction temperature is 170 ℃ and the reaction time is 4 hours, so as to obtain the prepolymer.
And vacuumizing the reaction kettle until the vacuum degree is 20Pa, and heating to 220 ℃ to perform polycondensation reaction for 7 hours. Taking out the product under the protection of nitrogen after the reaction is stopped to obtain the bio-based thermoplastic polyether ester elastomer, the structure of which is shown as the formula (1-13),
wherein x, y, m, n are integers, x=4, y=1, m=10-30, n=10-12.
The test shows that the initial deformation recovery rate of the bio-based thermoplastic polyether ester elastomer with the mass fraction of the soft segment of 60% obtained in the embodiment is 63%, the elongation at break is 748%, the tensile strength is 12MPa, the refractive index is 0.52, the cut-off is 700nm, and the visible light transmittance is 82%.
Comparative example 2
194.18g of dimethyl terephthalate, 98.1g of 1, 4-butanediol, 230g of polytetrahydrofuran with the molecular weight of 1000g/mol and 0.7g of tetrabutyl titanate are added into a reaction kettle, and the transesterification reaction is carried out under the protection of nitrogen, wherein the reaction temperature is 170 ℃ and the reaction time is 4 hours, thus obtaining the prepolymer.
And vacuumizing the reaction kettle until the vacuum degree is 20Pa, and heating to 280 ℃ to perform polycondensation reaction for 7 hours. Taking out the product under the protection of nitrogen after the reaction is stopped to obtain the bio-based thermoplastic polyether ester elastomer, the structure of which is shown as the formula (1-14),
wherein x, y, m, n are integers, x=6, y=1, m=10-30, n=10-12.
The test shows that the bio-based thermoplastic polyether ester elastomer with the mass fraction of the soft segment of 60% obtained in the embodiment has the initial deformation recovery rate of 80%, the elongation at break of 1248%, the tensile strength of 24MPa, the refractive index of 0.53, the cut-off of 700nm and the visible light transmittance of 81%.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A bio-based thermoplastic polyetherester elastomer characterized by having a structure represented by formula (1):
wherein X, y and m are integers, X is more than or equal to 1 and less than or equal to 10, y is more than or equal to 1 and less than or equal to 10, m is more than or equal to 2 and less than or equal to 60, R is selected from structural units of aliphatic or alicyclic dihydric alcohol with 4-10 carbon atoms, and X is selected from structural units of polyether dihydric alcohol with the number average molecular weight of 250g/mol-5000 g/mol.
2. The biobased thermoplastic polyetherester elastomer of claim 1, wherein the mass fraction of soft segments in the biobased thermoplastic polyetherester elastomer is 70% -80% ；
The number average molecular weight of the polyether glycol is 1000g/mol-3000g/mol.
3. The biobased thermoplastic polyetherester elastomer of claim 1, wherein the polyetherdiol is at least one selected from the group consisting of polyethylene glycol and polytetrahydrofuran;
the aliphatic or alicyclic diol with 4-10 carbon atoms is selected from at least one of 1, 4-butanediol, pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 4-cyclohexanedimethanol and 2, 4-tetramethyl-1, 3-cyclobutanediol.
4. A process for the preparation of a bio-based thermoplastic polyetherester elastomer according to any one of claims 1 to 3, comprising the steps of:
mixing 2, 5-thiophene dicarboxylic acid or diester thereof, aliphatic or alicyclic dihydric alcohol with 4-10 carbon atoms, polyether dihydric alcohol with the number average molecular weight of 250-5000 g/mol and an esterification or transesterification catalyst under a protective atmosphere, and carrying out esterification or transesterification reaction to obtain a prepolymer;
and (3) under the vacuum condition, carrying out polycondensation reaction on the prepolymer under the action of a polycondensation catalyst to obtain the bio-based thermoplastic polyether ester elastomer.
5. The method for producing a bio-based thermoplastic polyether ester elastomer according to claim 4, wherein the polyether glycol has a number average molecular weight of 1000g/mol to 3000g/mol.
6. The method for producing a bio-based thermoplastic polyether ester elastomer according to claim 4, wherein the molar ratio of the aliphatic or alicyclic diol having 4 to 10 carbon atoms to the polyether diol is 1:99 to 99:1;
and/or the molar ratio of the sum of the molar amounts of the aliphatic or alicyclic diol with the carbon number of 4-10 and the polyether diol to the 2, 5-thiophene dicarboxylic acid or diester thereof is 1.2:1-2:1.
7. The method for producing a bio-based thermoplastic polyether ester elastomer according to claim 4, wherein the 2, 5-thiophene dicarboxylic acid or diester thereof is at least one selected from the group consisting of 2, 5-thiophene dicarboxylic acid, dimethyl 2, 5-thiophene dicarboxylic acid, diethyl 2, 5-thiophene dicarboxylic acid, dipropyl 2, 5-thiophene dicarboxylic acid, dibutyl 2, 5-thiophene dicarboxylic acid;
the polyether glycol is at least one selected from polyethylene glycol and polytetrahydrofuran;
the aliphatic or alicyclic diol with 4-10 carbon atoms is selected from at least one of 1, 4-butanediol, pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 4-cyclohexanedimethanol and 2, 4-tetramethyl-1, 3-cyclobutanediol.
8. The method for preparing a bio-based thermoplastic polyether ester elastomer according to claim 4, wherein in the step of esterification or transesterification, the reaction temperature is 150 to 220 ℃ and the reaction time is 2 to 6 hours.
9. The method for producing a bio-based thermoplastic polyether ester elastomer according to claim 4, wherein in the step of polycondensation, the vacuum degree is 30Pa or less, the reaction temperature is 220 to 260 ℃, and the reaction time is 3 to 7 hours.
10. Use of a bio-based thermoplastic polyetherester elastomer according to any of claims 1 to 3 in plastic articles.
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| CN117304459B (en) * | 2023-11-29 | 2024-04-19 | 中国科学院宁波材料技术与工程研究所 | Bio-based sulfur-containing high-refraction polyester and preparation method and application thereof |
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