CN115417995A - Polythioester and stereocomplex-based thermoplastic elastomer thereof - Google Patents
Polythioester and stereocomplex-based thermoplastic elastomer thereof Download PDFInfo
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- CN115417995A CN115417995A CN202211016938.3A CN202211016938A CN115417995A CN 115417995 A CN115417995 A CN 115417995A CN 202211016938 A CN202211016938 A CN 202211016938A CN 115417995 A CN115417995 A CN 115417995A
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 53
- 229920000642 polymer Polymers 0.000 claims abstract description 52
- 229920006295 polythiol Polymers 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000009477 glass transition Effects 0.000 claims abstract description 20
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 15
- 229920000570 polyether Polymers 0.000 claims abstract description 15
- 238000012546 transfer Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 125000004122 cyclic group Chemical group 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- -1 episulfide alkane Chemical class 0.000 claims description 14
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 10
- 229920005862 polyol Polymers 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000012648 alternating copolymerization Methods 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- 125000005442 diisocyanate group Chemical group 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000000806 elastomer Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- YGKHJWTVMIMEPQ-UHFFFAOYSA-N 1,2-propanedithiol Chemical compound CC(S)CS YGKHJWTVMIMEPQ-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000011161 development Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 238000005481 NMR spectroscopy Methods 0.000 description 23
- 238000003756 stirring Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000009826 distribution Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000000746 purification Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229960004063 propylene glycol Drugs 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000002464 physical blending Methods 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- OROGUZVNAFJPHA-UHFFFAOYSA-N 3-hydroxy-2,4-dimethyl-2H-thiophen-5-one Chemical compound CC1SC(=O)C(C)=C1O OROGUZVNAFJPHA-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to polythioester and a stereocomplex-based thermoplastic elastomer thereof. The polythioester and the stereocomplex thereof based on the thermoplastic elastomer have high glass transition temperature or crystalline polythioester or a stereocomplex of the polythioester as a hard segment; the polyether or polythioether with low glass transition temperature is taken as a soft segment, and the hard segment and the soft segment which are formed by the chain transfer method or the chain extension method are in an alternating connection three-block or multi-block structure. Wherein the ratio of soft and hard segments in the triblock or multiblock polymer is adjustable. The polythioester-based thermoplastic elastomer prepared by the method has the service temperature window of-60 to 160 ℃, the tensile strength at break of 10 to 60MPa and the elongation at break of 200 to 750 percent. The development of the polythioester-based thermoplastic elastomer widens the application range of the polythioester and also has the prospect of realizing industrial production.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to polythioester and a stereocomplex-based thermoplastic elastomer thereof.
Background
The polyester material is an important component for solving the problem of the sustainability of petrochemical-based polymers, and the bio-based polyester has good renewability, biocompatibility and degradability. The excellent properties enable the polyester material to have wide application prospects. As a class of polyester analogs, polythioesters (a class of sulfur-containing polymeric materials in which at least one oxygen atom in the repeating unit of the polyester is replaced with a sulfur atom) have received less attention. The introduction of sulfur atoms in the polythioester endows the material with improved optical properties while maintaining the excellent properties of the polyester material. Therefore, the polythioester material has good research potential and application prospect. The traditional method for synthesizing polythioester mainly comprises polycondensation method and ring-opening polymerization method of thiolactone monomer. However, the polycondensation process is a high energy and "non-atomic economic" process; the ring-opening polymerization method tends to lack diversity in the structure of the resulting polymer due to the single structure of the thiolactone. Recently, the alternating copolymerization reaction of the cyclic sulfane and the cyclic thioanhydride developed by us is an atom-economical reaction, the reaction condition is mild, and the obtained polymer structure and the molecular weight thereof have excellent controllability and adjustability. The development of the method provides a solid foundation for the application of the materials. In particular, polythioesters obtained by alternating copolymerization of epithiopropane with thiosuccinic anhydride are crystalline polymers having a melting point of 81 ℃. When chiral epithiopropane is used, isotactic polythioesters are obtained, the melting point of which is raised to 91 ℃. The crystalline polythioester has high hardness and heat resistance stability. In addition, two isotactic polythioesters of opposite configuration are physically mixed to obtain a polythioester stereocomplex. The polythioester stereocomplex has a higher melting point (up to 160 ℃) and a higher hardness. However, the materials have the defects of insufficient toughness and large brittleness, and the application of the materials is greatly limited. The research on how to improve the toughness of the material has not been reported. Therefore, how to realize the performance upgrade of the polythioester material and realize the diversified application thereof through the topological structure optimization of the polymer is an urgent problem to be solved in the field.
Disclosure of Invention
In order to solve the problems, the invention provides a polythioester-based polymer containing hard to soft to hard triblock or multiblock based on the advantages of excellent heat-resistant stability and high hardness of polythioester and aiming at the defects of insufficient toughness and high brittleness of the polythioester, wherein the polythioester-based polymer is taken as a hard block, and a polymer chain segment with low glass transition temperature is taken as a soft block, and a high-performance polythioester-based thermoplastic elastomer material is obtained by a chain extension method and adjustment of the proportion of the hard block and the soft block. The usage temperature window of the polythioester-based thermoplastic elastomer is-60 to 160 ℃, the tensile strength at break is 10 to 60MPa, and the elongation at break is 200 to 750 percent. The invention not only provides a class of thermoplastic elastomer materials with high optical performance, but also widens the application range of polythioester, and simultaneously has the potential of practical industrial production.
The technical scheme of the invention is as follows:
a thermoplastic elastomer based on polythioester and its stereo composition is a triblock or multiblock polymer which is composed of hard segments (high glass transition temp), crystalline polythioester or its stereo composition, and soft segments (low glass transition temp), and is prepared from the two segments through chain transfer or chain extension. Wherein the proportion of soft and hard segments in the triblock or multiblock polymer is adjustable; the glass transition temperature of the hard segment is more than 100 ℃, and the glass transition temperature of the soft segment is less than-40 ℃.
The triblock or multiblock polymer has the following structure:
segment one: the polythioester hard segment is a polythioester stereocomplex formed by stereocomplex of atactic polythioester with high glass transition temperature, crystalline isotactic polythioester or two types of isotactic polythioester with opposite configuration formed by alternating copolymerization of episulfide alkane and cyclic anhydride; wherein, the crystalline polythioester is obtained by the high regioselectivity of chiral episulfide alkane and cyclic thioanhydride or the high stereoselectivity copolymerization of meso-episulfide alkane and cyclic thioanhydride; the general structural formula of each substance is as follows:
wherein: r is 1 ～R 4 Is a cyclic thioalkane or a cyclic thioanhydride, R 1 ～R 4 May be the same or different.
And a second chain segment: the polyether or polythioether soft segment is polyether polyol formed by homopolymerization of propylene oxide or polythioether polythiol formed by homopolymerization of cyclopropane, and the structural formula is as follows:
preferably, the cyclic thioalkane has the following structural formula:
preferably, the cyclic thioanhydride has the following structural formula:
preferably, the soft segment is poly (1, 2-propanedithiol) polythiol or polythioether polythiol formed by homopolymerization of cyclane in polythiol as an initiator.
The chain transfer method is characterized in that polyether polyol or polythioether polythiol is used as a macroinitiator to initiate the alternating copolymerization reaction of cyclic thioalkane and cyclic thioanhydride in situ to form a polythioester elastomer with a 'hard' -soft '-hard' triblock structure;
the chain extension method is characterized in that polyether polyol or polythioether soft segments are reacted with excessive diisocyanate to form isocyanate-terminated polyether or polythioether soft segments, and then the isocyanate-terminated polyether or polythioether soft segments are reacted with polythioester hard segments or polythioester with a triblock structure to form a high-molecular-weight multiblock polythioester elastomer;
the ratio of the soft segment to the hard segment in the triblock or multi-block polymer is adjustable, and the adjustable range of the content of the hard segment is as follows: 30 to 70 wt.%, preferably 35 wt.%.
The polythioester stereocomplex-based thermoplastic elastomer refers to the physical blending of an isotactic polythioester triblock or multiblock polymer and an isotactic polythioester with an opposite configuration or a triblock or multiblock polythioester according to the molar ratio of a polythioester chain segment 1, wherein a hard segment of the physical blending is a polythioester stereocomplex as follows.
The solvents used in the preparation of the polythioester and the stereocomplex-based thermoplastic elastomer thereof include but are not limited to: methylene chloride, methanol, tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, etc.;
the preparation temperature of the polythioester and the stereocomplex-based thermoplastic elastomer thereof is 25-80 ℃;
the number average molecular weight of the polythioester and the stereocomplex-based thermoplastic elastomer thereof is 30.0-200.0 kg/mol.
The polythioester and the stereocomplex thereof based on the thermoplastic elastomer have the use window temperature of-60 to 160 ℃, the tensile strength at break of 10 to 60MPa and the elongation at break of 200 to 750 percent.
The invention has the beneficial effects that:
(1) The polythioester and the stereocomplex-based thermoplastic elastomer thereof have mild preparation conditions, and the reaction process meets the requirement of atom economy.
(2) The polythioester and the stereocomplex based thermoplastic elastomer thereof have wide sources of synthetic raw materials and rich structures. The prepared thermoplastic elastomer has diversified application potentials according to different structures.
(3) The polythioester thermoplastic elastomer can obtain the polythioester stereocomplex-based thermoplastic elastomer with better performance by simple physical blending, can greatly improve the use window of the polythioester stereocomplex-based thermoplastic elastomer and expand the application range of the elastomer.
(4) The soft segment of the polythioester and the stereocomplex-based thermoplastic elastomer thereof is of a polyether or polythioether structure, has a good lithium ion transmission rate, and has a good application prospect in the field of lithium ion batteries.
Detailed Description
The technical solution of the present invention is further described by examples below.
The numbers of the cycloalkane and the cyclic thioanhydride used in the present invention are shown in the following formulae.
Episulfide alkane:
cyclic thioanhydride:
example 1
A100 mL reaction flask equipped with magnetons was dried at 120 ℃ for 12 hours or more, evacuated to room temperature, and flushed with nitrogen gas for use. Weighing appropriate amount of KH and poly (1, 2-propylene glycol) (M) at room temperature under nitrogen protection n =20kg/mol, PDI = 1.06), after 10min of reaction, 1, 4-dioxane was added as solvent, the episulfide alkane 1a and the cyclic thioanhydride 2a were added in an equimolar ratio to the reaction system, reaction was continued at 25 ℃ for 10h, stirring was stopped, and a very small amount of the reaction mixture was taken out for use in conducting the reaction 1 H NMR and GPC testing. 1 H NMR measurements showed that the degree of alternance of the polythioester was>99 percent, and the mass fraction of the polythioester in the triblock polymer is 30 percent. GPC measurement showed the polymerization molecular weight to be 30.3kg/mol and the molecular weight distribution to be 1.81. Purifying the residual reaction polymer, wherein the polymer purification comprises the following steps: dissolving the crude product in a small amount of dichloromethane, adding a large amount of methanol, and stirring vigorously to polymerizeThe compound precipitates, the process is repeated repeatedly, and white polymer can be obtained after vacuum drying. The thermodynamic property test shows that the glass transition temperature of the obtained polythioester-based thermoplastic elastomer is-60 ℃ and the melting point is 150 ℃. The mechanical property test shows that the obtained polythioester-based thermoplastic elastomer has the breaking tensile strength of 10MPa and the breaking elongation of 750 percent.
Example 2
In a 100mL reaction flask equipped with magnetons, drying at 120 ℃ for more than 12h, vacuumizing until the temperature is cooled to room temperature, and filling nitrogen for use. Under the protection of nitrogen, a certain amount of KH and benzyl mercaptan are weighed at room temperature, after 10min of reaction, 1, 4-dioxane is added as a solvent, and the cyclic thioalkane 1b and the cyclic thioanhydride 2b with equal molar ratio are added into a reaction system. After 10h of reaction at 30 ℃ the stirring was stopped and a very small amount of the reaction mixture was taken off for carrying out 1 H NMR and GPC testing. 1 H NMR measurements showed that the degree of alternance of the polythioester was>99 percent. GPC measurement showed the polymerization molecular weight to be 20.1kg/mol and the molecular weight distribution to be 1.14. Another 100mL reaction bottle with magnetons is taken, dried at 120 ℃ for more than 12h, vacuumized until the reaction bottle is cooled to room temperature, and filled with nitrogen for use. Under the protection of nitrogen, a certain amount of KH and ethanedithiol are weighed at room temperature, after 10min of reaction, glycol dimethyl ether is added as a solvent. A certain amount of epithiopropane was slowly added to the reaction system. After 5h of reaction at 25 ℃ the stirring was stopped. The reaction solution is dropwise added into a reaction flask filled with a diisocyanate tetrahydrofuran solution, and the reaction is continued for 2 hours. The stirring was stopped and a very small amount of the reaction mixture was taken out for GPC testing. GPC measurement showed a polymerization molecular weight of 60.1kg/mol and a molecular weight distribution of 1.64. Then slowly adding the polythioester 1, 4-dioxane solution synthesized in the above way into the reaction system, and adding stannous octoate as a catalyst to react for 2h. The stirring was stopped and a very small amount of the reaction mixture was taken out for carrying out 1 H NMR and GPC testing. According to 1 H NMR results calculated that the polythioester content of the triblock polymer was 40%. GPC measurement indicated a polymeric molecular weight of 101.4kg/mol and a molecular weight distribution of 1.94. The remaining reaction polymer is purified (the purification method is the same as that used in the practice ofExample 1). The thermodynamic property test shows that the glass transition temperature of the obtained polythioester-based thermoplastic elastomer is-50 ℃ and the melting point is 120 ℃. The mechanical property test shows that the obtained polythioester-based thermoplastic elastomer has the breaking tensile strength of 30MPa and the breaking elongation of 550 percent.
Example 3
A100 mL reaction flask equipped with magnetons was dried at 120 ℃ for 12 hours or more, evacuated to room temperature, and flushed with nitrogen gas for use. Weighing appropriate amount of KH and poly 1,2 propylene glycol polyol (M) at room temperature under nitrogen protection n =3.0kg/mol, PDI = 1.05), after 10min of reaction, 1, 4-dioxane was added as solvent, episulfide alkane 1c and cyclic thioanhydride 2c were added to the reaction system in an equimolar ratio, the temperature was raised to 50 ℃, reaction was continued for 10h, stirring was stopped, and a very small amount of the reaction mixture was taken out for use in conducting the reaction 1 H NMR and GPC testing. 1 H NMR measurements showed that the degree of alternance of the polythioester was>99 percent, and the mass fraction of the polythioester in the triblock polymer is 60 percent. GPC measurement showed a polymeric molecular weight of 10.6kg/mol and a molecular weight distribution of 1.81. The remaining reaction polymer was purified (the same purification method as in example 1). Slowly adding the 1, 4-dioxane solution of the polythioester into a polythioether solution capped by diisocyanate, adding stannous octoate as a catalyst, continuously reacting for 2 hours, and stopping the reaction. A very small amount of the reaction mixture is taken off for carrying out 1 H NMR and GPC testing. According to 1 H NMR measurement results calculated that the polythioester content in the triblock polymer was 50%. GPC measurement showed a polymeric molecular weight of 151.4kg/mol and a molecular weight distribution of 1.87. The remaining reaction polymer was purified (the purification method was the same as in example 1). The thermodynamic property test shows that the glass transition temperature of the obtained polythioester-based thermoplastic elastomer is-50 ℃ and 130 ℃, and the mechanical property test shows that the obtained polythioester-based thermoplastic elastomer has the tensile strength at break of 50MPa and the elongation at break of 400%.
Example 4
A100 mL reaction flask equipped with magnetons was dried at 120 ℃ for 12 hours or more, evacuated to room temperature, and flushed with nitrogen gas for use. Under the protection of nitrogenThen, a certain amount of KH and poly 1,2 propylene glycol polyol (M) were weighed at room temperature n =20kg/mol, PDI = 1.05), after 10min of reaction, 1, 4-dioxane was added as a solvent, epithioalkane 1d and cyclic thioanhydride 2d were added in an equimolar ratio to the reaction system, the temperature was raised to 80 ℃, reaction was continued for 12h, stirring was stopped, and a very small amount of the reaction mixture was taken out for proceeding 1 H NMR and GPC testing. 1 H NMR measurements showed that the degree of alternance of the polythioester was>99% according to 1 The mass fraction of polythioester in the obtained triblock polymer was calculated by H NMR as 70%. GPC measurement showed the polymerization molecular weight to be 60.3kg/mol and the molecular weight distribution to be 1.81. Purifying the residual reaction polymer, wherein the polymer purification comprises the following steps: the crude product is first dissolved in a small amount of dichloromethane, then a large amount of methanol is added, and the mixture is stirred vigorously to precipitate the polymer, the process is repeated, and the white polymer can be obtained after vacuum drying. Thermodynamic property tests show that the glass transition temperature of the obtained polythioester-based thermoplastic elastomer is-55 ℃ and 155 ℃. Mechanical property tests show that the obtained polythioester-based thermoplastic elastomer has the tensile strength at break of 60MPa and the elongation at break of 200 percent.
Example 5
A100 mL reaction flask equipped with magnetons is dried at 120 ℃ for more than 12h, vacuumized, cooled to room temperature, and flushed with nitrogen for use. Weighing appropriate amount of KH and poly (1, 2-propanedithiol) (M) at room temperature under nitrogen protection n =10kg/mol, PDI = 1.01), after 10min of reaction, 1, 4-dioxane was added as solvent, optically pure cyclic sulfanoalkane 1b and cyclic thioanhydride 2a were added to the reaction system in equimolar ratio, reaction was continued at 25 ℃ for 10h, stirring was stopped, and a very small amount of the reaction mixture was taken out for proceeding 1 H NMR and GPC testing. 1 H NMR measurements showed that the degree of alternance of the polythioester was>99 percent, and the mass fraction of the polythioester in the triblock polymer is 45 percent. GPC measurement showed a polymeric molecular weight of 18.2kg/mol and a molecular weight distribution of 1.78. The remaining reaction polymer was purified (the purification method was the same as in example 1). The 1, 4-dioxane solution of the polythioester was slowly added to the solution of the diisocyanate-terminated polythioether, and octyl was addedStannous chloride is used as a catalyst, and the reaction is continued for 2 hours and stopped. A very small amount of the reaction mixture is taken off for carrying out 1 H NMR and GPC testing. According to 1 H NMR results calculated that the polythioester content of the triblock polymer was 35%. GPC measurement showed the polymerization molecular weight to be 213.4kg/mol and the molecular weight distribution to be 1.97. The remaining reaction polymer was purified (the same purification method as in example 1). Mixing two multiblock polythioester stereocomplex with opposite configuration, dissolving with dichloromethane, stirring at 30 deg.C, adding methanol to precipitate, and vacuum drying to obtain white polymer. The thermodynamic property test shows that the glass transition temperature of the obtained polythioester-based thermoplastic elastomer is-48 ℃, the melting point is 157 ℃, and the mechanical property test shows that the obtained polythioester-based thermoplastic elastomer has the tensile strength at break of 45MPa and the elongation at break of 750 percent.
Example 6
A100 mL reaction flask equipped with magnetons was dried at 120 ℃ for 12 hours or more, evacuated to room temperature, and flushed with nitrogen gas for use. Weighing appropriate amount of KH and poly (1, 2-propanedithiol) (M) under nitrogen protection n =10kg/mol, PDI = 1.01), after 10min of reaction, 1, 4-dioxane was added as solvent, optically pure cyclic sulfanoalkane 1b and cyclic thioanhydride 2a were added to the reaction system in equimolar ratio, reaction was continued at 25 ℃ for 10h, stirring was stopped, and a very small amount of the reaction mixture was taken out for proceeding 1 H NMR and GPC testing. 1 H NMR measurements showed that the degree of alternance of the polythioester was>99 percent, and the mass fraction of the polythioester in the triblock polymer is 45 percent. GPC measurement showed a polymeric molecular weight of 18.2kg/mol and a molecular weight distribution of 1.78. The remaining reaction polymer was purified (the same purification method as in example 1). Slowly adding the 1, 4-dioxane solution of the polythioester into a polythioether solution capped by diisocyanate, adding stannous octoate as a catalyst, continuously reacting for 2 hours, and stopping the reaction. A very small amount of the reaction mixture is taken off for carrying out 1 H NMR and GPC testing. According to 1 H NMR measurement results calculation of polysulphides in triblock polymersThe content of the substituted ester was 35%. GPC measurement showed the polymerization molecular weight to be 213.4kg/mol and the molecular weight distribution to be 1.97. The remaining reaction polymer was purified (the same purification method as in example 1). Adding isotactic polythioester with the opposite configuration to polythioester (with the molar weight equal to that of polythioester in the multiblock polymer and the molecular weight of 4.5 kg/mol) into the methylene dichloride solution of the multiblock polythioester, stirring the mixture at 30 ℃ in an open way, adding methanol to precipitate the polymer after the methylene dichloride is volatilized, and drying the polymer in vacuum to obtain a white polymer. The thermodynamic property test shows that the glass transition temperature of the obtained polythioester-based thermoplastic elastomer is-45 ℃, the melting point is 158 ℃, and the mechanical property test shows that the obtained polythioester-based thermoplastic elastomer has the tensile strength at break of 57MPa and the elongation at break of 700 percent.
Example 7
A100 mL reaction flask equipped with magnetons was dried at 120 ℃ for 12 hours or more, evacuated to room temperature, and flushed with nitrogen gas for use. Weighing appropriate amount of KH and poly (1, 2-propylene glycol) (M) at room temperature under nitrogen protection n =40kg/mol, PDI = 1.10), after 10min of reaction, 1, 4-dioxane was added as solvent, optically pure cyclic sulfanoalkane 1c and cyclic thioanhydride 2a were added to the reaction system in equimolar ratio, reaction was continued at 25 ℃ for 10h, stirring was stopped, and a very small amount of the reaction mixture was taken out for proceeding 1 H NMR and GPC testing. 1 H NMR measurements showed that the degree of alternance of the polythioester was>99 percent, and the mass fraction of the polythioester in the triblock polymer is 50 percent. GPC measurement showed a polymeric molecular weight of 82.3kg/mol and a molecular weight distribution of 1.71. The remaining reaction polymer was purified (the same purification method as in example 1). Mixing two multiblock polythioester stereocomplex with opposite configuration, dissolving with dichloromethane, stirring at 30 deg.C, adding methanol to precipitate, and vacuum drying to obtain white polymer. The thermodynamic property test shows that the glass transition temperature of the obtained polythioester-based thermoplastic elastomer is-58 ℃ and the melting point is 160 ℃. The mechanical property test shows that the obtained polythioester-based thermoplastic elastomer has breaking tensionThe strength was 30MPa and the elongation at break was 630%.
Claims (10)
1. The polythioester and the stereocomplex-based thermoplastic elastomer thereof are characterized in that the polythioester and the stereocomplex-based thermoplastic elastomer thereof are three-block or multi-block polymers which are hard-block or hard-block polymers, wherein the three-block or multi-block polymers are formed by connecting high glass transition temperature or crystalline polythioester or a stereocomplex of the polythioester as a hard block and low glass transition temperature polyether or polythioether as a soft block by a chain transfer method or a chain extension method; wherein the proportion of soft and hard segments in the triblock or multiblock polymer is adjustable; the glass transition temperature of the hard segment is more than 100 ℃, and the glass transition temperature of the soft segment is less than-40 ℃.
2. The polythioester and stereocomplex-based thermoplastic elastomer thereof as claimed in claim 1, wherein said triblock or multiblock polymer has the following structure:
segment one: the polythioester hard segment is a polythioester stereocomplex formed by stereocomplex of atactic polythioester, crystalline isotactic polythioester or two isotactic polythioesters with opposite configurations, which are formed by alternating copolymerization of episulfide alkane and cyclic anhydride and have high glass transition temperature; wherein, the crystalline polythioester is obtained by the high regioselectivity of chiral episulfide alkane and cyclic thioanhydride or the high stereoselectivity copolymerization of meso-episulfide alkane and cyclic thioanhydride; the general structural formula of each substance is as follows:
wherein: r 1 ～R 4 Is a cycloalkane or a cyclic thioanhydride, R 1 ～R 4 May be the same or different;
and a second chain segment: the polyether or polythioether soft segment is polyether polyol formed by homopolymerization of propylene oxide or polythioether polythiol formed by homopolymerization of cyclopropane, and the structural formula is as follows:
3. the polythioester or the stereocomplex-based thermoplastic elastomer thereof as claimed in claim 2, wherein,
the structural formula of the episulfide alkane is as follows:
the structural formula of the cyclic thioanhydride is as follows:
the soft block is poly (1, 2-propanedithiol) polythiol or polythioether polythiol formed by homopolymerizing cyclane in polythiol as an initiator.
4. The polythioester or the stereocomplex-based thermoplastic elastomer thereof as claimed in claim 2, wherein,
the chain transfer method is characterized in that polyether polyol or polythioether polythiol is used as a macroinitiator to initiate the alternating copolymerization reaction of cyclic thioalkane and cyclic thioanhydride in situ to form a polythioester elastomer with a 'hard' -soft '-hard' triblock structure;
the chain extension method is characterized in that polyether polyol or polythioether soft segments are reacted with excessive diisocyanate to form isocyanate-terminated polyether or polythioether soft segments, and then the isocyanate-terminated polyether or polythioether soft segments are reacted with polythioester hard segments or polythioester with a triblock structure to form the high-molecular-weight multiblock polythioester elastomer.
5. The polythioester and its stereocomplex-based thermoplastic elastomer as claimed in claim 1,2, 3 or 4, wherein said triblock or multiblock polymer has an adjustable ratio of soft segments to hard segments, and the hard segment content is: 30 to 70 weight percent.
6. The polythioester and stereocomplex-based thermoplastic elastomer thereof as claimed in claim 5, wherein said triblock or multiblock polymer has an adjustable ratio of soft segments to hard segments, and the hard segment content is: 35wt%.
7. The polythioester stereocomplex-based thermoplastic elastomer according to claim 1,2, 3 or 4, wherein said polythioester stereocomplex-based thermoplastic elastomer is characterized in that isotactic polythioester triblock or multiblock polymer is physically blended with isotactic polythioester having an opposite configuration or with triblock or multiblock polythioester having a molar ratio of polythioester segment 1.
8. The polythioester and the stereocomplex-based thermoplastic elastomer thereof as claimed in claim 1,2, 3 or 4,
the solvents adopted in the preparation of the polythioester and the stereocomplex-based thermoplastic elastomer are dichloromethane, methanol, tetrahydrofuran, 1, 4-dioxane or ethylene glycol dimethyl ether;
the preparation temperature of the polythioester and the stereocomplex-based thermoplastic elastomer thereof is 25-80 ℃.
9. The polythioester and the stereocomplex thereof based on thermoplastic elastomer as claimed in claim 1,2, 3 or 4, wherein said polythioester and said stereocomplex thereof based on thermoplastic elastomer have a number average molecular weight of 30.0 to 200.0kg/mol.
10. The polythioester and the stereocomplex thereof based on thermoplastic elastomer as claimed in claim 1,2, 3 or 4, wherein said polythioester and said stereocomplex thereof based on thermoplastic elastomer have a window temperature of-60 to 160 ℃, a tensile strength at break of 10 to 60MPa and an elongation at break of 200 to 750%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20070265367A1 (en) * | 2003-11-17 | 2007-11-15 | Bi Le-Khac | Ultraviolet-curable polyols and polyurethane compositions made therefrom |
| CN106243319A (en) * | 2016-07-28 | 2016-12-21 | 上海维凯光电新材料有限公司 | Aqueous polyurethane emulsion of resistance to bending and preparation method thereof |
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| CN109134836A (en) * | 2018-08-26 | 2019-01-04 | 苏州大学 | A kind of polyester elastomer and the preparation method and application thereof that can be crosslinked with metallic ion coordination |
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- 2022-08-24 CN CN202211016938.3A patent/CN115417995A/en not_active Withdrawn
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|---|---|---|---|---|
| US20070265367A1 (en) * | 2003-11-17 | 2007-11-15 | Bi Le-Khac | Ultraviolet-curable polyols and polyurethane compositions made therefrom |
| CN107573483A (en) * | 2016-07-04 | 2018-01-12 | 科思创聚合物（中国）有限公司 | Curable composition, polythiourethane and its application for polythiourethane |
| CN106243319A (en) * | 2016-07-28 | 2016-12-21 | 上海维凯光电新材料有限公司 | Aqueous polyurethane emulsion of resistance to bending and preparation method thereof |
| CN109134836A (en) * | 2018-08-26 | 2019-01-04 | 苏州大学 | A kind of polyester elastomer and the preparation method and application thereof that can be crosslinked with metallic ion coordination |
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