CN115785471B - Carbon dioxide-based supermolecular polymer and preparation method and application thereof - Google Patents
Carbon dioxide-based supermolecular polymer and preparation method and application thereof Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 105
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920000642 polymer Polymers 0.000 title abstract description 66
- 150000003077 polyols Chemical class 0.000 claims abstract description 91
- 229920005862 polyol Polymers 0.000 claims abstract description 89
- 230000001070 adhesive effect Effects 0.000 claims abstract description 83
- 239000000853 adhesive Substances 0.000 claims abstract description 66
- 229920002677 supramolecular polymer Polymers 0.000 claims abstract description 40
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 35
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 35
- 230000002441 reversible effect Effects 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 230000003993 interaction Effects 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002023 wood Substances 0.000 claims abstract description 13
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
- 239000010959 steel Substances 0.000 claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 8
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 8
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000006260 foam Substances 0.000 claims abstract description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 239000000741 silica gel Substances 0.000 claims abstract description 4
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 4
- 239000000919 ceramic Substances 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 96
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 61
- 239000001263 FEMA 3042 Substances 0.000 claims description 61
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 61
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 61
- 235000015523 tannic acid Nutrition 0.000 claims description 61
- 229940033123 tannic acid Drugs 0.000 claims description 61
- 229920002258 tannic acid Polymers 0.000 claims description 61
- 239000011259 mixed solution Substances 0.000 claims description 44
- 239000003960 organic solvent Substances 0.000 claims description 37
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 12
- BJRNKVDFDLYUGJ-RMPHRYRLSA-N hydroquinone O-beta-D-glucopyranoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=C(O)C=C1 BJRNKVDFDLYUGJ-RMPHRYRLSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 8
- WMBWREPUVVBILR-WIYYLYMNSA-N (-)-Epigallocatechin-3-o-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=C(O)C=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-WIYYLYMNSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- AFSDNFLWKVMVRB-UHFFFAOYSA-N Ellagic acid Chemical compound OC1=C(O)C(OC2=O)=C3C4=C2C=C(O)C(O)=C4OC(=O)C3=C1 AFSDNFLWKVMVRB-UHFFFAOYSA-N 0.000 claims description 6
- ATJXMQHAMYVHRX-CPCISQLKSA-N Ellagic acid Natural products OC1=C(O)[C@H]2OC(=O)c3cc(O)c(O)c4OC(=O)C(=C1)[C@H]2c34 ATJXMQHAMYVHRX-CPCISQLKSA-N 0.000 claims description 6
- 229920002079 Ellagic acid Polymers 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- WMBWREPUVVBILR-UHFFFAOYSA-N GCG Natural products C=1C(O)=C(O)C(O)=CC=1C1OC2=CC(O)=CC(O)=C2CC1OC(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-UHFFFAOYSA-N 0.000 claims description 6
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 claims description 6
- 235000005487 catechin Nutrition 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- 235000004132 ellagic acid Nutrition 0.000 claims description 6
- 229960002852 ellagic acid Drugs 0.000 claims description 6
- 229940030275 epigallocatechin gallate Drugs 0.000 claims description 6
- 235000004515 gallic acid Nutrition 0.000 claims description 6
- 229940074391 gallic acid Drugs 0.000 claims description 6
- FAARLWTXUUQFSN-UHFFFAOYSA-N methylellagic acid Natural products O1C(=O)C2=CC(O)=C(O)C3=C2C2=C1C(OC)=C(O)C=C2C(=O)O3 FAARLWTXUUQFSN-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 claims description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 229960000271 arbutin Drugs 0.000 claims description 5
- 125000004965 chloroalkyl group Chemical group 0.000 claims description 5
- 229950001002 cianidanol Drugs 0.000 claims description 5
- BJRNKVDFDLYUGJ-UHFFFAOYSA-N p-hydroxyphenyl beta-D-alloside Natural products OC1C(O)C(O)C(CO)OC1OC1=CC=C(O)C=C1 BJRNKVDFDLYUGJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000001816 cooling Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229920006237 degradable polymer Polymers 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000123 paper Substances 0.000 abstract 1
- 229920001864 tannin Polymers 0.000 description 25
- 239000001648 tannin Substances 0.000 description 25
- 235000018553 tannin Nutrition 0.000 description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- 239000000463 material Substances 0.000 description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 12
- 230000006872 improvement Effects 0.000 description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000004043 responsiveness Effects 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920000379 polypropylene carbonate Polymers 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallyl group Chemical group C1(=C(C(=CC=C1)O)O)O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical compound N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001765 catechin Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention belongs to the field of degradable polymers, and discloses a carbon dioxide-based supermolecular polymer which is formed by interaction of carbon dioxide-based polyol and polyphenol through hydrogen bonds. The invention also discloses a preparation method and application of the carbon dioxide-based supramolecular polymer, wherein the preparation method does not need a complicated synthesis process and only needs to be obtained by a solution blending mode; the carbon dioxide-based supramolecular polymer can be applied as a degradable adhesive, especially a reversible adhesive, for adhesion of various substrates such as glass, paper, steel sheet, polymethyl methacrylate, polytetrafluoroethylene, polyethylene terephthalate, polyvinyl chloride, silica gel, wood, polyvinyl chloride foam, ceramic tile, paper, etc. The adhesive has high environmental friendliness, high adhesive strength and high adhesion speed, and can realize quick adhesion after being cooled to room temperature; reversible repeated recycling can be realized by a heating-cooling mode.
Description
Technical Field
The invention belongs to the technical field of degradable polymers, and particularly relates to a carbon dioxide-based supermolecular polymer, and a preparation method and application thereof.
Background
The adhesive is widely applied in daily life and industrial fields, but most adhesives (such as acrylic adhesives, phenolic adhesives, polyurethane adhesives and the like) in the prior art are non-biodegradable and non-biocompatible adhesives, and have the problems of poor cycle reversibility, biodegradability and the like. In addition, the adhesive strength of an adhesive is determined by both the surface energy and the cohesive energy of the adhesive, which are related to the viscoelastic properties of the material itself. The viscoelastic properties of the adhesive affect the wettability of the adhesive to the substrate, the interfacial interaction between the adhesive and the substrate material. Thus, adhesives with high adhesive properties should be liquid-like, but the lower cohesive energy of such adhesives results in reduced adhesive properties. Conversely, adhesives with high cohesive energy should be solid, but the adhesive strength of the adhesive to the substrate material is not high, which in turn reduces the adhesive properties (Angew.Chem., int.Ed.,2019,58 (3): 696-714). It is a challenge how to design a reversible adhesive with high adhesive strength.
The super molecular polymer has the functions of modularization, reversible self-assembly, stimulus response and the like due to the dynamic reversibility of non-covalent bonds. Thus, the adhesive strength of the adhesive can be controlled by introducing non-covalent interactions into the adhesive. Based on the dynamic reversibility of the non-covalent interactions, it is possible to impart reversible binding functions to the adhesive, while imparting biodegradability to the adhesive (j.am. Chem. Soc.2020,142,11, 5371-5379).
For the biodegradability of the adhesive, the poly (carbonate-ether) polyol is a carbon dioxide-based polymer synthesized by taking carbon dioxide and an epoxy compound as raw materials through a catalyst, has biocompatibility and biodegradability, and becomes one of the biodegradable polymers with the most application prospect. The polymer not only can solve the problem of white pollution, but also can utilize carbon dioxide as C1 resource to achieve the purpose of 'one stone and two birds'. The method is applied to the fields of biomedical materials, agriculture, packaging, new energy and the like (prog.in Polymer Science,2018, 80:163-182). However, carbon dioxide-based polymers have the problems of low adhesive strength and no stimulus responsiveness, and are generally difficult to apply directly to reversible adhesives.
In the prior art, a carbon dioxide-based polymer is grafted on a supermolecule group through a covalent bond so as to prepare the carbon dioxide-based supermolecule polymer, but the preparation process is complicated, and the synthetic adhesive has the defects of complex synthetic process, high cost, environmental protection and the like. Therefore, the development of the environment-friendly reversible adhesive with wide application range has important significance.
Disclosure of Invention
In view of one or more of the above-mentioned drawbacks or improvements of the prior art, the present invention provides a carbon dioxide-based supramolecular polymer, a method for preparing the same, and applications thereof, which utilize biodegradable carbon dioxide-based polyols and polyphenols to obtain a carbon dioxide-based supramolecular material by means of simple solution blending, which has good biodegradability and biocompatibility, and has good adhesive properties, in particular reversible adhesive properties (stimulus responsiveness to heat). In addition, the carbon dioxide-based supramolecular polymer not only can utilize carbon dioxide, but also can realize sustainable development of environment and resources.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a carbon dioxide-based supramolecular polymer formed by hydrogen bonding interaction of a carbon dioxide-based polyol and a polyphenol, the molar ratio of the polyphenol to the carbon dioxide-based polyol being 1:1 to 1:6.
As a further improvement of the present invention, the carbon dioxide-based polyol is one of a poly (carbonate-ether) diol, a poly (carbonate-ether) triol or a poly (carbonate-ether) tetrol, the carbon dioxide-based polyol having the following structure:
wherein ,indicating core->Representing an arm;
the nucleus is any one of cyclic polyphosphazene, aliphatic, benzene ring and polycyclic aromatic hydrocarbon; the core has the structural formula of Wherein represents a junction site;
the arm is poly (carbonate-ether), and the molecular structure of the arm is shown as a formula (I):
wherein ,R1 Selected from C1-C10 alkyl, -H or chloroalkyl; x is an integer of 2 to 50; y is an integer of 2 to 50; * Representing the ligation site.
As a further improvement of the invention, the carbon dioxide-based polyol is synthesized by taking carbon dioxide and an epoxy compound as raw materials.
As a further improvement of the present invention, the polyphenol includes any one or more of tannic acid, gallic acid, ellagic acid, epigallocatechin gallate, catechin or arbutin.
According to a second aspect of the present invention, there is provided a method for preparing a carbon dioxide-based supramolecular polymer, comprising the steps of:
adding the carbon dioxide-based polyol and the polyphenol into an organic solvent, and uniformly stirring to obtain a mixed solution; and drying the mixed solution to obtain the carbon dioxide-based supramolecular polymer.
As a further improvement of the present invention, the molar ratio of the polyphenol to the carbon dioxide-based polyol is 1:1 to 1:6; the molar ratio of the carbon dioxide-based polyol to the organic solvent is 1:5-1:30.
As a further improvement of the present invention, the carbon dioxide-based polyol is one of a poly (carbonate-ether) diol, a poly (carbonate-ether) triol or a poly (carbonate-ether) tetrol, the carbon dioxide-based polyol having the following structure:
wherein ,indicating core->Representing an arm;
the nucleus is any one of cyclic polyphosphazene, aliphatic, benzene ring and polycyclic aromatic hydrocarbon; the core has the structural formula of Wherein represents a junction site;
the arm is poly (carbonate-ether), and the molecular structure of the arm is shown as a formula (I):
wherein ,R1 Selected from C1-C10 alkyl, -H or chloroalkyl; x is an integer of 2 to 50; y is an integer of 2 to 50; * Representing the ligation site.
As a further improvement of the invention, the carbon dioxide-based polyol is synthesized by taking carbon dioxide and an epoxy compound as raw materials.
As a further improvement of the present invention, the polyphenol includes any one or more of tannic acid, gallic acid, ellagic acid, epigallocatechin gallate, catechin or arbutin.
As a further improvement of the present invention, the organic solvent includes any one or more of acetone, ethyl acetate, tetrahydrofuran, dimethyl sulfoxide, dioxane, and N, N-dimethylformamide.
As a further improvement of the invention, the drying temperature is 30-100 ℃.
According to a third aspect of the present invention there is provided the use of a carbon dioxide-based supramolecular polymer as an adhesive, the carbon dioxide-based supramolecular polymer being obtainable by said carbon dioxide-based supramolecular polymer or by a process for the preparation of said carbon dioxide-based supramolecular polymer, said adhesive being a heat-sensitive reversible adhesive, for adhering to a substrate, said substrate comprising glass, steel sheet, polymethyl methacrylate, polytetrafluoroethylene, polyethylene terephthalate, polyvinyl chloride, silica gel, wood, polyvinyl chloride foam, tile or paper.
Compared with the prior art, the carbon dioxide-based supramolecular polymer is prepared from carbon dioxide-based polyol and polyphenol serving as raw materials. The carbon dioxide-based polyol and the polyphenol are assembled into the intelligent supermolecular material with reversible thermal response and good adhesive property through hydrogen bonding. The carbon dioxide-based supramolecular polymer material prepared by the invention can be especially applied as a reversible adhesive.
The carbon dioxide-based supermolecular polymer adopts the carbon dioxide-based polyol and the polyphenol as main components of the supermolecular material, so that the high added value utilization of carbon dioxide can be realized, the material is endowed with good biodegradability and biocompatibility, and meanwhile, the adhesive strength of the carbon dioxide-based supermolecular polymer can be further regulated by regulating the topological structure, the molecular weight and the polycarbonate content of the carbon dioxide-based polyol and the proportion of the carbon dioxide-based polyol and the polyphenol. In addition, the carbon dioxide-based supermolecular material structure formed by hydrogen bond interaction between the carbon dioxide-based polyol and the polyphenol has reversible adhesive property.
Polyphenols are a generic term for polyhydroxy phenols and are widely derived from plants. Polyphenols include Tannins (TA), gallic acid, ellagic acid, epigallocatechin gallate, catechins, arbutins, and the like, and the polyphenols have multiple hydrophobic aromatic rings and hydrophilic hydroxyl groups that provide them with abundant reactive sites for covalent interactions with substrates, and also can interact with other groups or species through non-covalent interactions such as hydrogen bonding, hydrophobic interactions, coordination bonds, and van der waals forces. Polyphenols can be used for preparing biological materials with stimulating response due to their advantages of biocompatibility and biodegradability.
Since polyphenols contain catechol or pyrogallol groups that can act as hydrogen bond donors, the carbonyl groups and ether linkages in poly (carbonate-ether) polyols act as hydrogen bond acceptors, with strong hydrogen bond interactions between the two. Thus, carbon dioxide based polymers and polyphenols can be built into supramolecular materials. The supermolecular material also has thermal responsiveness due to the hydrogen bonding also has thermal responsiveness.
In addition, the preparation condition of the carbon dioxide-based supramolecular polymer is mild, the operation is simple, and the method is suitable for large-scale production. The novel green degradable reversible supermolecule adhesive can be prepared by a simple method, and has important significance for realizing the current double-carbon target.
In general, the above technical solutions conceived by the present invention have the following beneficial effects compared with the prior art:
(1) The biodegradable carbon dioxide-based supermolecular material is obtained by utilizing the biodegradable carbon dioxide-based polyol and polyphenol through a simple solution blending mode, has reversible adhesive property, good biodegradability and biocompatibility, and good adhesive property, and simultaneously has good stimulus responsiveness to heat.
(2) The carbon dioxide-based supramolecular polymer improves the interaction force of the carbon dioxide-based polyol through hydrogen bonding, and improves the glass transition temperature of the carbon dioxide-based supramolecular polymer. Glass transition temperature (T) of polymer g ) Regarding the mechanical properties and cohesive strength of the polymer, it is generally believed that the higher the glass transition temperature, the greater its cohesive strength. The greater the bond strength over a range of temperatures.
(3) The invention can adjust the adhesive strength of the carbon dioxide-based supermolecular polymer by changing the proportion of polyphenol and carbon dioxide-based polyol, the carbonate content in the carbon dioxide-based polyol, the molecular weight and the topological structure of the carbon dioxide-based polyol, and is suitable for different adhesive requirements.
(4) The preparation method disclosed by the invention does not need a complicated synthesis process, is simple to operate, mild in reaction condition, good in repeatability of the preparation process, low in preparation cost and suitable for large-scale production.
Drawings
FIG. 1 is a Differential Scanning Calorimeter (DSC) curve of a poly (carbonate-ether) polyol/tannin supramolecular polymer prepared in example 4 of the present invention;
FIG. 2 is a graph showing the comparison of the adhesive properties of poly (carbonate-ether) polyol/tannin supermolecular polymer and polypropylene carbonate prepared in example 10 of the present invention;
FIG. 3 is a graph showing the reversible adhesive properties of the poly (carbonate-ether) polyol/tannin supramolecular polymer prepared in example 11 of the present invention (the adhesive substrate is wood);
FIG. 4 is a graph showing the adhesive properties of the poly (carbonate-ether) polyol/tannin supramolecular polymers prepared in examples 13, 14, 15, 16 and 17 of the present invention, the polypropylene glycol/tannin supramolecular polymer prepared in comparative example 1 and the polyethylene glycol/tannin supramolecular polymer prepared in comparative example 2 (the adhesive substrate is a steel sheet);
FIG. 5 is a graph showing the results of the adhesion performance of the poly (carbonate-ether) polyol/tannin supramolecular polymers prepared in examples 15, 18, 19, 20 of the present invention (the adhesion substrate is a steel sheet).
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The carbon dioxide-based supermolecular polymer is formed by interaction of carbon dioxide-based polyol and polyphenol through hydrogen bonds, and the molar ratio of the polyphenol to the carbon dioxide-based polyol is 1:1-1:6.
Specifically, the carbon dioxide-based polyol is one of poly (carbonate-ether) diol, poly (carbonate-ether) triol or poly (carbonate-ether) tetraol; the carbon dioxide based polyol has the following structure:
wherein ,indicating core->Representing an arm;
further, the nucleus is any one of cyclotriphosphazene, aliphatic, benzene ring and polycyclic aromatic hydrocarbon; the core has the structural formula of Wherein represents a junction site;
further, the arm is poly (carbonate-ether), and the molecular structure of the arm is shown as a formula (I):
wherein ,R1 Selected from C1-C10 alkyl, -H or chloroalkyl, preferably-H, -CH 3 The method comprises the steps of carrying out a first treatment on the surface of the x and y are polymerization degree, x is an integer of 2 to 50, y is an integer of 2 to 50, preferably x is an integer of 3 to 30, and y is an integer of 3 to 30; * Representing the ligation site.
The carbon dioxide-based polyol is synthesized by using carbon dioxide and an epoxy compound as raw materials, and the method is the prior art and is not described herein.
Further, the polyphenol includes any one or more of tannic acid, gallic acid, ellagic acid, epigallocatechin gallate, catechin or arbutin, preferably tannic acid.
Further, the preparation method of the carbon dioxide-based supramolecular polymer comprises the following steps:
adding the carbon dioxide-based polyol and the polyphenol into an organic solvent, and uniformly stirring to obtain a mixed solution; and drying the mixed solution to obtain the carbon dioxide-based supramolecular polymer.
Preferably, the molar ratio of the carbon dioxide-based polyol to the organic solvent is 1:5-1:30, and the organic solvent is further preferably any one or more of acetone, ethyl acetate, tetrahydrofuran, dimethyl sulfoxide, dioxane and N, N-dimethylformamide.
Preferably, the drying temperature is 30-100 ℃, i.e. the mixed solution volatilizes the solvent at 30-100 ℃, to accelerate the volatilization of the solvent. In addition, the stirring is preferably performed at a certain temperature to accelerate the dissolution of the solvent, but in the production method of the present invention, the temperature is not limited, and complete dissolution may be achieved.
The carbon dioxide-based supramolecular polymer can be used as a thermosensitive reversible adhesive and applied to adhesion substrates, wherein the substrates comprise glass, steel sheets, polymethyl methacrylate, polytetrafluoroethylene, polyethylene terephthalate, polyvinyl chloride, silica gel, wood, polyvinyl chloride foam, ceramic tiles or paper.
After the substrate is adhered, heating to de-adhere the adhered substrate; after the de-adhered base material is heated, cooling is carried out again, and the adhesion of the base material can be realized; multiple cycles of adhesion-de-adhesion of the substrate can be achieved by means of heating-cooling. The adhesive has high environmental friendliness, high adhesive strength and high adhesion speed, and can realize quick adhesion after being cooled to room temperature; reversible repeated recycling can be realized by a heating-cooling mode.
The reagents used in the present invention may be commercially available or may be prepared by any of the methods described in the prior art.
The invention prepares the carbon dioxide-based supermolecular polymer by using the biodegradable carbon dioxide-based polyol prepared by carbon dioxide and epoxy compounds and polyphenol through a simple solution blending mode. The material has good thermal reversible response and reversible adhesive property; and is friendly to the environment, and can meet the requirements of biodegradable adhesives. According to the invention, the proportion of the polyphenol and the carbon dioxide-based polyol is controlled by selecting the carbon dioxide-based polyol with different structures, so that the carbon dioxide-based supermolecular polymer with different bonding strengths is obtained, the bonding strength of the carbon dioxide-based supermolecular polymer to steel sheets is 0.7-8.3 MPa, the bonding strength to wood is 4-9.8 MPa, the bonding strength to glass is 2.4-6.0 MPa, and the bonding strength to heterogeneous interfaces of the wood and the steel sheets is 2.4-5.0 MPa; the substrate (wood) can be reversibly cycled 4 times by heating without substantially attenuating the adhesive strength.
For a better illustration and understanding of the products, methods of preparation and uses of the invention, the following specific examples are provided:
example 1
15mol of core is taken asArms x=3, y=9, R 1 Poly (carbonate-ether) tetrahydric alcohol selected from-H and 5.1 kg (3 mol) tannic acid are added into 450mol of ethyl acetate, the mixture is stirred uniformly at 30 ℃ to obtain a mixed solution, the mixed solution is volatilized into an organic solvent at 30 ℃, and the organic solvent is dried to obtain the poly (carbonate-ether) polyatomic alcohol/tannic acid supermolecular polymer.
Example 2
15mol of core is taken asArms x=3, y=10, R 1 Poly (carbonate-ether) triol selected from-H and 25.5 kg (15 mol) tannic acid are added into 75mol of acetone, the mixture is stirred uniformly at 30 ℃ to obtain a mixed solution, the mixed solution is volatilized into an organic solvent at 40 ℃, and the organic solvent is dried to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
Example 3
15mol of core is taken asArms x=10, y=30, R 1 Poly (carbonate-ether) glycol selected from-H and 25.5 kg (15 mol) tannic acid are added into 150mol of N, N-dimethylformamide, the mixture is stirred uniformly at 60 ℃ to obtain a mixed solution, the mixed solution is volatilized into an organic solvent at 60 ℃, and the organic solvent is dried to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
Example 4
10mol of core is taken asArms x=10, y=3, R 1 Selected from-CH 3 Adding poly (carbonate-ether) tetraol and 8.5 kg (5 mol) tannic acid into 100mol tetrahydrofuran, stirring uniformly at 40 ℃ to obtain a mixed solution, volatilizing an organic solvent at 60 ℃, and drying to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
The DSC graph of the resulting poly (carbonate-ether) polyol/tannin supermolecular polymer is shown in FIG. 1.
Example 5
10mol of core is taken asArms x=18, y=8, R 1 Selected from-CH 3 Adding 8.5 kg (5 mol) tannic acid and poly (carbonate-ether) dihydric alcohol into 100mol dimethyl sulfoxide, stirring uniformly at 40 ℃ to obtain a mixed solution, volatilizing an organic solvent at 100 ℃, and drying to obtain the poly (carbonate-ether) polyhydric alcohol/tannic acid supermolecular polymer.
Example 6
Nucleation of 30mol intoArms x=30, y=3, R 1 Adding poly (carbonate-ether) tetrahydric alcohol selected from-H and 8.5 kg (5 mol) tannic acid into 150mol dioxane, stirring at 40deg.C to obtain mixtureAnd (3) mixing the solutions, volatilizing the organic solvent at 60 ℃, and drying to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
Example 7
50mol of the core is taken asArms x=10, y=7, R 1 Selected from-CH 3 Adding 17 kg (10 mol) of tannic acid and 17 kg (10 mol) of poly (carbonate-ether) glycol into 250mol of dioxane, stirring uniformly at 40 ℃ to obtain a mixed solution, volatilizing an organic solvent at 60 ℃ from the mixed solution, and drying to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
Example 8
Nucleation of 30mol intoArms x=13, y=30, R 1 Poly (carbonate-ether) glycol selected from-H, and 17 kg (10 mol) of tannic acid are added into 900mol of N, N-dimethylformamide, the mixture is stirred uniformly at 40 ℃ to obtain a mixed solution, the mixed solution is volatilized into an organic solvent at 60 ℃, and the organic solvent is dried to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
Example 9
10mol of core is taken asArms x=25, y=10, R 1 Poly (carbonate-ether) glycol selected from-H and 3.4 kg (2 mol) tannic acid are added into 300mol of N, N-dimethylformamide, the mixture is stirred uniformly at 40 ℃ to obtain a mixed solution, the mixed solution is volatilized into an organic solvent at 100 ℃, and the organic solvent is dried to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
Example 10
20mol of the core is taken asArms x=23, y=10, R 1 Selected from-CH 3 Adding 34 kg (20 mol) of tannic acid and poly (carbonate-ether) triol into 400mol of acetone, stirring uniformly at 40 ℃ to obtain a mixed solution, volatilizing an organic solvent at 60 ℃ from the mixed solution, and drying to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
The adhesive properties of the resulting poly (carbonate-ether) polyol/tannin supermolecular polymer are shown in FIG. 2.
Example 11
100mol of the core is taken asArms x=22, y=5, R 1 Selected from-CH 3 Adding 34 kg (20 mol) of tannic acid and poly (carbonate-ether) tetraol into 500mol of acetone, stirring uniformly at 30 ℃ to obtain a mixed solution, volatilizing an organic solvent at 30 ℃, and drying to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
The reversible adhesion properties of the resulting poly (carbonate-ether) polyol/tannin supermolecular polymer are shown in FIG. 3.
Example 12
Nucleation of 30mol intoArms x=3, y=30, R 1 Poly (carbonate-ether) triol selected from-H and 25.5 kg (15 mol) tannic acid are added into 150mol of ethyl acetate, the mixture is stirred uniformly at 40 ℃ to obtain a mixed solution, the mixed solution is volatilized into an organic solvent at 60 ℃, and the organic solvent is dried to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
Example 13
17mol of core is taken asArms x=24, y=5, R 1 Selected from-CH 3 Poly (carbonate-ether) glycol and 17 kg (10 mol) of tannic acid are added into 250mol of dioxane, and stirred uniformly at 40 ℃ to obtain a mixed solution,volatilizing the organic solvent at 60 ℃ from the mixed solution, and drying to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
The reversible adhesion properties of the resulting poly (carbonate-ether) polyol/tannin supermolecular polymer are shown in FIG. 4.
Example 14
17mol of core is taken asArms x=23, y=6, R 1 Selected from-CH 3 Adding 17 kg (10 mol) of tannic acid and poly (carbonate-ether) glycol into 250mol of chloroform, stirring uniformly at 40 ℃ to obtain a mixed solution, volatilizing an organic solvent at 50 ℃, and drying to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
The reversible adhesion properties of the resulting poly (carbonate-ether) polyol/tannin supermolecular polymer are shown in FIG. 4.
Example 15
17mol of core is taken asArms x=21, y=9, R 1 Selected from-CH 3 Adding 17 kg (10 mol) of tannic acid and 17 kg (10 mol) of poly (carbonate-ether) glycol into 150mol of ethyl acetate, stirring uniformly at 40 ℃ to obtain a mixed solution, volatilizing an organic solvent at 60 ℃ from the mixed solution, and drying to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
The reversible adhesion properties of the resulting poly (carbonate-ether) polyol/tannin supermolecular polymer are shown in FIG. 4.
Example 16
17mol of core is taken asArms x=19, y=10, R 1 Selected from-CH 3 Adding 17 kg (10 mol) of tannic acid and poly (carbonate-ether) glycol into 150mol of ethyl acetate, stirring at 40deg.C to obtain mixed solution, and addingThe mixed solution volatilizes the organic solvent at 50 ℃, and the poly (carbonate-ether) polyol/tannic acid supermolecular polymer is obtained after drying.
The reversible adhesion properties of the resulting poly (carbonate-ether) polyol/tannin supermolecular polymer are shown in FIG. 4.
Example 17
17mol of core is taken asArms x=19, y=13, R 1 Selected from-CH 3 Adding 17 kg (10 mol) of tannic acid and 17 kg (10 mol) of poly (carbonate-ether) glycol into 150mol of ethyl acetate, stirring uniformly at 40 ℃ to obtain a mixed solution, volatilizing an organic solvent at 70 ℃ from the mixed solution, and drying to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
The reversible adhesion properties of the resulting poly (carbonate-ether) polyol/tannin supermolecular polymer are shown in FIG. 4.
Example 18
13mol of core is taken asArms x=21, y=9, R 1 Selected from-CH 3 Adding 17 kg (10 mol) of tannic acid and 17 kg (10 mol) of poly (carbonate-ether) glycol into 150mol of ethyl acetate, stirring uniformly at 40 ℃ to obtain a mixed solution, volatilizing an organic solvent at 60 ℃ from the mixed solution, and drying to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
The reversible adhesion properties of the resulting poly (carbonate-ether) polyol/tannin supermolecular polymer are shown in FIG. 5.
Example 19
21mol of the core is taken asArms x=21, y=9, R 1 Selected from-CH 3 Adding 17 kg (10 mol) of tannic acid and 17 kg (10 mol) of poly (carbonate-ether) glycol into 250mol of ethyl acetate, stirring uniformly at 40 ℃ to obtain a mixed solution, mixing the aboveVolatilizing the organic solvent at 60 ℃ and drying the mixed solution to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
The reversible adhesion properties of the resulting poly (carbonate-ether) polyol/tannin supermolecular polymer are shown in FIG. 5.
Example 20
The 26mol core is taken asArms x=21, y=9, R 1 Selected from-CH 3 Adding 17 kg (10 mol) of tannic acid and poly (carbonate-ether) glycol into 200mol of chloroform, stirring uniformly at 40 ℃ to obtain a mixed solution, volatilizing an organic solvent at 60 ℃, and drying to obtain the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
The reversible adhesion properties of the resulting poly (carbonate-ether) polyol/tannin supermolecular polymer are shown in FIG. 5.
Comparative example 1
17mol of polypropylene glycol (number average molecular weight 2000, available from Aba Ding Shiji Co., ltd.) and 17 kg (10 mol) of tannic acid were added to 200mol of acetone, and the mixture was stirred uniformly at 40℃to obtain a mixed solution, and the mixed solution was subjected to evaporation of an organic solvent at 60℃and dried to obtain a polypropylene glycol/tannic acid supermolecular polymer.
The reversible adhesion performance of the prepared polypropylene glycol/tannic acid supermolecular polymer is shown in figure 4.
Comparative example 2
17mol of polyethylene glycol (number average molecular weight 2000, available from Aba Ding Shiji Co., ltd.) and 17 kg (10 mol) of tannic acid were added to 200mol of acetone, and stirred uniformly at 40℃to obtain a mixed solution, and the mixed solution was volatilized into an organic solvent at 60℃and dried to obtain a polyethylene glycol/tannic acid supermolecular polymer.
The reversible adhesion performance of the prepared polyethylene glycol/tannic acid supermolecular polymer is shown in figure 4.
Further, the products prepared in examples and comparative examples were subjected to performance test by the following test methods:
differential scanning thermal analysis (DSC) test: the thermal properties of the samples were tested using a TA company Q2000 differential scanning calorimeter. The test sample was first raised from 25 ℃ to 100 ℃ at a rate of 20 ℃/min and held at a constant temperature for 5min to eliminate the heat history. The temperature was reduced to-80℃at a rate of 20℃per minute. Finally, the temperature is raised to 100 ℃ at a speed of 10 ℃/min. The atmosphere is nitrogen.
Adhesive performance test: was performed on a Messaging E44.104 Universal tester according to ASTM D1002-02. The substrates to be bonded were 75mm by 25mm by 1.5mm stainless steel sheet, 75mm by 25mm by 1.5mm wood, 75mm by 25mm by 1.5mm glass sheet, and the drawing speed was 1mm/min. Each sample was tested 5 times in duplicate and averaged.
Reversible adhesion performance test: the overlap joint was placed in an oven at 80 ℃ for 5 minutes to restore the adhesion of the adhesive material, and then the adhesive joint was taken out of the oven and cooled at room temperature. The contact pressure between the two substrates (wood) was provided by two 32mm butterfly clips at a pressure of about 1.3MPa. The test was then carried out on a Messaging E44.104 universal tester according to ASTM D1002-02 at a tensile speed of 1mm/min, and each sample was repeated 5 times to average. The above operation was repeated five times in a cycle.
The test results were as follows:
as shown in the differential scanning thermal analysis (DSC) curve of fig. 1, the poly (carbonate-ether) polyol/tannic acid supramolecular polymer obtained by blending the poly (carbonate-ether) polyol and tannic acid in example 4 can be seen to have a glass transition temperature ranging from-17.5 ℃ to 48.2 ℃, indicating that the interaction force between polymer segments is enhanced by the supramolecular forces and thus the glass transition temperature is significantly raised.
The poly (carbonate-ether) polyol chain structure contains a polycarbonate hard segment and a polyether soft segment, carbonyl groups and ether bonds in the poly (carbonate-ether) polyol are used as hydrogen bond acceptors, polyphenol in tannic acid contains catechol or pyrogallol groups which can be used as hydrogen bond donors, and strong hydrogen bond interaction exists between the two. The carbonate groups in the poly (carbonate-ether) polyol/tannin supramolecular polymer have limited rotatability, higher polarity and higher hardness,thus, as the carbonate content increases, T of its poly (carbonate-ether) diol g And also increases. T of Poly (carbonate-ether) polyol/tannin supermolecular Polymer due to the carbonate content and Hydrogen bond interactions that hinder the movement of the Polymer chain g Increase obviously, its T g Up to 48.2 ℃. Whereas T conventionally produced as high molecular weight polypropylene carbonate g About 25-42 ℃, thus the method is also to solve the T of polypropylene carbonate g A scientific problem that is too low provides a concept.
As shown in the adhesive property test chart of FIG. 2, it can be seen that the adhesive strength of the lap joint made of polypropylene carbonate as an adhesive for bonding wood, stainless steel, glass, wood-stainless steel was 1.8MPa, 0.8MPa, 0.5MPa and 1.2MPa, respectively, and the adhesive strength of the lap joint made of poly (carbonate-ether) polyol/tannic acid supermolecular polymer prepared in example 10 as an adhesive for bonding wood, stainless steel, glass, wood-stainless steel was 9.8MPa, 8.3MPa, 6.0MPa and 5.0MPa, respectively, indicating that the supermolecular force significantly enhanced the adhesive strength of the poly (carbonate-ether) polyol/tannic acid supermolecular polymer.
As shown in the graph of the reversible adhesion test of FIG. 3, it can be seen that the poly (carbonate-ether) polyol/tannin supramolecular polymer prepared in example 11 showed substantially no decay in adhesion strength to wood after four thermal reversible cycles.
As shown in the adhesive property test chart of FIG. 4, it can be seen that the adhesive strength of the polyethylene glycol/tannic acid supermolecular polymer as an adhesive bonding steel sheet is 0.2MPa. The bonding strength of the polypropylene glycol/tannic acid supermolecular polymer serving as an adhesive bonding steel sheet is 0.1MPa, the polypropylene glycol can be regarded as poly (carbonate-ether) without carbon dioxide, and the bonding strength of the material to the steel sheet can be regulated and controlled by the content (the value of X, Y) of the carbon dioxide. The adhesive strength is 0.9-5.7 MPa.
The poly (carbonate-ether) polyol chain structure contains a hard polycarbonate segment and a soft polyether segment. Wherein the hard polycarbonate segment is a segment formed by copolymerization of epoxide and carbon dioxide, the soft polyether segment is a segment formed by homopolymerization of epoxide, the soft polyether segment can improve the capability of material to infiltrate an interface due to flexibility of a molecular chain, and the carbonate group has limited rotatability, higher polarity and higher hardness, so that the adhesive strength is increased with the increase of the carbonate content, and the reason is that the increase of the carbonate content (namely the content of carbon dioxide) can enhance cohesive energy of the super-molecular polymer. When the carbonate content reaches a certain value, the adhesive strength of the poly (carbonate-ether) polyol/tannin supramolecular polymer begins to decrease. The reason for this is that the cohesive energy is larger than the adhesive energy due to the further increase of the carbonate content, so that the adhesive strength thereof is lowered. The adhesive strength of the poly (carbonate-ether) polyol/tannic acid supermolecular polymer can thus be controlled by adjusting the carbonate content (i.e., the carbon dioxide content).
As shown in the adhesive property test chart of FIG. 5, it can be seen that the adhesive strength of the material to the steel sheet can be regulated by the ratio of the poly (carbonate-ether) polyol to the tannic acid, and the adhesive strength is 0.7-5.7 MPa.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The carbon dioxide-based supramolecular polymer is characterized in that the carbon dioxide-based supramolecular polymer is formed by interaction of carbon dioxide-based polyol and polyphenol through hydrogen bonds, and the molar ratio of the polyphenol to the carbon dioxide-based polyol is 1:1-1:6;
the carbon dioxide-based polyol is one of poly (carbonate-ether) diol, poly (carbonate-ether) triol or poly (carbonate-ether) tetraol, and has the following structure:
or->Or->，
wherein ,indicating core->Representing an arm;
the nucleus is any one of cyclic polyphosphazene, aliphatic, benzene ring and polycyclic aromatic hydrocarbon; the core has the structural formula of、/>、/>、/>、/>、/>Wherein represents a junction site;
the arm is poly (carbonate-ether), and the molecular structure of the arm is shown as a formula (I):
formula (I)
wherein ,R1 Selected from C1-C10 alkyl, -H or chloroalkyl; x is an integer of 2 to 50; y is an integer of 2 to 50; * Represents a ligation site;
the polyphenol comprises any one or more of tannic acid, gallic acid, ellagic acid, epigallocatechin gallate, catechin or arbutin.
2. The carbon dioxide-based supramolecular polymer according to claim 1, wherein the carbon dioxide-based polyol is synthesized from carbon dioxide and an epoxy compound.
3. The preparation method of the carbon dioxide-based supramolecular polymer is characterized by comprising the following steps:
adding the carbon dioxide-based polyol and the polyphenol into an organic solvent, and uniformly stirring to obtain a mixed solution; drying the mixed solution to obtain the carbon dioxide-based supramolecular polymer;
the carbon dioxide-based polyol is one of poly (carbonate-ether) diol, poly (carbonate-ether) triol or poly (carbonate-ether) tetraol, and has the following structure:
or->Or->，
wherein ,indicating core->Representing an arm;
the nucleus is any one of cyclic polyphosphazene, aliphatic, benzene ring and polycyclic aromatic hydrocarbon; the core has the structural formula of、/>、/>、/>、/>、/>Wherein represents a junction site;
the arm is poly (carbonate-ether), and the molecular structure of the arm is shown as a formula (I):
formula (I)
wherein ,R1 Selected from C1-C10 alkyl, -H or chloroalkyl; x is an integer of 2 to 50; y is an integer of 2 to 50; * Represents a ligation site;
the polyphenol comprises any one or more of tannic acid, gallic acid, ellagic acid, epigallocatechin gallate, catechin or arbutin.
4. The method for producing a carbon dioxide-based supramolecular polymer according to claim 3, wherein the molar ratio of the polyphenol to the carbon dioxide-based polyol is 1:1 to 1:6; the molar ratio of the carbon dioxide-based polyol to the organic solvent is 1:5-1:30.
5. A method of preparing a carbon dioxide-based supramolecular polymer according to claim 3, wherein the organic solvent comprises any one or more of acetone, ethyl acetate, tetrahydrofuran, dimethyl sulfoxide, dioxane, N-dimethylformamide.
6. The method for producing a carbon dioxide-based supramolecular polymer according to claim 3, wherein the drying temperature is 30 to 100 ℃.
7. Use of a carbon dioxide-based supramolecular polymer as binder, obtained with a carbon dioxide-based supramolecular polymer according to claim 1 or 2 or with a method for the preparation of a carbon dioxide-based supramolecular polymer according to any one of claims 3-6,
the adhesive is a thermosensitive reversible adhesive and is applied to adhesion substrates, wherein the substrates comprise glass, steel sheets, polymethyl methacrylate, polytetrafluoroethylene, polyethylene terephthalate, polyvinyl chloride, silica gel, wood, polyvinyl chloride foam, ceramic tiles or paper.
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