CN114410244B - Supermolecular polymer gel, preparation method thereof and application thereof as adhesive - Google Patents
Supermolecular polymer gel, preparation method thereof and application thereof as adhesive Download PDFInfo
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- CN114410244B CN114410244B CN202111670714.XA CN202111670714A CN114410244B CN 114410244 B CN114410244 B CN 114410244B CN 202111670714 A CN202111670714 A CN 202111670714A CN 114410244 B CN114410244 B CN 114410244B
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- cyclodextrin
- polymer gel
- adhesive
- carboxyl
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 54
- 239000000853 adhesive Substances 0.000 title claims abstract description 51
- 229920000642 polymer Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 36
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 28
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims description 11
- 229920002677 supramolecular polymer Polymers 0.000 claims description 11
- 239000001116 FEMA 4028 Substances 0.000 claims description 9
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 9
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 9
- 229960004853 betadex Drugs 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 6
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 6
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 2
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 12
- 239000003960 organic solvent Substances 0.000 abstract description 10
- 230000003670 easy-to-clean Effects 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 230000002411 adverse Effects 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 32
- 239000011521 glass Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 13
- 238000009864 tensile test Methods 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- -1 fluorine ions Chemical class 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920013657 polymer matrix composite Polymers 0.000 description 2
- 239000011160 polymer matrix composite Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012681 fiber drawing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
- C09J105/16—Cyclodextrin; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a supermolecular polymer gel, a preparation method thereof and application thereof as an adhesive, wherein the supermolecular polymer gel is obtained by bonding cyclodextrin and carboxyl-terminated hyperbranched polyester through hydrogen bond. The cyclodextrin-based supermolecular polymer gel provided by the invention does not contain an organic solvent, is nontoxic and pollution-free, is easy to clean, has strong binding power as an adhesive, is suitable for binding various materials, can be recycled, still has a binding effect under the adverse environmental conditions of low temperature, strong acid, strong alkali and the like, and has great market application prospect.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a supermolecular polymer gel, a preparation method thereof and application thereof as an adhesive.
Background
Along with the development of economy and society, the adhesive is gradually blended into the aspects of human life, is small enough to bond stamps and shoes and is large enough to bond fuselages and wings, and the adhesive is not available in the fields of industry, agriculture, traffic, medical treatment and national defense. Adhesive materials play an important role in life, scientific research and industry. Most of the natural adhesives have been replaced by industrial adhesives at present, but most of the industrial adhesives contain organic solvents, are not only toxic but also not easy to clean. The invention provides an adhesive which is free of organic solvents, nontoxic, easy to clean and reusable, and can maintain its own viscosity in a specific solution at low temperatures.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a supermolecular polymer gel, a preparation method thereof and application thereof as an adhesive, wherein the supermolecular polymer gel is free of organic solvent, nontoxic, odorless and easy to clean, and still has adhesive property at low temperature.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a supramolecular polymer gel is provided that is derived from cyclodextrin and carboxyl-terminated hyperbranched polyester by hydrogen bonding.
According to the scheme, the cyclodextrin is one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.
According to the scheme, the carboxyl-terminated hyperbranched polyester is one of DCHP-1, DCHP-2 and DCHP-3, and the DCHP-1 has the following structural formula:
the DCHP-2 has the following structural formula:
the DCHP-3 has the following structural formula:
according to the scheme, the molar ratio of the cyclodextrin to the carboxyl-terminated hyperbranched polyester is 1:0.5 to 3.
The invention also comprises a preparation method of the supermolecular polymer gel, which comprises the following specific steps:
3) The cyclodextrin and the carboxyl-terminated hyperbranched polyester are weighed according to a proportion for standby;
4) Mixing the cyclodextrin weighed in the step 1) with the carboxyl-terminated hyperbranched polyester, adding ultrapure water, and fully stirring at 10-40 ℃ to obtain a uniform solution;
5) And (3) drying the solution obtained in the step (2) until the quality is stable, and obtaining the adhesive based on the cyclodextrin-hyperbranched polymer.
According to the scheme, the molar volume ratio of the carboxyl-terminated hyperbranched polyester to the ultrapure water in the step 2) is 0.625-3.75 mmol/100mL.
According to the scheme, the stirring time in the step 2) is 0.5-3 h.
According to the scheme, the drying temperature in the step 3) is 50-120 ℃ and the drying time is 5-48 h.
The invention also includes the application of the supermolecular polymer gel as an adhesive. The adhesive is suitable for common base materials such as wood, glass, ceramics, iron sheets, steel sheets and the like, is particularly outstanding in the aspect of bonding glass, and still has bonding effect in low temperature (-60 ℃), acid-base solution and organic solvent (acetone, methylene dichloride and transformer oil).
The invention prepares the CD-DCHP adhesive by controlling the feeding ratio of cyclodextrin and carboxyl-terminated hyperbranched polyester, adopting a one-step method to link Cyclodextrin (CD) monomer containing a large number of hydroxyl groups to carboxyl-terminated hyperbranched polyester (DCHP) polymer branched chains, enabling a plurality of hydrogen bond sites on the cyclodextrin to react with carboxyl groups on the carboxyl-terminated hyperbranched polyester to form a dense hydrogen bond network system, namely using the cyclodextrin as a hydrogen bond donor and the carboxyl-terminated hyperbranched polyester as a hydrogen bond acceptor, mixing the cyclodextrin and the carboxyl-terminated hyperbranched polyester according to a certain proportion, using ultrapure water as a solvent, stirring for a period of time at room temperature until the mixture is completely dissolved to form a transparent solution, and heating until all unbound water is evaporated to completely obtain the supermolecular polymer gel containing a large number of hydrogen bonds. The supermolecular polymer gel does not contain organic solvent and toxic gas, and the bonding principle is mainly that the bonding property of the supermolecular polymer gel is maintained under the room temperature condition by utilizing hydrogen bonds formed between cyclodextrin and carboxyl-terminated hyperbranched polyester. The supermolecular polymer gel has certain bonding effect on different materials (glass, wood board, steel, iron sheet, copper sheet, etc.), such as a large number of hydroxyl groups contained on the surface of the glass, a large number of fluorine ions contained on the surface of polytetrafluoroethylene can form a rich hydrogen bond network system with hydrogen bonds of the supermolecular polymer gel material, and the hydrogen bonds can be reformed after being broken in the heating temperature rising-cooling temperature reducing process, so that the reversibility of the hydrogen bonds endows the supermolecular polymer gel with the characteristic of being capable of being repeatedly used.
The invention has the beneficial effects that: 1. the cyclodextrin-based supermolecular polymer gel provided by the invention does not contain an organic solvent, is nontoxic and pollution-free, is easy to clean, has strong binding power as an adhesive, is suitable for binding various materials, can be recycled, still has a binding effect under the adverse environmental conditions of low temperature, strong acid, strong alkali and the like, and has great market application prospect. 2. The cyclodextrin-hyperbranched polymer adhesive is generated by the reaction of cyclodextrin and hyperbranched polyester, the preparation method is simple, the reaction condition is mild, any organic solvent is not used in the preparation process, toxic and harmful wastes are not generated, and the method is environment-friendly, economical and practical, and is favorable for realizing industrial production.
Drawings
FIG. 1 is a photograph of a process for preparing a cyclodextrin-hyperbranched polymer-based adhesive according to example 1 of the invention;
FIG. 2 is an infrared spectrum analysis chart of the adhesive prepared in example 1;
FIG. 3 is a nuclear magnetic resonance spectrum of the adhesive prepared in example 2;
FIG. 4 is a differential scanning calorimeter test chart of the adhesive prepared in example 2;
FIG. 5 is a thermogravimetric analysis test chart of the adhesive prepared in example 2;
FIG. 6 is a fiber drawing photograph of the adhesive prepared in example 3 between copper sheets;
FIG. 7 is a photograph showing the bonding of the adhesive prepared in example 3 to various substrates;
FIG. 8 is a graph showing the bonding strength of the adhesive prepared in example 3 on various substrates;
FIG. 9 is a graph of the preparation of example 3 glass splines;
FIG. 10 is a photograph showing the tensile test of the adhesive prepared in example 3 on glass, steel sheet and copper sheet at room temperature;
FIG. 11 is a graph showing the repeated tensile test results of the adhesive prepared in example 3;
FIG. 12 is a graph of the vibration-frequency scanning rheological test of the adhesive prepared in example 3;
FIG. 13 is a flow-temperature scanning rheology test chart of the adhesive prepared in example 3;
FIG. 14 is a drawing showing the tensile test of the adhesive prepared in example 3 at low temperature;
FIG. 15 is a photograph showing the tensile test of the adhesive prepared in example 3 in liquid nitrogen, transformer oil and n-octane;
FIG. 16 is a photograph showing the tensile test of the adhesive prepared in example 3 after immersing in solvents such as hydrochloric acid, sodium hydroxide, acetone, and methylene chloride.
Detailed Description
The present invention will be described in further detail below with reference to the accompanying drawings, so that those skilled in the art can better understand the technical scheme of the present invention.
Example 1
A preparation method of the supermolecular polymer gel comprises the following specific steps:
4.865g of alpha-cyclodextrin (alpha-CD) and 2.321g of carboxyl-terminated hyperbranched polyester (DCHP-1 molecular weight 464.29, molar ratio of the two is 1:1) are added into a beaker, 80mL of ultrapure water is added, stirring is carried out for 30 minutes at 25 ℃ to obtain a uniformly mixed transparent solution, the transparent solution is placed into an oven at 80 ℃ to be heated for 12 hours until the quality is stable to obtain a low-fluidity supermolecular polymer gel, and the supermolecular polymer gel is cooled to room temperature to obtain the cyclodextrin-hyperbranched polymer-based adhesive which does not flow when inverted.
The procedure of this example is shown in FIG. 1, and clearly shows the transition from solid powder to fluid to gel, and finally a transparent gel-like supramolecular polymer gel (. Alpha. -CD-DCHP (1) -1) was obtained at room temperature.
It should be noted that the raw materials α -CD and DCHP-1 do not react when directly mixed and heated, but only the α -cyclodextrin and the hyperbranched polyester are dissolved in ultrapure water to achieve molecular level interaction, and then the water is gradually evaporated to obtain the cyclodextrin-hyperbranched polymer-based adhesive.
The supermolecular polymer gel prepared in the embodiment is subjected to infrared test on alpha-CD-DCHP (1) -1, and is compared with characteristic peaks of alpha-cyclodextrin and carboxyl-terminated hyperbranched polyester DCHP-1, an infrared spectrum is shown in figure 2, and the infrared spectrum result of DCHP-1 shows that: 3292cm -1 Is the vibration peak of-OH group 1750cm -1 The strong absorption peak is C=O absorption peak, 1172cm -1 An absorption peak of C-O-C; infrared spectrum of α -CD: 3321cm -1 Is the vibration peak of-OH group, 2932cm -1 Describes the C-H stretching vibration mode, from 1200 to 800cm -1 The absorption peak of (C) is mainly polysaccharide spectrogram, and is used for C-C and C-O stretching vibration, and the band is 900-600cm -1 The absorption peak at the position is mainly connected with the bending mode of the C-H bond; in the infrared spectrum of α -CD-DCHP (1) -1, the vibration peak of C=O is from 1750cm -1 Offset to 1716cm -1 The characteristic peak of the C-O-C group was attenuated at 2947cm -1 And 1032cm -1 New peaks appear indicating successful synthesis of the supramolecular polymer gel and hydrogen bonding between c=o and-OH as shown in fig. 2a, which can be considered: -COOH and-OH drive self-assembly to form a gel by electrostatic and hydrogen bonding interactions.
Example 2
A preparation method of the supermolecular polymer gel comprises the following specific steps:
molar ratio 1:1, namely 0.567g of beta-cyclodextrin (beta-CD) and 0.2321g of carboxyl-terminated hyperbranched polyester (DCHP-1) are added into a beaker, then 10mL of ultrapure water is added, stirring is carried out for 30 minutes at 25 ℃ to obtain a uniformly mixed transparent solution, the transparent solution is put into an oven at 80 ℃ to be heated for 12 hours until the quality is stable to obtain a low-fluidity supermolecular polymer gel, and the supermolecular polymer gel is cooled to room temperature to obtain the cyclodextrin-hyperbranched polymer-based adhesive which can not flow when inverted.
The raw materials used in this example, beta-cyclodextrin and DCHP-1, were mixed in a molar ratio of 1:1, mixing and heating at 80deg.C for 12 hr to obtain raw materials and products 1 The H-NMR spectrum is shown in FIG. 3a, and it is clearly seen in FIG. 3a that the nuclear magnetic spectrum of cyclodextrin and carboxyl-terminated hyperbranched polyester has no shift or increase of peaks compared with the spectrum result after the cyclodextrin and carboxyl-terminated hyperbranched polyester are directly mixed and heated, which indicates that no reaction occurs between the cyclodextrin and the carboxyl-terminated hyperbranched polyester.
The supramolecular Polymer gel prepared in this example 1 The H-NMR spectrum is shown in FIG. 3b, from which it is seen that the chemical shifts at the 2,5 positions in beta-cyclodextrin (beta-CD) are represented byThe hydroxyl groups at positions 3.82 and 3.73 shifted to the low fields to positions 4.03 and 3.98,4 and 6 fade away. These characterization results indicate that there is a hydrogen bond interaction between the hydroxyl groups of the cyclodextrin and the hyperbranched carboxyl groups.
The results of Differential Scanning Calorimetric (DSC) and thermogravimetric analysis (TGA) of the supramolecular polymer gel prepared in this example are shown in FIGS. 4 and 5, and the DSC test of the material shows that the glass transition temperature of the material is about 0 ℃, and the TGA test results show that the heat resistance of the material is lower than 214 ℃ and can be stably used below 200 ℃.
Example 3
A preparation method of the supermolecular polymer gel comprises the following specific steps:
5.67g of beta-cyclodextrin (beta-CD) and 6.066g of carboxyl-terminated hyperbranched polyester (DCHP-2, molecular weight 1213.1, mol ratio of the two raw materials 1:1) are added into a beaker, 80mL of ultrapure water is added, stirring is carried out for 30 minutes at 25 ℃ to obtain a uniformly mixed transparent solution, the transparent solution is dried for 12 hours in an oven at 80 ℃ until the quality is stable to obtain a low-fluidity supermolecular polymer gel, and the supermolecular polymer gel is cooled to room temperature to obtain the cyclodextrin-terminated hyperbranched polymer adhesive (beta-CD-DCHP (2) -1) which can not flow when inverted.
The adhesive prepared in this example is transient for bonding of many materials, such as glass sheets, iron sheets, copper sheets, and the like. Taking a copper sheet as an example, the adhesive prepared in the embodiment is uniformly coated on the copper sheet, pressed for 30 seconds, and pulled apart again, so that the wire drawing condition between two copper sheets can be clearly seen, as shown in fig. 6.
The adhesive beta-CD-DCHP (2) -1 prepared in the embodiment is used for carrying out adhesion test on articles with different materials, a spline is prepared according to the section 6 of the fatigue performance test method of polymer matrix composite materials of GB/T35465.6-2020, namely adhesive tensile shear fatigue, after one substrate is coated with the adhesive, the other same substrate is adhered together in the opposite direction, and the mixture is placed in an oven at 80 ℃ for heating for 1h and cooled to room temperature to be used for tensile test. The adhesive properties of polytetrafluoroethylene, paper box, ceramic, rubber, aluminum sheet, copper sheet, iron sheet, glass and silica gel are shown in fig. 7, and the adhesive prepared in this example has an adhesive effect on most materials.
The test results of the tensile test of the sample bars of different substrates on a universal material tester according to GB/T35465.6-2020 Polymer matrix composite fatigue Performance test method part 6 adhesive tensile shear fatigue are shown in FIG. 8. The tensile test shows that the bonding strength of the beta-CD-DCHP (2) -1 on the iron sheet is 1.21MPa, the bonding strength on the wood board is 2.41MPa, the bonding strength on the aluminum sheet and the steel sheet is 2.48MPa and 1.73MPa respectively, the bonding effect on glass is most prominent, and the bonding strength can reach 5.14MPa.
To prepare glass bars, a schematic diagram is shown in FIG. 9, and to better test the bonding properties of the adhesive prepared in this example between glass, steel sheets and copper sheets, macroscopic tensile tests were performed on the bonded bars at room temperature, as shown in FIG. 10, it can be seen that the bonding area was 25X 10mm 2 The dumbbell of 10KG can be pulled up by the glass sample and the steel sheet sample, and the bonding area is 25 multiplied by 10mm 2 Can pull up a dumbbell of 6 KG.
The adhesive prepared in this example was tested for its recycling properties, and after the glass strips were pulled apart, the glass plate was still stuck with a sample, and after the glass plate was heated at 80 c and then pressed again for 30 seconds, the glass plate was heated for 1 hour (the heated hydrogen bond was broken to be changed to a flowing gel again) and cooled to room temperature for the adhesion test, and the procedure was repeated three times, and the test results were shown in fig. 11, and the adhesion effect was reduced but still had a large adhesion force.
The adhesive prepared in this example was subjected to rheological tests on a model DHR-1 rotary rheometer by TA instruments in the united states, and it was seen that the adhesive had a higher modulus and low flowability by measuring the loss modulus (G ") and storage modulus (G') of the gel at a temperature of 30 c, a strain of 0.1%, an angular frequency of 1 to 100rad/s, and an increment of 5rad/s by oscillation-frequency scanning as shown in fig. 12; as shown in fig. 13 by flow-temperature scanning, it can be seen that the viscosity gradually decreases with increasing temperature. As the hydrogen bond is broken by the temperature rise, the bonding effect becomes poor, and when the temperature becomes room temperature, the hydrogen bond is formed again, as with the rheological result.
The invention also explores the bonding effect of the adhesive prepared in the embodiment in an ultralow temperature and organic solvent, taking glass as an example. When the temperature is lower than 0 ℃, the bonding effect is reduced but still has the bonding effect, and the tensile test is carried out on glass bars at the temperature of 0 ℃, 30 ℃ below zero and 60 ℃ below zero respectively, and as a result, as shown in fig. 14, the bonding strength can be up to 1.64MPa at 60 ℃ below zero. At the same time, macroscopic tensile tests are carried out on glass sample bars in different solvents, so that the glass sample bars still have bonding effect in liquid nitrogen, transformer oil (transformer oil prepared in CN 113234523A) and organic solvent n-octane, and the result is shown in figure 15. The prepared glass sample strips are respectively placed in HCl solution (2M), naOH solution (2M), acetone, dichloromethane, ethyl acetate and dimethyl sulfoxide for two days to carry out macroscopic tensile test, the materials are found to be not damaged, and the materials still have bonding effect, and the photo is shown in figure 16.
Claims (7)
1. The supermolecular polymer gel is characterized in that the supermolecular polymer gel is obtained by bonding cyclodextrin and carboxyl-terminated hyperbranched polyester through hydrogen bond;
the cyclodextrin is one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin;
the carboxyl-terminated hyperbranched polyester is one of DCHP-1, DCHP-2 and DCHP-3, and the DCHP-1 has the following structural formula:
；
the DCHP-2 has the following structural formula:
；
the DCHP-3 has the following structural formula:
。
2. the supramolecular polymer gel of claim 1, wherein the cyclodextrin to carboxyl-terminated hyperbranched polyester molar ratio is 1:0.5 to 3.
3. A method for preparing a supramolecular polymer gel according to claim 1 or 2, characterized by the specific steps of:
1) The cyclodextrin and the carboxyl-terminated hyperbranched polyester are weighed according to a proportion for standby;
2) Mixing the cyclodextrin weighed in the step 1) with the carboxyl-terminated hyperbranched polyester, adding ultrapure water, and fully stirring at 10-40 ℃ to obtain a uniform solution;
3) Drying the solution obtained in the step 2) until the quality is stable, and obtaining the supermolecular polymer gel based on the cyclodextrin-hyperbranched polymer.
4. The method for preparing a supramolecular polymer gel according to claim 3, wherein the molar volume ratio of the carboxyl-terminated hyperbranched polyester to ultrapure water in step 2) is 0.625-3.75 mmol/100mL.
5. The method for preparing a supramolecular polymer gel as claimed in claim 3, wherein the stirring time of step 2) is 0.5-3 h.
6. The method for preparing a supramolecular polymer gel according to claim 3, wherein the drying temperature in step 3) is 50-120 ℃ and the drying time is 5-48 h.
7. Use of the supramolecular polymer gel of claim 1 or 2 as an adhesive.
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| CN102241825A (en) * | 2010-05-14 | 2011-11-16 | 同济大学 | Preparation method of supermolecular polymer micelle |
| CN103159962A (en) * | 2011-12-08 | 2013-06-19 | 江南大学 | Preparation method of photosensitive cyclodextrin gel |
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| CN102241825A (en) * | 2010-05-14 | 2011-11-16 | 同济大学 | Preparation method of supermolecular polymer micelle |
| CN103159962A (en) * | 2011-12-08 | 2013-06-19 | 江南大学 | Preparation method of photosensitive cyclodextrin gel |
| CN104874031A (en) * | 2015-04-20 | 2015-09-02 | 苏州大学 | Polyurethane derivative for simulating human fibrinolysis system and blood vessel endothelium system, preparation method of polyurethane derivative and preparation method of related product |
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