CN117700686A - Repairable supermolecular plastic with high mechanical strength and high environmental stability and preparation method thereof - Google Patents
Repairable supermolecular plastic with high mechanical strength and high environmental stability and preparation method thereof Download PDFInfo
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- 239000004033 plastic Substances 0.000 title claims abstract description 52
- 229920003023 plastic Polymers 0.000 title claims abstract description 52
- 230000007613 environmental effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 28
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- YOOSAIJKYCBPFW-UHFFFAOYSA-N 3-[4-(3-aminopropoxy)butoxy]propan-1-amine Chemical compound NCCCOCCCCOCCCN YOOSAIJKYCBPFW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 238000010586 diagram Methods 0.000 description 5
- 230000008439 repair process Effects 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical group NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002677 supramolecular polymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses repairable supermolecular plastic with high mechanical strength and high environmental stability and a preparation method thereof. The supermolecular plastic is prepared by uniformly mixing 1, 4-butanediol-bis (3-aminopropyl) ether and isophorone diisocyanate according to a proportion and then performing polycondensation. The self-repairable supermolecular plastic with high mechanical strength and high environmental stability not only has high strength and high hardness, but also has better ductility, and is superior to common plastics. Meanwhile, the supermolecular plastic provided by the invention also has excellent thermal stability and water vapor resistance.
Description
Technical Field
The invention relates to repairable supermolecular plastic with high mechanical strength and high environmental stability and a preparation method thereof, belonging to the field of high molecular materials.
Background
The supermolecular polymer is self-assembled by utilizing supermolecular interaction, has high sensitivity and faster network reconstruction speed, does not need a catalyst in the whole process, can greatly reduce side reaction, and ensures the stability of mechanical performance and chemical performance in the use process. However, the dynamic nature of the rapid dissociation-exchange-recombination of non-covalent bonds and the lower bond energy greatly affect the mechanical robustness and durability of the supramolecular material, which is not comparable to conventional commercial thermoplastics.
Sun et al have prepared ultra-strong PAA-polyvinylpyrrolidone (PVPON) based on a complexation strategy by complexing it via hydrogen bond interactions and then compression molding the resulting product into the desired shape. The glassy PAA-PVPON composite material shows an ultra-high tensile strength of 81.1MPa and a very high Young's modulus of 4.5GPa. The fractured P AA-PVPON composite material was recovered by restoring its original mechanical properties at-45℃due to reversible hydrogen bonding (N.An, X.Wang, Y.Li, L.Zhang, Z.Lu, J.Sun.Healable and mechanically super-strong polymeric composites derivedfrom hydrogen-bonded polymeric complexes [ J ]. Advanced Materials,2019,31 (41): 1904882). Aida uses a high molecular building block strategy to stack low molecular weight polyether thioureas through thiourea hydrogen bonding interactions to form amorphous glassy polymers that exhibit high tensile strength-45 MPa and high Young's modulus-1.4 GPa, and can be fully repaired within 6 hours by application of external pressure (1.0 MPa) at 24 ℃ (Y.Yanagisawa, Y.Nan, K.Okuro, T.Aida.Mechanically robust, readily repairable polymers via tailored noncovalent cross-linking [ J ]. Science,359 (6371), 72-76). Although certain results have been achieved, the present supramolecular materials still face several problems: (1) The realization of high hardness and high strength of the material means that the movement of molecular chains is greatly limited, so that the high brittleness of the material is caused, and the possibility of danger in the use process is greatly improved, so that the development of the super-molecular polymer with high hardness and high toughness is an urgent problem to be solved in engineering application. But the high restriction on the segments also severely hampers the efficiency of repair. (2) The non-covalent bond has sensitivity to external stimuli such as heat, humidity, solvent, acid and alkali, etc., and the external stimuli can cause the mechanical properties of the material to be greatly reduced, so that the application range of the material is greatly limited. The improvement in environmental stability of the polymer is also a concern. Therefore, the construction of repairable supramolecular polymers with high mechanical strength and high environmental stability is a problem to be solved.
Disclosure of Invention
The invention aims to provide repairable supermolecular plastic with high mechanical strength and high environmental stability and a preparation method thereof.
The technical scheme for realizing the purpose of the invention is as follows:
the repairable supermolecular plastic with high mechanical strength and high environmental stability has the following structural formula:
n≥50。
the preparation method of the repairable supermolecular plastic with high mechanical strength and high environmental stability is formed by polycondensation of 1, 4-butanediol-bis (3-aminopropyl) ether and isophorone diisocyanate, and the synthetic route is as follows:
the method comprises the following specific steps:
step 1: under the nitrogen atmosphere, isophorone diisocyanate is dissolved in N, N' -Dimethylformamide (DMF) to prepare a solution I, and the solution I is stirred in an ice bath;
step 2: dissolving 1, 4-butanediol-bis (3-aminopropyl) ether in N, N' -dimethylformamide to obtain a solution II, dropwise adding the solution II into the solution I, and vigorously stirring under ice bath to obtain a reaction primary product solution III, wherein the molar ratio of isophorone diisocyanate to 1, 4-butanediol-bis (3-aminopropyl) ether is 1-1.05:1;
step 3: heat-treating the reaction initial product solution III at 50-80 ℃ for 8-9 h to obtain a final polymer solution IV;
step 4: and drying the polymer solution IV to remove the solvent, so as to obtain the repairable supermolecular plastic with high mechanical property and high environmental stability.
Preferably, in step 1 or 2, the ice bath temperature is 0 to 4 ℃.
Preferably, in step 1, the concentration of isophorone diisocyanate in solution I is 0.5-1 mmol/mL.
Preferably, in step 2, the solubility of 1, 4-butanediol-bis (3-aminopropyl) ether in solution II is the same as the concentration of isophorone diisocyanate in solution I.
Preferably, in step 2, the drop velocity is 200. Mu.L/min.
Preferably, in step 2, the stirring time is 1h.
Preferably, in step 4, the drying method is to dry for 48 hours at 90 ℃ and then continue drying for 24 hours under vacuum at 90 ℃.
Compared with the prior art, the invention has the following advantages:
(1) The self-repairable supermolecular plastic with high mechanical strength and high environmental stability not only has high strength (more than 60 MPa) and high hardness (1 GPa), but also has better ductility (more than 60 percent), and is superior to common plastics such as polymethyl methacrylate, polyethylene and the like.
(2) The self-repairable supermolecular plastic with high mechanical strength and high environmental stability has excellent thermal stability, and the mechanical property is hardly changed when the temperature reaches 90 ℃. In addition, the paint also has excellent steam resistance, and the mechanical properties are almost unchanged after the paint is placed for 4 weeks at 65% humidity.
(3) The preparation method is simple, has good repeatability and is suitable for large-scale production.
Drawings
FIG. 1 is an infrared spectrum of the supermolecular plastic prepared in example 1.
FIG. 2 is a stress-strain diagram of the supermolecular plastic prepared in example 1.
FIG. 3 is a stress-strain curve of the supermolecular plastic prepared in example 1 at various temperatures.
FIG. 4 is a stress-strain curve of the supermolecular plastic prepared in example 1 after being left at 65% humidity for various times.
FIG. 5 is a graph showing the repair stress-strain curve of the supermolecular plastic prepared in example 1 with the aid of isopropanol.
FIG. 6 is a stress-strain diagram of the supermolecular plastics prepared in example 1 and comparative example 2.
FIG. 7 is a water vapor adsorption-desorption isotherm plot of the supermolecular plastics prepared in example 1 and comparative example 3.
Detailed Description
The invention will be described in further detail with reference to specific embodiments and drawings.
Example 1
The preparation method of the self-repairable supermolecular plastic with high mechanical strength and high environmental stability comprises the following specific steps:
step 1: under the nitrogen atmosphere, isophorone diisocyanate is dissolved in N, N' -dimethylformamide solvent to prepare solution I with the concentration of 0.5mmol/mL, and the solution I is stirred in ice bath (0-4 ℃);
step 2: dissolving 1, 4-butanediol-bis (3-aminopropyl) ether in an N, N' -dimethylformamide solvent to obtain a solution II with the same concentration as the solution I, then dropwise adding the solution II into the solution I at the concentration of 200 mu L/min, and vigorously stirring for 1h under ice bath conditions to obtain a reaction primary product solution III, wherein the molar ratio of isophorone diisocyanate to 1, 4-butanediol-bis (3-aminopropyl) ether is 1.05:1;
step 3: heat-treating the reaction initial product solution III at 50 ℃ for 9 hours to obtain a final polymer solution IV;
step 4: and drying the polymer solution IV to remove the solvent, so as to obtain the repairable supermolecular plastic with high mechanical property and high environmental stability.
Example 2
The preparation method of the self-repairable supermolecular plastic with high mechanical strength and high environmental stability comprises the following specific steps:
step 1: under the nitrogen atmosphere, isophorone diisocyanate is dissolved in N, N' -dimethylformamide solvent to prepare solution I with the concentration of 1.0mmol/mL, and the solution I is stirred in ice bath (0-4 ℃);
step 2: dissolving 1, 4-butanediol-bis (3-aminopropyl) ether in an N, N' -dimethylformamide solvent to obtain a solution II with the same concentration as the solution I, then dropwise adding the solution II into the solution I at the concentration of 200 mu L/min, and vigorously stirring for 1h under ice bath conditions to obtain a reaction primary product solution III, wherein the molar ratio of isophorone diisocyanate to 1, 4-butanediol-bis (3-aminopropyl) ether is 1.05:1;
step 3: heat-treating the reaction initial product solution III at 50 ℃ for 9 hours to obtain a final polymer solution IV;
step 4: and drying the polymer solution IV to remove the solvent, so as to obtain the repairable supermolecular plastic with high mechanical property and high environmental stability.
Example 3
The preparation method of the self-repairable supermolecular plastic with high mechanical strength and high environmental stability comprises the following specific steps:
step 1: under the nitrogen atmosphere, isophorone diisocyanate is dissolved in N, N' -dimethylformamide solvent to prepare solution I with the concentration of 0.5mmol/mL, and the solution I is stirred in ice bath (0-4 ℃);
step 2: dissolving 1, 4-butanediol-bis (3-aminopropyl) ether in an N, N' -dimethylformamide solvent to obtain a solution II with the same concentration as the solution I, then dropwise adding the solution II into the solution I at the concentration of 200 mu L/min, and vigorously stirring for 3 hours under ice bath conditions to obtain a reaction primary product solution III, wherein the molar ratio of isophorone diisocyanate to 1, 4-butanediol-bis (3-aminopropyl) ether is 1.05:1;
step 3: heat-treating the reaction initial product solution III at 50 ℃ for 9 hours to obtain a final polymer solution IV;
step 4: and drying the polymer solution IV to remove the solvent, so as to obtain the repairable supermolecular plastic with high mechanical property and high environmental stability.
Example 4
The preparation method of the self-repairable supermolecular plastic with high mechanical strength and high environmental stability comprises the following specific steps:
step 1: under the nitrogen atmosphere, isophorone diisocyanate is dissolved in N, N' -dimethylformamide solvent to prepare solution I with the concentration of 0.5mmol/mL, and the solution I is stirred in ice bath (0-4 ℃);
step 2: dissolving 1, 4-butanediol-bis (3-aminopropyl) ether in an N, N' -dimethylformamide solvent to obtain a solution II with the same concentration as the solution I, then dropwise adding the solution II into the solution I at the concentration of 200 mu L/min, and vigorously stirring for 1h under ice bath conditions to obtain a reaction primary product solution III, wherein the molar ratio of isophorone diisocyanate to 1, 4-butanediol-bis (3-aminopropyl) ether is 1.05:1;
step 3: heat-treating the reaction initial product solution III at 60 ℃ for 8 hours to obtain a final polymer solution IV;
step 4: and drying the polymer solution IV to remove the solvent, so as to obtain the repairable supermolecular plastic with high mechanical property and high environmental stability.
Example 5
The preparation method of the self-repairable supermolecular plastic with high mechanical strength and high environmental stability comprises the following specific steps:
step 1: under the nitrogen atmosphere, isophorone diisocyanate is dissolved in N, N' -dimethylformamide solvent to prepare solution I with the concentration of 0.5mmol/mL, and the solution I is stirred in ice bath (0-4 ℃);
step 2: dissolving 1, 4-butanediol-bis (3-aminopropyl) ether in an N, N' -dimethylformamide solvent to obtain a solution II with the same concentration as the solution I, then dropwise adding the solution II into the solution I at the concentration of 200 mu L/min, and vigorously stirring for 1h under ice bath conditions to obtain a reaction primary product solution III, wherein the molar ratio of isophorone diisocyanate to 1, 4-butanediol-bis (3-aminopropyl) ether is 1.05:1;
step 3: heat-treating the reaction initial product solution III at 70 ℃ for 9 hours to obtain a final polymer solution IV;
step 4: and drying the polymer solution IV to remove the solvent, so as to obtain the repairable supermolecular plastic with high mechanical property and high environmental stability.
Example 6
The preparation method of the self-repairable supermolecular plastic with high mechanical strength and high environmental stability comprises the following specific steps:
step 1: under the nitrogen atmosphere, isophorone diisocyanate is dissolved in N, N' -dimethylformamide solvent to prepare solution I with the concentration of 0.5mmol/mL, and the solution I is stirred in ice bath (0-4 ℃);
step 2: dissolving 1, 4-butanediol-bis (3-aminopropyl) ether in an N, N' -dimethylformamide solvent to obtain a solution II with the same concentration as the solution I, then dropwise adding the solution II into the solution I at the concentration of 200 mu L/min, and vigorously stirring for 1h under ice bath conditions to obtain a reaction primary product solution III, wherein the molar ratio of isophorone diisocyanate to 1, 4-butanediol-bis (3-aminopropyl) ether is 1.05:1;
step 3: heat-treating the reaction initial product solution III at 80 ℃ for 9 hours to obtain a final polymer solution IV;
step 4: and drying the polymer solution IV to remove the solvent, so as to obtain the repairable supermolecular plastic with high mechanical property and high environmental stability.
Comparative example 1
This comparative example is essentially the same as example 1, except that in step 2, stirring is vigorously carried out at room temperature for 1h, the specific steps are as follows:
step 1: under the nitrogen atmosphere, isophorone diisocyanate is dissolved in N, N' -dimethylformamide solvent to prepare solution I with the concentration of 0.5mmol/mL, and the solution I is stirred at room temperature;
step 2: dissolving 1, 4-butanediol-bis (3-aminopropyl) ether in an N, N' -dimethylformamide solvent to obtain a solution II with the same concentration as the solution I, dropwise adding the solution II into the solution I at 200 mu L/min, and vigorously stirring at room temperature for 1h to obtain a reaction primary product solution III, wherein the molar ratio of isophorone diisocyanate to 1, 4-butanediol-bis (3-aminopropyl) ether is 1.05:1;
step 3: heat-treating the reaction initial product solution III at 50 ℃ for 9 hours to obtain a final polymer solution IV;
step 4: and drying the polymer solution IV to remove the solvent, and thus obtaining the supermolecular plastic.
The supermolecular plastic prepared by the comparative example has poor mechanical properties.
Comparative example 2
This comparative example is essentially the same as example 1, except that 1, 4-butanediol-bis (3-aminopropyl) ether is replaced with 1, 12-diaminododecane in step 2, as follows:
step 1: under the nitrogen atmosphere, isophorone diisocyanate is dissolved in N, N' -dimethylformamide solvent to prepare solution I with the concentration of 0.5mmol/mL, and the solution I is stirred in ice bath (0-4 ℃) at room temperature;
step 2: dissolving 1, 12-diaminododecane in an N, N' -dimethylformamide solvent to obtain a solution II with the same concentration as that of the solution I, dropwise adding the solution II into the solution I at 200 mu L/min, and vigorously stirring for 1h under the ice bath room temperature condition to obtain a reaction primary product solution III, wherein the molar ratio of isophorone diisocyanate to 1, 12-diaminododecane is 1.05:1;
step 3: heat-treating the reaction initial product solution III at 50 ℃ for 9 hours to obtain a final polymer solution IV;
step 4: and drying the polymer solution IV to remove the solvent, and thus obtaining the supermolecular plastic.
The mechanical properties of the supermolecular plastics prepared in this comparative example are poor.
Comparative example 3
This comparative example is essentially the same as example 1, except that in step 2 the 1, 4-butanediol-bis (3-aminopropyl) ether is replaced with 3,3- (butane-1, 4-ylidenedi (oxo)) bis (propan-1-ol) as follows:
step 1: under the nitrogen atmosphere, isophorone diisocyanate is dissolved in N, N' -dimethylformamide solvent to prepare solution I with the concentration of 0.5mmol/mL, and the solution I is stirred in ice bath (0-4 ℃) at room temperature;
step 2: dissolving 3,3- (butane-1, 4-methylene di (oxo)) di (propane-1-ol) in an N, N' -dimethylformamide solvent to obtain a solution II, adding the solution II into the solution I dropwise at the concentration of 200 mu L/min, and stirring vigorously for 1h under the ice bath temperature condition to obtain a reaction primary product solution III, wherein the molar ratio of isophorone diisocyanate to 3,3- (butane-1, 4-methylene di (oxo)) di (propane-1-ol) is 1.05:1;
step 3: heat-treating the reaction initial product solution III at 50 ℃ for 9 hours to obtain a final polymer solution IV;
step 4: and drying the polymer solution IV to remove the solvent, and thus obtaining the supermolecular plastic.
The supermolecular plastic prepared in the comparative example has poor environmental stability.
The self-repairable supermolecular plastics prepared in examples 1-6 are basically the same, have similar properties, and have similar mechanical strength and environmental stability. Specific characterization and performance test results are given below, as represented by the self-repairable supermolecular plastic with high mechanical strength and high environmental stability prepared in example 1.
FIG. 1 is an infrared spectrum of the supermolecular plastic prepared in example 1. Wavelength 3334cm -1 Is telescopic vibration of-NH-, and has the wavelength of 2935 cm and 2853cm -1 is-CH 3 Is stretched and vibrated at a wavelength of 1634cm -1 For C=O stretching vibration, wavelength 1555cm -1 Bending vibration of-NH-, wavelength 1364cm -1 is-CH 3 Bending vibration of 124cm wavelength -1 Is a C-C-stretching vibration with a wavelength of 1098cm -1 Is the telescopic vibration of-C-O-C-.
FIG. 2 is a stress-strain diagram of the supermolecular plastic prepared in example 1. From the stress-strain diagram it can be seen that the material has a high strength (> 60 MPa) and a high hardness (-1 GPa) and has a better ductility (> 60%).
FIG. 3 is a stress-strain curve of the supermolecular plastic prepared in example 1 at various temperatures. As shown in FIG. 3, the mechanical properties of the material were hardly changed even in the 90℃environment by stretching at 25℃at 60℃at 70℃at 80℃at 90℃indicating that the material has excellent thermal stability.
FIG. 4 is a stress-strain curve of the supermolecular plastic prepared in example 1 after being left at 65% humidity for various times. As shown in fig. 4, the mechanical properties of the materials were slightly changed after stretching at 65% humidity for 1, 2, 3, 4 weeks, indicating that the materials have excellent resistance to moisture.
FIG. 5 is a graph showing the repair of the supermolecular plastic prepared in example 1 with the aid of isopropanol. The material was cut into test bars, which were cut with a knife blade, and then a small amount of IPA was applied to the fracture surface, and the two surfaces were spliced together and repaired at 60 ℃ for 1 hour. The repair effect is tested by using a universal tensile tester, and as shown in fig. 5, after repair, the material can basically and completely recover the tensile length.
FIG. 6 is a stress-strain diagram of the supermolecular plastics prepared in example 1 and comparative example 2. Detailed mechanical properties such as Young's modulus, tensile strength, elongation and toughness are shown in FIG. 6. The material of example 1 has high hardness and strength, with a Young's modulus of about 0.95GPa, much greater than that of comparative example 2. In addition, the toughness of the material of example 1 was about 13 times that of comparative example 2.
FIG. 7 is a water vapor adsorption-desorption isotherm plot of the supermolecular plastics prepared in example 1 and comparative example 3. Comparative example 3 absorbs about 4.1% water vapor at 95% maximum humidity, whereas example 1 absorbs only 0.9%, indicating that the material of example 1 has significantly better resistance to water vapor than comparative example 3.
Claims (8)
1. The repairable supermolecular plastic with high mechanical strength and high environmental stability is characterized by having the following structural formula:
2. the method for preparing repairable supermolecular plastic according to claim 1, which is characterized by comprising the following specific steps:
step 1: under the nitrogen atmosphere, isophorone diisocyanate is dissolved in N, N' -dimethylformamide to prepare a solution I, and the solution I is stirred in an ice bath;
step 2: dissolving 1, 4-butanediol-bis (3-aminopropyl) ether in N, N' -dimethylformamide to obtain a solution II, dropwise adding the solution II into the solution I, and vigorously stirring under ice bath to obtain a reaction primary product solution III, wherein the molar ratio of isophorone diisocyanate to 1, 4-butanediol-bis (3-aminopropyl) ether is 1-1.05:1;
step 3: heat-treating the reaction initial product solution III at 50-80 ℃ for 8-9 h to obtain a final polymer solution IV;
step 4: and drying the polymer solution IV to remove the solvent, so as to obtain the repairable supermolecular plastic with high mechanical property and high environmental stability.
3. The method according to claim 2, wherein in step 1 or 2, the ice bath temperature is 0 to 4 ℃.
4. The process according to claim 2, wherein in step 1, the concentration of isophorone diisocyanate in solution I is 0.5 to 1mmol/mL.
5. The process according to claim 2, wherein in step 2 the solubility of 1, 4-butanediol-bis (3-aminopropyl) ether in solution II is the same as the concentration of isophorone diisocyanate in solution I.
6. The method according to claim 2, wherein in step 2, the dropping speed is 200. Mu.L/min.
7. The method according to claim 2, wherein in step 2, the stirring time is 1h.
8. The method according to claim 2, wherein in step 4, the drying is performed at 90 ℃ for 48 hours and then at 90 ℃ under vacuum for 24 hours.
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