CN114163606A - Preparation and detection method of dynamic cross-linked self-repairing film - Google Patents
Preparation and detection method of dynamic cross-linked self-repairing film Download PDFInfo
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- CN114163606A CN114163606A CN202111641432.7A CN202111641432A CN114163606A CN 114163606 A CN114163606 A CN 114163606A CN 202111641432 A CN202111641432 A CN 202111641432A CN 114163606 A CN114163606 A CN 114163606A
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- 238000001514 detection method Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 30
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000004814 polyurethane Substances 0.000 claims abstract description 14
- 229920002635 polyurethane Polymers 0.000 claims abstract description 14
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 13
- 150000002009 diols Chemical class 0.000 claims abstract description 13
- 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 13
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 13
- 239000004417 polycarbonate Substances 0.000 claims abstract description 13
- 229920006264 polyurethane film Polymers 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 238000009833 condensation Methods 0.000 claims abstract description 4
- 230000005494 condensation Effects 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 6
- 238000005452 bending Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007689 inspection Methods 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 238000010998 test method Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000008439 repair process Effects 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 206010063385 Intellectualisation Diseases 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000013003 healing agent Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
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- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2375/04—Polyurethanes
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
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- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
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Abstract
The invention discloses a preparation and detection method of a dynamic cross-linking self-repairing film, which comprises the steps of firstly adding isophorone diisocyanate, polycarbonate diol and a catalyst into a three-neck flask with mechanical stirring and condensation reflux, heating to 80 ℃ and reacting for 2 hours to obtain a polyurethane prepolymer; then dissolving N-methyldiethanolamine in tetrahydrofuran, slowly dripping the solution into the obtained polyurethane prepolymer by using a constant-pressure dropping funnel, and carrying out chain extension reaction at 80 ℃ for 2 hours after the dripping is finished; then adding citric acid and reacting for 0.5 hour at 80 ℃ to finally obtain the amphoteric polyurethane, wherein the amphoteric polyurethane has the following beneficial effects: the zwitterionic polyurethane film designed and synthesized by the experiment improves the multiple damage repair efficiency and the mechanical property of polyurethane, and provides a theoretical basis for designing and preparing self-repairing polyurethane.
Description
Technical Field
The invention relates to the technical field of material science, in particular to a preparation and detection method of a dynamic cross-linking self-repairing film.
Background
The science of materials, new energy, informatization and life science are considered as four major subjects of the development of the current times. The material science is the first and is the material basis for the development of various industries. Among them, organic polymer materials are most widely used. With the development of the times, the requirements of people on materials are increasingly higher, and the functionalization gradually turns to intellectualization. The self-repairing material is also a novel intelligent material, and in daily life, more convenient and efficient utilization is brought to people due to the function similar to biological self-repairing of the self-repairing material. In some high-end science and technology fields, self-repairing materials are also colorful, such as aerospace science and technology, artificial intelligence, electronic technology, sensors and the like, and the self-repairing materials have wide application prospects and huge values. The polymer material can be damaged under the external action of heat, light, ultraviolet and the like, so that the mechanical property strength of the polymer material is influenced, and the service life and the safety of the polymer material are reduced. The self-repairing material can perfectly solve the defect, prolong the service life of the material and improve the safety and reliability of the material.
Self-repairing of polyurethane materials can be divided into exopathic and intrinsic repair. The external aid type repair can be divided into: self-repairing by loading a repairing agent in the microcapsule; self-healing with a healing agent loaded on the pipe. The repairing effect is influenced by the effect of the external aid. The intrinsic polyurethane self-repairing is realized by utilizing an internal reversible molecular chemical structure of a high polymer material. Compared with the external-aid type, the self-repairing device can realize multiple self-repairing. Currently, the most used repair methods are microreactors and reversible chemical reactions. Although the micro-reactor method has high repair efficiency, the micro-reactor method cannot realize multiple repairs. Reversible chemical methods repair can be initiated by stimulation by heat, light, etc. In summary, the self-repairing polyurethane material in the current market has low flexibility, the mechanical property is reduced along with the increase of the repairing times, the self-repairing cycle times are limited, and the practical application performance is limited.
Disclosure of Invention
The invention aims to provide a preparation and detection method of a dynamic cross-linking self-repairing film, which aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a dynamic cross-linking self-repairing film comprises the following steps:
the method comprises the following steps: preparing 2-4 parts of isophorone diisocyanate, 1-2 parts of polycarbonate diol, 1-2 parts of N-methyldiethanolamine, 1-2 parts of citric acid, a proper amount of catalyst and 1-4 parts of tetrahydrofuran according to relative molecular mass;
step two: firstly, adding isophorone diisocyanate, polycarbonate diol and a catalyst into a three-neck flask with mechanical stirring and condensation reflux, and heating to 80 ℃ for reaction for 2 hours to obtain a polyurethane prepolymer;
step three: dissolving N-methyldiethanolamine in tetrahydrofuran, slowly dropwise adding the solution into the polyurethane prepolymer obtained in the step two by using a constant-pressure dropping funnel, and after dropwise adding, carrying out chain extension reaction at 80 ℃ for 2 hours;
step four: then adding citric acid and reacting for 0.5 hour at 80 ℃, and finally obtaining the amphoteric polyurethane.
As a further scheme of the invention: in the second step, the catalyst is specifically dibutyltin dilaurate, and the dropping amount of the catalyst is 5-10 g.
As a further scheme of the invention: in step three, when the chain extension reaction is carried out, tetrahydrofuran is continuously added to reduce the viscosity when the reactant becomes viscous.
As a further scheme of the invention: in the first step, the material is dried in vacuum for 1-2 hours when being prepared.
A detection test method of a dynamic cross-linked self-repairing film comprises the following steps:
s1: shearing an amphoteric polyurethane film into two sections from the middle by using scissors, then closely attaching the fracture parts of the two sections together, and adding deionized water at the room temperature of 30 ℃;
s2: repeating the step of S1, selecting 2-5 groups of samples, and performing record inspection on each group of samples;
s3: shooting a microscopic crack picture every 5 minutes until the crack between the two sections of the amphoteric polyurethane films is repaired and is not changed any more;
s4: and stretching and bending the repaired film, continuously testing the sample by adopting the amphoteric polyurethane films prepared in different proportions, and finally analyzing to obtain the optimal reagent proportion.
Compared with the prior art, the invention has the beneficial effects that: the zwitterionic polyurethane film designed and synthesized by the experiment improves the multiple damage repair efficiency and the mechanical property of polyurethane, and provides a theoretical basis for designing and preparing self-repairing polyurethane.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a table showing the ratios of films of different proportions according to the present invention;
FIG. 2 is a reaction principle of the present invention for synthesizing amphoteric polyurethanes;
FIG. 3 is a drawing curve of films according to the present invention at different ratios;
FIG. 4 is a graph of the infrared spectra of films of the present invention at different scales;
FIG. 5 is a thermogravimetric analysis of films at different ratios according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-3, in an embodiment of the present invention, a method for manufacturing a dynamically crosslinked self-healing film includes the following steps:
the method comprises the following steps: preparing 2-4 parts of isophorone diisocyanate, 1-2 parts of polycarbonate diol, 1-2 parts of N-methyldiethanolamine, 1-2 parts of citric acid, a proper amount of catalyst and 1-4 parts of tetrahydrofuran according to relative molecular mass;
step two: firstly, adding isophorone diisocyanate, polycarbonate diol and a catalyst into a three-neck flask with mechanical stirring and condensation reflux, and heating to 80 ℃ for reaction for 2 hours to obtain a polyurethane prepolymer;
step three: dissolving N-methyldiethanolamine in tetrahydrofuran, slowly dropwise adding the solution into the polyurethane prepolymer obtained in the step two by using a constant-pressure dropping funnel, and after dropwise adding, carrying out chain extension reaction at 80 ℃ for 2 hours;
step four: then adding citric acid and reacting for 0.5 hour at 80 ℃, and finally obtaining the amphoteric polyurethane.
A detection test method of a dynamic cross-linked self-repairing film comprises the following steps:
s1: shearing an amphoteric polyurethane film into two sections from the middle by using scissors, then closely attaching the fracture parts of the two sections together, and adding deionized water at the room temperature of 30 ℃;
s2: repeating the step of S1, selecting 2-5 groups of samples, and performing record inspection on each group of samples;
s3: shooting a microscopic crack picture every 5 minutes until the crack between the two sections of the amphoteric polyurethane films is repaired and is not changed any more;
s4: and stretching and bending the repaired film, continuously testing the sample by adopting the amphoteric polyurethane films prepared in different proportions, and finally analyzing to obtain the optimal reagent proportion.
The first embodiment is as follows:
preparing 4 parts of isophorone diisocyanate, 2 parts of polycarbonate diol, 2 parts of N-methyldiethanolamine, 2 parts of citric acid, 40 g of catalyst and 4 parts of tetrahydrofuran, wherein each part of isophorone diisocyanate is 222 g, each part of polycarbonate diol is 1000 g, each part of N-methyldiethanolamine is 119 g, each part of citric acid is 192 g, and each part of tetrahydrofuran is 8 ml;
detecting the tensile mechanical property, namely detecting a stress-strain curve of the amphoteric polyurethane film by using a stretching machine, wherein the stretching speed is 60mm/min, preferentially measuring the width and the thickness of the film, measuring for many times, taking the average value of the measured values, and drawing a stress-strain curve graph after data are obtained;
example two:
preparing 4 parts of isophorone diisocyanate, 2 parts of polycarbonate diol, 1 part of N-methyldiethanolamine, 2 parts of citric acid, 36 g of catalyst and 3 parts of tetrahydrofuran, wherein each part of isophorone diisocyanate is 222 g, each part of polycarbonate diol is 1000 g, each part of N-methyldiethanolamine is 119 g, each part of citric acid is 192 g, and each part of tetrahydrofuran is 8 ml;
infrared spectrum detection, namely performing infrared spectrum detection on the amphoteric polyurethane film by using an infrared spectrometer, wherein the test range is 4000-500cm-1Resolution of 4cm-1；
Example three:
preparing 4 parts of isophorone diisocyanate, 2 parts of polycarbonate diol, 2 parts of N-methyldiethanolamine, 0 part of citric acid, 30 g of catalyst and 3 parts of tetrahydrofuran, wherein each part of isophorone diisocyanate is 222 g, each part of polycarbonate diol is 1000 g, each part of N-methyldiethanolamine is 119 g, each part of citric acid is 192 g, and each part of tetrahydrofuran is 8 ml;
thermogravimetric analysis is carried out on the amphoteric polyurethane membrane, a thermal analyzer is used for testing the membrane, the temperature rise speed is 10 ℃/min, the test scanning range is 30-700 ℃, and the flow rate of protective nitrogen is 20 mL/min.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (5)
1. A preparation method of a dynamic cross-linking self-repairing film is characterized by comprising the following steps:
the method comprises the following steps: preparing 2-4 parts of isophorone diisocyanate, 1-2 parts of polycarbonate diol, 1-2 parts of N-methyldiethanolamine, 1-2 parts of citric acid, a proper amount of catalyst and 1-4 parts of tetrahydrofuran according to relative molecular mass;
step two: firstly, adding isophorone diisocyanate, polycarbonate diol and a catalyst into a three-neck flask with mechanical stirring and condensation reflux, and heating to 80 ℃ for reaction for 2 hours to obtain a polyurethane prepolymer;
step three: dissolving N-methyldiethanolamine in tetrahydrofuran, slowly dropwise adding the solution into the polyurethane prepolymer obtained in the step two by using a constant-pressure dropping funnel, and after dropwise adding, carrying out chain extension reaction at 80 ℃ for 2 hours;
step four: then adding citric acid and reacting for 0.5 hour at 80 ℃, and finally obtaining the amphoteric polyurethane.
2. The method for preparing the dynamic cross-linking self-repairing film according to claim 1, wherein: in the second step, the catalyst is specifically dibutyltin dilaurate, and the dropping amount of the catalyst is 5-10 g.
3. The method for preparing the dynamic cross-linking self-repairing film according to claim 1, wherein: in step three, when the chain extension reaction is carried out, tetrahydrofuran is continuously added to reduce the viscosity when the reactant becomes viscous.
4. The method for preparing the dynamic cross-linking self-repairing film according to claim 1, wherein: in the first step, the material is dried in vacuum for 1-2 hours when being prepared.
5. A detection test method of a dynamic cross-linked self-repairing film is characterized by comprising the following steps:
s1: shearing an amphoteric polyurethane film into two sections from the middle by using scissors, then closely attaching the fracture parts of the two sections together, and adding deionized water at the room temperature of 30 ℃;
s2: repeating the step of S1, selecting 2-5 groups of samples, and performing record inspection on each group of samples;
s3: shooting a microscopic crack picture every 5 minutes until the crack between the two sections of the amphoteric polyurethane films is repaired and is not changed any more;
s4: and stretching and bending the repaired film, continuously testing the sample by adopting the amphoteric polyurethane films prepared in different proportions, and finally analyzing to obtain the optimal reagent proportion.
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