CN117304447A - Self-repairing polyurethane elastomer based on multiple hydrogen bonds/nitrogen coordination boron-oxygen bonds and preparation method thereof - Google Patents
Self-repairing polyurethane elastomer based on multiple hydrogen bonds/nitrogen coordination boron-oxygen bonds and preparation method thereof Download PDFInfo
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- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 23
- 239000001257 hydrogen Substances 0.000 title claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 41
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 229920000909 polytetrahydrofuran Polymers 0.000 claims abstract description 21
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 14
- 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 14
- WWFMINHWJYHXHF-UHFFFAOYSA-N [6-(hydroxymethyl)pyridin-2-yl]methanol Chemical compound OCC1=CC=CC(CO)=N1 WWFMINHWJYHXHF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920002635 polyurethane Polymers 0.000 claims abstract description 11
- 239000004814 polyurethane Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002262 Schiff base Substances 0.000 claims abstract description 6
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 6
- JBFBFCTUNDSIRH-UHFFFAOYSA-N (2-formylphenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC=C1C=O JBFBFCTUNDSIRH-UHFFFAOYSA-N 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 9
- DGUWACLYDSWXRZ-UHFFFAOYSA-N (2-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1C=O DGUWACLYDSWXRZ-UHFFFAOYSA-N 0.000 claims description 8
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 22
- 230000009471 action Effects 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 20
- 239000000806 elastomer Substances 0.000 description 19
- 238000004064 recycling Methods 0.000 description 13
- 238000004090 dissolution Methods 0.000 description 6
- 238000005728 strengthening Methods 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- -1 terbium chloride Chemical class 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical group NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 125000002228 disulfide group Chemical group 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 150000003077 polyols Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
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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 provides a self-repairing polyurethane elastomer based on multiple hydrogen bonds/nitrogen coordination boron-oxygen bonds and a preparation method thereof, which belong to the technical field of new materials, wherein polytetrahydrofuran ether glycol is dehydrated and cooled in high temperature in vacuum, polyurethane reaction is carried out with dry isophorone diisocyanate under the action of a catalyst at the temperature of 20-40 ℃, then 2, 6-pyridine dimethanol is subjected to chain extension at the temperature of 70-90 ℃,4' -methylene bis (2-chloroaniline) is added for end sealing, finally 2-formylphenyl boric acid is added for Schiff base reaction, and solvent is removed to obtain a final product of the self-repairing polyurethane elastomer based on multiple hydrogen bonds/nitrogen coordination boron-oxygen bonds.
Description
Technical Field
The invention belongs to the field of new material application, in particular to a polyurethane elastomer and a preparation method thereof, and particularly relates to a self-repairing polyurethane elastomer with multiple bond interactions and a preparation method thereof.
Background
The self-repairing polymer material is a polymer material capable of realizing self-repairing of mechanical damage of the self-repairing polymer material spontaneously or under the action of some external stimulus. The self-repairing function not only can improve the service life of the material and reduce the total period use cost, but also improves the use safety of the material. Currently, a self-repairing polymer material is regarded as a functional material, and intensive studies are being conducted in many fields.
In the research process of self-repairing polymers in recent years, researchers find that the molecular structure or system designed by singly using one self-repairing mechanism cannot meet the application requirement, and the composite self-repairing mechanism formed by utilizing multiple mechanisms often has the composite performance which is not possessed by the single self-repairing structural material.
The elastomer material is one of the most common consumables in daily life, most of the current commercial elastomers are crosslinked through irreversible covalent bonds, cannot be repaired and recovered, and can only be scrapped and burned once damaged excessively, so that resource waste and environmental pollution are caused. In order to achieve sustainable development, it is desirable that next generation elastomeric materials be capable of repairable, recyclable properties for extended service life, but at the same time the preparation of elastomers meeting seemingly contradictory high mechanical strength, repairable, recyclable properties remains challenging. The dynamic hierarchical domain rich in coordination bonds and hydrogen bonds can not only serve as a rigid filler reinforced elastomer, but also deform and dissociate to dissipate energy, so that the sustainability of the material is improved. And because of the reversibility of hydrogen bond and coordination bond under the action of heat, the elastomer can be effectively repaired and recovered, and the original strength and integrity of the material are maintained.
Polyurethane elastomer young's model is between rubber and plastics, has excellent properties such as wear resistance, oil resistance, elasticity are high, chemical resistance, so the wide application in many fields is obtained. As the application field of polyurethane elastomers expands, the requirements on strength, self-healing property and recycling property of the polyurethane elastomers are increasing. In addition, many polymeric materials are typically in service under ordinary and mild conditions, and there is a need to explore polymeric materials that can achieve wound self-healing under more mild conditions.
Polyurethane self-healing materials have made significant research progress in recent years. Researchers repair the damaged parts of the polyurethane material by introducing repairable microcapsules, reversible covalent bonds (such as nitrogen coordination boron-oxygen bonds, amide bonds, diselenide bonds and the like), hydrogen bonds, coordination bonds and the like into a polymer matrix or a molecular chain and under the stimulation of external environment (such as light, heat, solvents and the like). The invention patent CN 11383149A discloses a self-repairing polyurethane elastomer containing six-fold intermolecular hydrogen bonds, the preparation process of the polyurethane elastomer is simple, 2, 6-diaminopyridine or a derivative of the 2, 6-diaminopyridine is used as a chain extender, and the prepared polyurethane elastomer has good mechanical properties, but the elastomer has no recycling property. The invention patent CN 110698635B discloses a polyurethane elastomer with high toughness and high mechanical strength and a preparation method thereof, wherein the polyurethane elastomer has the functions of recycling and self-repairing, and the elasticity and repairing performance of polyurethane are improved through the combination of hydrogen bonds and coordination bonds. Although the synthesized polyurethane has higher mechanical strength and healing property, the reaction time is long (more than or equal to 48 h), the energy consumption is high, and the preparation process is complex.
Chinese patent No. 108659188A discloses a polyurea self-repairing thermoplastic elastomer and a preparation method thereof, wherein the repairing efficiency of the polyurea self-repairing thermoplastic elastomer can be 95.45% at room temperature for 2 hours by utilizing disulfide exchange reaction, but the original tensile strength of the elastomer obtained by the technology is less than 3MPa, and the tensile strength is too low. Chinese patent No. 106750145A discloses polyether type self-repairing polyurethane, which has strength as high as 9MPa through coordination of aminopyridine units and chlorides such as terbium chloride, but has severe repairing conditions, and can only achieve 96% of self-repairing efficiency after repairing for 24 hours at 60 ℃ and can not achieve room temperature self-repairing.
In order to solve at least one of the problems, the invention provides a self-repairing polyurethane elastomer based on multiple hydrogen bonds/nitrogen coordination boron-oxygen bonds and a preparation method thereof.
Disclosure of Invention
The invention aims to avoid the defects of the prior art and provides a self-repairing polyurethane elastomer based on multiple hydrogen bonds/nitrogen coordination boron-oxygen bonds and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a self-repairing polyurethane elastomer based on multiple hydrogen bonds/nitrogen coordination boron-oxygen bonds and a preparation method thereof are characterized in that: the method comprises the following specific steps:
step (1): 10.0mmol of polytetrahydrofuran ether glycol is taken and added into a three-necked flask, isophorone diisocyanate and a catalyst are added in sequence, and N is introduced 2 Carrying out polyurethane reaction for 1-3 hours at 20-40 ℃ to obtain polyurethane prepolymer;
step (2): adding 2, 6-pyridine dimethanol and toluene into the reaction solution obtained in the step (1), installing a reflux condensing device, and heating to 70-90 ℃ and N 2 Chain extension reaction is carried out for 2-5 hours in the atmosphere to obtain a chain extension polyurethane prepolymer;
step (3): adding 4,4' -methylenebis (2-chloroaniline) and N, N-dimethylformamide to the reaction solution obtained in the step (2) at the same temperature as in the step (3) at N 2 Continuously reacting for 2-5h in the atmosphere to obtain primary amino-NH 2 A capped chain-extended polyurethane prepolymer;
step (4): adding 2-formylphenylboronic acid and toluene into the reaction solution obtained in the step (3), and carrying out N-phase reaction at the same temperature in the step (3) 2 Carrying out Schiff base reaction for 2-5h under the condition of molecular sieve in the atmosphere to obtain a final pale yellow viscous product, and removing solvent and impurities to obtain the target product self-repairing polyurethane elastomer;
wherein, the molar ratio of polytetrahydrofuran ether glycol, isophorone diisocyanate, 2, 6-pyridine dimethanol, 4' -methylene bis (2-chloroaniline) and 2-formylphenylboric acid is 1.0: (3.0-5.0): (0.4-2.5): (0.6-2.4): (0.2-0.8).
According to the invention, the polyurethane prepolymer containing the isocyanate end group is prepared, the micromolecular polyol chain extender reacts with the prepolymer, and then the prepared oligomer reacts with the diamine chain extender, so that the improvement of the molecular weight of the product and the reduction of the microphase separation degree are facilitated, and the design can adjust the microphase separation structure of the nanometer scale; the reversible nitrogen coordination boron-oxygen bond is introduced into the high-flexibility molecular chain to decompose the whole chain movement into a plurality of chain segment movements, so that the self-repairing performance of the material is further improved; and introducing a proper amount of reversible nitrogen coordination boron-oxygen bonds between molecules to improve the mechanical strength of the material, and preparing the high-strength room-temperature self-repairing polyurethane elastomer material by utilizing the synergistic effect of multiple dynamic reversible bonds.
In the self-repairing polyurethane molecular structure, isophorone diisocyanate, 2, 6-pyridine dimethanol, 2-formylphenylboric acid and 4,4' -methylene bis (2-chloroaniline) monomer units form a multi-layer hard segment structure, polytetrahydrofuran ether glycol forms a soft segment structure, multiple hydrogen bonds with different intensities are formed through the interaction among carbamate groups, pyridine and urea groups, and reversible nitrogen coordination boron-oxygen bonds are simultaneously introduced into a molecular chain, so that the self-repairing polyurethane molecular structure has stronger multiple self-repairing capability.
One embodiment of the invention is that the polytetrahydrofuran ether glycol is subjected to the following pretreatment prior to use: the polytetrahydrofuran ether glycol is decompressed and dehydrated for 20 to 40min at the temperature of 110 to 130 ℃ and cooled to 20 to 40 ℃.
One embodiment of the present invention is characterized in that the polytetrahydrofuran ether glycol added in the step (1) has a number average molecular weight of 1000 to 4000g/mol.
In one embodiment of the present invention, the catalyst added in the step (1) is dibutyltin dilaurate, and the addition amount of the catalyst is 0.1-1% of the mass of the monomer isophorone diisocyanate.
In one embodiment of the present invention, the toluene added in the step (2) and the step (4) is added in an amount of 0.4 to 1.0 times the total mass of the reaction monomers.
In one embodiment of the present invention, the N, N-dimethylformamide added in the step (3) is added in an amount of 0.5 to 1.0 times the total mass of the reaction monomers.
The invention also aims to disclose a self-repairing polyurethane elastomer based on multiple hydrogen bonds/nitrogen coordination boron-oxygen bonds, which is prepared by adopting any one of the above methods.
Compared with the prior art, the invention has the beneficial effects that:
the polyurethane elastomer disclosed by the invention has excellent tensile strength, high fracture toughness, high fracture energy and good tensile property, and also has excellent self-repairing property after fracture, and after the polyurethane elastomer is repaired for a period of time under the room temperature condition, the mechanical property recovery degree of the polyurethane elastomer after fracture is more than 90%, and the mechanical property recovery degree is respectively close to 100%, so that the polyurethane elastomer has the organic combination of high mechanical strength and good room temperature self-repairing capability. All stretching processes have strain strengthening behavior, namely when the stress is continuously increased in the middle and later stages of stretching, the material is not broken rapidly, but the strain is greatly increased.
Meanwhile, the polyurethane elastomer has excellent recycling performance, can be recycled after being dissolved by a solvent, and has the mechanical property which is more than 90% of the mechanical property under the initial condition and is respectively close to 100% when the recycling frequency is 5 times; meanwhile, after repeated use, the glass still has better room temperature self-repairing performance and strain strengthening behavior.
In addition, the polyurethane elastomer has excellent recycling property, and the mechanical property and the self-repairing efficiency of the polyurethane elastomer are not obviously reduced after recycling.
Drawings
FIG. 1 stress-strain curves for example 1 elastomer initial elongation and after 48 hours of room temperature (25 ℃) self-repair;
FIG. 2 stress-strain curves for the example 1 elastomer after 5 cycles of initial stretching and 48 hours of room temperature (25 ℃) self-repair.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
In the examples below, the methods employed are common in the art unless otherwise indicated.
In the examples described below, the raw materials used were conventional commercial products unless otherwise specified.
Example 1
The self-repairing polyurethane elastomer based on multiple hydrogen bonds/nitrogen coordination boron-oxygen bonds is prepared by the following method:
(1) 10.00mmol of polytetrahydrofuran ether glycol (number average molecular weight 2000 g/mol) are taken and added into a three-necked flask, 37.8mmol of isophorone diisocyanate and 0.01g of catalyst dibutyltin dilaurate are added in sequence, and N is introduced 2 Reacting gas at 20 ℃ for 2 hours to obtain polyurethane prepolymer;
(2) 24.46mmol of 2, 6-pyridine dimethanol and 25mL of toluene are added into the reaction solution obtained in the step (1), a reflux condensing device is arranged, the temperature is raised to 80 ℃, and N is added 2 Chain extension reaction is carried out for 3 hours in the atmosphere to obtain a chain extension polyurethane prepolymer;
(3) To the reaction solution obtained in the step (2), 5.96mmol of 4,4' -methylene was addedBis (2-chloroaniline) and 25mL of N, N-dimethylformamide at the same temperature as in step (2) at N 2 Continuously reacting for 3 hours in the atmosphere to obtain primary amino-NH 2 A capped chain-extended polyurethane prepolymer;
(4) To the reaction solution obtained in the step (3) were added 5.45mmol of 2-formylphenylboronic acid and 20mL of toluene at the same temperature as in the step (3) under N 2 And (3) carrying out Schiff base reaction for 3 hours under the condition of molecular sieve in the atmosphere to obtain a final light yellow viscous product, and removing solvent and impurities to obtain the self-repairing polyurethane elastomer.
Wherein, the polytetrahydrofuran ether glycol used in the step (1) is stirred at 120 ℃ and dehydrated in vacuum for 40min and cooled to 30 ℃; the molar ratio of polytetrahydrofuran ether glycol, isophorone diisocyanate, 2, 6-pyridine dimethanol, 4' -methylenebis (2-chloroaniline) and 2-formylphenylboronic acid monomer added in steps (1) to (4) is 1.0:3.78:2.45:0.6:0.55.
the cast elastomer is tested for mechanical property and self-repairing property, the tensile strength is 2.71MPa, and the fracture toughness is 33.12 MJ.m -3 The elongation at break is 2472%, and the tensile strength, the elongation at break and the fracture toughness after 48h of room temperature self-repair are 2.68MPa and 31.96 MJ.m respectively -3 2432%, and the self-repairing efficiency reaches 98.9%, 96.5% and 98.4%, respectively, so that the elastic mechanical property and the self-repairing property are good. As shown in fig. 1, the initial elastomer and the self-repairing elastomer prepared in this example begin to exhibit strain strengthening behavior at about 1200% of the strain, the curve becomes steeper, and the material does not break under continuous increase of the stress, but the strain is greatly increased.
The tensile strength of the elastomer recovered in the 5 th cycle was measured to be 2.67MPa and the fracture toughness was measured to be 33.06 MJ.m by 5 cycles of the test, namely, 5 cycles of cutting-self-repairing-stretching-dissolution casting -3 The elongation at break is 2457%, and the tensile strength, the elongation at break and the fracture toughness after 48h of room temperature self-repair are 2.57MPa and 31.77 MJ.m respectively -3 2408%, and the self-repairing efficiency reaches 96.2%, 96.1% and 98.0% respectively. It can be seen that the polyurethane bulletThe sex toy also has excellent dissolution recycling property, and the mechanical property and the self-repairing efficiency of the sex toy are not obviously reduced after recycling. As shown in fig. 2, the elastomer recovered in the 5 th cycle of this example and its self-repairing elastomer also start to exhibit strain strengthening behavior at about 1200% of the strain, the curve becomes steeper, and the material does not break under continuous increase of the stress, but the strain is greatly increased.
Example 2
The self-repairing polyurethane elastomer based on multiple hydrogen bonds/nitrogen coordination boron-oxygen bonds is prepared by the following method:
(1) 10.00mmol of polytetrahydrofuran ether glycol (number average molecular weight 3000 g/mol) are taken and added into a three-necked flask, 45.0mmol of isophorone diisocyanate and 0.01g of catalyst dibutyltin dilaurate are added in sequence, and N is introduced 2 Reacting gas at 20 ℃ for 3 hours to obtain polyurethane prepolymer;
(2) 18.34mmol of 2, 6-pyridine dimethanol and 25mL of toluene are added into the reaction solution obtained in the step (1), a reflux condensing device is arranged, the temperature is raised to 80 ℃, and N 2 Chain extension reaction is carried out for 4 hours in the atmosphere to obtain a chain extension polyurethane prepolymer;
(3) To the reaction solution obtained in the step (2) were added 12.21mmol of 4,4' -methylenebis (2-chloroaniline) and 30mL of N, N-dimethylformamide at the same temperature as in the step (2) 2 Continuously reacting for 4 hours in the atmosphere to obtain primary amino-NH 2 A capped chain-extended polyurethane prepolymer;
(4) To the reaction solution obtained in the step (3) were added 4.00mmol of 2-formylphenylboronic acid and 25mL of toluene at the same temperature as in the step (3) under N 2 And (3) carrying out Schiff base reaction for 5 hours under the condition of molecular sieve in the atmosphere to obtain a final light yellow viscous product, and removing solvent and impurities to obtain the self-repairing polyurethane elastomer.
Wherein, the polytetrahydrofuran ether glycol used in the step (1) is stirred at 110 ℃ and dehydrated for 30min in vacuum, and is cooled to 40 ℃; the molar ratio of polytetrahydrofuran ether glycol, isophorone diisocyanate, 2, 6-pyridine dimethanol, 4' -methylenebis (2-chloroaniline) and 2-formylphenylboronic acid monomer added in steps (1) to (4) is 1.0:4.5:1.83:1.22:0.4.
the mechanical property and the self-repairing property of the cast elastomer are tested, the tensile strength is 18.82MPa, and the fracture toughness is 117.14 MJ.m -3 The elongation at break is 2132%, and the tensile strength, the elongation at break and the fracture toughness after 48h of room temperature self-repair are 17.82MPa and 113.27 MJ.m respectively -3 The self-repairing efficiency reaches 94.7%, 96.7% and 91.7% respectively, and the elastic physical property and the self-repairing property are good.
The tensile strength of the elastomer recovered in the 5 th cycle was 18.82MPa and the fracture toughness was 116.99 MJ.m as measured by 5 cycles, i.e., repeating the cycle of cutting-self-repairing-stretching-dissolution casting 5 times -3 The elongation at break is 2131%, and the tensile strength, the elongation at break and the fracture toughness after 48h of room temperature self-repair are 17.82MPa and 112.90 MJ.m respectively -3 1952%, the self-repairing efficiency reaches 94.7%, 96.5% and 91.6% respectively. Therefore, the polyurethane elastomer also has excellent dissolution recycling property, and the mechanical property and the self-repairing efficiency of the polyurethane elastomer are not obviously reduced after recycling.
In the tensile test of this example, strain strengthening behavior was developed, and the material did not fracture under continuous increase of stress, but strain was greatly increased.
Example 3
The self-repairing polyurethane elastomer based on multiple hydrogen bonds/nitrogen coordination boron-oxygen bonds is prepared by the following method:
(1) 10.00mmol of polytetrahydrofuran ether glycol (number average molecular weight 1500 g/mol) are taken and added into a three-necked flask, 35.0mmol of isophorone diisocyanate and 0.01g of catalyst dibutyltin dilaurate are added in sequence, and N is introduced 2 Reacting gas at 20 ℃ for 1.5 hours to obtain polyurethane prepolymer;
(2) 15.52mmol of 2, 6-pyridine dimethanol and 20mL of toluene are added into the reaction solution obtained in the step (1), a reflux condensing device is arranged, the temperature is raised to 80 ℃, and N 2 Chain extension reaction is carried out for 3 hours in the atmosphere to obtain a chain extension polyurethane prepolymer;
(3) To the reaction solution obtained in the step (2) were added 15.52mmol of 4,4' -methylenebis (2-chloroaniline) and 20mL of N, N-dimethylformamide at the same temperature as in the step (2) 2 Continuously reacting for 3 hours in the atmosphere to obtain primary amino-NH 2 A capped chain-extended polyurethane prepolymer;
(4) To the reaction solution obtained in the step (3) were added 7.00mmol of 2-formylphenylboronic acid and 25mL of toluene at the same temperature as in the step (3) under N 2 And (3) carrying out Schiff base reaction for 4 hours under the condition of molecular sieve in the atmosphere to obtain a final light yellow viscous product, and removing solvent and impurities to obtain the self-repairing polyurethane elastomer.
Wherein, the polytetrahydrofuran ether glycol used in the step (1) is stirred at 130 ℃ and dehydrated in vacuum for 40min, and cooled to 20 ℃; the molar ratio of polytetrahydrofuran ether glycol, isophorone diisocyanate, 2, 6-pyridine dimethanol, 4' -methylenebis (2-chloroaniline) and 2-formylphenylboronic acid monomer added in steps (1) to (4) is 1.0:3.5:1.55:1.55:0.7.
the mechanical property and the self-repairing property of the cast elastomer are tested, the tensile strength is 1.81MPa, and the fracture toughness is 25.10 MJ.m -3 The elongation at break is 2479%, and the tensile strength, the elongation at break and the fracture toughness after 48h of room temperature self-repair are respectively 1.79MPa and 24.15 MJ.m -3 2449%, and the self-repairing efficiency reaches 98.7%, 96.2% and 98.8%, respectively, so that the elastic mechanical property and the self-repairing property are good.
The tensile strength of the elastomer recovered in the 5 th cycle was measured to be 2.40MPa and the fracture toughness was measured to be 33.01 MJ.m by 5 cycles, namely, 5 cycles of cutting-self-repairing-stretching-dissolution casting -3 The elongation at break is 2457%, and the tensile strength, the elongation at break and the fracture toughness after 48h of room temperature self-repair are 2.36MPa and 31.59 MJ.m -3 2452%, and the self-repairing efficiency reaches 98.4%, 95.7% and 99.8% respectively. Therefore, the polyurethane elastomer also has excellent dissolution recycling property, and the mechanical property and the self-repairing efficiency of the polyurethane elastomer are not obviously reduced after recycling.
In the tensile test of this example, strain strengthening behavior was developed, and the material did not fracture under continuous increase of stress, but strain was greatly increased.
In summary, the present invention is only limited to the preferred embodiments, and any changes or substitutions that are within the technical scope of the embodiments disclosed herein will be readily apparent to those skilled in the art. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (7)
1. The self-repairing polyurethane elastomer based on multiple hydrogen bonds/nitrogen coordination boron-oxygen bonds and the preparation method thereof are characterized by comprising the following specific preparation steps:
(1) 10.0mmol of polytetrahydrofuran ether glycol is taken and added into a three-necked flask, isophorone diisocyanate and a catalyst are added in sequence, and N is introduced 2 Carrying out polyurethane reaction for 1-3 hours at 20-40 ℃ to obtain polyurethane prepolymer;
(2) Adding 2, 6-pyridine dimethanol and toluene into the reaction solution obtained in the step (1), installing a reflux condensing device, and heating to 70-90 ℃ and N 2 Chain extension reaction is carried out for 2-5 hours in the atmosphere to obtain a chain extension polyurethane prepolymer;
(3) Adding 4,4' -methylenebis (2-chloroaniline) and N, N-dimethylformamide to the reaction solution obtained in the step (2) at the same temperature as in the step (3) at N 2 Continuously reacting for 2-5h in the atmosphere to obtain primary amino-NH 2 A capped chain-extended polyurethane prepolymer;
(4) Adding 2-formylphenylboronic acid and toluene into the reaction solution obtained in the step (3), and carrying out N-phase reaction at the same temperature in the step (3) 2 Carrying out Schiff base reaction for 2-5h in the presence of molecular sieve to obtain final light yellow viscous product, removing solvent and impurities to obtain the target product self-repairing polyurethane elastomer based on multiple hydrogen bonds/nitrogen coordination boron-oxygen bonds,
wherein, the molar ratio of polytetrahydrofuran ether glycol, isophorone diisocyanate, 2, 6-pyridine dimethanol, 4' -methylene bis (2-chloroaniline) and 2-formylphenylboric acid is 1.0: (3.0-5.0): (0.4-2.5): (0.6-2.4): (0.2-0.8).
2. The method according to claim 1, wherein the polytetrahydrofuran ether glycol, prior to use, is subjected to the following pretreatment: the polytetrahydrofuran ether glycol is decompressed and dehydrated for 20 to 40 minutes at the temperature of 110 to 130 ℃ and cooled to 20 to 40 ℃.
3. The process according to claim 1, wherein the polytetrahydrofuran ether glycol has a number average molecular weight of 1000 to 4000g/mol.
4. The method according to claim 1, wherein the catalyst is dibutyl tin dilaurate, and the catalyst is added in an amount of 0.1-1% by mass of monomeric isophorone diisocyanate.
5. The method according to claim 1, wherein toluene is added in the amount of 0.4 to 1.0 times the total mass of the reaction monomers in both the step (2) and the step (4).
6. The method according to claim 1, wherein the amount of the N, N-dimethylformamide added in the step (3) is 0.5 to 1.0 times the total mass of the reaction monomers.
7. A self-repairing polyurethane elastomer based on multiple hydrogen bonds/nitrogen coordination boron-oxygen bonds and a preparation method thereof, and the self-repairing polyurethane elastomer is prepared by adopting the method of any one of claims 1-6.
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