CN116102704B - A kind of ultra-high strength repairable and recyclable elastomeric material and preparation method thereof - Google Patents
A kind of ultra-high strength repairable and recyclable elastomeric material and preparation method thereof Download PDFInfo
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- CN116102704B CN116102704B CN202310157609.9A CN202310157609A CN116102704B CN 116102704 B CN116102704 B CN 116102704B CN 202310157609 A CN202310157609 A CN 202310157609A CN 116102704 B CN116102704 B CN 116102704B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000013536 elastomeric material Substances 0.000 title description 10
- 239000000463 material Substances 0.000 claims abstract description 97
- 229920001971 elastomer Polymers 0.000 claims abstract description 79
- 239000000806 elastomer Substances 0.000 claims abstract description 79
- 229920000642 polymer Polymers 0.000 claims abstract description 48
- 229920000547 conjugated polymer Polymers 0.000 claims abstract description 38
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 8
- 239000004697 Polyetherimide Substances 0.000 claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 8
- 229920002530 polyetherether ketone Polymers 0.000 claims description 8
- 229920001601 polyetherimide Polymers 0.000 claims description 8
- 229920001721 polyimide Polymers 0.000 claims description 8
- 229920000162 poly(ureaurethane) Polymers 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 229920002396 Polyurea Polymers 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004064 recycling Methods 0.000 abstract description 21
- 238000004132 cross linking Methods 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229920006247 high-performance elastomer Polymers 0.000 abstract description 5
- 230000021715 photosynthesis, light harvesting Effects 0.000 abstract description 3
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004154 testing of material Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical group 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
-
- 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
- C08G18/28—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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/6438—Polyimides or polyesterimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
The invention provides an ultra-high strength repairable and recyclable elastomer material and a preparation method thereof, and belongs to the technical field of high-performance elastomer materials. The conjugated polymer A and the linear polymer B react with isocyanate groups through amino groups (or hydroxyl groups) to realize copolymerization. The conjugated polymer A is used as a hard segment to provide a rigid skeleton for the elastomer, and can realize self-assembly in a polymer network so as to form a nano microphase area to further strengthen the elastomer material. The linear polymer B contains a large amount of hydrogen bonds, so that effective energy dissipation can be realized in the stretching process, and the stretching performance of the elastomer is improved. The invention combines two polymers together by means of chemical copolymerization, and the material does not show obvious phase-splitting structure in a macroscopic sense. Because permanent crosslinking sites are not introduced into the elastomer material, the functions of repairing and recycling can be realized.
Description
Technical Field
The invention relates to the technical field of high-performance elastomer materials, in particular to an ultra-high-strength repairable and recyclable elastomer material and a preparation method thereof.
Background
The elastomer material has excellent mechanical properties and is widely applied to various fields in life, such as the fields of automobiles, flexible devices, medical fields and the like. However, the existing high-performance elastomer materials are generally realized through permanent crosslinking, and cannot realize the repairing or recycling functions, so that a great deal of resource waste and environmental pollution are caused. With the progress of the age, it is necessary to impart repair and recycling properties to elastomeric materials.
The repairing and recycling functions imparted to the elastomer material are generally realized through reversible crosslinking, however, the reversible crosslinking elastomer material generally causes the mechanical property to be reduced, and the application in the practical field is difficult. In recent years, the introduction of nano-microstructures into elastomeric materials is an effective way to reinforce elastomers, while the process is easier to repair and recycle materials than permanent crosslinking. But elastomeric materials prepared by way of nanostructure enhancement remain limited in strength. Therefore, the preparation of the elastomer material which has excellent mechanical properties and can be repaired and recycled still has certain difficulty.
Disclosure of Invention
The invention aims to provide an ultra-high-strength repairable and recyclable elastomer material and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides an elastomer material which is formed by copolymerizing a conjugated polymer A and a linear polymer B, wherein the molar quantity of the conjugated polymer A is 25-50% of the total molar quantity of the conjugated polymer A and the linear polymer B;
the conjugated polymer A is an amino or hydroxyl terminated conjugated polymer;
the linear polymer B is a linear polymer containing hydrogen bonds and isocyanate groups.
Preferably, the conjugated polymer A is one or more of amino-terminated polyimide, hydroxyl-terminated polyimide, amino-terminated polyether ether ketone, hydroxyl-terminated polyether ether ketone, amino-terminated polyether imide and hydroxyl-terminated polyether imide.
Preferably, the linear polymer B is one or more of isocyanate-terminated polyurethanes, polyureas and polyureaurethanes.
The invention provides a preparation method of the elastomer material, which comprises the following steps of dissolving a conjugated polymer A and a linear polymer B into an organic solvent, carrying out copolymerization reaction, and removing the organic solvent to obtain the elastomer material.
Preferably, the temperature of the copolymerization reaction is 60-80 ℃.
Preferably, the copolymerization reaction time is 8-24 hours.
Preferably, the organic solvent comprises one or more of N, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide, acetonitrile, N-methylpyrrolidone and chloroform.
Preferably, the total concentration of the conjugated polymer A and the linear polymer B in the organic solvent is 40-100 mg/mL.
Preferably, the removal of the organic solvent comprises volatilizing the organic solvent when the polymer solution obtained by the copolymerization reaction is placed under the condition of 25-90 ℃.
Preferably, the copolymerization is carried out in the presence of a catalyst.
The invention provides an elastomer material which is formed by copolymerizing a conjugated polymer A and a linear polymer B, wherein the molar weight of the conjugated polymer A is 25-50% of the total molar weight of the conjugated polymer A and the linear polymer B, the conjugated polymer A is an amino or hydroxyl end-capped conjugated polymer, and the linear polymer B is a linear polymer containing hydrogen bonds and isocyanate groups.
The principle of the invention is that the conjugated polymer A and the linear polymer B react with isocyanate groups through amino (or hydroxyl) to realize copolymerization. The conjugated polymer A is used as a hard segment to provide a rigid skeleton for the elastomer, and can realize self-assembly in a polymer network so as to form a nano microphase area to further strengthen the elastomer material. The linear polymer B contains a large amount of hydrogen bonds, so that effective energy dissipation can be realized in the stretching process, and the stretching performance of the elastomer is improved. The invention combines two polymers together by means of chemical copolymerization, and the material does not show obvious phase-splitting structure in a macroscopic sense. Because permanent crosslinking sites are not introduced into the elastomer material, the functions of repairing and recycling can be realized.
When the elastomer material is damaged, the wound is soaked in a proper solvent, and then the solvent is volatilized by heating, so that the repair of the material can be realized. The used elastomer material can realize hot-pressing recovery under certain pressure and temperature. The elastomer material used is dissolved in an organic solvent, and the elastomer material can be recycled. The strength of the material is almost unchanged from that of the raw material, and the material has excellent repairing and recycling performances. The invention greatly reduces the maintenance cost of the elastomer material and also avoids the problems of material waste and environmental pollution. In addition, the elastomer material in the invention also has excellent scratch resistance and puncture resistance because the prepared elastomer has extremely excellent mechanical properties.
The elastomer material has simple synthesis process and can realize large-area preparation of the material.
Drawings
FIG. 1 is a display and a stretch graph of an elastomeric material of example 1 of the present invention;
FIG. 2 is a stretch graph of a repair of the elastomeric material of example 2 of the present invention;
FIG. 3 is a stretch graph of the recycling of elastomeric material of example 2 of the present invention;
FIG. 4 is a scratch-resistant photograph and corresponding scanning electron microscope image of the elastomeric material of example 3 of the present invention;
fig. 5 is a puncture resistant display of the elastomeric material of example 3 of the present invention.
Detailed Description
The invention provides an elastomer material which is formed by copolymerizing a conjugated polymer A and a linear polymer B, wherein the molar quantity of the conjugated polymer A is 25-50% of the total molar quantity of the conjugated polymer A and the linear polymer B;
the conjugated polymer A is an amino or hydroxyl terminated conjugated polymer;
the linear polymer B is a linear polymer containing hydrogen bonds and isocyanate groups.
In the present invention, the conjugated polymer a is preferably one or more of amino-terminated polyimide, hydroxyl-terminated polyimide, amino-terminated polyetheretherketone, hydroxyl-terminated polyetheretherketone, amino-terminated polyetherimide and hydroxyl-terminated polyetherimide.
In the present invention, the linear polymer B is preferably one or more of isocyanate group-terminated polyurethane, polyurea, and polyureaurethane.
The present invention is not particularly limited to the sources of the conjugated polymer A and the linear polymer B, and can be prepared by commercially available products known in the art or by methods known in the art.
In the present invention, the molar amount of the conjugated polymer a is preferably 30 to 45%, more preferably 35 to 40% of the total molar amount of the conjugated polymer a and the linear polymer B.
In the invention, the conjugated polymer A is used as a hard chain segment to provide a rigid framework for the elastomer, and the conjugated polymer A can realize self-assembly in a polymer network, thereby forming a nano microphase area and further enhancing the elastomer material. The linear polymer B contains a large amount of hydrogen bonds, so that effective energy dissipation can be realized in the stretching process, and the stretching performance of the elastomer is improved. The invention combines two polymers together by means of chemical copolymerization, and the material does not show obvious phase-splitting structure in a macroscopic sense. Because permanent crosslinking sites are not introduced into the elastomer material, the functions of repairing and recycling can be realized.
The invention provides a preparation method of the elastomer material, which comprises the following steps of dissolving a conjugated polymer A and a linear polymer B into an organic solvent, carrying out copolymerization reaction, and removing the organic solvent to obtain the elastomer material.
In the present invention, the organic solvent preferably includes one or more of N, N-dimethylformamide, dimethylsulfoxide, N-dimethylacetamide, acetonitrile, N-methylpyrrolidone and chloroform.
In the present invention, the total concentration of the conjugated polymer a and the linear polymer B in the organic solvent is preferably 40 to 100mg/mL, and in the embodiment of the present invention, specifically 50mg/mL or 60mg/mL.
The present invention has no special requirements for the dissolution process, and dissolution processes well known in the art can be used.
In the invention, the temperature of the copolymerization reaction is preferably 60-80 ℃, more preferably 70-80 ℃, and the time is preferably 8-24 hours, more preferably 12-20 hours, and even more preferably 24 hours.
In the present invention, the copolymerization is preferably carried out in the presence of a catalyst, and the present invention is not particularly limited to the specific kind and amount of the catalyst, and catalysts for copolymerization of amino (or hydroxyl) and isocyanate groups well known in the art and conventional amounts may be used. In an embodiment of the invention, the catalyst is specifically a dibutyltin dilaurate catalyst.
In the present invention, the conjugated polymer A and the linear polymer B are preferably dissolved in an organic solvent, the resulting solution is heated to a copolymerization reaction temperature, and then a catalyst is added to carry out a copolymerization reaction.
In the present invention, the copolymerization reaction is preferably carried out under stirring conditions, and the stirring speed is not particularly limited, and the stirring speed of the copolymerization reaction known to those skilled in the art may be used. In the copolymerization reaction process, the amino or hydroxyl in the conjugated polymer A reacts with the isocyanate group in the linear polymer B to realize copolymerization.
After the copolymerization reaction is completed, the organic solvent in the obtained polymer solution is removed, and the elastomer material is obtained.
In the invention, the removal of the organic solvent preferably comprises the step of volatilizing the organic solvent under the condition of 25-90 ℃ for the polymer solution. The present invention may further select an appropriate temperature within the above range according to the kind of solvent. The invention preferably pours the polymer solution into a glass petri dish or polytetrafluoroethylene mold, and then places the petri dish or mold containing the polymer solution in an oven to remove the organic solvent.
When the elastomer material is damaged, the wound is soaked in a proper solvent for a certain time, and then the solvent is volatilized by heating, so that the repair of the material can be realized. In the present invention, the solvent used for the repair is preferably one or more of N, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide, acetonitrile, N-methylpyrrolidone and chloroform, and in the present invention, the soaking time depends on the size of the sample and the selected repair solvent, and the heating temperature depends on the repair solvent.
When the elastomer material is to be recycled, the used elastomer material can realize hot-pressing recovery under certain pressure and temperature. In the invention, the hot pressing temperature is 150-230 ℃ and the pressure is 2-5 MPa.
Or the used elastomer material is dissolved in an organic solvent, and the elastomer material can be recycled. The concentration of the polymer solution after dissolution is preferably 100-200 mg/mL.
The ultra-high strength repairable and recyclable elastomer materials and methods of making the same provided by the present invention are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
A method for preparing an ultra-high strength repairable and recyclable elastomer comprises the following steps of calculating the consumption of each raw material according to mole fraction:
1) 25% of amino-terminated polyether-ether-ketone, 2) 75% of self-made isocyanate-terminated polyurethane.
The self-made isocyanate-terminated polyurethane is prepared by dissolving hydroxyl-terminated polytetrahydrofuran with the molecular weight of 2000 in a dry tetrahydrofuran solvent with the concentration of 200mg/mL, adding excessive dicyclohexylmethane-4, 4' -diisocyanate, heating to 60 ℃, dripping three drops of dibutyltin dilaurate, and then continuously reacting for 3 hours at the temperature to obtain the isocyanate-terminated polyurethane.
The amino-terminated polyether-ether-ketone and isocyanate-terminated polyurethane were dissolved in N, N-dimethylformamide at a concentration of 60mg/mL, then heated to 85℃and three drops of dibutyltin dilaurate catalyst were added and stirring was continued for 3 days until the reaction was completed to give a pale yellow polymer solution. Pouring the solution into a glass surface dish, putting the surface dish into a 50 ℃ oven to volatilize the solvent, and after 24 hours, volatilizing the solvent to obtain the complete elastomer film.
After testing by a universal material testing machine, the elastomer material has the strength of 128MPa and the toughness of 379 MJ.m -3 (figure 1) and belongs to an ultra-high performance elastomer material. Then, the material is cut off from the middle, the fracture is soaked in N, N-dimethylformamide for 20s, and then the material is placed in a 50 ℃ oven to dry the solvent, so that the elastomer can be repaired. The tensile test shows that the strength of the elastomer after repair is 125MPa, the toughness is 358 MJ.m -3, and the tensile property is almost consistent with that of the material before repair, thus the elastomer has good repair property.
After the elastomer material is chopped, the elastomer material can be redissolved in N, N-dimethylacetamide, and the elastomer material can be placed in a die for film paving, so that a new elastomer film can be obtained. In addition, the chopped elastomeric material is placed in a hot press, and recycling of the material can also be achieved at a pressure of 4MPa and a temperature of 220 ℃. By using the two recycling methods, the obtained material is found to be still capable of obtaining a complete film after being recycled for two times. The materials after the two recycling are tested by using a universal material testing machine, and the mechanical properties of the materials are hardly changed, and the specific results are shown in table 1. The material is proved to have extremely excellent recycling performance. The prepared elastomer material also has excellent scratch resistance and puncture resistance due to the extremely excellent mechanical properties.
TABLE 1 recycling results of elastomeric materials of example 1
Example 2
A method for preparing an ultra-high strength repairable and recyclable elastomer comprises the following steps of calculating the consumption of each raw material according to mole fraction:
1) 35% of amino-terminated polyimide, 2) a self-made isocyanate-terminated polyureaurethane, 65%.
The self-made isocyanate-terminated polyureaurethane is prepared by dissolving hydroxyl-terminated polytetrahydrofuran having a molecular weight of 2000 in dry N, N-dimethylacetamide at a concentration of 200mg/mL, adding an excess of dicyclohexylmethane-4, 4' -diisocyanate, heating to 60℃and then dropping three drops of dibutyltin dilaurate, then continuously reacting at this temperature for 3 hours, then adding isophthalic acid dihydrazide and continuously reacting for 30 minutes to obtain the isocyanate-terminated polyureaurethane.
The amino-terminated polyimide and isocyanate-terminated polyureaurethane were dissolved in N, N-dimethylacetamide at a concentration of 50mg/mL, followed by heating to 80℃and adding three drops of dibutyltin dilaurate catalyst and stirring was continued for 3 days until the reaction was completed to give a pale yellow polymer solution. Pouring the solution into a glass surface dish, putting the surface dish into a 50 ℃ oven to volatilize the solvent, and after 24 hours, volatilizing the solvent to obtain the complete elastomer film.
After testing with a universal material tester, the elastomer material was obtained with a strength of 142MPa and a toughness of 527 MJ.m -3, which was not found in the prior art. The material is cut off from the middle, then the fracture is soaked in N, N-dimethylformamide for 20s, and then the material is placed in a 50 ℃ oven to dry the solvent, so that the elastomer can be repaired. As can be seen from the tensile test, the tensile properties of the elastomer after repair are almost identical to those of the material before repair, showing good repair properties (fig. 2). After the elastomer material is chopped, the elastomer material can be redissolved in N, N-dimethylacetamide, and the elastomer material can be placed in a die for film paving, so that a new elastomer film can be obtained. In addition, the chopped elastomeric material is placed in a hot press, and recycling of the material can also be achieved at a pressure of 4MPa and a temperature of 220 ℃. The materials after tertiary recycling are tested by using a universal material testing machine, the mechanical properties of the materials are hardly changed, the specific results are shown in figure 3, and the data corresponding to figure 3 are shown in table 2. The prepared elastomer material also has excellent scratch resistance and puncture resistance due to the extremely excellent mechanical properties.
TABLE 2 recycling results of elastomeric materials of example 2
Example 3
A method for preparing an ultra-high strength repairable and recyclable elastomer comprises the following steps of calculating the consumption of each raw material according to mole fraction:
1) 45% of hydroxyl-terminated polyetherimide and 2) 55% of isocyanate-terminated polyurea.
The self-made isocyanate-terminated polyurea is prepared by dissolving amino-terminated polyethylene glycol with molecular weight of 2000 in dry tetrahydrofuran solvent at a concentration of about 200mg/mL, adding excessive dicyclohexylmethane-4, 4' -diisocyanate, and heating to 60deg.C for continuous reaction for 3 hr to obtain the final product.
The hydroxyl-terminated polyetherimide and isocyanate-terminated polyurea were dissolved in dimethyl sulfoxide at a concentration of 60mg/mL, then heated to 85 ℃, three drops of dibutyltin dilaurate catalyst were added, and stirring was continued for 3 days until the reaction was completed, to obtain a pale yellow polymer solution. Pouring the solution into a glass surface dish, putting the surface dish into a 50 ℃ oven to volatilize the solvent, and after 36 hours, volatilizing the solvent to obtain the complete elastomer film.
After being tested by a universal material testing machine, the elastomer material has the strength of 139MPa and the toughness of 513 MJ.m -3, and belongs to the ultra-high performance elastomer material. Since the prepared elastomer shows extremely excellent mechanical properties, the elastomer material in the invention also shows excellent scratch resistance at the same time, and no scratch is left after 2000 scratches (fig. 4). The elastomeric material was able to move 19mm under puncture test conditions, exhibiting excellent puncture resistance (fig. 5). Then, the material is cut off from the middle, the fracture is soaked in N, N-dimethylformamide for 20s, and then the material is placed in a 50 ℃ oven to dry the solvent, so that the elastomer can be repaired. The tensile test can obtain that the tensile property of the elastomer after repair is almost consistent with that of the material before repair, and the elastomer shows good repair property. After the elastomer material is chopped, the elastomer material can be redissolved in dimethyl sulfoxide, and the elastomer material is placed in a die again for film paving, so that a new elastomer film can be obtained. In addition, the chopped elastomeric material is placed in a hot press, and recycling of the material can also be achieved at a pressure of 4MPa and a temperature of 220 ℃. By using the two recycling methods, the obtained material is recycled for two times, and the complete film can be obtained. The materials after the two recycling are tested by using a universal material testing machine, the test results are shown in table 3, and the mechanical properties of the materials are hardly changed, so that the materials are excellent in recycling performance.
TABLE 3 recycling results of elastomeric materials of example 3
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The elastomer material is characterized by being formed by copolymerizing a conjugated polymer A and a linear polymer B, wherein the molar quantity of the conjugated polymer A is 25-50% of the total molar quantity of the conjugated polymer A and the linear polymer B;
The conjugated polymer A is one or more of amino-terminated polyimide, hydroxyl-terminated polyimide, amino-terminated polyether-ether-ketone, hydroxyl-terminated polyether-ether-ketone, amino-terminated polyether-imide and hydroxyl-terminated polyether-imide;
the linear polymer B is one or more of isocyanate-terminated polyurethanes, polyureas, and polyureaurethanes.
2. The method for preparing the elastomer material according to claim 1, wherein the method comprises the steps of dissolving the conjugated polymer A and the linear polymer B in an organic solvent, carrying out copolymerization reaction, and removing the organic solvent to obtain the elastomer material.
3. The method according to claim 2, wherein the temperature of the copolymerization reaction is 60 to 80 ℃.
4. The method according to claim 2 or 3, wherein the copolymerization is carried out for 8 to 24 hours.
5. The method according to claim 2, wherein the organic solvent comprises one or more of N, N-dimethylformamide, dimethylsulfoxide, N-dimethylacetamide, acetonitrile, N-methylpyrrolidone, and chloroform.
6. The preparation method according to claim 2 or 5, wherein the total concentration of the conjugated polymer a and the linear polymer B in the organic solvent is 40-100 mg/mL.
7. The method according to claim 2 or 5, wherein the removing the organic solvent comprises volatilizing the organic solvent under a condition of 25-90 ℃ from the polymer solution obtained by the copolymerization reaction.
8. A process according to claim 2 or 3, wherein the copolymerization is carried out in the presence of a catalyst.
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