CN116789932A - Recyclable polyurethane elastomer containing multiple hydrogen bonds and obtained through chain extension of aldehyde groups and preparation method of recyclable polyurethane elastomer - Google Patents
Recyclable polyurethane elastomer containing multiple hydrogen bonds and obtained through chain extension of aldehyde groups and preparation method of recyclable polyurethane elastomer Download PDFInfo
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- CN116789932A CN116789932A CN202310946213.2A CN202310946213A CN116789932A CN 116789932 A CN116789932 A CN 116789932A CN 202310946213 A CN202310946213 A CN 202310946213A CN 116789932 A CN116789932 A CN 116789932A
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- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 51
- 239000001257 hydrogen Substances 0.000 title claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 32
- 125000003172 aldehyde group Chemical group 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 229920005862 polyol Polymers 0.000 claims description 31
- 150000003077 polyols Chemical class 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 10
- 239000004417 polycarbonate Substances 0.000 claims description 10
- 229920000515 polycarbonate Polymers 0.000 claims description 10
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 150000001299 aldehydes Chemical class 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- 229920001610 polycaprolactone Polymers 0.000 claims description 8
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 7
- 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 7
- 150000004985 diamines Chemical class 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 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 description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000011253 protective coating Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 23
- 239000000806 elastomer Substances 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 15
- 229920002635 polyurethane Polymers 0.000 abstract description 9
- 239000004814 polyurethane Substances 0.000 abstract description 9
- 230000003993 interaction Effects 0.000 abstract description 8
- 239000004970 Chain extender Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 229920005570 flexible polymer Polymers 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000005191 phase separation Methods 0.000 abstract description 2
- 230000021715 photosynthesis, light harvesting Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 150000001412 amines Chemical group 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 7
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 4
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 4
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GKGXKPRVOZNVPQ-UHFFFAOYSA-N diisocyanatomethylcyclohexane Chemical compound O=C=NC(N=C=O)C1CCCCC1 GKGXKPRVOZNVPQ-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920006247 high-performance elastomer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to an aldehyde group chain extension recyclable polyurethane elastomer containing multiple hydrogen bonds and a preparation method thereof, belonging to the technical field of preparation of high-strength and high-toughness polyurethane elastomers. By introducing multiple hydrogen bonds into the hard polyurethane segment by adopting the amine chain extender containing the amide bond, the larger polarity difference between the hard segment and the soft segment and the stronger hydrogen bond action between the hard segments are increased, and the microphase separation degree of the soft segment and the hard segment is increased. The phase separation formed hard segment nano structure has similar physical crosslinking effect, endows the material with certain rigidity and deformation resistance, and has high toughness and energy dissipation effect. Because of the non-covalent interactions of hydrogen bonds, stretching of the flexible polymer segments can dissipate energy when the material undergoes small deformations; with the gradual increase of deformation, the hydrogen bond interaction is opened to further dissipate energy, so that the elastomer has high strength and high toughness, is broken and destroyed in the stretching process, absorbs energy, and simultaneously has higher toughness.
Description
Technical Field
The invention relates to an aldehyde group chain extension recyclable polyurethane elastomer containing multiple hydrogen bonds and a preparation method thereof, belongs to the technical field of preparation of high-strength and high-toughness polyurethane elastomers, and particularly relates to a preparation method of a recyclable high-performance elastomer based on multiple hydrogen bonds and dynamic imine bonds.
Background
The elastomer is a high polymer material with larger deformation and rebound capability under the action of external force. Deformation occurs under the action of external force, and the original shape is restored after the external force is removed. Polyurethane elastomer has good physical and mechanical properties, wear resistance, oil resistance, low temperature resistance, high insulativity and excellent dynamic mechanical properties, and is widely applied to industries such as railways, automobiles, shoemaking, buildings, sealing and the like. Polyurethane elastomers have become an important material in emerging frontier fields such as flexible wearable electronics, soft robots, 3D printing, and the like.
However, the great consumption and difficulty in recycling and degrading of polyurethane elastomer materials have resulted in serious resource waste and environmental pollution. Thermoplastic polyurethane elastomers can be reprocessed after melting, but the high temperature melting process can lead to polymer molecular chain breakage, which results in loss of mechanical properties and can only be used in a degraded manner. For chemical bond cross-linked thermosetting elastomers, the bond is generally not degradable or recyclable. Therefore, development of a repairable and recyclable polyurethane elastomer material is of great significance for resource utilization.
To achieve repair and recycling of polyurethane elastomeric materials, non-covalent interactions are typically employed to crosslink polymer segments to build elastomeric materials having rubbery properties. The non-covalent bonds used for preparing the elastomer material at present mainly comprise ionic bonds, coordination bonds, interaction of a host and a guest, and the popularization and application of the elastomer material are limited due to the fact that raw materials for constructing the covalent bonds are not easy to obtain, the operation process is complex, and the interaction force among the non-covalent bonds is weak, so that the elastomer material has limited capability of improving the performance of the elastomer and other adverse factors.
Disclosure of Invention
The technical solution of the invention is as follows: the polyurethane elastomer with the amide bond is prepared by introducing multiple hydrogen bonds into a hard polyurethane segment by adopting a chain extender containing the amide bond, so that the repairable characteristic of the polyurethane elastomer is endowed, the service life and the period of the elastomer are prolonged, and in order to further obtain a polyurethane elastomer material which can be recovered after use, an polyurethane oligomer blocked by an amino group is secondarily extended by an aldehyde group-containing compound, so that the polyurethane elastomer containing the imine bond is obtained, and the polyurethane elastomer is endowed with the recoverable and reutilization characteristic.
The technical scheme of the invention is as follows:
an aldehyde group chain extension recyclable polyurethane elastomer containing multiple hydrogen bonds, which has a structural general formula:
wherein n is 1 Repeating the number of units, n 1 The value range of (2) is 1-2;
a is a polyurethane prepolymer blocked by hydrazide, and the structure of A is as follows:
the value range of n is 4-6;
R 1 is one or more than one of diisocyanate monomers, R 1 The structure of (2) is as follows:
R 2 is one or more of polytetrahydrofuran polyol, polycaprolactone polyol, polycarbonate polyol or polyether polyol, R 2 The structure of (2) is as follows:
R 2 has a molecular weight of 1000 or 2000
R 3 Is dihydrazide, R 3 The structure of (2) is as follows:
b is aliphatic, aromatic or heterocyclic dialdehyde or trialdehyde, and the structure of B is as follows:
the preparation method of the recyclable polyurethane elastomer with multiple hydrogen bonds by aldehyde group chain extension comprises the steps of using raw materials including polyalcohol, isocyanate, catalyst, diamine containing amide bond, compound containing aldehyde group and solvent;
the method comprises the following steps:
step 1, under the protection of nitrogen, uniformly mixing polyol, isocyanate and a catalyst in a solvent, and reacting for 1-6 hours at 20-100 ℃ with the stirring speed of 50-300rpm to obtain a prepolymer;
step 2, reacting the prepolymer obtained in the step 1 with diamine containing an amide bond for 0.5-48 hours to obtain an amino-terminated oligomer;
step 3, carrying out secondary chain extension crosslinking on the oligomer obtained in the step 2 and the compound containing aldehyde groups, wherein the reaction time is 0.5-48h, and drying at 50-100 ℃ for 12-48h under vacuum condition to obtain the degradable recyclable polyurethane elastomer;
in the step 1, the polyol is at least one of polyether polyol, polyester polyol, polycarbonate polyol and polycaprolactone polyol, specifically polytetrahydrofuran polyol (molecular weight 1000 or 2000), polycarbonate polyol (molecular weight 1000 or 2000) and polycarbonate polyol (molecular weight 1000 or 2000);
in the step 1, the molar ratio of the polyol to the isocyanate is 1:2-10; the water content of the polyol is less than 0.05%; the catalyst is used in an amount of 0.05 to 1wt%, preferably 0.1wt%, based on the total mass of the reactants; reactants include polyols, isocyanates, catalysts, amide bond-containing diamines;
in the step 1, the isocyanate is at least one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI) and Hexamethylene Diisocyanate (HDI), preferably, the isocyanate is isophorone diisocyanate (IPDI) or dicyclohexylmethane diisocyanate (HMDI);
in the step 1, the catalyst is dibutyl tin dilaurate;
in the step 1, the solvent is N, N-dimethylacetamide or N, N-dimethylformamide, and the mass of the solvent is 2-3 times of the total mass of reactants;
in the step 2, the structural formula of the diamine containing the amide bond is as follows:
in the step 3, the structural formula of the aldehyde group-containing compound is as follows:
OHC-B-CHO。
performance testing was performed on the degradable recyclable polyurethane elastomer obtained as described above, using standard GB-T1040.3-2006 plastic tensile properties determination part 3: the performance test is carried out on the test conditions of the thin plastic and the thin sheet, and the test results are as follows: the tensile strength is 40-65MPa; the elongation at break is 300% -1200%, and the material has 100% self-repairing efficiency at 100-140 ℃;
stirring the obtained degradable recyclable polyurethane elastomer in a 1mol/L HCL solution at 30-50 ℃ for 90min, recovering an aldehyde group-containing compound and an amino-terminated oligomer by imine bond breakage, performing secondary chain extension crosslinking on the recovered aldehyde group-containing compound and the amino-terminated oligomer, reacting for 0.5-48h, and drying at 50-100 ℃ for 12-48h under vacuum condition to obtain the degradable recyclable polyurethane elastomer;
the degradable and recyclable polyurethane elastomer obtained by the method can be used for manufacturing impact-resistant protective coatings, electronic skins or high-strength and high-toughness polyurethane elastomers.
Advantageous effects
(1) The invention introduces multiple hydrogen bonds into the hard polyurethane segment by adopting the amine chain extender containing amide bonds, thereby increasing larger polarity difference between the hard segment and the soft segment and stronger hydrogen bond action between the hard segments and increasing the microphase separation degree of the soft segment and the hard segment. The phase separation formed hard segment nano structure has similar physical crosslinking effect, endows the material with certain rigidity and deformation resistance, and has high toughness and energy dissipation effect. Because of the non-covalent interactions of hydrogen bonds, stretching of the flexible polymer segments can dissipate energy when the material undergoes small deformations; with the gradual increase of deformation, the hydrogen bond interaction is opened to further dissipate energy, so that the elastomer has high strength and high toughness, is broken and destroyed in the stretching process, absorbs energy, and simultaneously has higher toughness;
(2) In the invention, the chain extender containing amide bonds is adopted to introduce multiple hydrogen bonds into the hard polyurethane segment, and the multiple hydrogen bonds are used as physical crosslinking points to form a strong three-dimensional crosslinking network. When multiple hydrogen bonds exist cooperatively, stronger interaction force can be obtained through superposition among the hydrogen bonds, and the elastomer has excellent mechanical properties. In addition, the hydrogen bond has dynamic reversibility, can realize dynamic fracture and recombination under temperature stimulation, endows the polyurethane elastomer with repairable characteristics, and prolongs the service life and the period of the elastomer.
(3) The polyurethane elastomer containing imine bonds is obtained through the compound secondary chain extension amino end-capped polyurethane oligomer containing aldehyde groups, and the polyurethane elastomer is endowed with the characteristic of recycling.
(4) The invention introduces multiple hydrogen bonds into the hard polyurethane segment by adopting the chain extender containing amide bonds, so as to endow the polyurethane elastomer with repairable characteristics and prolong the service life and the period of the elastomer. In order to further obtain a polyurethane elastomer material which can be recycled after use, an imine bond-containing polyurethane elastomer is obtained by secondarily extending a chain-amino-terminated polyurethane oligomer of an aldehyde group-containing compound, and the polyurethane elastomer is endowed with recycling characteristics.
Detailed Description
The invention is further illustrated by the following detailed description in conjunction with specific examples, which should not be taken as limiting the invention in any way.
Example 1
Slowly heating polytetrahydrofuran glycol (PTMG 1000) to 120 ℃ under stirring, and vacuum dehydrating for 2h, wherein the water content is measured to be less than 0.05% for standby.
8.892g,40mmol of isophorone diisocyanate (IPDI), 20g,20mmol of polytetrahydrofuran diol (PTMG 1000) and a catalyst dibutyltin dilaurate (0.1 wt%) are added into a 100ml three-port grinding bottle with a stirrer, a reflux condenser and a thermometer at room temperature, the reaction is carried out for 1h, then the temperature is increased to 80 ℃, and the reaction is carried out under the protection of nitrogen; and (3) measuring the-NCO content of the prepolymer, and stopping the reaction after the content reaches 5.81% of a set value to obtain the isocyanate-terminated polyurethane prepolymer.
The prepolymer was cooled to 40℃and a solution of adipic acid dihydrazide (6.97 g,40 mmol) in N, N-dimethylformamide was added dropwise and reacted for 24 hours to a clear solution. Then, a solution of terephthalaldehyde (2.68 g,20 mmol) in N, N-dimethylformamide was added dropwise and reacted at 40℃for 2 hours, and the solution was transparent. And finally, pouring the obtained polymer solution into a polytetrafluoroethylene sample box, defoaming in a vacuum oven at 50 ℃, and then drying in the oven at 80 ℃ for 48 hours to obtain a target elastomer sample.
The elastomer sheet was cut into dumbbell test pieces and tested for tensile properties, 54Mpa for tensile strength and 720% for elongation at break, the tensile broken bars were lapped and pressed at 120 ℃ for 10 minutes at 0.3Mpa, and again tested for tensile strength of 51Mpa.
Stirring the obtained degradable recyclable polyurethane elastomer in a 1mol/L HCL solution at 40 ℃ for 90min, recovering an aldehyde group-containing compound and an amino-terminated oligomer by imine bond breakage, performing secondary chain extension crosslinking on the recovered aldehyde group-containing compound and the amino-terminated oligomer, reacting for 24h, and drying at 80 ℃ for 24h under vacuum condition to obtain the degradable recyclable polyurethane elastomer;
the degradable and recyclable polyurethane elastomer obtained by the method can be used for manufacturing impact-resistant protective coatings, electronic skins or high-strength and high-toughness polyurethane elastomers.
Example 2
Slowly heating polycaprolactone diol (PCL 2000) to 120 ℃ under stirring, and vacuum dehydrating for 2 hours, wherein the measured moisture content is less than 0.05% for standby.
3.36g,20mmol of Hexamethylene Diisocyanate (HDI) and 20g,10mmol of polycaprolactone diol (PCL 2000) in a certain amount are added into a 100ml three-mouth grinding bottle provided with a stirrer, a reflux condenser and a thermometer, the mixture is reacted for 1h at 60 ℃, the catalyst dibutyltin dilaurate (0.1 wt%) is added after the temperature is reduced to below 50 ℃, then the temperature is increased to 80 ℃, and the mixture is stirred for 3h under the protection of nitrogen; and (3) measuring the-NCO content of the prepolymer, and stopping the reaction after the content reaches a set value of 3.59%, thus obtaining the isocyanate-terminated polyurethane prepolymer.
The prepolymer was cooled to 40℃and a solution of adipic acid dihydrazide (3.48 g,20 mmol) in N, N-dimethylformamide was added dropwise and reacted for 24 hours to a clear solution. Then, a solution of terephthalaldehyde (1.34 g,10 mmol) in N, N-dimethylformamide was added dropwise and reacted at 40℃for 2 hours, and the solution was transparent. And finally, pouring the obtained polymer solution into a polytetrafluoroethylene sample box, defoaming in a vacuum oven at 50 ℃, and then drying in the oven at 80 ℃ for 48 hours to obtain a target elastomer sample.
The elastomer sheet was cut into dumbbell-shaped test pieces and tested for tensile properties, tensile strength of 58Mpa and elongation at break of 920%.
Example 3
Slowly heating polycarbonate diol (PCDL 2000) to 120 ℃ under stirring, and vacuum dehydrating for 2 hours, wherein the water content is measured to be less than 0.05 percent for standby.
5.24g,20mmol of cyclohexylmethane diisocyanate (HMDI) and 20g,10mmol of a certain amount of polycarbonate diol (PCDL 2000) were added into a 100ml three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, reacted at 60℃for 1 hour, cooled to 50℃or lower, then added with dibutyltin dilaurate (0.1 wt%) as a catalyst, and then heated to 80℃and stirred under nitrogen for 3 hours; and (3) measuring the-NCO content of the prepolymer, and stopping the reaction after the content reaches 3.33% of a set value to obtain the isocyanate-terminated polyurethane prepolymer.
The prepolymer was cooled to 40℃and a solution of adipic acid dihydrazide (3.48 g,20 mmol) in N, N-dimethylformamide was added dropwise and reacted for 24 hours to a clear solution. Then, a solution of terephthalaldehyde (1.34 g,10 mmol) in N, N-dimethylformamide was added dropwise and reacted at 40℃for 2 hours, and the solution was transparent. And finally, pouring the obtained polymer solution into a polytetrafluoroethylene sample box, defoaming in a vacuum oven at 50 ℃, and then drying in the oven at 80 ℃ for 48 hours to obtain a target elastomer sample.
The elastomer sheet was cut into dumbbell-shaped test pieces and tested for tensile properties, tensile strength 56Mpa and elongation at break 620%.
Example 4
Slowly heating polytetrahydrofuran glycol (PTMG 1000) to 120 ℃ under stirring, and vacuum dehydrating for 2h, wherein the water content is measured to be less than 0.05% for standby.
In a 100ml three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 8.892g,40mmol of isophorone diisocyanate (IPDI) and 20g,20mmol of a certain amount of polytetrahydrofuran diol (PTMG 1000) were added at room temperature, after 1h of reaction, dibutyltin dilaurate (0.1 wt%) as a catalyst was added, and then the temperature was raised to 80℃and the reaction was stirred under nitrogen protection for 3h; and (3) measuring the-NCO content of the prepolymer, and stopping the reaction after the content reaches 5.81% of a set value to obtain the isocyanate-terminated polyurethane prepolymer.
The prepolymer was cooled to 40℃and a solution of terephthalic acid dihydrazide (7.77 g,40 mmol) in N, N-dimethylformamide was added dropwise and reacted for 24 hours to a clear solution. Then, a solution of terephthalaldehyde (2.68 g,20 mmol) in N, N-dimethylformamide was added dropwise and reacted at 40℃for 2 hours, and the solution was transparent. And finally, pouring the obtained polymer solution into a polytetrafluoroethylene sample box, defoaming in a vacuum oven at 50 ℃, and then drying in the oven at 80 ℃ for 48 hours to obtain a target elastomer sample.
The elastomer sheet was cut into dumbbell-shaped test pieces and tested for tensile properties, tensile strength 46Mpa and elongation at break 420%.
Example 5
Slowly heating polytetrahydrofuran glycol (PTMG 2000) to 120 ℃ under stirring, and vacuum dehydrating for 2h, wherein the water content is measured to be less than 0.05% for standby.
In a 100ml three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 8.892g,40mmol of isophorone diisocyanate (IPDI) and 20g,20mmol of a certain amount of polytetrahydrofuran diol (PTMG 1000) were added at room temperature, after 1h of reaction, dibutyltin dilaurate (0.1 wt%) as a catalyst was added, and then the temperature was raised to 80℃and the reaction was stirred under nitrogen protection for 3h; and (3) measuring the-NCO content of the prepolymer, and stopping the reaction after the content reaches 5.81% of a set value to obtain the isocyanate-terminated polyurethane prepolymer.
The prepolymer was cooled to 40℃and a solution of triacylhydrazine (6.97 g,40 mmol) in N, N-dimethylacetamide was added dropwise and reacted for 24h to a clear solution. Then, a solution of trimesic aldehyde (2.16 g,20 mmol) in N, N-dimethylacetamide was added dropwise, and the solution was transparent at 40℃for 2 hours. And finally, pouring the obtained polymer solution into a polytetrafluoroethylene sample box, defoaming in a vacuum oven at 50 ℃, and then drying in the oven at 80 ℃ for 48 hours to obtain a target elastomer sample.
The elastomer sheet was cut into dumbbell-shaped test pieces and tested for tensile properties, tensile strength of 62Mpa and elongation at break of 520%.
In summary, the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The recyclable polyurethane elastomer with multiple hydrogen bonds is characterized in that the structural formula of the polyurethane elastomer is as follows:
wherein n is 1 Repeating the number of units, n 1 The value range of (2) is 1-2;
a is a polyurethane prepolymer blocked with hydrazide;
b is aliphatic dialdehyde, aliphatic trialdehyde, aromatic dialdehyde, aromatic trialdehyde, heterocyclic dialdehyde or heterocyclic trialdehyde.
2. An aldehyde-based chain-extended recyclable polyurethane elastomer containing multiple hydrogen bonds as defined in claim 1, wherein:
the structural formula of A is as follows:
R 1 at least one of diisocyanate monomers;
R 2 at least one of a polytetrahydrofuran polyol, a polycaprolactone polyol, a polycarbonate polyol, or a polyether polyol;
R 3 is dihydrazide;
the value range of n is 4-6.
3. An aldehyde-based chain-extended recyclable polyurethane elastomer containing multiple hydrogen bonds as defined in claim 2, wherein:
the R is 1 The structural formula is as follows:
4. an aldehyde-based chain-extended recyclable polyurethane elastomer containing multiple hydrogen bonds as defined in claim 3, wherein:
the R is 2 The structural formula is as follows:
R 2 has a molecular weight of 1000 or 2000.
5. An aldehyde-based extended chain recoverable polyurethane elastomer comprising multiple hydrogen bonds according to claim 4, wherein:
the R is 3 The structural formula is as follows:
6. an aldehyde-based chain-extended recyclable polyurethane elastomer containing multiple hydrogen bonds as described in any one of claims 1-5, wherein:
the structural formula of the B is as follows:
7. a preparation method of an aldehyde group chain extension recyclable polyurethane elastomer containing multiple hydrogen bonds is characterized by comprising the following steps:
step 1, under the protection of nitrogen, uniformly mixing polyol, isocyanate and a catalyst in a solvent, and reacting for 1-6 hours at 20-100 ℃ with the stirring speed of 50-300rpm to obtain a prepolymer;
step 2, reacting the prepolymer obtained in the step 1 with diamine containing an amide bond for 0.5-48 hours to obtain an amino-terminated oligomer;
and 3, performing secondary chain extension crosslinking on the oligomer obtained in the step 2 and the compound containing the aldehyde group, wherein the reaction time is 0.5-48h, and drying at 50-100 ℃ for 12-48h under vacuum condition to obtain the degradable recyclable polyurethane elastomer.
8. The method for producing an aldehyde-based chain-extended recyclable polyurethane elastomer containing multiple hydrogen bonds as claimed in claim 7, wherein:
in the step 1, the polyol is at least one of polyether polyol, polyester polyol, polycarbonate polyol and polycaprolactone polyol;
the molar ratio of the polyol to the isocyanate is 1:2-10;
the water content of the polyol is less than 0.05%;
the dosage of the catalyst is 0.05% -1% of the total mass of reactants, and the reactants comprise polyalcohol, isocyanate, catalyst and diamine containing amide bond;
the isocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate;
the catalyst is dibutyl tin dilaurate;
the solvent is N, N-dimethylacetamide or N, N-dimethylformamide;
the mass of the solvent is 2-3 times of the total mass of the reactants;
in the step 2, the structural formula of the diamine containing the amide bond is as follows:
in the step 3, the structural formula of the aldehyde group-containing compound is as follows:
OHC-B-CHO。
9. the method for preparing the recyclable polyurethane elastomer with multiple hydrogen bonds by aldehyde chain extension according to claim 8, which is characterized in that:
in the step 1, the polyol is polytetrahydrofuran polyol, polycarbonate polyol or polycarbonate polyol, and the molecular weight of the polyol is 1000 or 2000;
the catalyst was used in an amount of 0.1wt% based on the total mass of the reactants.
10. An application of an aldehyde group chain extension recyclable polyurethane elastomer containing multiple hydrogen bonds is characterized in that: the degradable and recyclable polyurethane elastomer is stirred for 90min at 30-50 ℃ in a 1mol/L HCL solution, the aldehyde group-containing compound and the amino end-capped oligomer are recovered, the recovered aldehyde group-containing compound and amino end-capped oligomer can be subjected to secondary chain extension crosslinking, the reaction time is 0.5-48h, and the polyurethane elastomer is obtained by drying at 50-100 ℃ for 12-48h under the vacuum condition, and can be used for manufacturing an impact-resistant protective coating, electronic skin or high-strength and high-toughness polyurethane elastomer.
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| CN202310946213.2A CN116789932A (en) | 2023-07-31 | 2023-07-31 | Recyclable polyurethane elastomer containing multiple hydrogen bonds and obtained through chain extension of aldehyde groups and preparation method of recyclable polyurethane elastomer |
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| CN202310946213.2A CN116789932A (en) | 2023-07-31 | 2023-07-31 | Recyclable polyurethane elastomer containing multiple hydrogen bonds and obtained through chain extension of aldehyde groups and preparation method of recyclable polyurethane elastomer |
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