CN114752030A - Polyurethane based on room temperature self-repairing of multiple self-repairing units and preparation method thereof - Google Patents
Polyurethane based on room temperature self-repairing of multiple self-repairing units and preparation method thereof Download PDFInfo
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- CN114752030A CN114752030A CN202210548735.2A CN202210548735A CN114752030A CN 114752030 A CN114752030 A CN 114752030A CN 202210548735 A CN202210548735 A CN 202210548735A CN 114752030 A CN114752030 A CN 114752030A
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- self
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- polyurethane
- room temperature
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 74
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 66
- -1 dihydroxy borate compound Chemical class 0.000 claims description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 31
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 29
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 19
- 239000011261 inert gas Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 125000005442 diisocyanate group Chemical group 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003093 cationic surfactant Substances 0.000 claims description 12
- 238000007791 dehumidification Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 11
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- KWXIPEYKZKIAKR-UHFFFAOYSA-N 2-amino-4-hydroxy-6-methylpyrimidine Chemical compound CC1=CC(O)=NC(N)=N1 KWXIPEYKZKIAKR-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- IBYVJTUUDGIOJT-UHFFFAOYSA-N dihydroperoxyborinic acid Chemical compound OOB(O)OO IBYVJTUUDGIOJT-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- VBXDEEVJTYBRJJ-UHFFFAOYSA-N diboronic acid Chemical compound OBOBO VBXDEEVJTYBRJJ-UHFFFAOYSA-N 0.000 claims description 5
- AQZABFSNDJQNDC-UHFFFAOYSA-N 2-[2,2-bis(dimethylamino)ethoxy]-1-n,1-n,1-n',1-n'-tetramethylethane-1,1-diamine Chemical compound CN(C)C(N(C)C)COCC(N(C)C)N(C)C AQZABFSNDJQNDC-UHFFFAOYSA-N 0.000 claims description 4
- PYBVXNWDSBYQSA-UHFFFAOYSA-N 2-aminobutane-1,4-diol Chemical compound OCC(N)CCO PYBVXNWDSBYQSA-UHFFFAOYSA-N 0.000 claims description 4
- UEDDHBVGNLVMRQ-UHFFFAOYSA-N 2-aminopentane-1,5-diol Chemical compound OCC(N)CCCO UEDDHBVGNLVMRQ-UHFFFAOYSA-N 0.000 claims description 4
- KJJPLEZQSCZCKE-UHFFFAOYSA-N 2-aminopropane-1,3-diol Chemical compound OCC(N)CO KJJPLEZQSCZCKE-UHFFFAOYSA-N 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 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- AMEDKBHURXXSQO-UHFFFAOYSA-N azonous acid Chemical compound ONO AMEDKBHURXXSQO-UHFFFAOYSA-N 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- WEAYWASEBDOLRG-UHFFFAOYSA-N pentane-1,2,5-triol Chemical compound OCCCC(O)CO WEAYWASEBDOLRG-UHFFFAOYSA-N 0.000 claims description 4
- 229920006264 polyurethane film Polymers 0.000 claims description 4
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 3
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 3
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 229960004063 propylene glycol Drugs 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 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
- 239000012991 xanthate Substances 0.000 claims description 3
- HGDCPUWNNFKWOU-UHFFFAOYSA-N B(O)(O)OB(O)O.C(C1=CC=C(C(=O)O)C=C1)(=O)O Chemical compound B(O)(O)OB(O)O.C(C1=CC=C(C(=O)O)C=C1)(=O)O HGDCPUWNNFKWOU-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 229910052796 boron Inorganic materials 0.000 abstract description 5
- 239000004327 boric acid Substances 0.000 abstract description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009471 action Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- XXJYLEWWCJOUNU-UHFFFAOYSA-N B(O)OBO.C(C1=CC=C(C(=O)O)C=C1)(=O)O Chemical compound B(O)OBO.C(C1=CC=C(C(=O)O)C=C1)(=O)O XXJYLEWWCJOUNU-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3848—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing two nitrogen atoms in the ring
-
- 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
- C08G18/65—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
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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)
Abstract
The invention belongs to the technical field of self-repairing polyurethane materials, and discloses room temperature self-repairing polyurethane based on multiple self-repairing units and a preparation method thereof. The invention introduces multiple hydrogen bonds and boric acid ester bonds to synthesize the polyurethane self-repairing at room temperature under the assistance of water. The polyurethane utilizes the synergistic effect of various dynamic bonds, firstly comprises a dynamic hydrogen bond system inherent in a polyurethane system, and secondly forms dynamic coordination bonds and multiple hydrogen bonds by coordination of nitrogen and boron, the obtained material has good mechanical property, and simultaneously the boric acid ester bonds endow room temperature self-repairing performance under the action of water. The preparation method is simple in preparation process, low in cost and wide in application prospect.
Description
Technical Field
The invention relates to the technical field of self-repairing polyurethane materials, in particular to polyurethane based on room temperature self-repairing of multiple self-repairing units and a preparation method thereof.
Background
Polyurethane appears in the 30 s of the 20 th century, and through the technical development of nearly eighty years, the material is widely applied to the fields of home furnishing, buildings, daily necessities, traffic, household appliances and the like. The material inevitably generates damage and microcracks during the use process, and thus macroscopic cracks are caused, and macroscopic fracture and buried safety hazards occur. The self-repairing is a principle of simulating the healing of organism damage, and the micro damage of the material can be self-healed through energy or substance supply. The prepared polyurethane elastomer with high strength and high self-repairing performance has good prospect.
Self-repair can be classified into exopathic type self-repair and intrinsic type self-repair depending on whether a repair agent is used. Most of the exorbitant self-repairing methods are characterized in that a catheter or a microcapsule containing a self-repairing substance is embedded into a molecule, so that the material is released at a damaged part to heal, and the self-repairing times of the inevitable material are limited; intrinsic self-repair, also called reversible self-repair, is mainly achieved by the action of reversible properties of chemical bonds or characteristic functional groups peculiar to the interior of the material. If the polymer molecular chains possess reversible reactive groups, the polymer molecular chains can be recombined when damaged to reconstruct the network structure of the material, thereby realizing the self-repairing of the material.
Partial intrinsic self-repair requires high external conditions to open dynamic bonds and produce reversible motion, for example: high temperature, high pressure, strong acid and alkali, etc. to change the temperature, electromagnetic radiation or chemical environment. This limits the self-healing of the material after it is put into operation. The preparation of the high-performance polyurethane elastomer with the self-repairing function can prevent structural damage caused by light, electricity, heat and force in the using process, improve the service life and functional reliability of the material, and simultaneously realize the self-repairing capability under mild conditions and the improvement of mechanical property, which are the difficulties and challenges of the research in the field at present.
Disclosure of Invention
In view of the above, the invention provides a polyurethane self-repairing based on multiple self-repairing units at room temperature and a preparation method thereof, so as to solve the problems of low service life and functional reliability, poor mechanical properties and poor self-repairing capability under mild conditions of the existing polyurethane material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of polyurethane based on room temperature self-repair of multiple self-repair units, which comprises the following steps:
1) mixing polytetrahydrofuran, 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine and a solvent, and carrying out dehumidification and impurity removal reaction to obtain a first mixture;
2) mixing the first mixture, diisocyanate and a catalyst, and carrying out catalytic reaction to obtain an isocyanate-terminated prepolymer;
3) mixing the isocyanate-terminated prepolymer, 2-bis (hydroxymethyl) propionic acid and dihydric alcohol, and reacting to obtain a linear isocyanate-terminated polymer;
4) mixing the linear isocyanate-terminated polymer with dihydroxy borate ester, and reacting to obtain a second mixture;
5) and mixing the second mixture and the hydrophilic agent, reacting, and sequentially carrying out end-capping, phase inversion and curing reaction to obtain the polyurethane film.
Preferably, the dehumidifying and impurity-removing reaction in the step 1) and the reaction in the step 3) are carried out under the protection of inert gas, and the inert gas is independently argon or hydrogen; the molar ratio of the diisocyanate to the polytetrahydrofuran to the 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine to the dihydroxy borate compound to the 2, 2-bis (hydroxymethyl) propionic acid to the diol is 1: 0.24-0.3: 0.05-0.25: 0.05-0.3: 0.24-0.25: 0.1-0.5.
Preferably, in the step 1), the molecular weight of the polytetrahydrofuran is 900-1100 g/mol; the solvent is one or more of N, N-dimethylacetamide, nitrogen methyl pyrrolidone, tetrahydrofuran and N, N-dimethylacetamide; the mass-volume ratio of the polytetrahydrofuran to the solvent is 6 g: 5-8 mL; the temperature of the dehumidification and impurity removal reaction is 120-140 ℃, and the time of the dehumidification and impurity removal reaction is 10-40 min.
Preferably, the 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine is prepared by the following steps:
step S1: mixing 2-amino-4-hydroxy-6-methylpyrimidine and hexamethylene diisocyanate for a first reaction to obtain a first product;
step S2: mixing the first product, dihydroxyl ammonia alcohol and a solvent to perform a second reaction to obtain 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine;
In the step S1, the molar ratio of the 2-amino-4-hydroxy-6-methylpyrimidine to the hexamethylene diisocyanate is 1: 5-7;
in the step S2, the dihydroxyl alcohol is 2-amino-1, 3-propanediol, 2-amino-1, 4-butanediol or 2-amino-1, 5-pentanediol, and the molar ratio of the first product to the dihydroxyl alcohol is 1: 1-2.
Preferably, in the step S1, the temperature of the first reaction is 90 to 110 ℃, and the time of the first reaction is 15 to 25 hours;
in the step S2, the solvent is one or more of N, N-dimethylformamide, chloroform, dehydrated chloroform, dimethyl sulfoxide, diethyl ether, petroleum ether and ethyl acetate, the temperature of the second reaction is 90-110 ℃, and the time of the second reaction is 1-3 h.
Preferably, in the step 2), the diisocyanate is isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate or hexamethylene diisocyanate; the catalyst is one or more of dibutyltin dilaurate, stannous octoate, triethylamine, bis-dimethylaminoethyl ether, N-ethyl morpholine and triethylene diamine, and the adding amount of the catalyst is 0.05-0.2% of the total amount of polytetrahydrofuran, 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine and diisocyanate; the temperature of the catalytic reaction is 70-90 ℃, and the time of the catalytic reaction is 1-3 h.
Preferably, in the step 3), the dihydric alcohol is ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol or 1, 6-hexanediol; the reaction temperature is 70-90 ℃, and the reaction time is 1-3 h; in the step 4), the reaction temperature is 70-90 ℃, and the reaction time is 1-3 h.
Preferably, the preparation of the dihydroxy borate ester comprises the following steps: mixing terephthalic acid diborate, triol, tetrahydrofuran and anhydrous magnesium sulfate, and reacting to obtain a dihydroxy borate compound;
the triol is glycerol, 1,2, 4-butanetriol, 1,2, 5-pentanetriol or 1,2, 6-hexanetriol;
the molar ratio of the terephthalic diboronic acid to the triol is 1: 2-2.5; the reaction time is 20-30 h.
Preferably, in the step 5), the hydrophilic agent is sodium alkylsulfate, secondary alkyl sodium sulfate, sodium alkylaryl sulfonate, sodium alkyl sulfate, secondary sodium sulfate, amine salt type cationic surfactant, quaternary ammonium salt type cationic surfactant, heterocyclic type cationic surfactant, xanthate type cationic surfactant, polyoxyethylene ether, fatty alcohol polyoxyethylene ether or fatty acid methyl ester polyoxyethylene; the reaction time is 10-40 min; the reagent used for end capping is methanol, and the reagent used for phase inversion is water.
The invention also provides polyurethane prepared by the preparation method of the polyurethane based on room temperature self-repairing of the multiple self-repairing units.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, synthesized dihydroxy borate containing dihydroxy and 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine containing multiple hydrogen bonds are used as a chain extender, boron ester and a nitrogen donor are combined into the main chain of polyurethane, and boron-nitrogen coordination bonds are formed between the boron ester and the nitrogen donor, so that the boron ester is favorably formed and dissociated at room temperature, the mechanical properties of intermolecular coordination chain crosslinking and intramolecular coordination chain folding are obviously improved, and the quadruple hydrogen bonds of the 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine form a physical crosslinking net structure, so that the material has more excellent mechanical properties, and the material also has good reworkability due to the thermal reversibility of the hydrogen bonds;
(2) the room-temperature self-repairing polyurethane based on the multiple self-repairing units is obtained through the optimized steps, has self-repairing performance at room temperature, and has good mechanical properties;
(3) the invention achieves the self-repairing effect based on multiple self-repairing units, under the dynamic motion of multiple hydrogen bonds, borate bonds and nitrogen-oxygen coordination, water has obvious assistance effect on the self-repairing in view of reversible motion of the borate bonds and the nitrogen-oxygen coordination, and higher repairing efficiency can be achieved at room temperature.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a stress-strain curve of room temperature self-repairing polyurethanes obtained in example 3 of the present invention and comparative examples 1 to 3, wherein PB is a polyurethane containing only a dihydroxy borate ester, PY is a polyurethane containing only 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine, PBY is a polyurethane containing both a dihydroxy borate ester and 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine, PU is a conventional polyurethane containing no dihydroxy borate ester and 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine, and PB ', PY', PBY ', PU' are samples of polyurethanes in which PB, PY, PBY, PU are cut at room temperature and repaired for 24 hours after water treatment;
FIG. 2 is an infrared spectrum of a room temperature self-repairing polyurethane obtained in example 3 of the present invention and comparative examples 1 to 3, wherein PB is a polyurethane containing only a dihydroxy boronic ester, PY is a polyurethane containing only 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine, PBY is a polyurethane containing both a dihydroxy boronic ester and 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine, and PU is a conventional polyurethane containing no dihydroxy boronic ester and 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine;
FIG. 3 is a microscopic schematic diagram of self-repairing of room temperature self-repairing polyurethanes obtained in example 3 and comparative examples 1 to 3 of the present invention.
Detailed Description
The invention provides a preparation method of polyurethane based on room temperature self-repairing of multiple self-repairing units, which comprises the following steps:
1) mixing polytetrahydrofuran, 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine and a solvent, and carrying out dehumidification impurity removal reaction to obtain a first mixture;
2) mixing the first mixture, diisocyanate and a catalyst, and carrying out catalytic reaction to obtain an isocyanate-terminated prepolymer;
3) mixing the isocyanate-terminated prepolymer, 2-bis (hydroxymethyl) propionic acid and dihydric alcohol and then reacting to obtain a linear isocyanate-terminated polymer;
4) mixing a linear isocyanate-terminated polymer with dihydroxy borate, and reacting to obtain a second mixture;
5) and mixing the second mixture and a hydrophilic agent, reacting, and sequentially carrying out end-capping, phase inversion and curing reaction to obtain the polyurethane film.
In the invention, the dehumidification and impurity removal reaction of the step 1) and the reaction of the step 3) are carried out under the protection of inert gas, and the inert gas is independently preferably argon or hydrogen, and is further preferably hydrogen; the molar ratio of the diisocyanate, the polytetrahydrofuran, the 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine, the dihydroxy borate compound, the 2, 2-bis (hydroxymethyl) propionic acid and the dihydric alcohol is preferably 1: 0.24-0.3: 0.05-0.25: 0.05-0.3: 0.24-0.25: 0.1-0.5, and more preferably 1: 0.26-0.28: 0.12-0.2: 0.15-0.25: 0.25: 0.2-0.4.
In the invention, the molar ratio of-NCO to-OH in the polyurethane film system is preferably 1-1.4: 1, and more preferably 1.1-1.2: 1.
In the invention, in the step 1), the molecular weight of the polytetrahydrofuran is preferably 900-1100 g/mol, and more preferably 1000 g/mol; the solvent is preferably one or more of N, N-dimethylacetamide, nitrogen methyl pyrrolidone, tetrahydrofuran and N, N-dimethylacetamide, and is further preferably N, N-dimethylacetamide and/or tetrahydrofuran; the mass-to-volume ratio of polytetrahydrofuran to solvent is preferably 6 g: 5-8 mL, more preferably 6 g: 6-7 mL; the temperature of the dehumidification and impurity removal reaction is preferably 120-140 ℃, and is further preferably 125-135 ℃; the time for the dehumidification and impurity removal reaction is preferably 10-40 min, and more preferably 20-35 min.
In the invention, the 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine is prepared by the following steps:
step S1: mixing 2-amino-4-hydroxy-6-methylpyrimidine and hexamethylene diisocyanate for a first reaction to obtain a first product;
step S2: and mixing the first product, the dihydroxyl alcohol and the solvent for a second reaction to obtain the 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine.
In the present invention, in step S1, the molar ratio of 2-amino-4-hydroxy-6-methylpyrimidine to hexamethylene diisocyanate is preferably 1:5 to 7, and more preferably 1:6 to 6.5.
In the present invention, in the step S1, the temperature of the first reaction is preferably 90 to 110 ℃, and more preferably 100 to 105 ℃; the time of the first reaction is preferably 15 to 25 hours, and more preferably 18 to 24 hours.
In the invention, in the step S1, after the first reaction is finished, the reaction product is washed with petroleum ether for 3 times, and then dried in an oven at 40-80 ℃ for 0.5-2 h, and ground for 2-3 times during the drying period.
In the present invention, in the step S1, the first reaction is performed under the protection of nitrogen.
In the present invention, in the step S2, the dihydroxyalcohol is preferably 2-amino-1, 3-propanediol, 2-amino-1, 4-butanediol or 2-amino-1, 5-pentanediol, and is further preferably 2-amino-1, 4-butanediol or 2-amino-1, 5-pentanediol; the molar ratio of the first product to the dihydroxyl alcohol is preferably 1: 1-2, and more preferably 1: 1.5.
In the present invention, in the step S2, the solvent is preferably one or more of N, N-dimethylformamide, chloroform, dehydrated chloroform, dimethyl sulfoxide, diethyl ether, petroleum ether and ethyl acetate, and is further preferably dimethyl sulfoxide and petroleum ether; the mass-volume ratio of the 2-amino-4-hydroxy-6-methylpyrimidine to the solvent is preferably 1 g: 20-60 mL, more preferably 1 g: 30-40 mL; the temperature of the second reaction is preferably 90-110 ℃, and more preferably 95-105 ℃; the time of the second reaction is preferably 1 to 3 hours, and more preferably 1.5 to 2.5 hours.
In the present invention, before 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide-pyrimidine is obtained in step S2, the product obtained in the second reaction is subjected to a post-treatment, and the post-treatment comprises the following steps: adding a mixed solution of petroleum ether and ethyl acetate to precipitate a product obtained in the second reaction, performing suction filtration, washing with acetone for 2-3 times, drying at 40-80 ℃ for 0.5-2 h, grinding for 2-3 times, taking out after drying, grinding again, and sealing for storage;
the volume ratio of the petroleum ether to the ethyl acetate in the mixed solution of the petroleum ether and the ethyl acetate is 1: 1-2.
In the present invention, in the step 2), the diisocyanate is preferably isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate or hexamethylene diisocyanate, and is further preferably diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate or hexamethylene diisocyanate; the catalyst is preferably one or more of dibutyltin dilaurate, stannous octoate, triethylamine, bis-dimethylaminoethyl ether, N-ethylmorpholine and triethylenediamine, and is further preferably dibutyltin dilaurate and bis-dimethylaminoethyl ether; the addition amount of the catalyst is preferably 0.05-0.2% of the total amount of the polytetrahydrofuran, the 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine and the diisocyanate, and more preferably 0.1-0.15% of the total amount of the polytetrahydrofuran, the 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine and the diisocyanate; the temperature of the catalytic reaction is preferably 70-90 ℃, and further preferably 75-85 ℃; the time of the catalytic reaction is preferably 1 to 3 hours, and more preferably 1.5 to 2.5 hours.
In the present invention, in the step 3), the diol is preferably ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol or 1, 6-hexanediol, and is further preferably ethylene glycol or 1, 6-hexanediol; the reaction temperature is preferably 70-90 ℃, and further preferably 75-85 ℃; the reaction time is preferably 1 to 3 hours, and more preferably 1.5 to 2.5 hours.
In the present invention, in the step 3), the reaction is performed under the protection of an inert gas, and the inert gas is preferably hydrogen or argon, and more preferably hydrogen.
In the invention, in the step 4), the reaction temperature is preferably 70-90 ℃, and more preferably 75-85 ℃; the reaction time is preferably 1 to 3 hours, and more preferably 1.5 to 2 hours.
In the present invention, the preparation of the dihydroxy borate ester comprises the following steps: mixing terephthalic diboronic acid, triol, tetrahydrofuran and anhydrous magnesium sulfate, and then reacting to obtain the dihydroxy borate compound.
In the present invention, the triol is preferably glycerol, 1,2, 4-butanetriol, 1,2, 5-pentanetriol or 1,2, 6-hexanetriol, and more preferably 1,2, 5-pentanetriol or 1,2, 6-hexanetriol; the molar ratio of the terephthalic diboronic acid to the triol is preferably 1: 2-2.5, and more preferably 1: 2.1-2.3; the reaction time is preferably 20 to 30 hours, and more preferably 25 to 28 hours.
In the invention, the mixing mode of the terephthalic acid diboronic acid, the triol, the tetrahydrofuran and the anhydrous magnesium sulfate is as follows: terephthalic diboronic acid and triol are dissolved in tetrahydrofuran, and anhydrous magnesium sulfate is added to remove water generated in the reaction.
In the invention, before the dihydroxy borate compound is obtained, a product obtained by the reaction is filtered, and the filtrate is washed with n-hexane for 2-3 times.
In the present invention, in the step 5), the hydrophilic agent is preferably sodium alkylsulfate, secondary sodium alkylsulfate, sodium alkylaryl sulfonate, sodium alkylsulfate, secondary sodium sulfate, amine salt type cationic surfactant, quaternary ammonium salt type cationic surfactant, heterocyclic type cationic surfactant, xanthate type cationic surfactant, polyoxyethylene ether, fatty alcohol polyoxyethylene ether or fatty acid methyl ester polyoxyethylene, and is further preferably triethylamine, sodium alkylsulfate or fatty alcohol polyoxyethylene ether; the reaction time is preferably 10-40 min, and more preferably 15-35 min; the reagent used for end capping is methanol, and the reagent used for phase inversion is water.
In the present invention, the hydrophilic agent functions to neutralize the hydrophilic moieties on the chains of the second mixture.
In the present invention, the reaction formula of the 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide-pyrimidine is:
In the present invention, the dihydroxy boronic acid ester has the reaction formula:
in the invention, the reaction formula of the polyurethane based on room temperature self-repairing of multiple self-repairing units is as follows:
the invention also provides polyurethane prepared by the preparation method of the polyurethane based on room temperature self-repairing of the multiple self-repairing units.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparation of 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine:
1) reacting 2-amino-4-hydroxy-6-methylpyrimidine (40mmol) with hexamethylene diisocyanate (240mmol) at 100 ℃ for 20h, washing the reaction product with solvent petroleum ether for three times, and drying in an oven at 60 ℃ for 2h, wherein 3 times of grinding are carried out in the process;
2) dissolving the product (50mmol) obtained in the step 1) and 2-amino-1, 3-propanediol (63.7mmol) in a solvent N, N-dimethylformamide, reacting for 2h at 100 ℃, adding 100mL of a mixed solution of petroleum ether and ethyl acetate (the molar ratio of the petroleum ether to the ethyl acetate is 1:1) to precipitate the product, performing suction filtration, washing for 2-3 times with acetone, placing in an oven again, grinding for 3 times, taking out after drying, grinding, sealing and storing.
Example 2
Preparation of dihydroxy Borate ester:
p-phenylboronic acid (25mmol) and 1,2, 6-hexanetriol (55mmol) are dissolved in 100mL tetrahydrofuran, anhydrous magnesium sulfate (10g) is added to remove water generated in the reaction, the mixture is reacted at room temperature for 24 hours, and then the reaction product is filtered, and finally the filtrate is washed 2 times by using n-hexane to obtain the dihydroxy borate.
Example 3
Preparation of self-healing Polyurethane (PBY):
1) polytetrahydrofuran (Mn 1000, 6mmol) and 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine (3mmol) obtained in example 1 were added to a reaction kettle containing solvent N, N-dimethylacetamide (8mL) under inert gas protection, and dehumidification and impurity removal were carried out at 130 ℃ for 30 min;
2) adding isophorone diisocyanate (24.2mmol) and a catalyst dibutyltin dilaurate (30 mu L) into the reaction kettle in the step 1), and reacting for 2h at 80 ℃ to obtain an isocyanate-terminated prepolymer;
3) adding 2, 2-bis (hydroxymethyl) propionic acid (6mmol) and 1, 4-butanediol (2.5mmol) into the system reacted in the step 2), and reacting for 2h at 80 ℃ under the protection of inert gas to obtain a linear isocyanate-terminated polymer;
4) adding the dihydroxy borate (4.5mmol) obtained in example 2 into the system reacted in the step 3), and reacting for 2h at 80 ℃ under the protection of nitrogen;
5) Adding triethylamine (Mn is 101.19, 6mmol) into the system after the reaction in the step 4), reacting at room temperature for 25min, adding methanol (0.3g) for end capping, adding water (20g) for phase inversion, and finally drying and curing to obtain polyurethane.
And (3) investigating the mechanical property and the self-repairing property of the polyurethane by using a dynamic mechanical analyzer. The toughness value is 1487.63MJ/m3The tensile strength is 8.37MPa, the polyurethane is completely cut off, the sections of the two parts are soaked in deionized water for 10-15 min, and then the polyurethane is cut off on a laboratory bench under the state of applying external forceThe sections of the two parts are spliced together, placed at room temperature for 24 hours, and the morphology of the obtained material is characterized at 0 hour, 12 hours and 24 hours respectively, as shown in figure 3.
Comparative example 1
Preparation of self-repairing Polyurethane (PY):
1) polytetrahydrofuran (Mn 1000, 6mmol) and 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine (3mmol) obtained in example 1 were added to a reaction kettle containing solvent N, N-dimethylacetamide (8mL) under inert gas protection, and dehumidification and impurity removal were carried out at 130 ℃ for 30 min;
2) adding isophorone diisocyanate (24.2mmol) and dibutyltin dilaurate (30 mu L) serving as a catalyst into the reaction kettle in the step 1), and reacting for 2h at 80 ℃ to obtain an isocyanate-terminated prepolymer;
3) Adding 2, 2-bis (hydroxymethyl) propionic acid (6mmol) and 1, 4-butanediol (7mmol) into the system reacted in the step 2), and reacting for 2h at 80 ℃ under the protection of inert gas to obtain a linear isocyanate-terminated polymer;
4) adding triethylamine (Mn is 101.19, 6mmol) into the system after the reaction in the step 3), reacting at room temperature for 25min, adding methanol (0.3g) for end capping, adding water (20g) for phase inversion, and finally drying and curing to obtain the polyurethane.
And (3) inspecting the mechanical property and the self-repairing property of the polyurethane by using a dynamic mechanical analyzer. The toughness value is 1333.08MJ/m3And the tensile strength is 6.30MPa, the polyurethane is completely cut, the sections of the two parts are soaked in deionized water for 10-15 min, then the two cut sections are spliced together on a laboratory table under the state of applying external force, the spliced sections are placed for 24 hours at room temperature, and the appearance of the obtained material is characterized in 0 hour, 12 hours and 24 hours respectively, as shown in figure 3.
Comparative example 2
Preparation of self-repairing Polyurethane (PB):
1) adding polytetrahydrofuran (Mn 1000, 6mmol) into a reaction kettle filled with solvent N, N-dimethylacetamide (9mL) under the protection of inert gas, and removing moisture and impurities for 30min at 130 ℃;
2) adding isophorone diisocyanate (24.2mmol) and dibutyltin dilaurate (30 mu L) serving as a catalyst into the reaction kettle in the step 1), and reacting for 2h at 80 ℃ to obtain an isocyanate-terminated prepolymer;
3) Adding 2, 2-bis (hydroxymethyl) propionic acid (6mmol) and 1, 4-butanediol (5.5mmol) into the system reacted in the step 2), and reacting for 2h at 80 ℃ under the protection of inert gas to obtain a linear isocyanate-terminated polymer;
4) adding the dihydroxy borate (4.5mmol) obtained in example 2 into the system after the reaction in step 3), and reacting at 80 ℃ for 2 h;
5) adding triethylamine (Mn is 101.19, 6mmol) into the system after the reaction in the step 4), reacting at room temperature for 25min, adding methanol (0.3g) for end capping, adding water (20g) for phase inversion, and finally drying and curing to obtain polyurethane.
And (3) investigating the mechanical property and the self-repairing property of the polyurethane by using a dynamic mechanical analyzer. The toughness value is 814.536MJ/m3And the tensile strength is 4.21MPa, the polyurethane is completely cut, the sections of the two parts are soaked in deionized water for 10-15 min, then the two cut sections are spliced together on a laboratory table under the state of applying external force, the spliced sections are placed for 24 hours at room temperature, and the appearance of the obtained material is characterized in 0 hour, 12 hours and 24 hours respectively, as shown in figure 3.
Comparative example 3
Preparation of self-repairing Polyurethane (PU):
1) polytetrahydrofuran (Mn 1000, 6mmol) was added to a reaction kettle containing solvent N, N-dimethylacetamide (5mL) under inert gas, and the mixture was dehumidified and purified at 130 ℃ for 30 min.
2) Adding isophorone diisocyanate (24.2mmol) and dibutyltin dilaurate (30 mu L) serving as a catalyst into the reaction kettle in the step 1), and reacting for 2 hours at 80 ℃ to obtain an isocyanate-terminated prepolymer;
3) adding 2, 2-bis (hydroxymethyl) propionic acid (6mmol) and 1, 4-butanediol (10mmol) into the system reacted in the step 2), and reacting for 2h at 80 ℃ under the protection of inert gas to obtain a linear isocyanate-terminated polymer;
4) adding triethylamine (Mn is 101.19, 6mmol) into the system after the reaction in the step 3), reacting at room temperature for 25min, adding methanol (0.3g) for end capping, adding water (20g) for phase inversion, and finally drying and curing to obtain polyurethane.
And (3) investigating the mechanical property and the self-repairing property of the polyurethane by using a dynamic mechanical analyzer. The toughness value is 413.57MJ/m3And the tensile strength is 1.92MPa, the polyurethane is completely cut, the sections of the two parts are soaked in deionized water for 10-15 min, then the two cut sections are spliced together on a laboratory table under the condition of applying external force, the spliced sections are placed for 24 hours at room temperature, and the appearance of the obtained material is characterized in 0 hour, 12 hours and 24 hours respectively, as shown in figure 3.
The self-repairing polyurethane prepared by the invention utilizes the synergistic effect of various dynamic bonds, firstly comprises an inherent dynamic hydrogen bond system in a polyurethane system, secondly synthesizes a dihydroxy compound to introduce a boric acid bond, and finally coordinates nitrogen and boron to form a dynamic coordination bond;
As can be seen from figure 1, the self-repairing polyurethane prepared by the invention has good mechanical properties;
as can be seen from FIG. 3, the self-repairing polyurethane prepared by the invention has the characteristic of room temperature self-repairing, and is particularly remarkable under the assistance of water.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
1. A preparation method of polyurethane based on room temperature self-repairing of multiple self-repairing units is characterized by comprising the following steps:
1) mixing polytetrahydrofuran, 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine and a solvent, and carrying out dehumidification impurity removal reaction to obtain a first mixture;
2) mixing the first mixture, diisocyanate and a catalyst, and carrying out catalytic reaction to obtain an isocyanate-terminated prepolymer;
3) mixing the isocyanate-terminated prepolymer, 2-bis (hydroxymethyl) propionic acid and dihydric alcohol and then reacting to obtain a linear isocyanate-terminated polymer;
4) mixing a linear isocyanate-terminated polymer with dihydroxy borate, and reacting to obtain a second mixture;
5) And mixing the second mixture and the hydrophilic agent, reacting, and sequentially carrying out end-capping, phase inversion and curing reaction to obtain the polyurethane film.
2. The preparation method of the polyurethane self-repairing at room temperature based on the multiple self-repairing units according to claim 1, wherein the dehumidifying and impurity-removing reaction in the step 1) and the reaction in the step 3) are performed under the protection of inert gas, and the inert gas is independently argon or hydrogen; the molar ratio of diisocyanate to polytetrahydrofuran to 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine to dihydroxy borate compound to 2, 2-bis (hydroxymethyl) propionic acid to diol is 1: 0.24-0.3: 0.05-0.25: 0.05-0.3: 0.24-0.25: 0.1 to 0.5.
3. The preparation method of the polyurethane self-repairing at room temperature based on the multiple self-repairing units according to claim 1 or 2, wherein in the step 1), the molecular weight of polytetrahydrofuran is 900-1100 g/mol; the solvent is one or more of N, N-dimethylacetamide, nitrogen methyl pyrrolidone, tetrahydrofuran and N, N-dimethylacetamide; the mass-volume ratio of the polytetrahydrofuran to the solvent is 6 g: 5-8 mL; the temperature of the dehumidification and impurity removal reaction is 120-140 ℃, and the time of the dehumidification and impurity removal reaction is 10-40 min.
4. The preparation method of polyurethane self-repairing at room temperature based on multiple self-repairing units according to claim 3, wherein the 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine is prepared by the following steps:
step S1: mixing 2-amino-4-hydroxy-6-methylpyrimidine and hexamethylene diisocyanate for a first reaction to obtain a first product;
step S2: mixing the first product, dihydroxyl ammonia alcohol and a solvent to perform a second reaction to obtain 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine;
in the step S1, the molar ratio of 2-amino-4-hydroxy-6-methylpyrimidine to hexamethylene diisocyanate is 1: 5-7;
in the step S2, the dihydroxyl ammonia alcohol is 2-amino-1, 3-propanediol, 2-amino-1, 4-butanediol or 2-amino-1, 5-pentanediol, and the molar ratio of the first product to the dihydroxyl ammonia alcohol is 1: 1-2.
5. The preparation method of polyurethane based on room temperature self-repair of multiple self-repair units according to claim 4, wherein in the step S1, the temperature of the first reaction is 90-110 ℃, and the time of the first reaction is 15-25 h;
in the step S2, the solvent is one or more of N, N-dimethylformamide, chloroform, dehydrated chloroform, dimethyl sulfoxide, diethyl ether, petroleum ether and ethyl acetate, the temperature of the second reaction is 90-110 ℃, and the time of the second reaction is 1-3 hours.
6. The method for preparing the polyurethane self-repaired at room temperature based on multiple self-repairing units according to claim 1, wherein in the step 2), the diisocyanate is isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate or hexamethylene diisocyanate; the catalyst is one or more of dibutyltin dilaurate, stannous octoate, triethylamine, bis-dimethylaminoethyl ether, N-ethyl morpholine and triethylene diamine, and the addition amount of the catalyst is 0.05-0.2% of the total amount of polytetrahydrofuran, 5- (2-hydroxyethyl) -6-methyl-2-semicarbazide pyrimidine and diisocyanate; the temperature of the catalytic reaction is 70-90 ℃, and the time of the catalytic reaction is 1-3 h.
7. The preparation method of the polyurethane capable of self-repairing at room temperature based on multiple self-repairing units according to claim 1 or 2, wherein in the step 3), the dihydric alcohol is ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol or 1, 6-hexanediol; the reaction temperature is 70-90 ℃, and the reaction time is 1-3 h; in the step 4), the reaction temperature is 70-90 ℃, and the reaction time is 1-3 h.
8. The preparation method of the polyurethane self-healing at room temperature based on multiple self-healing units according to claim 7, wherein the preparation of the dihydroxy borate ester comprises the following steps: mixing terephthalic acid diborate, triol, tetrahydrofuran and anhydrous magnesium sulfate, and reacting to obtain a dihydroxy borate compound;
The triol is glycerol, 1,2, 4-butanetriol, 1,2, 5-pentanetriol or 1,2, 6-hexanetriol;
the molar ratio of the terephthalic diboronic acid to the triol is 1: 2-2.5; the reaction time is 20-30 h.
9. The method for preparing the polyurethane based on room temperature self-repairing of multiple self-repairing units according to claim 1, wherein in the step 5), the hydrophilic agent is alkyl sodium sulfonate, secondary alkyl sodium sulfate, alkyl aryl sodium sulfonate, alkyl sodium sulfate, secondary sodium sulfate, amine salt type cationic surfactant, quaternary ammonium salt type cationic surfactant, heterocyclic type cationic surfactant, xanthate type cationic surfactant, polyoxyethylene ether, fatty alcohol polyoxyethylene ether or fatty acid methyl ester polyoxyethylene; the reaction time is 10-40 min; the reagent used for end capping is methanol, and the reagent used for phase inversion is water.
10. The polyurethane prepared by the preparation method of the polyurethane self-repaired at room temperature based on the multiple self-repairing units in any one of claims 1 to 9.
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