CN116675828A - High-strength high-toughness aging-resistant double-component polyurethane and preparation method thereof - Google Patents
High-strength high-toughness aging-resistant double-component polyurethane and preparation method thereof Download PDFInfo
- Publication number
- CN116675828A CN116675828A CN202310808833.XA CN202310808833A CN116675828A CN 116675828 A CN116675828 A CN 116675828A CN 202310808833 A CN202310808833 A CN 202310808833A CN 116675828 A CN116675828 A CN 116675828A
- Authority
- CN
- China
- Prior art keywords
- component
- polyurethane
- toughness
- solvent
- strength
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 195
- 239000004814 polyurethane Substances 0.000 title claims abstract description 195
- 230000032683 aging Effects 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title description 4
- 239000012948 isocyanate Substances 0.000 claims abstract description 50
- 239000004970 Chain extender Substances 0.000 claims abstract description 42
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 42
- 229920005862 polyol Polymers 0.000 claims abstract description 38
- -1 aliphatic isocyanate Chemical class 0.000 claims abstract description 35
- 150000003077 polyols Chemical class 0.000 claims abstract description 33
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims description 73
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 58
- 239000003054 catalyst Substances 0.000 claims description 53
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 37
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 32
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 24
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 18
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 16
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 16
- 239000004417 polycarbonate Substances 0.000 claims description 16
- 229920000515 polycarbonate Polymers 0.000 claims description 16
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- QSBINWBNXWAVAK-PSXMRANNSA-N PE-NMe(16:0/16:0) Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(=O)OCCNC)OC(=O)CCCCCCCCCCCCCCC QSBINWBNXWAVAK-PSXMRANNSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 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 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- KJJPLEZQSCZCKE-UHFFFAOYSA-N 2-aminopropane-1,3-diol Chemical compound OCC(N)CO KJJPLEZQSCZCKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 2
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- PSIKPHJLTVSQFO-UHFFFAOYSA-N propanedihydrazide Chemical compound NNC(=O)CC(=O)NN PSIKPHJLTVSQFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 55
- 239000001257 hydrogen Substances 0.000 abstract description 55
- 229910052751 metal Inorganic materials 0.000 abstract description 50
- 239000002184 metal Substances 0.000 abstract description 50
- 150000002513 isocyanates Chemical class 0.000 abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 abstract description 18
- 239000011737 fluorine Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 6
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 67
- 238000003786 synthesis reaction Methods 0.000 description 56
- 238000003756 stirring Methods 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 238000007865 diluting Methods 0.000 description 15
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 15
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical group NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920006264 polyurethane film Polymers 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—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
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
- C08G18/3834—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing hydrazide or semi-carbazide groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/8087—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
-
- 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
- C08G18/83—Chemically modified polymers
- C08G18/838—Chemically modified polymers by compounds containing heteroatoms other than oxygen, halogens, nitrogen, sulfur, phosphorus or silicon
-
- 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
- C08J2375/06—Polyurethanes from polyesters
Landscapes
- 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)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a high-strength high-toughness aging-resistant double-component polyurethane with fluorescent property, which comprises a component A and a component B. Wherein the component A is prepared from oligomer polyol, aliphatic isocyanate, hydrazide chain extender, polyol micromolecular cross-linking agent and metal ion cross-linking agent. The component B is fluorine-containing chain segment modified isocyanate. According to the invention, by introducing hydrazide groups and metal ions into the component A, the component A is rich in hydrogen bonds and metal coordination bonds, so that the strength and toughness of the two-component polyurethane are enhanced; even the fluorescent property of the double-component polyurethane can be endowed by introducing rare earth ions, and the application of the double-component polyurethane can be expanded. After the component A and the component B are cured, the organic fluorine chain segment in the component B and the ageing-resistant material in the component A synergistically enhance the ageing-resistant performance of the double-component polyurethane.
Description
Belonging to the field of
The invention relates to the technical field of coatings, in particular to high-strength high-toughness aging-resistant double-component polyurethane and a preparation method thereof.
Background
The polyurethane has excellent performances of high wear resistance, high elasticity and the like, and is widely applied to various fields of aviation, navigation, construction and the like. However, as the service conditions are harsh, the requirements for multifunctional compatibility are increasing. In particular, polyurethane materials often have difficulty in achieving both strength and toughness, and polyurethanes with high tensile strength have low elongation at break and low toughness due to poor molecular segment mobility. At present, more researches are carried out on single-component tough polyurethane. However, one-component polyurethanes tend to have inadequate strength and toughness and are subject to aging.
Two-component polyurethanes have a number of advantages over one-component polyurethanes. When used in the coating field, the two-component polyurethane can be rapidly crosslinked to strength and its performance properties cover a wide range of mechanical properties from viscoelastic to highly structural. The pigment, filler and resin matrix in the two-component polyurethane coating have interface defects, and the solidification is easy to be interfered by moisture, so that the strength of the two-component paint film is insufficient. So the reported tough two-component polyurethane is less. The polyurethane pouring sealant with the tensile strength of 56MPa and the elongation at break of 581% is synthesized by curing 3,3 '-dichloro-4, 4' -diaminodiphenylmethane with the component A synthesized by adopting polytetrahydrofuran glycol, polyethylene adipate, polypropylene oxide ether polyol, toluene diisocyanate and the like as raw materials at Beijing university of chemical industry Jiang Zhiguo. However, the use of the aromatic curing agent makes the invented pouring sealant poor in weather resistance. Patent US 2019/032912 A1 also reports a two-component polyurethane with a maximum tensile strength of only 23MPa. In addition, the tensile strength of the rest of the reported two-component polyurethanes is also mostly concentrated at 10-25MPa.
In general, high performance two-component polyurethanes are obtained by several means: 1) Aromatic polyurethane is designed, and the mechanical property of the aromatic polyurethane is superior to that of aliphatic polyurethane; however, the presence of the benzene ring structure inevitably results in poor weather resistance of the resin, and aging is liable to occur. 2) Introducing nanofillers such as silicon dioxide, natural fibers and graphene into the system; but this approach sacrifices elongation while enhancing mechanical properties. In addition, the polyurethane coating is inevitably subjected to aging phenomena such as yellowing, cracking and the like in the outdoor use process, so that the appearance quality of the coating is affected, and the performance of a paint film is further reduced. In order to meet increasingly severe service conditions, research on ageing-resistant two-component polyurethane is also needed.
In view of this, developing a two-component polyurethane resin having high strength, high toughness and aging resistance is a problem to be solved by those skilled in the art.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides high-strength high-toughness aging-resistant double-component polyurethane so as to meet the protection requirements of a double-component polyurethane paint film outdoors and under severe conditions. The high-strength high-toughness aging-resistant two-component polyurethane contains hydrazide groups, not only can provide hydrogen bonding, but also can form metal ion coordination bonds with metal ions to provide metal coordination. The introduction of the hydrazide group and the metal ion makes the A component rich in hydrogen bond and metal coordination bond, and can enhance the strength and toughness of polyurethane. And the introduction of rare earth ions can further endow the two-component polyurethane with fluorescent property. Meanwhile, after the component A and the component B are cured, the ageing resistance of the double-component polyurethane is further enhanced by introducing an organic fluorine chain segment.
The invention aims at providing high-strength high-toughness aging-resistant two-component polyurethane. The two-component polyurethane comprises a component A and a component B; the weight ratio of the component A to the component B is 1:0.1 to 1.2; wherein, the liquid crystal display device comprises a liquid crystal display device,
The component A is prepared from the following raw materials:
the components are calculated according to the weight portions,
the structural formula of the component B is as follows
In a preferred embodiment of the invention, in the component A, each component is prepared from the following components in parts by weight,
in a preferred embodiment of the present invention, the aliphatic isocyanate is at least one of isophorone diisocyanate, 1, 4-cyclohexane diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate; the hydrazide chain extender is at least one of isophthalic dihydrazide, malonyl dihydrazide, succinic dihydrazide, adipic dihydrazide and sebacic dihydrazide; the catalyst is at least one of an organotin catalyst, an organobismuth catalyst and a tertiary amine catalyst; the oligomer polyol is polycarbonate polyol, polycaprolactone polyol and polytetrahydrofuranAt least one of a pyran polyol and a hydroxyl-terminated polybutadiene; the polyol small molecule cross-linking agent is at least one of trimethylolpropane, 2-amino-2-methyl-1, 3-propanediol, serinol and 2-amino-2-methyl-1, 3-propanediol; the metal ion cross-linking agent is ZnCl 2 、Zn(CF 3 SO 3 ) 2 、Zn(CF 3 COO) 2 、FeCl 3 、EuCl 3 、TbCl 3 At least one of them. The skilled person can optionally select suitable aliphatic isocyanate, hydrazide chain extender, oligomer polyol, polyol small molecule cross-linker, metal ion cross-linker, catalyst type and amount.
In a preferred embodiment of the present invention, the weight ratio of the aliphatic isocyanate, the catalyst, and the hydrazide-based chain extender is 20:0.2 to 5:0.5 to 20; preferably 20:0.2 to 3:1.6 to 12; more preferably, the weight ratio of the component A to the component B is 1:0.8 to 1.2. The skilled artisan can optionally select the appropriate weight ratio of catalyst to aliphatic isocyanate, weight ratio of aliphatic isocyanate to hydrazide-based chain extender, weight ratio of a component to B component.
In a preferred embodiment of the present invention, the a-component is prepared by the steps of:
(1) Respectively dissolving the aliphatic isocyanate and the hydrazide chain extender in a first solvent and a second solvent, mixing, adding a part of catalyst, and heating for reaction to obtain an aliphatic isocyanate-terminated polyurethane prepolymer;
(2) Adding the rest catalyst into the aliphatic isocyanate-terminated polyurethane prepolymer in the step (1), adding the oligomer polyol and the polyol micromolecular crosslinking agent at 100-120 ℃, and heating for reaction to obtain hydroxyl-terminated polyurethane;
(3) Adding the metal ion cross-linking agent dissolved in a third solvent into the hydroxyl terminated polyurethane in the step (2) to obtain a component A;
Wherein, in the step (1), the partial catalyst accounts for 30 to 40 weight percent of the total catalyst in the component A.
The invention adopts the following technical scheme:
the component A is prepared by the following steps:
(1) Synthesis of isocyanate-terminated polyurethane prepolymers: respectively dissolving aliphatic isocyanate and a hydrazide chain extender in a first solvent and a second solvent, dropwise adding the hydrazide chain extender dissolved in the second solvent into an isocyanate solution dissolved in the first solvent, and heating and reacting for a certain time in the presence of a part of catalyst to obtain an aliphatic isocyanate-terminated polyurethane prepolymer; wherein the partial catalyst accounts for 30-40 wt% of the total catalyst in the component A. Specifically, the aliphatic isocyanate terminated polyurethane prepolymer containing the hydrazide group is obtained through condensation reaction, wherein the hydrazide group can form a metal ion coordination bond with a metal ion to provide metal coordination besides hydrogen bonding. The aliphatic isocyanate terminated polyurethane prepolymer containing hydrazide groups is a compound having the following structure:
(2) Synthesis of hydroxyl terminated polyurethanes: adding the rest catalyst into the reaction system, taking the oligomer polyol and the polyol micromolecular crosslinking agent which are subjected to heating treatment in advance, adding the oligomer polyol and the polyol micromolecular crosslinking agent into the reaction system of the isocyanate-terminated polyurethane prepolymer, and heating and reacting for a period of time to obtain the hydroxyl-terminated polyurethane.
(3) Synthesis of hydroxyl terminated polyurethanes containing hydrogen and metal coordination bonds: dissolving a proper metal ion cross-linking agent in a third solvent, adding the third solvent into the hydroxyl-terminated polyurethane obtained in the step (2), stirring and mixing uniformly to obtain the hydroxyl-terminated polyurethane containing hydrogen bonds and metal coordination bonds, namely the component A, and further endowing the system with fluorescence performance if the metal ion cross-linking agent is rare earth ions.
In a preferred embodiment of the present invention, the first solvent is at least one of ethyl acetate, butyl acetate, xylene, propylene glycol methyl ether acetate, butanone, and n-hexane; the second solvent is at least one of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide, isophorone and cyclohexanone; the third solvent is at least one of acetonitrile, tetrahydrofuran, propylene glycol methyl ether acetate, chloroform, N-dimethylformamide and dichloromethane. The sum of the dosage of the first solvent, the second solvent and the third solvent is 1 to 100 parts by weight; preferably 80 to 100 parts by weight. The skilled person can optionally select the kinds and amounts of the suitable first solvent, second solvent, third solvent.
In a preferred embodiment of the present invention, the mass ratio of the first solvent to the aliphatic isocyanate is 1 to 3:1, preferably 2 to 3:1, a step of; the mass ratio of the second solvent to the hydrazide chain extender is 20:1 to 10, preferably 20:4 to 7; the mass ratio of the third solvent to the metal ion crosslinking agent is 10:0.1 to 3, preferably 10:0.1 to 1; the mass ratio of the first solvent to the catalyst is 100:0.1 to 2, preferably 100:0.5 to 1.5. The skilled artisan can optionally select the appropriate weight ratio of the first solvent to aliphatic isocyanate, the second solvent to hydrazide-based chain extender, the third solvent to metal ion crosslinker, and the first solvent to catalyst.
In a preferred embodiment of the present invention, in step (1), the reaction temperature is 50 to 100 ℃, preferably 70 to 90 ℃; the reaction time is 0.5 to 4 hours, preferably 1 to 2 hours; in the step (2), the reaction temperature is 70-110 ℃, preferably 80-100 ℃; the reaction time is 1 to 6 hours, preferably 2 to 4 hours. The skilled person can choose the appropriate reaction temperature and reaction time as appropriate.
The second object of the present invention is to provide a process for preparing a high-strength, high-toughness, aging-resistant two-component polyurethane of the object of the present invention. The method comprises the following steps: mixing the component A and the component B according to the amount, adding a solvent, volatilizing, heating and curing to obtain the high-strength high-toughness aging-resistant double-component polyurethane.
The solvent is the first solvent. The first solvent is at least one of ethyl acetate, butyl acetate, xylene, propylene glycol methyl ether acetate, butanone and n-hexane.
Specifically: and mixing and uniformly stirring the hydroxyl-terminated polyurethane (component A) containing hydrogen bonds and metal coordination bonds with the component B (fluorine-containing chain segment modified isocyanate curing agent), diluting with a proper amount of first solvent, placing the diluted solution in a tetrafluoroethylene mold to volatilize the solvent for film formation, and heating and curing to remove the solvent to obtain the high-strength high-toughness aging-resistant double-component polyurethane with fluorescent property.
Compared with the prior art, the invention has the following beneficial effects:
1) The high-strength high-toughness aging-resistant double-component polyurethane can be prepared into hydroxyl-terminated polyurethane (component A) rich in hydrogen bonds and metal coordination bonds by introducing hydrazide groups and metal ions. The introduction of supramolecular interactions (hydrogen bonding/metal coordination bonding) can simultaneously enhance the strength and toughness of the a-component. The strength and toughness of the product can be adjusted by adjusting the ratio and the type of the hydrazide group and the metal ion.
2) The high-strength high-toughness aging-resistant double-component polyurethane can also select rare earth ions and hydrazide groups to form metal ion coordination bonds, further endow the system with fluorescence performance and expand the application of the system.
3) The component B in the high-strength high-toughness aging-resistant double-component polyurethane is a fluorine-containing chain segment modified isocyanate curing agent, and the component A and the component B are crosslinked and cured to obtain the double-component polyurethane with both strength and toughness. The aging-resistant raw materials (isocyanate and oligomer polyol) in the component A and the fluorine-containing chain segment modified isocyanate curing agent in the component B have synergistic effect, so that the prepared high-strength high-toughness double-component polyurethane has excellent aging resistance.
4) The method for preparing the high-strength high-toughness aging-resistant double-component polyurethane has the advantages of easily available raw materials, simple and easily controlled synthesis process, no need of specific equipment and higher yield.
Drawings
FIG. 1 is a schematic view showing fluorescence properties of the high-strength, high-toughness and aging-resistant two-component polyurethane prepared in example 4 of the present invention under ultraviolet irradiation;
FIG. 2 is a schematic view showing fluorescence properties of the high-strength, high-toughness and aging-resistant two-component polyurethane prepared in example 5 of the present invention under ultraviolet irradiation.
Detailed Description
The present invention is described in detail below with reference to the specific drawings and examples, and it is necessary to point out that the following examples are given for further illustration of the present invention only and are not to be construed as limiting the scope of the present invention, since numerous insubstantial modifications and adaptations of the invention to those skilled in the art will still fall within the scope of the present invention.
The raw materials used in the examples were all conventional commercially available raw materials. The instruments used in the examples are all conventional instruments. The component B is obtained by the preparation method of example 2 in CN101143840A, and is not described herein.
Example 1
(1) Synthesis of isocyanate-terminated polyurethane prepolymers: taking 20 parts of 1, 4-cyclohexane diisocyanate cyanate and 2 parts of isophthalic dihydrazide chain extender, respectively dissolving in 35 parts of butyl acetate and 25 parts of N, N-dimethylformamide, dropwise adding the isophthalic dihydrazide chain extender dissolved in N, N-dimethylformamide into dicyclohexylmethane diisocyanate solution dissolved in butyl acetate, and reacting for 2 hours at 70 ℃ in the presence of 0.3 part of organotin catalyst to obtain aliphatic isocyanate terminated polyurethane prepolymer;
(2) Synthesis of hydroxyl terminated polyurethanes: 0.5 part by weight of an organotin catalyst was added to the above reaction system, and 100 parts by weight of a polycarbonate polyol at 110℃and 3 parts by weight of trimethylolpropane, which had been subjected to a heat water removal treatment in advance, were taken and added to the reaction system of the above isocyanate-terminated polyurethane prepolymer. And reacting for 3 hours at 90 ℃ to obtain the hydroxyl terminated polyurethane.
(3) Synthesis of hydroxyl terminated polyurethanes containing hydrogen and metal coordination bonds: 0.1 part of Zn (CF) 3 SO 3 ) 2 Dissolving a cross-linking agent in 10 parts of acetonitrile, adding the cross-linking agent into the hydroxyl-terminated polyurethane obtained in the step (2), and uniformly stirring and mixing to obtain the hydroxyl-terminated polyurethane containing hydrogen bonds and metal coordination bonds, namely the component A;
(4) Synthesis of high-strength high-toughness and aging-resistant double-component polyurethane: and (3) mixing and uniformly stirring 1 part of hydroxyl-terminated polyurethane (component A) containing hydrogen bonds and metal coordination bonds obtained in the step (3) and 1.2 parts of component B (fluorine-containing chain segment modified isocyanate curing agent), diluting 2 parts of butyl acetate, placing the mixture in a tetrafluoroethylene mold to volatilize a solvent for film formation, and heating for curing to remove the solvent to obtain the high-strength high-toughness aging-resistant double-component polyurethane.
Example 2
(1) Synthesis of isocyanate-terminated polyurethane prepolymers: taking 20 parts of 1, 4-cyclohexane diisocyanate cyanate and 2 parts of malonyl hydrazine chain extender, respectively dissolving in 35 parts of dimethylbenzene and 25 parts of N-methylpyrrolidone, dropwise adding the malonyl hydrazine chain extender dissolved in the N-methylpyrrolidone into isophorone diisocyanate solution dissolved in dimethylbenzene, and reacting for 2 hours at 70 ℃ in the presence of 0.3 part of organotin catalyst to obtain aliphatic isocyanate terminated polyurethane prepolymer;
(2) Synthesis of hydroxyl terminated polyurethanes: 0.5 part by weight of an organotin catalyst was added to the above reaction system, and 100 parts by weight of a polycarbonate polyol at 110℃and 3 parts by weight of trimethylolpropane, which had been subjected to a heat dehydration treatment in advance, were taken and added to the reaction system of the above isocyanate-terminated polyurethane prepolymer. Reacting for 3 hours at 90 ℃ to obtain hydroxyl-terminated polyurethane;
(3) Synthesis of hydroxyl terminated polyurethanes containing hydrogen and metal coordination bonds: 0.1 part of Zn (CF) 3 SO 3 ) 2 Dissolving a cross-linking agent in 10 parts of tetrahydrofuran, adding the cross-linking agent into the hydroxyl-terminated polyurethane obtained in the step (2), and uniformly stirring and mixing to obtain the hydroxyl-terminated polyurethane containing hydrogen bonds and metal coordination bonds, namely a component A;
(4) Synthesis of high-strength high-toughness and aging-resistant double-component polyurethane: and (3) mixing and uniformly stirring 1 part of hydroxyl-terminated polyurethane (component A) containing hydrogen bonds and metal coordination bonds obtained in the step (3) and 1.2 parts of component B (fluorine-containing chain segment modified isocyanate curing agent), diluting 2 parts of dimethylbenzene, placing the mixture in a tetrafluoroethylene mold, volatilizing a solvent to form a film, and heating, curing and removing the solvent to obtain the high-strength high-toughness aging-resistant double-component polyurethane.
Example 3
(1) Synthesis of isocyanate-terminated polyurethane prepolymers: taking 20 parts of 1, 4-cyclohexane diisocyanate cyanate and 2 parts of succinic acid dihydrazide chain extender, respectively dissolving in 35 parts of propylene glycol methyl ether acetate and 25 parts of N, N-dimethylacetamide, dropwise adding the succinic acid dihydrazide chain extender dissolved in the N, N-dimethylacetamide into an isocyanate solution dissolved in the propylene glycol methyl ether acetate, and reacting for 2 hours at 70 ℃ in the presence of 0.3 part of an organotin catalyst to obtain an aliphatic isocyanate-terminated polyurethane prepolymer;
(2) Synthesis of hydroxyl terminated polyurethanes: 0.5 part by weight of an organotin catalyst was added to the above reaction system, and 100 parts by weight of a polycarbonate polyol at 110℃and 3 parts by weight of trimethylolpropane, which had been subjected to a heat water removal treatment in advance, were taken and added to the reaction system of the above isocyanate-terminated polyurethane prepolymer. Reacting for 3 hours at 90 ℃ to obtain hydroxyl-terminated polyurethane;
(3) Synthesis of hydroxyl terminated polyurethanes containing hydrogen and metal coordination bonds: 0.1 part of Zn (CF) 3 SO 3 ) 2 Dissolving a cross-linking agent in 10 parts of dichloromethane, adding the cross-linking agent into the hydroxyl-terminated polyurethane obtained in the step (2), and uniformly stirring and mixing to obtain the hydroxyl-terminated polyurethane containing hydrogen bonds and metal coordination bonds, namely the component A;
(4) Synthesis of high-strength high-toughness and aging-resistant double-component polyurethane: and (3) mixing and uniformly stirring 1 part of hydroxyl-terminated polyurethane (component A) containing hydrogen bonds and metal coordination bonds obtained in the step (3) and 1.2 parts of component B (fluorine-containing chain segment modified isocyanate curing agent), diluting 2 parts of propylene glycol methyl ether acetate, placing the diluted mixture in a tetrafluoroethylene mold to volatilize a solvent for film formation, and heating, curing and removing the solvent to obtain the high-strength high-toughness aging-resistant double-component polyurethane.
Example 4
(1) Synthesis of isocyanate-terminated polyurethane prepolymers: taking 20 parts of 1, 4-cyclohexane diisocyanate cyanate and 2 parts of succinic acid dihydrazide chain extender, respectively dissolving in 35 parts of propylene glycol methyl ether acetate and 25 parts of N, N-dimethylacetamide, dropwise adding the succinic acid dihydrazide chain extender dissolved in the N, N-dimethylacetamide into an isocyanate solution dissolved in the propylene glycol methyl ether acetate, and reacting for 2 hours at 70 ℃ in the presence of 0.3 part of an organotin catalyst to obtain an aliphatic isocyanate-terminated polyurethane prepolymer;
(2) Synthesis of hydroxyl terminated polyurethanes: 0.5 part by weight of an organotin catalyst was added to the above reaction system, and 100 parts by weight of a polycarbonate polyol at 110℃and 3 parts by weight of trimethylolpropane, which had been subjected to a heat water removal treatment in advance, were taken and added to the reaction system of the above isocyanate-terminated polyurethane prepolymer. Reacting for 3 hours at 90 ℃ to obtain hydroxyl-terminated polyurethane;
(3) Synthesis of hydroxyl terminated polyurethanes containing hydrogen and metal coordination bonds: 0.1 part of EuCl is taken 3 Dissolving a cross-linking agent in 10 parts of acetonitrile, adding the cross-linking agent into the hydroxyl-terminated polyurethane obtained in the step (2), and uniformly stirring and mixing to obtain the hydroxyl-terminated polyurethane containing hydrogen bonds and metal coordination bonds, namely the component A;
(4) High-strength high-toughness aging-resistant double-component polyurethane with fluorescent performance is synthesized: and (3) mixing and uniformly stirring 1 part of hydroxyl-terminated polyurethane (component A) containing hydrogen bonds and metal coordination bonds obtained in the step (3) and 1.2 parts of component B (fluorine-containing chain segment modified isocyanate curing agent), diluting 2 parts of propylene glycol methyl ether acetate, placing the diluted mixture in a tetrafluoroethylene mold to volatilize a solvent for film formation, and heating, curing and removing the solvent to obtain the high-strength high-toughness aging-resistant double-component polyurethane with fluorescent property.
Example 5
(1) Synthesis of isocyanate-terminated polyurethane prepolymers: taking 20 parts of 1, 4-cyclohexane diisocyanate cyanate and 2 parts of succinic acid dihydrazide chain extender, respectively dissolving in 35 parts of propylene glycol methyl ether acetate and 25 parts of N, N-dimethylacetamide, dropwise adding the succinic acid dihydrazide chain extender dissolved in the N, N-dimethylacetamide into an isocyanate solution dissolved in the propylene glycol methyl ether acetate, and reacting for 2 hours at 70 ℃ in the presence of 0.3 part of an organotin catalyst to obtain an aliphatic isocyanate-terminated polyurethane prepolymer;
(2) Synthesis of hydroxyl terminated polyurethanes: 0.5 part by weight of an organotin catalyst was added to the above reaction system, and 100 parts by weight of a polycarbonate polyol at 110℃and 3 parts by weight of trimethylolpropane, which had been subjected to a heat water removal treatment in advance, were taken and added to the reaction system of the above isocyanate-terminated polyurethane prepolymer. Reacting for 3 hours at 90 ℃ to obtain hydroxyl-terminated polyurethane;
(3) Synthesis of hydroxyl terminated polyurethanes containing hydrogen and metal coordination bonds: 0.1 part of TbCl is taken 3 Dissolving a cross-linking agent in 10 parts of acetonitrile, adding the cross-linking agent into the hydroxyl-terminated polyurethane obtained in the step (2), and uniformly stirring and mixing to obtain the hydroxyl-terminated polyurethane containing hydrogen bonds and metal coordination bonds, namely the component A;
(4) High-strength high-toughness aging-resistant double-component polyurethane with fluorescent performance is synthesized: and (3) mixing and uniformly stirring 1 part of hydroxyl-terminated polyurethane (component A) containing hydrogen bonds and metal coordination bonds obtained in the step (3) and 1.2 parts of component B (fluorine-containing chain segment modified isocyanate curing agent), diluting 2 parts of propylene glycol methyl ether acetate, placing the diluted mixture in a tetrafluoroethylene mold to volatilize a solvent for film formation, and heating, curing and removing the solvent to obtain the high-strength high-toughness aging-resistant double-component polyurethane with fluorescent property.
Example 6
(1) Synthesis of isocyanate-terminated polyurethane prepolymers: taking 20 parts of 1, 4-cyclohexane diisocyanate cyanate and 5 parts of succinic acid dihydrazide chain extender, respectively dissolving in 35 parts of butyl acetate and 25 parts of N, N-dimethylformamide, dropwise adding the isophthalic acid dihydrazide chain extender dissolved in the N, N-dimethylformamide into dicyclohexylmethane diisocyanate solution dissolved in butyl acetate, and reacting for 2 hours at 70 ℃ in the presence of 0.3 part of organotin catalyst to obtain aliphatic isocyanate terminated polyurethane prepolymer;
(2) Synthesis of hydroxyl terminated polyurethanes: 0.5 part by weight of an organotin catalyst was added to the above reaction system, and 100 parts by weight of a polycarbonate polyol at 110℃and 3 parts by weight of trimethylolpropane, which had been subjected to a heat water removal treatment in advance, were taken and added to the reaction system of the above isocyanate-terminated polyurethane prepolymer. And reacting for 3 hours at 90 ℃ to obtain the hydroxyl terminated polyurethane.
(3) Synthesis of hydroxyl terminated polyurethanes containing hydrogen and metal coordination bonds: 0.1 part of Zn (CF) 3 SO 3 ) 2 Dissolving a cross-linking agent in 10 parts of acetonitrile, adding the cross-linking agent into the hydroxyl-terminated polyurethane obtained in the step (2), and stirring and mixing uniformly to obtain a polyurethane containing hydrogen bonds andhydroxyl terminated polyurethane with metal coordination bond is the component A;
(4) Synthesis of high-strength high-toughness and aging-resistant double-component polyurethane: and (3) mixing and uniformly stirring 1 part of hydroxyl-terminated polyurethane (component A) containing hydrogen bonds and metal coordination bonds obtained in the step (3) and 1.2 parts of component B (fluorine-containing chain segment modified isocyanate curing agent), diluting 2 parts of butyl acetate, placing the mixture in a tetrafluoroethylene mold to volatilize a solvent for film formation, and heating for curing to remove the solvent to obtain the high-strength high-toughness aging-resistant double-component polyurethane.
Example 7
(1) Synthesis of isocyanate-terminated polyurethane prepolymers: taking 20 parts of 1, 4-cyclohexane diisocyanate cyanate and 2 parts of succinic acid dihydrazide chain extender, respectively dissolving in 35 parts of butyl acetate and 25 parts of N, N-dimethylformamide, dropwise adding the isophthalic acid dihydrazide chain extender dissolved in the N, N-dimethylformamide into dicyclohexylmethane diisocyanate solution dissolved in butyl acetate, and reacting for 2 hours at 70 ℃ in the presence of 0.3 part of organotin catalyst to obtain aliphatic isocyanate terminated polyurethane prepolymer;
(2) Synthesis of hydroxyl terminated polyurethanes: 0.5 part by weight of an organotin catalyst was added to the above reaction system, and 100 parts by weight of a polycarbonate polyol at 110℃and 3 parts by weight of trimethylolpropane, which had been subjected to a heat water removal treatment in advance, were taken and added to the reaction system of the above isocyanate-terminated polyurethane prepolymer. And reacting for 3 hours at 90 ℃ to obtain the hydroxyl terminated polyurethane.
(3) Synthesis of hydroxyl terminated polyurethanes containing hydrogen and metal coordination bonds: 1 part of Zn (CF) 3 SO 3 ) 2 Dissolving a cross-linking agent in 10 parts of acetonitrile, adding the cross-linking agent into the hydroxyl-terminated polyurethane obtained in the step (2), and uniformly stirring and mixing to obtain the hydroxyl-terminated polyurethane containing hydrogen bonds and metal coordination bonds, namely the component A;
(4) Synthesis of high-strength high-toughness and aging-resistant double-component polyurethane: and (3) mixing and uniformly stirring 1 part of hydroxyl-terminated polyurethane (component A) containing hydrogen bonds and metal coordination bonds obtained in the step (3) and 1.2 parts of component B (fluorine-containing chain segment modified isocyanate curing agent), diluting 2 parts of butyl acetate, placing the mixture in a tetrafluoroethylene mold to volatilize a solvent for film formation, and heating for curing to remove the solvent to obtain the high-strength high-toughness aging-resistant double-component polyurethane.
Example 8
(1) Synthesis of isocyanate-terminated polyurethane prepolymers: taking 20 parts of 1, 4-cyclohexane diisocyanate cyanate and 2 parts of succinic acid dihydrazide chain extender, respectively dissolving in 35 parts of butyl acetate and 25 parts of N, N-dimethylformamide, dropwise adding the isophthalic acid dihydrazide chain extender dissolved in the N, N-dimethylformamide into dicyclohexylmethane diisocyanate solution dissolved in butyl acetate, and reacting for 2 hours at 70 ℃ in the presence of 0.3 part of organotin catalyst to obtain aliphatic isocyanate terminated polyurethane prepolymer;
(2) Synthesis of hydroxyl terminated polyurethanes: 0.5 part by weight of an organotin catalyst was added to the above reaction system, and 100 parts by weight of a polycarbonate polyol at 110℃and 3 parts by weight of trimethylolpropane, which had been subjected to a heat water removal treatment in advance, were taken and added to the reaction system of the above isocyanate-terminated polyurethane prepolymer. And reacting for 3 hours at 90 ℃ to obtain the hydroxyl terminated polyurethane.
(3) Synthesis of hydroxyl terminated polyurethanes containing hydrogen and metal coordination bonds: 0.5 part of Zn (CF) 3 SO 3 ) 2 Dissolving a cross-linking agent in 10 parts of acetonitrile, adding the cross-linking agent into the hydroxyl-terminated polyurethane obtained in the step (2), and uniformly stirring and mixing to obtain the hydroxyl-terminated polyurethane containing hydrogen bonds and metal coordination bonds, namely the component A;
(4) Synthesis of high-strength high-toughness and aging-resistant double-component polyurethane: and (3) mixing and uniformly stirring 1 part of hydroxyl-terminated polyurethane (component A) containing hydrogen bonds and metal coordination bonds obtained in the step (3) and 1.2 parts of component B (fluorine-containing chain segment modified isocyanate curing agent), diluting 2 parts of butyl acetate, placing the mixture in a tetrafluoroethylene mold to volatilize a solvent for film formation, and heating for curing to remove the solvent to obtain the high-strength high-toughness aging-resistant double-component polyurethane.
Example 9
(1) Synthesis of isocyanate-terminated polyurethane prepolymers: taking 20 parts of 1, 4-cyclohexane diisocyanate cyanate and 8 parts of succinic acid dihydrazide chain extender, respectively dissolving in 35 parts of butyl acetate and 25 parts of N, N-dimethylformamide, dropwise adding the isophthalic acid dihydrazide chain extender dissolved in the N, N-dimethylformamide into dicyclohexylmethane diisocyanate solution dissolved in butyl acetate, and reacting for 2 hours at 70 ℃ in the presence of 0.3 part of organotin catalyst to obtain aliphatic isocyanate terminated polyurethane prepolymer;
(2) Synthesis of hydroxyl terminated polyurethanes: 0.5 part by weight of an organotin catalyst was added to the above reaction system, and 100 parts by weight of a polycarbonate polyol at 110℃and 3 parts by weight of trimethylolpropane, which had been subjected to a heat water removal treatment in advance, were taken and added to the reaction system of the above isocyanate-terminated polyurethane prepolymer. And reacting for 3 hours at 90 ℃ to obtain the hydroxyl terminated polyurethane.
(3) Synthesis of hydroxyl terminated polyurethanes containing hydrogen and metal coordination bonds: 0.1 part of Zn (CF) 3 SO 3 ) 2 Dissolving a cross-linking agent in 10 parts of acetonitrile, adding the cross-linking agent into the hydroxyl-terminated polyurethane obtained in the step (2), and uniformly stirring and mixing to obtain the hydroxyl-terminated polyurethane containing hydrogen bonds and metal coordination bonds, namely the component A;
(4) Synthesis of high-strength high-toughness and aging-resistant double-component polyurethane: and (3) mixing and uniformly stirring 1 part of hydroxyl-terminated polyurethane (component A) containing hydrogen bonds and metal coordination bonds obtained in the step (3) and 1.2 parts of component B (fluorine-containing chain segment modified isocyanate curing agent), diluting 2 parts of butyl acetate, placing the mixture in a tetrafluoroethylene mold to volatilize a solvent for film formation, and heating for curing to remove the solvent to obtain the high-strength high-toughness aging-resistant double-component polyurethane.
Comparative example 1
(1) Synthesis of isocyanate-terminated polyurethane prepolymers: taking 20 parts of 1, 4-cyclohexane diisocyanate cyanate and 2 parts of 1, 4-butanediol, respectively dissolving in 35 parts of butyl acetate and 25 parts of N, N-dimethylformamide, dropwise adding a 1, 4-butanediol chain extender dissolved in N, N-dimethylformamide into an isocyanate solution dissolved in butyl acetate, and reacting for 2 hours at 70 ℃ in the presence of 0.3 part of an organotin catalyst to obtain an aliphatic isocyanate-terminated polyurethane prepolymer;
(2) Synthesis of hydroxyl terminated polyurethanes: 0.5 part by weight of an organotin catalyst was added to the above reaction system, and 100 parts by weight of a polycarbonate polyol at 110℃and 3 parts by weight of trimethylolpropane, which had been subjected to a heat water removal treatment in advance, were taken and added to the reaction system of the above isocyanate-terminated polyurethane prepolymer. Reacting for 3 hours at 90 ℃ to obtain hydroxyl-terminated polyurethane;
(3) Synthesis of hydroxyl terminated polyurethanes containing hydrogen and metal coordination bonds: 0.1 part of Zn (CF) 3 SO 3 ) 2 Dissolving a cross-linking agent in 10 parts of acetonitrile, adding the cross-linking agent into the hydroxyl-terminated polyurethane obtained in the step (2), and uniformly stirring and mixing to obtain the hydroxyl-terminated polyurethane containing hydrogen bonds and metal coordination bonds, namely the component A;
(4) Synthesis of polyurethanes containing hydrogen and metal coordination bonds: and (3) mixing and uniformly stirring 1 part of hydroxyl-terminated polyurethane (component A) containing hydrogen bonds and metal coordination bonds obtained in the step (3) and 1.2 parts of component B (fluorine-containing chain segment modified isocyanate curing agent), diluting 2 parts of butyl acetate, placing the mixture in a tetrafluoroethylene mold, volatilizing a solvent to form a film, and heating, curing and removing the solvent to obtain the bi-component polyurethane.
Comparative example 2
(1) Synthesis of isocyanate-terminated polyurethane prepolymers: taking 20 parts of 1, 4-cyclohexane diisocyanate cyanate and 2 parts of 1, 6-hexanediol, respectively dissolving in 35 parts of butyl acetate and 25 parts of N, N-dimethylformamide, dropwise adding a 1, 6-hexanediol chain extender dissolved in N, N-dimethylformamide into an isocyanate solution dissolved in butyl acetate, and reacting for 2 hours at 70 ℃ in the presence of 0.3 part of an organotin catalyst to obtain an aliphatic isocyanate-terminated polyurethane prepolymer;
(2) Synthesis of hydroxyl terminated polyurethanes: 0.5 part by weight of an organotin catalyst was added to the above reaction system, and 100 parts by weight of a polycarbonate polyol at 110℃and 3 parts by weight of trimethylolpropane, which had been subjected to a heat water removal treatment in advance, were taken and added to the reaction system of the above isocyanate-terminated polyurethane prepolymer. Reacting for 3 hours at 90 ℃ to obtain hydroxyl-terminated polyurethane;
(3) Synthesis of hydroxyl terminated polyurethanes containing hydrogen and metal coordination bonds: 0.1 part of Zn (CF) 3 SO 3 ) 2 The cross-linking agent is dissolved in 10 parts of acetonitrile, and is added into the hydroxyl seal obtained in the step (2)Stirring and mixing uniformly in the terminal polyurethane to obtain hydroxyl-terminated polyurethane containing hydrogen bonds and metal coordination bonds, namely a component A;
(4) Synthesis of polyurethanes containing hydrogen and metal coordination bonds: and (3) mixing and uniformly stirring 1 part of hydroxyl-terminated polyurethane (component A) containing hydrogen bonds and metal coordination bonds obtained in the step (3) and 1.2 parts of component B (fluorine-containing chain segment modified isocyanate curing agent), diluting 2 parts of butyl acetate, placing the mixture in a tetrafluoroethylene mold, volatilizing a solvent to form a film, and heating, curing and removing the solvent to obtain the bi-component polyurethane.
Comparative example 3
(1) Synthesis of isocyanate-terminated polyurethane prepolymers: taking 20 parts of 1, 4-cyclohexane diisocyanate cyanate and 2 parts of 1, 4-butanediol, respectively dissolving in 35 parts of butyl acetate and 25 parts of N, N-dimethylformamide, dropwise adding a 1, 4-butanediol chain extender dissolved in N, N-dimethylformamide into an isocyanate solution dissolved in butyl acetate, and reacting for 2 hours at 70 ℃ in the presence of 0.3 part of an organotin catalyst to obtain an aliphatic isocyanate-terminated polyurethane prepolymer;
(2) Synthesis of hydroxyl terminated polyurethanes: 0.5 part by weight of an organotin catalyst was added to the above reaction system, and 100 parts by weight of a polycarbonate polyol at 110℃and 3 parts by weight of trimethylolpropane, which had been subjected to a heat water removal treatment in advance, were taken and added to the reaction system of the above isocyanate-terminated polyurethane prepolymer. Reacting for 3 hours at 90 ℃ to obtain hydroxyl-terminated polyurethane, namely a component A;
(3) Synthesis of two-component polyurethane: and (3) mixing 1 part of hydroxyl-terminated polyurethane (component A) obtained in the step (2) with 1.2 parts of component B (fluorine-containing chain segment modified isocyanate curing agent), uniformly stirring, diluting 2 parts of butyl acetate, placing in a tetrafluoroethylene mold, volatilizing a solvent to form a film, and heating, curing and removing the solvent to obtain the double-component polyurethane.
Comparative example 4
(1) Synthesis of isocyanate-terminated polyurethane prepolymers: taking 20 parts of 1, 4-cyclohexane diisocyanate cyanate and 20 parts of succinic acid dihydrazide chain extender, respectively dissolving in 35 parts of butyl acetate and 25 parts of N, N-dimethylformamide, dropwise adding the isophthalic acid dihydrazide chain extender dissolved in the N, N-dimethylformamide into dicyclohexylmethane diisocyanate solution dissolved in butyl acetate, and reacting for 2 hours at 70 ℃ in the presence of 0.3 part of organotin catalyst to obtain aliphatic isocyanate terminated polyurethane prepolymer;
(2) Synthesis of hydroxyl terminated polyurethanes: 0.5 part by weight of an organotin catalyst was added to the above reaction system, and 100 parts by weight of a polycarbonate polyol at 110℃and 3 parts by weight of trimethylolpropane, which had been subjected to a heat water removal treatment in advance, were taken and added to the reaction system of the above isocyanate-terminated polyurethane prepolymer. And reacting for 3 hours at 90 ℃ to obtain the hydroxyl terminated polyurethane.
(3) Synthesis of hydroxyl terminated polyurethanes containing hydrogen and metal coordination bonds: 0.1 part of Zn (CF) 3 SO 3 ) 2 Dissolving a cross-linking agent in 10 parts of acetonitrile, adding the cross-linking agent into the hydroxyl-terminated polyurethane obtained in the step (2), and uniformly stirring and mixing to obtain the hydroxyl-terminated polyurethane containing hydrogen bonds and metal coordination bonds, namely the component A;
(4) Synthesis of polyurethanes containing hydrogen and metal coordination bonds: and (3) mixing and uniformly stirring 1 part of hydroxyl-terminated polyurethane (component A) containing hydrogen bonds and metal coordination bonds obtained in the step (3) and 1.2 parts of component B (fluorine-containing chain segment modified isocyanate curing agent), diluting 2 parts of butyl acetate, placing the diluted butyl acetate in a tetrafluoroethylene mold to volatilize a solvent for film formation, and heating for curing to remove the solvent to obtain the double-component polyurethane.
Comparative example 5
(1) Synthesis of isocyanate-terminated polyurethane prepolymers: taking 20 parts of 1, 4-cyclohexane diisocyanate cyanate and 2 parts of succinic acid dihydrazide chain extender, respectively dissolving in 35 parts of propylene glycol methyl ether acetate and 25 parts of N, N-dimethylacetamide, dropwise adding the succinic acid dihydrazide chain extender dissolved in the N, N-dimethylacetamide into an isocyanate solution dissolved in the propylene glycol methyl ether acetate, and reacting for 2 hours at 70 ℃ in the presence of 0.3 part of an organotin catalyst to obtain an aliphatic isocyanate-terminated polyurethane prepolymer;
(2) Synthesis of hydroxyl terminated polyurethanes: 0.5 part by weight of an organotin catalyst was added to the above reaction system, and 100 parts by weight of a polycarbonate polyol at 110℃and 3 parts by weight of trimethylolpropane, which had been subjected to a heat water removal treatment in advance, were taken and added to the reaction system of the above isocyanate-terminated polyurethane prepolymer. Reacting for 3 hours at 90 ℃ to obtain hydroxyl-terminated polyurethane, namely a component A;
(3) Synthesis of two-component polyurethane: and (3) mixing and uniformly stirring 1 part of hydroxyl-terminated polyurethane (component A) containing hydrogen bonds and 1.2 parts of component B (fluorine-containing chain segment modified isocyanate curing agent) obtained in the step (2) by weight, diluting 2 parts of propylene glycol methyl ether acetate, placing the diluted mixture into a tetrafluoroethylene mold to volatilize a solvent for film formation, and heating and curing to remove the solvent to obtain the high-strength high-toughness aging-resistant double-component polyurethane.
The two-component polyurethane films obtained in examples 1 to 9 and comparative examples 1 to 5 were subjected to mechanical property test, and the tensile strength and elongation at break were obtained by the test method in "measurement of tensile stress strain properties of vulcanized rubber or thermoplastic rubber" by GB/T528-2009. The toughness is obtained by drawing the tensile strength and elongation at break data obtained by the test into a tensile strength-elongation at break curve (namely a stress-strain curve) and then calculating the coverage area of the stress-strain curve. The test results are shown in tables 1 and 2. Further, after the two-component polyurethanes obtained in examples 1 to 3 were subjected to UVA test for 7 days, mechanical properties were further tested, and the test results are shown in Table 3.
TABLE 1 polyurethane Performance test results for examples 1-9
| Tensile strength, MPa | Elongation at break% | Toughness, (MJ/m) 3 ) | |
| Example 1 | 56.7 | 922.6 | 318.1 |
| Example 2 | 53.3 | 962.3 | 320.5 |
| Example 3 | 49.3 | 980.3 | 316.3 |
| Example 4 | 41.5 | 1004.5 | 304.2 |
| Example 5 | 39.8 | 1015.7 | 295.3 |
| Example 6 | 44.8 | 872.2 | 307.8 |
| Example 7 | 41.1 | 829.8 | 303.1 |
| Example 8 | 38.4 | 903.1 | 296.9 |
| Example 9 | 40.3 | 821.6 | 301.4 |
Table 2 results of polyurethane Performance test of comparative examples 1 to 5
| Tensile strength, MPa | Elongation at break% | Toughness, (MJ/m) 3 ) | |
| Comparative example 1 | 34.1 | 997.8 | 277.8 |
| Comparative example 2 | 33.6 | 1008.3 | 280.1 |
| Comparative example 3 | 24.9 | 1020.3 | 227.3 |
| Comparative example 4 | 38.2 | 794.4 | 287.7 |
| Comparative example 5 | 35.4 | 1232.7 | 285.6 |
The results of the polyurethane film performance tests obtained in examples 1 to 9 and comparative examples 1 to 5 are shown in tables 1 and 2, respectively. From the results of Table 2, it is seen that comparative example 3 is relatively poor in tensile strength, elongation at break and toughness, in which the tensile strength thereof is 24.9MPa, which is equivalent to that of a commercially available two-component polyurethane material. Since it does not add a metal ion cross-linker. The tensile strength and toughness of comparative examples 1 and 2 are both enhanced to some extent, and the elongation at break is slightly reduced, compared to comparative example 3, because 1, 4-butanediol or 1, 6-hexanediol as a chain extender can form hydrogen bonds, which can form metal ion coordination bonds with metal ions, enhancing the strength and toughness of the two-component polyurethane material. However, comparing specific values of tensile strength, elongation at break and toughness of comparative examples 1 to 2 and comparative example 3, it was found that the tensile strength and toughness of comparative examples 1 to 2 were not improved much.
Compared with comparative examples 1 to 3, the strength and toughness of the polyurethane materials prepared in examples 1 to 9 are both remarkably enhanced, because the hydrazide groups in the system can form metal ion coordination bonds with metal ions, so that the strength and toughness of the polyurethane materials are further enhanced. Meanwhile, due to the introduction of the hydrazide chain extender, more hydrogen bond groups are introduced into the system by the hydrazide groups, and the hydrogen bonds can also form metal ion coordination bonds with higher strength with metal ions, so that the reaction proceeds moreThe strength and toughness of the polyurethane material are enhanced in one step. In particular, the tensile strength of the example 1 reaches 56.7MPa, which is far higher than 10-25 MPa in the prior art, and solves the technical problem of insufficient paint film strength in the prior art. In Table 1, the toughness of each of examples 1 to 7 and example 9 was greater than 300MJ/m 3 . Therefore, the two-component polyurethane obtained by the invention has high strength and high toughness. However, the data in examples 6-9 show that as the amount of the metal ion crosslinking agent or the hydrazide-based chain extender is increased, the obtained two-component polyurethane becomes more and more brittle and the mechanical properties become worse gradually. In particular, the data of comparative example 4 show that if too many hydrogen bonds of hydrazide groups are introduced into the system, the high strength and high toughness can not be achieved. In addition, the data of comparative example 5 show that if only the hydrogen bond of the hydrazide group exists in the system and no metal coordination bond exists, the mechanical properties of the polyurethane are weaker than those of tough polyurethane with both the metal coordination bond and the hydrogen bond of the hydrazide group (examples 1 to 9).
TABLE 3 results of Performance test of the polyurethanes of examples 1-3 after 7 days of UVA test
| Tensile strength, MPa | Elongation at break% | Toughness, (MJ/m) 3 ) | |
| Example 1 | 48.1 | 890.1 | 285.3 |
| Example 2 | 49.2 | 928.4 | 300.4 |
| Example 3 | 48.9 | 943.9 | 291.6 |
As is clear from the results shown in Table 3, the two-component polyurethanes prepared in examples 1 to 3 have excellent aging resistance in addition to excellent tensile strength, elongation at break and toughness. This is due to the synergistic effect of the ageing resistant raw materials in component a and component B, which remain excellent tensile strength and toughness after 7 days of UVA test. Therefore, the double-component polyurethane obtained by the invention has high strength, high toughness and aging resistance, and can meet the protection requirement of a double-component polyurethane paint film in the outdoor or severe conditions for a long time.
The polyurethane films obtained in examples 4 to 5 were subjected to a fluorescence property test by irradiating the polyurethane films with ultraviolet light emitted from a commercially available 254nm ultraviolet lamp. The test results are shown in fig. 1 and 2, wherein fig. 1 is a test result diagram of example 4, and fig. 2 is a test result diagram of example 5. As can be seen from FIG. 1, example 4 is performed by adding EuCl 3 As a metal ion cross-linking agent, the two-component polyurethane prepared in the example 4 shows red fluorescence under the irradiation of an ultraviolet lamp; as can be seen from FIG. 2, example 5 is performed by adding TbCl 3 As a metal ion crosslinking agent, the two-component polyurethane prepared in example 5 shows green fluorescence under the irradiation of an ultraviolet lamp. From this, it is clear that the two-component polyurethanes prepared in examples 4 to 5 exhibited fluorescent properties under irradiation of ultraviolet lamp. This is due to the coordination of the rare earth ions with the hydrazide-based groups to form metal ion coordination bonds. The introduction of fluorescent properties gives the two-component polyurethane more application possibilities.
In conclusion, the double-component polyurethane obtained by the invention has high strength, high toughness and aging resistance, can be introduced with rare earth ions to have fluorescence performance, and has wide application range.
Claims (10)
1. A high-strength high-toughness aging-resistant two-component polyurethane is characterized in that: the two-component polyurethane comprises a component A and a component B; the weight ratio of the component A to the component B is 1:0.1 to 1.2;
the component A is prepared from the following raw materials:
the components are calculated according to the weight portions,
the structural formula of the component B is as follows
2. The high-strength, high-toughness, aging-resistant two-component polyurethane of claim 1, wherein:
in the component A, each component is calculated according to parts by weight,
3. the high-strength, high-toughness, aging-resistant two-component polyurethane of claim 1, wherein:
The aliphatic isocyanate is at least one of isophorone diisocyanate, 1, 4-cyclohexane diisocyanate, hexamethylene diisocyanate and dicyclohexylmethane diisocyanate; and/or
The hydrazide chain extender is at least one of isophthalic dihydrazide, malonyl dihydrazide, succinic dihydrazide, adipic dihydrazide and sebacic dihydrazide; and/or
The catalyst is at least one of an organotin catalyst, an organobismuth catalyst and a tertiary amine catalyst; and/or
The oligomer polyol is at least one of polycarbonate polyol, polycaprolactone polyol, polytetrahydrofuran polyol and hydroxyl-terminated polybutadiene; and/or
The polyol small molecule cross-linking agent is at least one of trimethylolpropane, 2-amino-2-methyl-1, 3-propanediol, serinol and 2-amino-2-methyl-1, 3-propanediol; and/or
The metal ion cross-linking agent is ZnCl 2 、Zn(CF 3 SO 3 ) 2 、Zn(CF 3 COO) 2 、FeCl 3 、EuCl 3 、TbCl 3 At least one of them.
4. The high-strength, high-toughness, aging-resistant two-component polyurethane of claim 1, wherein:
the weight ratio of the aliphatic isocyanate to the catalyst to the hydrazide chain extender is 20:0.2 to 5:0.5 to 20; preferably 20:0.2 to 3:1.6 to 12.
5. The high-strength, high-toughness, aging-resistant two-component polyurethane of claim 1, wherein:
the weight ratio of the component A to the component B is 1:0.8 to 1.2.
6. The high-strength, high-toughness, aging-resistant two-component polyurethane of claim 1, wherein:
the component A is prepared by the following steps:
(1) Respectively dissolving the aliphatic isocyanate and the hydrazide chain extender in a first solvent and a second solvent, mixing, adding a part of catalyst, and heating for reaction to obtain an aliphatic isocyanate-terminated polyurethane prepolymer;
(2) Adding the rest catalyst into the aliphatic isocyanate-terminated polyurethane prepolymer in the step (1), adding the oligomer polyol and the polyol micromolecular crosslinking agent at 110-120 ℃, and heating for reaction to obtain hydroxyl-terminated polyurethane;
(3) Adding the metal ion cross-linking agent dissolved in a third solvent into the hydroxyl terminated polyurethane in the step (2) to obtain a component A;
wherein, in the step (1), the partial catalyst accounts for 30 to 40 weight percent of the total catalyst in the component A.
7. The high-strength, high-toughness, aging-resistant two-component polyurethane of claim 6, wherein:
The first solvent is at least one of ethyl acetate, butyl acetate, dimethylbenzene, propylene glycol methyl ether acetate, butanone and n-hexane; and/or
The second solvent is at least one of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide, isophorone and cyclohexanone; and/or
The third solvent is at least one of acetonitrile, tetrahydrofuran, propylene glycol methyl ether acetate, chloroform, N-dimethylformamide and dichloromethane.
8. The high-strength, high-toughness, aging-resistant two-component polyurethane of claim 7, wherein:
the mass ratio of the first solvent to the aliphatic isocyanate is 1-3: 1, preferably 2 to 3:1, a step of; and/or
The mass ratio of the second solvent to the hydrazide chain extender is 20:1 to 10, preferably 20:4 to 7; and/or
The mass ratio of the third solvent to the metal ion crosslinking agent is 10:0.1 to 3, preferably 10:0.1 to 1; and/or
The mass ratio of the first solvent to the catalyst is 100:0.1 to 2, preferably 100:0.5 to 1.5.
9. The high-strength, high-toughness, aging-resistant two-component polyurethane of claim 6, wherein:
in the step (1), the reaction temperature is 50-100 ℃, preferably 70-90 ℃; the reaction time is 0.5 to 4 hours, preferably 1 to 2 hours; and/or
In the step (2), the reaction temperature is 70-110 ℃, preferably 80-100 ℃; the reaction time is 1 to 6 hours, preferably 2 to 4 hours.
10. The process for preparing a high-strength, high-toughness, ageing-resistant two-component polyurethane as claimed in any of claims 1 to 9, characterized in that
The method comprises the following steps: mixing the component A and the component B according to the dosage, adding a solvent, volatilizing, heating and curing to obtain the high-strength high-toughness aging-resistant double-component polyurethane; the solvent is at least one of ethyl acetate, butyl acetate, xylene, propylene glycol methyl ether acetate, butanone and n-hexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310808833.XA CN116675828A (en) | 2023-07-04 | 2023-07-04 | High-strength high-toughness aging-resistant double-component polyurethane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310808833.XA CN116675828A (en) | 2023-07-04 | 2023-07-04 | High-strength high-toughness aging-resistant double-component polyurethane and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116675828A true CN116675828A (en) | 2023-09-01 |
Family
ID=87791003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310808833.XA Pending CN116675828A (en) | 2023-07-04 | 2023-07-04 | High-strength high-toughness aging-resistant double-component polyurethane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116675828A (en) |
-
2023
- 2023-07-04 CN CN202310808833.XA patent/CN116675828A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101830749B1 (en) | Self-healing polyurethane polymer, and method of manufacturing the same | |
| JP4999228B2 (en) | Extrudable thermoplastic elastomeric urea chain extended polyurethane | |
| US5811506A (en) | Extrudable thermoplastic elastomeric urea-extended polyurethane | |
| CN1174015C (en) | Casted plastic potyurethane composition | |
| JP6984838B2 (en) | A method for producing a carboxyl group-containing aqueous resin composition, a molded product, and a polycarbodiimide compound. | |
| EP0900245B1 (en) | Extrudable thermoplastic elastomeric urea-extended polyurethane | |
| DE102004001100A1 (en) | Curable resin composition | |
| TWI813549B (en) | polycarbodiimide copolymer | |
| EP3433294B1 (en) | Melt processable thermoplastic polyurethane-urea elastomers | |
| CN109535374B (en) | Polyurethane elastomer and preparation method thereof | |
| EP4130180A1 (en) | Two-liquid curable adhesive composition | |
| CN116675828A (en) | High-strength high-toughness aging-resistant double-component polyurethane and preparation method thereof | |
| WO2015115291A1 (en) | Polyisocyanate composition, two-pack-type curable polyurethane resin, coating material, and adhesive | |
| Romanov et al. | Polyureas—a new promising class of binders for adhesives, sealants, and coatings | |
| CN112752819B (en) | Two-part curable adhesive composition | |
| WO2021193961A1 (en) | Two-liquid curable adhesive composition | |
| CN111072888A (en) | Plastic material and preparation method thereof | |
| KR101609806B1 (en) | Preparation of waterborne polyurethane resin using 2-methylcyclohexane-1,3,5-triamine and aterborne polyurethane resin | |
| JP2000073008A (en) | Waterproof material composed of quick curing polyurethane coating film curable at normal temperature, mending material and its production | |
| JPH107901A (en) | Urethane resin composition | |
| JP2001316618A (en) | Resin composition for thermosetting one-component coating material | |
| JP2003041085A (en) | Curable composition and sealing material composition | |
| KR100586037B1 (en) | Pro-environmental Urethane Sheet and The Process | |
| JPH03244624A (en) | Production of polyurethane resin and polyurethane resin composition | |
| JP2023017368A (en) | Two-pack type curable adhesive composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |