CN116730874A - Modified isocyanate monomer and preparation method thereof - Google Patents
Modified isocyanate monomer and preparation method thereof Download PDFInfo
- Publication number
- CN116730874A CN116730874A CN202310489592.7A CN202310489592A CN116730874A CN 116730874 A CN116730874 A CN 116730874A CN 202310489592 A CN202310489592 A CN 202310489592A CN 116730874 A CN116730874 A CN 116730874A
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- CN
- China
- Prior art keywords
- diol
- modified isocyanate
- isocyanate monomer
- diisocyanate
- monomer
- Prior art date
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- 239000000178 monomer Substances 0.000 title claims abstract description 112
- 239000012948 isocyanate Substances 0.000 title claims abstract description 91
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 150000002009 diols Chemical class 0.000 claims abstract description 57
- 229920003225 polyurethane elastomer Polymers 0.000 claims abstract description 57
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 28
- 150000004985 diamines Chemical class 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims description 44
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 21
- CTNICFBTUIFPOE-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=C(O)C=C1 CTNICFBTUIFPOE-UHFFFAOYSA-N 0.000 claims description 20
- 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 17
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 16
- -1 alkane diol Chemical class 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 12
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000004417 polycarbonate Substances 0.000 claims description 10
- 229920000515 polycarbonate Polymers 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 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 7
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- RVCHQYCXJDVJQF-UHFFFAOYSA-N (3,5-diethylphenyl)methanediamine Chemical compound CCC1=CC(CC)=CC(C(N)N)=C1 RVCHQYCXJDVJQF-UHFFFAOYSA-N 0.000 claims description 4
- 150000004984 aromatic diamines Chemical class 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 3
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- DNNXXFFLRWCPBC-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC=CC=C1 Chemical class N=C=O.N=C=O.C1=CC=CC=C1 DNNXXFFLRWCPBC-UHFFFAOYSA-N 0.000 claims description 3
- MRUXVMBOICABIU-UHFFFAOYSA-N [3,5-bis(methylsulfanyl)phenyl]methanediamine Chemical compound CSC1=CC(SC)=CC(C(N)N)=C1 MRUXVMBOICABIU-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical class C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 18
- 229920002635 polyurethane Polymers 0.000 abstract description 16
- 239000004814 polyurethane Substances 0.000 abstract description 16
- 238000012545 processing Methods 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 27
- 239000000463 material Substances 0.000 description 25
- 238000002329 infrared spectrum Methods 0.000 description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 11
- 239000004970 Chain extender Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 230000001376 precipitating effect Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 8
- 239000000806 elastomer Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 150000001412 amines Chemical group 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- DHTGRDDBCWWKQJ-UHFFFAOYSA-N 2-(2,2-dihydroxyethoxy)ethane-1,1-diol Chemical compound OC(O)COCC(O)O DHTGRDDBCWWKQJ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 4
- 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 3
- 241001112258 Moca Species 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- NDOVLWQBFFJETK-UHFFFAOYSA-N 1,4-thiazinane 1,1-dioxide Chemical compound O=S1(=O)CCNCC1 NDOVLWQBFFJETK-UHFFFAOYSA-N 0.000 description 1
- ZUFUSIMENKJSMG-UHFFFAOYSA-N 1-methyl-3,5-bis(methylsulfanyl)benzene Chemical compound CSC1=CC(C)=CC(SC)=C1 ZUFUSIMENKJSMG-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7843—Nitrogen containing -N-C=0 groups containing urethane groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
- C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
- C07C273/1818—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety from -N=C=O and XNR'R"
- C07C273/1827—X being H
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C275/40—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7825—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing ureum groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a modified isocyanate monomer with reasonable molecular design, which is obtained by utilizing the reaction of diol or diamine and diisocyanate, and the modified isocyanate monomer and oligomer diol are utilized to carry out curing polymerization, so that the heat resistance and the processing rheological property of the obtained polyurethane elastomer are improved, and the polyurethane elastomer can meet the requirements of the fields of plates, rubber rollers, rubber wheels, tires and the like on the polyurethane performance.
Description
Technical Field
The invention belongs to the technical field of polyurethane synthesis, and particularly relates to a modified isocyanate monomer and a preparation method thereof.
Background
Polyurethanes are a class of multi-block copolymers containing alternating hard and soft segments of repeating urethane and/or urea linkages in the molecular chain. The polyurethane elastomer material has wide mechanical property adjustable range due to rich and varied raw material types, and can have the advantages of good toughness, excellent elasticity, wear resistance, solvent resistance, corrosion resistance and the like through regulating and controlling the raw material structure and the proportion of each component. The alternating microphase separation structure of the soft and hard segments of the polyurethane leads the polyurethane material to be widely applied to a plurality of fields such as metal industry, artificial intelligence, biomedicine, constructional engineering, aerospace, emerging materials and the like.
By using a chain extender during the synthesis of polyurethane, its structure has an important influence on the properties of the polyurethane elastomer material. Commonly used chain extenders are alcohol and amine chain extenders. The alcohol chain extender reacts with isocyanate to generate a urethane bond, the amine chain extender reacts with isocyanate to generate a urea bond, the urethane bond and the urea bond can form hydrogen bonds among polymer molecules, microphase separation of the materials is induced, and the microphase separation degree is an important factor affecting the performance of polyurethane materials. On the premise of the same molecular structure and composition, the better and more ordered microphase separation degree is, and the better the physical and mechanical properties of the material are. Compared with a micromolecular amine chain extender, the diol chain extender has relatively moderate reactivity, is a main raw material for preparing the polyurethane elastomer material, and meanwhile, the abundant types and adjustable chemical structures of the micromolecular diol endow the polyurethane elastomer material with very wide adjustable range of performance, so that the material with excellent performances such as wear resistance, high bearing capacity, fatigue resistance, heat insulation, good biocompatibility and the like can be prepared to meet the requirements of different application occasions. Although more hydrogen bond structures can be formed in the molecular structure of the polyurethane elastomer material prepared by adopting the micromolecular amine chain extender, the material is induced to generate more perfect microphase separation, so that the physical and mechanical properties of the material are improved, the polyurethane elastomer material can be only used for casting polyurethane materials generally due to the fact that the reaction activity is too fast, is difficult to be used for producing thermoplastic polyurethane elastomers, and reduces the application range of the polyurethane material. In order to solve the problem, researchers have reduced the activity of amine chain extenders by introducing electron withdrawing structures, halogen atoms or groups with large steric hindrance into the molecular structure of diamines, but the reactivity of aromatic diamines is relatively rapid and difficult to apply directly to the production of thermoplastic polyurethane elastomer materials.
Among the existing methods for producing thermoplastic polyurethane elastomers, the one-step method or the prepolymer method is most commonly used. When the one-step method is adopted, the reaction simultaneously occurs among the oligomer diol, the chain extender and the isocyanate monomer, so that the generated polymer molecular chain is in a disordered structure, and the microphase separation of the material can be influenced, thereby influencing the processability of the material and the mechanical property of a product. In addition, with the advancement of technology, the thermoplastic polyurethane elastomer produced by the existing technology cannot meet the requirements of some new application occasions, such as sieve plates, rubber rollers, rubber wheels, tires and the like, on the physical and mechanical properties of the elastomer material. Therefore, the development of a synthetic method of the polyurethane elastomer material with a modified isocyanate monomer structure has important significance for improving the performance of the elastomer material.
Disclosure of Invention
In order to solve the problems, the invention provides a modified isocyanate monomer, which is obtained by reacting glycol or diamine with diisocyanate. The polyurethane prepared from the modified cyanate monomer and the oligomer diol has regular molecular structure, better heat resistance and processing rheological property, and the performance of the obtained elastomer material is effectively improved, so that the requirements of fields such as sieve plates, rubber rollers, rubber wheels, tires and the like on the performance of the polyurethane can be met.
An object of a first aspect of the present invention is to provide a modified isocyanate monomer having the following structure:
wherein R is 1 Selected from alkylene or diphenol-containing alkyl groups, preferably from alkylene or hydroquinone diethyl groups having a carbon number of 4 to 6, more preferably butylene (- (CH) 2 ) 4 (-) and hexamethylene (- (CH) 2 ) 6 (-) or hydroquinone diethyl.
The hydroquinone diethyl is:
R 3 、R 4 selected from arylene groups, preferably from benzene subunits, more preferably：
R 2 Selected from aromatic groups, preferably from substituted phenyl groups or 4,4' -methylenedianiline compounds, more preferably:
wherein X is halogen, preferably bromine or chlorine, more preferably chlorine.
The object of the second aspect of the present invention is to provide a modified isocyanate monomer obtained by reacting a diol or a diamine with a diisocyanate.
The diol is selected from one or more of alkane diol and dihydric alcohol containing diphenol, preferably one or more of alkane diol with carbon number of 4-6 and dihydroxyethyl ether of hydroquinone, more preferably 1, 4-Butanediol (BDO), 1, 6-Hexanediol (HDO) or dihydroxyethyl ether of Hydroquinone (HQEE).
The diamine is selected from one or more of aromatic diamine, preferably one or more of phenylenediamine compound and 4,4 '-methylenedianiline compound, more preferably 3, 5-diethyltoluenediamine (DETDA), 4' -methylenebis (3-chloro-2, 6-diethylaniline) (MCDEA) or 3, 5-dimethylthiotoluenediamine (DMTDA).
The diisocyanate is selected from one or more of aromatic structure-containing diisocyanates, preferably from one or more of benzene diisocyanate compounds, alkylbenzene diisocyanate compounds, naphthalene diisocyanate and diphenylalkane diisocyanate, more preferably from 2, 4-Toluene Diisocyanate (TDI), m-phenylene diisocyanate (XDI), 4' -diphenylmethane diisocyanate (MDI) or p-phenylene diisocyanate (PPDI).
The third aspect of the present invention is to provide a method for preparing the modified isocyanate monomer, wherein a diol or diamine solution is added to a diisocyanate monomer solution, preferably dropwise added, under an oxygen-free protective atmosphere, and the reaction is carried out at a constant temperature to obtain a reaction solution containing the modified isocyanate monomer. And then obtaining the modified isocyanate monomer through precipitation, washing, separation and drying.
The fourth aspect of the invention aims to provide a method for preparing a polyurethane elastomer from the modified isocyanate monomer, wherein the method takes the modified isocyanate monomer and the oligomer diol as raw materials to prepare the polyurethane elastomer.
The modified isocyanate monomer provided by the invention has the following beneficial effects:
(1) According to the invention, the diol or diamine is reacted with the diisocyanate, the diol or diamine chain segment is introduced into the modified isocyanate monomer, and the reaction activity is adjusted, so that the reaction rate is controlled in the process of preparing polyurethane, and the microphase separation of the polyurethane is controlled.
(2) The modified isocyanate monomer has reasonable molecular design, simple preparation process and easy control of synthesis, and is favorable for popularization and application in industrial production.
(3) The polyurethane prepared from the modified isocyanate monomer and the oligomer diol has regular molecular structure, better heat resistance and processing rheological property, and the performance of the obtained elastomer material is effectively improved, so that the requirements of fields such as sieve plates, rubber rollers, rubber wheels, tires and the like on the polyurethane performance can be met.
Drawings
FIG. 1 shows an infrared spectrum of a modified isocyanate monomer THT of the invention;
FIG. 2 shows an infrared spectrum of a modified isocyanate monomer TBT of the present invention;
FIG. 3 shows an infrared spectrum of modified isocyanate monomer XBX of the present invention;
FIG. 4 shows an infrared spectrum of a modified isocyanate monomer XHX of the present invention;
FIG. 5 shows an infrared spectrum of a modified isocyanate monomer TMT of the present invention;
FIG. 6 shows an infrared spectrum of a modified isocyanate monomer MBM of the present invention;
FIG. 7 shows an infrared spectrum of a modified isocyanate monomer PBP of the present invention;
FIG. 8 shows an infrared spectrum of the modified isocyanate monomer PHP of the present invention;
FIG. 9 shows an infrared spectrum of the modified isocyanate monomer XDEX of the present invention;
FIG. 10 shows an infrared spectrum of a modified isocyanate monomer XMCX of the present invention;
FIG. 11 shows an infrared spectrum of the modified isocyanate monomer XDMX of the present invention;
FIG. 12 shows an infrared spectrum of a modified isocyanate monomer PHDP of the present invention;
FIG. 13 shows the complex viscosity |η| -temperature curves of the polyurethane elastomer PU-1 and the polyurethane elastomer PU-1' according to the invention;
FIG. 14 shows the complex viscosity |η| -frequency curves of the polyurethane elastomer PU-1 and the polyurethane elastomer PU-1' of the invention;
FIG. 15 shows tan delta temperature curves of polyurethane elastomers PU-1 and PU-1' of the invention;
FIG. 16 shows the storage modulus vs. temperature curves of the polyurethane elastomers PU-1 and PU-1' of the invention.
Detailed Description
The features and advantages of the present invention will become more apparent and evident from the following detailed description of the invention.
The invention provides a modified isocyanate monomer which is obtained by reacting diol or diamine with diisocyanate.
The diol is selected from one or more of alkane diol and dihydric alcohol containing diphenol, preferably one or more of alkane diol with carbon number of 4-6 and dihydroxyethyl ether of hydroquinone, more preferably 1, 4-Butanediol (BDO), 1, 6-Hexanediol (HDO) or dihydroxyethyl ether of Hydroquinone (HQEE).
The diamine is selected from one or more of aromatic diamine, preferably one or more of phenylenediamine compound and 4,4 '-methylenedianiline compound, more preferably 3, 5-diethyltoluenediamine (DETDA), 4' -methylenebis (3-chloro-2, 6-diethylaniline) (MCDEA) or 3, 5-dimethylthiotoluenediamine (DMTDA).
The diisocyanate is selected from one or more of aromatic group-containing diisocyanates, preferably selected from one or more of benzene diisocyanate compounds, alkylbenzene diisocyanate compounds, naphthalene diisocyanate and diphenylalkane diisocyanate, more preferably 2, 4-Toluene Diisocyanate (TDI), m-phenylene diisocyanate (XDI), 4' -diphenylmethane diisocyanate (MDI) or p-phenylene diisocyanate (PPDI).
The modified isocyanate monomer has the following structure:
wherein R is 1 Selected from alkylene or diphenol-containing alkyl groups, preferably from alkylene or hydroquinone diethyl groups having a carbon number of 4 to 6, more preferably butylene (- (CH) 2 ) 4 (-) and hexamethylene (- (CH) 2 ) 6 (-) or hydroquinone diethyl.
The hydroquinone diethyl is:
R 3 、R 4 selected from arylene groups, preferably selected from benzene subunits, more preferably:
R 2 selected from arylene groups, preferably from substituted phenylene or 4,4' -methylenediphenyl, more preferably:
wherein X is halogen, preferably bromine or chlorine, more preferably chlorine.
Preferably, the modified isocyanate monomer is:
more preferably, the modified isocyanate monomer is:
the invention also provides a preparation method of the modified isocyanate monomer, which comprises the steps of adding glycol or diamine solution into diisocyanate monomer solution, preferably dripping, and carrying out heat preservation reaction to obtain reaction solution containing the modified isocyanate monomer under the oxygen-free atmosphere. And then obtaining the modified isocyanate monomer through precipitation, washing, separation and drying.
Preferably, the reaction is carried out in the presence of a catalyst selected from one or more of organotin, preferably one or more of tetraalkyltin compounds and stannous carboxylate compounds, more preferably one or more of dibutyltin diacetate, stannous octoate and dibutyltin dilaurate.
The ratio of the mass of the catalyst to the total mass of diisocyanate monomer and alcohol or amine monomer is (0.0005-0.003): 1, preferably (0.0005-0.0015): 1, more preferably (0.0007-0.0012): 1.
The molar ratio of diol or diamine to diisocyanate monomer is 1 (1.5-7.5), preferably 1 (2-6.5), more preferably 1 (2.5-5.5).
The reaction temperature is 30 to 60 ℃, preferably 35 to 55 ℃, more preferably 40 to 50 ℃. The dropping time is 1 to 3 hours, and the reaction time is 3 to 8 hours, preferably 3.5 to 7 hours, more preferably 4 to 6 hours.
The solvent of the diisocyanate monomer solution is selected from one or more of cyclic ether solvents, alkane solvents, halogenated aromatic solvents and ester solvents, preferably one or more of tetrahydrofuran, dioxane, chlorobenzene, o-dichlorobenzene, tertiary butyl acetate, ethyl butyrate and ethyl acetate, more preferably one or more of tetrahydrofuran, dioxane, chlorobenzene and ethyl acetate.
The diisocyanate monomer solution concentration is 0.15 to 7.5mol/L, preferably 0.25 to 6.5mol/L, more preferably 0.35 to 5.5mol/L.
The solvent of the glycol or diamine solution is selected from one or more of cyclic ether solvents, alkane solvents, halogenated aromatic solvents and ester solvents, preferably one or more of tetrahydrofuran, dioxane, chlorobenzene, o-dichlorobenzene, tertiary butyl acetate, ethyl butyrate and ethyl acetate, more preferably one or more of tetrahydrofuran, dioxane, chlorobenzene and ethyl acetate.
The concentration of the glycol or diamine solution is 0.05 to 1.8mol/L, preferably 0.08 to 1.5mol/L, more preferably 0.1 to 1.2mol/L.
The oxygen-free protective atmosphere is selected from nitrogen and/or argon.
The invention also provides a method for preparing the polyurethane elastomer by using the modified isocyanate monomer, and the method takes the modified isocyanate monomer and the oligomer diol as raw materials to prepare the polyurethane elastomer.
The oligomer diol is selected from one or more of polycarbonate diol (PCD), polytetrahydrofuran diol (PTMEG), polycaprolactone diol (PCL) and polypropylene diol (PPG), preferably polycarbonate diol (PCD) and/or polytetrahydrofuran diol (PTMEG), more preferably polycarbonate diol (PCD) or polytetrahydrofuran diol (PTMEG).
The weight average molecular weight (M of the oligomeric diol w ) 600-3000g/mol, preferably 700-2000g/mol, more preferably 800-1200g/mol.
The modified isocyanate monomer is added into the oligomer diol preheated to 70-100 ℃, stirred and mixed to form uniform liquid, and heated and solidified to react, thus obtaining the polyurethane elastomer.
The curing temperature is 65-145 ℃, preferably 75-135 ℃, more preferably 85-125 ℃. The curing time is 16 to 32 hours, preferably 18 to 30 hours, more preferably 20 to 28 hours.
Preferably, the curing is performed sequentially at 80-95 ℃ for 2-3 hours, 95-105 ℃ for 2-3 hours, 105-115 ℃ for 2-3 hours, and 115-125 ℃ for 16-20 hours.
The modified isocyanate monomer is obtained by reacting diol or diamine with diisocyanate, has reasonable molecular design, simple and easily controlled preparation process, and is favorable for popularization and application in large-scale production. The modified isocyanate monomer and the oligomer diol are utilized to carry out curing polymerization, so that the heat resistance and the processing rheological property of the obtained polyurethane elastomer are improved, the performance is improved, the application field of the polyurethane elastomer is expanded, and the requirements of the fields of plates, rubber rollers, rubber wheels, tires and the like on the polyurethane performance can be met.
Examples
Example 1
1.98g of hydroquinone dihydroxyethyl ether (HQEE) and 40mL of dry Tetrahydrofuran (THF) are stirred and mixed uniformly in a container for later use; 8.71g of 2, 4-Toluene Diisocyanate (TDI), 25mL of dioxane and 0.0086g of dibutyltin dilaurate were added to a reaction vessel under nitrogen atmosphere, stirred and mixed well, and the temperature was maintained at 50 ℃. Under the conditions of stirring and nitrogen, slowly adding the HQEE solution which is uniformly mixed into a reaction container, wherein the dropwise adding time is 3 hours; after the reaction was continued at 50℃for 5 hours with stirring, a reaction solution of the modified isocyanate monomer THT was obtained.
And adding the obtained reaction solution into dry n-hexane under the condition of stirring, and precipitating, washing, separating and drying to obtain the modified isocyanate monomer THT. The structure of the obtained modified isocyanate monomer THT is precisely analyzed by FT-IR (Fourier infrared spectroscopy), the infrared spectrogram is shown in figure 1, and the characteristic peak position is-NCO: 2276cm -1 ，-NH-：3298cm -1 ，C-N：1512cm -1 ，-CH 2 -：2943cm -1 ，-CH 3 ：2873cm -1 ，C＝O：1701cm -1 ，C-O-C：1226cm -1 And 1068cm -1 。
10.00g of THT and 17.43g of polycarbonate diol (PCD 1000, model NIPPOLLAN981, M, shanghai Jide Chemie Co., ltd.) which has been dehydrated and preheated to 90℃are mixed W =1000 g/mol, hydroxyl number=112±4KOH mg/g) was added to the reaction vessel and stirred rapidly until mixed to a homogeneous liquid state. And finally, putting the mixed materials into an oven for gradual heating and curing under the following curing conditions: heating to 90 ℃ for 2h, heating to 100 ℃ for 2h, heating to 110 ℃ for 2h, and heating to 120 ℃ for 18h. Naturally cooling to obtain the polyurethane elastomer PU-1 with regular and alternating soft and hard segments.
The infrared spectrum analysis of the polyurethane elastomer PU-1 obtained by the test shows that the characteristic peak position is-NH: 3300cm -1 And 1530cm -1 ，C＝O：1700cm -1 ，C-N:1520cm -1 ，-C-O-C-:1230cm -1 And 1160cm -1 。
Example 2
Polyurethane elastomer PU-2 was produced in the same manner as PU-1 in example 1, except that: 17.76g of polytetrahydrofuran diol (PTMEG, model PolyTHF 1000 (S), M, available from Shanghai Jide Chemie Co., ltd.) are added W =1000 g/mol, hydroxyl number=112±4KOH mg/g) instead of 17.43g of polycarbonate diol (PCD 1000).
The infrared spectrum analysis of the polyurethane elastomer PU-2 obtained by the test shows that the characteristic peak position is-NH: 3300cm -1 And 1530cm -1 ，C＝O：1690cm -1 And 1720cm -1 ，C-N:1520cm -1 ，-C-O-C-:1230cm -1 And 1160cm -1 。
Example 3
Uniformly stirring and mixing 0.90g of 1, 4-Butanediol (BDO) and 15mL of dry THF in a container for later use; 10.45g of 2, 4-Toluene Diisocyanate (TDI) and 30mL of n-hexane were added to a reaction vessel under nitrogen atmosphere, stirred and mixed uniformly, and the temperature was maintained at 60 ℃. Under the conditions of stirring and nitrogen, slowly adding the BDO solution which is uniformly mixed into a reaction container, wherein the dropwise adding time is 2 hours; after the reaction was continued at 60℃with stirring for 6 hours, a reaction solution containing modified isocyanate monomer TBT was obtained.
The obtained reaction solution is added into dry THF under the condition of stirring, and the modified isocyanate monomer TBT is obtained after precipitation, washing, separation and drying. The structure of the obtained monomer is accurately analyzed by characterization means such as FT-IR, and an infrared spectrogram of the monomer is shown in figure 2.
Polyurethane elastomer PU-6 was produced in the same manner as PU-1 in example 1, except that: 10.00g TBT was added in place of THT, 22.14g polytetrahydrofuran diol (PTMEG) (model PolyTHF 1000 (S), model M, shanghai Jide Chemie Co., ltd W =1000 g/mol, hydroxyl number=112±4KOH mg/g) instead of 17.43g of polycarbonate diol (PCD 1000).
The infrared spectrum analysis of the polyurethane elastomer PU-6 obtained by the test shows that the characteristic peak position is-NH: 3300cm -1 And 1530cm -1 ，C＝O：1690cm -1 And 1720cm -1 ，C-N:1520cm -1 ，-C-O-C-:1230cm -1 And 1160cm -1 。
Example 4
Stirring and mixing 0.90g of 1, 4-Butanediol (BDO) and 10mL of dry Tetrahydrofuran (THF) in a container uniformly for later use; 5.65g of m-Xylylene Diisocyanate (XDI), 15mL of n-hexane and 0.0066g of stannous octoate were added to the reaction vessel under nitrogen atmosphere, and stirred and mixed uniformly at a temperature of 40 ℃. Under the conditions of stirring and nitrogen, slowly adding the BDO solution which is uniformly mixed into a reaction container, wherein the dropwise adding time is 1h; and (3) continuously stirring and reacting for 5 hours at 40 ℃ to obtain a reaction solution of modified isocyanate monomer XBX.
And adding the obtained reaction solution into dry THF under stirring, precipitating, washing, separating and drying to obtain modified isocyanate monomer XBX. The structure of the obtained monomer is accurately analyzed by characterization means such as FT-IR.
Polyurethane elastomer PU-9 was produced in the same manner as PU-1 in example 1, except that: 10g of modified isocyanate monomer XBX was added in place of THT, 21.01g of polytetrahydrofuran diol (PTMEG) (Shanghai Jide chemical Co., ltd., model PolyTHF 1000 (S), M was added W =1000 g/mol, hydroxyl number=112±4KOH mg/g) instead of 17.43g of polycarbonate diol (PCD 1000).
The infrared spectrum analysis of the polyurethane elastomer PU-9 obtained by the test shows that the characteristic peak position is NH:3300cm -1 ，C＝O：1690cm -1 ，C-N:1520cm -1 ，-C-O-C-:1230cm -1 And 1160cm -1
Example 5
Stirring and uniformly mixing 1.98g of hydroquinone dihydroxyethyl ether (HQEE) and 40mL of dry THF in a container for later use; 7.53g XDI, 15mL dioxane and 0.0095g dibutyltin diacetate were added to a reaction vessel under nitrogen atmosphere, stirred and mixed well, and the temperature was maintained at 50 ℃. Under the conditions of stirring and nitrogen, slowly adding the HQEE solution which is uniformly mixed into a reaction container, wherein the dropwise adding time is 3 hours; after the reaction was continued at 50℃with stirring for 4 hours, a reaction solution of the modified isocyanate monomer XHX was obtained.
The obtained reaction solution is added into dry normal hexane under the condition of stirring, and the modified isocyanate monomer XHX is obtained after precipitation, washing, separation and drying. The structure of the obtained monomer is accurately analyzed by characterization means such as FT-IR.
PU-13 was produced by the method of producing PU-1 in example 1, except that: 10g of modified isocyanate monomer XHX was used in place of THT, 17.06g of polytetrahydrofuran diol (PTMEG) (model PolyTHF 1000 (S), model M, shanghai Jide Chemie Co., ltd.) was added W =1000 g/mol, hydroxyl number=112±4KOH mg/g).
The infrared spectrum analysis of the polyurethane elastomer PU-13 obtained by the test shows that the characteristic peak position is-NH: 3300cm -1 ，C＝O：1690cm -1 ，C-N:1520cm -1 ，-C-O-C-:1230cm -1 And 1160cm -1 。
Example 6
2.67g of 3, 3-dichloro-4, 4-diaminodiphenylmethane (MOCA) and 20mL of dried chlorobenzene are stirred and mixed uniformly in a container for later use; 6.97g of TDI and 20mL of chlorobenzene were added to the reaction vessel under nitrogen atmosphere, stirred and mixed well, and the temperature was maintained at 20 ℃. Slowly adding the MOCA solution which is uniformly mixed into a reaction container under the conditions of stirring and nitrogen, wherein the dropwise adding time is 2 hours; after continuing to stir and react for 5 hours at 20 ℃, a reaction solution of the modified isocyanate monomer TMT is obtained.
And adding the obtained reaction solution into dry n-hexane under the condition of stirring, precipitating, washing, separating and drying to obtain the modified isocyanate monomer TMT. The structure of the obtained monomer is accurately analyzed by characterization means such as FT-IR, and the like, and the structure is specifically shown in figure 5.
PU-29 was produced according to the preparation method of PU-1 in example 1, except that: 10g of modified isocyanate monomer TMT was used in place of THT, and 15.77g of polytetrahydrofuran diol (PTMEG) (Shanghai Jide chemical Co., ltd.) was addedPolyTHF 1000 (S), M W =1000 g/mol, hydroxyl number=112±4KOH mg/g).
The infrared spectrum analysis of the polyurethane elastomer PU-29 obtained by the test shows that the characteristic peak position is-NH: 3300cm -1 And 1530cm -1 ，C＝O：1650cm -1 And 1720cm -1 ，C-N:1520cm -1 ，-C-O-C-:1230cm -1 And 1160cm -1 。
Example 7
Uniformly stirring and mixing 0.90g of BDO and 15mL of dry THF in a container for later use; 10.01g of diphenylmethane diisocyanate (MDI), 30mL of THF solvent and 0.0109g of dibutyltin dilaurate were added to the reaction vessel under nitrogen atmosphere, stirred and mixed well, and the temperature was maintained at 50 ℃. Under the conditions of stirring and nitrogen, slowly adding the BDO solution which is uniformly mixed into a reaction container, wherein the dropwise adding time is 2 hours; after the reaction was continued at 50℃with stirring for 6 hours, a reaction solution of the modified isocyanate monomer MBM was obtained.
And adding the obtained reaction solution into dry n-hexane under the condition of stirring, precipitating, washing, separating and drying to obtain the modified isocyanate monomer MBM. The structure of the obtained monomer is accurately analyzed by characterization means such as FT-IR, and the like, and the structure is specifically shown in FIG. 6.
PU-33 was produced by the method of producing PU-1 in example 1, except that: 10g of modified isocyanate monomer MBM was used in place of THT, and 16.44g of polytetrahydrofuran diol (PTMEG) (model PolyTHF 1000 (S), model M, available from Shanghai Jide Chemie Co., ltd.) was added W =1000 g/mol, hydroxyl number=112±4KOH mg/g).
The infrared spectrum analysis of the polyurethane elastomer PU-33 obtained by the test shows that the characteristic peak position is-NH: 3300cm -1 And 1530cm -1 ，C＝O：1700cm -1 ，C-N:1520cm -1 ，-C-O-C-:1230cm -1 And 1160cm -1 。
Example 8
Uniformly stirring and mixing 0.90g of BDO and 15mL of dry THF in a container for later use; 6.41g of terephthalyl diisocyanate (PPDI) and 60mL of THF solvent were added to a reaction vessel under nitrogen atmosphere, stirred and mixed uniformly, and the temperature was maintained at 40 ℃. Under the conditions of stirring and nitrogen, slowly adding the BDO solution which is uniformly mixed into a reaction container, wherein the dropwise adding time is 1h; and (3) continuously stirring and reacting for 5 hours at 40 ℃ to obtain a reaction solution of the modified isocyanate monomer PBP.
And adding the obtained reaction solution into dry n-hexane under the condition of stirring, precipitating, washing, separating and drying to obtain the modified isocyanate monomer PBP. The structure of the obtained monomer is accurately analyzed by characterization means such as FT-IR, and the like, and the structure is specifically shown in FIG. 7.
PU-37 was produced by the method of producing PU-1 in example 1, except that: 10g of modified isocyanate monomer PBP was used in place of THT, and 23.65g of polytetrahydrofuran diol (PTMEG) (model PolyTHF 1000 (S), M, available from Shanghai Jide Chemie Co., ltd.) was added W =1000 g/mol, hydroxyl number=112±4KOH mg/g).
The infrared spectrum analysis of the polyurethane elastomer PU-37 obtained by the test shows that the characteristic peak position is-NH: 3300cm -1 ，C＝O：1690cm -1 ，C-N:1520cm -1 ，-C-O-C-:1230cm -1 And 1160cm -1 。
Example 9
Stirring and mixing 1.98g of HQEE and 65mL of dry THF in a container uniformly for later use; 6.41g of terephthalyl diisocyanate (PPDI) and 50mL of THF solvent were added to a reaction vessel under nitrogen atmosphere, stirred and mixed uniformly, and the temperature was maintained at 45 ℃. Under the conditions of stirring and nitrogen, slowly adding the HQEE solution which is uniformly mixed into a reaction container, wherein the dropwise adding time is 3 hours; stirring and reacting for 6h at 45 ℃ to obtain the reaction solution of the modified isocyanate monomer PHP.
And adding the obtained reaction solution into dry n-hexane under the condition of stirring, precipitating, washing, separating and drying to obtain the modified isocyanate monomer PHP. The structure of the obtained monomer is accurately analyzed by characterization means such as FT-IR, and the like, and the structure is specifically shown in FIG. 8.
PU-45 was produced according to the preparation method of PU-1 in example 1, except that: 10g of modified isocyanate monomer PHP was used in place of THT, and 19.29g of polytetrahydrofuran diol (PTMEG) (model PolyTHF 1000 (S), M, available from Shanghai Jide Chemie Co., ltd.) was added W =1000 g/mol, hydroxyl number=112±4KOH mg/g).
The infrared spectrum analysis of the polyurethane elastomer PU-45 obtained by the test shows that the characteristic peak position is-NH: 3300cm -1 ，C＝O：1690cm -1 ，C-N:1520cm -1 ，-C-O-C-:1230cm -1 And 1160cm -1 。
Example 10
1.78g of 3, 5-diethyl toluenediamine (DETDA) and 25mL of dry dioxane are stirred and mixed uniformly in a container for later use; 7.53g XDI, 15mL dioxane and 0.0093g dibutyltin dilaurate were added to a reaction vessel under nitrogen atmosphere, stirred and mixed well, and the temperature was maintained at 40 ℃. Slowly adding the uniformly mixed DETDA solution into a reaction container under the conditions of stirring and nitrogen, wherein the dropwise adding time is 2 hours; after the reaction was continued at 40℃with stirring for 4 hours, a reaction solution of the modified isocyanate monomer XDEX was obtained.
The obtained reaction solution is added into dry THF under stirring, and the precipitate is washed, separated and dried to obtain the modified isocyanate monomer XDEX. The structure of the obtained monomer was precisely analyzed by characterization means such as FT-IR, as shown in FIG. 9.
Example 11
3.79g of 4, 4-methylenebis (3-chloro-2, 6-diethylaniline) (MCDEA) and 40mL of dried chlorobenzene were stirred and mixed uniformly in a vessel for use; 9.41g XDI, 20mL chlorobenzene and 0.0132g dibutyltin dilaurate were added to the reaction vessel under nitrogen atmosphere, and the mixture was stirred and stirred well, and the temperature was maintained at 30 ℃. Slowly adding the uniformly mixed MCDEA solution into a reaction container under the conditions of stirring and nitrogen, wherein the dropwise adding time is 2 hours; after the reaction was continued with stirring at 40℃for 4 hours, a reaction solution of modified isocyanate monomer XMCX was obtained.
And adding the obtained reaction solution into dry n-hexane under the condition of stirring, precipitating, washing, separating and drying to obtain the modified isocyanate monomer XMCX. The structure of the obtained monomer is accurately analyzed by characterization means such as FT-IR, and the like, and the structure is specifically shown in FIG. 10.
Example 12
2.14g of 3, 5-dimethyl thiotoluene diamine (DMTDA) and 30mL of dry ethyl acetate are stirred and mixed uniformly in a container for later use; 13.17g of XDI, 40mL of ethyl acetate and 0.0153g of dibutyltin dilaurate were added to a reaction vessel under a nitrogen atmosphere, and the mixture was stirred and stirred uniformly while maintaining the temperature at 50 ℃. Slowly adding the uniformly mixed DMTDA solution into a reaction container under the conditions of stirring and nitrogen, wherein the dropwise adding time is 2 hours; after the reaction was continued at 50℃with stirring for 5 hours, a reaction solution of modified isocyanate monomer XDMX was obtained.
Adding the obtained reaction solution into dry n-hexane under stirring, precipitating, washing, separating and drying to obtain modified isocyanate monomer XDMX. The structure of the obtained monomer was precisely analyzed by characterization means such as FT-IR, as shown in FIG. 11.
Example 13
1.18g of 1, 6-Hexanediol (HDO) and 15mL of dry THF are stirred and mixed uniformly in a container for later use; 8.10g of terephthalyl diisocyanate (PPDI) and 65mL of THF solvent were added to a reaction vessel under nitrogen atmosphere, stirred and mixed uniformly, and the temperature was maintained at 45 ℃. Under the conditions of stirring and nitrogen, slowly adding the HDO solution which is uniformly mixed into a reaction container, wherein the dropwise adding time is 1h; after the reaction was continued at 45℃for 5 hours with stirring, a reaction solution of the modified isocyanate monomer PHDP was obtained.
And adding the obtained reaction solution into dry n-hexane under the condition of stirring, precipitating, washing, separating and drying to obtain the modified isocyanate monomer PHDP. The structure of the obtained monomer was precisely analyzed by characterization means such as FT-IR, as shown in FIG. 12.
Comparative example
Comparative example 1
7.50g of TDI was added to a reaction vessel of 17.43g of PCD1000 which had been dehydrated and preheated to 60℃and was stirred mechanically under nitrogen for 1 hour at 60℃and then heated to 110℃and 2.69g of HQEE was added thereto, followed by stirring and mixing for 10 minutes. Finally, pouring the mixture into a preheated tray, wherein the curing conditions are as follows: heating to 90 ℃ for 2h, heating to 100 ℃ for 2h, heating to 110 ℃ for 2h, and heating to 120 ℃ for 18h. Polyurethane elastomer PU-1' is obtained.
Comparative example 2
Polyurethane elastomer PU-2' was prepared in the same manner as in comparative example 1, except that: 21.76g of PTMEG was added in place of 17.43g of PCD1000.
Comparative example 3
Polyurethane elastomer PU-6' was prepared by the method of comparative example 1, except that: 21.76g of PTMEG was added in place of 17.43g of PCD1000 and 1.22g of BDO was added in place of 2.69g of HQEE.
Comparative example 4
Polyurethane elastomer PU-9' was prepared by the method of comparative example 1, except that: 15.34g XBX was added in place of TDI, 20g PTMEG was added in place of 17.43g PCD1000, and 5.43g BDO was added in place of 2.69g HQEE.
Comparative example 5
Polyurethane elastomer PU-13' was produced in the same manner as in comparative example 1, except that: 15.34g of XDI was added in place of TDI, 20g of PTMEG was added in place of 17.43g of PCD1000, and the mass of HQEE was added to be 6.76g.
Comparative example 6
Polyurethane elastomer PU-29' was produced in the same manner as in comparative example 1, except that 21.76g of PTMEG was added in place of 17.43g of PCD1000, and 3.39g of MOCA was added in place of 2.69g of HQEE.
Comparative example 7
Polyurethane elastomer PU-33' was prepared in the same manner as in comparative example 1, except that 10.79g of MDI was added in place of TDI, 21.76g of PTMEG was added in place of 17.43g of PCD1000, and 1.22g of BDO was added in place of 2.69g of HQEE.
Comparative example 8
Polyurethane elastomer PU-37' was prepared in the same manner as in comparative example 1, except that 6.91g of PPDI was added in place of TDI, 21.76g of PTMEG was added in place of 17.43g of PCD1000, and 1.22g of BDO was added in place of 2.69g of HQEE.
Comparative example 9
Polyurethane elastomer PU-45' was obtained in the same manner as in comparative example 1, except that 6.91g of PPDI was added in place of TDI, and 21.76g of PTMEG was added in place of 17.43g of PCD1000.
Experimental example
Experimental example 1
By using a dynamic mechanical analyzer TA-Q800 (test mode is a tensile mode, the frequency is 1Hz, the strain amplitude is 20 mu m, the temperature rising range is-80-150 ℃ and the temperature rising rate is 5 ℃/min) and an advanced rheometer AR200ex (under the air environment, the test mode is Oscillation procedure, the diameter of a rheometer flat plate is 25mm, the spacing between flat plates is 1mm, the scanning frequency is fixed to be 1Hz during dynamic temperature scanning test, the test temperature is 150-210 ℃, the temperature rising rate is 5 ℃/min by adopting a scanning mode from high temperature to low temperature, the strain is 0.1-15% during dynamic frequency scanning test, the test temperature was fixed at 180℃and the polyurethane elastomers PU-1 and PU-1' prepared in example 1 and comparative example 1 were subjected to dynamic temperature test, dynamic frequency test, mechanical loss (tan. Delta.) test and storage modulus test by scanning from low frequency to high frequency in the frequency range of 0.01 to 100Hz, respectively, to obtain a complex viscosity |η. Eta. -, a tan. Delta. -, and storage modulus-temperature, as shown in FIGS. 13, 14, 15 and 16.
As can be seen from fig. 13 and 14, the complex viscosity of the polyurethane elastomer PU-1 is always lower than that of the polyurethane elastomer PU-1' under different temperature or frequency conditions, indicating that the polyurethane elastomer prepared in example 1 has better melt processability than the polyurethane elastomer prepared in comparative example 1.
As shown by the analysis in FIGS. 15 and 16, the transition temperature (T) g ) At 33.9℃and a storage modulus of 2231MPa, the polyurethane elastomer PU-1 obtained in example 1 has a higher glass transition temperature (T g ) (44.3 ℃) and storage modulus (2543 MPa). This is because the polyurethane elastomer PU-1 has soft segments and hard segments which are regularly arranged alternately, a better microphase-separated structure and a higher crystallinity are formed, and the interaction between the two phases is also improved.
Experimental example 2
Polyurethane elastomers PU-2, PU-2', PU-6', PU-9', PU-13', and the like were tested in accordance with the method of Experimental example 1 PU-29, PU-29', PU-33', PU-37', PU-45', the test results are shown in Table 1.
Table 1:
| polyurethane elastomer | T g (℃) | Storage modulus (MPa) |
| PU-2 | 8.7 | 2860 |
| PU-2’ | -7.7 | 2450 |
| PU-6 | 0 | 2040 |
| PU-6’ | -8 | 1600 |
| PU-9 | -31 | 2420 |
| PU-9’ | -42 | 2160 |
| PU-13 | -28 | 2510 |
| PU-13’ | -36 | 2250 |
| PU-29 | 11 | 2780 |
| PU-29’ | -7 | 2405 |
| PU-33 | -8 | 2470 |
| PU-33’ | -19 | 2200 |
| PU-37 | -22 | 3560 |
| PU-37’ | -41 | 3310 |
| PU-45 | -26 | 3770 |
| PU-45’ | -35 | 3430 |
As can be seen from the data in Table 1, the storage modulus of the polyurethane elastomer prepared by using the modified isocyanate monomer provided in the present invention is significantly improved, and the glass transition temperature (T g ) And the improvement is also to a certain extent.
The present invention has been described in detail in connection with the detailed description and/or the exemplary examples and the accompanying drawings, but the description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A modified isocyanate monomer characterized in that it has the following structure:
wherein R is 1 Selected from alkylene or diphenol-containing alkyl, R 2 Selected from arylene radicals, R 3 And R is 4 Selected from the group consisting of arylene groups.
2. The modified isocyanate monomer of claim 1,
R 1 selected from alkylene groups having a carbon number of 4-6 or hydroquinone diethyl groups, preferably butylene groups (- (CH) 2 ) 4 (-) and hexamethylene (- (CH) 2 ) 6 (-) or hydroquinone diethyl group,
R 3 、R 4 selected from benzene subunits, preferably:
R 2 selected from substituted phenyl or 4,4' -methylenedianiline compounds, preferably:
wherein X is halogen, preferably bromine or chlorine, more preferablySelected as chlorine.
3. The modified isocyanate monomer of claim 1,
the modified isocyanate monomer is as follows:
preferably, the modified isocyanate monomer is:
4. a modified isocyanate monomer is characterized in that the modified isocyanate monomer is obtained by reacting diol or diamine with diisocyanate.
5. The modified isocyanate monomer according to claim 4, wherein the diol is one or more selected from the group consisting of an alkane diol and a diphenol-containing alkanol, preferably one or more selected from the group consisting of an alkane diol having a carbon number of 4 to 6 and a hydroquinone dihydroxyethyl ether, more preferably 1, 4-Butanediol (BDO), 1, 6-Hexanediol (HDO) or hydroquinone dihydroxyethyl ether (HQEE),
the diamine is selected from one or more of aromatic diamine, preferably one or more of phenylenediamine compound and 4,4 '-methylenedianiline compound, more preferably 3, 5-diethyltoluenediamine (DETDA), 4' -methylenebis (3-chloro-2, 6-diethylaniline) (MCDEA) or 3, 5-dimethylthiotoluenediamine (DMTDA),
the diisocyanate is selected from one or more of aromatic structure-containing diisocyanates, preferably from one or more of benzene diisocyanate compounds, alkylbenzene diisocyanate compounds, naphthalene diisocyanate and diphenylalkane diisocyanate, more preferably from 2, 4-Toluene Diisocyanate (TDI), m-phenylene diisocyanate (XDI), 4' -diphenylmethane diisocyanate (MDI) or p-phenylene diisocyanate (PPDI).
6. A process for the preparation of a modified isocyanate monomer according to any one of claims 1 to 5, wherein a diol or diamine solution is added to a diisocyanate monomer solution under an oxygen-free protective atmosphere and reacted at a constant temperature to give a reaction solution containing the modified isocyanate monomer; and then obtaining the modified isocyanate monomer through precipitation, washing, separation and drying.
7. The method according to claim 6, wherein,
the molar ratio of diol or diamine to diisocyanate monomer is 1 (1.5-7.5), preferably 1 (2-6.5), more preferably 1 (2.5-5.5),
the reaction temperature is 30 to 60 ℃, preferably 35 to 55 ℃, more preferably 40 to 50 ℃.
8. The method according to claim 6, wherein,
the diisocyanate monomer solution concentration is 0.15 to 7.5mol/L, preferably 0.25 to 6.5mol/L, more preferably 0.35 to 5.5mol/L,
the concentration of the glycol or diamine solution is 0.05 to 1.8mol/L, preferably 0.08 to 1.5mol/L, more preferably 0.1 to 1.2mol/L.
9. A process for preparing a polyurethane elastomer from a modified isocyanate monomer according to any one of claims 1 to 5, wherein the process comprises starting from the modified isocyanate monomer and an oligomeric diol.
10. A process for preparing a polyurethane elastomer as claimed in claim 9, wherein,
the oligomer diol is selected from one or more of polycarbonate diol (PCD), polytetrahydrofuran diol (PTMEG), polycaprolactone diol (PCL) and polypropylene diol (PPG), preferably polycarbonate diol (PCD) and/or polytetrahydrofuran diol (PTMEG), more preferably polycarbonate diol (PCD) or polytetrahydrofuran diol (PTMEG),
and adding the modified isocyanate monomer into the oligomer diol preheated to 70-100 ℃, stirring and mixing to form uniform liquid, and heating and curing to react to obtain the polyurethane elastomer.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4352858A (en) * | 1981-09-04 | 1982-10-05 | National Starch And Chemical Corp. | Polyurethane adhesive compositions modified with a dicarbamate ester useful in laminating substrates |
| CN112778499A (en) * | 2020-12-30 | 2021-05-11 | 王植源 | Preparation method of low free meta-xylylene isocyanate polyurethane prepolymer |
| KR20210059342A (en) * | 2019-11-15 | 2021-05-25 | 에스케이씨솔믹스 주식회사 | Polyol recycled from polishing pad and preparation method thereof |
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2023
- 2023-05-04 CN CN202310489592.7A patent/CN116730874A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4352858A (en) * | 1981-09-04 | 1982-10-05 | National Starch And Chemical Corp. | Polyurethane adhesive compositions modified with a dicarbamate ester useful in laminating substrates |
| KR20210059342A (en) * | 2019-11-15 | 2021-05-25 | 에스케이씨솔믹스 주식회사 | Polyol recycled from polishing pad and preparation method thereof |
| CN112778499A (en) * | 2020-12-30 | 2021-05-11 | 王植源 | Preparation method of low free meta-xylylene isocyanate polyurethane prepolymer |
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| Title |
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| CUNO, E: ""Emission behavior of reactive polyurethane hotmelt adhesives"", GEFAHRSTOFFE - REINHALTUNG DER LUFT, vol. 75, no. 11, 31 December 2015 (2015-12-31), pages 457 - 464 * |
| 李玲玲: "基于间苯二亚甲基二异氰酸酯聚氨酯弹性体的合成与表征", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, 15 January 2022 (2022-01-15), pages 016 - 928 * |
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