CN110964166A - Preparation method of polyurethane elastomer - Google Patents
Preparation method of polyurethane elastomer Download PDFInfo
- Publication number
- CN110964166A CN110964166A CN201811121628.1A CN201811121628A CN110964166A CN 110964166 A CN110964166 A CN 110964166A CN 201811121628 A CN201811121628 A CN 201811121628A CN 110964166 A CN110964166 A CN 110964166A
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- China
- Prior art keywords
- component
- polyurethane elastomer
- parts
- chain extender
- dimethyltin
- 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.)
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- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004970 Chain extender Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 150000002009 diols Chemical class 0.000 claims abstract description 18
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 18
- 239000004417 polycarbonate Substances 0.000 claims abstract description 18
- 229920002635 polyurethane Polymers 0.000 claims abstract description 9
- 239000004814 polyurethane Substances 0.000 claims abstract description 9
- 239000012948 isocyanate Substances 0.000 claims abstract description 6
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 150000001412 amines Chemical group 0.000 claims description 14
- -1 carbon diol Chemical class 0.000 claims description 12
- 125000003158 alcohol group Chemical group 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 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 6
- 239000000203 mixture Substances 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims description 5
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 4
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 4
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- SDTDHTCWRNVNAJ-UHFFFAOYSA-L dimethyltin(2+);diacetate Chemical compound CC(=O)O[Sn](C)(C)OC(C)=O SDTDHTCWRNVNAJ-UHFFFAOYSA-L 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012974 tin catalyst Substances 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- CBEVWPCAHIAUOD-UHFFFAOYSA-N 4-[(4-amino-3-ethylphenyl)methyl]-2-ethylaniline Chemical compound C1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=CC=2)=C1 CBEVWPCAHIAUOD-UHFFFAOYSA-N 0.000 claims description 3
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- SNZAWIWMBQMVSB-BGSQTJHASA-L dioctyltin(2+);(z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCC\C=C/CCCCCCCC SNZAWIWMBQMVSB-BGSQTJHASA-L 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 claims description 2
- PKZGKWFUCLURJO-GRHBHMESSA-L (z)-but-2-enedioate;dimethyltin(2+) Chemical compound C[Sn+2]C.[O-]C(=O)\C=C/C([O-])=O PKZGKWFUCLURJO-GRHBHMESSA-L 0.000 claims description 2
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- DDPRYTUJYNYJKV-UHFFFAOYSA-N 1,4-diethylpiperazine Chemical compound CCN1CCN(CC)CC1 DDPRYTUJYNYJKV-UHFFFAOYSA-N 0.000 claims description 2
- JUXXCHAGQCBNTI-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetramethylpropane-1,2-diamine Chemical compound CN(C)C(C)CN(C)C JUXXCHAGQCBNTI-UHFFFAOYSA-N 0.000 claims description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- ZRWNRAJCPNLYAK-UHFFFAOYSA-N 4-bromobenzamide Chemical compound NC(=O)C1=CC=C(Br)C=C1 ZRWNRAJCPNLYAK-UHFFFAOYSA-N 0.000 claims description 2
- AOFIWCXMXPVSAZ-UHFFFAOYSA-N 4-methyl-2,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(C)=C(N)C(SC)=C1N AOFIWCXMXPVSAZ-UHFFFAOYSA-N 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- DWRBCWYHLKHQAP-UHFFFAOYSA-L [butanoyloxy(dibutyl)stannyl] butanoate Chemical compound CCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCC DWRBCWYHLKHQAP-UHFFFAOYSA-L 0.000 claims description 2
- HAAANJSJNWKVMX-UHFFFAOYSA-L [butanoyloxy(dimethyl)stannyl] butanoate Chemical compound CCCC(=O)O[Sn](C)(C)OC(=O)CCC HAAANJSJNWKVMX-UHFFFAOYSA-L 0.000 claims description 2
- AWFFJJAOMMAGFE-BGSQTJHASA-L [dibutyl-[(z)-octadec-9-enoyl]oxystannyl] (z)-octadec-9-enoate Chemical compound CCCC[Sn+2]CCCC.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O AWFFJJAOMMAGFE-BGSQTJHASA-L 0.000 claims description 2
- PGQPMLCDSAVZNJ-BGSQTJHASA-L [dimethyl-[(z)-octadec-9-enoyl]oxystannyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)O[Sn](C)(C)OC(=O)CCCCCCC\C=C/CCCCCCCC PGQPMLCDSAVZNJ-BGSQTJHASA-L 0.000 claims description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 claims description 2
- PZGVVCOOWYSSGB-UHFFFAOYSA-L but-2-enedioate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn]1(CCCCCCCC)OC(=O)C=CC(=O)O1 PZGVVCOOWYSSGB-UHFFFAOYSA-L 0.000 claims description 2
- ODUCJAXGIAXRJA-UHFFFAOYSA-L butanoate;dioctyltin(2+) Chemical compound CCCCCCCC[Sn](OC(=O)CCC)(OC(=O)CCC)CCCCCCCC ODUCJAXGIAXRJA-UHFFFAOYSA-L 0.000 claims description 2
- 229960002887 deanol Drugs 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012972 dimethylethanolamine Substances 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims 1
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 claims 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 238000010926 purge Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- BXQLKGJCLJZZOP-UHFFFAOYSA-N methylsulfanylmethane;toluene Chemical compound CSC.CC1=CC=CC=C1 BXQLKGJCLJZZOP-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- 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
-
- 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
- C08G18/28—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
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of a polyurethane elastomer, which comprises the following steps: 1) the component A comprises: the preparation method of the polyurethane semi-prepolymer comprises the following steps: 50-100 parts of polycarbonate diol and 40-70 parts of isocyanate react for 1.5-3 hours at the temperature of 60-75 ℃; 2) and B component: 50-100 parts of polycarbonate diol, 0.5-5 parts of chain extender and 0.01-0.1 part of catalyst, uniformly mixing, pouring into a mold, curing at 25-30 ℃, demolding after curing for 4-6h, and then post-vulcanizing for 8h at 80 ℃ to obtain the polyurethane elastomer product. The preparation method of the polyurethane elastomer overcomes the defect of high viscosity of polyurethane prepolymer, and the prepared polyurethane elastomer has excellent mechanical property and is suitable for being applied to pouring fast curing products.
Description
Technical Field
The present invention relates to a high-performance polyurethane elastomer having good mechanical properties and excellent wear resistance and oil resistance.
Background
As is well known, the polyurethane elastomer is a high-molecular block polymer with more urethane groups on the main chain, has a unique polyurethane structure, and has excellent comprehensive mechanical properties, particularly wear resistance and oil resistance. The general preparation method of the polyurethane elastomer is a one-step method, but the preparation of the one-step method is not easy to control, and the viscosity of the polyurethane prepolymer prepared by the prepolymer method is large and is not easy to control, so that the viscosity of the prepolymer can be well controlled by adopting a semi-prepolymer method to prepare the polyurethane semi-prepolymer, the prepared prepolymer is more stable, and the performance of the elastomer is more excellent.
Disclosure of Invention
The invention aims to provide a preparation method of a polyurethane elastomer, and the prepared elastomer has excellent mechanical properties and excellent wear resistance and oil resistance. Meanwhile, a semi-prepolymer method is adopted, so that the preparation process is more stable. The curing time of the polyurethane elastomer can be prolonged by the matching use of the chain extender and the catalyst, and the polyurethane elastomer is suitable for preparing large-size products.
The preparation method of the polyurethane elastomer comprises the following steps:
1) the component A and the polyurethane semi-prepolymer are prepared by the following steps: according to the mass parts, 50-100 parts of polycarbonate diol, 2-4 parts of polydimethylsiloxane carbodiol and 40-70 parts of diisocyanate react for 1.5-3 hours at the temperature of 60-75 ℃ to obtain polyurethane semi-prepolymer;
2) the component B and the preparation method are as follows: by mass, 50-100 parts of polycarbonate diol, 0.5-5 parts of chain extender and 0.01-0.1 part of catalyst are uniformly mixed for later use.
3) The preparation process of the polyurethane elastomer comprises the following steps: and (3) mixing the component B and the component A for reaction, wherein the mixing temperature is 60-75 ℃, immediately pouring into a mold, curing at 25-30 ℃, demolding after curing for 4-6h, and then post-vulcanizing for 8h at 80 ℃ to obtain the polyurethane elastomer product.
Wherein the number average molecular weight of the polycarbonate diol in the component A is 1500-4000.
Wherein the polydimethyl methyl phenyl siloxane carbodiol in the component A is hydroxyl ethoxy propyl terminated polydimethyl methyl phenyl siloxane, and the number average molecular weight is 1000-4000.
Wherein, the diisocyanate in the component A is one or a mixture of two of toluene diisocyanate TDI-100, toluene diisocyanate TDI-80, 4, 4 '-diphenylmethane diisocyanate MDI-100, 4, 4' -diphenylmethane diisocyanate MDI-50 and diisocyanate.
Wherein, in the component A, the content of free isocyanic acid radical in the polyurethane semi-prepolymer is 4.0-16.0%.
Wherein the number average molecular weight of the polycarbonate diol in the component B is 1500-4000.
2. The chain extender in the component B is an amine chain extender and an alcohol chain extender, the amine chain extender comprises 4, 4 '-diamino-3, 3' -diethyl-diphenylmethane, 3-chloro-3 '-ethyl-4, 4' -diamino diphenylmethane, 3, 3 '-dichloro-4, 4' -diamino diphenylmethane, diethyl toluene diamine (DETDDA), dimethyl sulfur toluene diamine DMTDA and Diethylaminoethanol (DEAE), the alcohol chain extender comprises 1, 4-Butanediol (BDO), 1, 6-hexanediol, trimethylolpropane, diethylene glycol (DEG), triethylene glycol and neopentyl glycol (NPG), the chain extender in the component B is one or a mixture of more of the alcohol chain extender and the amine chain extender, and the using amount of the chain extender is 0.5-5 parts.
3. Wherein the catalyst in the component B is a tin catalyst and an amine catalyst, and the tin catalyst comprises dibutyltin dibutyrate, dimethyltin dibutyrate, dioctyltin dibutyrate, dibutyltin diacetate, dimethyltin diacetate, dioctyltin diacetate, stannous octoate, dibutyltin dilaurate, dimethyltin dilaurate, dioctyltin dilaurate, dibutyltin dioleate, dimethyltin dioleate, dioctyltin dioleate, tin acetate, dibutyltin diacetate, dimethyltin diacetate, dioctyltin diacetate, dimethyltin maleate, dibutyltin maleate, dioctyltin maleate, didodecylthio dibutyltin, didodecylthio dimethyltin, didodecylthio dioctyltin, stannous oxalate and the like; the amine catalyst comprises bis (dimethylaminoethyl) ether, pentamethyldiethylenetriamine, triethylene diamine, dimethylethanolamine, tetramethylethylenediamine, tetramethylpropylenediamine, N, N-dimethylcyclohexylamine, N, N, N ', N' -tetramethylalkylenediamine, triethylamine, N, N-dimethylbenzylamine, triethanolamine, N-ethylmorpholine, N, N '-diethylpiperazine, pyridine, N, N' -dimethylpyridine, wherein the catalyst in the component B is one or a mixture of tin catalysts and amine catalysts, and the dosage of the catalyst is 0.01-0.1 part.
Wherein the hardness of the prepared polyurethane elastomer product is between Shore A hardness 40A and Shore A hardness 85A.
According to the invention, by adopting the matching of the alcohol chain extender and the amine chain extender and adding the catalyst in a matching manner, the polyurethane elastomer which has long curing time and can have sufficient time for large-scale products is prepared, and the polyurethane elastomer is suitable for preparing large-size samples.
The invention relates to a method for preparing a polyurethane elastomer by a semi-prepolymerization method in combination with a novel combination of a proper chain extender and a catalyst. The preparation method of the polyurethane elastomer overcomes the defects of overhigh viscosity and instability of a one-step method in prepolymer preparation, and simultaneously adopts the matching of amine and alcohol chain extenders in the semi-prepolymer, so that the prepared polyurethane elastomer has long curing time, excellent mechanical property, and excellent wear resistance and oil resistance.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The component A comprises: 50 parts of polycarbonate diol PCL-1500 (with the number average molecular weight of 1500) and 2 parts of polydimethylsiloxane carbodiol (with the number average molecular weight of 1000), removing water for 2 hours at 120 ℃ in a nitrogen purging environment, adding TDI-10040 parts when the temperature is reduced to 60 ℃, and reacting for 1.5 hours to obtain the semi-prepolymer with the free isocyanate content of 4%.
The component B comprises: 50 parts of polycarbonate diol PCL-1500 (number average molecular weight 1500), 0.5 part of BDO and 0.01 part of catalyst stannous octoate:
elastomer: the component A and the component B are mixed according to the proportion of 1: 1, stirred for 30 seconds at the temperature of 60 ℃, poured into a mold, cured for 4 hours at the temperature of 25 ℃, and then post-vulcanized for 8 hours at the temperature of 80 ℃ to obtain the polyurethane elastomer.
Example 2
The component A comprises: 100 parts of polycarbonate diol PCL-4000 (with the number average molecular weight of 4000), 4 parts of polydimethylsiloxane carbodiol (with the number average molecular weight of 4000), removing water for 2 hours at 120 ℃ in a nitrogen purging environment, adding MDI-10070 parts when the temperature is reduced to 75 ℃, and reacting for 3 hours to obtain the semi-prepolymer with the free isocyanate content of 16%.
The component B comprises: 10 parts of polycarbonate diol PCL-1500 (number average molecular weight 1500), 5 parts of diethyl toluene diamine (DETDA) and 0.1 part of catalyst N-ethyl morpholine.
Elastomer: the component A and the component B are mixed according to the proportion of 1: 1, stirred for 30 seconds at the temperature of 75 ℃, poured into a mold, cured for 6 hours at the temperature of 30 ℃, and then post-vulcanized for 8 hours at the temperature of 80 ℃ to obtain the polyurethane elastomer.
Example 3
The component A comprises: 75 parts of polycarbonate diol PCL-2000 (number average molecular weight 2000), 2 parts of polydimethylsiloxane carbodiol (number average molecular weight 3000), removing water for 2 hours at 120 ℃ in a nitrogen purging environment, adding MDI-5060 parts when the temperature is reduced to 70 ℃, and reacting for 2 hours to obtain the semi-prepolymer with the free isocyanate content of 10%.
The component B comprises: 80 parts of polycarbonate diol PCL-3000 (number average molecular weight 3000), 2 parts of dimethylthiotoluenediamine DMTDA, 2 parts of 1, 6-hexanediol, 0.02 part of catalyst N, N, N ', N' -tetramethylalkylenediamine and 0.01 part of dibutyltin dilaurate.
Elastomer: the component A and the component B are mixed according to the proportion of 1: 1, stirred for 30 seconds at the temperature of 75 ℃, poured into a mold, cured for 5 hours at the temperature of 30 ℃, and then post-vulcanized for 8 hours at the temperature of 80 ℃ to obtain the polyurethane elastomer.
Example 4
The component A comprises: 60 parts of polycarbonate diol PCL-3000 (the number average molecular weight is 2000), 3 parts of polydimethylsiloxane carbodiol (the number average molecular weight is 2000), removing water for 2 hours at 120 ℃ in a nitrogen purging environment, adding TDI-8065 parts when the temperature is reduced to 70 ℃, and reacting for 2.5 hours to obtain the semi-prepolymer with the free isocyanate content of 12%.
The component B comprises: 75 parts of polycarbonate diol PCL-2000 (number average molecular weight 2000), 1 part of 4, 4 ' -diamino-3, 3 ' -diethyl-diphenylmethane, 0.5 part of trimethylolpropane, 0.01 part of catalyst N, N ' -dimethylpyridine and 0.01 part of dioctyltin dioleate;
elastomer: the component A and the component B are mixed according to the proportion of 1: 1, stirred for 30 seconds at the temperature of 75 ℃, poured into a mold, cured for 5 hours at the temperature of 25 ℃, and then post-vulcanized for 8 hours at the temperature of 80 ℃ to obtain the polyurethane elastomer.
The results of the performance testing experiments for examples 1-4 above are shown in Table 1:
table 1 test performance test results for examples 1-4
Item | Example 1 | Example 2 | Example 3 | Example 4 |
Gel time/min | 9 | 13 | 8 | 5 |
hardness/Shore A | 72 | 40 | 61 | 85 |
Tensile strength/MPa | 38 | 30 | 34 | 42 |
Tear Strength/kN.m-1 | 128 | 121 | 115 | 158 |
Elongation at break/%) | 510 | 640 | 550 | 420 |
DIN abrasion/mm3 | 31 | 27 | 30 | 35 |
Claims (8)
1. A preparation method of a polyurethane elastomer is characterized by comprising the following steps:
1) the preparation method of the component A and the polyurethane semi-prepolymer comprises the following steps: according to the mass parts, 50-100 parts of polycarbonate diol, 2-4 parts of polydimethyl methyl phenyl siloxane carbon diol and 40-70 parts of diisocyanate react at the temperature of 60-75 ℃ for 1.5-3 hours to obtain polyurethane semi-prepolymer;
2) the component B and the preparation method are as follows: by mass, 50-100 parts of polycarbonate diol, 0.5-5 parts of chain extender and 0.01-0.1 part of catalyst are uniformly mixed for later use;
3) the preparation process of the polyurethane elastomer comprises the following steps: and (3) mixing the component B and the component A for reaction at the mixing temperature of 60-75 ℃, immediately pouring into a mold, carrying out curing reaction at the temperature of 25-30 ℃, demolding after curing for 4-6h, and then carrying out post-vulcanization for 8h at the temperature of 80 ℃ to obtain the polyurethane elastomer product.
2. The process for producing a polyurethane elastomer as claimed in claim 1, wherein the polycarbonate diol in the component A has a number average molecular weight of 1500-4000.
3. The method for preparing polyurethane elastomer as claimed in claim 1, wherein said polydimethyl methyl phenyl siloxane carbon diol in component A is hydroxy ethoxy propyl terminated polydimethyl methyl phenyl siloxane with number average molecular weight of 1000-4000; the method of claim 1, wherein the diisocyanate in component A is one or a mixture of toluene diisocyanate TDI-100, toluene diisocyanate TDI-80, 4, 4 '-diphenylmethane diisocyanate MDI-100, 4, 4' -diphenylmethane diisocyanate MDI-50, and diisocyanate.
4. The process of claim 1, wherein the content of free isocyanate in the polyurethane semi-prepolymer in the component A is 4.0% -16.0%.
5. The process for preparing a polyurethane elastomer as claimed in claim 1, wherein the number average molecular weight of the polycarbonate diol in the component B is 1500-4000.
6. The method of claim 1, wherein the chain extender in the component B is one or more of amine chain extender and alcohol chain extender, the amine chain extender includes 4, 4 '-diamino-3, 3' -diethyl-diphenylmethane, 3-chloro-3 '-ethyl-4, 4' -diaminodiphenylmethane, 3, 3 '-dichloro-4, 4' -diaminodiphenylmethane, diethyltoluenediamine (DETDDA), dimethylthiotoluenediamine DMTDA, Diethylaminoethanol (DEAE), the alcohol chain extender includes 1, 4-Butanediol (BDO), 1, 6-hexanediol, trimethylolpropane, diethylene glycol (DEG), triethylene glycol, neopentyl glycol (NPG), and the chain extender in the component B is one or more of alcohol chain extender and amine chain extender, the using amount of the chain extender is 0.5-5 parts.
7. The process for producing a polyurethane elastomer according to claim 1, wherein the catalyst in the B component is a tin-based catalyst and an amine-based catalyst, and the tin-based catalyst includes dibutyltin dibutyrate, dimethyltin dibutyrate, dioctyltin dibutyrate, dibutyltin diacetate, dimethyltin diacetate, dioctyltin diacetate, stannous octoate, dibutyltin dilaurate, dimethyltin dilaurate, dioctyltin dilaurate, dibutyltin dioleate, dimethyltin dioleate, dioctyltin dioleate, tin acetate, dibutyltin diacetate, dimethyltin diacetate, dioctyltin diacetate, dimethyltin maleate, dibutyltin maleate, dioctyltin maleate, dibutyltin dilaurylthio, dimethyltin dilaurylthio, didodecylthio-dimethyltin, didodecylthio-dioctyltin oxalate, stannous oxalate, or the like; the amine catalyst comprises bis (dimethylaminoethyl) ether, pentamethyldiethylenetriamine, triethylene diamine, dimethylethanolamine, tetramethylethylenediamine, tetramethylpropylenediamine, N, N-dimethylcyclohexylamine, N, N, N ', N' -tetramethylalkylenediamine, triethylamine, N, N-dimethylbenzylamine, triethanolamine, N-ethylmorpholine, N, N '-diethylpiperazine, pyridine, N, N' -dimethylpyridine, wherein the catalyst in the component B is one or a mixture of tin catalysts and amine catalysts, and the dosage of the catalyst is 0.01-0.1 part.
8. The method for preparing the polyurethane elastomer as claimed in claim 1, wherein the hardness of the prepared polyurethane elastomer product is between 40A and 85A Shore A hardness.
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