CN116355174B - 一种基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯及其制备方法 - Google Patents
一种基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯及其制备方法 Download PDFInfo
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- CN116355174B CN116355174B CN202310401794.1A CN202310401794A CN116355174B CN 116355174 B CN116355174 B CN 116355174B CN 202310401794 A CN202310401794 A CN 202310401794A CN 116355174 B CN116355174 B CN 116355174B
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- Prior art keywords
- diisocyanate
- polyester polycarbonate
- semi
- polycarbonate diol
- aromatic polyester
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 45
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 45
- 150000002009 diols Chemical class 0.000 title claims abstract description 44
- 229920000728 polyester Polymers 0.000 title claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 28
- 239000004814 polyurethane Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 31
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 31
- 229920001971 elastomer Polymers 0.000 claims abstract description 22
- 239000000806 elastomer Substances 0.000 claims abstract description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000004970 Chain extender Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 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
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 229940049964 oleate Drugs 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 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
- RVCHQYCXJDVJQF-UHFFFAOYSA-N (3,5-diethylphenyl)methanediamine Chemical compound CCC1=CC(CC)=CC(C(N)N)=C1 RVCHQYCXJDVJQF-UHFFFAOYSA-N 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
- HTRQFOJLBFYLRS-KLXURFKVSA-N N=C=O.N=C=O.CCOC(=O)[C@@H](N)CCCCN Chemical compound N=C=O.N=C=O.CCOC(=O)[C@@H](N)CCCCN HTRQFOJLBFYLRS-KLXURFKVSA-N 0.000 claims description 2
- GOOJLMLGQNJKJW-ILKKLZGPSA-N N=C=O.N=C=O.COC(=O)[C@@H](N)CCCCN Chemical compound N=C=O.N=C=O.COC(=O)[C@@H](N)CCCCN GOOJLMLGQNJKJW-ILKKLZGPSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims 3
- NWYDEWXSKCTWMJ-UHFFFAOYSA-N 2-methylcyclohexane-1,1-diamine Chemical compound CC1CCCCC1(N)N NWYDEWXSKCTWMJ-UHFFFAOYSA-N 0.000 claims 1
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- 239000012948 isocyanate Substances 0.000 abstract description 10
- 150000002513 isocyanates Chemical class 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- 229920003225 polyurethane elastomer Polymers 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 150000003077 polyols Chemical group 0.000 description 11
- 229920005862 polyol Polymers 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
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- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
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- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
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- LCPNYLRZLNERIG-ZETCQYMHSA-N (2S)-6-amino-2-[2-(oxomethylidene)hydrazinyl]hexanoyl isocyanate Chemical compound NCCCC[C@H](NN=C=O)C(=O)N=C=O LCPNYLRZLNERIG-ZETCQYMHSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-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
- 239000002028 Biomass Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- IHBSVVZENGBQDY-BBWFWOEESA-N N-Methyl morphinan Chemical compound C1C2=CC=CC=C2[C@]23CCN(C)[C@H]1[C@@H]2CCCC3 IHBSVVZENGBQDY-BBWFWOEESA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
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- XFLSMWXCZBIXLV-UHFFFAOYSA-N n,n-dimethyl-2-(4-methylpiperazin-1-yl)ethanamine Chemical compound CN(C)CCN1CCN(C)CC1 XFLSMWXCZBIXLV-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
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- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- 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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
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Abstract
本发明公开了一种基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯的制备方法：通过将二氧化碳基半芳香聚酯聚碳酸酯二元醇与二（多）异氰酸酯聚合反应得到可生物降解的热塑性聚氨酯弹性体（TPU）。半芳香性的聚酯聚碳酸酯二元醇，是常压下由二氧化碳与低成本的二元醇直接反应得到的新型低聚物二元醇。本发明制备方法所获得的聚氨酯弹性体在具备优良耐候、耐水、耐氧化以及良好机械强度的同时，兼具可生物降解性能，并高效利用了二氧化碳，符合绿色发展的理念。
Description
技术领域
本发明属于热塑性聚氨酯弹性体（TPU）制备技术领域，具体涉及一种基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯及其制备方法。
背景技术
聚氨酯是一类综合性能优异的高分子材料，可用于制造塑料、橡胶、纤维、泡沫、胶粘剂、涂料及密封材料等，其中热塑性聚氨酯弹性体（TPU）作为一种具有优良的抗拉伸、抗冲击能力以及耐磨、耐水、耐油的聚合物高性能材料广泛应用于工业、制造、体育、医用等各个领域。聚氨酯主要由二（多）异氰酸酯与小分子扩链剂形成硬段，低聚物多元醇构成软段，通过选用不同种类的多元醇、二（多）异氰酸酯以及扩链剂，可以对其力学性能、玻璃化转变温度、耐磨性、透明度、硬度等进行调控。其中低聚物多元醇作为长链段，其不同的结构形态对合成的TPU材料的性能有显著的影响。
目前TPU合成应用的低聚物多元醇主要有聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、生物质多元醇及其衍生物等。目前国内市场上最常用的是聚醚多元醇和聚酯多元醇两大类。聚酯多元醇合成的TPU具有力学机械性能好、及抗磨性能优越等特点，但是多元醇分子主链上含有的酯基也导致聚氨酯产品耐水解性能较差、低温柔顺性差，同时生产成本较高；采用聚醚多元醇的TPU产品因为分子主链结构中的醚键的存在内聚能较低，容易旋转，因而具有良好的低温柔顺性以及耐水解性能，但机械性能较差。以上原因使得这两种多元醇基的TPU材料在许多应用场景下难以满足性能要求。
聚碳酸酯二元醇为原料制备出的聚碳酸酯型TPU不仅拥有聚酯型TPU优良的力学机械性能、耐磨性，同时具有优秀的耐水解、耐氧化性能。并且，碳酸酯键的存在让其拥有可生物降解性能。因此，聚碳酸酯二元醇也被认为是性能最优异的二元醇之一。
目前碳酸酯二元醇的来源主要是酯交换法合成，是以碳酸二甲酯和小分子脂肪族或者芳香族二元醇为原料在酯交换催化剂的存在下，通过进行酯交换反应逐步聚合得到聚碳酸酯二元醇。该法是目前工业合成聚碳酸酯二元醇工艺中最普遍的也是最成熟的工艺，但该方法能耗较大且制备过程需脱除副产物，所用的原料成本高，且得到的碳酸酯二元醇的分子量分散度大。同时该工艺路线中原料碳酸酯的合成往往利用到了光气，对生产设备要求高且有较大毒性，不符合日益增长的环保需求，以上因素都限制了聚碳酸酯二元醇在聚氨酯合成中的应用。
发明内容
针对以上现有技术存在的缺点和不足之处，本发明的目的在于提供一种低成本的基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯及其制备方法，制备得到的聚氨酯弹性体具有良好的耐候、耐水、耐氧化以及良好机械强度，兼具可生物降解性能。
本发明目的通过以下技术方案实现：
.一种基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯，其结构特征如式1所示：
式1
其中m ≥ 1，n≥ 1,q≥ 1，l≥ 1；m，n，q，l均为整数；所述R1为二（多）异氰酸酯的主链，R2为扩链剂主链，R3为包括但不限于碳数为2～6的脂肪族烃基，Ar表示苯环，苯环所连羰基互为邻位、间位或者对位；X为 -NH- 基团或 -O- 基团。
上述基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯的制备方法，包括如下步骤：
（1）将二氧化碳基半芳香聚酯聚碳酸酯二元醇、二（多）异氰酸酯、催化剂混合搅拌并加热反应，得到聚氨酯预聚物；所述加热反应在常压或减压条件下进行，加热反应温度为40~120℃，反应时间2-8 h；
（2）将聚氨酯预聚物与扩链剂共同注入挤出机内，在150-200℃温度区间、50-100rpm转速区间内反应5-20 min挤出造粒，干燥熟化后得到热塑性聚氨酯弹性体颗粒。
作为优选的，在上述基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯的制备方法中，各组分的重量百分比为：二氧化碳基半芳香聚酯聚碳酸酯二元醇77.95%-94.69%，二（多）异氰酸酯3.2%-12.0% ，扩链剂 2.1 %-10.0%，催化剂 0.01-0.05%。
作为优选的，在上述基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯的制备方法中，所述二氧化碳基半芳香聚酯聚碳酸酯二元醇记载于公开号为CN 114573799 A的中国发明专利中，其结构如式2表示：
式2
其中，q≥ 1，l≥ 1,q,l均为整数；所述R3为包括但不限于碳数为2～6的脂肪族烃基，Ar表示苯环，苯环所连羰基互为邻位、间位或者对位。
作为优选的，在上述基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯的制备方法中，所述二（多）异氰酸酯为脂肪族二（多）异氰酸酯、脂环族二（多）异氰酸酯或芳香族二（多）异氰酸酯。具体为六亚甲基二异氰酸酯(HDI)、1,4-丁二异氰酸酯(BDI)、L-赖氨酸二异氰酸酯(LDI)、L-赖氨酸乙酯二异氰酸酯(ELDI)、L-赖氨酸甲酯二异氰酸酯(MLDI)、异佛尔酮二异氰酸酯(IPDI)、二环己基甲烷二异氰酸酯(HMDI)、对甲苯二异氰酸酯(TDI)、二苯甲烷二异氰酸酯(MDI)和对苯二亚甲基二异氰酸酯(XDI)中的一种或多种。
作为优选的，在上述基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯的制备方法中，所述扩链剂为乙二醇、1,3-丙二醇、1,2-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,4-环己烷二甲醇、二甘醇、乙醇胺、三异丙醇胺、乙二胺、甲基环己二胺、3,5-二甲硫基甲苯二胺、3,5-二乙基甲苯二胺及其混合物。
作为优选的，在上述基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯的制备方法中，所述催化剂为金属烷基类、脂肪胺类、脂环胺类、醇胺类。具体为辛酸亚锡、油酸亚锡、二月桂酸二丁基锡、四丁基氯化铵、三乙胺、三亚乙基二胺、五甲基二亚乙基三胺、N-甲基吗啡琳、四甲基乙二胺、二甲基苄胺、1-甲基-4-二甲胺乙基哌嗪、N,N-二乙基-3-二乙胺基丙胺、三乙醇胺中的一种。
与现有技术相比，本发明具有如下有益效果：
本发明的基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯的制备方法，采用了低成本的二氧化碳基半芳香聚酯聚碳酸酯低聚物二元醇作为原料，不同于传统的高成本以及有间接污染的酯交换法合成路线，其合成路线直接使用了常压的二氧化碳，且绿色环保，可以为“碳中和及碳达峰”的目标做出直接贡献。本发明的基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯其生物降解性能来自于原料二氧化碳基半芳香聚酯聚碳酸酯二元醇单体中的碳酸酯键，以及聚氨酯中氨基甲酸酯键（-CONH-）。本发明所获得的聚氨酯弹性体材料具有50,000至200,000的数均分子量(M n )，具有1.5-4.0的多分散度(M w/M n)，在保证耐水、耐氧化以及良好机械强度的同时，兼具了良好的可降解性能，并有效利用了二氧化碳，符合绿色发展的理念。
附图说明
图1为本发明实施例5所制备的热塑性聚氨酯弹性体的核磁1HNMR图；
图2为本发明实施例2所制备的热塑性聚氨酯弹性体的力学性能图；
图3为本发明实施例4所制备的热塑性聚氨酯弹性体的热重分析图。
实施方式
下面结合实施例对本发明作进一步阐明，但本发明的实施方式不限于此：
实施例1
在配有氮气除水装置、搅拌器及冷凝管的反应器中加入20.0 g二氧化碳基半芳香聚酯聚碳酸酯二元醇，2.02 g六亚甲基二异氰酸酯(HDI)，0.004 g的辛酸亚锡，在65℃下搅拌混合，随后在通入氮气情况下升温至85℃下反应4 h得到聚氨酯预聚物，随后转移至双螺杆挤出机内反应并加入1.15 g的1,4-环己烷二甲醇，在180℃、转速60 rpm下混合反应8min，挤出造粒，干燥熟化后得到热塑性聚氨酯弹性体。产率87.7%（基于共聚物二元醇），M n=67600，PDI= 2.55。所得到的热塑性聚氨酯弹性体的结构式如下所示：
表1为本发明实施例1所制备的热塑性聚氨酯弹性体的水阻隔性能。
表1 实施例1水阻隔性能
实施例2
在配有氮气除水装置、搅拌器及冷凝管的反应器中加入27.2 g二氧化碳基半芳香聚酯聚碳酸酯二元醇，3.15 g二环己基甲烷二异氰酸酯(HMDI)，0.007 g的二月桂酸二丁基锡催化剂，在60℃下搅拌混合，随后在氮气通入（情况下升温至80℃下预聚合6 h得到预聚物，随后转移至至双螺杆挤出机内反应并加入1.71 g的3,5-二甲硫基甲苯二胺进行扩链，在160℃、转速80 rpm下混合反应10 min，挤出造粒，干燥熟化后得到热塑性聚氨酯弹性体。产率86.2%（基于共聚物二元醇），M n=91900，PDI=1.92。所得到的热塑性聚氨酯弹性体的结构式如下所示：
。
实施例3
在配有氮气除水装置、搅拌器及冷凝管的反应器中加入28.0 g二氧化碳基半芳香聚酯聚碳酸酯二元醇，1.68 g1,4-丁二异氰酸酯(BDI)，0.008 g的三乙胺催化剂，在90℃下搅拌混合，随后在氮气通入情况下升温至110℃下预聚合8 h得到预聚物，随后转移至至双螺杆挤出机内反应并加入0.95 g的1, 6-己二醇进行扩链，在180℃、转速60rpm下混合反应15 min，挤出造粒，干燥熟化后得到热塑性聚氨酯弹性体。产率90.9%（基于共聚物二元醇），Mn=94600，PDI=2.23。所得到的热塑性聚氨酯弹性体的结构式如下所示：
实施例4
在配有氮气除水装置、搅拌器及冷凝管的反应器中加入32.0 g二氧化碳基半芳香聚酯聚碳酸酯二元醇，1.53 g苯二亚甲基二异氰酸酯(XDI)，0.013 g的五甲基二亚乙基三胺催化剂，在100℃下搅拌混合，随后在氮气通入情况下升温至120 ℃下预聚合4 h得到预聚物，随后转移至至双螺杆挤出机内反应并加入0.85 g的二甘醇进行扩链，在190 ℃、转速80 rpm下混合反应10 min，挤出造粒，干燥熟化后得到热塑性聚氨酯弹性体。产率88.6%（基于共聚物二元醇），Mn=108200，PDI=2.98。所得到的热塑性聚氨酯弹性体的结构式如下所示：
表2 实施例4氧气阻隔性能
实施例5
在配有氮气除水装置、搅拌器及冷凝管的反应器中加入36.0 g二氧化碳基半芳香聚酯聚碳酸酯二元醇，3.0 g 二苯甲烷二异氰酸酯(MDI)，0.018g的油酸亚锡，在75 ℃下搅拌混合，随后在通入氮气的情况下升温至95 ℃下反应4 h得到聚氨酯预聚物，随后转移至至双螺杆挤出机内反应并加入0.72g的1,4-丁二醇进行扩链，在185 ℃、转速80 rpm下混合反应6 min，挤出造粒，干燥熟化后得到热塑性聚氨酯弹性体。产率82.0%（基于共聚物二元醇），M n=121700，PDI=2.72。所得到热塑性聚氨酯弹性体的核磁1HNMR图如图1所示。所得到的热塑性聚氨酯弹性体的结构式如下所示：
Claims (7)
1.一种基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯，其特征在于，其结构特征如式1所示：
其中m≥1，n≥1,q≥1，l≥1；m，n，q，l均为整数；所述R1为二异氰酸酯的主链，R2为扩链剂主链，R3为碳数为2～6的脂肪族烃基，Ar表示苯环，苯环所连羰基互为邻位、间位或者对位；X为-NH-基团或-O-基团；
并且所述基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯通过包括如下步骤的方法制备：
(1)将二氧化碳基半芳香聚酯聚碳酸酯二元醇、二异氰酸酯、催化剂混合搅拌并加热反应，得到聚氨酯预聚物；所述加热反应在常压或减压条件下进行，加热反应温度为40～120℃，反应时间2-8h；
(2)将聚氨酯预聚物与扩链剂共同注入挤出机内，在150-200℃温度区间、50-100rpm转速区间内反应5-20min挤出造粒，干燥熟化后得到热塑性聚氨酯弹性体颗粒；
所述各组分的重量百分比为：二氧化碳基半芳香聚酯聚碳酸酯二元醇77.95％-94.69％，二异氰酸酯3.2％-12.0％，扩链剂2.1％-10.0％，催化剂0.01-0.05％。
2.权利要求1所述的基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯的制备方法，其特征在于包括如下步骤：
(1)将二氧化碳基半芳香聚酯聚碳酸酯二元醇、二异氰酸酯、催化剂混合搅拌并加热反应，得到聚氨酯预聚物；所述加热反应在常压或减压条件下进行，加热反应温度为40～120℃，反应时间2-8h；
(2)将聚氨酯预聚物与扩链剂共同注入挤出机内，在150-200℃温度区间、50-100rpm转速区间内反应5-20min挤出造粒，干燥熟化后得到热塑性聚氨酯弹性体颗粒；
所述各组分的重量百分比为：二氧化碳基半芳香聚酯聚碳酸酯二元醇77.95％-94.69％，二异氰酸酯3.2％-12.0％，扩链剂2.1％-10.0％，催化剂0.01-0.05％。
3.如权利要求2所述的基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯的制备方法，其特征在于，所述二氧化碳基半芳香聚酯聚碳酸酯二元醇的结构如式2表示：
其中，q≥1，l≥1,q,l均为整数；所述R3为碳数为2～6的脂肪族烃基，Ar表示苯环，苯环所连羰基互为邻位、间位或者对位。
4.如权利要求2所述的基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯的制备方法，其特征在于，所述二异氰酸酯为脂肪族二异氰酸酯、脂环族二异氰酸酯或芳香族二异氰酸酯。
5.如权利要求4所述的基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯的制备方法，其特征在于，所述二异氰酸酯为六亚甲基二异氰酸酯、L-赖氨酸二异氰酸酯、L-赖氨酸乙酯二异氰酸酯、L-赖氨酸甲酯二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、对甲苯二异氰酸酯和二苯甲烷二异氰酸酯中的一种或多种。
6.如权利要求2所述的基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯的制备方法，其特征在于，所述扩链剂为乙二醇、1,3-丙二醇、1,2-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,4-环己烷二甲醇、二甘醇、乙醇胺、三异丙醇胺、乙二胺、甲基环己二胺、3,5-二甲硫基甲苯二胺、3,5-二乙基甲苯二胺及其混合物。
7.如权利要求2所述的基于半芳香聚酯聚碳酸酯二元醇的可生物降解聚氨酯的制备方法，其特征在于，所述催化剂为辛酸亚锡、油酸亚锡、二月桂酸二丁基锡、四丁基氯化铵、三乙胺、三亚乙基二胺、五甲基二亚乙基三胺、N-甲基吗啡啉、四甲基乙二胺、二甲基苄胺、三乙醇胺中的一种。
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