CN102869698A - 由可再生资源制备的聚合物 - Google Patents
由可再生资源制备的聚合物 Download PDFInfo
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- CN102869698A CN102869698A CN2011800148997A CN201180014899A CN102869698A CN 102869698 A CN102869698 A CN 102869698A CN 2011800148997 A CN2011800148997 A CN 2011800148997A CN 201180014899 A CN201180014899 A CN 201180014899A CN 102869698 A CN102869698 A CN 102869698A
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- Prior art keywords
- polycondensate
- acid
- ester
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- Prior art date
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- 229920000642 polymer Polymers 0.000 title description 2
- 150000002148 esters Chemical group 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 30
- -1 alkoxy compound Chemical class 0.000 claims description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 11
- 229920000728 polyester Polymers 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 150000001408 amides Chemical group 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000000123 paper Substances 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 150000002941 palladium compounds Chemical class 0.000 claims description 4
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical class [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 4
- 239000010408 film Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 235000019441 ethanol Nutrition 0.000 description 21
- 239000000203 mixture Substances 0.000 description 21
- VHDHONCVIHDOAO-UHFFFAOYSA-N pentacosanedioic acid Natural products OC(=O)CCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHDHONCVIHDOAO-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 13
- 239000000178 monomer Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 11
- FIGVVZUWCLSUEI-UHFFFAOYSA-N tricosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCC FIGVVZUWCLSUEI-UHFFFAOYSA-N 0.000 description 10
- 150000002632 lipids Chemical class 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 8
- 150000004985 diamines Chemical class 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000007707 calorimetry Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 5
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 description 4
- 229940066675 ricinoleate Drugs 0.000 description 4
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 235000003901 Crambe Nutrition 0.000 description 3
- 241000220246 Crambe <angiosperm> Species 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical group CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- FNXRYHQLYLSSPE-UHFFFAOYSA-N tricosane-1,23-diol Chemical compound OCCCCCCCCCCCCCCCCCCCCCCCO FNXRYHQLYLSSPE-UHFFFAOYSA-N 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 239000005700 Putrescine Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229920002988 biodegradable polymer Polymers 0.000 description 2
- 239000004621 biodegradable polymer Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- WFZQLUSOXHIVKL-QXMHVHEDSA-N ethyl (13Z)-docosenoate Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(=O)OCC WFZQLUSOXHIVKL-QXMHVHEDSA-N 0.000 description 2
- ZYNDJIBBPLNPOW-UHFFFAOYSA-N eurucic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCCCCCC(=O)OC ZYNDJIBBPLNPOW-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229940051250 hexylene glycol Drugs 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- ZYNDJIBBPLNPOW-KHPPLWFESA-N methyl erucate Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(=O)OC ZYNDJIBBPLNPOW-KHPPLWFESA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000021281 monounsaturated fatty acids Nutrition 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- TXVPLKQLMADQNG-UHFFFAOYSA-N nonadecanediamide Chemical compound C(CCCCCCCCCCCCCCCCCC(=O)N)(=O)N TXVPLKQLMADQNG-UHFFFAOYSA-N 0.000 description 2
- LUUFSCNUZAYHAT-UHFFFAOYSA-N octadecane-1,18-diol Chemical compound OCCCCCCCCCCCCCCCCCCO LUUFSCNUZAYHAT-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- OCJLSVQJNZKGKL-UHFFFAOYSA-N tricosane-1,23-diamine Chemical compound NCCCCCCCCCCCCCCCCCCCCCCCN OCJLSVQJNZKGKL-UHFFFAOYSA-N 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical class NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 description 1
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-FPLPWBNLSA-N (Z)-icos-13-enoic acid Chemical compound CCCCCC\C=C/CCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-FPLPWBNLSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- DVWSXZIHSUZZKJ-UHFFFAOYSA-N 18:3n-3 Natural products CCC=CCC=CCC=CCCCCCCCC(=O)OC DVWSXZIHSUZZKJ-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及具有长链线性亚甲基序列的缩聚物、其制备方法、一种线性的偶数C>20α,ω-二元羧酸及其衍生物的制备方法以及所述缩聚物的用途。
Description
本发明涉及在主链中具有较长线性亚甲基序列的缩聚物、其制备方法、其用途和单体的催化制备方法。
可再生资源被作为有限化石资源的替代物受人关注。此外,也可用其获得具有有利性能的新型材料。为此,将所述资源的分子结构反映在所得产品的结构中是可取的。
植物油和脂肪的具有吸引力的特性是存在脂肪酸的线性烃结构(呈甘油三酯形式)。这长期用于从蓖麻酸起始制备工业塑料聚酰胺-11。然而,在这种情况下,仅利用了一部分脂肪酸分子。蓖麻酸在脂肪酸链裂解下热重排产生十一碳-10-烯酸(其进一步反应生成聚酰胺-11)以及作为副产物的庚醛。此外,基本重排反应要求双键的邻位存在羟基,因此作为目前工业上可用的蓖麻酸及其衍生物的脂肪酸受到限制。也可由蓖麻酸获得癸二酸,使癸二酸反应生成缩聚物如聚酰胺-6,10。在这种情况下,形成作为副产物的2-辛醇。
将长链C>20脂肪酸完整地线性整合至聚合物是所期望的,这是因为这样的话,首先就用于构建聚合物的材料而言可完全利用底物,其次长线性亚甲基序列可导致所需的性能如结晶度以及与此相关的熔点和结晶点、机械性能和其他应用性能、聚合物共混物中的混合行为或低的吸水性。通过二聚,脂肪酸可转化成所谓的二聚脂肪酸,然而这些具有支化非线性结构且获得非结晶链段(Angew.Chem.2000,112,2292)。将脂肪酸完整地线性整合至单体和由其制备的聚合物中很难实现,这是因为不饱和脂肪酸的反应性双键位于分子中间且端甲基非常不容易反应。
当使获自可再生资源的资源反应时,通常应考虑到在大多数情况下这些包括可干扰反应进程且获得产物混合物而非纯物质的杂质。取决于(例如)不同的生物源,不同脂肪酸或其衍生物通常具有不同的杂质谱图。
此外,不论起始物质的实用性、特性和易得性,大多数的较长链的α,ω-二羧酸或其衍生物的合成工艺均产生偶数产物。
烯烃的催化烷氧基羰基化(即一氧化碳与醇的反应)是已知的制备酯的反应(Applied Homogeneous Catalysis with Organometallic Compounds,编辑B.Cornils和W.A.Herrmann,Wiley-VCH,Weinheim,2000)。因此,单不饱和脂肪酸的甲基酯的钴催化反应导致非选择性地生成线性α,ω-二羧酸二甲酯和支化二酯的60:40混合物(Fette,Seifen,Anstrichmittel 1985,87,403)。对于乙烯的甲氧基羰基化,已发现由1,2-双[(二叔丁基膦基)甲基]苯改性的钯(II)催化剂是非常适合的(Chem.Commun.1999,1877)。值得注意的是,这些催化剂也将内烯烃(如4-辛烯)转化成线性甲基酯(Chem.Commun.2004,1720)。内不饱和C18脂肪酸甲酯—油酸甲酯在甲醇溶液中的类似反应以及多不饱和类似物亚油酸甲酯和亚麻酸甲酯的类似反应也优先形成饱和α,ω-二羧酸酯、1,19-十九烷二酸二甲酯(Inorg.Chem.Commun.2005,8,878)。然而,这不能以制备缩聚物所需的纯度获得(Trans.FaradaySoc.1936,32,39)。
芥酸为易得不饱和C>20脂肪酸的一个实例。已证明芥酸甲酯与一氧化碳在含有三烷基二膦改性的钯(II)催化剂的甲醇中的反应是有问题的;未观察到令人满意的烷氧基羰基化。然而,令人惊讶地发现,通过使用处于高级醇中的芥酸和具有超过20个碳原子的其他不饱和脂肪酸(C>20脂肪酸),所述反应选择性地生成α,ω-二羧酸酯且这些以获得>99%的纯度获得。
此外,已发现相应α,ω-二羧酸及其酯、以及它们的还原羟基和氨基衍生物出人意料地适于作为制备缩聚物的单体。
因此,本发明提供了一种缩聚物,其包含一种或多种式(I)重复单元:
-Z-(CH2)2n+1-Z’-(I)
其中符号和指数具有以下含义:
Z,Z’相同或不同且为-X-C(=O)~、-C(=O)-HN-CH2~、-C(=O)-O-CH2~、-NH-C(=O)-O-CH2~、-O-C(=O)-NH-CH2~;
X为O或NH;
~表示与基团(CH2)2n+1连接的键,且
n为≥10的数。
本发明进一步提供了一种制备本发明缩聚物的方法,其中使至少一种式(II)单体化合物与至少一种二-或多元醇或至少一种二-或多元胺缩聚:
Z1-(CH2)2n+1-Z1’(II)
其中
Z1,Z1’为~C(=O)-Q或~CH2-NCO;
Q相同或不同且为OH,卤素或C1-C10烷氧基;
~表示与基团(CH2)2n+1连接的键,且
n为≥10的数,
和/或
使至少一种式(III)单体化合物与至少一种二-或多元羧酸、所述二-或多元羧酸的反应性衍生物或至少一种二或多异氰酸酯缩聚:
Z2-(CH2)2n+1-Z2’(III)
其中
Z2,Z2’相同或不同且为HO-CH2~或H2N-CH2~;
~表示与基团(CH2)2n+1连接的键,且
n为≥10的数。
本发明进一步提供了本发明缩聚物在模制品、涂料、泡沫、膜、箔和/或纤维中的用途,以及包含本发明缩聚物的相应目标。
本发明同样提供了一种制备在酸结构部分中具有在每种情况下为2n+3个碳原子(其中n≥10)的饱和或不饱和α,ω-二羧酸或酯的方法,包括如下步骤:使在酸结构部分中具有2n+2个碳原子(其中n≥10)的单或多不饱和脂肪酸酯在包含至少一种钯化合物和至少一种磷烷(phosphane)的催化剂存在下在50-120°C的温度和3-80atm的压力下羟基-或烷氧基羰基化。
根据本发明,用于制备本发明缩聚物的单体通过使具有至少22个碳原子的不饱和脂肪酸羟基-或烷氧基羰基化而获得。该反应在催化剂存在下进行。
所用催化剂为包含钯化合物和至少一种可经由一个或多个磷原子与金属中心配位的含磷配体的催化剂。在所述含磷配体中,磷原子PR”1R”2R”3上的合适取代基R”1至R”3相同或不同且彼此独立地为H、C1-C30开链或脂环族基团、C1-C30芳基,尤其是C5-C12芳基,以及经由杂原子如N、O或S键合的C1-C30,尤其是C5-C12开链或脂环族基团。基团R”1至R”3侧链中也可包含杂原子如O、N、S或P。特别合适的基团为叔丁基。所述配体可包含2个或更多个经由一个或多个基团R”桥接的磷原子。特别合适的桥接基团为经由3个或4个原子桥接磷原子的那些。特别合适的桥接基团为CH2-C6H4-CH2-和-(CH2)3-。
优选使用磷烷。特别优选使用三烷基磷烷和双齿磷烷。合适的含磷配体实例为1,3-双(二叔丁基膦基)丙烷、1,3-双(二叔丁基膦基)丁烷、1,3-双(二叔丁基膦基)-2,2’-二甲基丙烷、1,2-双[(二叔丁基膦基)甲基]苯、1,2-双[(环辛-1,5-二基膦基)甲基]苯、1,3-双(环辛-1,5-二基膦基)丙烷、1-[(二叔丁基膦基)甲基]-2-(二叔丁基膦基)苯。
可使用一种含磷配体或两种或更多种含磷配体的混合物。
合适的钯化合物实例为醋酸钯、己酸钯、辛酸钯、双(二亚苄基丙酮)钯、四(三苯基膦)钯、(1,5-环辛二烯)二甲基钯、(1,5-环辛二烯)二氯钯、(1,5-环辛二烯)甲基氯钯、四乙腈钯(II)四氟硼酸和二乙腈二氯钯。
所述催化剂任选包含其他组分,例如有机和/或无机酸和/或其盐。可作为实例加以提及的合适的其他组分为三氟甲磺酸、甲磺酸、高氯酸、对甲苯磺酸、[H(OEt2)[BArF 4]、NaBArF 4,其中ArF=3,5-双(三氟甲基)苯基。
所述催化剂组分可以以任何所需顺序混合在一起。混合可在羰基化反应釜内或釜外进行。尤其可使用预先形成的磷烷的钯配合物。其实例为[(二膦)PdX2],其中X=甲磺酸根,三氟甲磺酸根或甲苯磺酸根。
特别合适的催化剂为钯(II)盐与1,2-双[(二叔丁基膦基)甲基]苯的组合,尤其是与甲磺酸的组合。
钯(II)化合物与磷烷配体中的磷的分子比通常为1:0.5-1:100,优选为1:0.5-1:20,特别优选为1:2-1:10。
钯(II)化合物与任选存在的酸的分子比任选为1:0.5-1:200。
烷氧基羰基化所需的醇适于作为反应介质。优选C2-C36醇,如乙醇、正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、戊醇、己醇、庚醇、正辛醇、异辛醇、2-乙基己醇、环己醇、2-苯基乙醇、苯酚和苄醇或混合物。此外,合适的还有非质子有机溶剂如二氯甲烷、氯仿、二氯乙烷、苯、甲苯、氯苯、异丁烷、己烷、庚烷、辛烷、二乙醚、二苯醚、四氢呋喃、2-甲基四氢呋喃、环丁砜、N-甲基吡咯烷酮、二甲基乙酰胺、丙酮、环己酮、三乙胺、三丁胺以及这些化合物的混合物。反应介质通常可包含最高为50%体积的甲醇,优选小于20%体积的甲醇。反应混合物可为无水的或者包含水。为了通过羟基羰基化制备本发明所用的α,ω-二羧酸,必须存在水。如果实施烷氧基羰基化以制备α,ω-二酯,则反应混合物优选无水。
此外,所用的脂肪酸酯也可用作反应介质。反应混合物可为单相的或多相的。优选地,反应混合物仅包含一个液相。在反应期间,反应介质、试剂和催化剂或催化剂组分可任选连续添加或以脉冲方式添加。
反应混合物的温度为-10°C至+200°C,优选为50-120°C,特别优选为85-100°C。反应压力为0.1-200atm,优选为3-80atm,特别优选为10-40atm。
所用底物为酸结构部分中具有偶数碳原子的单或多不饱和脂肪酸的酯,其中碳原子数大于20,优选不超过34。因此,式中的符号n表示自然数。优选具有22、24、26、28、30、32或34个碳原子(在酸结构部分中),特别优选22、24或26个碳原子,尤其是22个碳原子的单或多不饱和脂肪酸酯,特别优选单不饱和脂肪酸酯。任选也可使用游离酸。优选的这些脂肪酸的酯为单官能醇的酯,特别优选C1-C10烷基酯。
尤其合适的为芥酸(顺-13-二十碳烯酸)的酯,尤其为乙酯。
可使用的底物为纯C>20脂肪酸酯或工业级C>20脂肪酸酯,其尤其包括多不饱和脂肪酸酯。尽管单官能醇的酯是优选的,但是也可使用多官能醇的酯,例如甘油三酯。
优选使用天然来源(例如来自植物油)的脂肪酸及其酯。为了获得芥酸的酯,特别优选含芥酸的油菜和海甘蓝品种例如阿比西尼亚(Abyssinia)海甘蓝的种子。
脂肪酸酯(优选芥酸酯)与本发明所用催化剂中的钯的摩尔量的摩尔比通常为10000000:1-10:1,优选1000000:1-100:1,特别优选10000:1-500:1。
当使用偶数脂肪酸的酯时,C>20脂肪酸酯的羰基化产生非偶数的线性C>21α,ω-二羧酸的酯。
根据本发明制备的α,ω-二元羧酸及其酯适于作为用于制备本发明缩聚物的单体。
同样合适的有这些酸的反应性衍生物,如酰基卤、活性酯、酐或咪唑盐(imidazolide)。
同样合适的(例如与二元酸或二酯组合)有通过本领域技术人员熟知的还原方法由二酸/二酯获得的相应α,ω-二醇。
可使用将羧酸衍生物还原成醇的已知方法,将例如1,23-二十三烷二酸二乙酯转化成纯度>99%的1,23-二羟基二十三烷。用于将羧酸或其衍生物还原以获得醇的合适方法的实例为用氢催化加氢、借助无机氢化试剂还原、以及用有机化合物(其发生氧化)还原。
此外,根据本发明制备的α,ω-二元羧酸及其酯以及由其获得的α,ω-二醇可通过本领域技术人员熟知的已知方法转化以获得相应的α,ω-二胺,所述α,ω-二胺又可用作合成本发明缩聚物的单体。作为实例,用于将羧酸或其酯转化成氨基的已知方法为酰胺化,随后消去水并加氢;对于将醇转化成胺而言,所述已知方法为卤化或甲苯磺酰化,随后与氨反应或转换成叠氮,然后还原。为了制备异氰酸酯,可使胺与光气或光气等效物反应。
线性非偶数C≥23脂族α,ω-二羧酸与线性非偶数C≥23脂族α,ω-二元醇的酯可转化成本发明所提供的聚合物。此处,所述二酯可原样使用或以活化形式如酸、氯化物或酸酐形式使用。优选地,为了转化成聚合物,使用1,23-二十三烷二羧酸或其酯、1,23-二十三烷二醇、1,23-二十三烷二胺和1,23-二十三烷二异氰酸酯。特别优选使用1,23-二十三烷二羧酸或其酯。
除了至少一种可根据本发明获得且在前段中所详述的α,ω-双官能化合物之外,也可将其他多官能醇、胺、酸或酯、氯化物或其酸酐、环状内酰胺或内酯和异氰酸酯用于制备本发明的聚合物。除了所述官能团之外,这些也可包含其他杂原子。合适醇的实例为乙二醇、1,3-丙二醇、1,2-丙二醇、1,4-丁二醇、环己二醇、1,6-己二醇、1,10-癸二醇、1,12-十二烷二醇、1,18-十八烷二醇、1,19-十九烷二醇、2,2-二(4-羟基苯基)丙烷、二甘醇、二羟基封端的聚乙二醇和三羟甲基丙烷以及芳族二-和多羟基化合物,如4,4’-二羟基联苯和双酚如双酚A和双酚AF。合适胺的实例为乙二胺、二亚乙基三胺、1,2-二氨基丙烷、1,3-二氨基丙烷、1,4-二氨基丁烷、1,5-二氨基戊烷、1,6-二氨基己烷、1,10-二氨基癸烷、1,12-二氨基十二烷,和芳族二胺如对苯二胺。合适羧酸的实例为马来酸、琥珀酸、富马酸、己二酸、癸二酸、1,19-十九烷二酸、邻苯二甲酸、对苯二甲酸。合适内酰胺的实例为ε-己内酰胺、十二内酰胺。合适内酯的实例为ε-己内酯和丁内酯。合适二异氰酸酯的实例为六亚甲基二异氰酸酯和4,4'-二苯基甲烷二异氰酸酯。
优选使1,23-二十三烷二羧酸或其单官能醇的酯在存在或不存在前段中作为实例加以提及的其他二元羧酸酯或其酯的情况下,与一种或多种二醇、二胺反应(任选存在内酰胺)。合适的二醇、二胺和内酰胺已在前段中作为实例加以描述。
特别优选使1,23-二十三烷二羧酸与一种或多种下述化合物缩聚:乙二醇、1,3-丙二醇、1,4-丁二醇、环己二醇、1,6-己二醇、1,10-癸二醇、1,12-十二烷二醇、1,18-十八烷二醇、1,19-十九烷二醇、1,23-二十三烷二醇、2,2-二(4-羟基苯基)丙烷、二甘醇、二羟基封端的聚乙二醇、乙二胺、二亚乙基三胺、1,3-二氨基丙烷、1,4-二氨基丁烷、1,5-二氨基戊烷、1,6-二氨基己烷、1,10-二氨基癸烷、1,12-二氨基十二烷、1,23-二十三烷二胺。
同样特别优选地,使本发明所用的α,ω-二元羧酸(优选1,23-二十三烷二羧酸)与琥珀酸、己二酸和/或对苯二甲酸一起,与一种或多种如下化合物缩聚:乙二醇、1,3-丙二醇、1,4-丁二醇、环己二醇、1,6-己二醇、1,10-癸二醇、1,12-十二烷二醇、1,18-十八烷二醇、1,19-十九烷二醇、1,23-二十三烷二醇、2,2-二(4-羟基苯基)丙烷、二甘醇、二羟基封端的聚乙二醇、乙二胺、二亚乙基三胺、1,3-二氨基丙烷、1,4-二氨基丁烷、1,5-二氨基戊烷、1,6-二氨基己烷、1,10-二氨基癸烷、1,12-二氨基十二烷、1,23-二十三烷二胺。
聚合方法是本领域技术人员所熟知的。聚合可在存在或不存在催化剂、溶剂、悬浮剂或其他添加剂的情况下进行。聚合可例如在溶液、熔体、悬浮液、非水性分散体或含水分散体中进行。合适的催化剂例如为有机或无机酸;以及过渡金属或主族金属的醇盐、羧酸盐和氧化物。聚合反应在0.00001毫巴至100巴的压力下进行。为了移除挥发性副产物,聚合反应可在真空下进行。可对聚合混合物进行强制混合,例如借助搅拌器或挤出机。聚合可在一步或多步中进行。
任选地,可在聚合期间或聚合之后借助合适试剂进行交联。其结果是,可获得或改进某些性能如弹性或流动性能。
此外,本发明缩聚物的性能可以通过扩链而改性,例如通过与羰基二己内酰胺(CBC)和/或亚苯基-1,4-双唑啉(1,4-PBO)反应。其他合适的扩链方法例如为与多官能异氰酸酯反应。本发明聚合物可用作缩聚和加聚反应的预聚物。例如,本发明的二羟基封端的聚合物可与多官能异氰酸酯或羧酸反应。
在优选实施方案中,式(I)中的基团Z,Z’对应于-X-C(=O)-或-X’-C(=O)-,其中X,X’相同或不同,优选相同,为O或NH,优选O。
该实施方案涉及包含重复单元-X-C(=O)-(CH2)2n+1-C(=O)-X’-的缩聚物,其中n≥10且X,X’为O或NH。
此外,优选其中Z为基团-C(=O)-O-CH2~、-C(=O)-NH-CH2~、-NH-C(=O)-O-CH2~或-O-C(=O)-NH-CH2~的缩聚物,即包含重复单元-M-(CH2)2n+3-M’-的缩聚物,其中n≥10且M,M’为酰胺,酯或尿烷官能团。
还优选除本发明单体之外,还包含其他单体的共聚酯,优选聚酯[{-A1-OC(=O)-(CH2)2n+1-C(=O)O-}x{-A1-OC(=O)-A2-C(=O)O-}y],其中n≥10且A1,A2为C2-C36的脂族、脂环族、芳族或混合基团。混合基团例如为芳脂族基团。x和y在每种情况下表示摩尔分数,即x+y=1。
同样还优选除本发明单体之外,还具有其他单体的共聚酰胺,尤其是聚酰胺[{A3-NHC(=O)-(CH2)2n+1-C(=O)NH-}x{-A3-NHC(=O)-A4-C(=O)NH-}y],其中n≥10且A3,A4在每种情况下为具有2-36个碳原子的脂族、脂环族、芳族或混合基团。
优选其中y=0的本发明聚酯和聚酰胺。
此外,优选其中n=10的本发明缩聚物,其中至少一些单体衍生自1,23-二十三烷二羧酸。
本发明聚合物通常包含至少1mol%,优选至少10mol%,特别优选50mol%的至少一种式(I)重复单元,优选重复单元-X-C(=O)-(CH2)2n+1-C(=O)-X’-或-M-(CH2)2n+3-M’-;其中n≥10,其中X,X’相同或不同且彼此独立地为O或NH;M,M’相同或不同且彼此独立地为酰胺、酯或尿烷官能团。
本发明缩聚物,尤其是聚酯,通常具有1000-2000000g/mol,优选5000-200000g/mol,特别优选10000-50000g/mol的数均分子量Mn。
本发明缩聚物(尤其是聚酯)的优点在于,首先其可基于可再生材料制备,例如基于例如海甘蓝的芥酸酯。本发明缩聚物(尤其是聚酯)的另一优点在于,其从根本上就适于作为可生物降解聚合物。就此而言,在本发明上下文中,可生物降解聚合物为用于指代可例如在土壤中通过微生物、酶或水解降解的材料的术语。生物降解性借助DIN标准EN 13432测定。可生物降解材料在大规模堆肥系统中必须在6-10周内降解。因此,在另一实施方案中,本发明涉及一种可生物降解的本发明聚酯。这是由于以所需方式影响长链结晶链段、熔融和结晶性能,且这些足够高以至于可进行热塑性加工。由于其结晶性,本发明聚酯表现出相应的高熔点和结晶点,其可例如为Tm>80°C和Tc>70°C,尤其为Tm>90°C和Tc>75°C。此外,该体系呈现出低吸水性。
本发明聚合物可有利地用于许多应用场合,例如用于模制品、涂料、泡沫、膜、箔和纤维中。本发明聚合物也可用于与其他塑料的混合物中。
可作为实例加以提及的本发明聚合物的加工方法为注射成型、共挤出、箔铸造、吹塑、箔吹塑、压延、熔融压制、湿纺、干纺、熔纺、深拉、粉末涂覆和由有机溶液或含水分散体涂覆。
通过实施例更详细地阐述本发明,因此并非限制本发明。
实施例
A单体的制备
实施例1合成1,23-二十三烷二酸二乙酯
在90°C和20巴的一氧化碳压力下将10ml乙醇、1.79g芥酸乙酯,0.079mmol乙酸钯(II),0.39mmol 1,2-双[(二叔丁基膦基)甲基]苯和0.79mmol甲磺酸的混合物在加压反应器中搅拌22小时。将所述反应混合物在200毫巴和50°C下在旋转蒸发器中浓缩。然后添加5ml二氯甲烷。将混合物过滤并在大气压和50°C下于旋转蒸发器中浓缩。残余物由乙醇重结晶。基于所用的芥酸乙酯,收率为76%。根据1H NMR谱,>99%为1,23-二十三烷二酸二乙酯。
(对比实施例)
在90°C和20bar的一氧化碳压力下将10ml甲醇、1.79g芥酸甲酯(95%)、0.079mmol乙酸钯(II)、0.39mmol 1,2-双[(二叔丁基膦基)甲基]苯和0.79mmol甲磺酸的混合物在加压反应器中搅拌22小时。该混合物主要包含未羰基化的单羧酸甲酯。
实施例2合成1,23-二十三烷二羧酸
将总计为55.2mmol的KOH添加至20ml甲醇与4.5mmol 1,23-二十三烷二酸二乙酯的悬浮液中。将所述混合物在搅拌下回流加热10小时。然后真空除去溶剂。向所得白色固体中添加30ml水,并用6N盐酸将该混合物酸化至pH=2。将所述混合物过滤,由甲醇重结晶白色固体。基于所用的1,23-二十三烷二酸二乙酯,收率为96%。根据1H NMR谱,>99%为1,23-二十三烷二羧酸。
实施例3合成1,23-二十三烷二醇(途径A)
将2.3mmol 1,23-二十三烷二酸二乙酯溶于10ml四氢呋喃中。在搅拌下将该溶液缓慢滴加至5.2mmol氢化铝锂于10ml四氢呋喃中的悬浮液中。将该混合物在搅拌下回流加热1小时,然后在室温下搅拌过夜。在搅拌的同时,依次缓慢添加0.2ml水、0.2ml 15%浓度的氢氧化钠水溶液和0.6ml水。将该混合物在40°C下过滤。将滤液在50°C和500毫巴下于旋转蒸发器中蒸发。残余物由乙醇重结晶。基于所用的1,23-二十三烷二酸二乙酯,收率为80%。根据1H NMR谱,>99%为1,23-二羟基二十三烷。
实施例4合成1,23-二十三烷二醇(途径B)
在100°C和50巴的氢气压力下,将40ml四氢呋喃、5.6mmol 1,23-二十三烷二酸二乙酯、5.6μmol二氯双[2-(二苯基膦基)乙胺]钌和0.56mmol甲醇钠的混合物在加压反应器中搅拌22小时。将反应混合物在40°C下过滤。将滤液在50°C和500毫巴下在旋转蒸发器中浓缩。残余物由甲苯重结晶。基于所用的1,23-二十三烷二酸二乙酯,收率为78%。
B缩聚和缩聚物
实施例5聚酯(23,23)
在带有塞子的10ml烧瓶中,将1.4mmol 1,23-二十三烷二酸二乙酯、1.4mmol 1,23-二羟基二十三烷和0.28mmol四丁酸钛在0.01毫巴下经17小时由110°C加热至150°C。冷却后,得到白色固体。
凝胶渗透色谱(溶剂:1,2,4-三氯苯,160°C,相对于线性聚乙烯标样)显示分子量Mn为104g mol-1(Mw/Mn为2)。差示热流量热法(DSC)显示在第一次和第二次加热曲线中,熔点峰值Tm为99°,结晶温度为84°C,熔融焓为180J g-1。
实施例6聚酯(23,12)
在具有机械搅拌器的100ml Schlenk中,将2.8mmol 1,23-二十三烷二酸二乙酯和1,12-十二烷二醇与处于0.1ml甲苯中的0.028mmol四丁酸钛一起经8小时由100°C加热至220°C。然后,将该混合物在220°C和0.01毫巴下搅拌1小时。冷却后,获得白色固体。
差示热流量热法(DSC)显示第二次加热曲线中的熔点峰值Tm为101°C,结晶温度Tc为76°C,熔融焓ΔHm为156J g-1。
实施例7聚酯(23,6)
在具有机械搅拌器的100ml Schlenk中,将2.8mmol 1,23-二十三烷二酸二乙酯和1,6-己二醇与处于0.1ml甲苯中的0.028mmol四丁酸钛一起经8小时由100°C加热至220°C。然后,将该混合物在220°C和0.01毫巴下搅拌1小时。冷却后,得到白色固体。
差示热流量热法(DSC)显示第二次加热曲线中的熔点峰值Tm为92°C,结晶温度Tc为75°C,熔融焓ΔHm为145J/g。
实施例8聚酯(23,4)
在具有机械搅拌器的100ml Schlenk中,将2.8mmol 1,23-二十三烷二酸二乙酯和1,4-丁二醇与处于0.1ml甲苯中的0.028mmol四丁酸钛一起经4小时由100°C加热到200°C。然后将该混合物在220°C下搅拌8小时,且在220°C和0.01毫巴下再搅拌1小时。冷却后,得到白色固体。
差示热流量热法(DSC)显示第二加热曲线的熔点峰值Tm为85°C,结晶温度Tc为71°C,熔融焓ΔHm为172J g-1。
实施例9聚酰胺(23,23)
在9ml乙醇中由1.04mmol 1,23-二氨基二十三烷与1.04mmol 1,23-二十三烷基二羧酸制备二十三亚甲基二胺二十三烷二酰胺。
在具有机械搅拌器的100ml Schlenk中,将1.04mmol的二十三亚甲基二胺二十三烷二酰胺与0.037mmol的1,23-二氨基二十三烷一起在氩气气氛下经3小时由120°C加热至210°C,在该温度下搅拌1.5小时。然后,在210°C下施加1×10-5巴的真空达17.5小时。冷却后,获得米色固体。
差示热流量热法(DSC)显示第二加热曲线中的熔点峰值Tm为151°C,结晶温度Tc为130°C,熔融焓ΔHm为88J g-1。
实施例10聚酰胺(12,23)
在9ml乙醇中,由1.43mmol 1,12-二氨基十二烷和1.43mmol 1,23-二十三烷二羧酸制备十二亚甲基二胺二十三烷二酰胺。
在具有机械搅拌器的100ml Schlenk中,将1.43mmol十二亚甲基二胺二十三烷二酰胺与0.045mmol 1,12-二氨基十二烷在氩气气氛下经5.5小时由100°C加热至200°C,在该温度下搅拌16.5小时。然后,在200°C下施加1×10-5巴的真空达4小时。冷却后,获得米色固体。
差示热流量热法(DSC)显示第二次加热曲线中的熔点峰值Tm为168°C,结晶温度Tc为150°C,熔融焓ΔHm为121J g-1。
实施例11聚酰胺(23,19)
在8ml乙醇中,由1.06mmol 1,23-二氨基二十三烷和1.06mmol 1,19-十九烷二羧酸制备二十三亚甲基二胺十九烷二酰胺。
在具有机械搅拌器的100ml Schlenk中,将1.06mmol的二十三亚甲基二胺十九烷二酰胺在氩气气氛下经4.5小时由100°C加热至230°C,在该温度下搅拌1.25小时。然后,在230°C下施加真空1×10-5巴的真空达16.5小时。冷却后,获得米色固体。
差示热流量热法(DSC)显示第二次加热曲线中的熔点峰值Tm为156°C,结晶温度Tc为132°C,熔融焓ΔHm为85J g-1。
Claims (15)
1.一种缩聚物,其包含一种或多种式(I)重复单元:
-Z-(CH2)2n+1-Z’- (I)
其中各符号和指数具有如下含义:
Z,Z’相同或不同且为-X-C(=O)~、-C(=O)-HN-CH2~、-C(=O)-O-CH2~、-NH-C(=O)-O-CH2~、-O-C(=O)-NH-CH2~;
X为O或NH;
~表示与基团(CH2)2n+1连接的键,且
n为≥10的数。
2.根据权利要求1的缩聚物,其包含重复单元-X-C(=O)-(CH2)2n+1-C(=O)-X’-,其中n≥10且X,X’为O或NH。
3.根据权利要求1的缩聚物,其包含重复单元-M-(CH2)2n+3-M’~,其中n≥10且M、M’为酰胺官能团(-C(=O)-NH~),酯官能团(-C(=O)或尿烷官能团(-NH-C(=O)-O~)。
4.根据权利要求1或2的聚酯,其具有重复单元[{-A1-OC(=O)-(CH2)2n+1-C(=O)O-}x{-A1-OC(=O)-A2-C(=O)O-}y],其中n≥10,A1、A2相同或不同且为C2-C36脂族、脂环族、芳族或混合基团且x+y=1。
5.根据权利要求1或2的聚酰胺,其具有重复单元[{A1-NHC(=O)-(CH2)2n+1-C(=O)NH-}x{-A1-NHC(=O)-A2-C(=O)NH-}y],其中n≥10,为C2-C36脂族、脂环族、芳族或混合基团且x+y=1。
6.根据权利要求3或4的缩聚物,其中y=0。
7.根据权利要求1-6中任一项的缩聚物,其中n=10。
8.根据权利要求1-7中任一项的缩聚物,其包含至少1mol%的一种或多种式(I)重复单元。
9.一种制备根据权利要求1-8中任一项的缩聚物的方法,其中使至少一种式(II)的单体化合物与至少一种二-或多元醇或至少一种二-或多元胺缩聚:
Z1-(CH2)2n+1-Z1’ (II)
其中
Z1,Z1’为~C(=O)-Q或~CH2-NCO;
Q相同或不同且为OH,卤素或C1-C10烷氧基;
~表示与基团(CH2)2n+1连接的键,且
n为≥10的数,
和/或
使至少一种式(III)的单体化合物与至少一种二-或多元羧酸、所述二-或多元羧酸的反应性衍生物或至少一种二-或多异氰酸酯缩聚:
Z2-(CH2)2n+1-Z2’ (III)
其中
Z,Z’相同或不同且为HO-CH2~或H2N-CH2~;
~表示与基团(CH2)n连接的键,且
n为≥10的数。
10.根据权利要求1-8中任一项的缩聚物在模制品、涂料、泡沫、膜、箔和/或纤维中的用途。
11.一种模制品、涂料、箔、泡沫或纤维,其包含一种或多种根据权利要求1-8中任一项的缩聚物。
12.一种制备在酸结构部分中具有在每种情况下为2n+3个碳原子的饱和或不饱和α,ω-二羧酸或酯的方法,其中n≥10,包括如下步骤:使在酸结构部分中具有2n+2个碳原子的单或多不饱和脂肪酸酯在包含至少一种钯化合物和至少一种磷烷的催化剂存在下,在50-120°C的温度和3-80atm的压力下羟基-或烷氧基羰基化,其中n≥10。
13.根据权利要求12的方法,其中烷氧基化合物为C2-C36醇。
14.根据权利要求12或13的方法,其中所述催化剂包含钯(II)盐和1,2双[(二叔丁基膦基)甲基]苯。
15.根据权利要求12-14中任一项的方法,其中所述脂肪酸酯为芥酸酯。
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