WO2023076999A1 - Thermoplastic polyester copolymer, preparation and use thereof - Google Patents
Thermoplastic polyester copolymer, preparation and use thereof Download PDFInfo
- Publication number
- WO2023076999A1 WO2023076999A1 PCT/US2022/078781 US2022078781W WO2023076999A1 WO 2023076999 A1 WO2023076999 A1 WO 2023076999A1 US 2022078781 W US2022078781 W US 2022078781W WO 2023076999 A1 WO2023076999 A1 WO 2023076999A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- polyester copolymer
- monomer
- copolymer
- repeating unit
- Prior art date
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- 229920000728 polyester Polymers 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920001169 thermoplastic Polymers 0.000 title abstract description 4
- 239000004416 thermosoftening plastic Substances 0.000 title abstract description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 74
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 33
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002596 lactones Chemical class 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims description 71
- 238000007334 copolymerization reaction Methods 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 18
- 125000002947 alkylene group Chemical group 0.000 claims description 18
- 239000000835 fiber Substances 0.000 claims description 17
- -1 co-pentadecalactone Chemical compound 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 9
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920005604 random copolymer Polymers 0.000 claims description 8
- 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 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 6
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 5
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- 210000000988 bone and bone Anatomy 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
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- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 4
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims description 3
- 238000012662 bulk polymerization Methods 0.000 claims description 3
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 3
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- 229940057867 methyl lactate Drugs 0.000 claims description 3
- QRPLZGZHJABGRS-UHFFFAOYSA-N xi-5-Dodecanolide Chemical compound CCCCCCCC1CCCC(=O)O1 QRPLZGZHJABGRS-UHFFFAOYSA-N 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
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- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
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- 239000004305 biphenyl Substances 0.000 claims description 2
- FYTRVXSHONWYNE-UHFFFAOYSA-N delta-octanolide Chemical compound CCCC1CCCC(=O)O1 FYTRVXSHONWYNE-UHFFFAOYSA-N 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 235000013305 food Nutrition 0.000 claims description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229940057995 liquid paraffin Drugs 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 229940089513 pentadecalactone Drugs 0.000 claims description 2
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- 230000002792 vascular Effects 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000006227 byproduct Substances 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 16
- 150000003384 small molecules Chemical class 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
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- 238000007142 ring opening reaction Methods 0.000 description 4
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- 238000003756 stirring Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
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- ZKLRYZNOOWOOMP-UHFFFAOYSA-N 2,2,2-trifluoroacetic acid;trifluoromethanesulfonic acid Chemical compound OC(=O)C(F)(F)F.OS(=O)(=O)C(F)(F)F ZKLRYZNOOWOOMP-UHFFFAOYSA-N 0.000 description 2
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
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- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
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- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- QXYCYSAGHGKNHM-UHFFFAOYSA-N dodecyl octadecanoate;magnesium Chemical compound [Mg].CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCCCCCC QXYCYSAGHGKNHM-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 229940087603 grape seed extract Drugs 0.000 description 1
- 235000002532 grape seed extract Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 239000001575 punica granatum l. bark extract Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229940092258 rosemary extract Drugs 0.000 description 1
- 235000020748 rosemary extract Nutrition 0.000 description 1
- 239000001233 rosmarinus officinalis l. extract Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940023144 sodium glycolate Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
- 229960002799 stannous fluoride Drugs 0.000 description 1
- 229940108184 stannous iodide Drugs 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- VYGSFTVYZHNGBU-UHFFFAOYSA-N trichloromethanesulfonic acid Chemical compound OS(=O)(=O)C(Cl)(Cl)Cl VYGSFTVYZHNGBU-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 1
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 1
- 239000001717 vitis vinifera seed extract Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
Definitions
- the present invention relates to a thermoplastic polyester copolymer, the preparation and the use thereof.
- PET polyethylene terephthalate
- CN106957412A disclosed the copolymerization of glycolide and 8-caprolactone monomers so as to produce a random copolymer.
- the application did not include any experimental data to demonstrate that the copolymer is indeed a random copolymer.
- Stannous octoate is used as catalyst in the copolymerization.
- the application did not disclose properties, performances and applications for the copolymer.
- CN101466763A disclosed the salt of trifluoromethane sulfonic acid and triaryl phosphine as catalyst for the polymerization of lactic acid.
- the copolymerization of glycolic acid and lactone was also discussed.
- glycolic acid and e-caprolactone were copolymerized, the product is a copolymer of glycolic acid and 8-caprolactone with more or less equal number of repeating units derived from glycolic acid and 8-caprolactone in one polymer chain.
- the present invention relates to a process for the preparation of a polyester copolymer, wherein at least a first monomer and a second monomer are copolymerized to form the polyester copolymer, wherein the first monomer is selected from the group consisting of hydroxyl carboxylic acids of Formula (I), C 1 -C 3 alkyl esters of hydroxyl carboxylic acids of Formula (I), and lactides of hydroxyl carboxylic acids of Formula (I),
- R 1 is a C 1 , C 2 or C 3 alkylene group
- the second monomer is a lactone of Formula (II) wherein R 2 is a C 2 -C 20 alkylene group, such as a C 2 -C 13 alkylene group, optionally substituted, for example by a C 1 -C 8 alkyl group, said alkyl group is further substituted, for example by a hydroxyl group, a halogen atom, a nitro group, or a cyano group.
- the present invention further relates to a polyester copolymer obtainable from the process listed above.
- the present invention also relates to a polyester copolymer comprising at least the first repeating unit having Formula (III),
- R 1 is a C 1 , C 2 or C 3 alkylene group
- the second repeating unit having Formula (IV), -O-R 2 -CH 2 -CO- (IV) wherein R 2 is a C 2 -C 20 alkylene group, such as a C 2 -C 13 alkylene group, optionally substituted, for example by a C 1 -C 8 alkyl group, said alkyl group is further substituted, for example by a hydroxyl group, a halogen atom, a nitro group, or a cyano group.
- the present invention also relates to the use of the polyester copolymer in packing such as flexible packaging and rigid packaging such as disposable meal box, or medical application.
- Figure 1 is the comparison of DSC curves of various copolymer of glycolic acid and e-caprolactone.
- Figure 2 is the 13 C-NMR spectrum of the polyester copolymer obtained in Example 1, with GA: CL of 70: 30.
- the present invention will be disclosed in detail in the following descriptions. [0013] The present invention is directed to a process for the preparation of a polyester copolymer, the polyester copolymer obtained therefrom, and the application of the polyester copolymer.
- alkyl refers to a normal alkyl group or an isomer thereof, or a cyclo-alkyl group.
- C 1 -C 3 alkyl can be a methyl group, an ethyl group, a w-propyl group, or an z-propyl group.
- alkylene as a group in the context of the present invention refers to a ⁇ , ⁇ -n --lkylene group or one of various isomers thereof, or a cyclo-alkylene group.
- a C 3 alkylene group can be any one of the following:
- the present invention relates to a process for the preparation of polyester copolymers, wherein at least the first monomer and the second monomer are copolymerized to form a polyester copolymer, wherein the first monomer is selected from the group consisting of hydroxyl carboxylic acids of Formula (I), C 1 -C 3 alkyl esters of hydroxyl carboxylic acids of Formula (I), and lactides of hydroxyl carboxylic acids of Formula (I),
- R 1 is a C 1 , C 2 or C 3 alkylene group
- the second monomer is a lactone of Formula (II) wherein R 2 is a C 2 -C 20 alkylene group, such as a C 2 -C 13 alkylene group, optionally substituted, for example by a C 1 -C 8 alkyl group, said alkyl group is further substituted, for example by a hydroxyl group, a halogen atom, a nitro group, or a cyano group.
- the process is carried out in the presence of a catalyst selected from the group consisting of the combination of an organic sulfonic acid and an organic phosphine, the combination of sulfuric acid and an organic phosphine, stannous oxide, stannous halide, stannous carboxylate, and organic tin compound.
- a catalyst selected from the group consisting of the combination of an organic sulfonic acid and an organic phosphine, the combination of sulfuric acid and an organic phosphine, stannous oxide, stannous halide, stannous carboxylate, and organic tin compound.
- the first monomer involved in the process of the present invention is selected from the group consisting of hydroxyl carboxylic acids of Formula (I), C 1 -C 3 alkyl esters of hydroxyl carboxylic acids of Formula (I), and lactides of hydroxyl carboxylic acids of Formula (I),
- the first monomer is selected from the group consisting of glycolic acid, lactic acid, methyl glycolate, ethyl glycolate, /7-propyl glycolate, z-propyl glycolate, methyl lactate, ethyl lactate, zz-propyl lactate, z-propyl lactate, glycolide, and lactide.
- R 1 is a methylene group, thus the first monomer is glycolic acid, or glycolide, or C 1 -C 3 alkyl glycolate such as methyl glycolate.
- R 1 is an ethylene group, thus the first monomer is lactic acid, lactide or C 1 -C 3 alkyl lactate such as methyl lactate.
- the second monomer is selected from the group consisting of compounds of the Formula (II) wherein R 2 is a C 2 -C 20 alkylene group, such as a C 2 -C 13 alkylene group, optionally substituted, for example by a C 1 -C 8 alkyl group, said alkyl group is further substituted, for example by a hydroxyl group, a halogen atom, a nitro group, or a cyano group.
- R 2 is a C 2 -C 20 alkylene group, such as a C 2 -C 13 alkylene group, optionally substituted, for example by a C 1 -C 8 alkyl group, said alkyl group is further substituted, for example by a hydroxyl group, a halogen atom, a nitro group, or a cyano group.
- the second monomer is selected from the group consisting of y-butyrolactone, y-valerolactone, 5-octalactone, e-caprolactone, co-pentadecalactone, 5-caprinolactone, y-decalactone, and 5-dodecalactone.
- the first monomer and the second monomer are selected the chemicals listed below, respectively.
- the first and the second monomer are glycolic acid and ⁇ -caprolactone, respectively.
- the ratio of the first monomer and the second monomer in the copolymerization mixture can be determined by those skilled in the art according to practical need, particularly according to the desired properties and performances of the copolymer.
- the molar ratio of the first and the second monomer in the copolymerization mixture is as high as (70 to 99):(1 to 30), such as (75 to 95): (5 to 25), which means that the content of the first monomer can be much higher than that of the second monomer.
- Such a copolymerization mixture produces a polyester copolymer with high molar content of the repeating unit corresponding to the first monomer.
- the process of the present invention is carried out in the presence of a catalyst selected from the group consisting of the combination of an organic sulfonic acid and an organic phosphine, the combination of sulfuric acid and an organic phosphine, stannous oxide, stannous halide, stannous carboxylate, and organic tin compound.
- a catalyst selected from the group consisting of the combination of an organic sulfonic acid and an organic phosphine, the combination of sulfuric acid and an organic phosphine, stannous oxide, stannous halide, stannous carboxylate, and organic tin compound.
- the organic sulfonic acid can be selected from the group consisting of methane sulfonic acid, ethane sulfonic acid, 1 -propane sulfonic acid, 1 -butane sulfonic acid, benzene sulfonic acid, p-toluene sulfonic acid, p-xylene sulfonic acid, naphthene- 1 -sulfonic acid, naphthene-2-sulfonic acid, trichloromethane sulfonic acid, and trifluoromethane sulfonic acid.
- the organic phosphine can be selected from the group consisting of trimethyl phosphine, triethyl phosphine, tri-1 -propyl phosphine, tri-1 -butyl phosphine, triphenyl phonphine, and tri-p-toly 1 phosphine.
- the stannous carboxylate can be selected from the group consisting of stannous hexanoate, stannous heptylate, stannous octoate, stannous nonanoate, stannous decanoate.
- the stannous halide can be selected from stannous fluoride, stannous chloride, stannous bromide and stannous iodide.
- the organic tin compound is a compound comprising at least one tin atom which is directly bonded with a carbon atom by Sn-C bond.
- organic tin compounds are di-w-butyl tin diacetate and di-w-butyl tin dilaurate.
- the catalyst is selected from the group consisting of the combination of trifluoromethane sulfonic acid and triphenylphosphine, the combination of sulfuric acid and triphenylphosphine, and stannous octoate.
- the molar ratio of trifluoromethane sulfonic acid and triphenylphosphine is, for example, 1 : (0.5 to 2), such as about 1: 1.
- the molar ratio of sulfuric acid and triphenylphosphine is, for example, 1 :(0.5 to 2), such as about 1:1.
- the amount of the catalyst can be selected by those skilled in the art by experimentation.
- the molar ratio of the total of the first monomer and the second monomer and the total of the catalyst islOOO: 1 to 10: 1, such as 100:(l to 4).
- a solvent can be used to facilitate dissolution and mixing of the monomers and the catalyst.
- the solvent may also contribute to the removal of by-product such as water due to the formation of a zeotropical mixture.
- the solvent can be added either as a separate raw material to the reaction mixture, or in a mixture with other ingredients, such as in a mixture with the catalyst.
- the solvent can be any material that can dissolve or disperse the monomers and the catalyst while not interfering with the reaction occurring in the system.
- Useful solvent can be selected from, for example, toluene, xylene, trimethylbenzene, biphenyl, liquid paraffin, liquid silicone oil, diphenyl ether and anisole, or any alkane with boiling point higher than 100°C at 1 atm.
- the amount of solvent can be determined by those skilled in the art according to practical need.
- the process of the present invention can be carried out as a bulk polymerization process.
- bulk polymerization means that, during the polymerization, the amount of solvent in the copolymerization system is less than 10%, or less than 5%, or less than 2.5%, or less than 1% by weight, or even the solvent is completely absent.
- the process of the present invention can be carried out in the presence of other chemicals that can be incorporated into the polyester chain as an additional repeating unit, or an end-group, or a pendent group, or can modify the structure of the polyester chain, such as that of the repeating unit, the end groups or the pendent groups.
- the copolymerization mixture may comprise a third monomer.
- the third monomer can be any compound that can be incorporated into the polyester chain and do not significantly interfere with the copolymerization of the first and the second monomer.
- the third monomer can be exemplified by ethylene oxalate (i.e.,
- the copolymerization mixture may comprise a carboxyl group-capping agent in order to modify the end groups of the polyester chain so as to enhance hydrolysis stability.
- the carboxyl group-capping agent can be selected from the group consisting of monocarbodiimides and polycarbodiimides, such as N,N-2,6-diisopropylphenylcarbodiimide; oxazoline compounds, such as 2,2’-m-phenylene-bis(2-oxazoline), 2.2'-/?-phenylene-bis(2-oxazoline). and
- 2-phenyl-2-oxazoline 2-phenyl-2-oxazoline
- oxazine compounds such as 2-methoxy-5,6-dihydro-4H-l,3-oxazine
- epoxy compounds such as N-glycidylphthalimide, cyclohexene oxide, and tris(2,3-epoxypropyl) isocyanurate.
- Conditions applied during the copolymerization process can be determined by those skilled in the art according to actual need, particularly taking into account of reaction kinetics and the mechanism for the copoly merizati on.
- the copolymerization is an esterification reaction combined with a ring-opening reaction. Small molecule by-product water will be generated during the reaction; ii) When the first monomer is a lactide of a hydroxyl carboxylic acid such as glycolide, the copolymerization is a ring-opening reaction combined with another ring-opening reaction.
- the copolymerization is a transesterification reaction combined with a ring-opening reaction. Small molecule by-product methanol will be generated during the reaction.
- conditions applied during the copolymerization process such as pressure and temperature, can be determined by those skilled in the art, particularly taking into account of reaction kinetics and the removal of small molecule by-product.
- the copolymerization can be carried out at 1 atm or a higher or lower pressure.
- the copolymerization is carried out at the boiling point of the solvent by refluxing the solvent.
- the copolymerization temperature can be around 110.6°C (boiling point of toluene at 1 atm), 138.4°C (boiling point of xylene at 1 atm), or 166.7°C (boiling point of trimethylbenzene at 1 atm), etc.
- the boiling point of a solvent is related to the pressure under which the copolymerization is carried out, and the formation of azeotropical mixture with the small molecule by-product such as water.
- the polyester copolymer can be purified to remove catalyst residue, solvent and by-product from the reaction mixture. Such purification process is also known to those skilled in the art.
- glycolic acid and e-caprolactone predetermined amounts of glycolic acid, e-caprolactone, catalyst such as trifluoromethane sulfonic acid and triphenyl phosphine, solvent such as toluene, are added to a closed reaction vessel.
- catalyst such as trifluoromethane sulfonic acid and triphenyl phosphine
- solvent such as toluene
- the reaction process is monitored by the amount of water removed from the system. When calculated amount of water has been removed, the reaction mixture is allowed to cool down to ambient temperature and the product is purified by, for example, precipitation in cold methanol.
- the polyester copolymer produced by the process of the invention should have a backbone consisting of two types of repeating units, which is referred to as the first repeating unit and the second repeating unit, respectively.
- the polyester copolymer of the present invention has a backbone comprising two types of repeating units, the structure of which corresponds to that of the first monomer and the second monomer in the copolymerization mixture.
- the first repeating unit is derived from the first monomer and has Formula (III),
- R 1 is a C 1 , C 2 or C 3 alkylene group; and the second repeating unit is derived from the second monomer and has Formula (IV),
- R 2 is a C 2 -C 20 alkylene group, such as a C 2 -C 13 alkylene group, optionally substituted, for example by a C 1 -C 8 alkyl group, said alkyl group is further substituted, for example by a hydroxyl group, a halogen atom, a nitro group, or a cyano group.
- the polyester copolymer has a T g of -20°C to 10°C and/or a T m of 120°C to 180°C.
- more than 60%, such as more than 80%, such as more than 90% by weight of the polyester copolymer is dissolved in Imol/L sodium hydroxide aqueous solution at room temperature within 10 minutes.
- the polyester copolymer is a copolymer of glycolic acid and e-caprolactone, that is, R 1 is -CH 2 - while R 2 is -(CFE)?-, respectively.
- the number average molecular weight of the copolymer of glycolic acid and e-caprolactone is 5,000 to 100,000, such as 10,000 to 50,000.
- the copolymerization process produces small molecule by-product, and the by-product is removed from the reaction system during the copolymerization process, the copolymerization can proceed virtually to completion.
- the molar ratio of the first repeating unit and the second repeating unit is also virtually the same as the molar ratio of the first monomer and the second monomer.
- the properties / performances of the polyester copolymer can be customized by applying a particular first repeating unit and second repeating unit and molar ratio thereof. This can be achieved by applying the corresponding first monomer and second monomer and molar ratio thereof during the copolymerization process.
- the polyester copolymer can be significantly different, depending on whether the copolymer is a random copolymer or a block copolymer. This relies on the reactivity ratio of the first and the second monomer.
- the present Inventor has found that, using a carefully selected catalyst, it is possible to obtain a random copolymer.
- a randomly copolymer for example, for the copolymerization of glycolic acid and e-caprolactone, the combination of trifluoromethane sulfonic acid and triphenyl phosphine as catalyst can result in a random copolymer.
- random copolymer is advantageous in that it offers reduced melt temperature ( ⁇ 150°C) and improved toughness.
- polyester copolymer can be demonstrated by analytical methods revealing detailed sequence of the repeating units in the polymer backbone.
- the polyester copolymer of the present invention has an average number of the first repeating unit in blocks made of the first repeating unit only is 2 to 8, such as 2 to 6, such as 2 to 4.
- the polyester copolymer of the present invention has an average number of the second repeating unit in blocks made of the second repeating unit only is 1 to 2, such as 1 to 1.5.
- the polyester copolymer of the present invention has a ratio of the total number of the first repeating unit to the total number of the second repeating unit in one copolymer chain of (70 to 99): (1 to 30), such as (75 to 95):(5 to 25).
- the copolymer will degrade quickly by breaking the ester linkage in the polymer backbone at room temperature under acidic or basic pH.
- the degradation products are the first monomer, the second monomer and/or derivatives thereof.
- the degradation product under basic conditions should be sodium glycolate and sodium 5-hydroxyl caproate.
- Additives can be added to the copolymerization mixture so as to either improve the copolymerization process or to modify the properties / performances of the polyester copolymer.
- Such additives are usually not a part of the polyester copolymer, but as an additional component mixed with the polyester copolymer. If the additive is to modify the properties / performances of the polyester copolymer only, it is also possible to add such additives to the polyester copolymer after the completion of the copolymerization process.
- a thermal stabilizer can be applied to improve thermal stability.
- the thermal stabilizer can be a reagent to deactivate the polymerization catalyst, which is selected from the group consisting of hydrazine compounds having a -CONHNH-CO- unit, such as N,N’-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]-hydrazine;
- the thermal stabilizer can also be other compounds such as phosphoric acid esters having a pentaerythritol skeleton and alkyl phosphate or phosphite esters having at least one hydroxyl group and at least one alkyl ester group.
- an antioxidant can be applied to improve oxidization stability.
- the antioxidant can be selected from the group consisting of calcium dodecyl stearate, zinc dodecyl stearate or magnesium lauryl stearate, and phenol-based antioxidant such as octadecyl-3- (3.5-di-/-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis
- the antioxidant can also be a natural antioxidant such as tea polyphenols, pomegranate peel extract, rosemary extract or grape seed extract.
- the filler can be selected from: fiber or whisker form fillers, such as glass fiber, PAN-based and pitch-based carbon fiber, metal fiber, such as stainless steel fiber, aluminum fiber and brass fiber, natural fiber of chitin, chitosan, cellulose, cotton, etc., organic synthetic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, and silicon nitride whisker; and powdery, particulate and plate-like fillers of natural inorganic minerals, such as mica, talc, kaolin, silica and sand, calcium carbonate, glass beads, glass flake, glass micro-balloon, clay, molybdenum disulfide,
- fiber or whisker form fillers such as glass fiber, PAN-based and pitch-based carbon fiber, metal fiber, such as stainless steel fiber, aluminum
- the filler can be used after surface treatment thereof with known coupling agents, such as silane coupling agents and titanate coupling agents, and other surface treating agents.
- the glass fiber can be coated or bundled with a thermoplastic resin, such as ethylene/vinyl acetate copolymer, or a thermosetting resin such as epoxy resin.
- the polyester copolymer of the present invention is particularly useful in packaging, such as flexible packaging and rigid packaging such as packaging for food, and in medical applications such as surgical sutures, vascular clamps, patches, staplers, bone nails, and bone plates, and other applications such as consumer goods, shopping bags, fibers, sheets.
- Glycolic acid, e-caprolactone, trifluoromethane sulfonic acid and triphenyl phosphine are obtained from Adamas Reagents Co. Ltd., Shanghai, China and are used as received.
- Toluene and xylene are purchased from Sigma-Aldrich and are used as received.
- DSC was performed on Perkin Elmer DSC8000 Differential Scanning Calorimeter equipped with a cooling accessary.
- the melting point T m is analyzed by peak analysis of the software and glass transition temperature T g is analyzed by T g analysis of the software.
- Polyester copolymer of glycolic acid and e-caprolactone was prepared using the combination of trifluoromethane sulfonic acid and triphenylphosphine as catalyst.
- polymer 2 with 155°C melt point and -3°C glass transition temperature is similar to the properties of polypropylene, indicating the opportunity for application penetration.
- the number of repeating units in a GA block and a CL block is determined by the process disclosed in Kasperczyk, J. (1999) “Copolymerization of Glycolide and G-Caprolactone. 1 Analysis of the Copolymer Microstructure by means of J H and 13 C NMR Spectroscopy,” Marcomol. Chem. Phys., v.200(4), pp. 903-910 and Bero, M. et al. (1999) “Copolymerization of Glycolide and £-Caprolactone, 2 a Random Copolymerization in the Presence of Tin Octoate,” Marcomol. Chem. Phys., v.200(4), pp. 911-916. The result is shown in Table 2. The small number of repeating units in GA blocks and the CL blocks proves that the copolymer is a random copolymer.
- the molar ratio of repeating unit GA: CL is close to the molar ratio of the first monomer to the second monomer in the copolymerization mixture. This is expected as virtually all the monomers are incorporated into the polymer chain due to the removal of small molecule by-product which shift the reaction equilibrium to the formation of copolymer.
- the example compares polyester copolymers with repeating units derived from glycolic acid and e-caprolactone which are obtained from different synthetic route.
- Example 1 The polymerization process in Example 1 is repeated except that glycolide is used as the first monomer and stannous octoate is used as the catalyst. Melting point and glass transition temperature obtained by DSC was shown in Table 3 and is compared with polymers obtained in Example 1.
- the polyester copolymer has much lower Tg, indicating better processability of the copolymer.
- This example demonstrates the copolymerization of monomers other than glycolic acid and e-caprolactone.
- MG methyl glycolate
- CL e-caprolactone
- TPP triphenylphosphine
- TMA trifluoromethane sulfonic acid
- Toluene and side product methanol are removed from the Dean-Stark apparatus during the reaction. After reaction for 24 hours, the mixture in the flask was shot to a beaker with cold methanol. The product precipitates as white cloudy solid. The solid is filtered, washed with methanol twice and dried in a vacuum oven at 60°C under vacuum. The product shows T m of 141 °C and T g of -26°C .
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Abstract
The present invention relates to a thermoplastic polyester copolymer, the preparation and the use thereof. The polyester copolymer is produced from hydroxyl carboxylic acids and derivatives thereof, such as glycolic acid, and lactone and derivatives thereof, such as ε-caprolactone, in the presence of a catalyst such as the combination of trifluoromethane sulfonic acid and triphenylphosphine.
Description
THERMOPLASTIC POLYESTER COPOLYMER, PREPARATION AND USE THEREOF
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of and priority to US Provisional Application No. 63/272834 filed October 28, 2021, the disclosure of which is incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to a thermoplastic polyester copolymer, the preparation and the use thereof.
BACKGROUND
[0003] The most common polyester in the market is polyethylene terephthalate (PET).
[0004] CN106957412A disclosed the copolymerization of glycolide and 8-caprolactone monomers so as to produce a random copolymer. However, the application did not include any experimental data to demonstrate that the copolymer is indeed a random copolymer. Stannous octoate is used as catalyst in the copolymerization. The application did not disclose properties, performances and applications for the copolymer.
[0005] CN101466763A disclosed the salt of trifluoromethane sulfonic acid and triaryl phosphine as catalyst for the polymerization of lactic acid. The copolymerization of glycolic acid and lactone was also discussed. When glycolic acid and e-caprolactone were copolymerized, the product is a copolymer of glycolic acid and 8-caprolactone with more or less equal number of repeating units derived from glycolic acid and 8-caprolactone in one polymer chain.
SUMMARY OF THE INVENTION
[0006] The present invention relates to a process for the preparation of a polyester copolymer, wherein at least a first monomer and a second monomer are copolymerized to form the polyester copolymer, wherein the first monomer is selected from the group consisting of hydroxyl carboxylic acids of Formula (I), C1-C3 alkyl esters of hydroxyl carboxylic acids of Formula (I), and lactides of hydroxyl carboxylic acids of Formula (I),
HO-R1-COOH (I) wherein R1 is a C1, C2 or C3 alkylene group; and the second monomer is a lactone of Formula (II)
wherein R2 is a C2-C20 alkylene group, such as a C2-C13 alkylene group, optionally substituted, for example by a C1-C8 alkyl group, said alkyl group is further substituted, for example by a hydroxyl group, a halogen atom, a nitro group, or a cyano group.
[0007] The present invention further relates to a polyester copolymer obtainable from the process listed above.
[0008] The present invention also relates to a polyester copolymer comprising at least the first repeating unit having Formula (III),
-O- R1-CO- (III) wherein R1 is a C1, C2 or C3 alkylene group; and the second repeating unit having Formula (IV), -O-R2-CH2-CO- (IV) wherein R2 is a C2-C20 alkylene group, such as a C2-C13 alkylene group, optionally substituted, for example by a C1-C8 alkyl group, said alkyl group is further substituted, for example by a hydroxyl group, a halogen atom, a nitro group, or a cyano group.
[0009] The present invention also relates to the use of the polyester copolymer in packing such as flexible packaging and rigid packaging such as disposable meal box, or medical application.
[0010] These and other features and attributes of the disclosed polyester copolymer of the present invention, the preparation thereof, and their advantageous applications and/or uses will be apparent from the detailed description which follows.
BRIEF DESCRIPTION TO THE FIGURES
[0011] To assist those skilled in the art in making and using the subject matter of the present invention, reference is made to the appended drawings, wherein:
Figure 1 is the comparison of DSC curves of various copolymer of glycolic acid and e-caprolactone.
Figure 2 is the 13C-NMR spectrum of the polyester copolymer obtained in Example 1, with GA: CL of 70: 30.
SPECIFIC MODE FOR CARRYING OUT THE INVENTION
[0012] The present invention will be disclosed in detail in the following descriptions.
[0013] The present invention is directed to a process for the preparation of a polyester copolymer, the polyester copolymer obtained therefrom, and the application of the polyester copolymer.
[0014] Unless specified otherwise, the term “alkyl” as a group in the context of the present invention refers to a normal alkyl group or an isomer thereof, or a cyclo-alkyl group. For example, the term “C1-C3 alkyl” can be a methyl group, an ethyl group, a w-propyl group, or an z-propyl group.
[0015] Similarly, the term “alkylene” as a group in the context of the present invention refers to a α,ω-n --lkylene group or one of various isomers thereof, or a cyclo-alkylene group. For example, a C3 alkylene group can be any one of the following:
COPOLYMERIZATION PROCESS
[0016] The present invention relates to a process for the preparation of polyester copolymers, wherein at least the first monomer and the second monomer are copolymerized to form a polyester copolymer, wherein the first monomer is selected from the group consisting of hydroxyl carboxylic acids of Formula (I), C1-C3 alkyl esters of hydroxyl carboxylic acids of Formula (I), and lactides of hydroxyl carboxylic acids of Formula (I),
HO-R1-COOH (I) wherein R1 is a C1, C2 or C3 alkylene group; and the second monomer is a lactone of Formula (II)
wherein R2 is a C2-C20 alkylene group, such as a C2-C13 alkylene group, optionally substituted, for example by a C1-C8 alkyl group, said alkyl group is further substituted, for example by a hydroxyl group, a halogen atom, a nitro group, or a cyano group.
[0017] In one embodiment of the invention, the process is carried out in the presence of a catalyst selected from the group consisting of the combination of an organic sulfonic acid and an organic phosphine, the combination of sulfuric acid and an organic phosphine, stannous oxide, stannous halide, stannous carboxylate, and organic tin compound.
MONOMERS
[0018] The first monomer involved in the process of the present invention is selected from the group consisting of hydroxyl carboxylic acids of Formula (I), C1-C3 alkyl esters of hydroxyl carboxylic acids of Formula (I), and lactides of hydroxyl carboxylic acids of Formula (I),
HO-R1-COOH (I) wherein R1 is a C1, C2 or C3 alkylene group.
[0019] In one embodiment of the invention, the first monomer is selected from the group consisting of glycolic acid, lactic acid, methyl glycolate, ethyl glycolate, /7-propyl glycolate, z-propyl glycolate, methyl lactate, ethyl lactate, zz-propyl lactate, z-propyl lactate, glycolide, and lactide.
[0020] In one embodiment of the present invention, R1 is a methylene group, thus the first monomer is glycolic acid, or glycolide, or C1-C3 alkyl glycolate such as methyl glycolate.
[0021] In one embodiment of the present invention, R1 is an ethylene group, thus the first monomer is lactic acid, lactide or C1-C3 alkyl lactate such as methyl lactate.
[0022] The second monomer is selected from the group consisting of compounds of the Formula (II)
wherein R2 is a C2-C20 alkylene group, such as a C2-C13 alkylene group, optionally substituted, for example by a C1-C8 alkyl group, said alkyl group is further substituted, for example by a hydroxyl group, a halogen atom, a nitro group, or a cyano group.
[0023] In one embodiment of the invention, the second monomer is selected from the group consisting of y-butyrolactone, y-valerolactone, 5-octalactone, e-caprolactone, co-pentadecalactone, 5-caprinolactone, y-decalactone, and 5-dodecalactone.
[0024] In one embodiment of the present invention, the first monomer and the second monomer are selected the chemicals listed below, respectively.
5-dodecalactone
[0025] In one embodiment of the present invention, the first and the second monomer are glycolic acid and ε-caprolactone, respectively.
[0026] The ratio of the first monomer and the second monomer in the copolymerization mixture can be determined by those skilled in the art according to practical need, particularly according to the desired properties and performances of the copolymer.
[0027] In one embodiment of the present invention, the molar ratio of the first and the second monomer in the copolymerization mixture is as high as (70 to 99):(1 to 30), such as (75 to 95): (5 to 25), which means that the content of the first monomer can be much higher than that of the second monomer. Such a copolymerization mixture produces a polyester copolymer with high molar content of the repeating unit corresponding to the first monomer. CATALYST
[0028] In one embodiment of the present invention, the process of the present invention is
carried out in the presence of a catalyst selected from the group consisting of the combination of an organic sulfonic acid and an organic phosphine, the combination of sulfuric acid and an organic phosphine, stannous oxide, stannous halide, stannous carboxylate, and organic tin compound.
[0029] The organic sulfonic acid can be selected from the group consisting of methane sulfonic acid, ethane sulfonic acid, 1 -propane sulfonic acid, 1 -butane sulfonic acid, benzene sulfonic acid, p-toluene sulfonic acid, p-xylene sulfonic acid, naphthene- 1 -sulfonic acid, naphthene-2-sulfonic acid, trichloromethane sulfonic acid, and trifluoromethane sulfonic acid.
[0030] The organic phosphine can be selected from the group consisting of trimethyl phosphine, triethyl phosphine, tri-1 -propyl phosphine, tri-1 -butyl phosphine, triphenyl phonphine, and tri-p-toly 1 phosphine.
[0031] The stannous carboxylate can be selected from the group consisting of stannous hexanoate, stannous heptylate, stannous octoate, stannous nonanoate, stannous decanoate.
[0032] The stannous halide can be selected from stannous fluoride, stannous chloride, stannous bromide and stannous iodide.
[0033] The organic tin compound is a compound comprising at least one tin atom which is directly bonded with a carbon atom by Sn-C bond. Examples of organic tin compounds are di-w-butyl tin diacetate and di-w-butyl tin dilaurate.
[0034] In one embodiment of the present invention, the catalyst is selected from the group consisting of the combination of trifluoromethane sulfonic acid and triphenylphosphine, the combination of sulfuric acid and triphenylphosphine, and stannous octoate.
[0035] When the combination of trifluoromethane sulfonic acid and triphenylphosphine is used as catalyst, the molar ratio of trifluoromethane sulfonic acid and triphenylphosphine is, for example, 1 : (0.5 to 2), such as about 1: 1.
[0036] When the combination of sulfuric acid and triphenylphosphine is used as catalyst, the molar ratio of sulfuric acid and triphenylphosphine is, for example, 1 :(0.5 to 2), such as about 1:1.
[0037] The Inventor has found that the selection of catalyst may have significant impact on the structural feature (and thus properties and performances) of the polyester copolymer of the present invention.
[0038] The amount of the catalyst can be selected by those skilled in the art by experimentation. In one embodiment of the present invention, the molar ratio of the total of
the first monomer and the second monomer and the total of the catalyst islOOO: 1 to 10: 1, such as 100:(l to 4).
SOLVENT
[0039] A solvent can be used to facilitate dissolution and mixing of the monomers and the catalyst. The solvent may also contribute to the removal of by-product such as water due to the formation of a zeotropical mixture.
[0040] The solvent can be added either as a separate raw material to the reaction mixture, or in a mixture with other ingredients, such as in a mixture with the catalyst.
[0041] The solvent can be any material that can dissolve or disperse the monomers and the catalyst while not interfering with the reaction occurring in the system. Useful solvent can be selected from, for example, toluene, xylene, trimethylbenzene, biphenyl, liquid paraffin, liquid silicone oil, diphenyl ether and anisole, or any alkane with boiling point higher than 100°C at 1 atm.
[0042] The amount of solvent can be determined by those skilled in the art according to practical need.
[0043] The process of the present invention can be carried out as a bulk polymerization process. The term “bulk polymerization” means that, during the polymerization, the amount of solvent in the copolymerization system is less than 10%, or less than 5%, or less than 2.5%, or less than 1% by weight, or even the solvent is completely absent.
OTHER CHEMICALS
[0044] The process of the present invention can be carried out in the presence of other chemicals that can be incorporated into the polyester chain as an additional repeating unit, or an end-group, or a pendent group, or can modify the structure of the polyester chain, such as that of the repeating unit, the end groups or the pendent groups.
[0045] For example, the copolymerization mixture may comprise a third monomer. In principle, the third monomer can be any compound that can be incorporated into the polyester chain and do not significantly interfere with the copolymerization of the first and the second monomer. The third monomer can be exemplified by ethylene oxalate (i.e.,
1.4-dioxane-2, 3-dione), 1,3-propylene carbonate, 1,3-dioxane, l,3-dioxan-2-one,
1.4-dioxan-2-one, 5,5-dimethyl-l,3-dioxane, ethylene glycol, 1,4-butanediol, succinic acid, adipic acid or an alkyl ester thereof. The third monomer will be incorporated into the polyester chain as an additional repeating unit, the structure of which can be determined by those skilled in the art according to common knowledge in the art.
[0046] For another example, the copolymerization mixture may comprise a carboxyl group-capping agent in order to modify the end groups of the polyester chain so as to enhance hydrolysis stability. The carboxyl group-capping agent can be selected from the group consisting of monocarbodiimides and polycarbodiimides, such as N,N-2,6-diisopropylphenylcarbodiimide; oxazoline compounds, such as 2,2’-m-phenylene-bis(2-oxazoline), 2.2'-/?-phenylene-bis(2-oxazoline). and
2-phenyl-2-oxazoline; oxazine compounds, such as 2-methoxy-5,6-dihydro-4H-l,3-oxazine; and epoxy compounds, such as N-glycidylphthalimide, cyclohexene oxide, and tris(2,3-epoxypropyl) isocyanurate.
CONDITIONS
[0047] Conditions applied during the copolymerization process, such as pressure and temperature, can be determined by those skilled in the art according to actual need, particularly taking into account of reaction kinetics and the mechanism for the copoly merizati on.
[0048] Depending on the nature of the first monomer, there are three mechanisms for the copoly merizati on : i) When the first monomer is a hydroxyl carboxylic acid such as glycolic acid, the copolymerization is an esterification reaction combined with a ring-opening reaction. Small molecule by-product water will be generated during the reaction; ii) When the first monomer is a lactide of a hydroxyl carboxylic acid such as glycolide, the copolymerization is a ring-opening reaction combined with another ring-opening reaction. There is no small molecule by-product generated during the reaction; iii) When the first monomer is an alkyl ester of a hydroxyl carboxylic acid such as methyl glycolate, the copolymerization is a transesterification reaction combined with a ring-opening reaction. Small molecule by-product methanol will be generated during the reaction.
[0049] If small molecule by-product is formed, the reaction equilibrium is shifted to the formation of polyester copolymer by removal of the by-product. The removal of the small molecule by-product can be achieved by azeotropic distillation of the by-product with solvent present in the system. In such case, the copolymerization of the first and the second monomer proceeds to virtually completion, and a very high yield of polyester copolymer can be achieved.
[0050] Based on this, conditions applied during the copolymerization process, such as
pressure and temperature, can be determined by those skilled in the art, particularly taking into account of reaction kinetics and the removal of small molecule by-product.
[0051] For example, the copolymerization can be carried out at 1 atm or a higher or lower pressure.
[0052] For another example, in the presence of a solvent, the copolymerization is carried out at the boiling point of the solvent by refluxing the solvent. In such case, the copolymerization temperature can be around 110.6°C (boiling point of toluene at 1 atm), 138.4°C (boiling point of xylene at 1 atm), or 166.7°C (boiling point of trimethylbenzene at 1 atm), etc. It should be noticed that the boiling point of a solvent is related to the pressure under which the copolymerization is carried out, and the formation of azeotropical mixture with the small molecule by-product such as water.
[0053] For yet another example, in the presence of high boiling solvent or in absence of any solvent, it is also possible to apply a reduced pressure and heating so as to remove the small molecule by-product.
PURIFICATION
[0054] The polyester copolymer can be purified to remove catalyst residue, solvent and by-product from the reaction mixture. Such purification process is also known to those skilled in the art.
[0055] For example, in a typical process for the copolymerization of glycolic acid and e-caprolactone, predetermined amounts of glycolic acid, e-caprolactone, catalyst such as trifluoromethane sulfonic acid and triphenyl phosphine, solvent such as toluene, are added to a closed reaction vessel. The temperature is raised to 130°C and water by-product is removed from the system. The reaction process is monitored by the amount of water removed from the system. When calculated amount of water has been removed, the reaction mixture is allowed to cool down to ambient temperature and the product is purified by, for example, precipitation in cold methanol.
POLYESTER COPOLYMER
[0056] When the copolymerization mixture consists of only two monomers, namely the first monomer and the second monomer as disclosed above, the polyester copolymer produced by the process of the invention should have a backbone consisting of two types of repeating units, which is referred to as the first repeating unit and the second repeating unit, respectively.
[0057] Therefore, the polyester copolymer of the present invention has a backbone
comprising two types of repeating units, the structure of which corresponds to that of the first monomer and the second monomer in the copolymerization mixture.
[0058] That is, the first repeating unit is derived from the first monomer and has Formula (III),
-O-R1-CO- (III) wherein R1 is a C1, C2 or C3 alkylene group; and the second repeating unit is derived from the second monomer and has Formula (IV),
-O-R2-CH2-CO- (IV) wherein R2 is a C2-C20 alkylene group, such as a C2-C13 alkylene group, optionally substituted, for example by a C1-C8 alkyl group, said alkyl group is further substituted, for example by a hydroxyl group, a halogen atom, a nitro group, or a cyano group.
[0059] In one embodiment of the invention, the polyester copolymer has a Tg of -20°C to 10°C and/or a Tm of 120°C to 180°C.
[0060] In one embodiment of the invention, more than 60%, such as more than 80%, such as more than 90% by weight of the polyester copolymer is dissolved in Imol/L sodium hydroxide aqueous solution at room temperature within 10 minutes.
[0061] In one embodiment of the present invention, the polyester copolymer is a copolymer of glycolic acid and e-caprolactone, that is, R1 is -CH2- while R2 is -(CFE)?-, respectively.
[0062] In one embodiment of the present invention, the number average molecular weight of the copolymer of glycolic acid and e-caprolactone is 5,000 to 100,000, such as 10,000 to 50,000.
[0063] When the copolymerization process produces small molecule by-product, and the by-product is removed from the reaction system during the copolymerization process, the copolymerization can proceed virtually to completion. In such case, the molar ratio of the first repeating unit and the second repeating unit is also virtually the same as the molar ratio of the first monomer and the second monomer.
[0064] The properties / performances of the polyester copolymer can be customized by applying a particular first repeating unit and second repeating unit and molar ratio thereof. This can be achieved by applying the corresponding first monomer and second monomer and molar ratio thereof during the copolymerization process.
[0065] Even with the same first repeating unit and second repeating unit and molar ratio thereof, at the same molecular weight of the polyester copolymer, the polyester copolymer
can be significantly different, depending on whether the copolymer is a random copolymer or a block copolymer. This relies on the reactivity ratio of the first and the second monomer.
[0066] The present Inventor has found that, using a carefully selected catalyst, it is possible to obtain a random copolymer. In particular, for example, for the copolymerization of glycolic acid and e-caprolactone, the combination of trifluoromethane sulfonic acid and triphenyl phosphine as catalyst can result in a random copolymer. Those skilled in the art will appreciate that random copolymer is advantageous in that it offers reduced melt temperature (<150°C) and improved toughness.
[0067] The random nature of the polyester copolymer can be demonstrated by analytical methods revealing detailed sequence of the repeating units in the polymer backbone. For example, in Kasperczyk, J. (1999) “Copolymerization of Glycolide and e-caprolactone, 1 - Analysis of the Copolymer Microstructure by Means of JH and 13C NMR Spectroscopy,” Marcomol. Chem. Phys., v.200(4), pp. 903-910 and Bero, M. et al. (1999) “Copolymerization of Glycolide and 8-caprolactone, 2a Random Copolymerization in the Presence of Tin Octoate,” Marcomol. Chem. Phys., v.200(4), pp. 911-916, Janusz Kasperczyk et al. has proposed a 13C-NMR-based method to determine the number of repeating units in a GA block and a CL block of the copolymer of glycolide and 8-caprolactone. Those skilled in the art will understand that such method can be applied to similar copolymers.
[0068] In one embodiment of the present invention, the polyester copolymer of the present invention has an average number of the first repeating unit in blocks made of the first repeating unit only is 2 to 8, such as 2 to 6, such as 2 to 4.
[0069] In one embodiment of the present invention, the polyester copolymer of the present invention has an average number of the second repeating unit in blocks made of the second repeating unit only is 1 to 2, such as 1 to 1.5.
[0070] In one embodiment of the present invention, the polyester copolymer of the present invention has a ratio of the total number of the first repeating unit to the total number of the second repeating unit in one copolymer chain of (70 to 99): (1 to 30), such as (75 to 95):(5 to 25).
[0071] The copolymer will degrade quickly by breaking the ester linkage in the polymer backbone at room temperature under acidic or basic pH. Typically, the degradation products are the first monomer, the second monomer and/or derivatives thereof. For example, when the first and the second monomer is glycolic acid and s-caprolactone, respectively, the degradation product under basic conditions should be sodium glycolate and sodium
5-hydroxyl caproate.
ADDITIVES
[0072] Additives can be added to the copolymerization mixture so as to either improve the copolymerization process or to modify the properties / performances of the polyester copolymer. Such additives are usually not a part of the polyester copolymer, but as an additional component mixed with the polyester copolymer. If the additive is to modify the properties / performances of the polyester copolymer only, it is also possible to add such additives to the polyester copolymer after the completion of the copolymerization process.
[0073] For example, a thermal stabilizer can be applied to improve thermal stability. The thermal stabilizer can be a reagent to deactivate the polymerization catalyst, which is selected from the group consisting of hydrazine compounds having a -CONHNH-CO- unit, such as N,N’-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]-hydrazine;
3-(N-salicyloyl)amino-l,2,4-triazole; and other triazine compounds. The thermal stabilizer can also be other compounds such as phosphoric acid esters having a pentaerythritol skeleton and alkyl phosphate or phosphite esters having at least one hydroxyl group and at least one alkyl ester group.
[0074] For another example, an antioxidant can be applied to improve oxidization stability. The antioxidant can be selected from the group consisting of calcium dodecyl stearate, zinc dodecyl stearate or magnesium lauryl stearate, and phenol-based antioxidant such as octadecyl-3- (3.5-di-/-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis|3-(3.5-di-/-butyl-4-hydroxyphenyl) propionate], and tris-(3.5-di-/-butyl-4-hydroxybenzyl) isocyanurate. The antioxidant can also be a natural antioxidant such as tea polyphenols, pomegranate peel extract, rosemary extract or grape seed extract.
[0075] For yet another example, it is possible to use a filler in order to impart a mechanical strength and other properties to polyester copolymer. The filler can be selected from: fiber or whisker form fillers, such as glass fiber, PAN-based and pitch-based carbon fiber, metal fiber, such as stainless steel fiber, aluminum fiber and brass fiber, natural fiber of chitin, chitosan, cellulose, cotton, etc., organic synthetic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, and silicon nitride whisker; and
powdery, particulate and plate-like fillers of natural inorganic minerals, such as mica, talc, kaolin, silica and sand, calcium carbonate, glass beads, glass flake, glass micro-balloon, clay, molybdenum disulfide, wollastonite, montmorillonite, titanium oxide, zinc oxide, calcium polyphosphate and graphite.
[0076] The filler can be used after surface treatment thereof with known coupling agents, such as silane coupling agents and titanate coupling agents, and other surface treating agents. Further, the glass fiber can be coated or bundled with a thermoplastic resin, such as ethylene/vinyl acetate copolymer, or a thermosetting resin such as epoxy resin.
INDUSTRIAL APPLICATIONS
[0077] The polyester copolymer of the present invention is particularly useful in packaging, such as flexible packaging and rigid packaging such as packaging for food, and in medical applications such as surgical sutures, vascular clamps, patches, staplers, bone nails, and bone plates, and other applications such as consumer goods, shopping bags, fibers, sheets.
[0078] All numerical values within the detailed description herein are modified by “about” before the indicated value, and take into account experimental error and variations that would be expected by those skilled in the art. For example, the numerical value can be within 20%, or 15%, or 10%, or 5%, or even 1% above or below the indicated value.
EXAMPLES
[0079] The following examples demonstrate the advantage of the present invention using, for example, glycolic acid and e-caprolactone as the first and the second monomer, and the combination of trifluoromethane sulfonic acid and triphenyl phosphine as catalyst, and various other aspects of the present invention.
MATERIALS
[0080] Glycolic acid, e-caprolactone, trifluoromethane sulfonic acid and triphenyl phosphine are obtained from Adamas Reagents Co. Ltd., Shanghai, China and are used as received.
[0081] Toluene and xylene are purchased from Sigma-Aldrich and are used as received.
TEST METHODS
[0082] DSC was performed on Perkin Elmer DSC8000 Differential Scanning Calorimeter equipped with a cooling accessary. The melting point Tm is analyzed by peak analysis of the software and glass transition temperature Tg is analyzed by Tg analysis of the software.
[0083] 13C-NMR is recorded on Bruker AVANCE NEO 600MHz.
EXAMPLE 1
COPOLYMERIZATION
[0084] Polyester copolymer of glycolic acid and e-caprolactone was prepared using the combination of trifluoromethane sulfonic acid and triphenylphosphine as catalyst.
[0085] To a 100 ml two-necked flask with a Dean-Stark apparatus, glycolic acid (GA) and e-caprolactone (CL) are added and mixed under stirring with a magnetic stirring bar at 100°C until completely dissolved. Triphenylphosphine (TPP) is dissolved in 3 ml xylene in a small vial and trifluoromethane sulfonic acid (TFA) is added to the vial to form the catalyst mixture. The catalyst mixture is added to the flask quickly and the temperature is raised to 130°C, and vacuum is applied to keep the system at 50 KPa. Water is removed from the Dean-Stark apparatus during the reaction. After reaction for 24 hours, the mixture in the flask was shot to a beaker with cold methanol. The product precipitates as white cloudy solid. The solid is filtered, washed with methanol twice and dried in a vacuum oven at 60°C under vacuum. The reaction details are shown in Table 1. Melting point Tm and glass transition temperature Tg of the product are also listed in Table 1.
DSC ANALYSIS
[0086] DSC analysis was performed to determine melting point Tm and glass transition temperature Tg of the samples. DSC curves are shown in Figure 1.
Table 1. Preparation and DSC analysis of the polyester copolymer
* No crystallization observed
[0087] Clearly, in the copolymerization of glycolic acid and e-caprolactone with various molar ratios, using the combination of trifluoromethane sulfonic acid and triphenylphosphine as catalyst, it is possible to obtain polymers with the different properties such as Tm and Tg.
[0088] It can be seen from Figure 1 that, when the molar ratio of GA:CL is 90:10 (polymer 1, PGACL91), the polymer has a 186°C melting point and around 8°C glass transition point. Decreasing the molar ratio of GA:CL to 80:20 (polymer 2, PGACL82), the melt point and glass transition point will decrease to 155°C and -3°C, respectively. When
the molar ratio of GA:CL reaches to 70:30 (polymer 3, PGACL73), the polymer is totally amorphous and the glass transition point will further decrease to -18°C.
[0089] Clearly, it is possible to customize the properties (such as Tm and Tg) of the polyester copolymer by selecting a proper GA: CL molar ratio. The properties can be made similar to that of commonly used PE (Tm = 160°C, Tg =0°C) and PP (Tm = 110 - 140°C, Tg < 60°C).
[0090] It should be noted that polymer 2 with 155°C melt point and -3°C glass transition temperature is similar to the properties of polypropylene, indicating the opportunity for application penetration.
13C-NMR ANALYSIS
[0091] 13C-NMR analysis was performed in DMSO-d6 to provide insight on the sequence of repeating units in the copolymer backbone. The spectrum is shown in Figure 2.
[0092] The number of repeating units in a GA block and a CL block is determined by the process disclosed in Kasperczyk, J. (1999) “Copolymerization of Glycolide and G-Caprolactone. 1 Analysis of the Copolymer Microstructure by means of JH and 13C NMR Spectroscopy,” Marcomol. Chem. Phys., v.200(4), pp. 903-910 and Bero, M. et al. (1999) “Copolymerization of Glycolide and £-Caprolactone, 2a Random Copolymerization in the Presence of Tin Octoate,” Marcomol. Chem. Phys., v.200(4), pp. 911-916. The result is shown in Table 2. The small number of repeating units in GA blocks and the CL blocks proves that the copolymer is a random copolymer.
Table 2. 13C -NMR analysis of the polyester copolymer
[0093] It should be noticed that, in the example, the molar ratio of repeating unit GA: CL is close to the molar ratio of the first monomer to the second monomer in the copolymerization mixture. This is expected as virtually all the monomers are incorporated into the polymer chain due to the removal of small molecule by-product which shift the reaction equilibrium to the formation of copolymer.
[0094] Small pieces of polymers 1, 2 and 3 are put into aqueous sodium hydroxide
solution (1 mol/L) solution at ambient temperature with stirring. After 10 minutes, the polymer disappeared and a clear solution is obtained, indicating polymer is decomposed into small molecules successfully.
[0095] The procedure is repeated using water instead of aqueous sodium hydroxide solution. The polymer remains insoluble after one hour.
EXAMPLE 2
[0096] The example compares polyester copolymers with repeating units derived from glycolic acid and e-caprolactone which are obtained from different synthetic route.
[0097] The polymerization process in Example 1 is repeated except that glycolide is used as the first monomer and stannous octoate is used as the catalyst. Melting point and glass transition temperature obtained by DSC was shown in Table 3 and is compared with polymers obtained in Example 1.
Table 3. Preparation and DSC analysis of the polyester copolymer by different synthetic route
[0098] Clearly, with GA as the first monomer and the combination of TFA and TPP as catalyst, at the same monomer feed ratio, the polyester copolymer has much lower Tg, indicating better processability of the copolymer.
EXAMPLE 3
[0099] This example demonstrates the copolymerization of monomers other than glycolic acid and e-caprolactone.
[0100] To a 50 ml two-necked flask with a Dean-Stark apparatus, 7.66 g methyl glycolate (MG) and 1.10 g e-caprolactone (CL) are added and mixed under stirring with a magnetic stirring bar. 0.05 g triphenylphosphine (TPP) is dissolved in 3 ml toluene in a small vial and 0.03 g trifluoromethane sulfonic acid (TFA) is added to the vial to form the catalyst mixture. The catalyst mixture is added to the flask quickly and the temperature is raised to 140°C. Toluene and side product methanol are removed from the Dean-Stark apparatus during the reaction. After reaction for 24 hours, the mixture in the flask was shot to a beaker with cold methanol. The product precipitates as white cloudy solid. The solid is filtered, washed with methanol twice and dried in a vacuum oven at 60°C under vacuum. The product shows Tm of 141 °C and Tg of -26°C .
EXAMPLE 4
[0101] This example demonstrates the copolymerization in the presence of catalyst other than the combination of trifluoromethane sulfonic acid and triphenyl phosphine.
[0102] To a 50 ml two-necked flask, 2.00 g glycolic acid (GA), 0.83 g e-caprolactone (CL) are added and mixed under stirring with a magnetic stirring bar at 100°C until completely dissolved. 0.015 g stannous octoate is then added to the flask to start reaction. The reaction is conducted at 150°C for 24 hours. After the reaction, the mixture in the flask was shot to a beaker with cold methanol. The product precipitates as white cloudy solid. The solid is filtered, washed with methanol twice and dried in a vacuum oven at 60°C under vacuum. The product shows Tm of 191 °C and Tg of 11 °C.
[0103] Any alterations, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description without departing from the spirit or scope of the present disclosure and when numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated.
Claims
1. A process for the preparation of a polyester copolymer, which comprises a step of co-polymerizing a first monomer and a second monomer to form the polyester copolymer, wherein: the first monomer is selected from the group consisting of hydroxyl carboxylic acids of Formula (I), C1-C3 alkyl esters of hydroxyl carboxylic acids of Formula (I), and lactides of hydroxyl carboxylic acids of Formula (I),
HO-R1-COOH (I) wherein R1 is selected from a C1, C2 or C3 alkylene group; and the second monomer is a lactone of Formula (II)
wherein R2 is a C2-C20 alkylene group, preferably a C2-C13 alkylene group.
2. The process of claim 1, wherein the first monomer is selected from the group consisting of glycolic acid, methyl glycolate, glycolide, lactic acid, methyl lactate and lactide.
3. The process of claim 1 or 2, wherein the alkylene group of R2 is substituted, for example by a C1-C8 alkyl group, said alkyl group is further substituted, for example by a hydroxyl group, a halogen atom, a nitro group, or a cyano group.
4. The process of any one of claims 1 to 3, wherein the second monomer is selected from the group consisting of y-butyrolactone, y-valerolactone, 5-octalactone, e-caprolactone, co-pentadecalactone, 5-caprinolactone, y-decalactone, and 5-dodecalactone.
5. The process of any one of claims 1 to 4, wherein the molar ratio of the first monomer and the second monomer in the copolymerization mixture is (70 to 99):(1 to 30), preferably (75 to 95):(5 to 25).
6. The process of any one of claims 1 to 5, which is carried out in the presence of a catalyst selected from the group consisting of the combination of an organic sulfonic acid and an organic phosphine, the combination of sulfuric acid and an organic phosphine, stannous oxide, stannous halide, stannous carboxylate, and organic tin compound, such as a catalyst
selected from the group consisting of the combination of trifluoromethane sulfonic acid and triphenylphosphine, the combination of sulfuric acid and triphenylphosphine, stannous chloride, stannous octoate, di-/7-butyl tin diacetate and di-w-butyl tin dilaurate.
7. The process of claim 6, wherein the catalyst is a combination of trifluoromethane sulfonic acid and triphenylphosphine, and the molar ratio of trifluoromethane sulfonic acid and triphenylphosphine is 1 : (0.5 to 2), preferably about 1:1.
8. The process of any one of claims 1 to 7, wherein the molar ratio of the total of the first and the second monomer and the total of the catalyst is 1000:1 to 10:1, preferably 100:(l to 4).
9. The process of any one of claims 1 to 8, which is a bulk polymerization process.
10. The process of any one of claims 1 to 9, which is carried out in the presence of a solvent, preferably toluene, xylene, trimethylbenzene, biphenyl, liquid paraffin, liquid silicone oil, diphenyl ether and anisole, or any alkane with boiling point higher than 100°C.
11. A polyester copolymer obtainable from the process of any one of claims 1 to 10.
12. The polyester copolymer of claim 11, wherein the polyester copolymer has number average molecular weight of 5,000 to 100,000, such as 10,000 to 50,000.
13. The polyester copolymer of claim 11 or 12, wherein the polyester copolymer has a Tg of -50°C to 20°C, preferably -20°C to 10°C; and/or a Tm of 100°C to 180°C, preferably 120°C to 180°C.
14. The polyester copolymer of any one of claims 11 to 13, wherein more than 60%, preferably more than 80%, more preferably more than 90% by weight of the polyester copolymer is dissolved in Imol/L sodium hydroxide aqueous solution at room temperature within 10 minutes.
15. A polyester copolymer, comprising a first repeating unit having Formula (III),
-O-R1-CO- (III) wherein R1 is a C1, C2 or C3 alkylene group; and a second repeating unit having Formula (IV),
-O-R2-CH2-CO- (IV)
wherein R2 is a C2-C20 alkylene group, such as a C2-C13 alkylene group, optionally substituted by a C1-C8 alkyl group or a C1-C8 hydroxyalkyl group.
16. The polyester copolymer of claim 15, wherein R1 is a methylene group or an ethylene group.
17. The polyester copolymer of claim 15 or 16, wherein the alkylene group of R2 is substituted, for example by a C1-C8 alkyl group, said alkyl group is further substituted, for example by a hydroxyl group, a halogen atom, a nitro group, or a cyano group.
18. The polyester copolymer of claim 16 or 17, wherein R2 is selected from the group consisting of -CH2CH2-, -(CH2)3-, -CH2CH2-CH(CH2CH2CH3)-, -(CH2)4-, -(CH2)13-, -CH2CH2-CH((CH2)4CH3)-, -CH2CH2-CH((CH2)5CH3)-, and -CH2CH2-CH((CH2)6CH3)-.
19. The polyester copolymer of any one of claims 16 to 18, wherein the copolymer is a random copolymer.
20. The polyester copolymer of any one of claims 16 to 19, wherein the average number of the first repeating unit in blocks made of the first repeating unit only is 2 to 8, preferably 2 to 6, more preferably 2 to 4.
21. The polyester copolymer of any one of claims 16 to 20, wherein the average number of the second repeating unit in blocks made of the second repeating unit only is 1 to 2, preferably 1 to 1.5.
22. The polyester copolymer of any one of claims 16 to 21, wherein the ratio of the total number of the first repeating unit and the total number of the second repeating unit in one copolymer chain is (70 to 99):(1 to 30), preferably (75 to 95):(5 to 25).
23. The polyester copolymer of any one of claims 16 to 22, wherein the polyester copolymer has a number average molecular weight of 5,000 to 100,000, preferably 10,000 to 50,000.
24. The use of the polyester copolymer of any one of claims 11 to 23, in packing, preferably flexible packaging and rigid packaging, more preferably packaging for food, in medical applications including but not limited to surgical sutures, vascular clamps, patches, staplers, bone nails, and bone plates, and consumer goods, shopping bags, fibers, and sheets.
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| CN101466763A (en) | 2006-06-15 | 2009-06-24 | 国立大学法人京都工芸纤维大学 | Organic acid catalyst for polylactic acid synthesis |
| CN102911347A (en) * | 2012-10-22 | 2013-02-06 | 长沙理工大学 | Method for preparing high molecular weight poly(L-lactide-co-caprolactone) random copolymer |
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| US11078327B2 (en) * | 2017-08-17 | 2021-08-03 | Toray Industries, Inc. | Polyester copolymer and method of producing same |
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2022
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| CN101466763A (en) | 2006-06-15 | 2009-06-24 | 国立大学法人京都工芸纤维大学 | Organic acid catalyst for polylactic acid synthesis |
| CN102911347A (en) * | 2012-10-22 | 2013-02-06 | 长沙理工大学 | Method for preparing high molecular weight poly(L-lactide-co-caprolactone) random copolymer |
| CN106957412A (en) | 2017-03-27 | 2017-07-18 | 苏州岸谷纳米技术有限公司 | It is a kind of biodegradable poly-（Glycolide ε caprolactones）The preparation method of random copolymer |
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| BERO M ET AL: "COPOLYMERIZATION OF GLYCOLIDE AND EPSILON-CAPROLACTONE, 2A. RANDOM COPOLYMERIZATION IN THE PRESENCE OF TIN OCTOATE", MACROMOLECULAR CHEMISTRY AND PHYSICS, WILEY-VCH VERLAG, WEINHEIM, DE, vol. 200, no. 4, 26 March 1999 (1999-03-26), pages 911 - 916, XP000834933, ISSN: 1022-1352, DOI: 10.1002/(SICI)1521-3935(19990401)200:4<911::AID-MACP911>3.3.CO;2-1 * |
| BERO, M. ET AL.: "Copolymerization of Glycolide and ε-caprolactone, 2a Random Copolymerization in the Presence of Tin Octoate", MARCOMOL. CHEM. PHYS., vol. 200, no. 4, 1999, pages 911 - 916, XP000834933, DOI: 10.1002/(SICI)1521-3935(19990401)200:4<911::AID-MACP911>3.3.CO;2-1 |
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