CA3219000A1 - Polyester impact modifiers - Google Patents
Polyester impact modifiers Download PDFInfo
- Publication number
- CA3219000A1 CA3219000A1 CA3219000A CA3219000A CA3219000A1 CA 3219000 A1 CA3219000 A1 CA 3219000A1 CA 3219000 A CA3219000 A CA 3219000A CA 3219000 A CA3219000 A CA 3219000A CA 3219000 A1 CA3219000 A1 CA 3219000A1
- Authority
- CA
- Canada
- Prior art keywords
- acid
- anhydride
- polymer composition
- polyester
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 112
- 239000004609 Impact Modifier Substances 0.000 title description 11
- 239000000203 mixture Substances 0.000 claims abstract description 181
- 229920000642 polymer Polymers 0.000 claims abstract description 151
- -1 poly(lactic acid) Polymers 0.000 claims abstract description 111
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000000178 monomer Substances 0.000 claims abstract description 53
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims abstract description 51
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 49
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 45
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 44
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 43
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 38
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical group C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims abstract description 37
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical group O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims abstract description 36
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract description 30
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 30
- 239000001384 succinic acid Substances 0.000 claims abstract description 30
- 229920002988 biodegradable polymer Polymers 0.000 claims abstract description 26
- 239000004621 biodegradable polymer Substances 0.000 claims abstract description 26
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical group O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims abstract description 20
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 20
- 229960002479 isosorbide Drugs 0.000 claims abstract description 19
- AMOKUAKXKXBFIW-WJDWOHSUSA-N 9-[(z)-non-3-enyl]-10-octylnonadecanedioic acid Chemical compound OC(=O)CCCCCCCCC(CCCCCCCC)C(CCCCCCCC(O)=O)CC\C=C/CCCCC AMOKUAKXKXBFIW-WJDWOHSUSA-N 0.000 claims description 67
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 42
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 39
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 28
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 21
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 17
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 17
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 15
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 15
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 15
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 14
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 14
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 14
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 claims description 14
- 229940100573 methylpropanediol Drugs 0.000 claims description 14
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 14
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 14
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 14
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 12
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 12
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 12
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 claims description 12
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 11
- SJZRECIVHVDYJC-UHFFFAOYSA-M 4-hydroxybutyrate Chemical compound OCCCC([O-])=O SJZRECIVHVDYJC-UHFFFAOYSA-M 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 8
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 7
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 7
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 claims description 7
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical compound CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 claims description 7
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 7
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 7
- 239000001361 adipic acid Substances 0.000 claims description 7
- 235000011037 adipic acid Nutrition 0.000 claims description 7
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 7
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 7
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 claims description 7
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 7
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 7
- NNYHMCFMPHPHOQ-UHFFFAOYSA-N mellitic anhydride Chemical compound O=C1OC(=O)C2=C1C(C(OC1=O)=O)=C1C1=C2C(=O)OC1=O NNYHMCFMPHPHOQ-UHFFFAOYSA-N 0.000 claims description 7
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 7
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 7
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000002667 nucleating agent Substances 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- WXSRRNYRGPTTNP-UHFFFAOYSA-N 3-(hydroxymethyl)pentane-1,5-diol Chemical compound OCCC(CO)CCO WXSRRNYRGPTTNP-UHFFFAOYSA-N 0.000 claims description 5
- WHBMMWSBFZVSSR-UHFFFAOYSA-M 3-hydroxybutyrate Chemical group CC(O)CC([O-])=O WHBMMWSBFZVSSR-UHFFFAOYSA-M 0.000 claims description 4
- HPMGFDVTYHWBAG-UHFFFAOYSA-N 3-hydroxyhexanoic acid Chemical group CCCC(O)CC(O)=O HPMGFDVTYHWBAG-UHFFFAOYSA-N 0.000 claims description 4
- WHBMMWSBFZVSSR-UHFFFAOYSA-N R3HBA Natural products CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 238000010102 injection blow moulding Methods 0.000 claims description 4
- 238000001746 injection moulding Methods 0.000 claims description 4
- 229920009537 polybutylene succinate adipate Polymers 0.000 claims description 4
- 239000011118 polyvinyl acetate Substances 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 4
- 229920001897 terpolymer Polymers 0.000 claims description 4
- 238000003856 thermoforming Methods 0.000 claims description 4
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 229940035437 1,3-propanediol Drugs 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000007795 chemical reaction product Substances 0.000 description 14
- 229920003023 plastic Polymers 0.000 description 13
- 239000004033 plastic Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229910052582 BN Inorganic materials 0.000 description 9
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 6
- 229920001222 biopolymer Polymers 0.000 description 6
- 229940093476 ethylene glycol Drugs 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- PLONEVHFXDFSLA-UHFFFAOYSA-N ethyl hexanoate;tin(2+) Chemical compound [Sn+2].CCCCCC(=O)OCC PLONEVHFXDFSLA-UHFFFAOYSA-N 0.000 description 5
- 229920005692 JONCRYL® Polymers 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- UTPYTEWRMXITIN-YDWXAUTNSA-N 1-methyl-3-[(e)-[(3e)-3-(methylcarbamothioylhydrazinylidene)butan-2-ylidene]amino]thiourea Chemical compound CNC(=S)N\N=C(/C)\C(\C)=N\NC(=S)NC UTPYTEWRMXITIN-YDWXAUTNSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 150000001860 citric acid derivatives Chemical class 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- HJHVQCXHVMGZNC-JCJNLNMISA-M sodium;(2z)-2-[(3r,4s,5s,8s,9s,10s,11r,13r,14s,16s)-16-acetyloxy-3,11-dihydroxy-4,8,10,14-tetramethyl-2,3,4,5,6,7,9,11,12,13,15,16-dodecahydro-1h-cyclopenta[a]phenanthren-17-ylidene]-6-methylhept-5-enoate Chemical compound [Na+].O[C@@H]([C@@H]12)C[C@H]3\C(=C(/CCC=C(C)C)C([O-])=O)[C@@H](OC(C)=O)C[C@]3(C)[C@@]2(C)CC[C@@H]2[C@]1(C)CC[C@@H](O)[C@H]2C HJHVQCXHVMGZNC-JCJNLNMISA-M 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 1
- 229960000367 inositol Drugs 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
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000003903 lactic acid esters Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000005015 poly(hydroxybutyrate) Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940086735 succinate Drugs 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229920003002 synthetic resin 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
- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
A polyester is disclosed which is made up of: (1) from about 15 to about 40 weight percent monomer repeat units of isosorbide; (2) from about 25 to about 60 weight percent monomer repeat units of a dicarboxylic acid or anhydride such as succinic acid or anhydride; and (3) from about 10 to about 20 weight percent monomer repeat units of a polyhydric alcohol such as 1,3 -propan ediol. In some instances, the polymer may also include monomer repeat units of methyl nadic anhydride or nadic anhydride. A polymer composition is also disclosed, which includes the polyester as well as a biodegradable polymer selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoates), and mixtures thereof.
Description
2 POLYESTER IMPACT MODIFIERS
FIELD
10011 This disclosure relates to polyesters suitable for use as impact modifiers and to biodegradable polymeric compositions incorporating such impact modifiers BACKGROUND
10021 For decades, petroleum-based polymers such as polyethylene (PE), polypropylene (PP), or polyethylene terephthalate (PET) have been used for a wide variety of applications.
While these polymers may provide good strength, barrier, and/or printability characteristics, unfortunately, such polymers do not readily degrade or decompose after disposal ¨ either in landfills or by home composting techniques. Thus, films, bags, and other materials made from such polymers may exist in landfills for centuries after disposal.
10031 Consequently, there is an increasing demand for alternative polymers which may be biosourced, biodegradable, and/or compostable. Examples of such polymers include poly(lactic acid) and poly(hydroxyalkanoates). While these biopolymers offer clear advantages in biodegradability and/or compostability, it is typically desirable to blend various additives with the biopolymers to improve the physical properties of the biopolymers.
10041 If the additives blended into the biopolymers are not biodegradable and/or not compostable, then the biopolymer's environmental benefits are reduced.
Consequently, it would be desirable to provide additives for use with biopolymers, such as incorporating poly(lactic acid) and poly(hydroxyalkanoates), which are themselves biodegradable and/or compostable.
SUMMARY OF THE INVENTION
10051 The above and other needs are met by a compostable polyester according to the present disclosure.
10061 In a first aspect, the present disclosure provides a polyester.
According to certain embodiments, this polyester is made up of: (1) from about 15 to about 40 weight percent monomer repeat units of isosorbide; (2) from about 25 to about 60 weight percent monomer repeat units of a dicarboxylic acid or anhydride; and (3) from about 10 to about 20 weight percent monomer repeat units of a polyhydric alcohol. All of these weight percentages are based on the total weight on the polyester.
10071 The polyester also has a weight average molecular weight of at least 8000 Daltons, as determined by ASTM D5296-05. More preferably, the polyester has a weight average molecular weight from about 10,000 to about 15,000 Daltons, as determined by ASTM
D5296-05.
10081 In certain embodiments, the dicarboxylic acid or anhydride is preferably selected from the group consisting of succinic acid, succinic anhydride, glutaric acid, pimelic acid, undccanoic acid, dodccanoic acid, dodccancdioic acid, subcric acid, azclaic acid, scbacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, terephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalic dicarboxylic acid, 1,8-dimethyl naphthalate, dimethyl isophthalate, phthalic acid, pyromellitic anhydride, mellitic anhydride, mellitic acid, trimellitic anhydride, 3,3'4,4'-benzophenone tetracarboxylic anhydride,
FIELD
10011 This disclosure relates to polyesters suitable for use as impact modifiers and to biodegradable polymeric compositions incorporating such impact modifiers BACKGROUND
10021 For decades, petroleum-based polymers such as polyethylene (PE), polypropylene (PP), or polyethylene terephthalate (PET) have been used for a wide variety of applications.
While these polymers may provide good strength, barrier, and/or printability characteristics, unfortunately, such polymers do not readily degrade or decompose after disposal ¨ either in landfills or by home composting techniques. Thus, films, bags, and other materials made from such polymers may exist in landfills for centuries after disposal.
10031 Consequently, there is an increasing demand for alternative polymers which may be biosourced, biodegradable, and/or compostable. Examples of such polymers include poly(lactic acid) and poly(hydroxyalkanoates). While these biopolymers offer clear advantages in biodegradability and/or compostability, it is typically desirable to blend various additives with the biopolymers to improve the physical properties of the biopolymers.
10041 If the additives blended into the biopolymers are not biodegradable and/or not compostable, then the biopolymer's environmental benefits are reduced.
Consequently, it would be desirable to provide additives for use with biopolymers, such as incorporating poly(lactic acid) and poly(hydroxyalkanoates), which are themselves biodegradable and/or compostable.
SUMMARY OF THE INVENTION
10051 The above and other needs are met by a compostable polyester according to the present disclosure.
10061 In a first aspect, the present disclosure provides a polyester.
According to certain embodiments, this polyester is made up of: (1) from about 15 to about 40 weight percent monomer repeat units of isosorbide; (2) from about 25 to about 60 weight percent monomer repeat units of a dicarboxylic acid or anhydride; and (3) from about 10 to about 20 weight percent monomer repeat units of a polyhydric alcohol. All of these weight percentages are based on the total weight on the polyester.
10071 The polyester also has a weight average molecular weight of at least 8000 Daltons, as determined by ASTM D5296-05. More preferably, the polyester has a weight average molecular weight from about 10,000 to about 15,000 Daltons, as determined by ASTM
D5296-05.
10081 In certain embodiments, the dicarboxylic acid or anhydride is preferably selected from the group consisting of succinic acid, succinic anhydride, glutaric acid, pimelic acid, undccanoic acid, dodccanoic acid, dodccancdioic acid, subcric acid, azclaic acid, scbacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, terephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalic dicarboxylic acid, 1,8-dimethyl naphthalate, dimethyl isophthalate, phthalic acid, pyromellitic anhydride, mellitic anhydride, mellitic acid, trimellitic anhydride, 3,3'4,4'-benzophenone tetracarboxylic anhydride,
3,3'4,4'-benzophenone tetracarboxylic acid, trimellitic acid, nadic anhydride, methyl nadic anhydride, C36 dimer acid, partially hydrogenated C36 dimer acid, polyethylene terephthalate recycled polymer, polybutylene terephthalate recycled polymer, polyethylene terephthalate virgin polymer, polybutylene terephthalate virgin polymer, and mixtures thereof 10091 More preferably, the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadic anhydride, methyl nadic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof [010] In a particularly preferred embodiment, the dicarboxylic acid or anhydride is made up of a mixture of (1) succinic acid or succinic anhydride and (2) nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof For this embodiment, the polyester is preferably from about 25to about 35 weight percent succinic acid or succinic anhydride and from about 10 to about 25 weight percent nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.
[011] In some embodiments, the polyhydric alcohol is preferably selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, 1,1,1-trimethylol ethane, 1,2,3-trimethylolpropane, methyl propanediol, pentaerythritol, and poly(oxyalkylene) polyols comprising monomer repeat units of ethylene oxide, propylene oxide, or butylene oxide, and mixtures thereof.
10121 More preferably, the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methyl propanediol, and mixtures thereof Even more preferably, the polyhydric alcohol includes 1,3-propanediol.
[013] In some instances, the dicarboxylic acid or anhydride preferably includes succinic acid or anhydride, and the polyhydric alcohol preferably includes 1,3-propanediol.
10141 In an alternative embodiment, the isosorbide may be omitted from the polyester.
In such instances, the polyester is made up of: (1) from about 35 to about 65 weight percent monomer repeat units of a dicarboxylic acid or anhydride selected from the group consisting of the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadic anhydride, methyl nadic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof;
and (2) from about 35 to about 65 weight percent monomer repeat units of a polyhydric alcohol.
10151 In a preferred embodiment, the dicarboxylic acid or anhydride is made up of a mixture of (1) succinic acid or succinic anhydride and (2) nadic anhydride, methyl nadic
[011] In some embodiments, the polyhydric alcohol is preferably selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, 1,1,1-trimethylol ethane, 1,2,3-trimethylolpropane, methyl propanediol, pentaerythritol, and poly(oxyalkylene) polyols comprising monomer repeat units of ethylene oxide, propylene oxide, or butylene oxide, and mixtures thereof.
10121 More preferably, the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methyl propanediol, and mixtures thereof Even more preferably, the polyhydric alcohol includes 1,3-propanediol.
[013] In some instances, the dicarboxylic acid or anhydride preferably includes succinic acid or anhydride, and the polyhydric alcohol preferably includes 1,3-propanediol.
10141 In an alternative embodiment, the isosorbide may be omitted from the polyester.
In such instances, the polyester is made up of: (1) from about 35 to about 65 weight percent monomer repeat units of a dicarboxylic acid or anhydride selected from the group consisting of the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadic anhydride, methyl nadic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof;
and (2) from about 35 to about 65 weight percent monomer repeat units of a polyhydric alcohol.
10151 In a preferred embodiment, the dicarboxylic acid or anhydride is made up of a mixture of (1) succinic acid or succinic anhydride and (2) nadic anhydride, methyl nadic
4 anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof.
For this embodiment, the polyester is preferably from about 30 to about 40 weight percent succinic acid or succinic anhydride and from about 10 to about 20 weight percent nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.
10161 Suitable polyhydric alcohols for this alternative polyester are the same as the polyhydric alcohols noted above for the polyester, including the isosorbide.
Also, for the alternative polyester, the weight average molecular weight of the polyester is at least 8000 Daltons, as determined by ASTM D5296-05. More preferably, the polyester has a weight average molecular weight from about 10,000 to about 15,000 Daltons, as determined by ASTM D5296-05.
10171 In a second aspect, the present disclosure provides a polymer composition. The polymer composition typically includes from about 50 to about 95 weight percent of a biodegradable polymer selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoates), and mixtures thereof. The polymer composition also includes from about 5 to about 50 weight percent of an impact modifying polyester. The impact modifying polyester, in turn, is made up of: (1) from about 15 to about 40 weight percent monomer repeat units of isosorbide, based on the total weight of the polyester; (2) from about 25 to about 60 weight percent monomer repeat units of a dicarboxylic acid or anhydride, based on the total weight of the polyester; and (3) from about 10 to about 20 weight percent monomer repeat units of a polyhydric alcohol, based on the total weight of the polyester. The impact modifying polyester also has a weight average molecular weight of at least 8000 Daltons, as determined by ASTM D5296-05.
10181 In certain embodiments, the dicarboxylic acid or anhydride is preferably selected from the group consisting of succinic acid, succinic anhydride, glutaric acid, pimelic acid, undecanoic acid, dodecanoic acid, dodecanedioic acid, suberic acid, azelaic acid, sebacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, terephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalic dicarboxylic acid, 1,8-dimethyl naphthalate, dimethyl isophthalate, phthalic acid, pyromellitic anhydride, mellitic anhydride, mellitic acid, trimellitic anhydride, 3,3'4,4'-benzophenone tetracarboxylic anhydride, 3,34,4'-benzophenone tetracarboxylic acid, trimellitic acid, nadic anhydride, methyl nadic anhydride, C36 dimer acid, partially hydrogenated C36 dimer acid, polyethylene terephthalate recycled polymer, polybutylene terephthalate recycled polymer, polyethylene terephthal ate virgin polymer, polybutyl ene terephthalate virgin polymer, and mixtures thereof 10191 More preferably, the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadic anhydride, methyl nadic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof.
10201 In a particularly preferred embodiment, the dicarboxylic acid or anhydride is made up of a mixture of (1) succinic acid or succinic anhydride and (2) nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof For this embodiment, the polyester is preferably from about 25 to about 35 weight percent succinic acid or succinic anhydride and from about 10 to about 25 weight percent nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.
10211 In some embodiments, the polyhydric alcohol is preferably selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropyl ene glycol, tri m ethyl ene glycol, 1,1,1-tri m ethyl ol ethane, 1,2,3 -trimethylolpropane, methyl propanediol, pentaerythritc-)1, and pc-dy(oxyalkylene) polyols comprising monomer repeat units of ethylene oxide, propylene oxide, or butylene oxide, and mixtures thereof.
10221 More preferably, the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methyl propanediol, and mixtures thereof Even more preferably, the polyhydric alcohol includes 1,3-propanediol.
10231 In some instances, the dicarboxylic acid or anhydride preferably includes succinic acid or anhydride, and the polyhydric alcohol preferably includes 1,3-propanediol.
10241 According to certain embodiments, the polymer composition more preferably includes from about 60 to about 85 weight percent of the biodegradable polymer and from about 5 to about 30 weight percent of the impact modifying polyester. Even more preferably, the polymer composition includes from about 7.5 to about 15 weight percent of the impact modifying polyester.
10251 In some instances, the biodegradable polymer preferably includes poly(lactic acid).
In other embodiments, the biodegradable polymer preferably includes at least one poly(hydroxyalkanoate). In some embodiments, the biodegradable polymer preferably includes a mixture of poly(lactic acid) and poly(hydroxyalkanoates). For instance, in some embodiments, the polymer composition may include from about 5 to about 25 weight percent of poly(lactic acid) and from about 70 to about 90 weight percent of at least one poly(hydroxyalkanoate), based on the total weight of the polymer composition.
10261 According to certain embodiments wherein the polymer composition includes a poly(hydroxyalkanoate), the at least one poly(hydroxyalkanoate) is preferably made up of poly-3 -hydroxybutyrate-co-3 -hy droxyhexan oate ("P(3HB-co-3HHx)").
10271 In some instances, this (3HB-co-3HHx) is preferably made up of from about 75 to about 99 mole percent hydroxybutyrate and from about 1 to about 25 mole percent hydroxyhexanoate. More preferably, the (3HB-co-31-111x) is made up of from about 93 to about 98 mole percent hydroxybutyrate and from about 2 to about 7 mole percent hy droxyh ex an oate.
10281 In still other embodiments, the at least one poly(hydroxyalkanoate) may include a terpolymer made up from about 75 to about 99.9 mole percent monomer repeat units of 3-hydroxybutyrate, from about 0.1 to about 25 mole percent monomer repeat units of 3-hydroxyhexanoate, and from about 0.1 to about 25 mole percent monomer repeat units of a third 3-hydoxyalkanoate having from 5 to 12 carbon atoms.
10291 According to certain embodiments the at least one poly(hydroxyalkanoate) preferably has a weight average molecular weight from about 50,000 Daltons to about 2.5 million Daltons, as determined by ASTM D5296-05. More preferably, the at least one poly(hydroxyalkanoate) has a weight average molecular weight from about 500,000 Daltons to about 750,000 Daltons, as determined by ASTM D5296-05.
10301 The polymer composition may also include further additives. In some embodiments, the polymer compositions may also include from about 1 to about 10 weight percent of at least one plasticizer; from about 0.1 to about 5 weight percent of at least one nucleating agent; and from about 0.1 to about 10 weight percent of a filler.
10311 In some instances, the polymer composition may include an additional biodegradable polymer besides poly(lactic acid) and/or poly(hydroxyalkanoates). Thus, in certain embodiments, the polymer composition may also include comprising from about 5 to about 50 weight percent of at least one biodegradable polymer selected from the group consisting of pol y(caprol actone), p oly(ethyl en e sebacate), poly(butyl en e succi nate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate) and mixtures thereof.
10321 According to certain embodiments, the polymer composition is preferably biodegradable as determined using ASTM standard D5988. Further, in some embodiments, the polymer composition is preferably home compostable as determined using ASTM
standard D6868.
10331 The present disclosure also provides various end-use products which may be formed from the aforementioned polymer composition.
Thus, according to one embodiment, the present disclosure provides a molded sheet made up of the polymer composition. In a second embodiment, the present disclosure provides a molded article made up of the polymer composition, wherein the molded article is formed by thermoforming, injection molding, or blow molding. In another embodiment, the present disclosure provides a film made up of the polymer composition, wherein the film is a blown film or a cast film. In still another embodiment, the present disclosure provides a fiber made up of the polymer composition.
DETAILED DESCRIPTION
10341 The present disclosure first provides novel polyesters which are suitable for use as impact modifiers in biodegradable and/or compostable polymer compositions.
10351 In general, the polyester is made up of at least three different types of monomer repeat units, which are derived from: (1) isosorbide; (2) succinic acid or anhydride; and (3) 1,3-propanediol. In terms of amounts, the polyester is typically made up of:
(1) from about 15 to about 40 weight percent monomer repeat units of isosorbide; (2) from about 25 to about 60 weight percent monomer repeat units of a dicarboxylic acid or anhydride; and (3) from about 10 to about 20 weight percent monomer repeat units of a polyhydric alcohol.
10361 A variety of dicarboxylic acids and anhydrides are believed to be suitable for use in the preparation of the polyester. For example, the dicarboxylic acid or anhydride may be suitably selected from the group consisting of succinic acid, succinic anhydride, glutaric acid, pimelic acid, undecanoic acid, dodecanoic acid, dodecanedioic acid, suberic acid, azelaic acid, sebacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, terephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalic dicarboxylic acid, 1,8-dimethyl naphthalate, dimethyl isophthalate, phthalic acid, pyromellitic anhydride, mellitic anhydride, mellitic acid, trimellitic anhydride, 3,3'4,4'-benzophenone tetracarboxylic anhydride, 3,3'4,4'-benzophenone tetracarboxylic acid, trimellitic acid, nadic anhydride, methyl nadic anhydride, C36 dimer acid, partially hydrogenated C36 dim er acid, polyethylene terephthal ate recycled polymer, polybutylene terephthal ate recycled polymer, polyethylene terephth al ate virgin polymer, polybutylene terephthal ate virgin polymer, and mixtures thereof.
10371 More preferably, the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadic anhydride, methyl nadic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof.
10381 In a particularly preferred embodiment, the dicarboxylic acid or anhydride is made up of a mixture of (1) succinic acid or succinic anhydride and (2) nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof For this embodiment, the polyester is preferably from about 25 to about 35 weight percent succinic acid or succinic anhydride and from about 10 to about 25weight percent nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.
10391 A range of polyhydric alcohols is also believed to be suitable for the polyester.
Examples of suitable polyhydric alcohols may be selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, 1,1,1-trimethylol ethane, 1,2,3-trimethylolpropane, methyl propanediol, pentaerythritol, and poly(oxyalkylene) polyols comprising monomer repeat units of ethylene oxide, propylene oxide, or butylene oxide, and mixtures thereof.
10401 More preferably, the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methyl propanediol, and mixtures thereof Still more preferably, the polyhydric alcohol comprises 1,3-propanediol.
10411 In a particularly preferred embodiment, the dicarboxylic acid or anhydride preferably comprises succinic acid or anhydride, and the polyhydric alcohol preferably comprises 1,3-propanediol.
10421 The polyester also has a weight average molecular weight of at least 8000 Daltons, as determined by ASTM D5296-05. More preferably, the polyester has a weight average molecular weight from about 10,000 to about 15,000 Daltons, as determined by A
STM
D5296-05.
10431 In general, the polyesters may be prepared by charging isosorbide to a reaction flask or other reactor, complete with a nitrogen inlet, vacuum capability, heating, and agitation.
First, the isosorbide is melted and then vacuum degassed as a molten mass Subsequently, diacids are added, and the contents of the flask are reacted at temperatures of up to 220 C
until water evolution slows, at which time all remaining glycols are charged.
Esterification is completed at temperatures of up to 220 C and vacuum pressures as low as 3.3 kPa.
10441 In an alternative embodiment, the isosorbide may be omitted from the polyester.
In such instances, the polyester is made up of: (1) from about 35 to about 65 weight percent monomer repeat units of a dicarboxylic acid or anhydride selected from the group consisting of the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadic anhydride, methyl nadic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof;
and (2) from about 35 to about 65 weight percent monomer repeat units of a polyhydric alcohol.
10451 In a preferred embodiment, the dicarboxylic acid or anhydride is made up of a mixture of (1) succinic acid or succinic anhydride and (2) nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof For this embodiment, the polyester is preferably from about 30 to about 40 weight percent succinic acid or succinic anhydride and from about 10 to about 20 weight percent nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.
10461 Suitable polyhydric alcohols for this alternative polyester are the same as the polyhydric alcohols noted above for the polyester, including the isosorbide.
Also, for the alternative polyester, the weight average molecular weight of the polyester is at least 8000 Daltons, as determined by ASTM D5296-05. More preferably, the polyester has a weight average molecular weight from about 10,000 to about 15,000 Daltons, as determined by ASTM D5296-05.
10471 The polyesters, according to the present disclosure, are suitable for use as impact modifiers in polymer compositions. As used herein, an "impact modifier" is an additive used to improve the durability and toughness of a polymer resin, whereby toughness is measured as the area underneath the stress-strain curve of a standard tensile elongation and modulus test. In addition, the toughness of a polymer can be correlated by the testing via a notched Izod test. A polymer exhibiting a higher impact number would indicate increased toughness.
10481 The polyesters, according to the present disclosure, are also preferably biodegradable as determined using ASTM standard D5511. Further, in some embodiments, the polyesters are preferably home compostable as determined using ASTM
standard D6868.
10491 The present disclosure also provides a polymer composition that includes a polyester as described. In general, the polymer composition combines the impact modifier polyester with at least one biodegradable polymer selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoates), and mixtures thereof. Typically, the polymer composition includes from about 5 to about 50 weight percent of the impact modifying polyester and from about 50 to about 95 weight percent of the biodegradable polymer selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoates), and mixtures thereof 10501 The polymer composition more preferably includes from about 60 to about weight percent of the biodegradable polymer and from about 5 to about 30 weight percent of the impact modifying polyester. Still more preferably, the polymer composition includes from about 7.5 to about 15 weight percent of the impact modifying polyester.
10511 Again, the impact modifier used in the polymer composition is a polyester in accordance with the foregoing disclosure. Thus, the impact modifying polyester is made up of: (1) from about 15 to about 40 weight percent monomer repeat units of isosorbide;
(2) from about 25 to about 60 weight percent monomer repeat units of a dicarboxylic acid or anhydride; and (3) from about 10 to about 20 weight percent monomer repeat units of a polyhydric alcohol. The impact modifying polyester also has a weight average molecular weight of at least g000 Daltons, as determined by ASTM D5296-05 10521 In some instances, the biodegradable polymer preferably includes poly(lactic acid).
In other embodiments, the biodegradable polymer preferably includes at least one poly(hydroxyalkanoate). Moreover, in certain embodiments, the biodegradable polymer preferably includes a mixture of poly(lactic acid) and poly(hydroxyalkanoates). For instance, in some embodiments, the polymer composition may include from about
For this embodiment, the polyester is preferably from about 30 to about 40 weight percent succinic acid or succinic anhydride and from about 10 to about 20 weight percent nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.
10161 Suitable polyhydric alcohols for this alternative polyester are the same as the polyhydric alcohols noted above for the polyester, including the isosorbide.
Also, for the alternative polyester, the weight average molecular weight of the polyester is at least 8000 Daltons, as determined by ASTM D5296-05. More preferably, the polyester has a weight average molecular weight from about 10,000 to about 15,000 Daltons, as determined by ASTM D5296-05.
10171 In a second aspect, the present disclosure provides a polymer composition. The polymer composition typically includes from about 50 to about 95 weight percent of a biodegradable polymer selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoates), and mixtures thereof. The polymer composition also includes from about 5 to about 50 weight percent of an impact modifying polyester. The impact modifying polyester, in turn, is made up of: (1) from about 15 to about 40 weight percent monomer repeat units of isosorbide, based on the total weight of the polyester; (2) from about 25 to about 60 weight percent monomer repeat units of a dicarboxylic acid or anhydride, based on the total weight of the polyester; and (3) from about 10 to about 20 weight percent monomer repeat units of a polyhydric alcohol, based on the total weight of the polyester. The impact modifying polyester also has a weight average molecular weight of at least 8000 Daltons, as determined by ASTM D5296-05.
10181 In certain embodiments, the dicarboxylic acid or anhydride is preferably selected from the group consisting of succinic acid, succinic anhydride, glutaric acid, pimelic acid, undecanoic acid, dodecanoic acid, dodecanedioic acid, suberic acid, azelaic acid, sebacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, terephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalic dicarboxylic acid, 1,8-dimethyl naphthalate, dimethyl isophthalate, phthalic acid, pyromellitic anhydride, mellitic anhydride, mellitic acid, trimellitic anhydride, 3,3'4,4'-benzophenone tetracarboxylic anhydride, 3,34,4'-benzophenone tetracarboxylic acid, trimellitic acid, nadic anhydride, methyl nadic anhydride, C36 dimer acid, partially hydrogenated C36 dimer acid, polyethylene terephthalate recycled polymer, polybutylene terephthalate recycled polymer, polyethylene terephthal ate virgin polymer, polybutyl ene terephthalate virgin polymer, and mixtures thereof 10191 More preferably, the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadic anhydride, methyl nadic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof.
10201 In a particularly preferred embodiment, the dicarboxylic acid or anhydride is made up of a mixture of (1) succinic acid or succinic anhydride and (2) nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof For this embodiment, the polyester is preferably from about 25 to about 35 weight percent succinic acid or succinic anhydride and from about 10 to about 25 weight percent nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.
10211 In some embodiments, the polyhydric alcohol is preferably selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropyl ene glycol, tri m ethyl ene glycol, 1,1,1-tri m ethyl ol ethane, 1,2,3 -trimethylolpropane, methyl propanediol, pentaerythritc-)1, and pc-dy(oxyalkylene) polyols comprising monomer repeat units of ethylene oxide, propylene oxide, or butylene oxide, and mixtures thereof.
10221 More preferably, the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methyl propanediol, and mixtures thereof Even more preferably, the polyhydric alcohol includes 1,3-propanediol.
10231 In some instances, the dicarboxylic acid or anhydride preferably includes succinic acid or anhydride, and the polyhydric alcohol preferably includes 1,3-propanediol.
10241 According to certain embodiments, the polymer composition more preferably includes from about 60 to about 85 weight percent of the biodegradable polymer and from about 5 to about 30 weight percent of the impact modifying polyester. Even more preferably, the polymer composition includes from about 7.5 to about 15 weight percent of the impact modifying polyester.
10251 In some instances, the biodegradable polymer preferably includes poly(lactic acid).
In other embodiments, the biodegradable polymer preferably includes at least one poly(hydroxyalkanoate). In some embodiments, the biodegradable polymer preferably includes a mixture of poly(lactic acid) and poly(hydroxyalkanoates). For instance, in some embodiments, the polymer composition may include from about 5 to about 25 weight percent of poly(lactic acid) and from about 70 to about 90 weight percent of at least one poly(hydroxyalkanoate), based on the total weight of the polymer composition.
10261 According to certain embodiments wherein the polymer composition includes a poly(hydroxyalkanoate), the at least one poly(hydroxyalkanoate) is preferably made up of poly-3 -hydroxybutyrate-co-3 -hy droxyhexan oate ("P(3HB-co-3HHx)").
10271 In some instances, this (3HB-co-3HHx) is preferably made up of from about 75 to about 99 mole percent hydroxybutyrate and from about 1 to about 25 mole percent hydroxyhexanoate. More preferably, the (3HB-co-31-111x) is made up of from about 93 to about 98 mole percent hydroxybutyrate and from about 2 to about 7 mole percent hy droxyh ex an oate.
10281 In still other embodiments, the at least one poly(hydroxyalkanoate) may include a terpolymer made up from about 75 to about 99.9 mole percent monomer repeat units of 3-hydroxybutyrate, from about 0.1 to about 25 mole percent monomer repeat units of 3-hydroxyhexanoate, and from about 0.1 to about 25 mole percent monomer repeat units of a third 3-hydoxyalkanoate having from 5 to 12 carbon atoms.
10291 According to certain embodiments the at least one poly(hydroxyalkanoate) preferably has a weight average molecular weight from about 50,000 Daltons to about 2.5 million Daltons, as determined by ASTM D5296-05. More preferably, the at least one poly(hydroxyalkanoate) has a weight average molecular weight from about 500,000 Daltons to about 750,000 Daltons, as determined by ASTM D5296-05.
10301 The polymer composition may also include further additives. In some embodiments, the polymer compositions may also include from about 1 to about 10 weight percent of at least one plasticizer; from about 0.1 to about 5 weight percent of at least one nucleating agent; and from about 0.1 to about 10 weight percent of a filler.
10311 In some instances, the polymer composition may include an additional biodegradable polymer besides poly(lactic acid) and/or poly(hydroxyalkanoates). Thus, in certain embodiments, the polymer composition may also include comprising from about 5 to about 50 weight percent of at least one biodegradable polymer selected from the group consisting of pol y(caprol actone), p oly(ethyl en e sebacate), poly(butyl en e succi nate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate) and mixtures thereof.
10321 According to certain embodiments, the polymer composition is preferably biodegradable as determined using ASTM standard D5988. Further, in some embodiments, the polymer composition is preferably home compostable as determined using ASTM
standard D6868.
10331 The present disclosure also provides various end-use products which may be formed from the aforementioned polymer composition.
Thus, according to one embodiment, the present disclosure provides a molded sheet made up of the polymer composition. In a second embodiment, the present disclosure provides a molded article made up of the polymer composition, wherein the molded article is formed by thermoforming, injection molding, or blow molding. In another embodiment, the present disclosure provides a film made up of the polymer composition, wherein the film is a blown film or a cast film. In still another embodiment, the present disclosure provides a fiber made up of the polymer composition.
DETAILED DESCRIPTION
10341 The present disclosure first provides novel polyesters which are suitable for use as impact modifiers in biodegradable and/or compostable polymer compositions.
10351 In general, the polyester is made up of at least three different types of monomer repeat units, which are derived from: (1) isosorbide; (2) succinic acid or anhydride; and (3) 1,3-propanediol. In terms of amounts, the polyester is typically made up of:
(1) from about 15 to about 40 weight percent monomer repeat units of isosorbide; (2) from about 25 to about 60 weight percent monomer repeat units of a dicarboxylic acid or anhydride; and (3) from about 10 to about 20 weight percent monomer repeat units of a polyhydric alcohol.
10361 A variety of dicarboxylic acids and anhydrides are believed to be suitable for use in the preparation of the polyester. For example, the dicarboxylic acid or anhydride may be suitably selected from the group consisting of succinic acid, succinic anhydride, glutaric acid, pimelic acid, undecanoic acid, dodecanoic acid, dodecanedioic acid, suberic acid, azelaic acid, sebacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, terephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalic dicarboxylic acid, 1,8-dimethyl naphthalate, dimethyl isophthalate, phthalic acid, pyromellitic anhydride, mellitic anhydride, mellitic acid, trimellitic anhydride, 3,3'4,4'-benzophenone tetracarboxylic anhydride, 3,3'4,4'-benzophenone tetracarboxylic acid, trimellitic acid, nadic anhydride, methyl nadic anhydride, C36 dimer acid, partially hydrogenated C36 dim er acid, polyethylene terephthal ate recycled polymer, polybutylene terephthal ate recycled polymer, polyethylene terephth al ate virgin polymer, polybutylene terephthal ate virgin polymer, and mixtures thereof.
10371 More preferably, the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadic anhydride, methyl nadic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof.
10381 In a particularly preferred embodiment, the dicarboxylic acid or anhydride is made up of a mixture of (1) succinic acid or succinic anhydride and (2) nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof For this embodiment, the polyester is preferably from about 25 to about 35 weight percent succinic acid or succinic anhydride and from about 10 to about 25weight percent nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.
10391 A range of polyhydric alcohols is also believed to be suitable for the polyester.
Examples of suitable polyhydric alcohols may be selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, 1,1,1-trimethylol ethane, 1,2,3-trimethylolpropane, methyl propanediol, pentaerythritol, and poly(oxyalkylene) polyols comprising monomer repeat units of ethylene oxide, propylene oxide, or butylene oxide, and mixtures thereof.
10401 More preferably, the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methyl propanediol, and mixtures thereof Still more preferably, the polyhydric alcohol comprises 1,3-propanediol.
10411 In a particularly preferred embodiment, the dicarboxylic acid or anhydride preferably comprises succinic acid or anhydride, and the polyhydric alcohol preferably comprises 1,3-propanediol.
10421 The polyester also has a weight average molecular weight of at least 8000 Daltons, as determined by ASTM D5296-05. More preferably, the polyester has a weight average molecular weight from about 10,000 to about 15,000 Daltons, as determined by A
STM
D5296-05.
10431 In general, the polyesters may be prepared by charging isosorbide to a reaction flask or other reactor, complete with a nitrogen inlet, vacuum capability, heating, and agitation.
First, the isosorbide is melted and then vacuum degassed as a molten mass Subsequently, diacids are added, and the contents of the flask are reacted at temperatures of up to 220 C
until water evolution slows, at which time all remaining glycols are charged.
Esterification is completed at temperatures of up to 220 C and vacuum pressures as low as 3.3 kPa.
10441 In an alternative embodiment, the isosorbide may be omitted from the polyester.
In such instances, the polyester is made up of: (1) from about 35 to about 65 weight percent monomer repeat units of a dicarboxylic acid or anhydride selected from the group consisting of the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadic anhydride, methyl nadic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof;
and (2) from about 35 to about 65 weight percent monomer repeat units of a polyhydric alcohol.
10451 In a preferred embodiment, the dicarboxylic acid or anhydride is made up of a mixture of (1) succinic acid or succinic anhydride and (2) nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof For this embodiment, the polyester is preferably from about 30 to about 40 weight percent succinic acid or succinic anhydride and from about 10 to about 20 weight percent nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.
10461 Suitable polyhydric alcohols for this alternative polyester are the same as the polyhydric alcohols noted above for the polyester, including the isosorbide.
Also, for the alternative polyester, the weight average molecular weight of the polyester is at least 8000 Daltons, as determined by ASTM D5296-05. More preferably, the polyester has a weight average molecular weight from about 10,000 to about 15,000 Daltons, as determined by ASTM D5296-05.
10471 The polyesters, according to the present disclosure, are suitable for use as impact modifiers in polymer compositions. As used herein, an "impact modifier" is an additive used to improve the durability and toughness of a polymer resin, whereby toughness is measured as the area underneath the stress-strain curve of a standard tensile elongation and modulus test. In addition, the toughness of a polymer can be correlated by the testing via a notched Izod test. A polymer exhibiting a higher impact number would indicate increased toughness.
10481 The polyesters, according to the present disclosure, are also preferably biodegradable as determined using ASTM standard D5511. Further, in some embodiments, the polyesters are preferably home compostable as determined using ASTM
standard D6868.
10491 The present disclosure also provides a polymer composition that includes a polyester as described. In general, the polymer composition combines the impact modifier polyester with at least one biodegradable polymer selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoates), and mixtures thereof. Typically, the polymer composition includes from about 5 to about 50 weight percent of the impact modifying polyester and from about 50 to about 95 weight percent of the biodegradable polymer selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoates), and mixtures thereof 10501 The polymer composition more preferably includes from about 60 to about weight percent of the biodegradable polymer and from about 5 to about 30 weight percent of the impact modifying polyester. Still more preferably, the polymer composition includes from about 7.5 to about 15 weight percent of the impact modifying polyester.
10511 Again, the impact modifier used in the polymer composition is a polyester in accordance with the foregoing disclosure. Thus, the impact modifying polyester is made up of: (1) from about 15 to about 40 weight percent monomer repeat units of isosorbide;
(2) from about 25 to about 60 weight percent monomer repeat units of a dicarboxylic acid or anhydride; and (3) from about 10 to about 20 weight percent monomer repeat units of a polyhydric alcohol. The impact modifying polyester also has a weight average molecular weight of at least g000 Daltons, as determined by ASTM D5296-05 10521 In some instances, the biodegradable polymer preferably includes poly(lactic acid).
In other embodiments, the biodegradable polymer preferably includes at least one poly(hydroxyalkanoate). Moreover, in certain embodiments, the biodegradable polymer preferably includes a mixture of poly(lactic acid) and poly(hydroxyalkanoates). For instance, in some embodiments, the polymer composition may include from about
5 to about 25 weight percent of poly(lactic acid) and from about 70 to about 90 weight percent of at least one poly(hydroxyalkanoate), based on the overall weight of the polymer composition.
10531 According to certain embodiments wherein the polymer composition includes a poly(hydroxyalkanoate), the at least one poly(hydroxyalkanoate) is preferably made up of poly-3 -hydroxybutyrate-co-3 -hydroxyhexanoate ("P(3HB-co-3HHx)").
10541 In some instances, this (3HB-co-3HHx) is preferably made up of from about 75 to about 99 mole percent hydroxybutyrate and from about 1 to about 25 mole percent hydroxyhexanoate. More preferably, the (3HB-co-3HHx) is made up of from about 93 to about 98 mole percent hydroxybutyrate and from about 2 to about 7 mole percent hydroxyhexanoate.
10551 In still other embodiments, the at least one poly(hydroxyalkanoate) may include a terpolymer made up from about 75 to about 99.9 mole percent monomer repeat units of 3-hydroxybutyrate, from about 0.1 to about 25 mole percent monomer repeat units of 3-hydroxyhexanoate, and from about 0.1 to about 25 mole percent monomer repeat units of a third 3-hydoxyalkanoate having from 5 to 12 carbon atoms.
10561 According to certain embodiments the at least one poly(hydroxyalkanoate) preferably has a weight average molecular weight from about 50,000 Daltons to about 2.5 million Daltons, as determined by ASTM D5296-05. More preferably, the at least one poly(hydroxyalkanoate) has a weight average molecular weight from about 500,000 Daltons to about 750,000 Daltons, as determined by ASTM D5296-05.
10571 The polymer composition may also include further additives. For instance, the polymer composition may include a plasticizer, a nucleating agent, and/or a filler. In some embodiments, the polymer compositions may also include from about 1 to about 10 weight percent of at least one plasticizer; from about 0.1 to about 5 weight percent of at least one nucleating agent; and from about 0.1 to about 10 weight percent of a filler.
10581 Suitable nucleating agents for use in the polymer composition may, for example, be selected from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
10591 Suitable fillers for use in the polymer composition may, for example, be selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof.
10601 Suitable plasticizers for use in the polymer composition may, for example, be selected from the group consisting of sebacates, citrates, fatty esters of adipic, succinic, and glucaric acids, lactates, alkyl diesters, citrates, alkyl methyl esters, dibenzoates, propylene carbonate, caprolactone diols having a number average molecular weight from 200-10,000 g/mol, poly(ethylene) glycols having a number average molecular weight of 400-10,000 g/mol, esters of vegetable oils, long-chain alkyl acids, adipates, glycerol, isosorbide derivatives or mixtures thereof, HALLGREEN IM-8830 ester, HALLGREEN
R-8010 ester, polyhydroxyalkanoate copolymers comprising at least 18 mole percent monomer repeat units of hydroxyalkanoates other than hydroxybutyrate and mixtures thereof 10611 Moreover, in certain embodiments, the polymer composition may also include an additional biodegradable polymer besides poly(lactic acid) and/or poly(hydroxyalkanoates). Thus, in certain embodiments, the polymer composition may also include comprising from about 5 to about 50 weight percent of at least one biodegradable polymer selected from the group consisting of poly(caprolactone), poly(ethylene sebacate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate) and mixtures thereof, 10621 According to certain embodiments, the overall polymer composition is preferably biodegradable as determined using A STM standard D5988 Further, in some embodiments, the polymer composition is preferably home compostable as determined using ASTM
standard D6868.
10631 A variety of end products may be formed from the polymer composition in accordance with the present disclosure. Thus, according to one embodiment, the present disclosure provides a molded sheet made up of the polymer composition. In a second embodiment, the present disclosure provides a molded article made up of the polymer composition, wherein the molded article is formed by thermoforming, injection molding, or blow molding. In another embodiment, the present disclosure provides a film made up of the polymer composition, wherein the film is a blown film or a cast film.
In still another embodiment, the present disclosure provides a fiber made up of the polymer composition.
10651 The present disclosure is also further illustrated by the following embodiments:
10661 Embodiment 1 A polyester comprising: from about 15 to about 40 weight percent monomer repeat units of isosorbide, based on the total weight of the polyester; from about 25 to about 60 weight percent monomer repeat units of a dicarboxylic acid or anhydride, based on the total weight of the polyester; and from about 10 to about 20 weight percent monomer repeat units of a polyhydric alcohol, based on the total weight of the polyester, wherein the polyester has a weight average molecular weight of at least 8000 Daltons, as determined by ASTM D5296-05.
Embodiment 2. The polyester of Embodiment 1, wherein the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, glutaric acid, pimelic acid, undecanoic acid, dodecanoic acid, dodecanedioic acid, suberic acid, azelaic acid, sebacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, tcrephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalic dicarboxylic acid, 1,8-dimethyl naphthalate, dimethyl isophthalate, phthalic acid, pyromellitic anhydride, mellitic anhydride, mellitic acid, trimellitic anhydride, 3,3'4,4'-benzophenone tetracarboxylic anhydride, 3,3'4,4'-benzophenone tetracarboxylic acid, trimellitic acid, nadic anhydride, methyl nadic anhydride, C36 dimer acid, partially hydrogenated C36 dimer acid, polyethylene terephthal ate recycled polymer, polybutylene terephthal ate recycled polymer, polyethylene terephthalate virgin polymer, polybutylene terephthalate virgin polymer, and mixtures thereof.
10681 Embodiment 3. The polyester of Embodiments 1 or 2, wherein the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadic anhydride, methyl nadic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof.
10691 Embodiment 4. The polyester of any of the preceding Embodiments, wherein the dicarboxylic acid or anhydride comprises a mixture of (1) succinic acid or succinic anhydride and (2) nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof.
[070] Embodiment 5. The polyester of any of the preceding Embodiments, wherein the polyester comprises from about 25 to about 35 weight percent succinic acid or succinic anhydride and from about 10 to about 25 weight percent nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.
[071] Embodiment 6. The polyester of any of the preceding Embodiments, wherein the polyhydric alcohol is selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trim ethylen e glycol, 1, 1, 1-trim ethyl ol ethane, 1,2,3 -tri m ethylolprop ane, methyl propanediol, pentaerythritol, and poly(oxyalkylene) polyols comprising monomer repeat units of ethylene oxide, propylene oxide, or butylene oxide, and mixtures thereof [072] Embodiment 7. The polyester of any of the preceding Embodiments, wherein the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methyl propanediol, and mixtures thereof.
[073] Embodiment 8. The polyester of any of the preceding Embodiments, wherein the polyhydric alcohol comprises 1,3-propanediol.
[074] Embodiment 9. The polyester of any of the preceding Embodiments, wherein the dicarboxylic acid or anhydride comprises succinic acid or anhydride, and the polyhydric alcohol comprises 1,3-propanediol.
[075] Embodiment 10. The polyester of any of the preceding Embodiments, wherein the polyester has a weight average molecular weight from about 10,000 to about 15,000 Daltons, as determined by ASTM D5296-05.
10761 Embodiment 11. A polymer composition comprising: from about 50 to about weight percent of a biodegradable polymer selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoates), and mixtures thereof, and from about 5 to about 50 weight percent of an impact modifying polyester, wherein the impact modifying polyester comprises from about 15 to about 40 weight percent monomer repeat units of isosorbide, based on the total weight of the polyester; from about 25 to about 60 weight percent monomer repeat units of a di carboxylic acid or anhydride, based on the total weight of the polyester; and from about 10 to about 20 weight percent monomer repeat units of a polyhydric alcohol, based on the total weight of the polyester, wherein the polyester has a weight average molecular weight of at least 8000 Daltons, as determined by 05.
10771 Embodiment 12. The polymer composition of Embodiment 11, wherein the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, glutaric acid, pimelic acid, undecanoic acid, dodecanoic acid, dodecanedioic acid, sub eric acid, azelaic acid, sebacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, terephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalic dicarboxylic acid, 1,8-dimethyl naphthalate, dimethyl isophthalate, phthalic acid, pyromellitic anhydride, mellitic anhydride, mellitic acid, trimellitic anhydride, 3,3'4,4'-benzophenone tetracarboxylic anhydride, 3,3'4,4'-benzophenone tetracarboxylic acid, trimellitic acid, nadic anhydride, methyl nadic anhydride, C36 dimer acid, partially hydrogenated C36 dimer acid, polyethylene terephthalate recycled polymer, polybutylene terephthalate recycled polymer, polyethylene terephthalate virgin polymer, polybutylene terephthalate virgin polymer, and mixtures thereof.
10781 Embodiment 13. The polymer composition of Embodiments 11 or 12, wherein the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadic anhydride, methyl nadic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof.
10791 Embodiment 14. The polymer composition of any of Embodiments 11 - 13, wherein the dicarboxylic acid or anhydride comprises a mixture of (1) succinic acid or succinic anhydride and (2) nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof.
10801 Embodiment 15. The polymer composition of any of Embodiments 11 - 14, wherein the polyester comprises from about 25 to about 35 weight percent succinic acid or succinic anhydride and from about 10 to about 25 weight percent nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.
10811 Embodiment 16. The polymer composition of any of Embodiments 11 ¨ 15, the polyhydric alcohol is selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trim ethylen e glycol, 1, 1,1-trim ethyl ol ethane, 1 ,2,3 -tri m ethylolprop ane, methyl propanediol, pentaerythritol, and poly(oxyalkylene) polyols comprising monomer repeat units of ethylene oxide, propylene oxide, or butylene oxide, and mixtures thereof 10821 Embodiment 17. The polymer composition of any of Embodiments 11 - 16, wherein the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methyl propanediol, and mixtures thereof.
10831 Embodiment 18. The polymer composition of any of Embodiments 11 ¨ 17, wherein the polyhydric alcohol comprises 1,3-propanediol.
10841 Embodiment 19. The polymer composition of any of Embodiments 11 - 18, wherein the dicarboxylic acid or anhydride comprises succinic acid or anhydride, and the polyhydric alcohol comprises 1,3-propanediol.
10851 Embodiment 20. The polymer composition of any of Embodiments 11 - 19, wherein the impact modifying polyester has a weight average molecular weight from about 10,000 to about 15,000 Daltons, as determined by ASTM D5296-05.
10861 Embodiment 21. The polymer composition of any of Embodiments 11 - 20, wherein the polymer composition comprises from about 60 to about 85 weight percent of the biodegradable polymer and from about 5 to about 30 weight percent of the impact modifying polyester.
10871 Embodiment 22. The polymer composition of any of Embodiments 11 -21, wherein the biodegradable polymer comprises poly(lactic acid).
10881 Embodiment 23. The polymer composition of any of Embodiments 11 - 22, wherein the biodegradable polymer comprises at least one poly(hydroxyalkanoate).
10891 Embodiment 24. The polymer composition of Embodiment 23, wherein the at least one poly(hydroxyalkanoate) comprises poly-3-hydroxybutyrate-co-3-hydroxyhexanoate ("P(3HB-co-3HEN)").
10901 Embodiment 25. The polymer composition of Embodiment 24, wherein the P(3HB-co-3HHx) comprises from about 75 to about 99 mole percent hydroxybutyrate and from about 1 to about 25 mole percent hydroxyhexanoate.
10911 Embodiment 26. The polymer composition of Embodiment 24, wherein the P(3HB-co-3HHx) comprises from about 93 to about 98 mole percent hydroxybutyrate and from about 2 to about 7 mole percent hydroxyhexanoate.
10921 Embodiment 27. The polymer composition of Embodiment 23, wherein the at least one poly(hydroxyalkanoate) comprises a terpolymer made up from about 75 to about 99.9 mole percent monomer repeat units of 3-hydroxybutyrate, from about 0.1 to about 25 mole percent monomer repeat units of 3-hydroxyhexanoate, and from about 0.1 to about 25 mole percent monomer repeat units of a third 3-hydoxyalkanoatc having from 5 to 12 carbon atoms.
10931 Embodiment 28. The polymer composition of Embodiment 23, wherein the at least one poly(hydroxyalkanoate) has a weight average molecular weight from about 50,000 Daltons to about 2.5 million Daltons, as determined by ASTM D5296-05.
10941 Embodiment 29. The polymer composition of Embodiment 23, wherein the at least one poly(hydroxyalkanoate) has a weight average molecular weight from about 500,000 Daltons to about 750,000 Daltons, as determined by ASTM D5296-05.
10951 Embodiment 30. The polymer composition of any of Embodim ents 11 -29, wherein the polymer composition comprises from about 5 to about 25 weight percent of poly(lactic acid) and from about 70 to about 90 weight percent of at least one poly(hydroxyalkanoate).
10961 Embodiment 31. The polymer composition of any of Embodiments 11 -30, further comprising [097] from about 1 to about 10 weight percent of at least one plasticizer;
[098] from about 0.1 to about 5 weight percent of at least one nucleating agent; and [099] from about 0.1 to about 10 weight percent of a filler.
[0100] Embodiment 32. The polymer composition of any of Embodiments 11 - 31, wherein the polymer composition is biodegradable as determined using ASTM standard D5988.
[0101] Embodiment 33. The polymer composition of any of Embodiments 11 - 32, wherein the polymer composition is home compostable as determined using ASTM standard D6868.
101021 Embodiment 34. The polymer composition of any of Embodiments 11 - 33, further comprising from about 5 to about 50 weight percent of at least one biodegradable polymer selected from the group consisting of poly(caprolactone), poly(ethylene sebacate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate) and mixtures thereof [0103] Embodiment 35. A molded sheet comprising the polymer composition of any of Embodiments 11 - 34.
[0104] Embodiment 36. A molded article comprising the polymer composition of any of Embodiments 11 - 34, wherein the molded article is formed by thermoforming, injection molding, or blow molding.
[0105] Embodiment 37. A film comprising the polymer composition of any of Embodiments 11 - 34, wherein the film is a blown film or a cast film.
[0106] Embodiment 38. A fiber comprising the polymer composition of any of Embodiments 11 - 34.
[0107] EXAMPLES
[0108] The following non-limiting examples illustrate various additional aspects of the invention. Unless otherwise indicated, temperatures are in degrees Celsius and percentages are by weight based on the dry weight of the formulation.
101101 To a reaction flask equipped with a nitrogen inlet and vacuum capability, 800 grams of isosorbide and 5 grams of phosphorous acid were charged. The reaction temperature was raised to 100 C, and three vacuum cycles were performed by pulling the contents of the flask to maximum vacuum and then releasing the vacuum with an inert gas such as nitrogen. Subsequently, 1279 grams of succinic acid was charged, and one more vacuum cycle was performed. Next, the reactor temperature was raised to a maximum of 220 C, all the while distilling water over into a receiver. Once water evolution slowed, 416 grams of propanediol was charged to the reactor. Again, the temperature was slowly raised to a maximum of 210 'C. Towards the end of the reaction, 1 gram of tin (II) ethyl hexanoate was added, and a vacuum was applied. The material was held until appropriate molecular weight specifications were obtained.
101121 To a 1514 L stainless steel reactor equipped with a nitrogen inlet and vacuum capability, 416 kg of isosorbide and 2.27 kg of phosphorous acid were charged.
The reaction temperature was raised to 100 C, and three vacuum cycles were performed by pulling the contents of the reactor to maximum vacuum and then releasing the vacuum with an inert gas such as nitrogen. Subsequently, 590 kg of succinic acid was charged, and one more vacuum cycle was performed. Next, the reactor temperature was raised to a maximum of 220 C, all the while distilling water over into a receiver. Once water evolution slowed, 216 kg of propa.nediol was charged to the reactor. Again, the temperature was slowly raised to a maximum of 210 C. Towards the end of the reaction, 453 grams of tin (II) ethyl hexanoate was added. The material was held until appropriate molecular weight specifications were obtained.
101141 To a reaction flask equipped with a nitrogen inlet and vacuum capability, 575 grams of isosorbide, 888 grams of a partially hydrogenated, distilled dimer acid, and 5 grams of phosphorous acid were charged. The reaction temperature was raised to 100 C, and three vacuum cycles were performed by pulling the contents of the flask to maximum vacuum and then releasing the vacuum with an inert gas such as nitrogen.
Subsequently, 733 grams of succinic acid was charged, and one more vacuum cycle was performed. Next, the reactor temperature was raised to a maximum of 220 C, all the while distilling water over into a receiver. Once water evolution slowed, 299 grams of propanediol was charged to the reactor. Again, the temperature was slowly raised to a maximum of 220 C.
Towards the end of the reaction, 1 gram offin(I') ethyl hexanoate was added, and a vacuum was applied.
The material was held until appropriate molecular weight specifications were obtained.
[0115] EXAMPLE 4 [0116] To a reaction flask equipped with a nitrogen inlet and vacuum capability, 2314 grams of the polyester from Example 2 and 186 grams of methyl nadic anhydride were charged. The reactor temperature was raised to a maximum of 220 C, all the while distilling water over into a receiver. Towards the end of the reaction, 0.63 grams of tin(II) ethyl hexanoate was added. The material was held until appropriate molecular weight specifications were obtained.
[0117] EXAMPLE 5 [0118] To a reaction flask equipped with a nitrogen inlet and vacuum capability, 1124 grams of 1,6 hexanediol, 548 grams of succinic acid, and 827 grams of methyl nadic anhydride were charged. Next, the reactor temperature was raised to a maximum of 210 C, all the while distilling water over into a receiver. Towards the end of the reaction, 0.63 grams of ti n (II) ethyl hexanoate was added. The material was held until appropriate molecular weight specifications were obtained [0119] EXAMPLE 6 [0120] To a reaction flask equipped with a nitrogen inlet and vacuum capability, 1155 grams of 1,6 hexanediol, 563 grams of succinic acid, and 783 grams of nadic anhydride were charged. Next, the reactor temperature was raised to a maximum of 210 C, all the while distilling water over into a receiver. Towards the end of the reaction, 0.63 grams of tin(II) ethyl hexanoate was added. The material was held until appropriate molecular weight specifications were obtained 101221 To a reaction flask equipped with a nitrogen inlet and vacuum capability, 1191 grams of 1,6 hexanediol, 871 grams of succinic acid, and 438 grams of methyl nadic anhydride were charged. Next, the reactor temperature was raised to a maximum of 210 C, all the while distilling water over into a receiver. Towards the end of the reaction, 0.63 grams of tin(II) ethyl hexanoate was added. The material was held until appropriate molecular weight specifications were obtained 101231 EXAMPLES 8 ¨ 20.
101241 In each of these Examples, a polymer composition was prepared, incorporating one of the impact modifier polyesters of Examples 1 ¨ 7. The polymer composition was extruded on a 27 mm twin-screw Entek extruder. In Examples 8 ¨ 15, 19, and 20, a sample of the extruded material was tested for tensile strength and elongation using an Instron 34TM-10 in accordance with ATSM D638 (Type I Specimen). Impact strength testing was carried out in accordance with ATSM D256 (Test Method A) using an Instron tester. In Examples 16 ¨ 18, a sample of the extruded material was tested for resilience in accordance with ASTM D4812-19, using a Instron CEAST 9050 Pendulum Impact System testing apparatus.
101251 For each example, a control sample was also prepared, extruded, and tested similarly to the test sample. In each example, the composition of the control sample was the same as the tested sample, except the impact modifier polyester was omitted from the polymer composition.
101271 To a 27 mm extruder, 2.27 kg of the reaction product of Example I was added to 42.5 kg of PHA, 453 grams of pentaerythritol, and 172 grams of Joncryl 4468 and ran through the extruder. The plastic was tested and exhibited a tensile strength of 26379 kPa (versus the control 24097 kPa); an elongation of 8.9% (versus a control of 10.6%), and an impact strength of 0.344 J/cm (versus a control of 0.288 J/cm) [0129] To a 27 mm extruder, 4.53 kg of the reaction product of Example 1 was added to 40 kg of PHA, 453 grams of pentaerythritol, and 340 grams of Joncryl 4468 and ran through the extruder. The plastic was tested and exhibited a tensile strength of 24242 kPa (versus the control 24097 kPa); an elongation of 11.3% (versus a control of 10.6%), and an impact strength of 0.408 J/cm (versus a control of 0.288 J/cm) [0130] EXAMPLE 10 101311 To a 27 mm extruder, 4.5 kg of the reaction product of Example 1 was added to 40 kg of PHA, 317 grams of Joncryl 4468, and 453 grams of pentaerythritol and ran through the extruder. The plastic was tested and exhibited a tensile strength of 19981 kPa (versus the control 27303 kPa); an elongation of 2.2% (versus a control of 9.3%), and an impact strength of 0.259 J/cm (versus a control of 0.301 J/cm) [0132] EXAMPLE 11 [0133] To a 27 mm extruder, 6.8 kg of the reaction product of Example 1 was added to 37.6 kg of PHA, 498 grams of Joncryl 4468, and 453 grams of pentaerythritol and ran through the extruder. The plastic was tested and exhibited a tensile strength of 26745 kPa (versus the control 27303 kPa); an elongation of 11.5% (versus a control of 9.3%), and an impact strength of 0.256 J/cm (versus a control of 0.301 J/cm) [0134] EXAMPLE 12 [0135] To a 27 mm extruder, 4.53 kg of the reaction product of Example 1 was added to 40.6 kg of PHA and 227 kg of boron nitride and ran through the extruder. The plastic was tested and exhibited a tensile strength of 19960 kPa (versus the control 24097 kPa); an elongation of 11.8% (versus a control of 10.6%), and an impact strength of 0.232 J/cm (versus a control of 0.288 J/cm) [0136] EXAMPLE 13 101371 To a 27 mm extruder, 2.27 kg of the reaction product of Example 6 was added to 42.9 kg of PT-TA and 227 grams of Boron nitride and ran through the extruder.
The plastic was tested and exhibited a tensile strength of 16899 kPa (versus the control 24097 kPa); an elongation of 15.5% (versus a control of 10.6%), and an impact strength of 0.275 J/cm (versus a control of 0.288 J/cm) [0138] EXAMPLE 14 [0139] To a 27 mm extruder, 4.53 kg of the reaction product of Example 6 was added to 40.6 kg of PHA and 227 grams of boron nitride and ran through the extruder.
The plastic was tested and exhibited a tensile strength of 12941 kPa (versus the control 24097 kPa); an elongation of 16.6% (versus a control of 10.6%), and an impact strength of 0.324 J/cm (versus a control of 0.288 J/cm) [0140] EXAMPLE 15 [0141] To a 27 mm extruder, 4.53 kg of the reaction product of Example 5 was added to 40.6 kg of PHA and 277 grams of boron nitride and ran through the extruder.
The plastic was tested and exhibited a tensile strength of 19167 kPa (versus the control 24097 kPa); an elongation of 18.4% (versus a control of 10.6%), and an impact strength of 0.277 J/cm (versus a control of 0.288 J/cm) [0142] EXAMPLE 16 [0143] To a 27 mm extruder, 2.27 kg of the reaction product of Example 6 was added to 42.87 kg of PHA and 227 grams of boron nitride and ran through the extruder.
The plastic was tested and exhibited a resilience of 66.9 kJ/m2 versus the control of 14.5 kJ/m2 [0144] EXAMPLE 17 [0145] To a 27 mm extruder, 4.53 kg of the reaction product of Example 6 was added to 40.6 kg of PHA and 227 grams of boron nitride and ran through the extruder.
The plastic was tested and exhibited a resilience of 67.1 kJ/m2 versus the control of 14.5 kJ/m2 [0146] EXAMPLE 18 [0147] To a 27 mm extruder, 4.53 kg of the reaction product of Example 7 was added to 40.6 kg of PHA and 227 grams of boron nitride and ran through the extruder.
The plastic was tested and exhibited a resilience of 39.5 kJ/m2 versus the control of 14.5 kJ/m2 [0148] EXAMPLE 19 101491 To a 27 mm extruder, 4.53 kg of the reaction product of Example 4 was added to 40.6 kg of PHA and 227 grams of boron nitride and ran through the extruder.
The plastic was tested and exhibited a resilience of 11.1 kJ/m2 versus the control of 2.34 kJ/m2.
101511 To a 27 mm extruder, 1.36 kg of the reaction product of Example 3 was added to 44 kg of PHA and ran through the extruder. The plastic was tested and exhibited a tensile strength of 1386 kPa versus a control of 1572 kPa, an elongation of 5.3%
versus a control of 5.6%, and an impact strength of 0.167 J/cm versus the control of 0.301 J/cm.
101521 From the foregoing, it may be seen that the impact modifying polyesters according to the present disclosure can provide a broad variety of mechanical property improvements to a bio-plastic system. For instance, a fourfold increase in impact strength or an 11%
increase in elongation may be achieved without a corresponding loss of tensile strength.
Thus, the impact modifying polyesters of the present disclosure allow for the mechanical properties of a bio-plastic system to be tailored to a particular end use application.
101531 The foregoing description of preferred embodiments for this invention has been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obvious modifications or variations are possible in light of the above teachings. The embodiments are chosen and described in an effort to provide the best illustrations of the principles of the invention and its practical application and to thereby enable one of ordinary skill in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally, and equitably entitled.
10531 According to certain embodiments wherein the polymer composition includes a poly(hydroxyalkanoate), the at least one poly(hydroxyalkanoate) is preferably made up of poly-3 -hydroxybutyrate-co-3 -hydroxyhexanoate ("P(3HB-co-3HHx)").
10541 In some instances, this (3HB-co-3HHx) is preferably made up of from about 75 to about 99 mole percent hydroxybutyrate and from about 1 to about 25 mole percent hydroxyhexanoate. More preferably, the (3HB-co-3HHx) is made up of from about 93 to about 98 mole percent hydroxybutyrate and from about 2 to about 7 mole percent hydroxyhexanoate.
10551 In still other embodiments, the at least one poly(hydroxyalkanoate) may include a terpolymer made up from about 75 to about 99.9 mole percent monomer repeat units of 3-hydroxybutyrate, from about 0.1 to about 25 mole percent monomer repeat units of 3-hydroxyhexanoate, and from about 0.1 to about 25 mole percent monomer repeat units of a third 3-hydoxyalkanoate having from 5 to 12 carbon atoms.
10561 According to certain embodiments the at least one poly(hydroxyalkanoate) preferably has a weight average molecular weight from about 50,000 Daltons to about 2.5 million Daltons, as determined by ASTM D5296-05. More preferably, the at least one poly(hydroxyalkanoate) has a weight average molecular weight from about 500,000 Daltons to about 750,000 Daltons, as determined by ASTM D5296-05.
10571 The polymer composition may also include further additives. For instance, the polymer composition may include a plasticizer, a nucleating agent, and/or a filler. In some embodiments, the polymer compositions may also include from about 1 to about 10 weight percent of at least one plasticizer; from about 0.1 to about 5 weight percent of at least one nucleating agent; and from about 0.1 to about 10 weight percent of a filler.
10581 Suitable nucleating agents for use in the polymer composition may, for example, be selected from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
10591 Suitable fillers for use in the polymer composition may, for example, be selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof.
10601 Suitable plasticizers for use in the polymer composition may, for example, be selected from the group consisting of sebacates, citrates, fatty esters of adipic, succinic, and glucaric acids, lactates, alkyl diesters, citrates, alkyl methyl esters, dibenzoates, propylene carbonate, caprolactone diols having a number average molecular weight from 200-10,000 g/mol, poly(ethylene) glycols having a number average molecular weight of 400-10,000 g/mol, esters of vegetable oils, long-chain alkyl acids, adipates, glycerol, isosorbide derivatives or mixtures thereof, HALLGREEN IM-8830 ester, HALLGREEN
R-8010 ester, polyhydroxyalkanoate copolymers comprising at least 18 mole percent monomer repeat units of hydroxyalkanoates other than hydroxybutyrate and mixtures thereof 10611 Moreover, in certain embodiments, the polymer composition may also include an additional biodegradable polymer besides poly(lactic acid) and/or poly(hydroxyalkanoates). Thus, in certain embodiments, the polymer composition may also include comprising from about 5 to about 50 weight percent of at least one biodegradable polymer selected from the group consisting of poly(caprolactone), poly(ethylene sebacate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate) and mixtures thereof, 10621 According to certain embodiments, the overall polymer composition is preferably biodegradable as determined using A STM standard D5988 Further, in some embodiments, the polymer composition is preferably home compostable as determined using ASTM
standard D6868.
10631 A variety of end products may be formed from the polymer composition in accordance with the present disclosure. Thus, according to one embodiment, the present disclosure provides a molded sheet made up of the polymer composition. In a second embodiment, the present disclosure provides a molded article made up of the polymer composition, wherein the molded article is formed by thermoforming, injection molding, or blow molding. In another embodiment, the present disclosure provides a film made up of the polymer composition, wherein the film is a blown film or a cast film.
In still another embodiment, the present disclosure provides a fiber made up of the polymer composition.
10651 The present disclosure is also further illustrated by the following embodiments:
10661 Embodiment 1 A polyester comprising: from about 15 to about 40 weight percent monomer repeat units of isosorbide, based on the total weight of the polyester; from about 25 to about 60 weight percent monomer repeat units of a dicarboxylic acid or anhydride, based on the total weight of the polyester; and from about 10 to about 20 weight percent monomer repeat units of a polyhydric alcohol, based on the total weight of the polyester, wherein the polyester has a weight average molecular weight of at least 8000 Daltons, as determined by ASTM D5296-05.
Embodiment 2. The polyester of Embodiment 1, wherein the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, glutaric acid, pimelic acid, undecanoic acid, dodecanoic acid, dodecanedioic acid, suberic acid, azelaic acid, sebacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, tcrephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalic dicarboxylic acid, 1,8-dimethyl naphthalate, dimethyl isophthalate, phthalic acid, pyromellitic anhydride, mellitic anhydride, mellitic acid, trimellitic anhydride, 3,3'4,4'-benzophenone tetracarboxylic anhydride, 3,3'4,4'-benzophenone tetracarboxylic acid, trimellitic acid, nadic anhydride, methyl nadic anhydride, C36 dimer acid, partially hydrogenated C36 dimer acid, polyethylene terephthal ate recycled polymer, polybutylene terephthal ate recycled polymer, polyethylene terephthalate virgin polymer, polybutylene terephthalate virgin polymer, and mixtures thereof.
10681 Embodiment 3. The polyester of Embodiments 1 or 2, wherein the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadic anhydride, methyl nadic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof.
10691 Embodiment 4. The polyester of any of the preceding Embodiments, wherein the dicarboxylic acid or anhydride comprises a mixture of (1) succinic acid or succinic anhydride and (2) nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof.
[070] Embodiment 5. The polyester of any of the preceding Embodiments, wherein the polyester comprises from about 25 to about 35 weight percent succinic acid or succinic anhydride and from about 10 to about 25 weight percent nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.
[071] Embodiment 6. The polyester of any of the preceding Embodiments, wherein the polyhydric alcohol is selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trim ethylen e glycol, 1, 1, 1-trim ethyl ol ethane, 1,2,3 -tri m ethylolprop ane, methyl propanediol, pentaerythritol, and poly(oxyalkylene) polyols comprising monomer repeat units of ethylene oxide, propylene oxide, or butylene oxide, and mixtures thereof [072] Embodiment 7. The polyester of any of the preceding Embodiments, wherein the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methyl propanediol, and mixtures thereof.
[073] Embodiment 8. The polyester of any of the preceding Embodiments, wherein the polyhydric alcohol comprises 1,3-propanediol.
[074] Embodiment 9. The polyester of any of the preceding Embodiments, wherein the dicarboxylic acid or anhydride comprises succinic acid or anhydride, and the polyhydric alcohol comprises 1,3-propanediol.
[075] Embodiment 10. The polyester of any of the preceding Embodiments, wherein the polyester has a weight average molecular weight from about 10,000 to about 15,000 Daltons, as determined by ASTM D5296-05.
10761 Embodiment 11. A polymer composition comprising: from about 50 to about weight percent of a biodegradable polymer selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoates), and mixtures thereof, and from about 5 to about 50 weight percent of an impact modifying polyester, wherein the impact modifying polyester comprises from about 15 to about 40 weight percent monomer repeat units of isosorbide, based on the total weight of the polyester; from about 25 to about 60 weight percent monomer repeat units of a di carboxylic acid or anhydride, based on the total weight of the polyester; and from about 10 to about 20 weight percent monomer repeat units of a polyhydric alcohol, based on the total weight of the polyester, wherein the polyester has a weight average molecular weight of at least 8000 Daltons, as determined by 05.
10771 Embodiment 12. The polymer composition of Embodiment 11, wherein the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, glutaric acid, pimelic acid, undecanoic acid, dodecanoic acid, dodecanedioic acid, sub eric acid, azelaic acid, sebacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, terephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalic dicarboxylic acid, 1,8-dimethyl naphthalate, dimethyl isophthalate, phthalic acid, pyromellitic anhydride, mellitic anhydride, mellitic acid, trimellitic anhydride, 3,3'4,4'-benzophenone tetracarboxylic anhydride, 3,3'4,4'-benzophenone tetracarboxylic acid, trimellitic acid, nadic anhydride, methyl nadic anhydride, C36 dimer acid, partially hydrogenated C36 dimer acid, polyethylene terephthalate recycled polymer, polybutylene terephthalate recycled polymer, polyethylene terephthalate virgin polymer, polybutylene terephthalate virgin polymer, and mixtures thereof.
10781 Embodiment 13. The polymer composition of Embodiments 11 or 12, wherein the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadic anhydride, methyl nadic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof.
10791 Embodiment 14. The polymer composition of any of Embodiments 11 - 13, wherein the dicarboxylic acid or anhydride comprises a mixture of (1) succinic acid or succinic anhydride and (2) nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof.
10801 Embodiment 15. The polymer composition of any of Embodiments 11 - 14, wherein the polyester comprises from about 25 to about 35 weight percent succinic acid or succinic anhydride and from about 10 to about 25 weight percent nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.
10811 Embodiment 16. The polymer composition of any of Embodiments 11 ¨ 15, the polyhydric alcohol is selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trim ethylen e glycol, 1, 1,1-trim ethyl ol ethane, 1 ,2,3 -tri m ethylolprop ane, methyl propanediol, pentaerythritol, and poly(oxyalkylene) polyols comprising monomer repeat units of ethylene oxide, propylene oxide, or butylene oxide, and mixtures thereof 10821 Embodiment 17. The polymer composition of any of Embodiments 11 - 16, wherein the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methyl propanediol, and mixtures thereof.
10831 Embodiment 18. The polymer composition of any of Embodiments 11 ¨ 17, wherein the polyhydric alcohol comprises 1,3-propanediol.
10841 Embodiment 19. The polymer composition of any of Embodiments 11 - 18, wherein the dicarboxylic acid or anhydride comprises succinic acid or anhydride, and the polyhydric alcohol comprises 1,3-propanediol.
10851 Embodiment 20. The polymer composition of any of Embodiments 11 - 19, wherein the impact modifying polyester has a weight average molecular weight from about 10,000 to about 15,000 Daltons, as determined by ASTM D5296-05.
10861 Embodiment 21. The polymer composition of any of Embodiments 11 - 20, wherein the polymer composition comprises from about 60 to about 85 weight percent of the biodegradable polymer and from about 5 to about 30 weight percent of the impact modifying polyester.
10871 Embodiment 22. The polymer composition of any of Embodiments 11 -21, wherein the biodegradable polymer comprises poly(lactic acid).
10881 Embodiment 23. The polymer composition of any of Embodiments 11 - 22, wherein the biodegradable polymer comprises at least one poly(hydroxyalkanoate).
10891 Embodiment 24. The polymer composition of Embodiment 23, wherein the at least one poly(hydroxyalkanoate) comprises poly-3-hydroxybutyrate-co-3-hydroxyhexanoate ("P(3HB-co-3HEN)").
10901 Embodiment 25. The polymer composition of Embodiment 24, wherein the P(3HB-co-3HHx) comprises from about 75 to about 99 mole percent hydroxybutyrate and from about 1 to about 25 mole percent hydroxyhexanoate.
10911 Embodiment 26. The polymer composition of Embodiment 24, wherein the P(3HB-co-3HHx) comprises from about 93 to about 98 mole percent hydroxybutyrate and from about 2 to about 7 mole percent hydroxyhexanoate.
10921 Embodiment 27. The polymer composition of Embodiment 23, wherein the at least one poly(hydroxyalkanoate) comprises a terpolymer made up from about 75 to about 99.9 mole percent monomer repeat units of 3-hydroxybutyrate, from about 0.1 to about 25 mole percent monomer repeat units of 3-hydroxyhexanoate, and from about 0.1 to about 25 mole percent monomer repeat units of a third 3-hydoxyalkanoatc having from 5 to 12 carbon atoms.
10931 Embodiment 28. The polymer composition of Embodiment 23, wherein the at least one poly(hydroxyalkanoate) has a weight average molecular weight from about 50,000 Daltons to about 2.5 million Daltons, as determined by ASTM D5296-05.
10941 Embodiment 29. The polymer composition of Embodiment 23, wherein the at least one poly(hydroxyalkanoate) has a weight average molecular weight from about 500,000 Daltons to about 750,000 Daltons, as determined by ASTM D5296-05.
10951 Embodiment 30. The polymer composition of any of Embodim ents 11 -29, wherein the polymer composition comprises from about 5 to about 25 weight percent of poly(lactic acid) and from about 70 to about 90 weight percent of at least one poly(hydroxyalkanoate).
10961 Embodiment 31. The polymer composition of any of Embodiments 11 -30, further comprising [097] from about 1 to about 10 weight percent of at least one plasticizer;
[098] from about 0.1 to about 5 weight percent of at least one nucleating agent; and [099] from about 0.1 to about 10 weight percent of a filler.
[0100] Embodiment 32. The polymer composition of any of Embodiments 11 - 31, wherein the polymer composition is biodegradable as determined using ASTM standard D5988.
[0101] Embodiment 33. The polymer composition of any of Embodiments 11 - 32, wherein the polymer composition is home compostable as determined using ASTM standard D6868.
101021 Embodiment 34. The polymer composition of any of Embodiments 11 - 33, further comprising from about 5 to about 50 weight percent of at least one biodegradable polymer selected from the group consisting of poly(caprolactone), poly(ethylene sebacate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate) and mixtures thereof [0103] Embodiment 35. A molded sheet comprising the polymer composition of any of Embodiments 11 - 34.
[0104] Embodiment 36. A molded article comprising the polymer composition of any of Embodiments 11 - 34, wherein the molded article is formed by thermoforming, injection molding, or blow molding.
[0105] Embodiment 37. A film comprising the polymer composition of any of Embodiments 11 - 34, wherein the film is a blown film or a cast film.
[0106] Embodiment 38. A fiber comprising the polymer composition of any of Embodiments 11 - 34.
[0107] EXAMPLES
[0108] The following non-limiting examples illustrate various additional aspects of the invention. Unless otherwise indicated, temperatures are in degrees Celsius and percentages are by weight based on the dry weight of the formulation.
101101 To a reaction flask equipped with a nitrogen inlet and vacuum capability, 800 grams of isosorbide and 5 grams of phosphorous acid were charged. The reaction temperature was raised to 100 C, and three vacuum cycles were performed by pulling the contents of the flask to maximum vacuum and then releasing the vacuum with an inert gas such as nitrogen. Subsequently, 1279 grams of succinic acid was charged, and one more vacuum cycle was performed. Next, the reactor temperature was raised to a maximum of 220 C, all the while distilling water over into a receiver. Once water evolution slowed, 416 grams of propanediol was charged to the reactor. Again, the temperature was slowly raised to a maximum of 210 'C. Towards the end of the reaction, 1 gram of tin (II) ethyl hexanoate was added, and a vacuum was applied. The material was held until appropriate molecular weight specifications were obtained.
101121 To a 1514 L stainless steel reactor equipped with a nitrogen inlet and vacuum capability, 416 kg of isosorbide and 2.27 kg of phosphorous acid were charged.
The reaction temperature was raised to 100 C, and three vacuum cycles were performed by pulling the contents of the reactor to maximum vacuum and then releasing the vacuum with an inert gas such as nitrogen. Subsequently, 590 kg of succinic acid was charged, and one more vacuum cycle was performed. Next, the reactor temperature was raised to a maximum of 220 C, all the while distilling water over into a receiver. Once water evolution slowed, 216 kg of propa.nediol was charged to the reactor. Again, the temperature was slowly raised to a maximum of 210 C. Towards the end of the reaction, 453 grams of tin (II) ethyl hexanoate was added. The material was held until appropriate molecular weight specifications were obtained.
101141 To a reaction flask equipped with a nitrogen inlet and vacuum capability, 575 grams of isosorbide, 888 grams of a partially hydrogenated, distilled dimer acid, and 5 grams of phosphorous acid were charged. The reaction temperature was raised to 100 C, and three vacuum cycles were performed by pulling the contents of the flask to maximum vacuum and then releasing the vacuum with an inert gas such as nitrogen.
Subsequently, 733 grams of succinic acid was charged, and one more vacuum cycle was performed. Next, the reactor temperature was raised to a maximum of 220 C, all the while distilling water over into a receiver. Once water evolution slowed, 299 grams of propanediol was charged to the reactor. Again, the temperature was slowly raised to a maximum of 220 C.
Towards the end of the reaction, 1 gram offin(I') ethyl hexanoate was added, and a vacuum was applied.
The material was held until appropriate molecular weight specifications were obtained.
[0115] EXAMPLE 4 [0116] To a reaction flask equipped with a nitrogen inlet and vacuum capability, 2314 grams of the polyester from Example 2 and 186 grams of methyl nadic anhydride were charged. The reactor temperature was raised to a maximum of 220 C, all the while distilling water over into a receiver. Towards the end of the reaction, 0.63 grams of tin(II) ethyl hexanoate was added. The material was held until appropriate molecular weight specifications were obtained.
[0117] EXAMPLE 5 [0118] To a reaction flask equipped with a nitrogen inlet and vacuum capability, 1124 grams of 1,6 hexanediol, 548 grams of succinic acid, and 827 grams of methyl nadic anhydride were charged. Next, the reactor temperature was raised to a maximum of 210 C, all the while distilling water over into a receiver. Towards the end of the reaction, 0.63 grams of ti n (II) ethyl hexanoate was added. The material was held until appropriate molecular weight specifications were obtained [0119] EXAMPLE 6 [0120] To a reaction flask equipped with a nitrogen inlet and vacuum capability, 1155 grams of 1,6 hexanediol, 563 grams of succinic acid, and 783 grams of nadic anhydride were charged. Next, the reactor temperature was raised to a maximum of 210 C, all the while distilling water over into a receiver. Towards the end of the reaction, 0.63 grams of tin(II) ethyl hexanoate was added. The material was held until appropriate molecular weight specifications were obtained 101221 To a reaction flask equipped with a nitrogen inlet and vacuum capability, 1191 grams of 1,6 hexanediol, 871 grams of succinic acid, and 438 grams of methyl nadic anhydride were charged. Next, the reactor temperature was raised to a maximum of 210 C, all the while distilling water over into a receiver. Towards the end of the reaction, 0.63 grams of tin(II) ethyl hexanoate was added. The material was held until appropriate molecular weight specifications were obtained 101231 EXAMPLES 8 ¨ 20.
101241 In each of these Examples, a polymer composition was prepared, incorporating one of the impact modifier polyesters of Examples 1 ¨ 7. The polymer composition was extruded on a 27 mm twin-screw Entek extruder. In Examples 8 ¨ 15, 19, and 20, a sample of the extruded material was tested for tensile strength and elongation using an Instron 34TM-10 in accordance with ATSM D638 (Type I Specimen). Impact strength testing was carried out in accordance with ATSM D256 (Test Method A) using an Instron tester. In Examples 16 ¨ 18, a sample of the extruded material was tested for resilience in accordance with ASTM D4812-19, using a Instron CEAST 9050 Pendulum Impact System testing apparatus.
101251 For each example, a control sample was also prepared, extruded, and tested similarly to the test sample. In each example, the composition of the control sample was the same as the tested sample, except the impact modifier polyester was omitted from the polymer composition.
101271 To a 27 mm extruder, 2.27 kg of the reaction product of Example I was added to 42.5 kg of PHA, 453 grams of pentaerythritol, and 172 grams of Joncryl 4468 and ran through the extruder. The plastic was tested and exhibited a tensile strength of 26379 kPa (versus the control 24097 kPa); an elongation of 8.9% (versus a control of 10.6%), and an impact strength of 0.344 J/cm (versus a control of 0.288 J/cm) [0129] To a 27 mm extruder, 4.53 kg of the reaction product of Example 1 was added to 40 kg of PHA, 453 grams of pentaerythritol, and 340 grams of Joncryl 4468 and ran through the extruder. The plastic was tested and exhibited a tensile strength of 24242 kPa (versus the control 24097 kPa); an elongation of 11.3% (versus a control of 10.6%), and an impact strength of 0.408 J/cm (versus a control of 0.288 J/cm) [0130] EXAMPLE 10 101311 To a 27 mm extruder, 4.5 kg of the reaction product of Example 1 was added to 40 kg of PHA, 317 grams of Joncryl 4468, and 453 grams of pentaerythritol and ran through the extruder. The plastic was tested and exhibited a tensile strength of 19981 kPa (versus the control 27303 kPa); an elongation of 2.2% (versus a control of 9.3%), and an impact strength of 0.259 J/cm (versus a control of 0.301 J/cm) [0132] EXAMPLE 11 [0133] To a 27 mm extruder, 6.8 kg of the reaction product of Example 1 was added to 37.6 kg of PHA, 498 grams of Joncryl 4468, and 453 grams of pentaerythritol and ran through the extruder. The plastic was tested and exhibited a tensile strength of 26745 kPa (versus the control 27303 kPa); an elongation of 11.5% (versus a control of 9.3%), and an impact strength of 0.256 J/cm (versus a control of 0.301 J/cm) [0134] EXAMPLE 12 [0135] To a 27 mm extruder, 4.53 kg of the reaction product of Example 1 was added to 40.6 kg of PHA and 227 kg of boron nitride and ran through the extruder. The plastic was tested and exhibited a tensile strength of 19960 kPa (versus the control 24097 kPa); an elongation of 11.8% (versus a control of 10.6%), and an impact strength of 0.232 J/cm (versus a control of 0.288 J/cm) [0136] EXAMPLE 13 101371 To a 27 mm extruder, 2.27 kg of the reaction product of Example 6 was added to 42.9 kg of PT-TA and 227 grams of Boron nitride and ran through the extruder.
The plastic was tested and exhibited a tensile strength of 16899 kPa (versus the control 24097 kPa); an elongation of 15.5% (versus a control of 10.6%), and an impact strength of 0.275 J/cm (versus a control of 0.288 J/cm) [0138] EXAMPLE 14 [0139] To a 27 mm extruder, 4.53 kg of the reaction product of Example 6 was added to 40.6 kg of PHA and 227 grams of boron nitride and ran through the extruder.
The plastic was tested and exhibited a tensile strength of 12941 kPa (versus the control 24097 kPa); an elongation of 16.6% (versus a control of 10.6%), and an impact strength of 0.324 J/cm (versus a control of 0.288 J/cm) [0140] EXAMPLE 15 [0141] To a 27 mm extruder, 4.53 kg of the reaction product of Example 5 was added to 40.6 kg of PHA and 277 grams of boron nitride and ran through the extruder.
The plastic was tested and exhibited a tensile strength of 19167 kPa (versus the control 24097 kPa); an elongation of 18.4% (versus a control of 10.6%), and an impact strength of 0.277 J/cm (versus a control of 0.288 J/cm) [0142] EXAMPLE 16 [0143] To a 27 mm extruder, 2.27 kg of the reaction product of Example 6 was added to 42.87 kg of PHA and 227 grams of boron nitride and ran through the extruder.
The plastic was tested and exhibited a resilience of 66.9 kJ/m2 versus the control of 14.5 kJ/m2 [0144] EXAMPLE 17 [0145] To a 27 mm extruder, 4.53 kg of the reaction product of Example 6 was added to 40.6 kg of PHA and 227 grams of boron nitride and ran through the extruder.
The plastic was tested and exhibited a resilience of 67.1 kJ/m2 versus the control of 14.5 kJ/m2 [0146] EXAMPLE 18 [0147] To a 27 mm extruder, 4.53 kg of the reaction product of Example 7 was added to 40.6 kg of PHA and 227 grams of boron nitride and ran through the extruder.
The plastic was tested and exhibited a resilience of 39.5 kJ/m2 versus the control of 14.5 kJ/m2 [0148] EXAMPLE 19 101491 To a 27 mm extruder, 4.53 kg of the reaction product of Example 4 was added to 40.6 kg of PHA and 227 grams of boron nitride and ran through the extruder.
The plastic was tested and exhibited a resilience of 11.1 kJ/m2 versus the control of 2.34 kJ/m2.
101511 To a 27 mm extruder, 1.36 kg of the reaction product of Example 3 was added to 44 kg of PHA and ran through the extruder. The plastic was tested and exhibited a tensile strength of 1386 kPa versus a control of 1572 kPa, an elongation of 5.3%
versus a control of 5.6%, and an impact strength of 0.167 J/cm versus the control of 0.301 J/cm.
101521 From the foregoing, it may be seen that the impact modifying polyesters according to the present disclosure can provide a broad variety of mechanical property improvements to a bio-plastic system. For instance, a fourfold increase in impact strength or an 11%
increase in elongation may be achieved without a corresponding loss of tensile strength.
Thus, the impact modifying polyesters of the present disclosure allow for the mechanical properties of a bio-plastic system to be tailored to a particular end use application.
101531 The foregoing description of preferred embodiments for this invention has been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obvious modifications or variations are possible in light of the above teachings. The embodiments are chosen and described in an effort to provide the best illustrations of the principles of the invention and its practical application and to thereby enable one of ordinary skill in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally, and equitably entitled.
Claims (38)
- Claim 1. A polyester comprising:
from 15 to 40 weight percent monomer repeat units of isosorbide, based on the total weight of the polyester;
from 25 to 60 weight percent monomer repeat units of a dicarboxylic acid or anhydride, based on the total weight of the polyester; and from 10 to 20 weight percent monomer repeat units of a polyhydric alcohol, based on the total weight of the polyester, wherein the polyester has a weight average molecular weight of at least 8000 Daltons, as determined by ASTM D5296-05. - Claim 2. The polyester of claim 1, wherein the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, glutaric acid, pimelic acid, undecanoic acid, dodecanoic acid, dodecanedioic acid, suberic acid, azelaic acid, sebacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, terephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalic dicarboxylic acid, 1,8-dimethyl naphthalate, dimethyl isophthalate, phthalic acid, pyromellitic anhydride, mellitic anhydride, mellitic acid, trimellitic anhydride, 3,3'4,4'-benzophenone tetracarboxylic anhydride, 3,3'4,4'-benzophenone tetracarboxylic acid, trimellitic acid, nadic anhydride, methyl nadic anhydride, C36 dimer acid, partially hydrogenated C36 dimer acid, polyethylene terephthalate recycled polymer, polybutylene terephthalate recycled polymer, polyethylene terephthalate virgin polymer, polybutylene terephthalate virgin polymer, and mixtures thereof.
- Claim 3. The polyester of claim 1, wherein the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadic anhydride, methyl nadic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof.
- Claim 4. The polyester of claim 1, wherein the dicarboxylic acid or anhydride comprises a mixture of (1) succinic acid or succinic anhydride and (2) nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof
- Claim 5. The polyester of Claim 4, wherein the polyester comprises from 25 to weight percent succinic acid or succinic anhydride and from 10 to 25 weight percent nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.
- Claim 6. The polyester of claim 1, wherein the polyhydric alcohol is selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, 1,1,1-trimethylol ethane, 1,2,3-trimethylolpropane, methyl propanediol, pentaerythritol, and poly(oxyalkylene) polyols comprising monomer repeat units of ethylene oxide, propylene oxide, or butylene oxide, and mixtures thereof.
- Claim 7. The polyester of claim 1, wherein the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methyl propanediol, and mixtures thereof
- Claim 8. The polyester of claim 1, wherein the polyhydric alcohol comprises 1,3-propanediol.
- Claim 9. The polyester of claim 1, wherein the dicarboxylic acid or anhydride comprises succinic acid or anhydride, and the polyhydric alcohol comprises 1,3-propanediol.
- Claim 10. The polyester of Claim 1, wherein the polyester has a weight average molecular weight from 10,000 to 15,000 Daltons, as determined by ASTM D5296-05.
- Claim 11. A polymer composition comprising:
from 50 to 95 weight percent of a biodegradable polymer selected from the group consisting of poly(lactic acid), poly(hydroxyalkanoates), and mixtures thereof; and from 5 to 50 weight percent of an impact modifying polyester, wherein the impact modifying polyester comprises from 15 to 40 weight percent monomer repeat units of isosorbide, based on the total weight of the polyester;
from 25 to 60 weight percent monomer repeat units of a dicarboxylic acid or anhydride, based on the total weight of the polyester; and from 10 to 20 weight percent monomer repeat units of a polyhydric alcohol, based on the total weight of the polyester, wherein the polyester has a weight average molecular weight of at least 8000 Daltons, as determined by A STM D5296-05. - Claim 12. The polymer composition of claim 11, wherein the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, glutaric acid, pimelic acid, undecanoic acid, dodecanoic acid, dodecanedioic acid, suberic acid, azelaic acid, sebacic acid, adipic acid, phthalic anhydride, dimethyl terephthalate, terephthalic acid, isophthalic acid, 1,8-naphthalic anhydride, 1,8-naphthalic dicarboxylic acid, 1,8-dimethyl naphthalate, dimethyl isophthalate, phthalic acid, pyromellitic anhydride, mellitic anhydride, mellitic acid, trimellitic anhydride, 3,3'4,4'-benzophenone tetracarboxylic anhydride, 3,3'4,4'-benzophenone tetracarboxylic acid, trimellitic acid, nadic anhydride, methyl nadic anhydride, C36 dimer acid, partially hydrogenated C36 dimer acid, polyethylene terephthalate recycled polymer, polybutylene terephthalate recycled polymer, polyethylene terephthalate virgin polymer, polybutylene terephthalate virgin polymer, and mixtures thereof.
- Claim 13. The polymer composition of claim 11, wherein the dicarboxylic acid or anhydride is selected from the group consisting of succinic acid, succinic anhydride, nadic anhydride, methyl nadic anhydride, sebacic acid, C36 dimer acid, partially hydrogenated C36 dimer acid, and mixtures thereof
- Claim 14 The polymer composition of claim 11, wherein the dicarboxylic acid or anhydride comprises a mixture of (1) succinic acid or succinic anhydride and (2) nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid, and mixtures thereof.
- Claim 15. The polymer composition of claim 11, wherein the polyester comprises from 25 to 35 weight percent succinic acid or succinic anhydride and from 10 to 25 weight percent nadic anhydride, methyl nadic anhydride, C36 dimer acid, or partially hydrogenated C36 dimer acid.
- Claim 16. The polymer composition of claim 11, the polyhydric alcohol is selected from the group consisting of glycerin, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl, neopentyl glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, trimethylene glycol, 1,1,1-trimethylol ethane, 1,2,3-trimethylolpropane, methyl propanediol, pentaerythritol, and poly(oxyalkylene) polyols comprising monomer repeat units of ethylene oxide, propylene oxide, or butylene oxide, and mixtures thereof.
- Claim 17. The polymer composition of claim 11, wherein the polyhydric alcohol is selected from the group consisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, methyl propanediol, and mixtures thereof.
- Claim 18. The polymer composition of claim 11, wherein the polyhydric alcohol comprises 1,3-propanediol.
- Claim 19. The polymer composition of claim 11, wherein the dicarboxylic acid or anhydride comprises succinic acid or anhydride, and the polyhydric alcohol comprises 1,3-propanediol.
- Claim 20. The polymer composition of Claim 11, wherein the impact modifying polyester has a weight average molecular weight from 10,000 to 15,000 Daltons, as determined by ASTM D5296-05.
- Claim 21. The polymer composition of Claim 11, wherein the polymer composition comprises from 60 to 85 weight percent of the biodegradable polymer and from 5 to 30 weight percent of the impact modifying polyester.
- Claim 22. The polymer composition of Claim 11, wherein the biodegradable polymer comprises poly(lactic acid).
- Claim 23. The polymer composition of Claim 11, wherein the biodegradable polymer comprises at least one poly(hydroxyalkanoate).
- Claim 24. The polymer composition of Claim 23, wherein the at least one poly(hydroxyalkanoate) comprises poly-3 -hydroxybutyrate-co-3-hydroxyhexanoate ("P(3131B-co-3HHx)").
- Claim 25. The polymer composition of Claim 24, wherein the P(31-1B-co-3HHx) comprises from 75 to 99 mole percent hydroxybutyrate and from 1 to 25 mole percent hydroxyhexanoate.
- Claim 26. The polymer composition of Claim 24, wherein the P(31-11B-co-3HHx) comprises from 93 to 98 mole percent hydroxybutyrate and from 2 to 7 mole percent hydroxyhexanoate.
- Claim 27. The polymer composition of Claim 23, wherein the at least one poly(hydroxyalkanoate) comprises a terpolymer made up from 75 to 99.9 mole percent monomer repeat units of 3-hydroxybutyrate, from 0.1 to 25 mole percent monomer repeat units of 3-hydroxyhexanoate, and from 0.1 to 25 mole percent monomer repeat units of a third 3-hydoxyalkanoate having from 5 to 12 carbon atoms.
- Claim 28. The polymer composition of Claim 23, wherein the at least one poly(hydroxyalkanoate) has a weight average molecular weight from 50,000 Daltons to 2.5 million Daltons, as determined by ASTM D5296-05.
- Claim 29. The polymer composition of Claim 23, wherein the at least one poly(hydroxyalkanoate) has a weight average molecular weight from 500,000 Daltons to 750,000 Daltons, as determined by ASTM D5296-05.
- Claim 30. The polymer composition of Claim 11, wherein the polymer composition comprises from 5 to 25 weight percent of poly(lactic acid) and from 70 to 90 weight percent of at least one poly(hydroxyalkanoate), based on the overall weight of the polymer composition.
- Claim 31. The polymer composition of Claim 11, further comprising from 1 to 10 weight percent of at least one plasticizer;
from 0.1 to 5 weight percent of at least one nucleating agent; and from 0.1 to 10 weight percent of a filler. - Claim 32. The polymer composition of Claim 11, wherein the polymer composition is biodegradable as determined using ASTM standard D5988.
- Claim 33. The polymer composition of Claim 11, wherein the polymer composition is home compostable as determined using ASTM standard D6868.
- Claim 34. The polymer composition of Claim 11 further comprising from 5 to 50 weight percent of at least one biodegradable polymer selected from the group consisting of poly(caprolactone), poly(ethylene sebacate), poly(butylene succinate), poly(butylene succinate-co-adipate), poly(butylene adipate terephthalate), poly(vinyl acetate) and mixtures thereof
- Claim 35. A molded sheet comprising the polymer composition of Claim 11.
- Claim 36. A molded article comprising the polymer composition of Claim 11, wherein the molded article is formed by thermoforming, injection molding, or blow molding.
- Claim 37. A film comprising the polymer composition of Claim 11, wherein the film is a blown film or a cast film.
- Claim 38. A fiber comprising the polymer composition of Claim 11.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202163188668P | 2021-05-14 | 2021-05-14 | |
| US63/188,668 | 2021-05-14 | ||
| US17/744,109 US11952458B2 (en) | 2021-05-14 | 2022-05-13 | Polyester impact modifiers |
| PCT/US2022/029234 WO2022241242A1 (en) | 2021-05-14 | 2022-05-13 | Polyester impact modifiers |
| US17/744,109 | 2022-05-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA3219000A1 true CA3219000A1 (en) | 2022-11-17 |
Family
ID=82019565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA3219000A Pending CA3219000A1 (en) | 2021-05-14 | 2022-05-13 | Polyester impact modifiers |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP2024517969A (en) |
| KR (1) | KR20240044387A (en) |
| AU (1) | AU2022272729A1 (en) |
| BR (1) | BR112023023648A2 (en) |
| CA (1) | CA3219000A1 (en) |
| WO (1) | WO2022241242A1 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101801703B1 (en) * | 2011-11-18 | 2017-11-28 | 에스케이케미칼주식회사 | Blend of polylactic acid resin and copolyester resin and articles using the same |
-
2022
- 2022-05-13 CA CA3219000A patent/CA3219000A1/en active Pending
- 2022-05-13 AU AU2022272729A patent/AU2022272729A1/en active Pending
- 2022-05-13 WO PCT/US2022/029234 patent/WO2022241242A1/en active Application Filing
- 2022-05-13 JP JP2023570386A patent/JP2024517969A/en active Pending
- 2022-05-13 BR BR112023023648A patent/BR112023023648A2/en unknown
- 2022-05-13 KR KR1020237043186A patent/KR20240044387A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU2022272729A1 (en) | 2024-01-04 |
| KR20240044387A (en) | 2024-04-04 |
| WO2022241242A1 (en) | 2022-11-17 |
| BR112023023648A2 (en) | 2024-01-30 |
| JP2024517969A (en) | 2024-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101216846B1 (en) | Biodegradable aliphatic-aromatic polyesters | |
| EP2500378A1 (en) | Bio-resins | |
| KR20110008318A (en) | Aliphatic-aromatic biodegradable polyester | |
| JP2001335623A (en) | Impact resistance-imparting agent and polyester composition containing it | |
| CN116171297A (en) | Bio-based material for consumer product packaging | |
| JP2013057039A (en) | Aliphatic polyester resin composition | |
| US11952458B2 (en) | Polyester impact modifiers | |
| CA3219000A1 (en) | Polyester impact modifiers | |
| WO2004067639A1 (en) | Plasticizer for resin and resin composition | |
| US20120259028A1 (en) | Reactive polymeric mixture | |
| KR101850514B1 (en) | Biodegradable resin composition for 3D printer filament and 3D printer filament with excellent flexibility and impact resistance using the same | |
| JP7481879B2 (en) | Crystallization promoter and its uses | |
| JP4205403B2 (en) | Polylactic acid resin composition, molded article, and plasticizer for polyester resin | |
| KR0146231B1 (en) | Biodegradable resin composition | |
| KR101523092B1 (en) | Copolyester and method for manufacturing of it | |
| JP2021155683A (en) | Crystallization accelerator and use thereof | |
| CN105849172A (en) | Compositions comprising tetrahydrofurfuryl and alkoxylated alkyl esters as plasticisers for biodegradable resins |