CN108779234A - 聚乳酸树脂组合物和包含该聚乳酸树脂组合物的模塑产品 - Google Patents
聚乳酸树脂组合物和包含该聚乳酸树脂组合物的模塑产品 Download PDFInfo
- Publication number
- CN108779234A CN108779234A CN201780016664.9A CN201780016664A CN108779234A CN 108779234 A CN108779234 A CN 108779234A CN 201780016664 A CN201780016664 A CN 201780016664A CN 108779234 A CN108779234 A CN 108779234A
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- resin composition
- polylactic
- acid resin
- repetitive unit
- 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
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 81
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 79
- 239000011342 resin composition Substances 0.000 title claims abstract description 51
- 229920005989 resin Polymers 0.000 claims description 84
- 239000011347 resin Substances 0.000 claims description 84
- 230000003252 repetitive effect Effects 0.000 claims description 81
- 229920005862 polyol Polymers 0.000 claims description 43
- 150000003077 polyols Chemical class 0.000 claims description 41
- 229920002635 polyurethane Polymers 0.000 claims description 24
- 239000004814 polyurethane Substances 0.000 claims description 24
- 229920000570 polyether Polymers 0.000 claims description 21
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 20
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 16
- 239000002667 nucleating agent Substances 0.000 claims description 13
- 238000001746 injection moulding Methods 0.000 claims description 11
- 125000005442 diisocyanate group Chemical group 0.000 claims description 10
- 239000000454 talc Substances 0.000 claims description 10
- 229910052623 talc Inorganic materials 0.000 claims description 10
- 235000012222 talc Nutrition 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 229920001400 block copolymer Polymers 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims 2
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000004643 cyanate ester Substances 0.000 claims 1
- 150000001913 cyanates Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 10
- 239000004014 plasticizer Substances 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 15
- 239000000203 mixture Substances 0.000 description 9
- -1 polyethylene terephthalate Polymers 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 235000006708 antioxidants Nutrition 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 150000005846 sugar alcohols Polymers 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003863 metallic catalyst Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 210000000481 breast Anatomy 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- MOQRZWSWPNIGMP-UHFFFAOYSA-N stearic acid pentyl ester Natural products CCCCCCCCCCCCCCCCCC(=O)OCCCCC MOQRZWSWPNIGMP-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical class [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- IXAWXWACDBWEJF-UHFFFAOYSA-L C(CCCCCCC)[Sn+2]CCCCCCCC.C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].[Sn+4] Chemical compound C(CCCCCCC)[Sn+2]CCCCCCCC.C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].[Sn+4] IXAWXWACDBWEJF-UHFFFAOYSA-L 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- PESZCXUNMKAYME-UHFFFAOYSA-N Citroflex A-4 Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)C(C(C)=O)C(=O)OCCCC PESZCXUNMKAYME-UHFFFAOYSA-N 0.000 description 1
- 244000147058 Derris elliptica Species 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 1
- GWGWXYUPRTXVSY-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=C(C)C=C1 Chemical compound N=C=O.N=C=O.CC1=CC=C(C)C=C1 GWGWXYUPRTXVSY-UHFFFAOYSA-N 0.000 description 1
- UQBRAHLFLCMLBA-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=CC(C)=C1 Chemical compound N=C=O.N=C=O.CC1=CC=CC(C)=C1 UQBRAHLFLCMLBA-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical class C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SFSRMWVCKNCASA-JSUSWRHTSA-N methyl (z,12r)-2-acetyl-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCC(C(C)=O)C(=O)OC SFSRMWVCKNCASA-JSUSWRHTSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- FIBARIGPBPUBHC-UHFFFAOYSA-N octyl 8-(3-octyloxiran-2-yl)octanoate Chemical compound CCCCCCCCOC(=O)CCCCCCCC1OC1CCCCCCCC FIBARIGPBPUBHC-UHFFFAOYSA-N 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000005498 phthalate group Chemical group 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical class S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urethanes or thiourethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/72—Heating or cooling
- B29C45/7207—Heating or cooling of the moulded articles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/04—Polyesters derived from hydroxycarboxylic acids
- B29K2067/046—PLA, i.e. polylactic acid or polylactide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2509/00—Use of inorganic materials not provided for in groups B29K2503/00 - B29K2507/00, as filler
- B29K2509/02—Ceramics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0077—Yield strength; Tensile strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0089—Impact strength or toughness
-
- 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
- C08G2230/00—Compositions for preparing biodegradable polymers
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/13—Morphological aspects
- C08G2261/134—Rod and coil building blocks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
本发明涉及聚乳酸树脂组合物和使用其的模塑产品。根据本发明的聚乳酸树脂组合物具有优异的环境友好性和生物降解性,并且由于热变形温度(HDT)高而具有优异的耐热性,由于结晶度和结晶速率高而可以在商业上合理的循环时间内进行注塑,因此可适用于模塑产品的制备。
Description
技术领域
本发明涉及聚乳酸树脂组合物和包含该聚乳酸树脂组合物的模塑产品。
背景技术
诸如聚对苯二甲酸乙二醇酯(PET)、尼龙、聚烯烃或柔性聚氯乙烯(PVC)的原油树脂已广泛用作各种应用的材料,例如包装材料。然而,由于原油树脂不可生物降解,因此它们在处理时可能造成环境污染,例如通过排放大量使全球变暖的气体二氧化碳。此外,随着石油资源逐渐耗尽,人们正在广泛探讨聚乳酸树脂作为生物质可生物降解树脂的潜在用途。
然而,当聚乳酸树脂用于注射成型应用时,由于聚乳酸树脂本身结晶度低和结晶缓慢,使得工艺生产率可能降低,因为这样的性能降低了耐热性(热变形温度(HDT):55℃)并增加从模具中取出所需的冷却时间,导致整个循环时间增加。
为了解决上述限制,已知一种方法可将HDT提高到100℃以上,其中通过将聚D-乳酸(PDLA)树脂作为成核剂引入聚乳酸树脂,使结晶度增加。然而即使应用这种方法,结晶速率对于商业应用来说仍然很低,因此在注塑期间循环时间增加。
为了解决这个问题,可以通过在聚乳酸树脂中引入成核剂和增塑剂来提高结晶速率,但是增塑剂会从注塑制品中渗出,并且无法实现所需的快速结晶效果。
因此,最近提出了一种共聚聚乳酸(PLA)作为替代方案,其中将柔性组分引入PLA分子结构中(参见韩国专利申请公开号2013-0135758)。特别地,对于引入聚氨酯多元醇重复单元的PLA共聚物,由于引入柔性组分,可以确保所需的柔性而不降低分子量并避免增塑剂的渗出,因此这种PLA共聚物因其技术价值或商业价值而受到认可。
由于具有聚氨酯多元醇重复单元的柔性PLA共聚物包含在其自身内充当增塑剂的软链段,结晶速率比常规普通PLA树脂快,但仍需要开发具有更高结晶度和更快结晶速率的PLA树脂,以便将PLA树脂用于注塑成型的商业应用。
发明内容
技术问题
因此,本发明的目的是提供一种聚乳酸树脂组合物,该组合物由于热变形温度(HDT)高而显示出优异的耐热性,并且由于结晶度和结晶速率高而可用于商业注塑。此外,本发明的目的是提供包含聚乳酸树脂组合物的模塑产品。
解决方案
为了实现上述目的,本发明提供一种聚乳酸树脂组合物,其包括聚乳酸树脂,该聚乳酸树脂包括含有由式1表示的聚乳酸重复单元的硬链段,以及含有聚氨酯多元醇重复单元的软链段,所述聚氨酯多元醇重复单元中由式2表示的聚醚型多元醇重复单元通过氨基甲酸酯键线性连接;作为成核剂的聚D-乳酸(PDLA)树脂;和滑石:
[式1]
[式2]
其中,在式1中,n是700-5000的整数;和
在式2中,A是具有2-5个碳原子的直链亚烷基或支链亚烷基,m是10-100的整数。
此外,本发明提供包含聚乳酸树脂组合物的模塑产品。
有益效果
根据本发明的聚乳酸树脂组合物具有优异的环境友好性和生物降解性,并且由于热变形温度(HDT)高而具有优异的耐热性,由于结晶度和结晶速率高而可以在商业上合理的循环时间内进行注塑,因此可适用于模塑产品的制备。
具体实施方式
在下文中,将详细描述本发明。
聚乳酸树脂
根据本发明的聚乳酸树脂组合物包括聚乳酸树脂,该聚乳酸树脂包括含有由以下式1表示的聚乳酸重复单元的硬链段,以及含有聚氨酯多元醇重复单元的软链段,所述聚氨酯多元醇重复单元中由以下式2表示的聚醚型多元醇重复单元通过氨基甲酸酯键线性连接;作为成核剂的聚D-乳酸(PDLA)树脂;和滑石:
[式1]
[式2]
其中,在式1中,n是700-5000的整数;和
在式2中,A是具有2-5个碳原子的直链亚烷基或支链亚烷基,m是10-100的整数。
所述聚乳酸树脂包括含有由以下式1表示的聚乳酸重复单元硬链段,以及含有聚氨酯多元醇重复单元的软链段,该聚氨酯多元醇重复单元中由以下式2表示的聚醚型多元醇重复单元通过氨基甲酸酯键(-C(=O)-NH-)线性连接。聚乳酸树脂可以是包括硬链段和软链段的嵌段共聚物。具体地,聚乳酸树脂是其中包含在硬链段中的聚乳酸重复单元的端羧基和聚氨酯多元醇重复单元的端羟基通过酯键连接的嵌段共聚物。
在根据本发明实施方案的聚乳酸树脂中,包含在硬链段中的式1的聚乳酸重复单元可以是聚L-乳酸重复单元(参见以下式1a)、聚D-乳酸重复单元(参见以下式1b),或它们共聚的重复单元。具体地,式1的聚乳酸重复单元可以是聚L-乳酸重复单元。
[式1a]
[式1b]
其中,在式1a和式1b中,p和q是1以上的整数,其表示重复单元的数目。
聚L-乳酸重复单元可以衍生自以下式3a的L-丙交酯或L-乳酸,并且聚D-乳酸重复单元可以衍生自以下式3b的D-丙交酯或D-乳酸。
[式3a]
[式3b]
例如,聚L-乳酸重复单元和聚D-乳酸重复单元共聚的聚乳酸重复单元可以是无规立构或杂同立构共聚重复单元,其中不存在特殊的立构规整性或有规立构。
通过基本上包含聚乳酸重复单元作为硬链段,本发明的聚乳酸树脂可以具有生物质树脂特异性生物降解性,并且通过包含聚氨酯多元醇重复单元作为软链段,由聚乳酸树脂获得的制品的柔性可以同时得到显着改善。而且,由于硬链段和软链段结合成嵌段共聚物,可以减少软链段的渗出现象,并且通过添加软链段,可以显着减少由树脂获得的制品的耐湿性、机械性能、耐热性、透明度或雾度特性下降。
根据本发明实施方案的聚乳酸树脂可包含基于聚乳酸树脂总重量的65wt%-95wt%的上述硬链段和5wt%-35wt%的软链段,特别是80wt%-95wt%的硬链段和5wt%-20wt%的软链段,更特别是82wt%-94wt%的硬链段和6wt%-18wt%的软链段。
当硬链段的量在上述范围内时,聚乳酸树脂的分子量性质可以更好(例如,可以获得相对高的分子量和相对窄的分子量分布),以及这样获得的模塑产品的机械性能可以更好。同时,当软链段的量在上述范围内时,可以在注塑期间确保聚乳酸树脂的柔性,并且由于聚氨酯多元醇重复单元充分起到聚合引发剂的作用,因此可以表现出优异的分子量性质。
包含在软链段中的聚氨酯多元醇重复单元具有这样的结构:其中式2的聚醚型多元醇重复单元通过氨基甲酸酯键(-C(=O)-NH-)线性连接。具体地,聚醚型多元醇重复单元通过环氧烷烃等单体的开环(共)聚合获得,其中聚醚型多元醇重复单元具有端羟基。如上所述的端羟基可以与二异氰酸酯化合物的异氰酸酯基反应以形成氨基甲酸酯键,并且聚醚型多元醇重复单元可以通过氨基甲酸酯键彼此线性连接以形成聚氨酯多元醇重复单元。
聚醚型多元醇重复单元可以和二异氰酸酯化合物反应,使得聚醚型多元醇重复单元的端羟基与二异氰酸酯化合物的异氰酸酯基的摩尔比在1:0.50-1:0.99的范围内。因此,可以形成聚氨酯多元醇重复单元。具体地,摩尔比可以在1:0.60-1:0.90的范围内,例如,1:0.70-1:0.85。
例如,聚醚型多元醇重复单元可以是通过至少一种环氧烷烃的开环(共)聚合获得的聚醚型多元醇(共)聚合物的重复单元。环氧烷烃的实例可以是环氧乙烷、环氧丙烷、环氧丁烷或四氢呋喃。
由此获得的聚醚型多元醇重复单元的实例可以是聚乙二醇(PEG)的重复单元;聚(1,2-丙二醇)的重复单元;聚(1,3-丙二醇)的重复单元;聚四亚甲基二醇的重复单元;聚丁二醇的重复单元;由环氧丙烷和四氢呋喃共聚的多元醇的重复单元;由环氧乙烷和四氢呋喃共聚的多元醇的重复单元;或由环氧乙烷和环氧丙烷共聚的多元醇的重复单元。
考虑到赋予聚乳酸树脂制品柔性、对聚乳酸重复单元的亲和性和保湿性,可以将聚(1,3-丙二醇)的重复单元或聚四亚甲基二醇的重复单元用作聚醚型多元醇重复单元。
此外,聚醚型多元醇重复单元的数均分子量(Mn)可以为1000-100000,例如10000-50000。如果聚醚型多元醇重复单元的分子量过大或过小,则聚乳酸树脂的分子量性能可能劣化,因此,由聚乳酸树脂得到的制品的柔性、机械性能和耐热性可能会下降。
另外,可以通过与聚醚型多元醇重复单元的端羟基键合而形成氨基甲酸酯键的二异氰酸酯化合物可以是分子中具有两个异氰酸酯基的任意化合物。
二异氰酸酯化合物的实例可以是1,6-六亚甲基二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、1,3-二甲苯二异氰酸酯、1,4-二甲苯二异氰酸酯、1,5-萘二异氰酸酯、间亚苯基二异氰酸酯、对亚苯基二异氰酸酯、3,3'-二甲基-4,4'-二苯基甲烷二异氰酸酯、4,4'-双亚苯基二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或氢化二苯基甲烷二异氰酸酯。另外,可以使用本领域技术人员公知的各种其他二异氰酸酯化合物而没有任何限制。
基于聚乳酸树脂组合物的总重量,聚乳酸树脂的含量可以为60wt%-95wt%,例如80wt%-95wt%。当聚乳酸树脂的量在上述范围内时,可以在不降低包含聚乳酸树脂的聚乳酸树脂组合物的机械性能、耐热性、抗粘连性和透明性的同时提高热变形温度和结晶度。
成核剂
根据本发明的聚乳酸树脂组合物包含聚D-乳酸(PDLA)树脂和滑石作为成核剂。
聚D-乳酸树脂的重均分子量(Mw)可以为100000-400000,例如100000-320000。
基于聚乳酸树脂组合物的总重量,聚D-乳酸树脂的含量可以为1wt%-20wt%,例如1wt%-10wt%。当重均分子量(Mw)和聚D-乳酸树脂的量在上述范围内时,可以进一步改善聚乳酸树脂组合物的耐热性和结晶度。
滑石的平均粒径可以为0.5μm-2.5μm,例如0.5μm-1.5μm。
基于聚乳酸树脂组合物的总重量,滑石的含量可以为1wt%-20wt%,例如1wt%-15wt%。当滑石的量在上述范围内时,可以进一步改善聚乳酸树脂组合物的结晶度。
附加组分
不是所有包含在聚乳酸树脂组合物中的聚乳酸重复单元都必须具有与聚氨酯多元醇重复单元键合的嵌段共聚物的构型,并且至少一些聚乳酸重复单元可具有不与聚氨酯多元醇重复单元键合的聚乳酸树脂构型。在这种情况下,聚乳酸树脂组合物可包括上述嵌段共聚物和不与聚氨酯多元醇重复单元键合的单一聚乳酸树脂。
聚乳酸树脂组合物可以进一步包括磷系稳定剂和/或抗氧化剂,以抑制软链段在其制备过程中的氧化或热分解。
每一种磷系稳定剂和抗氧化剂可以适当地选自本领域中通常使用的那些。抗氧化剂的实例可以是受阻酚类抗氧化剂、胺类抗氧化剂、硫代酯类抗氧化剂或亚磷酸酯类抗氧化剂。
除了稳定剂和抗氧化剂之外,聚乳酸树脂组合物可以进一步包含多种添加剂,例如增塑剂、紫外线稳定剂、色阻剂、消光剂、除臭剂、阻燃剂、抗风化剂、抗静电剂、脱模剂、氧化抑制剂、离子交换剂、着色颜料以及无机或有机颗粒,其量应不会对树脂的物理性质产生负面影响。
增塑剂的实例可以是邻苯二甲酸酯增塑剂,例如邻苯二甲酸二乙酯、邻苯二甲酸二辛酯和邻苯二甲酸二环己酯;脂肪族二元酸酯类增塑剂,例如己二酸二-1-丁酯、己二酸二正辛酯、癸二酸二正丁酯、壬二酸二(2-乙基己基)酯;磷酸酯类增塑剂,例如2-乙基己基二苯基磷酸酯和辛基二苯基磷酸酯;多元羟基羧酸酯增塑剂,例如乙酰柠檬酸三丁酯、乙酰柠檬酸三(2-乙基己)酯和柠檬酸三丁酯;脂族酯增塑剂,例如乙酰蓖麻油酸甲酯和硬脂酸戊酯;多元醇酯增塑剂,例如甘油三乙酸酯;或环氧增塑剂,例如环氧大豆油、环氧亚麻籽油脂肪酸丁酯和环氧硬脂酸辛酯。
此外,着色颜料的实例可以是无机颜料,例如炭黑、氧化钛、氧化锌和氧化铁;或有机颜料,例如青色素类、含磷有机颜料、奎宁类、紫环酮类,异吲哚啉酮类和硫靛类。
物理性质
根据本发明的聚乳酸树脂(嵌段共聚物)可具有相当窄的分子量分布以及相对大的分子量。
聚乳酸树脂的数均分子量(Mn)可以为50000-200000,例如50000-150000,并且重均分子量(Mw)可以为100000-400000,例如100000-320000。当Mn和Mw在上述范围内时,由原料树脂获得的制品的机械性能可能更好。
此外,聚乳酸树脂分子量分布(Mw/Mn)可以为1.60-2.30,例如1.80-2.20,其定义为Mw与Mn的比例。当分子量分布在上述范围内时,原料树脂可以容易地进行注塑,并且由此获得的模塑产品可以表现出优异的机械性能。
聚乳酸树脂的玻璃化转变温度(Tg)可以为20℃-80℃,例如30℃-70℃。由具有上述Tg范围的聚乳酸树脂进行模塑得到的模塑产品的柔性或刚性可能更优。
此外,聚乳酸树脂的熔融温度(Tm)可以为150℃-180℃,例如160℃-180℃。当Tm在上述范围内时,原料树脂的加工特性和耐热性可以进一步改善。
此外,包含聚乳酸树脂和成核剂(聚D-乳酸树脂,滑石)的聚乳酸树脂组合物可具有100℃以上的热变形温度(HDT)。
本发明提供一种包含聚乳酸树脂组合物的模塑产品。特别地,聚乳酸树脂组合物可适用于制备注塑产品。
此外,包含聚乳酸树脂组合物的模塑产品可通过包括注塑方法在内的一系列方法制备。具体地,聚乳酸树脂组合物可以通过在100℃-150℃的温度下冷却10秒-35秒而自动注塑,并且由此制备的模塑产品可具有100℃-150℃的热变形温度(HDT)。
如上所述,根据本发明的聚乳酸树脂组合物具有优异的环境友好性和生物降解性,并且由于热变形温度(HDT)高而表现出优异的耐热性,由于结晶度和结晶速率高而可以在商业上合理的循环时间内进行注塑,因此可适用于模塑产品的制备。
制备方法
根据本发明的聚乳酸树脂组合物中的聚乳酸树脂的制备方法如下。
制备聚乳酸树脂(嵌段共聚物)的方法
聚乳酸树脂可通过包括以下步骤的方法制备:对至少一种单体例如环氧烷烃进行开环(共)聚合,以形成具有聚醚型多元醇重复单元的(共)聚合物;使(共)聚合物与二异氰酸酯化合物在催化剂的存在下进行反应,形成具有聚氨酯多元醇重复单元的(共)聚合物;在具有聚氨酯多元醇重复单元的(共)聚合物的存在下,使乳酸(D-乳酸或L-乳酸)缩聚或使丙交酯(D-丙交酯或L-丙交酯)开环聚合。
在下文中,将更详细地描述制备本发明的聚乳酸树脂的方法。
首先,通过至少一种单体(例如环氧烷烃)的开环(共)聚合制备具有聚醚型多元醇重复单元的(共)聚合物,其中这可以根据制备聚醚型多元醇(共)聚合物的典型方法进行。
其后,将具有聚醚型多元醇重复单元的(共)聚合物、二异氰酸酯化合物和氨基甲酸酯反应催化剂装入反应器中,并在加热和搅拌的同时进行氨基甲酸酯反应。通过该反应,二异氰酸酯化合物的两个异氰酸酯基和(共)聚合物的端羟基结合形成氨基甲酸酯键。由此可以形成具有聚氨酯多元醇重复单元构型的(共)聚合物,其中聚醚型多元醇重复单元通过氨基甲酸酯键线性连接,并且其作为软链段被包括在上述聚乳酸树脂中。
氨基甲酸酯反应可在常规锡(Sn)系催化剂的存在下进行,例如辛酸亚锡(2-乙基己酸亚锡)、二月桂酸二丁基锡或二月桂酸二辛基锡。此外,氨基甲酸酯反应可在用于制备聚氨酯树脂的典型反应条件下进行。例如,在氮气氛中加入二异氰酸酯化合物和聚醚型多元醇(共)聚合物,然后通过加入氨基甲酸酯反应催化剂在70℃-80℃的反应温度下进行反应1小时-5小时,以制备具有聚氨酯多元醇重复单元的(共)聚合物。
随后,当乳酸(D-或L-乳酸)的缩聚或丙交酯(D-或L-丙交酯)的开环聚合在具有聚氨酯多元醇重复单元的(共)聚合物的存在下进行,可形成聚乳酸重复单元,同时可以制备聚乳酸树脂嵌段共聚物,其包含分别作为硬链段和软链段的聚乳酸重复单元和聚氨酯多元醇重复单元。
丙交酯的开环聚合可以在金属催化剂的存在下进行,金属催化剂包括碱土金属、稀土金属、过渡金属、铝、锗、锡或锑。具体地,金属催化剂可以是这些金属的羧酸盐、醇盐、卤化物、氧化物或碳酸盐的形式。例如,辛酸亚锡、四异丙氧基钛或三异丙氧基铝可用作金属催化剂。
聚乳酸树脂组合物可以通过将如上所述制备的聚乳酸树脂与成核剂混合来形成。具体地,聚乳酸树脂组合物可以通过将聚乳酸树脂与成核剂混合并将该混合物在诸如双螺杆挤出机的设备中在180℃-200℃下混合而形成。
具体实施方式
实施例
以下通过实施例对本发明进行详细说明。以下实施例旨在进一步说明本发明而不用于限制其范围。
[原料]
-树脂A(柔性PLA树脂):f-PLLA,SK化学
-树脂B(普通PLLA树脂):PLA 3251D,自然工厂公司
-树脂C(第一成核剂:PDLA树脂):将6g 1-十二烷醇和4kg D-丙交酯加入到配备有氮气入口管、搅拌器、催化剂入口、流出冷凝器和真空系统的8升反应器中,并进行5次氮气冲洗。通过将混合物的温度升至150℃使D-丙交酯完全溶解,并将作为催化剂的120ppmw的2-乙基己酸亚锡在500ml甲苯中蒸馏并通过催化剂入口加入反应器中。随后,在1kg的氮气压力下在185℃下进行反应2小时,通过催化剂入口添加200ppmw的磷酸,然后混合15分钟以使残留的催化剂失活。通过真空反应除去未反应的D-丙交酯直至压力达到0.5torr,得到树脂C(PDLA树脂)。
-滑石(第二成核剂):平均粒径为1.0μm
通过以下方法测量树脂A、B和C的玻璃化转变温度(Tg)、熔融温度(Tm)、数均分子量(Mn)和重均分子量(Mw),并且其结果示于下表1中。
(1)重均分子量(Mw)和数均分子量(Mn)
将聚乳酸树脂以0.25wt%的浓度溶解在氯仿中,通过凝胶渗透色谱法(ViscotekTDA 305制造,柱:Shodex LF804*2ea)测量Mw和Mn,并使用聚苯乙烯作为标准材料来计算重均分子量(Mw)和数均分子量(Mn)。
(2)玻璃化转变温度(Tg,℃)
在将样品熔融并淬火后,以10℃/分钟的速率升高样品的温度,同时通过使用差示扫描量热计(TA Instruments)测量其玻璃化转变温度。Tg被确定为每条切线的中间值和吸热曲线的基线。
(3)熔融温度(Tm,℃)
在将样品熔融并淬火后,以10℃/分钟的速率升高样品的温度,同时通过使用差示扫描量热计(TA Instruments)测量其熔融温度。Tm被确定为晶体的吸热熔融峰的最大温度值。
[表1]
[实施例]
实施例1和2以及对比例1和2:聚乳酸树脂组合物的制备
树脂A、B和C,和/或滑石以下表2中列出的量(wt%)混合,并在200℃下在双螺杆挤出机(Toshiba-machine)中混合以制备聚乳酸树脂组合物。
实验例
将实施例和对比例中制备的聚乳酸树脂组合物分别引入注塑机(Victory 80,Engel)中,然后注塑制品在110℃下结晶以制备样品。在这种情况下,根据以下测量标准将样品制备成具有不同的尺寸。另外,将每个注塑制品自动注入所需的时间确定为冷却时间。
(1)拉伸强度(kgf/cm2)测量
根据ASTM D638,使用万能试验机(UTM,INSTRON)测量每个样品的拉伸强度。将5次测试的平均值示出作为为结果值。
(2)拉伸伸长率(%)测量
根据ASTM D638,使用万能试验机(UTM,INSTRON)测量每个样品的拉伸伸长率。将5次测试的平均值示出作为结果值。
(3)冲击强度(J/m)测量
在对具有1/8英寸厚度的样品进行开缺口之后,根据ASTM D256在室温(23℃)下测量每个样品的缺口Izod冲击强度。
(4)热变形温度(HDT,℃)测量
根据ASTM D648测量每个样品的热变形温度,其结果示于下表2中。
[表2]
参照表2的结果,对于包含柔性PLA树脂的实施例1和2,可以确认即使添加少量PDLA作为成核剂,注塑期间的冷却时间也减少了。而且,证实了拉伸强度、伸长率、冲击强度和HDT值提高了,因此机械性能和耐热性能也得到了显着改善。相反,对于包含普通PLA树脂(普通PLLA树脂)的对比例1和2,证实了冷却时间比实施例的冷却时间更长,并且机械性能和耐热性能均较差。
[参考例]
参考例1-4:聚乳酸树脂混合物的制备
将树脂A、B和/或C以下表3中列出的量(wt%)混合(对于参考例3,进一步加入聚乙二醇(PEG)作为增塑剂)并在200℃下在双螺杆挤出机(Toshiba-machine)中混合以制备聚乳酸树脂混合物。
参考实验例
将参考例中制备的聚乳酸树脂混合物分别引入注塑机(Victory 80,Engel)中,然后注塑制品在110℃下结晶以制备样品。在这种情况下,根据以下测量标准将样品制备成具有不同的尺寸。另外,将每个注塑制品自动注入所需的时间确定为冷却时间。
(1)半结晶时间的测量
通过差示扫描量热法(DSC)测量参考例1-4中制备的聚乳酸树脂混合物的半结晶时间。具体而言,将各聚乳酸树脂混合物在高于熔融温度(Tm)的温度下熔融。此后,将各混合物在100℃、110℃、120℃和130℃下淬火,然后获得结晶峰开始和结束之间的中间值(拐点),同时将温度等温保持在将每个温度,将中间值(拐点)定义为半结晶时间。
(2)热变形温度的测量(HDT,℃)
根据ASTM D648测量每个样品的热变形温度。
(3)评估渗出
将样品在80℃的热空气烘箱中储存24小时后,评价增塑剂的渗出。当在样品表面上可观察到粘稠时,用“ⅹ”表示,当没有观察到粘稠时,用“○”表示。
(4)注塑性能的评价
将在参考例1-4中制备的聚乳酸树脂混合物注入注塑机,以注塑拉伸样品,然后注塑制品在在110℃下结晶,这时通过察看自动注射的冷却时间(由“A”表示)和半自动注射的冷却时间(由“1/2”表示)来比较结晶速率。在这种情况下,空白表示注射失败。
测量结果分别列于下表3和4中。
[表3]
[表4]
参照表3和4的结果,证实了随着作为成核剂的PDLA的量增加,结晶速率增加,并且HDT值也得到提高。
具体地,证实了包含柔性PLA的聚乳酸树脂(参考例1)的结晶速率与包含普通PLA的聚乳酸树脂(参考例3)相比增加了2-3倍,即使少量加入了5%的PDLA。此外,证实了参考例1的HDT值大于包括普通PLA的聚乳酸树脂(参考例3和4)的HDT值。特别地,参考例4通过进一步包括增塑剂(PEG),其HDT值略微增加,但是,由于参考例4的HDT值小于参考例1的HDT值,可以理解为其耐热性能比参考例1的耐热性能差。另外,通过目视观察识别增塑剂的渗出。
Claims (14)
1.一种聚乳酸树脂组合物,包括:
聚乳酸树脂,所述聚乳酸树脂包括含有由式1表示的聚乳酸重复单元的硬链段,以及含有聚氨酯多元醇重复单元的软链段,所述聚氨酯多元醇重复单元中由式2表示的聚醚型多元醇重复单元通过氨基甲酸酯键线性连接;
作为成核剂的聚D-乳酸(PDLA)树脂;和
滑石:
[式1]
[式2]
其中,在式1中,n是700-5000的整数;和
在式2中,A是具有2-5个碳原子的直链亚烷基或支链亚烷基,m是10-100的整数。
2.根据权利要求1所述的聚乳酸树脂组合物,其中所述聚乳酸树脂组合物包含60wt%-95wt%的所述聚乳酸树脂,1wt%-20wt%的所述聚D-乳酸树脂和1wt%-20wt%的所述滑石。
3.根据权利要求2所述的聚乳酸树脂组合物,其中所述聚乳酸树脂组合物包含80wt%-95wt%的所述聚乳酸树脂,1wt%-10wt%的所述聚D-乳酸树脂和1wt%-15wt%的所述滑石。
4.根据权利要求1所述的聚乳酸树脂组合物,其中所述聚乳酸树脂的数均分子量为50000-200000,重均分子量为100000-400000。
5.根据权利要求1所述的聚乳酸树脂组合物,其中所述聚乳酸树脂的玻璃化转变温度(Tg)为20℃-80℃,熔融温度(Tm)为150℃-180℃。
6.根据权利要求1所述的聚乳酸树脂组合物,其中所述聚乳酸树脂包含65wt%-95wt%的所述硬链段和5wt%-35wt%的所述软链段。
7.根据权利要求1所述的聚乳酸树脂组合物,其中所述聚乳酸树脂是嵌段共聚物,其中所述硬链段中包含的所述聚乳酸重复单元的端羧基和所述聚氨酯多元醇重复单元的端羟基通过酯键连接。
8.根据权利要求1所述的聚乳酸树脂组合物,其中所述聚乳酸重复单元是聚L-乳酸重复单元。
9.根据权利要求1所述的聚乳酸树脂组合物,其中所述聚氨酯多元醇重复单元通过氨基甲酸酯键线性连接,所述氨基甲酸酯键通过所述聚醚型多元醇重复单元的端羟基与二异氰酸酯化合物的异氰酸酯基团的反应形成。
10.根据权利要求9所述的聚乳酸树脂组合物,其中所述聚醚型多元醇重复单元的所述端羟基与所述二异氰酸酯化合物的所述异氰酸酯基团的反应摩尔比在1:0.50-1:0.99的范围内。
11.根据权利要求1所述的聚乳酸树脂组合物,其中所述聚D-乳酸树脂的重均分子量为100000-400000。
12.一种模塑产品,包含根据权利要求1所述的聚乳酸树脂组合物。
13.根据权利要求12所述的模塑产品,其中所述模塑产品通过在100℃-150℃的温度下冷却10秒-35秒而自动注塑成型。
14.根据权利要求12所述的模塑产品,其中所述模塑产品的热变形温度为100℃-150℃。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2016-0035223 | 2016-03-24 | ||
KR1020160035223A KR102456006B1 (ko) | 2016-03-24 | 2016-03-24 | 폴리유산 수지 조성물 및 이를 포함한 성형용품 |
PCT/KR2017/000819 WO2017164504A1 (ko) | 2016-03-24 | 2017-01-24 | 폴리유산 수지 조성물 및 이를 포함한 성형용품 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108779234A true CN108779234A (zh) | 2018-11-09 |
Family
ID=59900639
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201780016664.9A Pending CN108779234A (zh) | 2016-03-24 | 2017-01-24 | 聚乳酸树脂组合物和包含该聚乳酸树脂组合物的模塑产品 |
Country Status (6)
Country | Link |
---|---|
US (1) | US11118051B2 (zh) |
EP (1) | EP3434710A4 (zh) |
KR (1) | KR102456006B1 (zh) |
CN (1) | CN108779234A (zh) |
TW (1) | TWI829619B (zh) |
WO (1) | WO2017164504A1 (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108003581B (zh) * | 2017-11-27 | 2019-10-11 | 金发科技股份有限公司 | 一种聚乳酸复合材料及其应用 |
US11485852B2 (en) * | 2020-02-18 | 2022-11-01 | Northern Technologies International Corporation | High impact resistant poly(lactic acid) blends |
CN113150520B (zh) * | 2021-04-26 | 2022-08-16 | 北京工商大学 | 一种用于一次性勺子的生物降解塑料 |
KR20230137736A (ko) * | 2022-03-22 | 2023-10-05 | 주식회사 엘지화학 | 폴리락타이드 수지 조성물, 및 이의 제조 방법 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100056700A1 (en) * | 2008-09-02 | 2010-03-04 | Cheil Industries Inc. | Environmentally-Friendly Polylactic Acid Resin Composition |
WO2010056089A2 (ko) * | 2008-11-17 | 2010-05-20 | 제일모직 주식회사 | 클레이 강화 폴리유산 수지 조성물, 이의 제조 방법 및 이를 이용한 성형품 |
CN103328535A (zh) * | 2010-11-08 | 2013-09-25 | Sk化学株式会社 | 聚乳酸树脂、其制备方法以及包含所述聚乳酸树脂的包装膜 |
CN103890089A (zh) * | 2011-10-24 | 2014-06-25 | 普拉克生化公司 | 包含plla和pdla的组合物 |
CN104245811A (zh) * | 2012-03-07 | 2014-12-24 | 胡赫塔迈基股份有限公司 | 基本上基于生物的,可热成型的组合物以及由其形成的容器 |
CN104487478A (zh) * | 2012-06-01 | 2015-04-01 | Sk化学株式会社 | 聚乳酸树脂和包含该聚乳酸树脂的包装膜 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20110054400A (ko) * | 2009-11-17 | 2011-05-25 | 제일모직주식회사 | 클레이 강화 폴리유산 수지 조성물, 이의 제조 방법 및 이를 이용한 성형품 |
KR101225944B1 (ko) * | 2009-07-08 | 2013-01-24 | 제일모직주식회사 | 천연 보강제 강화 폴리유산 복합 수지 조성물 및 이를 이용한 성형품 |
KR101191961B1 (ko) * | 2010-11-08 | 2012-10-17 | 에스케이케미칼주식회사 | 폴리유산 수지 및 이를 포함하는 포장용 필름 |
EP2669320B1 (en) * | 2011-01-25 | 2019-07-10 | SK Chemicals Co., Ltd. | Polylactic acid resin film |
WO2014157597A1 (ja) * | 2013-03-25 | 2014-10-02 | 帝人株式会社 | 樹脂組成物 |
KR101569247B1 (ko) * | 2013-06-19 | 2015-11-13 | 롯데케미칼 주식회사 | 결정화 속도가 향상된 폴리유산 스테레오 복합수지 조성물 및 이의 성형방법 |
KR101526690B1 (ko) * | 2013-10-07 | 2015-06-05 | 현대자동차주식회사 | 고내열 내충격성 폴리유산 복합재료 조성물 |
-
2016
- 2016-03-24 KR KR1020160035223A patent/KR102456006B1/ko active IP Right Grant
-
2017
- 2017-01-24 US US16/081,998 patent/US11118051B2/en active Active
- 2017-01-24 CN CN201780016664.9A patent/CN108779234A/zh active Pending
- 2017-01-24 WO PCT/KR2017/000819 patent/WO2017164504A1/ko active Application Filing
- 2017-01-24 EP EP17770475.6A patent/EP3434710A4/en active Pending
- 2017-02-08 TW TW106104096A patent/TWI829619B/zh active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100056700A1 (en) * | 2008-09-02 | 2010-03-04 | Cheil Industries Inc. | Environmentally-Friendly Polylactic Acid Resin Composition |
WO2010056089A2 (ko) * | 2008-11-17 | 2010-05-20 | 제일모직 주식회사 | 클레이 강화 폴리유산 수지 조성물, 이의 제조 방법 및 이를 이용한 성형품 |
CN103328535A (zh) * | 2010-11-08 | 2013-09-25 | Sk化学株式会社 | 聚乳酸树脂、其制备方法以及包含所述聚乳酸树脂的包装膜 |
CN103890089A (zh) * | 2011-10-24 | 2014-06-25 | 普拉克生化公司 | 包含plla和pdla的组合物 |
CN104245811A (zh) * | 2012-03-07 | 2014-12-24 | 胡赫塔迈基股份有限公司 | 基本上基于生物的,可热成型的组合物以及由其形成的容器 |
CN104487478A (zh) * | 2012-06-01 | 2015-04-01 | Sk化学株式会社 | 聚乳酸树脂和包含该聚乳酸树脂的包装膜 |
Also Published As
Publication number | Publication date |
---|---|
EP3434710A1 (en) | 2019-01-30 |
US11118051B2 (en) | 2021-09-14 |
KR20170110876A (ko) | 2017-10-12 |
US20200283622A1 (en) | 2020-09-10 |
WO2017164504A1 (ko) | 2017-09-28 |
TW201803914A (zh) | 2018-02-01 |
KR102456006B1 (ko) | 2022-10-18 |
EP3434710A4 (en) | 2019-11-27 |
TWI829619B (zh) | 2024-01-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20100113734A1 (en) | Process for producing polylactide-urethane copolymers | |
CN102643419B (zh) | 一种脂肪-芳香族共聚酯的制备方法 | |
CN108779234A (zh) | 聚乳酸树脂组合物和包含该聚乳酸树脂组合物的模塑产品 | |
CN107522852A (zh) | 一种含二聚酸聚酯链段的生物基可生物降解三嵌段、多嵌段共聚物及其制备方法和应用 | |
CN106574103B (zh) | 包括基于聚丙交酯的聚合物的组合物 | |
JP4200340B2 (ja) | 樹脂組成物および成形体 | |
TWI609039B (zh) | 聚乳酸樹脂組成物 | |
KR101690082B1 (ko) | 생분해성 수지 조성물 및 그로부터 제조되는 생분해성 필름 | |
KR102103524B1 (ko) | 폴리유산-폴리아미드 얼로이 수지 조성물 | |
US9102782B2 (en) | Transparent copolyester, preparing method thereof and articles made from the same | |
EP2891674B1 (en) | Lactide copolymer, and resin composition and film comprising same | |
TW201604218A (zh) | 可熱密封可撓性聚乳酸樹脂組成物 | |
WO2015076560A1 (ko) | 폴리유산/아크릴로니트릴-부타디엔-스타이렌 공중합체 얼로이 수지 조성물 | |
CN102942687A (zh) | 一种阻燃脂肪-芳香族共聚酯及其制备方法 | |
KR102003480B1 (ko) | 폴리유산-폴리올레핀 얼로이 수지 조성물 | |
TWI742035B (zh) | 包含除水劑之可撓性聚乳酸樹脂組成物 | |
JP3622386B2 (ja) | 生分解性ブロック共重合体の製造方法 | |
JP3726401B2 (ja) | ポリ乳酸系共重合体の製造方法及びポリ乳酸系共重合体 | |
JP5050610B2 (ja) | 低温特性に優れた樹脂組成物の成型体 | |
EP4442766A1 (en) | Biodegradable film | |
KR101921697B1 (ko) | 유연 폴리유산 수지 조성물 | |
CN102924902A (zh) | 一种塑料制品及其制备方法 | |
CN116410452A (zh) | 一种聚酯增容剂及其制备方法和应用 | |
KR20050006384A (ko) | 개선된 충격강도를 갖는 생분해성 폴리락트산 블렌드 수지조성물 및 이의 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181109 |