CN114921090A - Optical polylactic acid composition, preparation method and application thereof - Google Patents
Optical polylactic acid composition, preparation method and application thereof Download PDFInfo
- Publication number
- CN114921090A CN114921090A CN202210642829.6A CN202210642829A CN114921090A CN 114921090 A CN114921090 A CN 114921090A CN 202210642829 A CN202210642829 A CN 202210642829A CN 114921090 A CN114921090 A CN 114921090A
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- optical
- acid composition
- polyurethane copolymer
- ring
- 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.)
- Granted
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 155
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 142
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 142
- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000004814 polyurethane Substances 0.000 claims abstract description 75
- 229920002635 polyurethane Polymers 0.000 claims abstract description 73
- -1 thiol compound Chemical class 0.000 claims abstract description 48
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 25
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 19
- 239000000155 melt Substances 0.000 claims description 18
- 125000001424 substituent group Chemical group 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 239000004970 Chain extender Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000001746 injection moulding Methods 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 6
- 230000000655 anti-hydrolysis Effects 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 4
- ISKHPWRCJVAJPP-UHFFFAOYSA-N SCSSSC(CCCCCCCCCC)(S)S Chemical compound SCSSSC(CCCCCCCCCC)(S)S ISKHPWRCJVAJPP-UHFFFAOYSA-N 0.000 claims description 3
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 2
- HAQZWTGSNCDKTK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOC(=O)CCS HAQZWTGSNCDKTK-UHFFFAOYSA-N 0.000 claims description 2
- ACBOBKJKSFYJML-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-sulfanylpropanoic acid Chemical compound CC(S)C(O)=O.CC(S)C(O)=O.CC(S)C(O)=O.CCC(CO)(CO)CO ACBOBKJKSFYJML-UHFFFAOYSA-N 0.000 claims description 2
- BVLURFHKVMKQQN-UHFFFAOYSA-N [3-(sulfanylmethyl)dithian-3-yl]methanethiol Chemical compound SCC1(CS)CCCSS1 BVLURFHKVMKQQN-UHFFFAOYSA-N 0.000 claims description 2
- HGWOEEVMFFQINI-UHFFFAOYSA-N [3-(sulfanylmethylsulfanyl)dithian-3-yl]sulfanylmethanethiol Chemical compound SCSC1(SSCCC1)SCS HGWOEEVMFFQINI-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 claims description 2
- 239000000047 product Substances 0.000 description 24
- 239000000463 material Substances 0.000 description 23
- 238000012545 processing Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000002834 transmittance Methods 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 239000012467 final product Substances 0.000 description 8
- 230000014509 gene expression Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 150000003573 thiols Chemical group 0.000 description 7
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- 125000006413 ring segment Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229920001432 poly(L-lactide) Polymers 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- 229930182843 D-Lactic acid Natural products 0.000 description 2
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 229920006392 biobased thermoplastic Polymers 0.000 description 2
- 229940022769 d- lactic acid Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002103 osmometry Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000010421 standard material Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- SKEZDZQGPKHHSH-UHFFFAOYSA-J 2-hydroxypropanoate;tin(4+) Chemical compound [Sn+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O SKEZDZQGPKHHSH-UHFFFAOYSA-J 0.000 description 1
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000001313 C5-C10 heteroaryl group Chemical group 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
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- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
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- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 238000010309 melting process Methods 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
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- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 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 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/428—Lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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- Chemical & Material Sciences (AREA)
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
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Abstract
The invention relates to an optical polylactic acid composition, a preparation method thereof and application thereof in optical components and/or lenses. The optical polylactic acid composition comprises: a polylactic acid optical resin obtained by blending a polylactic acid-polyurethane copolymer with a thiol compound, wherein the polylactic acid-polyurethane copolymer comprises a structure of the following formula (I):
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an optical polylactic acid composition, a preparation method thereof, and application thereof in optical components and/or lenses.
Background
In recent years, the optical industry technology is continuously advanced, the imaging optical system is rapidly developed towards the direction of light weight, simple structure, low cost and high benefit, and the application of the plastic optical device in the imaging optical system is more and more extensive. The resin lens has a low market share in China, so the resin lens has good development prospect and development potential in China market.
Since the optical plastics have been put into practice since the beginning of the last century, the basic main varieties are mainly: PMMA, polycarbonate, polystyrene, etc., however these have difficulties to meet the increasingly different industrial requirements in a wide range of application fields. The synthesis of new and high-performance optical resin materials is a trend of necessity.
The PU series polymerized monomer is an excellent optical material and has the characteristics of high refractive index, high Abbe number, low specific gravity, high impact resistance and the like. The PU material has high wear resistance, and the wear resistance of the lens is improved by about 20 percent compared with the wear resistance of the common lens by adding the film layer on the surface of the lens; high rigidity, high strength and strong shock resistance, and is particularly suitable for diamond edge cutting glasses which are most popular in processing.
CN102775608B discloses a thioether-modified polyacrylate optical plastic and a preparation method thereof, wherein a mixture of mercaptan containing a plurality of thioether bonds and a plurality of sulfydryl groups, acrylate containing a plurality of double bonds and an initiator are used as raw materials to prepare the thioether-modified polyacrylate optical resin, and the thioether-modified polyacrylate optical resin has high refractive index and good transmittance.
CN105294970A discloses a preparation method of a bio-based thermoplastic polyurethane elastomer material with good optical properties, and a polylactic acid-based thermoplastic polyurethane elastomer film obtained by the method, which specifically comprises the following steps: 1) reacting polylactic acid, stannous chloride and 1, 4-butanediol to obtain modified polylactic acid; 2) reacting modified polylactic acid with isocyanate to obtain a prepolymer; 3) reacting the prepolymer obtained in the step 2) with an ethylene glycol chain extender, then injecting the obtained product into a mold, pressing, demolding, vulcanizing, and standing at room temperature for 7 days to obtain the film of the bio-based thermoplastic polyurethane elastomer.
Disclosure of Invention
In one aspect, the present invention relates to an optical polylactic acid composition comprising: polylactic acid-polyurethane copolymer and thiol compound, wherein,
the polylactic acid-polyurethane copolymer comprises a structure of the following formula (I):
a is an integer from 20 to 200;
b is an integer from 20 to 200;
n is an integer of 15 to 75
X is a connecting structure;
the thiol compound contains more than 2 mercapto functional groups.
In another aspect, the present invention relates to a method for preparing the optical polylactic acid composition of the present invention, which comprises the steps of: reacting an oligomer prepared by a dehydration condensation reaction of lactic acid or lactide with ethylene glycol to prepare a polylactic acid prepolymer; reacting the polylactic acid prepolymer with an isocyanate chain extender to prepare a polylactic acid-polyurethane copolymer; and (2) extruding the polylactic acid-polyurethane copolymer, the thiol compound and optionally an antioxidant and/or an anti-hydrolysis agent through an extruder to prepare the optical polylactic acid composition.
In a further aspect, the present invention also relates to the use of the optical polylactic acid composition of the present invention in an optical member, preferably in an optical lens.
In another aspect, the present invention relates to an optical lens comprising the optical polylactic acid composition of the present invention.
In yet another aspect, the present invention relates to a method of making an optical lens comprising: drying the optical polylactic acid composition master batch, then putting the dried optical polylactic acid composition master batch into a charging barrel, and further plasticizing and melting to obtain optical polylactic acid composition melt adhesive; : enabling the optical polylactic acid composition molten gel to enter a mold cavity; maintaining the pressure and cooling; and taking the optical lens out of the mold after the mold is opened, wherein the molten glue is injected into the mold cavity by adopting a multi-section glue injection process.
Detailed Description
General definitions and terms
All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety if not otherwise indicated.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the definitions provided herein will control.
All percentages, parts, ratios, etc. are by weight unless otherwise indicated.
When an amount, concentration, or other value or parameter is given as either a range, preferred range, or a pair of upper and lower preferable values or specific values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. When numerical ranges are recited herein, unless otherwise stated, the stated ranges are meant to include the endpoints thereof, and all integers and fractions within the ranges. The scope of the invention is not limited to the specific values recited when defining a range. For example, "1-8" encompasses 1, 2, 3, 4, 5, 6, 7, 8, as well as any subrange consisting of any two values therein, e.g., 2-6, 3-5.
The terms "about" and "approximately," when used in conjunction with a numerical variable, generally mean that the value of the variable and all values of the variable are within experimental error (e.g., within 95% confidence interval for the mean) or within ± 10% of the specified value, or more.
The terms "comprising," "including," "having," "containing," or "involving," and other variations thereof herein, are inclusive or open-ended and do not exclude additional unrecited elements or method steps. It will be understood by those skilled in the art that terms such as "comprising" and "comprises" are intended to have the meaning of …. The expression "consisting of …" excludes any element, step or ingredient not specified. The expression "consisting essentially of …" means that the scope is limited to the specified elements, steps or components, plus optional elements, steps or components that do not materially affect the basic and novel characteristics of the claimed subject matter. It is to be understood that the expression "comprising" covers the expressions "consisting essentially of …" and "consisting of …".
The term "selected from …" means that one or more elements in the later listed groups are independently selected and may include a combination of two or more elements.
When values or range ends are described herein, it is to be understood that the disclosure includes the particular values or ends recited.
The term "one or more" or "at least one" as used herein refers to one, two, three, four, five, six, seven, eight, nine or more.
Unless otherwise indicated, the terms "combination thereof" and "mixture thereof" refer to a multi-component mixture of the elements described, such as two, three, four, and up to the maximum possible multi-component mixture.
Furthermore, no number of elements or components of the invention has been previously indicated and no limitation on the number of occurrences (or presence) of an element or component is intended. Thus, it should be read to include one or at least one and singular forms of a component or ingredient also include the plural unless the numerical value explicitly indicates the singular.
The terms "optional" or "optionally" as used herein mean that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
When methods, components or steps are described, they are identified by letters or numbers for distinguishing purposes only, and there is no limitation that such methods, components or steps must be performed in the order or sequence identified. Those skilled in the art can make reasonable adjustments.
When the lower and upper limits of a range of values are disclosed, any value falling within the range and any included range is specifically disclosed. In particular, each range of values (in the form "about a to b", or equivalently, "about a-b") disclosed herein is to be understood as meaning each number and range encompassed within the broader range.
For example, the expression "C 1-6 "is to be understood to cover any subrange therein as well as each point value, e.g. C 2 - 5 、C 3-4 、C 1-2 、C 1-3 、C 1-4 、C 1-5 Etc. and C 1 、C 2 、C 3 、C 4 、C 5 、C 6 And so on. For example, the expression "C 3-10 "should also be read in a similar manner to encompass any subranges and point values subsumed therein, for example. The expression "5-to 10-membered" should also be understood in a similar manner, e.g. any sub-ranges and point values comprised therein may be covered, e.g. 5-to 6-membered, 5-to 7-membered,5-8, 5-9, 5-10, 6-7, 6-8, 6-9, 6-10, 7-8, etc., as well as 5, 6, 7, 8, 9, 10, etc.
The term "alkyl", used herein alone or in combination with other groups, refers to a saturated straight or branched chain hydrocarbon group. The alkyl group may be C 1-6 An alkyl group. As used herein, the term "C 1-6 Alkyl "refers to a saturated straight or branched chain hydrocarbon group having 1 to 6 carbon atoms (e.g., 1, 2, 3, 4, 5, or 6 carbon atoms). For example "C 1-6 Alkyl "may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl and the like.
The term "alkoxy", used herein alone or in combination with other groups, refers to an alkyl group attached to the rest of the molecule through an oxygen atom. The alkoxy group may be C 1-6 An alkoxy group.
The term "cycloalkyl (ring)", used herein alone or in combination with other groups, refers to aliphatic hydrocarbons comprising a cyclic structure. The cycloalkyl group may be C 3-8 A cycloalkyl ring. Examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.
The term "aryl (ring)", used herein alone or in combination with other groups, refers to an all-carbon monocyclic or fused polycyclic (e.g., bicyclic) aromatic group having a conjugated pi-electron system. The aryl group may be "C 6-10 Aromatic ring ". As used herein, the term "C 6-10 Aromatic ring "refers to an aromatic group containing 6 to 10 carbon atoms. Examples include, but are not limited to, phenyl, naphthyl.
The term "heteroaryl (ring)", used herein alone or in combination with other groups, refers to an aromatic group wherein one or more (e.g., 1, 2 or 3) ring atoms are heteroatoms selected from N, O and S, and the remaining ring atoms are C. Heteroaryl groups can be characterized by the number of ring atoms. The heteroaryl ring may be C 5-10 Heteroaryl ring, wherein one or more (e.g. 1, 2 or 3) ring atoms is a heteroatom selected from N, O and S. E.g. C 5-10 The heteroaromatic ring may contain 5 to 10 carbon atoms (e.g. 5, 6, 7,8. 9 or 10), in particular containing 5, 6, 9, 10 ring atoms. And in each case the heteroaryl ring may optionally be further benzo-fused. For example, examples of heteroaromatic rings are thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, pyrazinyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl and the like, and benzo derivatives thereof; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, benzofuranyl, benzothienyl, indolyl, isoindolyl, and the like, and benzo derivatives thereof.
The term "halogen" refers to fluorine, chlorine, bromine, iodine.
When a group as described herein is located in the middle of a molecule, it will be understood by those skilled in the art that it may represent the corresponding subunit, if desired. For example, when an alkyl group is located between other groups, it may represent the corresponding alkylene group, if desired.
The terms "substituted" and "substituted" mean that one or more (e.g., one, two, three, or four) hydrogens on the designated atom is replaced with a selection from the indicated group, provided that the designated atom's normal valency under the present circumstances is not exceeded and that the substitution results in a stable compound. Combinations of substituents and/or variables are permissible only if such combinations result in stable compounds.
If a substituent is described as "optionally … substituted," the substituent may be (1) unsubstituted or (2) substituted. If an atom or group is described as optionally substituted with one or more of a list of substituents, one or more hydrogens on the atom or group may be replaced with an independently selected, optional substituent. If substituents are described as "independently selected from" or "each independently is", then each substituent is selected independently of the other. Thus, each substituent may be the same as or different from another (other) substituent. For example, a certain substituent or substitution position or different substituents or substitution positions have R groups (such as but not limited to R) that may be designated by the same or different symbols 3 、R a 、R b 、R c And/or R x ) In the selection of (2), R's may be independently selected from each other, and may be the same or different. The same is true with regard to the selection of values such as m, n, a, b, etc.
Herein, when a wavy line is shown on a chemical bond in a structural fragment, it means that the bond is linked to another structure. For example:
indicating that the benzene ring is linked to another structure through a bond with a wavy line shown thereon.
As used herein, unless otherwise indicated, the point of attachment of a substituent may be from any suitable position of the substituent.
When a bond of a substituent is shown through a bond connecting two atoms in a ring, then such substituent may be bonded to any ring atom in the substitutable ring.
The term "repeating unit" refers to a combination of atoms linked in a certain manner on a polymer chain, which is an essential unit constituting a polymer.
The term "molecular weight distribution (Mw/Mn)" is the ratio of the weight average molecular weight to the number average molecular weight. This can be determined herein by the following method: the polylactic acid-b-polyethylene glycol block copolymer was dissolved in chloroform at a concentration of 0.25 wt%, and measured by gel permeation chromatography (Viscotek TDA 305) using polystyrene as a standard material.
The term "number average molecular weight" as used herein is alternatively referred to as number average molar mass. If the molecular weight in the polymer is M j Has a mole fraction of x j The number of molecules is N j Number average molecular weight
Is composed of
Wherein
The measurement can be carried out by methods such as end group measurement, gel chromatography, membrane osmometry, vapor osmometry, boiling point elevation, mass spectrometry, etc. Molecular weights described herein are number average molecular weights unless otherwise specified. The number average molecular weight and the distribution thereof in the present invention can be measured, for example, by using a Gel Permeation Chromatograph (GPC) or a mass spectrometer.
As used herein, the term "room temperature" (RT) refers to about 20 to 35 ℃, preferably about 25 ℃.
In one aspect, the present invention relates to an optical polylactic acid composition comprising: polylactic acid-polyurethane copolymer and thiol compound through blending to obtain polylactic acid optical resin.
Polylactic acid-polyurethane copolymer
Obtaining a polylactic acid-polyurethane copolymer comprising the structure of the following formula (I) by reaction of an isocyanate chain extender with a polylactic acid prepolymer:
wherein,
a. b represents the number of repeating units in the polylactic acid moiety, each independently selected from integers of 20-200, such as: 20. 40, 60, 80, 100, 120, 140, 160, 180, 200, etc.;
x is a connecting structure.
The polylactic acid-polyurethane copolymer contains a structure composed of polylactic acid-polyurethane copolymerized units, which is prepared by the reaction of a polylactic acid prepolymer and an isocyanate chain extender.
The polylactic acid prepolymer is introduced into the polylactic acid part, so that the final product, namely the optical polylactic acid composition has excellent biodegradability, and the optical polylactic acid composition is used in optical components (such as optical lenses) to obtain an environment-friendly product.
The polylactic acid portion of the polylactic acid-polyurethane copolymer has a single optical activity so that the resulting final product has good optical properties. In one embodiment, the polylactic acid moiety in the polylactic acid-polyurethane copolymer is a poly (L-lactic acid) (PLLA), which can be prepared by using a poly (L-lactic acid) prepolymer. In one embodiment, the polylactic acid moiety in the polylactic acid-polyurethane copolymer is a dextrorotatory polylactic acid (PDLA), which can be prepared by using a dextrorotatory polylactic acid prepolymer.
In one embodiment, the polylactic acid prepolymer has a number average molecular weight of about 0.2 to 3 ten thousand, preferably about 0.5 to 2 ten thousand, for example about 1 ten thousand. The number average molecular weight of the polylactic acid prepolymer influences the reactivity and rate of the polylactic acid prepolymer participating in the latter-stage polymerization, side reactions, and the like. The excessively high number average molecular weight results in the reduction of the activity of the reactive groups (i.e., hydroxyl groups) at both ends of the polylactic acid prepolymer, which is not favorable for the subsequent reaction with diisocyanate; the molecular weight of the final branched block copolymer is low due to the low number average molecular weight, and the mechanical properties are poor.
a. b represents the number of the repeating units of the polylactic acid part in the polylactic acid-polyurethane copolymer, influences the chain length of the polylactic acid part, further influences the proportion of the polylactic acid part in the product, and influences the performance of the final product. In one embodiment of the invention, a, b in formula (I) are integers each independently selected from 20 to 200, for example: 20. 40, 60, 80, 100, 120, 140, 160, 180, 200, etc. The chain length of the polylactic acid part is too long, the proportion of the polylactic acid part is too high, the refractive property and the toughness of the optical polylactic acid composition of a final product are reduced, and the heat resistance is lower; the chain length of the polylactic acid part is too short, the proportion of the polylactic acid part is too small, the light transmittance of the final product of the optical polylactic acid composition is reduced, the color is whitish, and the processing thermal stability is poor.
n represents the number of repeating polylactic acid-polyurethane copolymer units. In one embodiment of the invention, n in formula (I) is an integer selected from 15 to 75, such as 15, 25, 35, 45, 65, 75, and the like. The repeated number of the polylactic acid-polyurethane copolymerization units is too high, the molecular weight of the final product is too high, the melt fluidity is poor, and the injection molding processing is difficult; the repeated number is too low, the molecular weight of the finally prepared copolymer of the final product is low, the mechanical properties are poor, and the processing thermal stability is poor. X is a connecting structure, and the structure of the connecting structure depends on an isocyanate chain extender used in the preparation process of the polylactic acid-polyurethane copolymer. By reaction of the isocyanate chain extender with the polylactic acid prepolymer, the linking structure X is introduced, into which the corresponding polyurethane moiety is introduced. The introduction of the polyurethane structure helps to improve the mechanical properties (e.g., toughness) of the product and improve the optical characteristics of the product, thereby obtaining a high-light-transmission, high-refractive-index product.
In one embodiment, the linking structure X is: - (L) 1 ) p - (A ring) q -(L 2 ) r - (B ring) s -(L 3 ) t -。
Wherein p, q, r, s, t are each independently 0 or 1, and p, q, r, s, t are not simultaneously 0. 0 indicates that the corresponding fragment is not present in the connecting structure X, and the adjacent fragments are directly connected through chemical bonds. As an example to illustrate in detail: when p is 0, the linking structure X is- (A ring) q -(L 2 ) r - (B ring) s -(L 3 ) t -; when q is 0, the linking structure X is: - (L) 1 ) p -(L 2 ) r - (B ring) s -(L 3 ) t -。
In one embodiment, p, q are 1, r, s, t are 0. In another embodiment, p, t are 0 and p, r, s are 1. In another embodiment, p, r, s, t are 0 and q is 1. In another embodiment, p is 0 and q, r, s, t are 1.
L 1 、L 2 、L 3 Each independently selected from C 1-6 An alkyl group. Said C is 1-6 The alkyl group may optionally be interrupted by one or more O atoms. Herein "C 1-6 An alkyl O atom interrupted "means that there is an O atom between two C atoms, forming a structure of" -C-O-C- ". In particular, for "C 1 Alkyl ", when interrupted by an O oxygen atom, means that it forms a" -O-C- "or" -C-O- "structure.
Ring A and ring B are each independently selected from: c 3-8 Cycloalkyl ring, C 6-10 Aromatic ring and C 5-10 A heteroaromatic ring. The connection manner of the A-ring and B-ring to the adjacent fragment is not particularly limited.
L 1 、L 2 、L 3 Ring a and ring B are each independently and optionally substituted with one or more substituents selected from R, which is independently selected from: c 1-6 Alkyl radical, C 2-6 Ester group, halogen, cyano, C 1-6 Alkoxy radical, C 3-8 Cycloalkyl ring, C 6-10 Aromatic ring, C 5-10 A heteroaromatic ring.
In a particular embodiment, the linking structure X is selected from the following structures: -Ph (CH) 3 )-、-(CH 2 ) 6 -、
In one embodiment, the polylactic acid-polyurethane copolymer of the present invention further comprises an isocyanate group. In the process of blending the polylactic acid-polyurethane copolymer and the thiol compound, the isocyanate group reacts with the sulfydryl in the thiol compound, so that the obtained polylactic acid optical resin has a three-dimensional structure and excellent performance.
The number average molecular weight, also referred to as viscosity average molecular weight, can be determined using methods conventional in the art, such as by: the polylactic acid-b-polyethylene glycol block copolymer was dissolved in chloroform at a concentration of 0.25 wt%, and measured by gel permeation chromatography (Viscotek TDA 305) using polystyrene as a standard material. In one embodiment, the polylactic acid-polyurethane copolymer has a number average molecular weight of about 5 to 15 ten thousand, preferably about 10 to 15 ten thousand, for example about 12 ten thousand. The polylactic acid-polyurethane copolymer has proper number average molecular weight, which is favorable for obtaining better mechanical property, processing property, refractive index, light transmittance and the like. The number average molecular weight is too high, the melt viscosity is high, the injection molding processing is difficult, and the refractive index is reduced; the number average molecular weight is too low, and various mechanical properties and processing stability of the prepared copolymer are poor.
The melt index, also known as melt flow index, melt flow index or melt flow index, is used to indicate the flowability of a material during processing. The larger the melt index, the lower the viscosity of the polymer material. The melt index can be determined using methods customary in the art, for example by measuring the number of grams of melt flowing out in 10min at 160 ℃ under a load of 2.16kg using a melt index tester (MFI-1211). In one embodiment, the polylactic acid-polyurethane copolymer has a melt index from 5g/10min to 45g/10min, preferably from 5g/10min to 30g/10min, more preferably from 8 to 25g/10min, for example about 20g/10 min. The polylactic acid-polyurethane copolymer has proper melt index, is favorable for better melt flowability and is convenient for injection molding processing. The melt index is too high, the viscosity of the polylactic acid-polyurethane copolymer is too low, the injection molding processing shrinkage is severe, and the mechanical property of the product is poor; the melt index is too low, the injection molding pressure is too high, and the temperature is too high.
The glass transition temperature, which is the temperature at which a polymer transitions from a high elastic state to a glassy state, is generally indicated by Tg. The glass transition temperature (Tg) can be determined using methods conventional in the art, for example using a differential scanning calorimeter (DSC, TA instruments) with a temperature ramp rate of, for example, 10 deg.C/min. In one embodiment, the Tg is from about 40 to about 70 deg.C, preferably from about 50 to about 70 deg.C, for example about 65 deg.C. The proper glass transition temperature is beneficial to make the polylactic acid-polyurethane copolymer have proper segmental motion capability, proper use temperature and processing temperature.
The melting point of the polymer refers to the temperature at which the polymer is changed from a solid state to a molten state, and the melting process of the polymer has a wide melting temperature range, namely, a melting limit exists. The temperature at which the melt is finally completely melted is generally referred to as the melting point. The melting point (Tm) can be determined using methods conventional in the art, for example using a differential scanning calorimeter (DSC, TA instruments) with a temperature ramp rate of, for example, 10 deg.C/min. In one embodiment, the polylactic acid-polyurethane copolymer has a melting point (Tm) of about 110-. The proper melting point (Tm) is favorable for enabling the polylactic acid-polyurethane copolymer to have proper segmental motion capability, proper use temperature and processing temperature.
Thiol compounds
Herein, the polylactic acid optical resin is obtained by blending a thiol compound with a polylactic acid-polyurethane copolymer. The introduction of the thiol compound can increase the refractive index and Abbe number of the product and improve the impact resistance of the product to some extent. The thiol compound used herein has 2 or more thiol functional groups, has characteristics of high transparency, no color, low acid value, high refractive index, and the like, and can improve optical characteristics (e.g., transparency, refractive index, and the like) of a product. Meanwhile, the thiol compound used herein has good compatibility with the polylactic acid-polyurethane copolymer, has low viscosity, and can be well dispersed in a matrix material. The thiol compound contains more than 2 thiol functional groups, and the multifunctionality of the thiol enables the obtained polylactic acid optical resin to present a three-dimensional structure and have excellent performance. In one embodiment, the thiol compounds used herein contain 2-10 thiol functional groups, for example 2, 3, 4, 5, 6, 7, 8, 9, 10 thiol functional groups.
The polylactic acid optical resin obtained by blending the thiol compound and the polylactic acid-polyurethane copolymer has high sulfur content, so that the polylactic acid optical resin has high refractive index and low dispersibility.
The term "blending" herein means mixing the thiol compound together with the polylactic acid-polyurethane copolymer. It includes physical blending and also includes reactive blending. Reactive blending means: when the raw materials contain functional groups that can react under the blending conditions, a corresponding chemical reaction occurs during the blending process. In one embodiment, the polylactic acid-polyurethane copolymer of the present invention comprises an isocyanate group. In the blending process of the polylactic acid-polyurethane copolymer and the thiol compound, the isocyanate group reacts with the mercapto group in the thiol compound, so that the obtained polylactic acid optical resin has a body structure and excellent performance.
In one embodiment, the thiol compounds include, but are not limited to, one or more of the following: bis (mercaptomethyl) trithioundecanedithiol, mercaptomethyl bisthiodithiaoctane, bis (mercaptomethyl) dithiane, bis (mercaptomethylthio) dithiane, (bis (mercaptomethylthio) ethyl) dithetane, trimethylolpropane tris (mercaptopropionate), butanediol bis (mercaptoacetate), diethylene glycol bis (mercaptoacetate), ethylene glycol bis (mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate).
Optical polylactic acid composition
The optical polylactic acid composition of the present invention comprises: a polylactic acid optical resin obtained by blending a polylactic acid-polyurethane copolymer with a thiol compound, wherein the polylactic acid-polyurethane copolymer and the thiol compound are as described above.
In one embodiment, the weight ratio of the polylactic acid-polyurethane copolymer to the thiol compound in the blending process to obtain the polylactic acid optical resin is 200:1 to 10: 1. The proper weight ratio is helpful for the product to obtain better transparency, matrix resin compatibility, optical stability, processability and the like. The weight ratio is too high, phase separation is easy to cause, the light transmittance of the product is greatly reduced, and the product is easy to yellow and dark; the weight ratio is too low to improve the refractive property of the product.
In one embodiment, the optical polylactic acid composition of the present invention further comprises an antioxidant. The antioxidant is also called as a stabilizer, can effectively inhibit or reduce the thermal oxidation and photo-oxidation reaction speed of the resin, remarkably improves the heat resistance and light resistance of the resin material, and delays the degradation and aging processes of the resin material.
The proper type and content of antioxidant helps to improve the performance of the optical polylactic acid composition product. In one embodiment, the antioxidant is selected from one or more of the following: hindered phenolic antioxidants (e.g., AO-1010), aminic antioxidants, thio antioxidants, and phosphate antioxidants (e.g., AO-626). In one embodiment, the antioxidant is present in an amount of about 0.2 to 2 wt%, preferably about 0.5 to 1.2 wt%, for example about 0.5 wt%, 0.8 wt%, 1 wt%, based on the total weight of the optical polylactic acid composition.
In one embodiment, the optical polylactic acid composition of the present invention further comprises an anti-hydrolysis agent. The material performance is deteriorated due to hydrolysis in the high polymer material, and an active group in the hydrolysis-resistant agent reacts with a reactive group (such as a hydroxyl group, a carboxyl group, an amino group, a thioether group and the like) in the high polymer material, so that the hydrolysis resistance and the performance stability under high temperature and high humidity of the material are improved, and the viscosity reduction, yellowing, cracking and the like of the material due to hydrolysis are improved.
The appropriate type and content of hydrolysis resistant agent helps to improve the performance of the optical polylactic acid composition product. In one embodiment, the hydrolysis resistance agent is selected from: isocyanates, oxazolines, epoxies, carbodiimides, and combinations thereof. In one embodiment, the hydrolysis resistant agent is present in an amount of about 0.2 to 2 wt%, preferably about 0.5 to 1.2 wt%, for example about 0.5 wt%, 0.8 wt%, 1 wt%, based on the total weight of the optical polylactic acid composition.
Preparation method
In another aspect, the present invention also relates to a method for preparing an optical polylactic acid composition, comprising the steps of:
reacting an oligomer prepared by a dehydration condensation reaction of lactic acid or lactide with ethylene glycol to prepare a polylactic acid prepolymer;
reacting the polylactic acid prepolymer with an isocyanate chain extender to prepare a polylactic acid-polyurethane copolymer;
and (2) carrying out reactive extrusion on the polylactic acid-polyurethane copolymer, the thiol compound and optionally an antioxidant and/or an anti-hydrolysis agent through an extruder to prepare the optical polylactic acid composition.
(1) Adding glycol into oligomer prepared by lactic acid or lactide dehydration condensation reaction for reaction to prepare polylactic acid prepolymer;
the polylactic acid prepolymer generally comprises a structure of the following formula (II):
wherein a and b represent the number of repeating units of the polylactic acid moiety in the polylactic acid prepolymer. In one embodiment of the invention, a, b in formula (II) are integers each independently selected from 20 to 200, for example: 20. 40, 60, 80, 100, 120, 140, 160, 180, 200, etc.
In one embodiment, the polylactic acid prepolymer is a poly-L-lactic acid (PLLA) prepolymer, which can be prepared by using L-lactic acid or L-lactide as a raw material. In one embodiment, the polylactic acid prepolymer is a dextrorotatory polylactic acid (PDLA) prepolymer, which may be prepared by using D-lactic acid or D-lactide as a raw material.
In one embodiment, the polylactic acid prepolymer has a number average molecular weight of about 0.2 to 3 ten thousand, preferably about 0.5 to 2 ten thousand, for example about 1 ten thousand. The proper number average molecular weight of the polylactic acid prepolymer is beneficial to obtaining better mechanical property, processing property, refractive index, light transmittance and the like. The number average molecular weight is too high, the melt viscosity is high, the injection molding processing is difficult, and the refractive index is reduced; the number average molecular weight is too low, and various mechanical properties and processing stability of the prepared copolymer are poor.
The ratio of the oligomer of polylactic acid to ethylene glycol needs to be in a suitable range to obtain the objective polylactic acid prepolymer. The proportion is too high, and the glycol is excessive, so that excessive crosslinking appears in the subsequent reaction for preparing the polylactic acid-polyurethane copolymer, and the final product is whitish and opaque; the ratio is too low, and the low polymer of the polylactic acid has insufficient reaction, so that the subsequently prepared polylactic acid-polyurethane copolymer has wide molecular weight distribution and poor processing stability. In one embodiment, the ratio of the oligomer of polylactic acid to ethylene glycol in (1) is from about 10:1 to 100: 1.
In one embodiment, a catalyst is used to catalyze the polymerization of oligomers of polylactic acid with ethylene glycol. The addition of the catalyst can accelerate the polymerization reaction, wherein the proper catalyst can effectively accelerate the reaction rate, the reaction can not be influenced by the chemical properties of the catalyst, such as acidity, alkalinity, oxidizability, reducibility and the like, the proper catalyst can avoid side reactions and improve the concentration of the product.
In one embodiment, the catalyst used in (1) is selected from: tin-based catalysts, zinc-based catalysts, and combinations thereof. The tin-based catalyst refers to a compound containing elemental tin, which may be an organotin compound or an inorganic tin compound. The zinc-based catalyst refers to a compound containing elemental zinc, which may be an organozinc compound or an inorganic zinc compound.
In one embodiment, the catalyst used in (1) is selected from: stannous benzoate, stannous octoate, aluminum isopropoxide, stannous chloride, zinc divinyl, zinc acetate and tin lactate.
(2) And reacting the polylactic acid prepolymer with an isocyanate chain extender to obtain the polylactic acid-polyurethane copolymer.
Wherein the isocyanate functional group contained in the isocyanate chain extender reacts with the terminal hydroxyl group of the polylactic acid prepolymer to introduce a polyurethane structure, thereby obtaining a polylactic acid-polyurethane copolymer, which is as described above.
The ratio of the polylactic acid prepolymer to the isocyanate chain extender needs to be in a suitable range to obtain the target polylactic acid-polyurethane copolymer. The ratio of the polylactic acid prepolymer to the isocyanate chain extender is too high, the melt index of the copolymer is too low, the fluidity is poor, and the product is yellow and opaque in color; the proportion is too low, the molecular weight is too low, and the mechanical property and the processing property of the product are not ideal. In one embodiment, the weight ratio of polylactic acid-polyurethane copolymer to isocyanate chain extender is from about 8:1 to 60: 1.
(3) And extruding the polylactic acid-polyurethane copolymer and the thiol compound through an extruder to prepare the optical polylactic acid composition.
And extruding the mixture by an extruder, and blending the polylactic acid-polyurethane copolymer and the thiol compound to obtain the optical polylactic acid composition.
The ratio of the polylactic acid-polyurethane copolymer to the thiol compound needs to be within a proper range, and the ratio is too low to improve the refractive property of the product; too high a proportion causes phase separation and a decrease in mechanical properties, resulting in a decrease in the properties of the product. In one embodiment, (3), the weight ratio of polylactic acid-polyurethane copolymer to thiol compound is about 200:1 to 10: 1.
In one embodiment, an antioxidant and/or hydrolysis resistant agent may be added and extruded together with the polylactic acid-polyurethane copolymer and the thiol compound to enhance the antioxidant and hydrolysis resistance of the optical polylactic acid composition.
In one embodiment, the polylactic acid-polyurethane copolymer, the thiol compound, is reactive extruded through an extruder. Reactive extrusion refers to a technique of simultaneously performing a chemical reaction and extrusion processing in a processing and molding apparatus (e.g., an extruder), and is also called reactive extrusion. The principle is as follows: a plasticizing extrusion system consisting of a screw and a charging barrel is used as a continuous reaction, various pre-reacted raw material components (polylactic acid-polyurethane copolymer and mercaptan compound in the invention) are added into the screw, and the processes of mixing, conveying, plasticizing, reacting and extruding from a die head of the raw materials are realized under the rotation of the screw. The method has the advantages of high reaction efficiency, convenient processing process, continuous large-scale production and low cost, and the process does not use or uses little solvent and is friendly to human body and environment. The screw can play the roles of conveying, stirring, mixing, shearing and the like, and the screw extruder has the advantages of easy feeding, good dispersibility, good mixing property, controllable residence time, continuous production and the like.
In one embodiment, reactive extrusion in (3) comprises a melt blending, extrusion process.
In one embodiment, the extruder of the present invention is a screw extruder, preferably a twin screw extruder. The rotating speed of the screw has influence on the mixing uniformity, the residence time and the like, the rotating speed of the screw is too high, the residence time of the materials is too short, the reaction is not fully carried out, and the target product is difficult to obtain; the screw rotating speed is too slow, and the production efficiency is too low. In one embodiment, the screw speed of the extruder during extrusion is 100-. In one embodiment, the temperature of the melt blending is 150 ℃ to 200 ℃ to allow uniform mixing and sufficient reaction.
Properties of optical polylactic acid composition
The mechanical properties of the optical polylactic acid composition can be characterized by tensile strength, elongation at break and notched impact strength.
Elongation at break: the relative elongation at break, i.e. the ratio of the elongation at break of the optical polylactic acid composition to its initial length, is generally expressed in percentage. It is an index for characterizing the softness and elasticity of the material. The greater the elongation at break, the better the softness and elasticity. When the optical polylactic acid composition fiber is broken by external force, the ratio of the elongation length before and after stretching to the length before stretching is called the elongation at break. The elongation at break of the optical polylactic acid composition can be measured using means conventional in the art, for example, using GB/T1040.2-2006. The breaking elongation of the optical polylactic acid composition is about 100-300%, preferably about 150-250%.
Tensile strength: representing the resistance of the maximum uniform plastic deformation of the material, wherein the deformation of the tensile sample is uniform and consistent before the tensile sample bears the maximum tensile stress, but after the maximum tensile stress is exceeded, the necking phenomenon begins to occur, namely, the concentrated deformation is generated; for brittle materials with no (or little) uniform plastic deformation, it reflects the fracture resistance of the material. The tensile strength of the optical polylactic acid composition can be measured using means conventional in the art, for example, using GB/T1040.2-2006. The tensile strength of the optical polylactic acid composition of the present invention is about 20 to 50MPa, preferably about 25 to 40 MPa.
The notched impact strength can represent the impact resistance of the optical polylactic acid composition, and reflects the toughness of the polylactic acid resin composition. The notched impact strength of the optical polylactic acid composition can be measured using means conventional in the art, for example using GB/T1043.1-2008. The optical polylactic acid composition of the invention has a notched impact strength of about 3 to 20KJ/m 2 Preferably about 7-20KJ/m 2 。
In another aspect, the present invention also relates to the use of the optical polylactic acid composition in an optical member. Preferably, the present invention also relates to the use of the optical polylactic acid composition in optical lenses.
In yet another aspect, the present invention also relates to an optical lens comprising the optical polylactic acid composition of the present invention.
In yet another aspect, the invention also relates to a method of making an optical lens comprising:
drying the optical polylactic acid composition master batch, then putting the dried optical polylactic acid composition master batch into a charging barrel, and further plasticizing and melting to obtain optical polylactic acid composition melt adhesive;
enabling the molten glue to enter a mold cavity;
maintaining the pressure and cooling;
and taking the optical lens out of the mold after opening the mold.
In one embodiment, the molten gel is injected into the mold cavity using a multi-shot injection molding process. Injection molding processes using multi-stage injection of the plastic help to obtain better injection molded products, which typically include 1 stage: filling the mold quickly; and 2, section: compaction (slow); and 3, section: pressure maintaining; it is also possible to include 4 stages: and (5) removing pressure and cooling.
In one embodiment, the injection molding process is carried out using the following parameters: the temperature of each zone extruded by the screw is 180 ℃ and 210 ℃, the injection pressure is 60-110MPa, the injection speed is 3-10mm/s, the pressure maintaining pressure is 50-100MPa, and the pressure maintaining time is 5-15 seconds.
Performance of optical lenses
Refractive index, the ratio of the propagation speed of light in vacuum to the propagation speed of light in the medium. The higher the refractive index of the material, the greater the ability to refract incident light. The measurement can be carried out in a manner conventional in the art, for example, by measuring the refractive index of the optical lens using an Abbe refractometer (NAR-1T solid), and measuring the refractive index at 20 ℃ with light having wavelengths of F 'line (488.0nm), C' line (643.9nm), and e-line (546.1 nm). In one embodiment, the refractive index (n) of the optical lens made of the optical polylactic acid composition of the invention e ) Is about 1.5 or more, preferably about 1.6 or more.
The abbe number is an index indicating the dispersive power of the transparent medium. Generally, the larger the refractive index of the medium, the more severe the dispersion, and the smaller the abbe number; conversely, the smaller the refractive index of the medium, the more slight the dispersion and the larger the Abbe number. The measurements can be made using means conventional in the art, for example using an Abbe refractometer (NAR-1T solid). At 20 deg.C, using light with F 'line (488.0nm), C' line (643.9nm) and e line (546.1nm) wavelength according to Abbe number v e ＝(n e -1)/(n F' -n C' ) The Abbe number of the optical lens can be obtained, wherein n e Refractive index, n, measured with light of e-line wavelength F' Is made of F' light of linear wavelength measured refractive index, n C' Is the refractive index measured with light at the wavelength of the C' line. In one embodiment, the Abbe number (v) of an optical lens made from the optical polylactic acid composition of the invention e ) Above about 35, preferably above about 40.
The yellowness index refers to the degree to which a polymer material deviates from white or yellows. The yellowness index can be used to indicate product quality or degree of aging. The measurement can be carried out in a manner conventional in the art, for example by measuring the yellowness index of an optical lens using a yellowness index meter. In one embodiment, the optical polylactic acid composition of the present invention can be used to prepare an optical lens having a yellowness index of about 15 or less.
Light transmittance, which represents the ability of light to transmit through a medium, is the percentage of the luminous flux transmitted through a transparent or translucent body as compared to the luminous flux incident upon it. The measurement can be carried out in a manner customary in the art, for example by measuring the light transmission with a spectrocolorimeter (hunter pro lab). In one embodiment, the optical transmittance of the optical lens (lens power 0 °, lens center thickness 1.2 ± 0.1mm, temperature 25 ℃) prepared from the optical polylactic acid composition of the present invention is about 98% or more, preferably about 99% or more.
Haze is the percentage of the total transmitted light intensity that is transmitted above an angle of 2.5 ° from the incident light. In one embodiment, the optical lens (lens power 0 °, lens center thickness 1.2 ± 0.1mm, temperature 25 ℃) prepared from the optical polylactic acid composition of the present invention has a haze of about 1.5% or less, preferably about 1% or less.
Advantageous effects
According to the invention, the polyurethane structure with high refractive index and the multi-sulfhydryl compound are introduced, the optical property of polylactic acid is improved through composite modification, and the optical polylactic acid composition with high light transmittance and high refractive index is prepared and has excellent mechanical property. The optical lens obtained by the optical polylactic acid composition of the present invention has good optical characteristics such as portability, moldability, abbe number, transparency, and blocking of ultraviolet rays.
Examples
The present invention will be described in further detail with reference to specific examples.
It should be noted that the following examples are only for clearly illustrating the technical solutions of the present invention, and are not intended to limit the present invention. It will be apparent to those skilled in the art that other variations and modifications may be made in the foregoing disclosure without departing from the spirit or essential characteristics of the invention, and it is not desired to exhaustively enumerate all embodiments, but rather those obvious variations and modifications are within the scope of the invention. Unless otherwise indicated, both the instrumentation and reagent materials used herein are commercially available.
Material
Lactic acid: l-lactic acid, D-lactic acid: anhui Fengyuan group, Inc.
Polylactic acid-polyurethane copolymer: homemade by the process of the invention according to the parameters of table 1. The performance index is shown in table 2.
TABLE 1
TABLE 2
For PLA-PU04 and PLA-PU05, in the process of preparing the polylactic acid prepolymer again, 1, 4-butanediol is used as a raw material to participate in the reaction, the prepared polylactic acid prepolymer further reacts with isocyanate, and finally the obtained polylactic acid-polyurethane copolymers PLA-PU04 and PLA-PU05 respectively have the defects of yellowing, darkening and the like in forms, and are not beneficial to optical application.
Molecular weights and their distributions were measured using GPC. Melting points were measured using a differential scanning calorimeter (Q10): 5-10mg of sample is taken, cooled to 0 ℃, maintained for 3min and raised to 200 ℃ at the speed of 10 ℃/min.
Thiol compounds containing thiol functional groups: thiol compound a: bis (mercaptomethyl) trithioundecanedithiol; a thiol compound B: pentaerythritol tetrakis (2-mercaptoacetate); all purchased from Shenzhen Bofulong New Material science and technology Co
Antioxidant: antioxidant 1010/626 was purchased from Changzhou Xinze polymer materials, Inc.;
hydrolysis resistance agent: AH3000, Kunshandingmu chemical Co Ltd
Preparation of
Preparation of polylactic acid composition
Uniformly mixing the dried polylactic acid-polyurethane copolymer, thiol compound containing thiol functional groups, antioxidant and anti-hydrolysis agent by a high-speed blender to obtain a blended material premix, wherein the dosage of each component is shown in table 3.
The obtained pre-mixture of the blending materials is melted and blended by a double-screw extrusion granulator, the extrusion materials are cooled by wind and then granulated by a granulator, wherein the heating temperature of each section of the extruder from a feed inlet to a discharge outlet of a die head is set to 185-.
Preparation of optical lenses
Pellets of the optical polylactic acid compositions (examples 1 to 12 and comparative examples 1 to 7) were plasticized, melted, and molded by an injection molding machine to prepare optical lenses comprising the optical polylactic acid compositions.
TABLE 3
Testing
The optical polylactic acid composition was tested for its properties according to the following test methods, and the results are shown in table 4:
tensile strength and elongation at break: measured using a universal tester, referred to GB/T1043.1-2008.
Notched impact strength: measured using a universal tester, see GB/T1040.2-2006.
Melt index: measured using a melt index tester (MFI-1211) with reference to GB/T3682-2000.
The optical lens comprising the optical polylactic acid composition was tested for performance according to the following test method, the results of which are shown in table 5:
refractive index: measured using an Abbe refractometer (NAR-1T solid) according to GB/T39691-.
Yellow index: measured using a yellowness index apparatus, reference HG/T3862-2006.
Light transmittance and haze: measured using a spectrocolorimeter (hunter prolob) with reference to GB/T2410-.
TABLE 4
As shown in Table 4, the samples of the examples all have higher elongation at break and notched impact strength, and show better toughness, and the obtained optical polylactic acid composition undergoes a flexible transition due to the polyurethane soft segment contained in the polylactic acid-polyurethane copolymer. The samples of comparative examples 1, 7-9 had low elongation at break, and in comparative examples 7-9, the mechanical properties were reduced due to phase separation caused by the use of too high an amount of thiol compound.
TABLE 5
| Refractive index | Abbe number | Light transmittance | Haze degree | Yellow index | |
| Example 1 | 1.54 | 35 | 98.9 | 1.21 | 6.21 |
| Example 2 | 1.54 | 34 | 98.7 | 1.17 | 6.54 |
| Example 3 | 1.57 | 36 | 99.1 | 0.88 | 6.18 |
| Example 4 | 1.56 | 35 | 99.1 | 0.86 | 5.95 |
| Example 5 | 1.52 | 36 | 98.4 | 1.36 | 8.82 |
| Example 6 | 1.57 | 35 | 98.2 | 1.37 | 8.69 |
| Example 7 | 1.56 | 38 | 98.9 | 1.22 | 8.11 |
| Example 8 | 1.56 | 37 | 99.1 | 0.91 | 7.98 |
| Example 9 | 1.57 | 38 | 99.2 | 0.89 | 5.26 |
| Example 10 | 1.57 | 37 | 99.2 | 0.83 | 5.37 |
| Example 11 | 1.61 | 41 | 99.3 | 0.75 | 4.85 |
| Example 12 | 1.63 | 42 | 99.5 | 0.66 | 5.02 |
| Comparative example 1 | 1.44 | 28 | 94.3 | 4.54 | 4.27 |
| Comparative example 2 | 1.49 | 33 | 98.1 | 1.68 | 6.48 |
| Comparative example 3 | 1.51 | 33 | 97.6 | 1.89 | 9.12 |
| Comparative example 4 | 1.53 | 34 | 98.2 | 1.65 | 6.12 |
| Comparative example 5 | 1.46 | 32 | 92.3 | 3.13 | 12.51 |
| Comparative example 6 | 1.40 | 31 | 90.5 | 5.57 | 8.31 |
| Comparative example 7 | 1.45 | 32 | 90.4 | 2.34 | 6.55 |
| Comparative example 8 | 1.47 | 32 | 91.7 | 2.27 | 6.28 |
| Comparative example 9 | 1.42 | 31 | 90.2 | 2.33 | 5.37 |
Table 5 shows the optical property test results of the optical lenses prepared by the examples and comparative examples. Abbe number, refractive index, and light transmittance are important properties of an optical member, and are directions that need to be considered in practical use. Wherein, the general optical material needs to satisfy the refractive index more than or equal to 1.50 and Abbe number more than or equal to 30.
The optical lenses obtained in examples 1 to 12 have better refractive index, Abbe number and light transmittance and lower haze, and particularly, the samples of examples 11 to 12 have excellent refractive index, Abbe number and light transmittance.
The optical lens manufactured by the comparative examples 1 to 4 has less than ideal optical characteristics, particularly the comparative example 1 has the refractive index, the haze and the light transmission average ratio which do not meet the requirements of the optical resin. The optical lenses of comparative examples 5 to 7 were obtained which had lower light transmittance and higher haze and greatly reduced refractive index and Abbe number because of phase separation in the matrix due to the use of too much thiol compound.
The optical test results show that the optical lenses prepared in the comparative examples 5 and 6 have poor optical characteristics, and the refractive index, the haze and the light transmission uniformity of the optical lenses do not meet the requirements of optical resins. The optical lenses obtained by comparative examples 5 and 6 still have a large gap in optical characteristics compared to comparative examples 2 to 4, and thus do not have a prospect for use in the optical field.
The above examples are merely illustrative of the preferred embodiments of the present invention and any obvious variations and modifications which would occur to persons skilled in the art without departing from the spirit of the invention are to be considered as part of the invention.
Claims (13)
1. An optical polylactic acid composition comprising: polylactic acid-polyurethane copolymer and thiol compound, wherein,
the polylactic acid-polyurethane copolymer comprises a structure of the following formula (I):
a is an integer from 20 to 200;
b is an integer from 20 to 200;
n is an integer from 15 to 75;
x is a connecting structure;
the thiol compound contains more than 2 mercapto functional groups.
2. The optical polylactic acid composition according to claim 1, wherein,
the polylactic acid-polyurethane copolymer contains an isocyanate group.
3. The optical polylactic acid composition according to claim 1 or 2, further comprising:
an antioxidant; and/or
An anti-hydrolysis agent.
4. The optical polylactic acid composition according to any one of claims 1 to 3, wherein,
the connecting structure X is as follows: - (L) 1 ) p - (A ring) q -(L 2 ) r - (B ring) s -(L 3 ) t -，
Wherein,
p, q, r, s, t are each independently 0 or 1, and p, q, r, s, t are not simultaneously 0;
L 1 、L 2 、L 3 each independently selected from C 1-6 Alkyl radical, and theC 1-6 Alkyl is optionally interrupted by one or more O atoms;
ring A and ring B are each independently selected from: c 3-8 Cycloalkyl ring, C 6-10 Aromatic ring and C 5-10 A heteroaromatic ring;
L 1 、L 2 、L 3 ring a and ring B are each independently and optionally substituted with one or more substituents selected from R, which is independently selected from: c 1-6 Alkyl radical, C 2-6 Ester group, halogen, cyano, C 1-6 Alkoxy radical, C 3-8 Cycloalkyl ring, C 6-10 Aromatic ring, C 5-10 A heteroaromatic ring;
preferably, the linking structure X is selected from the following structures: -Ph (CH) 3 )-、-(CH 2 ) 6 -、
5. The optical polylactic acid composition according to any one of claims 1 to 4, wherein,
the thiol compound is selected from: bis (mercaptomethyl) trithioundecanedithiol, mercaptomethyl bisthiodithiaoctane, bis (mercaptomethyl) dithiane, bis (mercaptomethylthio) dithiane, (bis (mercaptomethylthio) ethyl) dithetane, trimethylolpropane tris (mercaptopropionate), butanediol bis (mercaptoacetate), diethylene glycol bis (mercaptoacetate), ethylene glycol bis (mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), and combinations thereof.
6. The optical polylactic acid composition according to any one of claims 1 to 5, wherein,
the number average molecular weight of the polylactic acid-polyurethane copolymer is 5-15 ten thousand, and/or
The melt index of the polylactic acid-polyurethane copolymer is 5-45g/10min, and/or
The melting point of the polylactic acid-polyurethane copolymer is 110-180 ℃, and/or
The glass transition temperature of the polylactic acid-polyurethane copolymer is 40-70 ℃.
7. The optical polylactic acid composition according to any one of claims 1 to 6, wherein,
in the blending for obtaining the polylactic acid optical resin, the weight ratio of the polylactic acid-polyurethane copolymer to the thiol compound is 200:1-10: 1.
8. The method for preparing the optical polylactic acid composition according to any one of claims 1 to 7, comprising the steps of:
reacting an oligomer prepared by a dehydration condensation reaction of lactic acid or lactide with ethylene glycol to prepare a polylactic acid prepolymer;
reacting the polylactic acid prepolymer with an isocyanate chain extender to prepare a polylactic acid-polyurethane copolymer;
and (2) extruding the polylactic acid-polyurethane copolymer and the thiol compound by an extruder, optionally adding an antioxidant and/or an anti-hydrolysis agent, and thus obtaining the optical polylactic acid composition.
9. The production process according to claim 8, wherein,
the weight ratio of the low polymer of the polylactic acid to the glycol is 10:1-100: 1; and/or
The molar ratio of the polylactic acid-polyurethane copolymer to the isocyanate chain extender is 8:1-60: 1; and/or
The weight ratio of the polylactic acid-polyurethane copolymer to the thiol compound is 200:1-10: 1.
10. The production method according to claim 8 or 9, wherein,
the extrusion comprises a melt blending, extrusion process, wherein,
the temperature of the melt blending is 150-200 ℃; and/or
The extruder is a double-screw extruder; and/or
The rotating speed of the extruder is 100-500 rpm.
11. Use of the optical polylactic acid composition according to any of claims 1 to 7 in an optical member, preferably in an optical lens.
12. An optical lens comprising the optical polylactic acid composition according to any one of claims 1 to 7.
13. A method for producing an optical lens according to claim 12, which comprises:
drying the optical polylactic acid composition master batch, then putting the dried optical polylactic acid composition master batch into a charging barrel, and further plasticizing and melting to obtain optical polylactic acid composition melt adhesive;
enabling the molten glue to enter a mold cavity;
maintaining the pressure and cooling;
taking the optical lens out of the mold after opening the mold, wherein,
injecting molten glue into a mold cavity by adopting a multi-section glue injection process;
preferably, ,
the injection molding process is carried out by adopting the following parameters:
the temperature of each extrusion zone of the injection molding machine screw is 180-210 ℃,
the injection pressure is 60-110MPa,
the injection speed is 3-10mm/s,
the pressure for maintaining the pressure is 50-100Mpa,
the dwell time is 5-15 seconds.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130012664A1 (en) * | 2010-03-31 | 2013-01-10 | Dow Global Technologies Llc | Polyurethane compositions having improved impact resistance and optical properties |
| CN105294970A (en) * | 2015-11-24 | 2016-02-03 | 深圳光华伟业股份有限公司 | Bio-based thermoplastic polyurethane elastomer material and preparation method thereof |
| CN109790272A (en) * | 2016-10-11 | 2019-05-21 | 三井化学株式会社 | Polymerizable composition for optical material and application thereof |
| WO2021132559A1 (en) * | 2019-12-26 | 2021-07-01 | 三井化学株式会社 | Polymerizable composition for optical material, molded object obtained from said composition, and use application thereof |
-
2022
- 2022-06-08 CN CN202210642829.6A patent/CN114921090B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130012664A1 (en) * | 2010-03-31 | 2013-01-10 | Dow Global Technologies Llc | Polyurethane compositions having improved impact resistance and optical properties |
| CN105294970A (en) * | 2015-11-24 | 2016-02-03 | 深圳光华伟业股份有限公司 | Bio-based thermoplastic polyurethane elastomer material and preparation method thereof |
| CN109790272A (en) * | 2016-10-11 | 2019-05-21 | 三井化学株式会社 | Polymerizable composition for optical material and application thereof |
| WO2021132559A1 (en) * | 2019-12-26 | 2021-07-01 | 三井化学株式会社 | Polymerizable composition for optical material, molded object obtained from said composition, and use application thereof |
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