CN116375999A - Thermoplastic resin composition, method for producing same, and optical lens - Google Patents
Thermoplastic resin composition, method for producing same, and optical lens Download PDFInfo
- Publication number
- CN116375999A CN116375999A CN202310000452.9A CN202310000452A CN116375999A CN 116375999 A CN116375999 A CN 116375999A CN 202310000452 A CN202310000452 A CN 202310000452A CN 116375999 A CN116375999 A CN 116375999A
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- China
- Prior art keywords
- carbon atoms
- group
- thermoplastic resin
- resin composition
- general formula
- Prior art date
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- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 53
- 239000011342 resin composition Substances 0.000 title claims abstract description 49
- 230000003287 optical effect Effects 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 6
- 239000004793 Polystyrene Substances 0.000 claims abstract description 4
- 229920002223 polystyrene Polymers 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 15
- -1 dicarboxylic acid ester Chemical class 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000005809 transesterification reaction Methods 0.000 claims description 10
- 150000004650 carbonic acid diesters Chemical class 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- 238000002834 transmittance Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000005577 anthracene group Chemical group 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 125000003375 sulfoxide group Chemical group 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 230000032050 esterification Effects 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- 239000000289 melt material Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- OZGFLBCWIQDWLO-UHFFFAOYSA-N 2-[1-[2-(carboxymethoxy)naphthalen-1-yl]naphthalen-2-yl]oxyacetic acid Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3OCC(=O)O)=C(OCC(O)=O)C=CC2=C1 OZGFLBCWIQDWLO-UHFFFAOYSA-N 0.000 description 1
- ADVCVPSUVXTJFT-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)-1-naphthalen-1-yl-6,6-diphenylnaphthalen-2-yl]oxyethanol Chemical group C1=CC=C(C=C1)C2(C=CC3=C(C(C=CC3=C2)(OCCO)OCCO)C4=CC=CC5=CC=CC=C54)C6=CC=CC=C6 ADVCVPSUVXTJFT-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VKDPSTNROWSESS-UHFFFAOYSA-N OCCOC1(C(=C2C=CC=CC2=CC1)C1=CC=CC2=CC=CC=C12)OCCO Chemical group OCCOC1(C(=C2C=CC=CC2=CC1)C1=CC=CC2=CC=CC=C12)OCCO VKDPSTNROWSESS-UHFFFAOYSA-N 0.000 description 1
- PTXDFAXNCPMQHM-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].C1(=CC=CC=C1)[Mg+].C1(=CC=CC=C1)[Mg+].C1(=CC=CC=C1)[Mg+] Chemical compound P(=O)([O-])([O-])[O-].C1(=CC=CC=C1)[Mg+].C1(=CC=CC=C1)[Mg+].C1(=CC=CC=C1)[Mg+] PTXDFAXNCPMQHM-UHFFFAOYSA-K 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- UCVMQZHZWWEPRC-UHFFFAOYSA-L barium(2+);hydrogen carbonate Chemical compound [Ba+2].OC([O-])=O.OC([O-])=O UCVMQZHZWWEPRC-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006269 biphenyl-2-yl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C1=C(*)C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- FLLNLJJKHKZKMB-UHFFFAOYSA-N boron;tetramethylazanium Chemical compound [B].C[N+](C)(C)C FLLNLJJKHKZKMB-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000010237 calcium benzoate Nutrition 0.000 description 1
- 239000004301 calcium benzoate Substances 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- UUECMXWHHRNLLE-UHFFFAOYSA-N carbonic acid;1,2-di(propan-2-yl)benzene Chemical compound OC(O)=O.CC(C)C1=CC=CC=C1C(C)C UUECMXWHHRNLLE-UHFFFAOYSA-N 0.000 description 1
- PKPMMGIFZKHHPY-UHFFFAOYSA-N carbonic acid;1,2-xylene Chemical compound OC(O)=O.CC1=CC=CC=C1C PKPMMGIFZKHHPY-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- FYIBPWZEZWVDQB-UHFFFAOYSA-N dicyclohexyl carbonate Chemical compound C1CCCCC1OC(=O)OC1CCCCC1 FYIBPWZEZWVDQB-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- LNGAGQAGYITKCW-UHFFFAOYSA-N dimethyl cyclohexane-1,4-dicarboxylate Chemical compound COC(=O)C1CCC(C(=O)OC)CC1 LNGAGQAGYITKCW-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- OCSXMIBZIHMVCP-UHFFFAOYSA-N dimethyl naphthalene-1,4-dicarboxylate Chemical compound C1=CC=C2C(C(=O)OC)=CC=C(C(=O)OC)C2=C1 OCSXMIBZIHMVCP-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- AGVBNFDTLFAABM-UHFFFAOYSA-N methyl 2-[1-[2-(2-methoxy-2-oxoethoxy)naphthalen-1-yl]naphthalen-2-yl]oxyacetate Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3OCC(=O)OC)=C(OCC(=O)OC)C=CC2=C1 AGVBNFDTLFAABM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- WJMMDJOFTZAHHS-UHFFFAOYSA-L strontium;carbonic acid;carbonate Chemical compound [Sr+2].OC([O-])=O.OC([O-])=O WJMMDJOFTZAHHS-UHFFFAOYSA-L 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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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
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A thermoplastic resin composition comprising a structural unit derived from a compound represented by the general formula (A) and a structural unit derived from a compound represented by the general formula (B), wherein the molecular weight distribution curve of dw/dlog (M) obtained by measuring the thermoplastic resin by gel permeation chromatography on a polystyrene basis, wherein the log (M) of the molecular weight M is on the horizontal axis and the dw/dlog (M) obtained by differentiating the concentration fraction w by the log (M) of the molecular weight is on the vertical axis, satisfies the following conditions: (1) The value of dw/dlog (M) reaches the maximum in the range of 4.5.ltoreq.log (M). Ltoreq.5.2, (2) in the differential molecular weight distribution curve, the value obtained by integrating the dw/dlog (M) in the range of 4.0.ltoreq.log (M). Ltoreq.4.3 is 20% or less with respect to the value obtained by integrating the dw/dlog (M) in the whole range of log (M).
Description
Technical Field
The present invention relates to the field of optical resins, and more particularly to a thermoplastic resin composition, a method for producing the same, and an optical lens.
Background
The glass lens has complex process and good light transmittance and stability, and is commonly used for professional equipment such as single-lens reflex cameras, high-end scanners and the like. The glass-plastic mixed lens has the advantages of reduced cost and various indexes between those of the plastic lens and the glass lens on the premise of ensuring the performance and stability of the product. The security and vehicle-mounted lenses are matched by using glass-plastic mixed lenses, and the outermost lenses are still glass lenses because the plastic lenses cannot bear severe outdoor or driving environment conditions; the internal lens is replaced by a plastic lens, so that the weight of the lens can be reduced, the production efficiency is improved, and the cost is reduced. The field of mobile phones does not relate to high-temperature and high-humidity application scenes, so that plastic lenses are completely adopted.
At present, the optical polycarbonate has the advantages of high refractive index, easy molding, high production efficiency and the like. Patent US4810771 proposes a high refractive polyester resin material for optical lenses, which is prepared by using 9, 9-bis- (4-hydroxyphenyl) fluorene as a monomer, and has a refractive index of about 1.64. Later, the konika patent JP2001072872 discloses a thermoplastic resin material for optical lenses and a method for manufacturing the same, which mainly uses 2, 2-bis- (2-hydroxyethoxy) -1, 1-binaphthyl as a polymerization monomer, can be used for preparing optical resin materials such as polyester, polycarbonate, polyurethane, sulfone polymer and the like, and has a higher refractive index of about 1.66. However, due to the existence of the conjugated benzene ring structure in the polymerization monomers and the defect of low polymerization degree in the synthesis process, the color of the optical polycarbonate is yellow, so that the light transmittance of the plastic lens at a short wavelength (320-400 nm) is affected.
To solve this problem, the present inventors have found that by controlling the molecular weight distribution of polycarbonate, the segment length of the polymer and the oligomer content can be effectively controlled, thereby improving the high temperature resistance, yellowing resistance, high transparency, and the like of the polymer molecule.
Disclosure of Invention
The invention aims to provide a thermoplastic resin composition, a manufacturing method thereof and application thereof in the field of optical lenses, wherein the thermoplastic resin has the characteristics of high refractive index, high temperature resistance, yellowing resistance and high transparency, and can meet the use requirements of the optical lenses.
In order to solve the above problems, the present invention provides a thermoplastic resin composition, wherein a differential molecular weight distribution curve of dw/dlog (M) obtained by differentiating a concentration fraction w by a log (M) of a molecular weight on the horizontal axis and a log (M) of a molecular weight on the vertical axis, which is obtained by measuring the thermoplastic resin composition by gel permeation chromatography based on polystyrene, satisfies the following conditions:
(1) The value of dw/dlog (M) is maximized in the range of 4.5.ltoreq.log (M). Ltoreq.5.2, preferably in the range of 4.6.ltoreq.log (M). Ltoreq.5.0;
(2) In the differential molecular weight distribution curve, the value obtained by integrating dw/dlog (M) values over the entire range of log (M) is 20% or less, preferably 10% or less, relative to the value obtained by integrating dw/dlog (M) values over the entire range of log (M).
The composition comprises a structural unit derived from a compound represented by the general formula (A) and a structural unit derived from a compound represented by the general formula (B), wherein,
in the general formula (A), Z 1 And Z 2 Aryl having 6 to 14 carbon atoms, preferably a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring; x is X 1 And X 2 Respectively represent an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, more preferably a methylene group, an ethylene group or a propylene group; r is R 1 ～R 4 Each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms; the value of m can be independently 0 to 10; the value of n can be independently 0 to 4;
in the general formula (B), Y 1 And Y 2 Respectively represents alkylene with 1-10 carbon atoms or a connecting group with 1-6 carbon atoms, wherein the main chain of the connecting group is substituted by sulfur atoms with 1-2 carbon atoms; r is R 5 ～R 8 Each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms; w represents a direct bond, -O-, -S-, -NH-, a sulfonyl group or a sulfoxide group, an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; q is independently 0, 1, 2, 3;
wherein the molar ratio of the structural unit derived from the compound represented by the general formula (A) to the structural unit derived from the compound represented by the general formula (B) is 1/99 to 99/1, preferably 10/90 to 80/20;
the form in which the structural units derived from the compounds represented by the general formulae (a) and (B) according to the present invention are contained in the resin is not particularly limited. For example, in the present invention, the thermoplastic resin composition may contain a copolymer containing structural units derived from the compounds represented by the general formulae (a) and (B), or may be a binary resin composition containing a homopolymer constituted of the respective structural units; alternatively, the polymer may be a blend obtained by blending a homopolymer containing a structural unit derived from the compound represented by the general formula (a) with a homopolymer containing a structural unit derived from the compound represented by the general formula (B), or a blend obtained by blending a homopolymer containing a structural unit derived from the general formula (a) with a copolymer containing a structural unit derived from the compound represented by the general formula (B).
The thermoplastic resin composition of the present invention may contain any of random, block and alternating copolymer structures.
The optical thermoplastic resin composition of the invention has a weight average molecular weight Mw of 10000-200000, preferably 20000-90000;
the thermoplastic resin composition of the present invention has a refractive index nD of 1.63 to 1.75 at a wavelength of 589nm at 20 ℃ and an Abbe number of not more than 24, and an orientation birefringence Δn of 2.0X10 -3 The glass transition temperature Tg is 130-180 ℃;
the thermoplastic resin composition has a length of 10cm when measured according to ISO 1133 at 260℃under a load of 2.16kg 3 10 minutes to 60cm 3 Melt volume rate of/10 minutes;
the thermoplastic resin composition has a yellowness index b value of not more than 4.0 measured at a thickness of 1mm and not more than 8.0 measured at a thickness of 3 mm;
the thermoplastic resin composition has an average transmittance of 85% or more at a wavelength of 780nm to 1000nm when the thickness is 1 mm.
In the thermoplastic resin composition of the present invention, an auxiliary agent such as a mold release agent, an ultraviolet absorber, a fluidity improver, a crystallization nucleating agent, a reinforcing agent, a dye, an antistatic agent, or an antibacterial agent may be added.
The thermoplastic resin composition of the present invention can be produced by reacting a dihydroxy compound represented by general formula (A) and general formula (B) with a carbonic acid diester and/or a dicarboxylic acid ester;
preferably, the dihydroxy compound and carbonic acid diester and/or dicarboxylic acid ester are produced by a melt transesterification polycondensation method in the presence of a basic compound catalyst, a transesterification catalyst or a mixed catalyst comprising both, or in the absence of a catalyst;
preferably, the dihydroxy compound represented by general formula (a) is at least one of the following structures:
preferably, the dihydroxy compound represented by general formula (B) is at least one of the following structures:
in the invention, the carbonic diester is one or more of diphenyl carbonate, dimethylbenzene carbonate, diethylbenzene carbonate, diisopropylbenzene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like, preferably diphenyl carbonate;
the dicarboxylic acid is any one or a combination of at least two of terephthalic acid, 1, 4-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 2-biphenyl dicarboxylic acid, 1, 4-cyclohexane dicarboxylic acid and 2,2 '-bis (carboxymethoxy) -1,1' -binaphthyl, preferably terephthalic acid and/or 2, 6-naphthalene dicarboxylic acid;
the dicarboxylic acid ester is any one or a combination of at least two of dimethyl terephthalate, diethyl terephthalate, dimethyl terephthaloate, dimethyl 1, 4-naphthalene dicarboxylate, dimethyl 2, 6-naphthalene dicarboxylate, dimethyl 2, 2-diphthalic acid, dimethyl 1, 4-cyclohexane dicarboxylate and 2,2 '-bis (carbomethoxy methoxy) -1,1' -binaphthyl, preferably dimethyl terephthalate and/or dimethyl 2, 6-naphthalene dicarboxylate;
the molar ratio of carbonic acid diester and/or dicarboxylic acid ester to the sum of the added dihydroxy compounds of the general formulae (A), (B) is from 0.90 to 1.20:1, preferably from 0.94 to 1.1:1;
the alkaline compound catalyst is one or more of lithium chloride, sodium chloride, potassium chloride, cesium chloride, lanthanum acetylacetonate, cerium acetylacetonate, sodium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, sodium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium benzoate, phenyl magnesium phosphate, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide, triethylamine, dimethylbenzylamine, triphenylamine, diethylamine, tetramethyl ammonium borohydride, tetrabutyl ammonium tetraphenyl borate, tetraphenyl ammonium tetraphenyl tetraborate and the like, preferably one or more of sodium hydroxide, sodium bicarbonate and cesium carbonate;
the transesterification catalyst of the invention can use one or more of zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, stannic chloride, stannic acetate, cerium acetylacetonate, zirconium acetate, tetrabutoxyzirconium and the like, preferably one or more of lanthanum acetylacetonate, zirconium acetate and zinc acetate;
the molar ratio of the sum of the basic compound catalyst and/or the transesterification catalyst added to the sum of the dihydroxy compounds according to the invention is 1X 10 -7 ～1×10 -2 The preferred ratio is 1X 10 -6 ～5×10 -4 。
The inventor finds that the polymerization activity of the dihydroxy compound shown in the general formula (B) is higher than that of the dihydroxy compound shown in the general formula (A) in the experimental process, and only the dihydroxy compound shown in the general formula (B) can be put into a reaction kettle for prepolymerization in the experimental process to obtain a macromolecular prepolymer; and then the dihydroxy compound shown in the general formula (A) is put into a reaction kettle for transesterification and polycondensation, so that the chain segment length of the polymer is increased, the generation of oligomers is reduced, and the purpose of controlling the molecular weight distribution of the polymer is achieved.
In some preferred embodiments of the present invention, the method for preparing a thermoplastic resin composition includes: the dihydroxyl compound shown in the general formula (B), carbonic acid diester and/or dicarboxylic acid ester, a catalyst and optional auxiliary agent are added into a reactor, the air in the reactor is fully replaced by nitrogen for 3-5 times, then the temperature is raised to melt the materials in the reactor, the melting temperature is 180-240 ℃, preferably 190-220 ℃, and the residence time at the stage is 40-100 min, preferably 50-80 min. After the materials are melted, stirring is started, the control of the pressure of decompression or pressurization is started, the temperature is increased to the transesterification reaction temperature, the transesterification reaction temperature is 210-250 ℃, preferably 220-240 ℃, and the residence time at the stage is 60-240 min, preferably 100-180 min. Then the dihydroxy compound shown in the general formula (A) is added into a reactor to continue the reaction for 20 to 150min, preferably 40 to 100min. Then, the pressure is continuously reduced and the temperature is increased to start the polycondensation reaction, the system pressure is 10 Pa (A) to 500Pa (A), preferably 50Pa (A) to 100Pa (A), the reaction temperature is 230 ℃ to 270 ℃, preferably 230 ℃ to 255 ℃, and the residence time is 10 min to 120min, preferably 20min to 60min. During the reaction, the small molecular compound is immediately removed by distillation, and finally a high molecular weight thermoplastic resin composition is obtained in the reactor.
The blend of the present invention can be obtained by blending different thermoplastic resin compositions obtained by polymerization in an extruder, kneader, mixer or the like.
The invention also relates to the application of the thermoplastic resin composition in the field of optical lenses.
The invention has the beneficial effects that:
the thermoplastic resin composition has high refractive index, good fluidity, easy processing, high temperature resistance, yellowing resistance and high transparency, and can be used in the field of optical lenses. The optical lens adopting the thermoplastic resin composition can make the lens lighter and thinner, lighten the weight of the lens and reduce the number of the lenses, thereby reducing the cost and having wide application prospect.
Drawings
FIG. 1 is a graph of the differential molecular weight distribution of the product of example 1.
Detailed Description
The invention will now be described with reference to specific embodiments. It should be understood that the embodiments are merely for further illustrating the present invention and should not be construed as limiting the scope of the invention, but are merely illustrative of the invention that insubstantial modifications and adaptations thereof may be made in accordance with the principles of the present invention.
1) Weight average molecular weight (Mw): using Gel Permeation Chromatography (GPC), tetrahydrofuran was used as a developing solvent, and a standard curve was prepared using standard polystyrene having a known molecular weight (molecular weight distribution=1). Based on the standard curve, mw was calculated from the retention time of GPC.
2) Refractive index (nD): the refractive index (nD) of the thermoplastic resin composition of the present invention was measured at 20℃and a wavelength of 589nm by the method of JIS-K-7142 using an Abbe refractometer for a film having a thickness of 1mm and composed of the thermoplastic resin composition obtained in the examples.
3) Abbe number: the refractive indices of 486nm (F light), 589nm (D light) and 656nm (C light) of a film having a thickness of 0.1mm and formed of the polycarbonate resin obtained in the examples were measured by an Abbe refractometer, and Abbe numbers v were calculated by the following formulas,
ν＝(nD－1)/(nF－nC)。
4) Orientation birefringence (Δn): after cutting a casting film having a thickness of 0.1mm into square with a square of 5.0cm, both ends of the film were inserted into chucks (3.0 cm between the chucks), and stretched to 1.5 times at Tg+5℃. The retardation (Re) at 589nm was measured using an ellipsometer, and the orientation birefringence (. DELTA.n) was determined from the following formula:
Δn＝Re/d
an: orientation birefringence; re: a phase difference; d: thickness.
5) Melt and indicate: the measurement was carried out at 260℃under a load of 2.16kg according to ISO 1133.
6) Transmittance: a film having a thickness of 1mm formed from the polycarbonate resin obtained in the example was tested for light transmittance at a wavelength of 780nm to 1000nm by a method of JIS-K-7361-1 using a haze meter.
7) b value: the polycarbonate resin obtained was dried at 120℃for 4 hours in vacuo, and then injection-molded using an injection molding machine at a cylinder temperature of 270℃and a mold temperature of Tg-10℃to obtain a disk-shaped test plate sheet having a diameter of 50mm and a thickness of 1 mm. The b value was measured in accordance with JIS K7105 using the sheet.
The sources of some of the reagent raw materials used in the examples and comparative examples of the present invention are as follows, and the remaining reagent raw materials are all commercially available products unless otherwise specified:
a-1 is prepared by the following method:
194.3g of beta-anthracenol and 68.6g of 9-fluorenone are weighed into a three-necked flask, 500mL of toluene is added, and the mixture is fully stirred until the mixture is dissolved. A mixture of 0.99g of concentrated sulfuric acid and 0.25g of mercaptopropionic acid was slowly added dropwise to the above solution, and the mixture was heated to 65℃to react for 3 hours. After the reaction, the reaction mixture was cooled to room temperature, and then a sodium hydroxide solution was added to neutralize the reaction mixture to neutrality. 600mL of anhydrous methanol is added, the solid is fully separated out, stirred, filtered, washed by methanol and dried to obtain bisphenol compound intermediate A.
200g of intermediate A and 4.56g of potassium hydroxide are weighed and added into 600mL of N, N-dimethylformamide, 0.5MPa of nitrogen is filled for 3 times of replacement, the temperature is raised to 125 ℃, ethylene oxide gas is filled, the mol ratio of ethylene oxide to the intermediate A is kept to be 2.45:1, and the reaction is carried out for 5 hours. After the reaction is finished, cooling to room temperature, filtering, washing with water, and drying to obtain A-1, wherein the nuclear magnetic resonance result of the target product is as follows: 1H-NMR (400 MHz, CDCl) 3 )/δ×10 -6 ：8.25(s,4H),7.87-7.84(m,6H),7.7(s,2H),7.25(m,2H),7.38-7.11(m,10H),4.43(t,4H),3.69-3.65(m,6H)。
2, 2-bis (2-hydroxyethoxy) -6, 6-diphenyl-1, 1-binaphthyl (B-1) is prepared by the following method:
the compound B-1 can be produced by the methods disclosed in Japanese patent application laid-open publication No. 2014-227387, japanese patent application laid-open publication No. 2014-227388 and Japanese patent application laid-open publication No. 2015-168658, including (1) a method of reacting 1, 1-binaphthol with ethylene glycol monomethylenesulfonate, (2) a method of reacting binaphthol with haloalkol or alkylene carbonate, (3) a method of reacting 1, 1-binaphthol with ethylene carbonate or propylene carbonate, etc., wherein the compound B-1 is produced by a method of reacting binaphthol with alkylene carbonate, and the nuclear magnetic properties of the aimed product are as follows: 1H-NMR (400 MHz, CDCl) 3 )δ/×10 -6 ：8.07(d,2H),7.95-7.77(m,6H),7.52-7.41(m,10H),7.11(d,2H),4.43(m,4H),3.69-3.65(m,6H)。
The B-2 compound can be prepared by the method disclosed in Chinese patent CN112175178A, and the B-3 compound can be prepared by the method disclosed in patent RO105571B 1. The nuclear magnetic properties of the B-2 compound were as follows: 1H-NMR (400 MHz, CDCl 3) delta/. Times.10 -6 ：8.05-8.01(m,4H),7.55(m,4H),7.44(m,2H),6.85(d,2H),4.43(t,4H),3.69(m,4H),3.65(m, 2H). The nuclear magnetic properties of the B-3 compound were as follows: 1H-NMR (400 MHz, CDCl 3) delta/. Times.10 -6 ：8.11-8.02(m,4H),7.65(m,2H),7.54-7.41(m,4H),6.92(m,2H),4.84(s,2H),4.43(t,4H),3.69-3.65(m,6H)。
Example 1
26.31g (0.05 mol) of B1, 23.14g (0.108 mol) of diphenyl carbonate, 84.01. Mu.g (1.0X10) -6 mol) sodium bicarbonate was placed in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, nitrogen was substituted 4 times, heating was performed under a nitrogen atmosphere of 101Kpa (A) to 200℃for 60 minutes, after which complete dissolution of the raw material was confirmed, stirring was started, the pressure was adjusted to 20Kpa (A), and at the same time, the temperature was raised to 230℃at a rate of 30℃per hr, at this time, it was confirmed that phenol formed as a by-product began to distill off, the reaction was continued at 230℃for 150 minutes, and 29.51g (0.05 mol) of A2 was further added to the flask to continue the reaction for 80 minutes. Then, the temperature was raised to 250℃at a rate of 60℃per hour, and after the temperature reached 250℃the pressure was gradually reduced to 50Pa (A) over 1 hour, and the reaction was stirred under the conditions for 40 minutes to terminate the reaction. After the completion of the reaction, the four-necked flask was purged with nitrogen gas to return to normal pressure, and the resulting thermoplastic resin composition was taken out to evaluate the properties, and the results are shown in Table 1.
Example 2
15.79g (0.03 mol) of B1, 12.18g (0.03 mol) of B2, 22.06g (0.103 mol) of diphenyl carbonate, 3.274mg (1.0X10) -5 mol) zirconium acetate was placed in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, the same operation as in example 1 was conducted, 23.61g (0.04 mol) of A2 was further added to the flask, the same operation as in example 1 was continued, and the obtained thermoplastic resin composition was subjected to performance evaluation, and the results are shown in Table 1.
Example 3
11.65g (0.03 mol) of B3, 23.56g (0.11 mol) of diphenyl carbonate, 1.835mg (1.0X10) -5 mol) Zinc acetate was put into a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, the same operation as in example 1 was conducted, 11.81g (0.02 mol) of A2 and 21.93g (0.05 mol) of A3 were further added to the flask, the same operation as in example 1 was continued, and the obtained thermoplastic resin composition was subjected to property evaluation, and the results are shown in Table 1。
Example 4
40.21g (0.099 mol) of B2, 19.28g (0.09 mol) of diphenyl carbonate, 4. Mu.g (1.0X10) -7 mol) sodium hydroxide was placed in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, the same operation as in example 1 was performed, 0.64g (0.001 mol) of A1 was further added to the flask, the same operation as in example 1 was continued, and the obtained thermoplastic resin composition was subjected to performance evaluation, and the results are shown in Table 1.
Example 5
0.3882g (0.001 mol) of B3, 25.71g (0.12 mol) of diphenyl carbonate, 84mg (1.0X10) -3 mol) sodium hydrogencarbonate was placed in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, the same operations as in example 1 were conducted, 31.27g (0.049 mol) of A1 and 29.51g (0.05 mol) of A2 were further added to the flask, and the same operations as in example 1 were continued to give thermoplastic resin compositions, and the results of which were shown in Table 1 were evaluated.
Example 6
26.31g (0.05 mol) of B1, 15.53g (0.04 mol) of B3, 20.14g (0.094 mol) of diphenyl carbonate, 436.23. Mu.g (1.0X10) -6 mol) lanthanum acetylacetonate was introduced into a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, the same operations as in example 1 were carried out, 4.39g (0.01 mol) of A3 was further introduced into the flask, and the same operations as in example 1 were continued to give a thermoplastic resin composition, and performance evaluation was carried out, and the results are shown in Table 1.
Example 7
8.12g (0.02 mol) of B2, 22.49g (0.105 mol) of diphenyl carbonate, 162.9mg (5.0X10) -4 mol) cesium carbonate was placed in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, the same operations as in example 1 were performed, 19.15g (0.03 mol) of A1 and 29.51g (0.05 mol) of A2 were further added to the flask, and the same operations as in example 1 were continued to obtain thermoplastic resin compositions, and the results of which were shown in Table 1 were evaluated.
Comparative example 1
29.51g (0.05 mol) of A2, 26.31g (0.05 mol) of B1, 23.14g (0.108 mol) of carbonic acid dicarbonatePhenyl ester, 84.01. Mu.g (1.0X10) -6 mol) sodium hydrogencarbonate in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, the same operations as in example 1 were carried out to obtain thermoplastic resin compositions, and performance evaluation was carried out, and the results are shown in Table 1.
TABLE 1
Claims (10)
1. A thermoplastic resin composition characterized in that a differential molecular weight distribution curve of dw/dlog (M) obtained by differentiating a concentration fraction w by a molecular weight log (M) on the horizontal axis and a molecular weight log (M) on the vertical axis, which is obtained by measuring the thermoplastic resin by gel permeation chromatography on the basis of polystyrene conversion, satisfies the following conditions:
(1) The dw/dlog (M) value reaches a maximum in the range of 4.5.ltoreq.log (M). Ltoreq.5.2,
(2) In the differential molecular weight distribution curve, the value obtained by integrating dw/dlog (M) values in the range of 4.0.ltoreq.log (M). Ltoreq.4.3 is 20% or less relative to the value obtained by integrating dw/dlog (M) values in the whole range of log (M).
2. The thermoplastic resin composition according to claim 1, which comprises a structural unit derived from a compound represented by the general formula (A) and a structural unit derived from a compound represented by the general formula (B), wherein,
in the general formula (A), Z 1 And Z 2 Aryl having 6 to 14 carbon atoms, preferably a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring; x is X 1 And X 2 Respectively represent an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, more preferably a methylene group, an ethylene groupA propyl group; r is R 1 ～R 4 Each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms; the value of m can be independently 0 to 10; the value of n can be independently 0 to 4;
in the general formula (B), Y 1 And Y 2 Respectively represents alkylene with 1-10 carbon atoms or a connecting group with 1-6 carbon atoms, wherein the main chain of the connecting group is substituted by sulfur atoms with 1-2 carbon atoms; r is R 5 ～R 8 Each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms; w represents a direct bond, -O-, -S-, -NH-, a sulfonyl group or a sulfoxide group, an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; q is independently 0, 1, 2, or 3.
3. Thermoplastic resin composition according to claim 1 or 2, characterized in that dw/dlog (M) has a value in the range of 4.6.ltoreq.log (M). Ltoreq.5.0 to the maximum.
4. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the value obtained by integrating dw/dlog (M) values over the entire range of log (M) in the differential molecular weight distribution curve in the range of 4.0.ltoreq.log (M). Ltoreq.4.3 is 10% or less.
5. The thermoplastic resin composition according to any one of claims 2 to 4, wherein the thermoplastic resin composition comprises a structural unit derived from the compound represented by the general formula (A) and a structural unit derived from the compound represented by the general formula (B), and wherein the molar ratio of the structural unit derived from the compound represented by the general formula (A) to the structural unit derived from the compound represented by the general formula (B) is 1/99 to 99/1, preferably 10/90 to 80/20.
6. Thermoplastic resin composition according to any one of claims 1 to 5, characterized in that the weight average molecular weight Mw of the thermoplastic resin is 10000 to 200000, preferably 20000 to 90000; and/or
The thermoplastic resin composition has a refractive index nD of 1.63-1.75 at a wavelength of 589nm at 20 ℃ and an Abbe number of not more than 24, and an orientation birefringence Δn of 2.0X10 -3 The glass transition temperature Tg is 130-180 ℃; and/or
The thermoplastic resin composition has a length of 10cm when measured according to ISO 1133 at 260℃under a load of 2.16kg 3 10 minutes to 60cm 3 Melt volume rate of/10 minutes; and/or
The thermoplastic resin composition has a yellowness index b value of not more than 4.0 measured at a thickness of 1mm and not more than 8.0 measured at a thickness of 3 mm; and/or
The thermoplastic resin composition has an average transmittance of 85% or more at a wavelength of 780nm to 1000nm when the thickness is 1 mm.
7. The process for producing a thermoplastic resin composition according to any one of claims 1 to 6, wherein the dihydroxy compound represented by general structural formulae (A) and (B) is subjected to transesterification polycondensation or esterification polycondensation with a carbonic acid diester and/or a dicarboxylic acid ester;
wherein,,
in the general formula (A), Z 1 And Z 2 Aryl having 6 to 14 carbon atoms, preferably a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring; x is X 1 And X 2 Respectively represent an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, more preferably a methylene group, an ethylene group or a propylene group; r is R 1 ～R 4 Each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms; the value of m can be independently 0 to 10; the value of n can be independently 0 to 4;
in the general formula (B), Y 1 And Y 2 Respectively represents alkylene with 1-10 carbon atoms or a connecting group with 1-6 carbon atoms, wherein the main chain of the connecting group is substituted by sulfur atoms with 1-2 carbon atoms; r is R 5 ～R 8 Each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms; w represents a direct bond, -O-, -S-, -NH-, a sulfonyl group or a sulfoxide group, an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; q is independently 0, 1, 2, or 3.
8. The method for producing a thermoplastic resin composition according to claim 7, comprising: adding a dihydroxyl compound shown in a general formula (B), carbonic acid diester and/or dicarboxylic acid ester, a catalyst and optional auxiliary agents into a reactor, heating to melt materials in the reactor, wherein the melting temperature is 180-240 ℃, and the residence time at the stage is 40-100 min;
after the materials are melted, heating to the transesterification reaction temperature, wherein the transesterification reaction temperature is 210-250 ℃, the residence time at the stage is 60-240 min, then adding the dihydroxy compound shown in the general formula (A) into a reactor, continuing to react for 20-150 min, then continuing to reduce the pressure and raise the temperature, and starting the polycondensation reaction, wherein the system pressure at the stage is 10-500 PaA, the reaction temperature is 230-270 ℃, and the residence time is 10-120 min.
9. The process for preparing a thermoplastic resin composition according to claim 7 or 8, wherein the molar ratio of the carbonic acid diester and/or dicarboxylic acid ester to the sum of the added dihydroxy compounds of the general formulae (a) and (B) is from 0.90 to 1.20:1, preferably from 0.94 to 1.1:1.
10. Use of the thermoplastic resin composition according to any one of claims 1 to 6 or the thermoplastic resin composition prepared by the preparation method according to any one of claims 7 to 9 for an optical lens.
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