CN117980374A - Cyclic diol compound, resin modifier, resin using the resin modifier, and use of the resin - Google Patents
Cyclic diol compound, resin modifier, resin using the resin modifier, and use of the resin Download PDFInfo
- Publication number
- CN117980374A CN117980374A CN202380013563.1A CN202380013563A CN117980374A CN 117980374 A CN117980374 A CN 117980374A CN 202380013563 A CN202380013563 A CN 202380013563A CN 117980374 A CN117980374 A CN 117980374A
- Authority
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- China
- Prior art keywords
- resin
- formula
- polycarbonate resin
- group
- modifier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920005989 resin Polymers 0.000 title claims abstract description 204
- 239000011347 resin Substances 0.000 title claims abstract description 204
- 239000003607 modifier Substances 0.000 title claims abstract description 85
- -1 Cyclic diol compound Chemical class 0.000 title abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 118
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 107
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 107
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 45
- 229920000728 polyester Polymers 0.000 claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 claims abstract description 33
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 10
- 230000003287 optical effect Effects 0.000 claims description 41
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 22
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 21
- 230000009477 glass transition Effects 0.000 claims description 20
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 12
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 11
- 229920001225 polyester resin Polymers 0.000 claims description 9
- 239000004645 polyester resin Substances 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000178 monomer Substances 0.000 description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical group O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 238000002329 infrared spectrum Methods 0.000 description 9
- 239000012788 optical film Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 description 7
- ZETHHMPKDUSZQQ-UHFFFAOYSA-N Betulafolienepentol Natural products C1C=C(C)CCC(C(C)CCC=C(C)C)C2C(OC)OC(OC)C2=C1 ZETHHMPKDUSZQQ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- HEOKFDGOFROELJ-UHFFFAOYSA-N diacetal Natural products COc1ccc(C=C/c2cc(O)cc(OC3OC(COC(=O)c4cc(O)c(O)c(O)c4)C(O)C(O)C3O)c2)cc1O HEOKFDGOFROELJ-UHFFFAOYSA-N 0.000 description 6
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 150000001924 cycloalkanes Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- 125000005023 xylyl group Chemical group 0.000 description 4
- OQIDYCVWAFZRTR-UHFFFAOYSA-N 4-(4-oxocyclohexyl)cyclohexan-1-one Chemical compound C1CC(=O)CCC1C1CCC(=O)CC1 OQIDYCVWAFZRTR-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 238000006359 acetalization reaction Methods 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000006713 (C5-C10) cycloalkyl group Chemical group 0.000 description 1
- 125000006585 (C6-C10) arylene group Chemical group 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- 125000005976 1-phenylethyloxy group Chemical group 0.000 description 1
- HJZJMARGPNJHHG-UHFFFAOYSA-N 2,6-dimethyl-4-propylphenol Chemical compound CCCC1=CC(C)=C(O)C(C)=C1 HJZJMARGPNJHHG-UHFFFAOYSA-N 0.000 description 1
- BPZIYBJCZRUDEG-UHFFFAOYSA-N 2-[3-(1-hydroxy-2-methylpropan-2-yl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropan-1-ol Chemical compound C1OC(C(C)(CO)C)OCC21COC(C(C)(C)CO)OC2 BPZIYBJCZRUDEG-UHFFFAOYSA-N 0.000 description 1
- HXEWWQYSYQOUSD-UHFFFAOYSA-N 2-[5-ethyl-5-(hydroxymethyl)-1,3-dioxan-2-yl]-2-methylpropan-1-ol Chemical compound CCC1(CO)COC(C(C)(C)CO)OC1 HXEWWQYSYQOUSD-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- YVPZFPKENDZQEJ-UHFFFAOYSA-N 4-propylcyclohexan-1-ol Chemical compound CCCC1CCC(O)CC1 YVPZFPKENDZQEJ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- XCOBLONWWXQEBS-KPKJPENVSA-N N,O-bis(trimethylsilyl)trifluoroacetamide Chemical compound C[Si](C)(C)O\C(C(F)(F)F)=N\[Si](C)(C)C XCOBLONWWXQEBS-KPKJPENVSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- RABVYVVNRHVXPJ-UHFFFAOYSA-N [3-(hydroxymethyl)-1-adamantyl]methanol Chemical compound C1C(C2)CC3CC1(CO)CC2(CO)C3 RABVYVVNRHVXPJ-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 description 1
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 1
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 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
- GPTJTTCOVDDHER-UHFFFAOYSA-N cyclononane Chemical compound C1CCCCCCCC1 GPTJTTCOVDDHER-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 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
- KYTNZWVKKKJXFS-UHFFFAOYSA-N cycloundecane Chemical compound C1CCCCCCCCCC1 KYTNZWVKKKJXFS-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229960002479 isosorbide Drugs 0.000 description 1
- 238000005907 ketalization reaction Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/08—1,3-Dioxanes; Hydrogenated 1,3-dioxanes condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a resin modifier for a polycarbonate resin or a polyester carbonate resin, a resin using the same, and uses thereof. The present invention also provides a cyclic diol compound useful as a resin modifier and a raw material for a polycarbonate resin, a polyester carbonate resin, or the like, and a method for producing the same. Relates to a resin modifier for a polycarbonate resin or a polyester polycarbonate resin containing a compound represented by the formula (1), a resin using the resin modifier, and uses of the resin.[ In formula (1), R 1, which are the same or different, are a hydrogen atom, a C1-4 alkyl group or a phenyl group. X is a direct bond or a divalent group represented by formula (Y). [ in the formula (Y), R 2 and R 3 are the same or different and are a hydrogen atom, an alkyl group or an aryl group, or R 2 and R 3 may be bonded to each other and form a ring together with the adjacent carbon atom, and the ring may be substituted with an alkyl group. n is 0 or 1.* Represents a bonding position ] ].
Description
Technical Field
The present invention relates to a cyclic diol compound, a resin modifier, a resin using the resin modifier, and use of the resin.
Background
As resin raw materials for polyester resins and polycarbonate resins, various cyclic diol compounds are known. Examples of industrially available cyclic diol compounds include 1, 4-cyclohexanedimethanol, 1, 4-cyclohexanediol, and 2, 2-bis (4-hydroxycyclohexyl) propane (hydrogenated bisphenol A). In addition, various cyclic diol compounds have been reported depending on the use of the resin to be produced.
For example, regarding a polycarbonate resin used for optical applications (for example, an optical lens), a method of producing the resin by using a diol component containing a specific aromatic diol compound having a fluorene ring structure has been reported for the purpose of reducing coloration and improving optical properties of the resin such as transparency (patent document 1), and a method of producing the resin by using a specific fluorene-containing dihydroxy compound and another dihydroxy compound in a specific ratio has been reported (patent document 2).
However, the characteristics of resins such as polyester resins and polycarbonate resins are various depending on the application fields in which the resins are used, and cyclic diol compounds capable of satisfying the resin characteristics required in these fields have been studied. In particular, when the resin is used for optical applications, a cyclic diol compound capable of improving the optical properties of the resin is required.
Patent document 3 describes a diol compound having a diacetal structure (dispiro structure) of 1, 4-cyclohexanedione. Patent documents 4 and 5 describe the use of a diol compound having a dispiro structure as a raw material of a resin, but do not describe a resin modifier which can be used as a polycarbonate resin or a polyester carbonate resin.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2012-214803
Patent document 2: japanese patent laid-open No. 2013-001867
Patent document 3: international publication No. 2018/074305
Patent document 4: japanese patent application laid-open No. 2021-134151
Patent document 5: japanese patent application laid-open No. 2019-014711
Disclosure of Invention
Problems to be solved by the invention
The present invention provides a resin modifier for a polycarbonate resin or a polyester carbonate resin, a resin using the resin modifier, and uses thereof. The present invention also provides a cyclic diol compound useful as a resin modifier and a raw material for a polycarbonate resin, a polyester carbonate resin, or the like, and a method for producing the same.
Means for solving the problems
The present inventors have made intensive studies to solve the above problems, and as a result, have found that a novel resin having physical properties can be produced by incorporating a cyclic diol compound having a diacetal structure represented by the formula (1) as a structural unit into a polycarbonate resin or a polyester carbonate resin, and modifying the physical properties of the resin. Further studies have been made based on the findings, and the present invention has been completed.
Namely, the present invention provides the following resin modifier comprising a cyclic diol compound, a resin using the resin modifier, and uses of the resin.
[ Item 1]
A polycarbonate resin or a resin modifier for a polyester polycarbonate resin, which comprises a compound represented by the formula (1).
[ Wherein R 1, which are the same or different, are a hydrogen atom, a C1-4 alkyl group or a phenyl group. X is a direct bond (single bond) or a divalent group represented by formula (Y).
[ Wherein R 2 and R 3 are the same or different and are a hydrogen atom, an alkyl group or an aryl group, or R 2 and R 3 may be bonded to each other and form a ring together with the adjacent carbon atom, and the ring may be substituted with an alkyl group. n is 0 or 1.* Indicating the bonding location. ]]
[ Item 2]
The resin modifier according to item 2, wherein, in the divalent group represented by the formula (Y), R 2 and R 3 are the same or different and are a hydrogen atom, a C1-6 alkyl group or a phenyl group, or R 2 and R 3 may be bonded to each other and form a 5-12 membered ring together with the adjacent carbon atom, the ring may be substituted with a C1-3 alkyl group, and R 2 and R 3 are the same or different and are a hydrogen atom or a C1-6 alkyl group when n is 1.
[ Item 3]
The resin modifier of [ item 1] or [ 2], wherein X is a direct bond (single bond).
[ Item 4]
The resin modifier of [ 3], wherein R 1 is the same or different and is a C1-4 alkyl group.
[ Item 5]
The resin modifier according to [ item 1] or [ 2], wherein the case where X is a divalent group represented by the formula (Y), n is 0, R 2 and R 3 are each methyl is excluded.
[ Item 6]
The resin modifier according to item [ 5], wherein either one of R 2 or R 3 is an aryl group (particularly phenyl group), and the other is a hydrogen atom or a C1-6 alkyl group (particularly C1-3 alkyl group).
[ Item 7]
The resin modifier according to any one of [1] to [ 6], wherein the resin modifier is a polycarbonate resin for an optical material or a resin modifier for a polyester polycarbonate resin.
[ Item 8]
A compound represented by the formula (1B).
[ Wherein R 11, which are the same or different, are a hydrogen atom, a methyl group or an ethyl group. ]
[ Item 9]
A resin modifier comprising the compound according to [ 8 ].
[ Item 10]
The resin modifier according to item [ 9], wherein the resin modifier is a polyester resin, a polycarbonate resin or a resin modifier of a polyester polycarbonate resin.
[ 11]
The resin modifier of [ 9] or [ 10], wherein the resin modifier is a resin modifier for a resin of an optical material.
[ Item 12]
A method for producing a compound represented by formula (1B), which comprises a step of reacting a compound represented by formula (3B) with a compound represented by formula (4A).
[ Wherein R 11, which are the same or different, are a hydrogen atom, a methyl group or an ethyl group. ]
[ Item 13]
A method for modifying a polycarbonate resin or a polyester polycarbonate resin, which comprises modifying the polycarbonate resin or the polyester polycarbonate resin with the resin modifier according to any one of [1] to [ 11 ].
[ Item 14]
The method according to item [ 13], wherein the above-mentioned method of performing the modification is a method of adjusting at least 1 property selected from the group consisting of glass transition temperature, refractive index and Abbe number of a polycarbonate resin or a polyester polycarbonate resin obtained after the copolymerization by adjusting the content of the resin modifier according to any one of item [ 1] to 11] in the whole of the polyhydric alcohols as a raw material.
[ Item 15]
A resin comprising a structural unit represented by the formula (2), wherein the resin is a polycarbonate resin or a polyester carbonate resin.
[ Wherein R 1, which are the same or different, are a hydrogen atom, a C1-4 alkyl group or a phenyl group. X is a direct bond or a divalent group represented by formula (Y).
[ Wherein R 2 and R 3 are the same or different and are a hydrogen atom, an alkyl group or an aryl group, or R 2 and R 3 may be bonded to each other and form a ring together with the adjacent carbon atom, and the ring may be substituted with an alkyl group. n is 0 or 1.* Indicating the bonding location. ]]
[ Item 16]
A resin comprising a structural unit represented by the formula (2A).
[ Wherein R 11, which are the same or different, are a hydrogen atom, a methyl group or an ethyl group. X A is a direct bond (single bond) or a divalent group represented by formula (Y1).
[ Wherein either one of R 21 and R 31 is a hydrogen atom, the other is a hydrogen atom or a methyl group, or R 21 and R 31 may be bonded to each other and form a 6-membered ring together with the adjacent carbon atoms, and the ring may be substituted with 1 to 3 methyl groups. * Indicating the bonding location. ]]
[ Item 17]
The resin according to item [ 16], wherein the resin is a resin having at least 1 selected from the group consisting of an ester bond, a carbonate bond and a urethane bond.
[ Item 18]
An optical member comprising the resin according to any one of [ 15] to [ 17 ].
[ Item 19]
The optical member according to item 18, wherein the optical member is at least 1 selected from the group consisting of an optical lens, an optical film and an optical sheet.
Effects of the invention
The compound represented by the formula (1) (cyclic diol compound) is useful as a resin modifier for a polycarbonate resin or a polyester polycarbonate resin (i.e., a resin having a carbonate bond and an ester bond if necessary). Among them, the compound represented by the formula (1B) is a novel compound and is useful as a resin modifier or a monomer raw material for a wide range of resins including the above resins.
The polycarbonate resin or the polyester carbonate resin obtained by using the resin modifier of the present invention has the characteristics of a small refractive index and a high glass transition temperature (Tg). Thus, by adjusting the content of the resin modifier in the monomer, the characteristics (glass transition temperature, refractive index, abbe number, etc.) of the obtained resin can be adjusted to a wide range.
In addition, the resin modifier of the present invention can adjust the refractive index of the resulting resin by copolymerizing with various dihydroxy compounds in an appropriate ratio. Therefore, the resin can be suitably used for optical applications (optical lenses, optical films, optical sheets, etc.).
Drawings
FIG. 1 is an IR spectrum of compound No. 1 obtained in example 1.
FIG. 2 is a 1 H-NMR spectrum of compound 1 obtained in example 1.
FIG. 3 is an IR spectrum of compound No. 2 obtained in example 2.
FIG. 4 is a 1 H-NMR spectrum of compound 2 obtained in example 2.
FIG. 5 is an IR spectrum of compound No. 4 obtained in example 3.
Detailed Description
1. Resin modifier
The resin modifier of the present invention comprises a compound represented by the formula (1), and is a polycarbonate resin or a resin modifier of a polyester polycarbonate resin.
[ Wherein R 1, which are the same or different, are a hydrogen atom, a C1-4 alkyl group or a phenyl group. X is a direct bond (single bond) or a divalent group represented by formula (Y).
[ Wherein R 2 and R 3 are the same or different and are a hydrogen atom, an alkyl group or an aryl group, or R 2 and R 3 may be bonded to each other and form a ring together with the adjacent carbon atom, and the ring may be substituted with an alkyl group. n is 0 or 1.* Indicating the bonding location. ]]
R 1, which are identical or different, are preferably C1-4 linear or branched alkyl or phenyl. Examples of the linear or branched alkyl group of C1-4 represented by R 1 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. Among them, methyl, ethyl, isobutyl or tert-butyl is preferred. Further preferred is methyl or ethyl. Methyl is particularly preferred.
Examples of the alkyl group represented by R 2 and R 3 include a C1-12 alkyl group, a C1-6 alkyl group, and a C1-4 linear or branched alkyl group. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. Among them, methyl, ethyl, isobutyl or tert-butyl is preferred. Further preferred is methyl or ethyl. Methyl is particularly preferred.
Examples of the aryl group represented by R 2 and R 3 include phenyl, tolyl, xylyl, and naphthyl.
When R 2 and R 3 are bonded to each other and form a ring together with the adjacent carbon atom, examples of the ring include a 3-to 12-membered ring (for example, a 3-to 12-membered cycloalkane, etc.), a 5-to 12-membered ring (for example, a 5-to 12-membered cycloalkane, etc.), and a 6-to 12-membered ring (for example, a 6-to 12-membered cycloalkane, etc.), etc. Specifically, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, and the like can be cited. The ring may be substituted with 1 to 6 (preferably 1 to 3) alkyl groups. Examples of the alkyl group include a linear or branched alkyl group having 1 to 4 carbon atoms (particularly 1 to 3 carbon atoms), and methyl or ethyl is preferable. When the alkyl group is two or more, they may be the same or different.
N is preferably 0. Specifically, the divalent group represented by formula (Y) is preferably a divalent group represented by formula (Y1).
[ Wherein either one of R 21 and R 31 is a hydrogen atom, the other is a hydrogen atom or a methyl group, or R 21 and R 31 may be bonded to each other and form a 6-membered ring together with the adjacent carbon atoms, and the ring may be substituted with 1 to 3 methyl groups. * Indicating the bonding location. ]
Examples of the divalent group represented by the formula (Y) include divalent groups represented by the following formulas (Ya) to (Yc), and among these, the divalent group represented by the formula (Yb) is preferable.
Wherein R 2、R3, n and are the same as described above. ]
Among the compounds represented by the formula (1), as an example of a preferable resin modifier, a compound in which X is a direct bond (single bond) is exemplified. Further, compounds in which R 1 are the same or different and are C1-4 alkyl groups are preferred.
Among the compounds represented by the formula (1), other examples of preferable resin modifiers include compounds in which R 1 is a hydrogen atom, methyl or ethyl, and X is a direct bond (single bond), which are the same or different.
Among the compounds represented by the formula (1), other examples of preferable resin modifiers include compounds excluding the case where X is a divalent group represented by the formula (Y), n is 0, and R 2 and R 3 are both methyl groups. Further, a compound in which either R 2 or R 3 is an aryl group (particularly a phenyl group), and the other is a hydrogen atom or a C1-6 alkyl group (further, a C1-3 alkyl group, particularly a methyl group) is preferable.
Among the compounds represented by the formula (1), the following compounds are preferable as other examples of the resin modifier: in the divalent group represented by the formula (Y), when n is 0, R 2 and R 3 are the same or different and are a hydrogen atom, a C1-6 alkyl group or a phenyl group, or R 2 and R 3 may be bonded to each other and form a 5-12 membered ring together with the adjacent carbon atom, and the ring may be substituted with a C1-3 alkyl group; when n is 1, R 2 and R 3 are the same or different and are hydrogen atom or C1-6 alkyl.
Among the compounds represented by the formula (1), the following compounds are preferable as other examples of the resin modifier: in the divalent group represented by the formula (Y), n is 0, R 2 and R 3 are the same or different and are a hydrogen atom, a C1-6 alkyl group or a phenyl group, or R 2 and R 3 may be bonded to each other and form a 5-12 membered ring together with the adjacent carbon atom, and the ring may be substituted with a C1-3 alkyl group.
Among the compounds represented by the formula (1), R 1 is the same or different hydrogen atom, methyl or ethyl, and R 2 and R 3 are the same or different hydrogen atom or C1-4 alkyl in the divalent group represented by the formula (Y) are mentioned as other examples of the preferable resin modifier.
Among the compounds represented by the formula (1), the compound represented by the formula (1A) is preferable as another example of the resin modifier.
[ Wherein R 11, which are the same or different, are a hydrogen atom, a methyl group or an ethyl group. X A is a direct bond (single bond) or a divalent group represented by formula (Y1).
[ Wherein either one of R 21 and R 31 is a hydrogen atom, the other is a hydrogen atom or a methyl group, or R 21 and R 31 may be bonded to each other and form a 6-membered ring together with the adjacent carbon atoms, and the ring may be substituted with 1 to 3 methyl groups. * Indicating the bonding location. ]]
Among the divalent groups represented by the formula (Y1), either one of R 21 and R 31 is preferably a hydrogen atom or a C1-3 alkyl group, and the other is preferably an aryl group.
Examples of the C1-3 alkyl group represented by R 21 or R 31 include methyl, ethyl, n-propyl and isopropyl. Among them, methyl is preferable.
Examples of the aryl group represented by R 31 or R 31 include phenyl, tolyl, xylyl, and naphthyl. Among them, phenyl is preferable.
R 11, which are identical or different, are preferably methyl or ethyl.
Specific examples of the compound represented by the formula (1) include the following compounds (1 a) to (1 g). Specific examples of the compound represented by the formula (1A) include, for example, (1A) to (1 d) and (1 g).
Among the compounds represented by the formula (1), the compound represented by the formula (1B) is preferable as another example of the resin modifier.
[ Wherein R 11 is the same as described above. ]
R 11, which are identical or different, are preferably methyl or ethyl.
Among the compounds represented by the formula (1), the compound represented by the formula (1C) is preferable as another example of the resin modifier.
[ Wherein R 22 is a hydrogen atom or a C1-3 alkyl group, and R 32 is an aryl group. R 11 is the same as described above. ]
Examples of the C1-3 alkyl group represented by R 22 include methyl, ethyl, n-propyl and isopropyl. Among them, methyl is preferable.
Examples of the aryl group represented by R 32 include phenyl, tolyl, xylyl, and naphthyl. Among them, phenyl is preferable.
The resin modifier used in the present invention is used in the meaning of a reagent which can modify the properties of a resin by introducing the resin. The modified resin has structural units derived from a resin modifier. Specifically, the resin of the present invention is a resin having a structural unit derived from a cyclic diol compound represented by formula (1) (including cyclic diol compounds represented by formula (1A), formula (1B) and formula (1C): the same applies hereinafter). In other words, the term "resin" refers to a resin containing a divalent structural unit obtained by removing a hydrogen atom of a hydroxyl group from a cyclic diol compound represented by the formula (1).
The resin modifier containing the cyclic diol compound represented by the formula (1) can be used as a resin modifier for a polycarbonate resin or a polyester polycarbonate resin. That is, the resin composition can be used as a resin modifier for a resin having a carbonate bond in the molecule.
In addition, a resin modifier containing a cyclic diol compound represented by the formula (1A), the formula (1B) and the formula (1C) can be widely used as a modifier of a resin having an ester bond, a carbonate bond, a urethane bond or the like in the molecule, for example. Examples of the resin include polyester resins, polyester carbonate resins, polycarbonate resins, epoxy resins, polyurethane resins, polyacrylate resins, polymethacrylate resins, and polyester polyol resins. The polyester resin, the polyester carbonate resin, the polycarbonate resin, and the polyurethane resin are preferable, and the polyester carbonate resin and the polycarbonate resin are more preferable.
2. Method for producing resin modifier
The method for producing the compound represented by the formula (1) is not particularly limited, and for example, the compound represented by the formula (3) and the compound represented by the formula (4) can be produced by a reaction (acetalization reaction) as shown in the following < reaction formula 1 >. The compounds represented by the formula (1A), the formula (1B) and the formula (1C) included in the compound represented by the formula (1) can be produced in the same manner.
< Reaction No. 1>
[ Wherein R 1 and X are the same as defined above. ]
Specifically, the compound represented by the formula (1) can be produced by reacting the compound represented by the formula (3) with the compound represented by the formula (4) in the presence of an acidic catalyst (acetalization reaction).
The reaction may generally be carried out in a solvent (e.g., toluene, etc.). The reaction may be performed while heating and refluxing the solvent and azeotropically removing the water formed with the solvent. The acid catalyst is not particularly limited as long as it has a catalytic action, and a known acid catalyst can be used. Examples include: inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid; solid acids such as cation exchange resins, zeolites, silica-alumina, and heteropolyacids (e.g., phosphotungstic acid, phosphomolybdic acid, etc.); other various lewis acids, and the like.
The amount of the compound represented by the formula (4) to be used is usually about 0.5 to 3 moles, preferably about 0.8 to 2 moles, based on 1 mole of the compound represented by the formula (3).
The compounds represented by the formulas (1A), (1B) and (1C) included in the compound represented by the formula (1) can be specifically produced as follows < formula 2 >, < formula 3 > and < formula 4 >, respectively.
< Reaction No. 2>
[ Wherein R 11 and X A are the same as defined above. ]
< Reaction No. 3>
[ Wherein R 11 is the same as described above. ]
< Reaction 4>
[ Wherein R 11、R22 and R 32 are the same as described above. ]
3. Manufacture of resins using resin modifiers
The compound represented by the formula (1) (cyclic diol compound) can be used as a raw material monomer for producing a resin, and used alone or in combination with other monomers to carry out (co) polymerization to produce a resin containing a structural unit represented by the formula (2).
[ Wherein R 1 and X are the same as defined above. ]
The resin obtained by using the resin modifier containing the compound represented by the formula (1) may be a polycarbonate resin or a polyester carbonate resin having a carbonate bond.
In the formula (2), specific examples and preferred examples of R 1 and X are the same as those of R 1 and X described in the above formula (1).
In the case of a polycarbonate resin containing a structural unit represented by the formula (2), it can be produced by (polymerizing) a raw material monomer containing a compound represented by the formula (1) with a carbonyl precursor compound.
As a raw material monomer of the polycarbonate resin, the compound represented by formula (1) may be used alone. The polycarbonate resin obtained is a homopolymer obtained by polymerizing a compound represented by the formula (1) alone with a carbonyl precursor compound, and contains only the structural unit represented by the formula (2).
The raw material monomer of the polycarbonate resin may contain a dihydroxy compound which is usually used as a structural unit of the polycarbonate resin, in addition to the compound represented by formula (1). Examples of the dihydroxy compound include aliphatic dihydroxy compounds and aromatic dihydroxy compounds.
That is, the polycarbonate resin may be a copolymer containing a structural unit derived from a general dihydroxy compound in addition to a structural unit derived from a compound represented by formula (2) of formula (1). The copolymer having two or more structural units may be any of a block copolymer and a random copolymer.
Examples of the aliphatic dihydroxy compound include various aliphatic dihydroxy compounds, and in particular, 1, 4-cyclohexanedimethanol, tricyclodecanedimethanol, 1, 3-adamantanedimethanol, 2-bis (4-hydroxycyclohexyl) -propane, 3, 9-bis (2-hydroxy-1, 1-dimethylethyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane, 2- (5-ethyl-5-hydroxymethyl-1, 3-dioxane-2-yl) -2-methylpropan-1-ol, isosorbide, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, and the like.
Examples of the aromatic dihydroxy compound include various aromatic dihydroxy compounds, particularly 2, 2-bis (4-hydroxyphenyl) propane [ bisphenol A ], bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 4' -dihydroxybiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, diphenoxyglycolfluorene (BPEF), and the like. In addition, hydroquinone, resorcinol, catechol, and the like can be cited.
As another embodiment of the dihydroxy compound, a dihydroxy compound represented by formula (5) is mentioned. The dihydroxy compound represented by formula (5) may contain 1 or 2 or more.
[ Wherein R 4 and R 5 are each independently a hydrogen atom, a C1-10 alkyl group, a C5-10 cycloalkyl group or a C6-10 aryl group. W is each independently C2-6 alkylene, C5-10 cycloalkylene, or C6-10 arylene. p and m are each independently integers from 0 to 5. ]
The C1-10 alkyl group represented by R 4 or R 5 may be either a straight chain or a branched chain. Preferably C1-3 alkyl, more preferably methyl.
Examples of the C5-10 alkyl group represented by R 4 or R 5 include cyclopentyl and cyclohexyl.
Examples of the aryl group having 6 to 10 carbon atoms represented by R 4 or R 5 include phenyl, tolyl, xylyl, and naphthyl.
R 4 and R 5 are each preferably a hydrogen atom.
The alkylene group of C2-6 shown in W may be either a straight chain or a branched chain, and is preferably an alkylene group of C2-4, more preferably ethylene group (-CH 2CH2 -), propylene group (-CH 2CH(CH3)-、-CH2CH2CH2 -), or the like.
W is preferably ethylene.
P is preferably an integer of 1 to 3, preferably 1.
M is preferably an integer of 1 to 3, preferably 1.
Among the dihydroxy compounds represented by formula (5), compounds in which R 4 and R 5 are each independently a hydrogen atom, a C1-3 alkyl group (particularly methyl group) or phenyl group, an alkylene group (particularly ethylene group) in which X is C2-3, and p and m are 1, are exemplified. BPEF is particularly preferred.
The proportion of the compound represented by the formula (1) in the raw material monomer to be used is not particularly limited, but is, for example, 1 mol% or more, preferably 1 to 80 mol%, more preferably 1 to 60 mol%, still more preferably 5 to 50 mol%, and particularly preferably 15 to 35 mol% in the total amount of the monomers. That is, the proportion of the structural unit represented by the formula (2) derived from the compound represented by the formula (1) in the polycarbonate resin is not particularly limited, but is, for example, 1 mol% or more, preferably 1 to 80 mol%, more preferably 1 to 60 mol%, still more preferably 5 to 50 mol%, and particularly preferably 15 to 35 mol% in the total structural units.
Examples of the carbonyl precursor compound include phosgene, triphosgene, diphenyl carbonate, and the like.
The raw material monomer of the polyester carbonate resin may contain, in addition to the compound represented by the formula (1), a dihydroxy compound, a dicarboxylic acid compound, a dicarboxylic anhydride compound, a hydroxycarboxylic acid ester compound, a dicarboxylic acid ester compound, or the like, which are generally used as a structural unit of the polyester carbonate resin. Examples of the dihydroxy compound include aliphatic dihydroxy compounds, aromatic dihydroxy compounds, and dihydroxy compounds represented by formula (5). The raw material monomer preferably further contains a structural unit derived from at least one monomer selected from the following monomer groups, for example.
[ Wherein R 6 and R 7 each independently represent a hydrogen atom, a methyl group or an ethyl group, and R 8 and R 9 each independently represent a hydrogen atom, a methyl group, an ethyl group or a monovalent group obtained by removing 1 hydroxyl group from a C2-5 alkylene glycol. ]
That is, the polyester carbonate resin may contain a structural unit derived from a general dihydroxy compound, a dicarboxylic acid compound, a dicarboxylic anhydride compound, a hydroxycarboxylic acid ester compound, a dicarboxylic acid ester compound, or the like, in addition to the structural unit derived from the compound represented by the formula (2) shown by the formula (1). The copolymer having two or more structural units may be any of a block copolymer and a random copolymer.
The carbonate resin and the polyester carbonate resin containing the structural unit represented by the formula (2) preferably contain a structural unit derived from a dihydroxy compound (particularly BPEF) represented by the formula (5) and a structural unit derived from a compound represented by the formula (1), respectively. The molar ratio of the two structural units in the resin is, for example, 99:1 to 1:99, preferably 95: 5-20: 80, more preferably 90: 10-30: 70, further preferably 85: 15-40: 60, particularly preferably 85: 15-45: 55.
As another embodiment of the carbonate resin and the polyester carbonate resin, resins each including (only) a structural unit derived from a dihydroxy compound represented by formula (5) (particularly BPEF) and a structural unit derived from a compound represented by formula (1) are exemplified. In this case, the range of the molar ratio of the two structural units in the resin may be preferably used.
The polycarbonate resin or the polyester carbonate resin containing the structural unit represented by the formula (2) has a number average molecular weight (Mn) of about 4000 to 100000, preferably about 10000 to 50000, a weight average molecular weight (Mw) of about 5000 to 100000, preferably about 6000 to 80000, and a polydispersity index (Mw/Mn) of about 1 to 5, preferably about 1.5 to 4.5. The glass transition temperature (Tg) is about 100 to 200℃and preferably about 120 to 160 ℃.
The refractive index (n D) of the polycarbonate resin or the polyestercarbonate resin containing the structural unit represented by the formula (2) is large, usually 1.500 to 1.750, and preferably 1.520 to 1.650. The refractive index is a value measured by the method described in examples.
The Abbe number (. Nu d) of the polycarbonate resin or the polyester carbonate resin containing the structural unit represented by the formula (2) is usually 20.0 to 55.0, preferably 24.0 to 45.0. The Abbe number is a value measured by the method described in examples.
The compounds represented by the formulas (1A), (1B) and (1C) included in the compound represented by the formula (1) can be produced in the same manner as described above. The polymerization can be carried out by using the resin alone or in combination with other monomers, and the resin containing the structural units represented by the following formulas (2A), (2B) and (2C) can be produced.
[ Wherein R 11 and X A are the same as defined above. ]
[ Wherein R 11 is the same as described above. ]
[ Wherein R 11、R22 and R 32 are the same as described above. ]
Resins having an ester bond, a carbonate bond, a urethane bond, or the like in the molecule can be widely used as resins obtained by using a resin modifier containing a compound represented by the formula (1A), the formula (1B), or the formula (1C). Specifically, polyester resins, polyester carbonate resins, polycarbonate resins, polyurethane resins, polyester polyol resins, and the like can be cited. The polyester resin, the polyester carbonate resin, the polycarbonate resin, and the polyurethane resin are preferable, and the polyester carbonate resin and the polycarbonate resin are more preferable.
The resin containing the structural units represented by the formulas (2A), (2B) and (2C) may contain, in the molecule, structural units derived from raw material monomers other than the compounds represented by the formulas (1A), (1B) and (1C), respectively. The structural unit may contain an ether bond, an amide bond, a urethane bond, a urea bond, or the like.
In the formula (2A), specific examples and preferred examples of R 11 and X A are the same as specific examples and preferred examples of R 11 and X A described in the above formula (1A).
In the formula (2B), specific examples and preferred examples of R 11 are the same as those of R 11 described in the above formula (1B).
In the formula (2C), specific examples and preferred examples of R 11、R22、R32 and X A are the same as specific examples and preferred examples of R 11、R22、R32 and X A described in the above formula (1C).
Resins containing structural units represented by the formulae (2A), (2B) and (2C) can be widely used for resins other than the polycarbonate resins and the polyester carbonate resins, and therefore, in addition to the above-described characteristics, various characteristics (optical characteristics, mechanical characteristics, dimensional stability, and the like) can be imparted to the resins according to purposes.
4. Use of modified resins
The properties of the resin can be modified by polymerizing the compound represented by the formula (1) using it as a single monomer or a comonomer. For example, by adjusting the amount of the compound represented by the formula (1) to be added and copolymerizing with other monomers, the refractive index, glass transition temperature, abbe number, birefringence and other properties of the resin obtained after copolymerization can be adjusted.
Thus, the resin obtained using the resin modifier of the present invention can be suitably used for, for example, an optical member. The optical member includes, but is not limited to, an optical disc, a transparent conductive substrate, an optical card, a sheet, a film, an optical fiber, a lens, a prism, an optical film, a base, an optical filter, a hard coat film, and the like. The resin of the present invention is particularly suitable for producing a thin optical member because it has high fluidity and can be molded by a casting method. In a preferred embodiment of the present invention, as the optical member produced using the resin of the present invention, there are exemplified an optical lens, an optical film, an optical sheet, and the like.
The resin of the present invention can be suitably used for an optical lens. The optical lens produced using the resin (particularly, polycarbonate resin) of the present invention has a high refractive index and excellent heat resistance, and therefore is useful in the field of use of expensive high refractive index glass lenses in the past, such as telescopes, binoculars, and television projectors.
In addition, the resin of the present invention can adjust the refractive index of the resin to a wide range according to the design of various optical lenses by adjusting the content of the structural unit derived from the compound represented by formula (1).
The resin of the present invention may be suitably used for an optical film. An optical film produced using the resin (particularly, polycarbonate resin) of the present invention is suitable for use as a film for a liquid crystal substrate, an optical memory card, or the like, because of excellent transparency and heat resistance.
The resins for optical members that are generally used include various resins, and particularly include polyester resins, polyester carbonate resins, polycarbonate resins, and the like, and particularly polyester carbonate resins or polycarbonate resins, which are excellent in transparency, impact resistance, heat resistance, dimensional stability, and the like.
The resin can be suitably used for applications requiring adjustment of refractive index, in particular, optical members such as optical lenses, optical films, and optical sheets. The applicable optical member is not particularly limited, and examples thereof include a lens of a camera of a smartphone, a lens of a vehicle-mounted camera, a lens for goggles for VR (virtual reality) or MR (mixed reality), a lens for crime prevention cameras, and the like.
In this specification, the expression "comprising" or "containing" includes the meaning of "must consist of … …" and "consist of only … …".
Examples
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In this example, various measurements of the cyclic diol compound were performed by the following methods. In addition, no particular mention of the compounds uses reagents.
< Use Compounds >)
4,4' -Bicyclohexanone: manufactured by Tokyo chemical industry Co., ltd
P-toluenesulfonic acid monohydrate: made by naproaster corporation
Trimethylolethane and trimethylolpropane: manufactured by Tokyo chemical industry Co., ltd
Bisphenol Phenylethanofluorene (BPEF): manufactured by Tokyo chemical industry Co., ltd
Diphenyl carbonate: manufactured by Tokyo chemical industry Co., ltd
Analysis by Gas Chromatography (GC)
The purity of the cyclic diol compound was determined by the area percentage method by Gas Chromatography (GC) analysis under the following conditions and methods.
(Sample preparation)
To 10mg of a cyclic diol compound, 1g of pyridine was added, and then N, O-bis (trimethylsilyl) trifluoroacetamide (containing 1% trimethylchlorosilane) was added, followed by shaking and mixing at room temperature to prepare a pyridine solution of the cyclic diol compound as a sample for analysis.
[ Measurement conditions ]
Instrument: GC-2020 manufactured by Shimadzu corporation
Column: DB-1 30m x 0.25mm x 0.25 μm manufactured by Agilent technologies Co., ltd
Column temperature: 80 ℃ (retention time 5 minutes) -heating rate 10 ℃/min-320 ℃ (retention time 5 minutes)
Sample injection temperature/detector temperature: 300 ℃/325 DEG C
Split ratio: 30
Column flow rate: 1.17 ml/min
Purge flow rate: 10.0 ml/min
A detector: FID (FID)
Carrier gas: helium gas
Gas linear velocity: 30 cm/sec
Sample injection amount: 1 μl
< IR Spectrum > (IR Spectrum)
The IR Spectrum of the cyclic diol compound was performed by ATR (attenuated total reflectance) method using an infrared Spectrum analyzer (Spectrum 400 manufactured by perkin elmer japan, ltd.).
Proton Nuclear magnetic resonance Spectroscopy (1 H-NMR) >
The 1 H-NMR of the cyclic diol compound was dissolved in a deuterated solvent (deuterated chloroform or deuterated dimethyl sulfoxide), and then measured by using a nuclear magnetic resonance apparatus (AVIII-400, 1 H-NMR (400 MHz) manufactured by Bruker Co.).
In the solvent used for 1 H-NMR measurement, a water peak was observed in some cases. The peak from water contained in deuterated chloroform was present at around 1.56ppm, and the peak from water contained in deuterated dimethyl sulfoxide was present at around 3.33 ppm. In addition, the peak derived from the residual proton contained in deuterated chloroform was present in the vicinity of 7.27ppm, and the peak derived from the residual proton contained in deuterated dimethyl sulfoxide was present in the vicinity of 2.50 ppm.
< Glass transition temperature (Tg) >)
The glass transition temperature of the obtained polycarbonate resin was measured using a differential calorimeter DSC6220 manufactured by SII nanotechnology Co. 6.7mg of the sample was placed in an aluminum pan manufactured by this company, and sealed, and the temperature was raised from 30℃to 220℃at a temperature-raising rate of 10℃per minute under a nitrogen gas stream, cooled from 220℃to 30℃at a temperature-lowering rate of 10℃per minute, and raised from 30℃to 220℃at a temperature-raising rate of 10℃per minute, whereby the inflection point (the differential maximum value of DSC) in 2ndRUN was regarded as the glass transition temperature.
< Number average molecular weight, weight average molecular weight and polydispersity index >)
About 30mg of the polycarbonate resin was dissolved in 8ml of tetrahydrofuran to prepare a sample solution for molecular weight measurement. The number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity index (Mw/Mn) of the polycarbonate resin contained in the sample solution were determined by Gel Permeation Chromatography (GPC) under the following measurement conditions.
(Measurement conditions)
The device comprises: pump (LC-20 AD type manufactured by Shimadzu corporation)
Automatic sampler (SIL-20A HT manufactured by Shimadzu corporation)
Detector RI (RID-10A type manufactured by Shimadzu corporation)
Column incubator (CTO-20A manufactured by Shimadzu corporation)
Column: shodex LF-802, 2 root (Zhaohe electric Co., ltd.)
Eluent: tetrahydrofuran (THF) made by Katsuk Co., ltd., contains about 0.025% of BHT
Column temperature: 40 DEG C
Flow rate: 1.0 mL/min
Sample injection amount: 100 μl of
Analysis method: PS conversion molecular weight
Standard polymers were used: shodex STANDARD SM-105
< Refractive index >
The polycarbonate resin obtained in each production example described below was heated at 200℃for 3 minutes by applying a pressure of 10MPa to 0.8g of the resin amount using an IMC-48IE type manual hydraulic heating and cooling compressor manufactured by Seisakusho Co., ltd. After that, the mixture was cooled for 3 minutes to obtain a polycarbonate film having a thickness of 0.1 mm.
A rectangular test piece having a length of 40mm and a width of 8mm was cut out from the film having a thickness of 0.1mm, and the cut piece was used as a measurement sample. The refractive index n D was measured by a method of JIS-K-7142 using an interference filter having a wavelength of 589nm (D-ray) by using a multi-wavelength Abbe refractometer DR-M2 manufactured by Ipith of Kyowa Co., ltd. In the measurement, diiodomethane (manufactured by tokyo chemical industry Co., ltd.) was used as an intermediate solution.
< Total light transmittance >)
The total light transmittance was measured by the method of JIS-K-7136 using HazeMaterNDH7000SPII manufactured by Nippon Denshoku corporation as a measurement sample with a film having a thickness of 0.1mm produced by the method of < refractive index > described above. The measurement was performed on 3 films, and the average value of the measured values obtained in the measurement was used as a measurement value.
< Abbe number >
A rectangular test piece having a length of 40mm and a width of 8mm was cut out from the film having a thickness of 0.1mm produced by the method of < refractive index > as a measurement sample. Abbe number v d was determined from the measured values and the following formula by measuring refractive index n C、nD、nF at each wavelength by using a multi-wavelength Abbe refractometer DR-M2 manufactured by Kagaku corporation using an interference filter having a wavelength of 656nm (C-ray), 589nm (D-ray) and 486nm (F-ray) in accordance with the method of JIS-K-7142.
vD＝(nD-1)/(nF-nC)
In the measurement, diiodomethane (manufactured by tokyo chemical industry Co., ltd.) was used as an intermediate solution.
< Production of cyclic diol Compound >
Example 1 (production of cyclic diol Compound 1)
To a 1000ML four-necked flask equipped with a stirrer, a thermometer and a dean-stark equipped with a condenser, 25.2g (0.13 mol) of 4,4' -bicyclohexanone, 0.63g of p-toluenesulfonic acid monohydrate, 32.8g (0.27 mol) of trimethylolethane, 300ML of xylene and 100g of N-methyl-2-pyrrolidone were charged, and then the temperature was raised, and the resultant water was removed under reflux conditions and stirred for about 3 hours.
After the completion of the reaction, about 250g of xylene was distilled off under reduced pressure. The reaction mixture was cooled to 90℃and neutralized with 10.35g of a 3.4wt% aqueous sodium carbonate solution, 250g of ion exchange water at 90℃was added thereto, and the mixture was cooled to 25 ℃. The crystals formed were filtered off, and the crystals obtained were washed once with 200g of ion-exchanged water and then with 50g of isopropyl alcohol. The wet crystals were dried under reduced pressure at 100℃to thereby obtain 40.1g (0.10 mol) of 4,4' -cyclohexanone trimethylolethane diacetal having a purity of 98.1% (GC area percentage). The 4,4' -cyclohexanone trimethylolethane diacetal is hereinafter referred to as compound 1.
The IR spectrum and 1 H-NMR spectrum of the obtained compound 1 were measured, and the results thereof are shown in FIG. 1 and FIG. 2.
(Compound 1)
IR(cm-1)：674，901，932，987，1005，1026，1047，1086，1097，1207，1371，2860，2939，3390
Example 2 (production of cyclic diol Compound 2)
To a 1000ML four-necked flask equipped with a stirrer, a thermometer and a dean-stark equipped with a condenser, 21.2g (0.11 mol) of 4,4' -bicyclohexanone, 0.53g (p-toluenesulfonic acid monohydrate), 26.4g (0.20 mol) of trimethylolpropane, 300ML of xylene and 100g of N-methyl-2-pyrrolidone were charged, and then the temperature was raised, and the resultant water was removed under reflux conditions and stirred for about 6 hours.
After the completion of the reaction, about 250g of xylene was distilled off under reduced pressure. The reaction mixture was cooled to 60℃and neutralized with 10.35g of a 3.4wt% aqueous sodium carbonate solution, 250g of ion-exchanged water at 60℃was added thereto, and the mixture was cooled to 25 ℃. The crystals formed were filtered off, and the crystals obtained were washed once with 200g of ion-exchanged water and then with 50g of isopropyl alcohol. The wet crystals obtained were put into a 1000ML four-necked flask equipped with a stirrer, a thermometer and a dean-stark with a condenser, 200g of isopropyl alcohol was added, and the temperature was raised to 80℃and the mixture was stirred for about 30 minutes, and then cooled to 25℃to filter out precipitated crystals. The resulting crystals were rinsed once with 35g of isopropanol. The wet crystals were dried under reduced pressure at 100℃to thereby obtain 26.5g (0.06 mol) of 4,4' -cyclohexanone trimethylolpropane diacetal having a purity of 98.1% (GC area percentage). The 4,4' -cyclohexanone trimethylolpropane diacetal is hereinafter referred to as compound 2.
The IR spectrum and 1 H-NMR spectrum of the obtained compound 2 were measured, and the results thereof are shown in FIG. 3 and FIG. 4.
(Compound 2)
IR(cm-1)：906，932，1011，1037，1088，1104，1204，1370，2861，2942，3388
Reference example 1 (production of cyclic diol Compound 3)
2, 2-Bis (4-oxocyclohexyl) propane-bis (trimethylolethane acetal) (compound 3) was synthesized according to example 1 of Japanese patent application laid-open No. 2019-14711 (patent document 5).
Example 3 (production of cyclic diol Compound 4)
A1500 ML stainless steel (SUS) reactor was charged with 1.8g of Pd/C (from Utility Co., ltd.), 90.0g (0.30 mol) of bisphenol AP (4, 4' - (1-phenylethoxy) bisphenol), 0.2g of sodium carbonate, and 512g of xylene as palladium catalysts. Thereafter, hydrogen gas was filled into the reactor to 1.0MPa, and the temperature was raised to 170 ℃. Hydrogen was supplied at 170 c to react for 7 hours while the reaction pressure was brought to 1.0 MPa.
Then cooling, recovering the content in the reactor, filtering, and removing the catalyst. The recovery amount of the filtrate was 596g, and as a result of analysis of the filtrate by GC, the conversion of bisphenol AP of the raw material was 100%, and the purity of the target diketone (4, 4' - (1-phenylethane-1, 1-diyl) bis (cyclohexane-1-one)) was 68.5% (GC area percentage). The content was concentrated to 100g by a rotary evaporator at a water temperature of 70℃and a reduced pressure of 30 mmHg. Since the reaction mixture was a viscous liquid, 100g of toluene was added thereto to carry out the subsequent ketalization reaction.
To a 1000ML four-necked flask equipped with a stirrer, a thermometer and a dean-stark equipped with a condenser, 50g of a mixture of viscous liquid and toluene, 1.4g of methanesulfonic acid, 47.5g (0.40 mol) of trimethylolethane and 450g of toluene were charged, and the temperature was raised, and the resultant water was removed under reflux conditions and stirred for about 5 hours. The reaction mixture was cooled to 80℃and was then neutralized by adding an aqueous sodium carbonate solution (a mixture of 2.12g of sodium carbonate and 10g of distilled water). Then, the mixture was cooled to room temperature, and concentrated by a rotary evaporator at a water temperature of 70℃and a reduced pressure of 30mmHg to obtain 80.5g of a viscous liquid. The viscous liquid was dried with a reduced pressure dryer to give 32.5g of 4,4' - (1-phenylethane) cyclohexanone trimethylolethane diacetal as a crude product.
Into a 100ML four-necked flask equipped with an oil bath, a stirrer, a thermometer and a distillation apparatus, 30.0g of the crude product was charged. The four-necked flask was immersed in an oil bath heated to 250℃and was depressurized from normal pressure to vacuum in stages to distill off the low boiling point compound. The solid remaining in the flask was taken out to obtain 18g of 4,4' - (1-phenylenetriazinone) trimethylolethane diacetal (compound 4) having a purity of 97.5% (GC area percentage) as a solid. This compound is hereinafter referred to as compound 4.
(Compound 4)
IR(cm-1)：878，963，1005，1022，1050，1395，2873，2941，3307
< Production of resin and evaluation of physical Properties >
Production example 1 (production of polycarbonate resin 1)
5.6G (0.01 mol), 24.6g (0.06 mol) of diphenoxyglycolfluorene, 15.9g (0.07 mol) of diphenyl carbonate and 17.0. Mu.L (4.2X10 -7 mol) of an aqueous sodium hydrogencarbonate solution of 2.5X10 mol/L of the compound obtained in example 1 were added to a 300mL four-necked flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200 ℃.
After the substrate was dissolved, the temperature was raised to 240℃in stages over 80 minutes, and the pressure was reduced to 150mmHg in stages. After the pressure was further reduced to vacuum in stages for 40 minutes and maintained for 20 minutes, 25g of the polycarbonate resin (hereinafter referred to as "polycarbonate resin 1") thus produced was taken out. During the reaction, the associated phenol was distilled off. The polycarbonate resin 1 thus removed was pulverized, and the glass transition temperature was measured, resulting in 142.7 ℃. The number average molecular weight Mn was 14600, the weight average molecular weight Mw was 26300, and the polydispersity index Mw/Mn was 1.8.
The refractive index was 1.611. The Abbe number is 26.0. The total light transmittance was 90%. The results obtained are shown in Table 1.
Production example 2 (production of polycarbonate resin 2)
1.0 G (0.02 mol), 20.6g (0.05 mol) of diphenoxyglycolfluorene, 15.2g (0.07 mol) of diphenyl carbonate and 16.3. Mu.L (4.1X10 -7 mol) of an aqueous sodium hydrogencarbonate solution of 2.5X10. 10 -2 mol/L of the compound obtained in example 1 were added to a 300mL four-necked flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200 ℃.
After the substrate was dissolved, the temperature was raised to 240℃in stages over 80 minutes, and the pressure was reduced to 150mmHg in stages. After the pressure was further reduced to vacuum in stages for 40 minutes and maintained for 20 minutes, 25g of the polycarbonate resin (hereinafter referred to as "polycarbonate resin 2") thus produced was taken out. During the reaction, the associated phenol was distilled off. The polycarbonate resin 2 thus removed was pulverized, and the glass transition temperature was measured, resulting in 142.2 ℃. The number average molecular weight Mn was 12700, the weight average molecular weight Mw was 25800, and the polydispersity index Mw/Mn was 2.0.
The refractive index is 1.597. The Abbe number is 30.2. The total light transmittance was 91%. The results obtained are shown in Table 1.
Production example 3 (production of polycarbonate resin 3)
6.5G (0.02 mol), 26.0g (0.06 mol) of diphenoxyglycolfluorene, 16.3g (0.08 mol) of diphenyl carbonate and 30.0. Mu.L (7.5X10 -7 mol) of an aqueous sodium hydrogencarbonate solution of 2.5X10 mol/L of the compound obtained in referential example 1 were added to a 300mL four-necked flask equipped with a stirrer and a distillation apparatus, and stirred under a nitrogen atmosphere and heated to 200 ℃.
After the substrate was dissolved, the temperature was raised to 240℃in stages over 80 minutes, and the pressure was reduced to 150mmHg in stages. After the pressure was further reduced to vacuum in stages for 40 minutes and maintained for 20 minutes, 27g of the polycarbonate resin (hereinafter referred to as "polycarbonate resin 3") thus produced was taken out. During the reaction, the associated phenol was distilled off. The polycarbonate resin 3 thus removed was pulverized, and the glass transition temperature was measured, resulting in 148.8 ℃. The number average molecular weight Mn was 15700, the weight average molecular weight Mw was 32200 and the polydispersity index Mw/Mn was 2.1.
The refractive index was 1.610. The Abbe number is 26.2. The total light transmittance was 90%.
Production example 4 (production of polycarbonate resin 4)
7.9G (0.02 mol), 18.4g (0.04 mol) of diphenoxyglycolfluorene, 13.2g (0.06 mol) of diphenyl carbonate and 24.3. Mu.L (6.1X10 -7 mol) of an aqueous sodium hydrogencarbonate solution of 2.5X10. 10 -2 mol/L of the compound obtained in referential example 1 were added to a 300mL four-necked flask equipped with a stirrer and a distillation apparatus, and stirred under a nitrogen atmosphere and heated to 200 ℃.
After the substrate was dissolved, the temperature was raised to 240℃in stages over 80 minutes, and the pressure was reduced to 150mmHg in stages. After the pressure was further reduced to vacuum in stages for 40 minutes and maintained for 20 minutes, 29g of the polycarbonate resin (hereinafter referred to as "polycarbonate resin 4") thus produced was taken out. During the reaction, the associated phenol was distilled off. The polycarbonate resin 4 thus removed was pulverized, and the glass transition temperature was measured, resulting in 149.0 ℃. The number average molecular weight Mn was 17000, the weight average molecular weight Mw was 35800, and the polydispersity index Mw/Mn was 2.1.
The refractive index was 1.594. The Abbe number is 28.5. The total light transmittance was 90%.
Production example 5 (production of polycarbonate resin 5)
6.8G (0.01 mol), 23.8g (0.05 mol) of diphenoxyglycolfluorene, 15.0g (0.07 mol) of diphenyl carbonate and 24.8. Mu.L (6.9X10 -7 mol) of an aqueous sodium hydrogencarbonate solution of 2.5X10. 10 -2 mol/L of the compound obtained in example 3 were added to a 300mL four-necked flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200 ℃.
After the substrate was dissolved, the temperature was raised to 240℃in stages over 80 minutes, and the pressure was reduced to 150mmHg in stages. After the pressure was further reduced to vacuum in stages for 40 minutes and maintained for 20 minutes, 25g of the polycarbonate resin (hereinafter referred to as "polycarbonate resin 5") thus produced was taken out. During the reaction, the associated phenol was distilled off. The polycarbonate resin 5 thus removed was pulverized, and the glass transition temperature was measured, resulting in 147.6 ℃. The number average molecular weight Mn was 13400, the weight average molecular weight Mw was 28100, and the polydispersity index Mw/Mn was 2.1. The refractive index was 1.620. The Abbe number is 25.0. The total light transmittance was 90%. The results obtained are shown in Table 1.
Production example 6 (production of polycarbonate resin 5)
9.2G (0.02 mol), 18.8g (0.04 mol) of diphenoxyglycolfluorene, 13.5g (0.07 mol) of diphenyl carbonate and 24.7. Mu.L (6.2X10 -7 mol) of an aqueous sodium hydrogencarbonate solution of 2.5X10. 10 -2 mol/L of the compound obtained in example 3 were added to a 300mL four-necked flask equipped with a stirrer and a distillation apparatus, stirred under a nitrogen atmosphere, and heated to 200 ℃.
After the substrate was dissolved, the temperature was raised to 240℃in stages over 80 minutes, and the pressure was reduced to 150mmHg in stages. After the pressure was further reduced to vacuum in stages for 40 minutes and maintained for 20 minutes, 25g of the polycarbonate resin (hereinafter referred to as "polycarbonate resin 5") thus produced was taken out. During the reaction, the associated phenol was distilled off. The polycarbonate resin 5 thus removed was pulverized, and the glass transition temperature was measured, resulting in 147.9 ℃. The number average molecular weight Mn was 14100, the weight average molecular weight Mw was 29600, and the polydispersity index Mw/Mn was 2.1. The refractive index is 1.609. The Abbe number is 26.2. The total light transmittance was 90%. The results obtained are shown in Table 1.
Comparative production example 1 (production of polycarbonate resin A)
To a 300mL four-necked flask equipped with a stirrer and a distillation apparatus, 59.0g (0.13 mol), 30.0g (0.14 mol) of diphenyl carbonate, and 55.0. Mu.L (137.5X10 -8 mol) of an aqueous sodium hydrogencarbonate solution (2.5X10 -2 mol/L) were added, followed by stirring under a nitrogen atmosphere and heating to 200 ℃.
After the substrate was dissolved, the temperature was raised to 240℃in stages over 80 minutes, and the pressure was reduced to 150mmHg in stages. Further, the pressure was reduced to vacuum in stages for 40 minutes, and after holding for 20 minutes, 55g of the polycarbonate resin (hereinafter referred to as "polycarbonate resin A") thus produced was taken out. During the reaction, the associated phenol was distilled off. The polycarbonate resin A thus removed was pulverized, and the glass transition temperature was measured, resulting in 147 ℃. The number average molecular weight Mn was 21940, the weight average molecular weight Mw was 41680, and the polydispersity index Mw/Mn was 1.90.
The refractive index was 1.638. The birefringence was-0.023X 10 -2 at a wavelength of 588.8 nm. The Abbe number is 23.5. The total light transmittance was 90%.
As is clear from the results in table 1, the polycarbonate resins obtained by using the compounds 1 and 3 have lower refractive indices and higher abbe numbers than the polycarbonate resin formed by BPEF of comparative production example 1. When production examples 1 and 2, production examples 3 and 4, and production examples 5 and 6 were compared with each other, it was found that a polycarbonate resin having a lower refractive index and a higher abbe number could be obtained by increasing the copolymerization ratio of the monomer (resin modifier) represented by the formula (1). That is, it is known that the refractive index and abbe number of the polycarbonate resin can be adjusted to desired ranges by using the resin modifier.
According to the results of table 1, by increasing the compounding ratio of compound 1, a polycarbonate resin having a higher abbe number was obtained. It is also known that if the blending ratio is increased, the Abbe number is increased greatly.
It is found that even if the compounding ratio of the compound 4 is increased, the decrease in refractive index of the polycarbonate resin is small. By increasing the compounding ratio of compound 4, a polycarbonate resin having a higher glass transition temperature and a higher abbe number than those of the polycarbonate resin formed of BPEF of comparative production example 1 was obtained.
By increasing the blending ratio of the compound 3, the refractive index is reduced and the glass transition temperature is increased, and therefore, a resin having both good optical properties such as refractive index, birefringence and Abbe number and good heat resistance as represented by the glass transition temperature can be obtained. Moreover, the raw materials are industrially readily available and therefore useful.
Industrial applicability
The resin modifier of the present invention is useful as a resin modifier for a polycarbonate resin, or the like. By using the resin modifier, the physical properties such as glass transition temperature, refractive index, birefringence, abbe number, etc. of the resin can be widely adjusted. Therefore, the optical film is suitable for use as an optical member such as an optical lens, an optical film, and an optical sheet.
Claims (16)
1. A polycarbonate resin or a resin modifier for a polyester polycarbonate resin, which comprises a compound represented by the formula (1),
In the formula (1), R 1 are the same or different and are hydrogen atoms, C1-4 alkyl or phenyl, X is a direct bond or a bivalent group shown in the formula (Y),
In formula (Y), R 2 and R 3 are the same or different and are a hydrogen atom, an alkyl group or an aryl group, or R 2 and R 3 may be bonded to each other and form a ring together with the adjacent carbon atom, the ring may be substituted with an alkyl group, and n is 0 or 1.
2. The resin modifier according to claim 1, wherein, in the divalent group represented by the formula (Y), R 2 and R 3 are the same or different and are a hydrogen atom, a C1-6 alkyl group or a phenyl group, or R 2 and R 3 may be bonded to each other and form a 5-12 membered ring together with the adjacent carbon atom, the ring may be substituted with a C1-3 alkyl group, and R 2 and R 3 are the same or different and are a hydrogen atom or a C1-6 alkyl group when n is 1.
3. The resin modifier of claim 1, wherein X is a direct bond.
4. The resin modifier according to claim 3, wherein R 1, which are the same or different, are C1-4 alkyl groups.
5. The resin modifier according to claim 1, wherein the case where X is a divalent group represented by the formula (Y), n is 0, and R 2 and R 3 are each methyl is excluded.
6. The resin modifier according to claim 5, wherein either one of R 2 or R 3 is an aryl group, and the other is a hydrogen atom or a C1-6 alkyl group.
7. The resin modifier according to any one of claims 1 to 6, wherein the resin modifier is a polycarbonate resin or a polyester polycarbonate resin for an optical material.
8. A compound represented by the formula (1B),
In the formula (1B), R 11, which are the same or different, are a hydrogen atom, a methyl group or an ethyl group.
9. A resin modifier comprising the compound of claim 8.
10. The resin modifier according to claim 9, wherein the resin modifier is a polyester resin, a polycarbonate resin, or a resin modifier of a polyester polycarbonate resin.
11. The resin modifier according to claim 8, wherein the resin modifier is a resin modifier for a resin of an optical material.
12. A method for producing a compound represented by formula (1B), which comprises a step of reacting a compound represented by formula (3B) with a compound represented by formula (4A),
Wherein R 11 are the same or different and are hydrogen atom, methyl or ethyl.
13. A method for modifying a polycarbonate resin or a polyester polycarbonate resin, which comprises modifying the polycarbonate resin or the polyester polycarbonate resin with the resin modifier according to claim 1.
14. The method according to claim 13, wherein the method for performing the modification is a method for adjusting at least 1 property selected from the group consisting of glass transition temperature, refractive index and abbe number of a polycarbonate resin or a polyester polycarbonate resin obtained after the copolymerization by adjusting the content of the resin modifier according to any one of claims 1 to 6 and 8 to 11 in the whole of the polyhydric alcohols as the raw material.
15. A resin comprising a structural unit represented by the formula (2), wherein the resin is a polycarbonate resin or a polyester carbonate resin,
In the formula (2), R 1 are the same or different and are hydrogen atoms, C1-4 alkyl or phenyl, X is a direct bond or a bivalent group shown in the formula (Y),
In formula (Y), R 2 and R 3 are the same or different and are a hydrogen atom, an alkyl group or an aryl group, or R 2 and R 3 may be bonded to each other and form a ring together with the adjacent carbon atom, the ring may be substituted with an alkyl group, and n is 0 or 1.
16. An optical member comprising the resin according to claim 15.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022-117955 | 2022-07-25 | ||
| JP2022117955 | 2022-07-25 | ||
| PCT/JP2023/026512 WO2024024607A1 (en) | 2022-07-25 | 2023-07-20 | Cyclic diol compound, resin modifier, resin using said resin modifier, and use application of said resin |
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|---|---|
| CN117980374A true CN117980374A (en) | 2024-05-03 |
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| CN202380013563.1A Pending CN117980374A (en) | 2022-07-25 | 2023-07-20 | Cyclic diol compound, resin modifier, resin using the resin modifier, and use of the resin |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN117980374A (en) |
| TW (1) | TW202406900A (en) |
| WO (1) | WO2024024607A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7004913B2 (en) * | 2017-07-06 | 2022-02-04 | 新日本理化株式会社 | New alicyclic diol compound |
| JP2021134151A (en) * | 2020-02-25 | 2021-09-13 | 三菱瓦斯化学株式会社 | Diol, diketone, method for producing diol, and method for producing diketone |
| WO2023074439A1 (en) * | 2021-10-29 | 2023-05-04 | 帝人株式会社 | Thermoplastic resin and optical member |
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2023
- 2023-07-20 TW TW112127158A patent/TW202406900A/en unknown
- 2023-07-20 WO PCT/JP2023/026512 patent/WO2024024607A1/en active Application Filing
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| TW202406900A (en) | 2024-02-16 |
| WO2024024607A1 (en) | 2024-02-01 |
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