JP5166923B2 - Copolycarbonate resin and method for producing the same - Google Patents
Copolycarbonate resin and method for producing the same Download PDFInfo
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- JP5166923B2 JP5166923B2 JP2008060792A JP2008060792A JP5166923B2 JP 5166923 B2 JP5166923 B2 JP 5166923B2 JP 2008060792 A JP2008060792 A JP 2008060792A JP 2008060792 A JP2008060792 A JP 2008060792A JP 5166923 B2 JP5166923 B2 JP 5166923B2
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- carbon atoms
- polycarbonate resin
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- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229920005989 resin Polymers 0.000 title claims description 9
- 239000011347 resin Substances 0.000 title claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 51
- -1 ether diol Chemical class 0.000 claims description 49
- 229920005668 polycarbonate resin Polymers 0.000 claims description 39
- 239000004431 polycarbonate resin Substances 0.000 claims description 39
- 229920001577 copolymer Polymers 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000004417 polycarbonate Substances 0.000 claims description 26
- 229920000515 polycarbonate Polymers 0.000 claims description 25
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 24
- 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 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229960002479 isosorbide Drugs 0.000 claims description 21
- 150000003505 terpenes Chemical class 0.000 claims description 20
- 235000007586 terpenes Nutrition 0.000 claims description 20
- 238000010521 absorption reaction Methods 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 claims description 18
- 230000000035 biogenic effect Effects 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 239000000470 constituent Substances 0.000 claims description 14
- 239000002685 polymerization catalyst Substances 0.000 claims description 13
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 10
- GQVMHMFBVWSSPF-SOYUKNQTSA-N (4E,6E)-2,6-dimethylocta-2,4,6-triene Chemical compound C\C=C(/C)\C=C\C=C(C)C GQVMHMFBVWSSPF-SOYUKNQTSA-N 0.000 claims description 9
- JSNRRGGBADWTMC-UHFFFAOYSA-N alpha-farnesene Natural products CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 claims description 9
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 claims description 9
- GQVMHMFBVWSSPF-UHFFFAOYSA-N cis-alloocimene Natural products CC=C(C)C=CC=C(C)C GQVMHMFBVWSSPF-UHFFFAOYSA-N 0.000 claims description 9
- IHPKGUQCSIINRJ-UHFFFAOYSA-N β-ocimene Natural products CC(C)=CCC=C(C)C=C IHPKGUQCSIINRJ-UHFFFAOYSA-N 0.000 claims description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 7
- CXENHBSYCFFKJS-UHFFFAOYSA-N α-farnesene Chemical compound CC(C)=CCCC(C)=CCC=C(C)C=C CXENHBSYCFFKJS-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- JSNRRGGBADWTMC-QINSGFPZSA-N (E)-beta-Farnesene Natural products CC(C)=CCC\C(C)=C/CCC(=C)C=C JSNRRGGBADWTMC-QINSGFPZSA-N 0.000 claims description 3
- JXBSHSBNOVLGHF-UHFFFAOYSA-N 10-cis-Dihydrofarnesen Natural products CC=C(C)CCC=C(C)CCC=C(C)C JXBSHSBNOVLGHF-UHFFFAOYSA-N 0.000 claims description 3
- YSNRTFFURISHOU-UHFFFAOYSA-N beta-farnesene Natural products C=CC(C)CCC=C(C)CCC=C(C)C YSNRTFFURISHOU-UHFFFAOYSA-N 0.000 claims description 3
- 150000007823 ocimene derivatives Chemical class 0.000 claims description 3
- 229960002920 sorbitol Drugs 0.000 claims description 3
- XJPBRODHZKDRCB-UHFFFAOYSA-N trans-alpha-ocimene Natural products CC(=C)CCC=C(C)C=C XJPBRODHZKDRCB-UHFFFAOYSA-N 0.000 claims description 3
- 150000005690 diesters Chemical class 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000000465 moulding Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 10
- 150000004650 carbonic acid diesters Chemical class 0.000 description 10
- 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 9
- 239000003054 catalyst Substances 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 8
- 150000001991 dicarboxylic acids Chemical class 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 7
- 229930185605 Bisphenol Natural products 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 6
- KLDXJTOLSGUMSJ-KVTDHHQDSA-N (3r,3ar,6r,6ar)-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound O[C@@H]1CO[C@@H]2[C@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-KVTDHHQDSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000001530 fumaric acid Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001339 alkali metal compounds Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 3
- KLDXJTOLSGUMSJ-UNTFVMJOSA-N (3s,3ar,6s,6ar)-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound O[C@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-UNTFVMJOSA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- UDYLZILYVRMCJW-UHFFFAOYSA-L disodium;oxido carbonate Chemical compound [Na+].[Na+].[O-]OC([O-])=O UDYLZILYVRMCJW-UHFFFAOYSA-L 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000004714 phosphonium salts Chemical class 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 238000011191 terminal modification Methods 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical group OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 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 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 125000006178 methyl benzyl group Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- GPFJHNSSBHPYJK-UHFFFAOYSA-N (3-methylphenyl) hydrogen carbonate Chemical compound CC1=CC=CC(OC(O)=O)=C1 GPFJHNSSBHPYJK-UHFFFAOYSA-N 0.000 description 1
- KLDXJTOLSGUMSJ-UHFFFAOYSA-N 2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound OC1COC2C(O)COC21 KLDXJTOLSGUMSJ-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- NJMIRMHNYQIHST-UHFFFAOYSA-M 2-dodecylbenzenesulfonate;tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O NJMIRMHNYQIHST-UHFFFAOYSA-M 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- ICYDRUIZSPKQOH-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)decyl]phenol Chemical compound C=1C=C(O)C=CC=1C(CCCCCCCCC)C1=CC=C(O)C=C1 ICYDRUIZSPKQOH-UHFFFAOYSA-N 0.000 description 1
- KOWHWSRFLBFYRR-UHFFFAOYSA-N 4-[1-[3-[2-(4-hydroxyphenyl)propyl]phenyl]propan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)CC(C=1)=CC=CC=1CC(C)C1=CC=C(O)C=C1 KOWHWSRFLBFYRR-UHFFFAOYSA-N 0.000 description 1
- VHLLJTHDWPAQEM-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)-4-methylpentan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CC(C)C)C1=CC=C(O)C=C1 VHLLJTHDWPAQEM-UHFFFAOYSA-N 0.000 description 1
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- WQZGKKKJIJFFOK-ZNVMLXAYSA-N L-idopyranose Chemical compound OC[C@@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-ZNVMLXAYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- MUCRFDZUHPMASM-UHFFFAOYSA-N bis(2-chlorophenyl) carbonate Chemical compound ClC1=CC=CC=C1OC(=O)OC1=CC=CC=C1Cl MUCRFDZUHPMASM-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- QYJXDIUNDMRLAO-UHFFFAOYSA-N butyl 4-methylbenzenesulfonate Chemical compound CCCCOS(=O)(=O)C1=CC=C(C)C=C1 QYJXDIUNDMRLAO-UHFFFAOYSA-N 0.000 description 1
- NIKBCKTWWPVAIC-UHFFFAOYSA-N butyl benzenesulfonate Chemical compound CCCCOS(=O)(=O)C1=CC=CC=C1 NIKBCKTWWPVAIC-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004651 carbonic acid esters Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical group OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- KXLNRTHAZOEDNA-UHFFFAOYSA-N dibutyl(didodecyl)stannane Chemical compound CCCCCCCCCCCC[Sn](CCCC)(CCCC)CCCCCCCCCCCC KXLNRTHAZOEDNA-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- XDRMBCMMABGNMM-UHFFFAOYSA-N ethyl benzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=CC=C1 XDRMBCMMABGNMM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- CZXGXYBOQYQXQD-UHFFFAOYSA-N methyl benzenesulfonate Chemical compound COS(=O)(=O)C1=CC=CC=C1 CZXGXYBOQYQXQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- KDQQMEAEIKFPLQ-UHFFFAOYSA-N n-(1-cyanocyclohexyl)-2-fluorobenzamide Chemical compound FC1=CC=CC=C1C(=O)NC1(C#N)CCCCC1 KDQQMEAEIKFPLQ-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GVMDZMPQYYHMSV-UHFFFAOYSA-N octyl benzenesulfonate Chemical compound CCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVMDZMPQYYHMSV-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RJMTUAMLNHKEJL-UHFFFAOYSA-N octyl phenylmethanesulfonate Chemical compound CCCCCCCCOS(=O)(=O)CC1=CC=CC=C1 RJMTUAMLNHKEJL-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000002908 osmium compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KZQFPRKQBWRRHQ-UHFFFAOYSA-N phenyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC1=CC=CC=C1 KZQFPRKQBWRRHQ-UHFFFAOYSA-N 0.000 description 1
- CGEXUOTXYSGBLV-UHFFFAOYSA-N phenyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OC1=CC=CC=C1 CGEXUOTXYSGBLV-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical class CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Description
本発明は、共重合ポリカーボネートに関する。さらに詳しくは生物起源物質から誘導される繰り返し単位を含有し、熱安定性、耐熱性、成形加工性、耐吸水性に優れた共重合ポリカーボネートであり、各種成形材料やポリマーアロイ材料の素材として有用な共重合ポリカーボネート樹脂とその製造方法に関するものである。 The present invention relates to a copolymerized polycarbonate. More specifically, it is a copolymer polycarbonate that contains repeating units derived from biogenic substances and has excellent thermal stability, heat resistance, molding processability, and water absorption resistance, and is useful as a material for various molding materials and polymer alloy materials. The present invention relates to a copolymer polycarbonate resin and a method for producing the same.
ポリカーボネートは、芳香族もしくは脂肪族ジオキシ化合物を炭酸エステルにより連結させたポリマーであり、その中でも２，２−ビス（４−ヒドロキシフェニル）プロパン（通称ビスフェノールＡ）より得られるポリカーボネート（以下「ＰＣ−Ａ」と称することがある）は、透明性、耐熱性、耐衝撃性に優れ、多くの分野に用いられている。 Polycarbonate is a polymer in which an aromatic or aliphatic dioxy compound is linked by a carbonic ester, and among them, a polycarbonate obtained from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A) (hereinafter “PC-A”). Is sometimes excellent in transparency, heat resistance and impact resistance, and is used in many fields.
一般的にポリカーボネートは石油資源からの原料を用いて製造されるが、石油資源の枯渇が懸念されており、植物などの生物起源物質からの原料を用いたポリカーボネートが求められている。そこで、糖質から製造可能なエーテルジオールを用いたポリカーボネートが検討されている。 Polycarbonate is generally produced using raw materials from petroleum resources. However, there is concern about the exhaustion of petroleum resources, and polycarbonates using raw materials from biogenic substances such as plants are required. Thus, polycarbonates using ether diols that can be produced from carbohydrates have been studied.
例えば、下記式（ａ）
イソソルビド、イソマンニド、イソイディッドは、それぞれＤ−グルコース、Ｄ−マンノース、Ｌ−イドースから得られる。例えばイソソルビドの場合、Ｄ−グルコースを水添した後、酸触媒を用いて脱水することにより得ることができる。 Isosorbide, isomannide, and isoidide are obtained from D-glucose, D-mannose, and L-idose, respectively. For example, isosorbide can be obtained by hydrogenating D-glucose and then dehydrating it using an acid catalyst.
これまで式（ａ）で表されるエーテルジオールの中でも、特に、イソソルビドをポリカーボネートに組み込むことが検討されてきた。特許文献１には、イソソルビドを含有するホモポリカーボネートが開示されている。このホモポリカーボネートは、比粘度が高く、またイソソルビド骨格の剛直な構造のため、溶融粘度が非常に高くなり、成形加工が困難であるという欠点がある。 So far, among the ether diols represented by the formula (a), it has been particularly studied to incorporate isosorbide into polycarbonate. Patent Document 1 discloses a homopolycarbonate containing isosorbide. This homopolycarbonate has a high specific viscosity and a rigid structure of isosorbide skeleton, so that the melt viscosity becomes very high and molding processing is difficult.
ホモポリカーボネートの欠点を改良するため種々のビスヒドロキシ化合物との共重合が提案されている。特許文献２には、イソソルビドと芳香族ビスフェノールとの共重合ポリカーボネートが提案されている。芳香族ビスフェノールを共重合に用いると熱安定性は向上するが、溶融粘度は改善されず、成形加工性が充分でない。また芳香族ビスフェノールは石油由来であるという問題を抱えている。 Copolymerization with various bishydroxy compounds has been proposed to improve the disadvantages of homopolycarbonates. Patent Document 2 proposes a copolymerized polycarbonate of isosorbide and aromatic bisphenol. When aromatic bisphenol is used for copolymerization, the thermal stability is improved, but the melt viscosity is not improved and the molding processability is not sufficient. In addition, aromatic bisphenol has a problem that it is derived from petroleum.
特許文献３〜６には、イソソルビドと脂肪族ジオールとの共重合ポリカーボネートが提案されている。脂肪族ジオールを共重合に用いると溶融粘度は低くなり成形加工性は向上する。しかしながら、脂肪族ジオールについても石油由来であるものが多く、分子量の低いジオール成分は沸点が低いため、減圧下高温にて溶融重合する際に、未反応脂肪族ジオールが反応系から留去してしまい得られるポリマーの組成比が仕込み比に対してずれてしまうといった問題が生じる。更に熱安定性についてもこういった低沸点の脂肪族ジオールと共重合することで、充分でなくなる場合がある。また、イソソルビド含有ポリカーボネートは、酸素原子を多く含み、ＰＣ−Ａなどのエーテル部分を持たないジオールから得られるポリカーボネートに比べて極性が高い。そのため、イソソルビド含有ポリカーボネートはＰＣ−Ａに比べて吸水性が高く、吸水による成形品の寸法安定性の低下および湿熱時における耐熱性低下を引き起こし易いという欠点を有する。 Patent Documents 3 to 6 propose a copolymer polycarbonate of isosorbide and an aliphatic diol. When an aliphatic diol is used for copolymerization, the melt viscosity is lowered and the moldability is improved. However, many aliphatic diols are also derived from petroleum, and diol components having a low molecular weight have a low boiling point. Therefore, when melt polymerization is performed at high temperature under reduced pressure, unreacted aliphatic diol is distilled off from the reaction system. In other words, there arises a problem that the composition ratio of the obtained polymer is deviated from the charging ratio. Furthermore, thermal stability may not be sufficient by copolymerizing with such a low-boiling point aliphatic diol. Moreover, the isosorbide-containing polycarbonate has a higher polarity than a polycarbonate obtained from a diol containing many oxygen atoms and not having an ether moiety such as PC-A. For this reason, isosorbide-containing polycarbonate has higher water absorption than PC-A, and has the disadvantage that it tends to cause reduction in dimensional stability of the molded product due to water absorption and heat resistance during wet heat.
このような生物起源物質からの原料を用いたポリカーボネートの工業用途への展開を考えた場合、用途に応じて熱安定剤、可塑剤、難燃剤、衝撃吸収剤、強化剤など、各種添加剤を添加する必要があるが、これらの添加剤は石油由来のものがほとんどである。そのために樹脂組成物とした時点で生物起源物質の含有率は低下してしまうために、樹脂そのものの生物起源物質の含有率は可能な限り高くしておく必要がある。 When considering the expansion of polycarbonate using raw materials from such biogenic materials to industrial applications, various additives such as heat stabilizers, plasticizers, flame retardants, shock absorbers, reinforcing agents, etc. are used depending on the application. Although it is necessary to add, most of these additives are derived from petroleum. For this reason, since the content of the biogenic substance is reduced when the resin composition is obtained, the content of the biogenic substance of the resin itself needs to be as high as possible.
植物などの生物起源物質から得られるビスヒドロキシ化合物は、上記式（ａ）で表されるエーテルジオール以外には、エチレングリコール、１，３−プロパンジオール、１，４−ブタンジオールなどの直鎖脂肪族ジオールが挙げられる。これらの直鎖脂肪族ジオールと上記式（ａ）で表されるエーテルジオールとの共重合については、特許文献４で報告されているが、先に示したようにこれらの直鎖脂肪族ジオールは沸点が低いために、重合性、熱安定性に問題がある。 Bishydroxy compounds obtained from biological materials such as plants are linear fats such as ethylene glycol, 1,3-propanediol, 1,4-butanediol other than the ether diol represented by the above formula (a). Group diols. The copolymerization of these linear aliphatic diols with the ether diol represented by the above formula (a) has been reported in Patent Document 4, but as indicated above, these linear aliphatic diols are Since the boiling point is low, there is a problem in polymerizability and thermal stability.
一方、特許文献７において報告されているテルペン系ジメチロール化合物は、生物起源物質由来の脂環式ジオールであり、低沸点の直鎖脂肪族ジオールに比べて、重合性、熱安定性ともに向上する可能性があるが、上記式（５）で表されるエーテルジオールとの共重合については、報告例がない。 On the other hand, the terpene-based dimethylol compound reported in Patent Document 7 is an alicyclic diol derived from a biogenic substance and can be improved in both polymerizability and thermal stability as compared with a linear aliphatic diol having a low boiling point. However, there is no report on the copolymerization with the ether diol represented by the above formula (5).
以上のように、上記式（ａ）からなるポリカーボネートは、高い生物起源物質含有率を維持しつつ熱安定性および成形加工性をさらに改良する余地がある。また上記式（ａ）からなるポリカーボネートは、耐吸水性を改良する余地がある。 As described above, the polycarbonate composed of the above formula (a) has room for further improvement in thermal stability and moldability while maintaining a high biogenic substance content. Moreover, the polycarbonate which consists of said Formula (a) has room to improve water absorption resistance.
本発明は上記問題点を解決し、高い生物起源物質含有率を持ち、成形加工性と耐吸水性に優れ、かつ耐熱性と熱安定性のいずれも良好な共重合ポリカーボネート樹脂を提供することを目的とする。 The present invention provides a copolymer polycarbonate resin that solves the above-mentioned problems, has a high content of biogenic substances, is excellent in moldability and water absorption resistance, and has both good heat resistance and thermal stability. Objective.
本発明者は、上記目的を達成すべく、鋭意検討を行った結果、下記式（１）
すなわち、本発明によれば、
１．下記式（１）で表されるカーボネート構成単位、およびテルペン系ジメチロール由来のカーボネート構成単位を含んでなる共重合ポリカーボネート樹脂であって、ＡＳＴＭ Ｄ６８６６ ０５に準拠して測定された生物起源物質含有率が８０％〜１００％であり、式（１）で表されるカーボネート構成単位が全カーボネート構成単位中、５０〜９８重量％を占める共重合ポリカーボネート樹脂、
３．樹脂０．７ｇを塩化メチレン１００ｍｌに溶解した溶液の２０℃における比粘度が０．２０〜０．６０であり、かつガラス転移温度が１００〜１７０℃である前項１記載の共重合ポリカーボネート樹脂、
４．ＯＨ価が５×１０３ｇ／ｔｏｎ以下である前項１記載の共重合ポリカーボネート樹脂、
５．上記式（１）で表されるカーボネート構成単位がイソソルビド（１，４；３，６−ジアンヒドロ−Ｄ−ソルビトール）由来のカーボネート構成単位である前項１記載の共重合ポリカーボネート樹脂、
６．テルペン系ジメチロール化合物がアロオシメン、ミルセン、オシメン、α−ファルネセン、β−ファルネセンからなる群より選ばれた少なくとも１種の化合物から誘導されるジメチロール化合物であることを特徴とする請求項１記載の共重合ポリカーボネート樹脂、
７．前項１記載の共重合ポリカーボネート重合鎖末端に下記式（２）または（３）
で表される末端基がポリマー主鎖構造に対して０．３〜９.０重量％含まれていることを特徴とする末端変性共重合ポリカーボネート樹脂、
８．末端基が炭素原子数８〜２２の脂肪族アルコールである前項７記載の末端変性共重合ポリカーボネート樹脂、
９．末端基が植物由来である炭素原子数１４〜２２の直鎖脂肪族アルコールである前項７記載の末端変性共重合ポリカーボネート樹脂、
１０．重合触媒の存在下、下記式（ａ）
１１．前項１記載の共重合ポリカーボネート樹脂から形成された成形品、
が提供される。
That is, according to the present invention,
1. A polycarbonate polycarbonate resin comprising a carbonate constituent unit represented by the following formula (1) and a carbonate constituent unit derived from a terpene-based dimethylol, wherein the biogenic substance content measured according to ASTM D686605 is 80% to 100% copolymer polycarbonate resin in which the carbonate constituent unit represented by the formula (1) accounts for 50 to 98% by weight in all carbonate constituent units,
3. The copolymeric polycarbonate resin according to item 1 above, wherein a solution obtained by dissolving 0.7 g of resin in 100 ml of methylene chloride has a specific viscosity at 20 ° C. of 0.20 to 0.60 and a glass transition temperature of 100 to 170 ° C.
4). The copolymeric polycarbonate resin according to item 1, wherein the OH value is 5 × 10 3 g / ton or less,
5. The copolymeric polycarbonate resin according to item 1, wherein the carbonate constituent unit represented by the formula (1) is a carbonate constituent unit derived from isosorbide (1,4; 3,6-dianhydro-D-sorbitol).
6). 2. The copolymer according to claim 1, wherein the terpene-based dimethylol compound is a dimethylol compound derived from at least one compound selected from the group consisting of alloocimene, myrcene, ocimene, α-farnesene and β-farnesene. Polycarbonate resin,
7). The following formula (2) or (3) is added to the terminal of the copolymerized polycarbonate polymer chain described in the preceding item 1.
A terminal-modified copolymer polycarbonate resin characterized by containing 0.3 to 9.0 wt% of terminal groups represented by the formula:
8). The terminal-modified copolymer polycarbonate resin according to 7 above, wherein the terminal group is an aliphatic alcohol having 8 to 22 carbon atoms,
9. The terminal-modified copolymer polycarbonate resin according to 7 above, wherein the terminal group is a linear aliphatic alcohol having 14 to 22 carbon atoms derived from a plant,
10. In the presence of a polymerization catalyst, the following formula (a)
Is provided.
以下、本発明について詳細に説明する。
本発明の共重合ポリカーボネート樹脂は、上記式（１）のカーボネート構成単位およびテルペン系ジメチロール由来のカーボネート構成単位よりなる共重合ポリカーボネート樹脂であり、ＡＳＴＭ Ｄ６８６６ ０５に準拠して測定された生物起源物質含有率が８０％〜１００％であり、８３％〜１００％がより好ましい。
Hereinafter, the present invention will be described in detail.
The copolymer polycarbonate resin of the present invention is a copolymer polycarbonate resin comprising a carbonate constituent unit of the above formula (1) and a terpene-based dimethylol-derived carbonate constituent unit, and contains a biogenic substance measured in accordance with ASTM D686605. The rate is 80% to 100%, more preferably 83% to 100%.
本発明の共重合ポリカーボネート樹脂は、上記式（１）で表されるカーボネート構成単位が全カーボネート構成単位中、５０〜９８重量％が好ましく、６０〜９５重量％がより好ましく、更により好ましくは７０〜９５重量％である。上記式（１）のカーボネート構成単位が９８重量％を超えると、テルペン系ジメチロール由来カーボネート構成単位の添加による耐吸水性、成形加工性の改善効果が不充分となり、５０重量％より低くなると、樹脂そのものの耐熱性が低下してしまい好ましくない。 In the copolymeric polycarbonate resin of the present invention, the carbonate structural unit represented by the above formula (1) is preferably 50 to 98% by weight, more preferably 60 to 95% by weight, and still more preferably 70% of all carbonate structural units. ~ 95 wt%. If the carbonate structural unit of the above formula (1) exceeds 98% by weight, the effect of improving the water absorption resistance and molding processability due to the addition of the terpene-based dimethylol-derived carbonate structural unit is insufficient, and if it is lower than 50% by weight, the resin The heat resistance itself is undesirably lowered.
本発明の共重合ポリカーボネート樹脂は、ＯＨ価が好ましくは５×１０３ｇ／ｔｏｎ以下であり、より好ましくは４×１０３ｇ／ｔｏｎ以下であり、さらに好ましくは３×１０３ｇ／ｔｏｎ以下である。ＯＨ価が５×１０３ｇ／ｔｏｎよりも大きくなると、ポリカーボネート樹脂の耐吸水性が悪化するだけでなく、熱安定性が低下してしまい好ましくない。ＯＨ価は、試料を塩化メチレンに溶解し、触媒存在下、過剰のフェニルイソシアナートを加え反応させた後に、余剰分のフェニルイソシアナートをジイソブチルアミンを用いて滴定を行う方法により測定した。 The copolymer polycarbonate resin of the present invention has an OH value of preferably 5 × 10 3 g / ton or less, more preferably 4 × 10 3 g / ton or less, and further preferably 3 × 10 3 g / ton or less. It is. When the OH value is larger than 5 × 10 3 g / ton, not only the water absorption resistance of the polycarbonate resin is deteriorated but also the thermal stability is lowered, which is not preferable. The OH value was measured by a method in which a sample was dissolved in methylene chloride, an excess of phenyl isocyanate was added and reacted in the presence of a catalyst, and then the excess phenyl isocyanate was titrated with diisobutylamine.
本発明の共重合ポリカーボネート樹脂は、厚さ１ｍｍの成型板における２３℃水中での、飽和吸水率が５％以下が好ましく、４．８％以下がより好ましい。吸水率が上記範囲であると、耐湿熱性、低寸法変化率という点で好ましい。 The copolymer polycarbonate resin of the present invention preferably has a saturated water absorption of 5% or less, more preferably 4.8% or less in 23 ° C. water in a 1 mm-thick molded plate. A water absorption rate in the above range is preferable in terms of moisture and heat resistance and a low dimensional change rate.
本発明の共重合ポリカーボネート樹脂は、樹脂０．７ｇを塩化メチレン１００ｍｌに溶解した溶液の２０℃における比粘度が０．２０〜０．６０であることが好ましく、より好ましくは０．２２〜０.５０であり、更により好ましくは０．２２〜０．４５である。比粘度が０．２０より低くなると得られた成形品に充分な機械強度を持たせることが困難となる。また比粘度が０．６０より高くなると溶融流動性が高くなりすぎて、成形に必要な融解温度が分解温度より高くなってしまい好ましくない。 The copolymer polycarbonate resin of the present invention preferably has a specific viscosity at 20 ° C. of 0.20 to 0.60, more preferably 0.22 to 0.00 of a solution obtained by dissolving 0.7 g of resin in 100 ml of methylene chloride. 50, even more preferably 0.22 to 0.45. When the specific viscosity is lower than 0.20, it is difficult to give the obtained molded article sufficient mechanical strength. On the other hand, if the specific viscosity is higher than 0.60, the melt fluidity becomes too high, and the melting temperature necessary for molding becomes higher than the decomposition temperature, which is not preferable.
本発明の共重合ポリカーボネート樹脂は、そのガラス転移温度（Ｔｇ）が好ましくは１００〜１７０℃であり、より好ましくは１１０〜１６０℃である。Ｔｇが１００℃未満だと耐熱性に劣り、１７０℃を超えると成形時の溶融流動性に劣る。 The copolymer polycarbonate resin of the present invention has a glass transition temperature (Tg) of preferably 100 to 170 ° C, more preferably 110 to 160 ° C. When Tg is less than 100 ° C, the heat resistance is poor, and when it exceeds 170 ° C, the melt fluidity at the time of molding is poor.
本発明の共重合ポリカーボネート樹脂は、上記式（ａ）で表されるエーテルジオール、テルペン系ジメチロール、および炭酸ジエステルとから溶融重合法により製造することができる。 The copolymer polycarbonate resin of the present invention can be produced from the ether diol represented by the above formula (a), terpene dimethylol, and carbonic acid diester by a melt polymerization method.
エーテルジオールとしては、具体的には上記式（ｂ）、（ｃ）および（ｄ）で表されるイソソルビド、イソマンニド、イソイディッドなどが挙げられる。これら糖質由来のエーテルジオールは、自然界のバイオマスからも得られる物質で、再生可能資源と呼ばれるものの１つである。イソソルビドは、でんぷんから得られるＤ−グルコースに水添した後、脱水を受けさせることにより得られる。その他のエーテルジオールについても、出発物質を除いて同様の反応により得られる。特に、カーボネート構成単位がイソソルビド（１，４；３，６−ジアンヒドロ−Ｄ−ソルビトール）由来のカーボネート構成単位を含んでなるポリカーボネート樹脂が好ましい。イソソルビドはでんぷんなどから簡単に作ることができるエーテルジオールであり資源として豊富に入手することができる上、イソマンニドやイソイディッドと比べても製造の容易さ、性質、用途の幅広さの全てにおいて優れている。 Specific examples of the ether diol include isosorbide, isomannide, and isoidide represented by the above formulas (b), (c), and (d). These saccharide-derived ether diols are substances obtained from natural biomass and are one of so-called renewable resources. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can be obtained by the same reaction except for the starting materials. In particular, a polycarbonate resin in which the carbonate structural unit includes a carbonate structural unit derived from isosorbide (1,4; 3,6-dianhydro-D-sorbitol) is preferable. Isosorbide is an ether diol that can be easily made from starch, and can be obtained in abundant resources, and is superior in all ease of manufacture, properties, and versatility of use compared to isomannide and isoidide. .
テルペン系ジメチロール化合物は、特許文献７にあるようにアロオシメン、ミルセン、オシメン、α−ファルネセン、β−ファルネセンから選ばれた少なくとも一種の天然由来化合物と不飽和ジカルボン酸、その無水物、不飽和カルボン酸ジアルキルエステルから選ばれた少なくとも一種の化合物を反応させ、つづいて還元反応を行うことにより得ることができる。上記天然由来化合物は、単独または２種以上を併用して使用してもよい。好ましくは、コスト面等から、アロオシメン、ミルセンである。また上記不飽和ジカルボン酸、その無水物、不飽和ジカルボン酸ジアルキルエステルについては、通常、マレイン酸、無水マレイン酸、マレイン酸ジアルキルエステル、フマル酸、フマル酸ジアルキルエステルなどを用いることができる。不飽和ジカルボン酸ジアルキルエステルのアルキル成分としては、特に制限はなく、例えば、ジメチル、ジエチル、ジプロピル、ジブチルなどが挙げられる。これらの中で、好ましくは、コスト面等から、フマル酸である。また、これら不飽和ジカルボン酸、不飽和ジカルボン酸無水物、不飽和ジカルボン酸ジアルキルエステルは、単独または２ 種以上を併用して使用してもよい。 As disclosed in Patent Document 7, the terpene-based dimethylol compound includes at least one naturally-derived compound selected from alloocimene, myrcene, ocimene, α-farnesene, and β-farnesene, an unsaturated dicarboxylic acid, an anhydride thereof, and an unsaturated carboxylic acid. It can be obtained by reacting at least one compound selected from dialkyl esters, followed by a reduction reaction. You may use the said naturally derived compound individually or in combination of 2 or more types. From the viewpoint of cost and the like, alloocimene and myrcene are preferable. Moreover, about the said unsaturated dicarboxylic acid, its anhydride, and unsaturated dicarboxylic acid dialkyl ester, maleic acid, maleic anhydride, maleic acid dialkyl ester, fumaric acid, fumaric acid dialkyl ester, etc. can be used normally. There is no restriction | limiting in particular as an alkyl component of unsaturated dicarboxylic acid dialkyl ester, For example, dimethyl, diethyl, dipropyl, dibutyl etc. are mentioned. Among these, fumaric acid is preferable from the viewpoint of cost. These unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides and unsaturated dicarboxylic acid dialkyl esters may be used alone or in combination of two or more.
炭酸ジエステルとしては、水素原子が置換されていてもよい炭素数６〜１２のアリール基またはアラルキル基、もしくは炭素数１〜４のアルキル基などのエステルが挙げられる。具体的にはジフェニルカーボネート、ビス（クロロフェニル）カーボネート、ｍ―クレジルカーボネート、ジナフチルカーボネート、ビス（ジフェニル）カーボネート、ジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネートなどが挙げられ、なかでも反応性、コスト面からジフェニルカーボネートが好ましい。 Examples of the carbonic acid diester include esters such as an aryl group or aralkyl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 4 carbon atoms, in which a hydrogen atom may be substituted. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Diphenyl carbonate is preferred.
炭酸ジエステルはエーテルジオールに対してモル比で１．０５〜０．９８となるように混合することが好ましく、より好ましくは１．０３〜０．９８であり、さらに好ましくは１．０１〜０．９９である。炭酸ジエステルのモル比が１．０５より多くなると、炭酸エステル残基が末端封止として働いてしまい充分な重合度が得られなくなってしまい好ましくない。また炭酸ジエステルのモル比が０．９８より少ない場合、重合が進行しないばかりでなく、未反応のエーテルジオールやヒドロキシ化合物が残存する。 The carbonic acid diester is preferably mixed so that the molar ratio with respect to the ether diol is 1.05 to 0.98, more preferably 1.03 to 0.98, and still more preferably 1.01 to 0.00. 99. If the molar ratio of the carbonic acid diester is more than 1.05, the carbonic acid ester residue acts as a terminal block and a sufficient degree of polymerization cannot be obtained, which is not preferable. When the molar ratio of the carbonic acid diester is less than 0.98, not only the polymerization does not proceed, but also unreacted ether diol or hydroxy compound remains.
溶融重合法は、重合触媒の存在下、ジオール成分と炭酸ジエステルとを混合し、エステル交換反応によって生成するアルコールまたはフェノールを高温減圧下にて留出させることによって行う。 The melt polymerization method is carried out by mixing a diol component and a carbonic acid diester in the presence of a polymerization catalyst, and distilling alcohol or phenol produced by transesterification under high temperature and reduced pressure.
反応温度は、ジオール成分の分解を抑え、着色が少なく高粘度の樹脂を得るために、できるだけ低温の条件を用いることが好ましいが、重合反応を適切に進める為には重合温度は１８０℃〜２８０℃の範囲であることが好ましく、より好ましくは１８０℃〜２６０℃の範囲である。 The reaction temperature is preferably as low as possible in order to suppress decomposition of the diol component and obtain a highly viscous resin with little coloration, but the polymerization temperature is from 180 ° C. to 280 ° C. in order to proceed the polymerization reaction appropriately. It is preferably in the range of ° C, more preferably in the range of 180 ° C to 260 ° C.
また、反応初期にはジオール成分と炭酸ジエステルとを常圧で加熱し、予備反応させた後、徐々に減圧にして反応後期には系を１．３×１０−３〜１．３×１０−５ＭＰａ程度に減圧して生成するアルコールまたはフェノールの留出を容易にさせる方法が好ましい。反応時間は通常１〜４時間程度である。 In the initial stage of the reaction, the diol component and the carbonic acid diester are heated at normal pressure and pre-reacted, and then the pressure is gradually reduced to 1.3 × 10 −3 to 1.3 × 10 − in the late stage of the reaction. A method of facilitating the distillation of alcohol or phenol produced by reducing the pressure to about 5 MPa is preferred. The reaction time is usually about 1 to 4 hours.
重合触媒としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、二価フェノールのナトリウム塩、二価フェノールのカリウム塩等のアルカリ金属化合物が挙げられる。また水酸化カルシウム、水酸化バリウム、水酸化マグネシウム等のアルカリ土類金属化合物が挙げられる。 Examples of the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium salt of dihydric phenol, potassium salt of dihydric phenol, and the like. Moreover, alkaline-earth metal compounds, such as calcium hydroxide, barium hydroxide, magnesium hydroxide, are mentioned.
またテトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、トリメチルアミン、トリエチルアミン等の含窒素塩基性化合物が挙げられる。 Moreover, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylamine, and triethylamine are listed.
またアルカリ金属やアルカリ土類金属のアルコキシド類、アルカリ金属やアルカリ土類金属の有機酸塩類、亜鉛化合物類、ホウ素化合物類、アルミニウム化合物類、珪素化合物類、ゲルマニウム化合物類、有機スズ化合物類、鉛化合物類、オスミウム化合物類、アンチモン化合物類マンガン化合物類、チタン化合物類、ジルコニウム化合物類などが挙げられる。これらは単独で使用してもよいし、２種以上組み合わせて使用してもよい。 Alkali metals and alkaline earth metal alkoxides, alkali metal and alkaline earth metal organic acid salts, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead Examples thereof include compounds, osmium compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds. These may be used alone or in combination of two or more.
重合触媒として、含窒素塩基性化合物、アルカリ金属化合物およびアルカリ土類金属化合物からなる群から選ばれる少なくとも一種の化合物を使用することが好ましい。なかでも、含窒素塩基性化合物とアルカリ金属化合物とを併用して使用することが好ましい。
これらの重合触媒の使用量は、それぞれ炭酸ジエステル１モルに対し、好ましくは１×１０−９〜１×１０−３当量、より好ましくは１×１０−８〜５×１０−４当量の範囲で選ばれる。
As the polymerization catalyst, it is preferable to use at least one compound selected from the group consisting of nitrogen-containing basic compounds, alkali metal compounds, and alkaline earth metal compounds. Among these, it is preferable to use a nitrogen-containing basic compound and an alkali metal compound in combination.
The amount of these polymerization catalysts used is preferably in the range of 1 × 10 −9 to 1 × 10 −3 equivalent, more preferably 1 × 10 −8 to 5 × 10 −4 equivalent, relative to 1 mol of carbonic acid diester. To be elected.
反応系は、原料、反応混合物、反応生成物に対し不活性な窒素などのガスの雰囲気に保つことが好ましい。窒素以外の不活性ガスとしては、アルゴンなどを挙げることができる。さらに、必要に応じて酸化防止剤等の添加剤を加えてもよい。 The reaction system is preferably maintained in an atmosphere of a gas such as nitrogen that is inert to the raw materials, the reaction mixture, and the reaction product. Examples of inert gases other than nitrogen include argon. Furthermore, you may add additives, such as antioxidant, as needed.
本発明の共重合ポリカーボネートには、触媒失活剤を添加することもできる。触媒失活剤としては、公知の触媒失活剤を用いることができる。なかでもスルホン酸のアンモニウム塩、ホスホニウム塩が好ましい。さらにドデシルベンゼンスルホン酸テトラブチルホスホニウム塩等のドデシルベンゼンスルホン酸のアンモニウム塩、ホスホニウム塩が好ましい。パラトルエンスルホン酸テトラブチルアンモニウム塩等のパラトルエンスルホン酸のアンモニウム塩、ホスホニウム塩が好ましい。またスルホン酸のエステルとしてベンゼンスルホン酸メチル、ベンゼンスルホン酸エチル、ベンゼンスルホン酸ブチル、ベンゼンスルホン酸オクチル、ベンゼンスルホン酸フェニル、パラトルエンスルホン酸メチル、パラトルエンスルホン酸エチル、パラトルエンスルホン酸ブチル、パラトルエンスルホン酸オクチル、パラトルエンスルホン酸フェニル等が好ましく用いられる。なかでもドデシルベンゼンスルホン酸テトラブチルホスホニウム塩が最も好ましく使用される。これらの触媒失活剤の使用量は、アルカリ金属化合物および／またはアルカリ土類金属化合物より選ばれた重合触媒１モル当たり、好ましくは０．５〜５０モル、より好ましくは０．５〜１０モル、さらに好ましくは０．８〜５モルの割合である。 A catalyst deactivator can also be added to the copolymer polycarbonate of the present invention. A known catalyst deactivator can be used as the catalyst deactivator. Of these, ammonium salts and phosphonium salts of sulfonic acids are preferred. Furthermore, ammonium salts and phosphonium salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid are preferable. Ammonium salts and phosphonium salts of paratoluenesulfonic acid such as paratoluenesulfonic acid tetrabutylammonium salt are preferred. As esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, para Octyl toluenesulfonate, phenyl paratoluenesulfonate, and the like are preferably used. Of these, dodecylbenzenesulfonic acid tetrabutylphosphonium salt is most preferably used. The amount of the catalyst deactivator used is preferably 0.5 to 50 mol, more preferably 0.5 to 10 mol, per mol of the polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds. More preferably, the proportion is 0.8 to 5 mol.
本発明の共重合ポリカーボネートの末端構造は、必然的に、水酸基または重合の際に用いる炭酸ジエステル残基となりうるが、耐吸水性、成型加工性をより向上させるために、下記式（２）または（３）で表される末端基を導入しても良い。 The terminal structure of the copolymeric polycarbonate of the present invention can inevitably be a hydroxyl group or a carbonic acid diester residue used in polymerization, but in order to further improve water absorption resistance and molding processability, the following formula (2) or You may introduce | transduce the terminal group represented by (3).
上記式（２）、（３）において、Ｒ１は炭素原子数４〜３０のアルキル基、炭素原子数７〜３０のアラルキル基、炭素原子数４〜３０のパーフルオロアルキル基、または下記式（４）
Ｒ１のアルキル基の炭素原子数は、好ましくは４〜２２、より好ましくは８〜２２である。アルキル基として、ヘキシル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、ペンタデシル基、ヘキサデシル基、オクタデシル基等が挙げられる。 The number of carbon atoms of the alkyl group for R 1 is preferably 4-22, more preferably 8-22. Examples of the alkyl group include hexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, pentadecyl group, hexadecyl group, octadecyl group and the like.
Ｒ１のアラルキル基の炭素原子数は、好ましくは８〜２０、より好ましくは１０〜２０である。アラルキル基として、ベンジル基、フェネチル基、メチルベンジル基、２−フェニルプロパン−２−イル基、ジフェニルメチル基等が挙げられる。 The number of carbon atoms of the aralkyl group of R 1 is preferably 8-20, more preferably 10-20. Examples of the aralkyl group include a benzyl group, a phenethyl group, a methylbenzyl group, a 2-phenylpropan-2-yl group, and a diphenylmethyl group.
Ｒ１のパーフルオロアルキル基の炭素原子数は好ましくは２〜２０である。パーフルオロアルキル基として４，４，５，５，６，６，７，７，７−ノナフルオロヘプチル基、４，４，５，５，６，６，７，７，８，８，９，９，９−トリデカフルオロノニル基、４，４，５，５，６，６，７，７，８，８，９，９，１０，１０，１１，１１，１１−ヘプタデカフルオロウンデシル基などが挙げられる。 The number of carbon atoms of the perfluoroalkyl group for R 1 is preferably 2-20. 4,4,5,5,6,6,7,7,7-nonafluoroheptyl group as a perfluoroalkyl group, 4,4,5,5,6,6,7,7,8,8,9, 9,9-tridecafluorononyl group, 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecyl group Etc.
式（４）中、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６は夫々独立して、炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のシクロアルキル基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１０のアリール基および炭素原子数７〜２０のアラルキル基からなる群より選ばれる少なくとも１種の基を表す。 In formula (4), R 2 , R 3 , R 4 , R 5 and R 6 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or the number of carbon atoms. It represents at least one group selected from the group consisting of an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
式（４）中の炭素原子数１〜１０のアルキル基として、メチル基、エチル基、プロピル基、ブチル基、ヘプチル基等が挙げられる。炭素原子数６〜２０のシクロアルキル基として、シクロへキシル基、シクロオクチル基、シクロへキシル基、シクロデシル基等が挙げられる。炭素原子数２〜１０のアルケニル基として、エテニル基、プロペニル基、ブテニル基、ヘプテニル基等が挙げられる。炭素原子数６〜１０のアリール基として、フェニル基、トリル基、ジメチルフェニル基、ナフチル基等が挙げられる。炭素原子数７〜２０のアラルキル基として、ベンジル基、フェネチル基、メチルベンジル基、２−フェニルプロパン−２−イル基、ジフェニルメチル基等が挙げられる。 Examples of the alkyl group having 1 to 10 carbon atoms in the formula (4) include a methyl group, an ethyl group, a propyl group, a butyl group, and a heptyl group. Examples of the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group, a cyclooctyl group, a cyclohexyl group, and a cyclodecyl group. Examples of the alkenyl group having 2 to 10 carbon atoms include ethenyl group, propenyl group, butenyl group and heptenyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a dimethylphenyl group, and a naphthyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, phenethyl group, methylbenzyl group, 2-phenylpropan-2-yl group, diphenylmethyl group and the like.
式（４）中、Ｒ２、Ｒ３、Ｒ４、Ｒ５およびＲ６は、夫々独立して炭素原子数１〜１０のアルキル基および炭素原子数６〜１０のアリール基からなる群から選ばれる少なくとも一種の基であることが好ましい。特に夫々独立してメチル基およびフェニル基からなる群から選ばれる少なくとも一種の基であることが好ましい。 In formula (4), R 2 , R 3 , R 4 , R 5 and R 6 are each independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms. It is preferable that it is at least one kind of group. In particular, at least one group selected from the group consisting of a methyl group and a phenyl group is preferable.
ｂは０〜３の整数、好ましくは１〜３の整数、より好ましくは２〜３の整数である。ｃは４〜１００の整数、より好ましくは４〜５０の整数、さらに好ましくは８〜５０の整数である。 b is an integer of 0-3, preferably an integer of 1-3, more preferably an integer of 2-3. c is an integer of 4 to 100, more preferably an integer of 4 to 50, and still more preferably an integer of 8 to 50.
式（３）のＸは、単結合、エーテル結合、チオエーテル結合、エステル結合、アミノ結合およびアミド結合からなる群より選ばれる少なくとも１種の結合を表わす。Ｘは、好ましくは単結合、エーテル結合およびエステル結合からなる群より選ばれる少なくとも一種の結合である。なかでも単結合、エステル結合が好ましい。
ａは１〜５の整数、より好ましくは１〜３の整数、さらに好ましくは１である。
X in Formula (3) represents at least one bond selected from the group consisting of a single bond, an ether bond, a thioether bond, an ester bond, an amino bond, and an amide bond. X is preferably at least one bond selected from the group consisting of a single bond, an ether bond and an ester bond. Of these, a single bond and an ester bond are preferable.
a is an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1.
上記式（２）または（３）で表される末端基は、生物起源物質由来であることが好ましい。生物起源物質として、炭素数１４以上の長鎖アルキルアルコール、例えばセタノール、ステアリルアルコール、ベヘニルアルコールが挙げられる。 The terminal group represented by the above formula (2) or (3) is preferably derived from a biological material. Examples of biogenic substances include long-chain alkyl alcohols having 14 or more carbon atoms, such as cetanol, stearyl alcohol, and behenyl alcohol.
式（２）または（３）で表される末端基の含有量は、ポリマー主鎖に対して０．３〜９重量％、好ましくは０．３〜７．５重量％、より好ましくは０．５〜６重量％である。式（２）または（３）で表される末端基が上記範囲内にある場合、末端変性による効果（耐吸水性、成型加工性）が好適に発現する。 The content of the end group represented by the formula (2) or (3) is 0.3 to 9% by weight, preferably 0.3 to 7.5% by weight, more preferably 0. 5 to 6% by weight. When the terminal group represented by Formula (2) or (3) is in the above range, the effects (water absorption resistance, molding processability) due to terminal modification are suitably expressed.
このような末端基の本発明の共重合ポリカーボネートへの導入は、重合時に下記式（５）または（６）
上記式（５）または（６）で表されるヒドロキシ化合物において、Ｒ１、Ｘ、ａ、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、ｂ、ｃは、式（２）および（３）と同じである。ヒドロキシ化合物は単独でまたは２種以上混合して使用してもよい。２種類以上使用する場合は、式（５）または（６）で表されるヒドロキシ化合物とそれ以外のヒドロキシ化合物とを組み合わせて使用してもよい。 In the hydroxy compound represented by the above formula (5) or (6), R 1 , X, a, R 2 , R 3 , R 4 , R 5 , R 6 , b, c are represented by the formulas (2) and ( Same as 3). Hydroxy compounds may be used alone or in admixture of two or more. When using 2 or more types, you may use combining the hydroxy compound represented by Formula (5) or (6), and other hydroxy compounds.
ヒドロキシ化合物の量は、エーテルジオールおよびテルペン系ジメチロールの合計量に対して、好ましくは０．３〜１５重量％、より好ましくは０．３〜１０重量％、さらに好ましくは０．５〜１０重量％である。ヒドロキシ化合物が０．３重量％より少なくなると、末端変性の効果が得られない。ヒドロキシ化合物が１５重量％より多くなると、末端停止剤の量が多すぎて、成形加工に充分な重合度を持つ末端変性共重合ポリカーボネートが得られない。ヒドロキシ化合物を添加する時期は、反応初期、反応後期いずれでも良い。 The amount of the hydroxy compound is preferably 0.3 to 15% by weight, more preferably 0.3 to 10% by weight, still more preferably 0.5 to 10% by weight, based on the total amount of ether diol and terpene dimethylol. It is. When the hydroxy compound is less than 0.3% by weight, the effect of terminal modification cannot be obtained. When the amount of the hydroxy compound exceeds 15% by weight, the amount of the end terminator is too large to obtain a terminal-modified copolymer polycarbonate having a sufficient degree of polymerization for molding. The timing of adding the hydroxy compound may be either the initial reaction stage or the late reaction stage.
また、本発明で得られる共重合ポリカーボネート樹脂の特性を損なわない範囲で、他の脂肪族ジオール類または芳香族ビスフェノール類との共重合としても良い。かかる他の脂肪族ジオール類または芳香族ビスフェノール類の共重合割合は好ましくは５〜０モル％、より好ましくは２〜０モル％である。 Moreover, it is good also as copolymerization with other aliphatic diols or aromatic bisphenols in the range which does not impair the characteristic of the copolymerization polycarbonate resin obtained by this invention. The copolymerization ratio of such other aliphatic diols or aromatic bisphenols is preferably 5 to 0 mol%, more preferably 2 to 0 mol%.
脂肪族ジオールとしては、炭素数２〜２０の脂肪族ジオールが好ましく、炭素数３〜１５の脂肪族ジオールがより好ましい。具体的には１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオールなどの直鎖状ジオール類や、シクロヘキサンジオール、シクロヘキサンジメタノールなどの脂環式アルキレン類などが挙げられ、中でも１，３−プロパンジオール、１，４−ブタンジオール、ヘキサンジオール、およびシクロヘキサンジメタノールが好ましい。 As the aliphatic diol, an aliphatic diol having 2 to 20 carbon atoms is preferable, and an aliphatic diol having 3 to 15 carbon atoms is more preferable. Specifically, linear diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol, and alicyclic rings such as cyclohexanediol and cyclohexanedimethanol Among them, 1,3-propanediol, 1,4-butanediol, hexanediol, and cyclohexanedimethanol are preferable.
芳香族ビスフェノールとしては、２，２−ビス（４−ヒドロキシフェニル）プロパン（通称塔rスフェノールＡ煤j、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、１，１−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサン、４，４’−（ｍ−フェニレンジイソプロピリデン）ジフェノール、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン、２，２−ビス（４−ヒドロキシフェニル）−４−メチルペンタン、１，１−ビス（４−ヒドロキシフェニル）デカン、１，３−ビス｛２−（４−ヒドロキシフェニル）プロピル｝ベンゼン等が挙げられる。 Aromatic bisphenols include 2,2-bis (4-hydroxyphenyl) propane (commonly called tower r sphenol A 煤 j, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy). Phenyl) -3,3,5-trimethylcyclohexane, 4,4 ′-(m-phenylenediisopropylidene) diphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) decane, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene and the like.
また、他のジオール残基を含むこともでき、例えばジメタノールベンゼン、ジエタノールベンゼンなどの芳香族ジオールなどを挙げることができる。
また、本発明のポリカーボネート樹脂には、用途に応じて各種の機能付与剤を添加してもよく、例えば熱安定剤、安定化助剤、可塑剤、酸化防止剤、光安定剤、衝撃吸収剤、難燃剤、滑剤、帯電防止剤、紫外線吸収剤などである。
Moreover, other diol residues can also be included, for example, aromatic diols, such as dimethanolbenzene and diethanolbenzene, etc. can be mentioned.
In addition, various function-imparting agents may be added to the polycarbonate resin of the present invention, for example, a heat stabilizer, a stabilizing aid, a plasticizer, an antioxidant, a light stabilizer, and an impact absorber. Flame retardants, lubricants, antistatic agents, UV absorbers and the like.
また、本発明のポリカーボネート樹脂には、用途に応じて各種の有機および無機のフィラー、繊維などを複合化して用いることもできる。フィラーとしては例えばカーボン、タルク、マイカ、ワラストナイト、モンモリロナイト、ハイドロタルサイトなどを上げることができる。また、繊維としては例えばケナフなどの天然繊維のほか、各種の合成繊維、ガラス繊維、石英繊維、炭素繊維などが挙げられる。
どが見られる。
In addition, various organic and inorganic fillers, fibers and the like can be used in combination in the polycarbonate resin of the present invention depending on the application. Examples of the filler include carbon, talc, mica, wollastonite, montmorillonite, and hydrotalcite. Examples of the fibers include natural fibers such as kenaf, various synthetic fibers, glass fibers, quartz fibers, and carbon fibers.
I can see.
本発明の共重合ポリカーボネート樹脂組成物は、生物起源物質から誘導される部分を含有し、優れた熱安定性、耐熱性、成形加工性、耐吸水性を有することから、光学用シート、光学用ディスク、情報ディスク、光学レンズ、プリズム等の光学用部品、各種機械部品、建築材料、自動車部品、各種の樹脂トレー、食器類をはじめとする様々な用途に幅広く用いることができ、その奏する産業上の効果は格別である。 The copolymer polycarbonate resin composition of the present invention contains a portion derived from a biogenic substance and has excellent thermal stability, heat resistance, molding processability, and water absorption resistance. It can be used widely in various applications including optical parts such as discs, information discs, optical lenses, prisms, various mechanical parts, building materials, automobile parts, various resin trays, tableware, etc. The effect is exceptional.
以下に実施例を挙げて本発明をさらに説明する。但し、本発明はこれら実施例に何ら制限されるものではない。なお実施例中の部は重量部であり、％は重量％である。なお、評価は下記の方法によった。 The following examples further illustrate the present invention. However, the present invention is not limited to these examples. In addition, the part in an Example is a weight part and% is weight%. The evaluation was based on the following method.
（１）生物起源物質含有率（植物由来度）
ＡＳＴＭ Ｄ６８６６ ０５に準拠し、放射性炭素濃度（ｐｅｒｃｅｎｔ ｍｏｄｅｒｎ ｃａｒｂｏｎ；Ｃ１４）による生物起源物質含有率試験から、生物起源物質含有率を測定した。
(1) Biogenic substance content (Degree of plant origin)
In accordance with ASTM D6866 05, the biogenic substance content rate was measured from the biogenic substance content rate test using the radiocarbon concentration (percent carbon) (C14).
（２）ＯＨ価
特開２００３−４３０２７号公報を参考にした。すなわちペレットを塩化メチレンに溶解し、ジブチルジラウリル錫の存在下、過剰量のフェニルイソシアネートを加え反応させた後に、余剰分のフェニルイソシアナート量は、ジブチルアミンを用いた滴定によって定量した。ＯＨ価は、前記滴定結果から反応したフェニルイソシアナート量を求め、算出した。
(2) OH value Reference was made to JP-A-2003-43027. That is, the pellet was dissolved in methylene chloride, an excess amount of phenyl isocyanate was added and reacted in the presence of dibutyl dilauryl tin, and then the excess amount of phenyl isocyanate was quantified by titration with dibutyl amine. The OH value was calculated by obtaining the amount of phenyl isocyanate reacted from the titration result.
（３）飽和吸水率
予め１００℃で２４時間乾燥した６０×６０×１（単位：ｍｍ）の成形板を２３℃の水中に浸し、定期的に取り出してその重量を測定し、吸水率を下記式（１）から計算した。
（４）比粘度（ηｓｐ）
ペレットを塩化メチレンに溶解、濃度を０．７ｇ／ｄＬとして、温度２０℃にて、オストワルド粘度計（装置名：ＲＩＧＯ ＡＵＴＯ ＶＩＳＣＯＳＩＭＥＴＥＲ ＴＹＰＥ ＶＭＲ−０５２５・ＰＣ）を使用して測定した。なお、比粘度ηｓｐは下記式から求めた。
ηｓｐ＝ｔ／ｔｏ−１
ｔ ：試料溶液のフロータイム
ｔｏ ：溶媒のみのフロータイム
(4) Specific viscosity (η sp )
The pellet was dissolved in methylene chloride, the concentration was 0.7 g / dL, and the temperature was measured at 20 ° C. using an Ostwald viscometer (device name: RIGO AUTO VISOSIMETER TYPE VMR-0525 · PC). In addition, specific viscosity (eta) sp was calculated | required from the following formula.
η sp = t / t o −1
t: Flow time of sample solution t o : Flow time of solvent only
（５）ガラス転移温度（Ｔｇ）
ペレットを用いてＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製 ＤＳＣ （型式 ＤＳＣ２９１０）により測定した。
(5) Glass transition temperature (Tg)
It measured by DSC (model DSC2910) made from TA Instruments using the pellet.
（６）成形加工性
ペレットを日本製鋼所（株）製 ＪＳＷＪ−７５ＥＩＩＩを用いて射出成形を行い、厚み２ｍｍの成形板の形状を目視にて評価した（金型温度：７０〜９０℃、成形温度：２２０〜２５０℃）。
成形加工性
○；濁り、割れ、ヒケ、分解によるシルバーなどが見られない。
×；濁り、割れ、ヒケ、分解によるシルバーなどが見られる。
(6) Formability The pellets were injection molded using JSWJ-75EIII manufactured by Nippon Steel Works, Ltd., and the shape of a 2 mm thick molded plate was visually evaluated (mold temperature: 70 to 90 ° C., molding) Temperature: 220-250 ° C).
Moldability ○: Turbidity, cracks, sink marks, silver due to decomposition, etc. are not seen.
X: Turbidity, cracks, sink marks, silver due to decomposition, etc. are observed.
（７）末端変性基含有率
ＪＥＯＬ製ＪＮＭ−ＡＬ４００を用いてペレットの重クロロホルム溶液中における１Ｈ−ＮＭＲを測定し、主鎖骨格中に含まれるエーテルジオール由来の特定プロトンおよび末端ヒドロキシ化合物由来の特定プロトンとの積分比から末端変性基含有率を求めた。なお末端変性基含有率（重量％）は下記式から求めた。
(7) Terminal modification group content rate 1 H-NMR in a heavy chloroform solution of pellets was measured using JNM-JNM-AL400, and a specific proton derived from an ether diol contained in the main chain skeleton and derived from a terminal hydroxy compound The terminal modified group content was determined from the integration ratio with the specific proton. The terminal modified group content (% by weight) was determined from the following formula.
Ｍｔ：末端ヒドロキシ化合物構成単位の分子量
Ｒｅ：１Ｈ−ＮＭＲの積分比から求めた主鎖中におけるエーテルジオールの組成比
Ｍｅ：エーテルジオール構成単位の分子量
Mt: Molecular weight of terminal hydroxy compound structural unit Re: Composition ratio of ether diol in main chain determined from integral ratio of 1 H-NMR Me: Molecular weight of ether diol structural unit
＜製造例１：テルペン系ジメチロール（Ａ−１）の製造＞
冷却管、温度計、撹拌棒を備えた５００ｍＬの三つ口フラスコに、ヤスハラケミカル（株）製アロオシメン７４重量部（純度９２％、０．５モル）およびフマル酸５８重量部（０．５モル）を仕込み、撹拌しながら昇温して、１５０〜１６０℃で１２時間反応した。反応後、アセトンから再結晶することにより、フマル化アロオシメン８３重量部（アロオシメン基準で収率６２％、純度９４％）を得た。続いて、電磁撹拌装置を備えた内容５００ｍＬのオートクレーブに、上記で得られたフマル化アロオシメン７２重量部（０．２７モル）、２−プロパノール１４０重量部、および粉末状の５％パラジウムカーボン触媒０．７重量部を仕込んだ。次いで、これを密閉し、雰囲気を窒素ガスで置換した後、水素ガス１５ｋｇ／ｃｍ２の圧力をかけながら導入した。そして、撹拌を開始すると、内温が２７℃から３２℃へ上昇した。吸収された水素を補うことで圧力を１５〜２０ｋｇ／ｃｍ２に保ちながら４時間反応させた。その後、得られた懸濁液をブフナーロートで吸引ろ過を行い、触媒をろ別した。その後、ろ液を減圧濃縮することにより、水添フマル化アロオシメン７２重量部（収率９５％、純度９２％）を得た。次に、冷却管、温度計、撹拌棒、滴下ロートを備えた２Ｌ四つ口フラスコに、窒素気流下、脱水テトラヒドロフランを５００ｍＬ入れ、水素化リチウムアルミニウム２６重量部（０．６８モル）を加えた。混合液を、６５℃で３０分間環流させた後、加熱をやめ、ここに上記のようにして得られた水添フマル化アロオシメン６１重量部（０．２２モル）を脱水テトラヒドロフラン３００ｍＬに溶解した溶液を３時間かけて滴下した。混合液を６５℃で１２時間環流させた後、０℃付近に冷却し、水を２６ｍＬ、４規定水酸化ナトリウム水溶液を２６ｍＬ、水８０ｍＬを順次加えた。灰色の部分がなくなるまで撹拌し、酢酸エチルを加え、油層と水層に分離した。油層を減圧蒸留にて溶媒を除去し、粗生成物５０重量部を得た。これをカラムクロマトグラフィーで精製することにより、下記式（７）で代表されるジメチロール化合物の粘稠液体３０重量部（収率５６％、純度９６％）を得た。
<Production Example 1: Production of terpene-based dimethylol (A-1)>
In a 500 mL three-necked flask equipped with a condenser, a thermometer, and a stirring rod, 74 parts by weight (purity 92%, 0.5 mol) of Yaohara Chemical Co., Ltd. and 58 parts by weight (0.5 mol) of fumaric acid Was heated with stirring and reacted at 150 to 160 ° C. for 12 hours. After the reaction, 83 parts by weight of fumarated alloocimene (yield 62%, purity 94% based on alloocimene) was obtained by recrystallization from acetone. Subsequently, in a 500 mL autoclave equipped with an electromagnetic stirrer, 72 parts by weight (0.27 mol) of fumarated alloocimene obtained above, 140 parts by weight of 2-propanol, and powdered 5% palladium carbon catalyst 0 .7 parts by weight were charged. Next, this was sealed and the atmosphere was replaced with nitrogen gas, and then introduced while applying a pressure of 15 kg / cm 2 of hydrogen gas. And when stirring was started, internal temperature rose from 27 degreeC to 32 degreeC. The reaction was performed for 4 hours while maintaining the pressure at 15 to 20 kg / cm 2 by supplementing the absorbed hydrogen. Thereafter, the obtained suspension was subjected to suction filtration with a Buchner funnel to separate the catalyst. Thereafter, the filtrate was concentrated under reduced pressure to obtain 72 parts by weight of hydrogenated fumarated alloocimene (yield 95%, purity 92%). Next, 500 mL of dehydrated tetrahydrofuran was placed in a 2 L four-necked flask equipped with a condenser, a thermometer, a stirring rod, and a dropping funnel under a nitrogen stream, and 26 parts by weight (0.68 mol) of lithium aluminum hydride was added. . The mixture was refluxed at 65 ° C. for 30 minutes, then the heating was stopped, and a solution in which 61 parts by weight (0.22 mol) of the hydrogenated fumarated alloocimene obtained as described above was dissolved in 300 mL of dehydrated tetrahydrofuran. Was added dropwise over 3 hours. The mixture was refluxed at 65 ° C. for 12 hours, cooled to around 0 ° C., and 26 mL of water, 26 mL of 4N aqueous sodium hydroxide solution and 80 mL of water were sequentially added. The mixture was stirred until the gray portion disappeared, ethyl acetate was added, and the mixture was separated into an oil layer and an aqueous layer. The solvent was removed from the oil layer by distillation under reduced pressure to obtain 50 parts by weight of a crude product. This was purified by column chromatography to obtain 30 parts by weight (yield 56%, purity 96%) of a viscous liquid of a dimethylol compound represented by the following formula (7).
＜製造例２：テルペン系ジメチロール（Ａ−２）の製造＞
冷却管、温度計、撹拌棒を備えた５００ｍＬ三つ口フラスコに、ヤスハラケミカル（株）製ミルセン９０重量部（純度７６％、０．５モル）およびフマル酸５８重量部（０．５モル）を仕込み、撹拌しながら昇温して、１５０〜１６０℃で１２時間反応した。反応後、アセトンから再結晶することにより、フマル化ミルセン８４重量部（ミルセン基準で収率６５％ 、純度９８％）を得た。続いて、電磁撹拌装置を備えた内容５００ｍＬのオートクレーブに、上記で得られたフマル化ミルセン７２重量部（０．２８モル）、２−プロパノール１４０重量部、および粉末状の５％パラジウムカーボン触媒０ ．７重量部を仕込んだ。次いで、これを密閉し、雰囲気を窒素ガスで置換した後、水素ガス１５ｋｇ／ｃｍ２の圧力をかけながら導入した。そして、撹拌を開始すると、内温が２７℃から３２℃へ上昇した。吸収された水素を補うことで圧力を１５〜２０ｋｇ／ｃｍ２に保ちながら４時間反応させた。その後、得られた懸濁液をブフナーロートで吸引ろ過を行い、触媒をろ別した。その後、ろ液を減圧濃縮することにより、水添フマル化ミルセン７１重量部（収率９４％、純度９５％）を得た。次に、冷却管、温度計、撹拌棒、滴下ロートを備えた２Ｌ四つ口フラスコに、窒素気流下、脱水テトラヒドロフランを５００ｍＬ入れ、水素化リチウムアルミニウム２６重量部（０．６８モル）を加えた。混合液を、６５℃で３０分間環流させた後、加熱をやめ、ここに上記のようにして得られた水添フマル化ミルセン６０重量部（０．２２モル）を脱水テトラヒドロフラン３００ｍＬに溶解した溶液を３時間かけて滴下した。混合液を６５℃で１２時間環流させた後、０℃付近に冷却し、水を２６ｍＬ、４規定水酸化ナトリウム水溶液を２６ｍＬ、水８０ｍＬを順次加えた。灰色の部分がなくなるまで撹拌し、酢酸エチルを加え、油層と水層に分離した。油層を減圧蒸留にて溶媒を除去し、粗生成物４７重量部を得た。これをカラムクロマトグラフィーで精製することにより、下記式（８）で表されるジメチロール化合物の白色結晶２０重量部（収率４０％、純度９９％）を得た。
<Production Example 2: Production of terpene-based dimethylol (A-2)>
In a 500 mL three-necked flask equipped with a condenser, a thermometer, and a stir bar, 90 parts by weight (purity 76%, 0.5 mol) and 58 parts by weight (0.5 mol) of fumaric acid manufactured by Yashara Chemical Co., Ltd. The mixture was charged and heated with stirring, and reacted at 150 to 160 ° C. for 12 hours. After the reaction, 84 parts by weight of fumarated myrcene (yield 65%, purity 98% based on myrcene) was obtained by recrystallization from acetone. Subsequently, in a 500 mL autoclave equipped with an electromagnetic stirrer, 72 parts by weight (0.28 mol) of fumarized myrcene obtained above, 140 parts by weight of 2-propanol, and a powdered 5% palladium carbon catalyst 0 . 7 parts by weight were charged. Next, this was sealed and the atmosphere was replaced with nitrogen gas, and then introduced while applying a pressure of 15 kg / cm 2 of hydrogen gas. And when stirring was started, internal temperature rose from 27 degreeC to 32 degreeC. The reaction was performed for 4 hours while maintaining the pressure at 15 to 20 kg / cm 2 by supplementing the absorbed hydrogen. Thereafter, the obtained suspension was subjected to suction filtration with a Buchner funnel to separate the catalyst. Thereafter, the filtrate was concentrated under reduced pressure to obtain 71 parts by weight of hydrogenated fumarated myrcene (yield 94%, purity 95%). Next, 500 mL of dehydrated tetrahydrofuran was placed in a 2 L four-necked flask equipped with a condenser, a thermometer, a stirring rod, and a dropping funnel under a nitrogen stream, and 26 parts by weight (0.68 mol) of lithium aluminum hydride was added. . The mixture was refluxed at 65 ° C. for 30 minutes, then the heating was stopped, and a solution in which 60 parts by weight (0.22 mol) of hydrogenated fumarated myrcene obtained as described above was dissolved in 300 mL of dehydrated tetrahydrofuran. Was added dropwise over 3 hours. The mixture was refluxed at 65 ° C. for 12 hours, cooled to around 0 ° C., and 26 mL of water, 26 mL of 4N aqueous sodium hydroxide solution and 80 mL of water were sequentially added. The mixture was stirred until the gray portion disappeared, ethyl acetate was added, and the mixture was separated into an oil layer and an aqueous layer. The solvent was removed from the oil layer by distillation under reduced pressure to obtain 47 parts by weight of a crude product. This was purified by column chromatography to obtain 20 parts by weight of white crystals (yield 40%, purity 99%) of the dimethylol compound represented by the following formula (8).
［実施例１］
イソソルビド８８４重量部（６．０５モル）と製造例１で製造したテルペン系ジメチロール（Ａ−１）９９２重量部（４．９５モル）およびジフェニルカーボネート２３８０重量部（１１．１１モル）とを反応器に入れ、重合触媒としてテトラメチルアンモニウムヒドロキシドを０．３０重量部（ジフェニルカーボネート成分１モルに対して３×１０−４モル）、および水酸化ナトリウムを１．３×１０−３重量部（ジフェニルカーボネート成分１モルに対して３×１０−６モル）仕込んで窒素雰囲気下、常圧で１８０℃に加熱し溶融させた。撹拌下、反応槽内を３０分かけて徐々に減圧し、生成するフェノールを留去しながら１３．３×１０−３ＭＰａまで減圧した。この状態で２０分反応させた後に２００℃に昇温した後、２０分かけて徐々に減圧し、フェノールを留去しながら４．０×１０−３ＭＰａで２０分間反応させ、さらに、２２０℃に昇温し３０分間、２５０℃に昇温し３０分間反応させた。次いで、徐々に減圧し、２．６７×１０−３ＭＰａで１０分間、１．３３×１０−３ＭＰａで１０分間反応を続行し、さらに減圧し、４．００×１０−５ＭＰａに到達したら、徐々に２５０℃まで昇温し、最終的に２５０℃、６．６６×１０−５ＭＰａで１時間反応せしめた。その結果、比粘度が０．３７のポリマーが得られた。このポリマーの評価結果については表１に示した。
[Example 1]
884 parts by weight (6.05 mol) of isosorbide, 992 parts by weight (4.95 mol) of terpene-based dimethylol (A-1) produced in Production Example 1, and 2380 parts by weight (11.11 mol) of diphenyl carbonate And 0.30 parts by weight of tetramethylammonium hydroxide as a polymerization catalyst (3 × 10 −4 mol relative to 1 mol of diphenyl carbonate component) and 1.3 × 10 −3 parts by weight of sodium hydroxide (diphenyl) 3 × 10 −6 mol with respect to 1 mol of the carbonate component), and heated to 180 ° C. and melted under a nitrogen atmosphere at normal pressure. Under stirring, the pressure in the reaction vessel was gradually reduced over 30 minutes, and the pressure was reduced to 13.3 × 10 −3 MPa while the produced phenol was distilled off. After reacting in this state for 20 minutes, the temperature was raised to 200 ° C., then the pressure was gradually reduced over 20 minutes, and the reaction was carried out at 4.0 × 10 −3 MPa for 20 minutes while distilling off the phenol. The mixture was heated to 250 ° C. for 30 minutes and reacted for 30 minutes. Next, the pressure was gradually reduced, and the reaction was continued at 2.67 × 10 −3 MPa for 10 minutes and 1.33 × 10 −3 MPa for 10 minutes, and further reduced in pressure to reach 4.00 × 10 −5 MPa. The temperature was gradually raised to 250 ° C., and the reaction was finally carried out at 250 ° C. and 6.66 × 10 −5 MPa for 1 hour. As a result, a polymer having a specific viscosity of 0.37 was obtained. The evaluation results of this polymer are shown in Table 1.
［実施例２］
イソソルビド１２８６重量部（８．８モル）と製造例２で製造したテルペン系ジメチロール（Ａ−２）５０２重量部（２．２モル）およびジフェニルカーボネート２４０４重量部（１１．２２モル）とを反応器に入れ、重合触媒としてテトラメチルアンモニウムヒドロキシドを０．３１重量部（ジフェニルカーボネート成分１モルに対して３×１０−４モル）、および水酸化ナトリウムを１．４×１０−３重量部（ジフェニルカーボネート成分１モルに対して３×１０−６モル）とした以外は実施例１と同様に重合させてポリマーを得た。得られたポリマーの評価結果については表１に示した。
[Example 2]
1286 parts by weight (8.8 moles) of isosorbide, 502 parts by weight (2.2 moles) of terpene dimethylol (A-2) produced in Production Example 2 and 2404 parts by weight (11.22 moles) of diphenyl carbonate And 0.31 part by weight of tetramethylammonium hydroxide as a polymerization catalyst (3 × 10 −4 mole relative to 1 mole of diphenyl carbonate component) and 1.4 × 10 −3 part by weight of sodium hydroxide (diphenyl) A polymer was obtained by polymerization in the same manner as in Example 1 except that 3 × 10 −6 mol) per mol of the carbonate component. The evaluation results of the obtained polymer are shown in Table 1.
［実施例３］
イソソルビド１１２５重量部（７．７モル）と製造例１で製造したテルペン系ジメチロール（Ａ−１）６６１重量部（３．３モル）とステアリルアルコール６０重量部（０．２２モル）およびジフェニルカーボネート２４０４重量部（１１．２２モル）とを反応器に入れ、重合触媒としてテトラメチルアンモニウムヒドロキシドを０．３１重量部（ジフェニルカーボネート成分１モルに対して３×１０−４モル）、および水酸化ナトリウムを１．４×１０−３重量部（ジフェニルカーボネート成分１モルに対して３×１０−６モル）とした以外は実施例１と同様に重合させてポリマーを得た。得られたポリマーの評価結果については表１に示した。
[Example 3]
1125 parts by weight (7.7 moles) of isosorbide, 661 parts by weight (3.3 moles) of terpene dimethylol (A-1) produced in Production Example 1, 60 parts by weight (0.22 moles) of stearyl alcohol, and 2404 diphenyl carbonate Parts by weight (11.22 moles), 0.31 part by weight of tetramethylammonium hydroxide (3 × 10 −4 moles per mole of diphenyl carbonate component) as a polymerization catalyst, and sodium hydroxide Was polymerized in the same manner as in Example 1 except that the amount was 1.4 × 10 −3 parts by weight (3 × 10 −6 mol with respect to 1 mol of the diphenyl carbonate component) to obtain a polymer. The evaluation results of the obtained polymer are shown in Table 1.
［実施例４］
イソソルビド１５２７重量部（１０．４５モル）と製造例２で製造したテルペン系ジメチロール（Ａ−２）１２６重量部（０．５５モル）とステアリルアルコール８９重量部（０．３３モル）およびジフェニルカーボネート２４２７重量部（１１．３３モル）とを反応器に入れ、重合触媒としてテトラメチルアンモニウムヒドロキシドを０．３１重量部（ジフェニルカーボネート成分１モルに対して３×１０−４モル）、および水酸化ナトリウムを１．４×１０−３重量部（ジフェニルカーボネート成分１モルに対して３×１０−６モル）とした以外は実施例１と同様に重合させてポリマーを得た。得られたポリマーの評価結果については表１に示した。
[Example 4]
1527 parts by weight (10.45 mol) of isosorbide, 126 parts by weight (0.55 mol) of terpene-based dimethylol (A-2) produced in Production Example 2, 89 parts by weight (0.33 mol) of stearyl alcohol, and 2427 of diphenyl carbonate Parts by weight (11.33 moles), 0.31 part by weight of tetramethylammonium hydroxide (3 × 10 −4 moles per mole of diphenyl carbonate component) as a polymerization catalyst, and sodium hydroxide Was polymerized in the same manner as in Example 1 except that the amount was 1.4 × 10 −3 parts by weight (3 × 10 −6 mol with respect to 1 mol of the diphenyl carbonate component) to obtain a polymer. The evaluation results of the obtained polymer are shown in Table 1.
［比較例１］
イソソルビド１６０８重量部（１１モル）とジフェニルカーボネート２３３３重量部（１０．８９モル）とを反応器に入れ、重合触媒としてテトラメチルアンモニウムヒドロキシドを０．３０重量部（ジフェニルカーボネート成分１モルに対して３×１０−４モル）、および水酸化ナトリウムを１．４×１０−３重量部（ジフェニルカーボネート成分１モルに対して３×１０−６モル）とした以外は実施例１と同様に重合させてポリマーを得た。得られたポリマーの評価結果については表１に示した。
[Comparative Example 1]
1608 parts by weight (11 moles) of isosorbide and 2333 parts by weight (10.89 moles) of diphenyl carbonate are placed in a reactor, and 0.30 part by weight of tetramethylammonium hydroxide is used as a polymerization catalyst (based on 1 mole of the diphenyl carbonate component). 3 × 10 −4 mol) and 1.4 × 10 −3 parts by weight of sodium hydroxide (3 × 10 −6 mol with respect to 1 mol of the diphenyl carbonate component). To obtain a polymer. The evaluation results of the obtained polymer are shown in Table 1.
［比較例２］
イソソルビド６４３重量部（４．４モル）と製造例２で製造したテルペン系ジメチロール（Ａ−２）１５０７重量部（６．６モル）、およびジフェニルカーボネート２２６２重量部（１０．５６モル）とを反応器に入れ、重合触媒としてテトラメチルアンモニウムヒドロキシドを０．３０重量部（ジフェニルカーボネート成分１モルに対して３×１０−４モル）、および水酸化ナトリウムを１．３×１０−３重量部（ジフェニルカーボネート成分１モルに対して３×１０−６モル）とした以外は実施例１と同様に重合させてポリマーを得た。得られたポリマーの評価結果については表１に示した。
[Comparative Example 2]
Reaction of 643 parts by weight (4.4 moles) of isosorbide with 1507 parts by weight (6.6 moles) of terpene dimethylol (A-2) produced in Production Example 2 and 2262 parts by weight (10.56 moles) of diphenyl carbonate Into the vessel, 0.30 parts by weight of tetramethylammonium hydroxide as a polymerization catalyst (3 × 10 −4 mol relative to 1 mol of diphenyl carbonate component), and 1.3 × 10 −3 parts by weight of sodium hydroxide ( A polymer was obtained by polymerizing in the same manner as in Example 1 except that 3 × 10 −6 mol) per 1 mol of the diphenyl carbonate component. The evaluation results of the obtained polymer are shown in Table 1.
Claims (11)
で表される末端基がポリマー主鎖構造に対して０．３〜９.０重量％含まれていることを特徴とする末端変性共重合ポリカーボネート樹脂。 The following formula (2) or (3) at the polymer chain end of the copolymerized polycarbonate according to claim 1
A terminal-modified copolymer polycarbonate resin characterized by containing 0.3 to 9.0% by weight of terminal groups represented by formula (1).
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