CN114524928B - Copolycarbonate with high refractive index and high fluidity - Google Patents
Copolycarbonate with high refractive index and high fluidity Download PDFInfo
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- CN114524928B CN114524928B CN202011318910.6A CN202011318910A CN114524928B CN 114524928 B CN114524928 B CN 114524928B CN 202011318910 A CN202011318910 A CN 202011318910A CN 114524928 B CN114524928 B CN 114524928B
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- 150000001875 compounds Chemical class 0.000 claims abstract description 74
- -1 1, 1-bis (2-hydroxyethoxy naphthyl) methyl Chemical group 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 12
- 238000005809 transesterification reaction Methods 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 6
- 150000004650 carbonic acid diesters Chemical class 0.000 claims description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 4
- 125000006835 (C6-C20) arylene group Chemical group 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 125000001174 sulfone group Chemical group 0.000 claims description 4
- 125000003375 sulfoxide group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000012763 reinforcing filler Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000003054 catalyst Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000203 mixture Substances 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 15
- 239000000178 monomer Substances 0.000 description 14
- 239000004417 polycarbonate Substances 0.000 description 14
- 229920000515 polycarbonate Polymers 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 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 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- CJLPIPXJJJUBIV-UHFFFAOYSA-N 4-[3-(4-hydroxyphenoxy)phenoxy]phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC(OC=2C=CC(O)=CC=2)=C1 CJLPIPXJJJUBIV-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 2
- 238000012660 binary copolymerization Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 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
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 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
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JRFBLFCZOPUKBM-UHFFFAOYSA-N 2-(1-naphthalen-1-ylnaphthalen-2-yl)oxyethanol Chemical group OCCOC1=C(C2=CC=CC=C2C=C1)C1=CC=CC2=CC=CC=C12 JRFBLFCZOPUKBM-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- OVJPYIRGUFWANT-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)naphthalen-1-yl]naphthalen-2-yl]oxyethanol Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3OCCO)=C(OCCO)C=CC2=C1 OVJPYIRGUFWANT-UHFFFAOYSA-N 0.000 description 1
- MDOBPGJMVOGJQP-UHFFFAOYSA-N 2-[4-(9h-fluoren-1-yl)phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C21 MDOBPGJMVOGJQP-UHFFFAOYSA-N 0.000 description 1
- NQXNYVAALXGLQT-UHFFFAOYSA-N 2-[4-[9-[4-(2-hydroxyethoxy)phenyl]fluoren-9-yl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C1(C=2C=CC(OCCO)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 NQXNYVAALXGLQT-UHFFFAOYSA-N 0.000 description 1
- FHZQOYSKWUJKDZ-UHFFFAOYSA-N 2-[6-[9-[6-(2-hydroxyethoxy)naphthalen-2-yl]fluoren-9-yl]naphthalen-2-yl]oxyethanol Chemical compound C1=C(OCCO)C=CC2=CC(C3(C4=CC=CC=C4C4=CC=CC=C43)C3=CC4=CC=C(C=C4C=C3)OCCO)=CC=C21 FHZQOYSKWUJKDZ-UHFFFAOYSA-N 0.000 description 1
- FLMZHPQIDVOWEJ-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-phenylphenyl)fluoren-9-yl]-2-phenylphenol Chemical compound OC1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(O)=CC=2)C=2C=CC=CC=2)C=C1C1=CC=CC=C1 FLMZHPQIDVOWEJ-UHFFFAOYSA-N 0.000 description 1
- HUYGPVIUBANDBQ-UHFFFAOYSA-N 7h-dibenzo(c,g)fluoren-7-one Chemical group C1=CC2=CC=CC=C2C2=C1C(=O)C1=CC=C(C=CC=C3)C3=C12 HUYGPVIUBANDBQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
-
- 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
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
- C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
- C08G64/081—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to copolycarbonates with high refractive index and high fluidity, comprising the following structure: compounds from the group comprising binaphtholone structuresIs derived from a compound having a multi-benzene ring structure
Description
Technical Field
The present invention relates to a copolycarbonate, and more particularly to a copolycarbonate having a high refractive index and high fluidity.
Background
The polycarbonate is one of five engineering plastics, has good mechanical property, weather resistance and fatigue resistance, is odorless and odorless, is harmless to human body, accords with sanitation and safety, and has wide use temperature range.
In the field of optical applications, polycarbonates have good transparency and are one of the preferred materials. With the rapid development of the mobile phone industry, the requirements of mobile phone lenses are also improved. Although the conventional polycarbonate has better transparency, the refractive index is lower, and the requirement of a mobile phone lens can not be met far enough, so that development of the high-refractive-index polycarbonate is urgently needed.
At present, mitsubishi gas chemistry is used for producing industrialized high-refractive-index polycarbonate, and the highest refractive index can reach 1.68. However, as the trend of light and thin mobile phones becomes increasingly clear, higher requirements are put on the refractive index of the lens. According to Lorentz-Lorentz equation, the introduction of high molar index monomers is beneficial to increasing the refractive index of the polymer. Compared with binaphthyl structure, binaphthyl structure has higher molar refractive index, and can obviously improve the refractive index of the polymer. In addition, the utilization of the polymer during the molding of the lens has been low, resulting in a large amount of polymer being wasted. This is not only related to the shaping die but also to the flowability of the polymer melt. By introducing flexible groups such as ether bonds into the multi-benzene ring structure, the fluidity of the polymer can be remarkably improved. Thus, the utilization rate of the polymer is improved, and the formed lens can have higher optical quality.
Chinese patent CN109476835a describes high refractive index polycarbonates comprising 9, 9-bis [6- (2-hydroxyethoxy) naphthalen-2-yl ] fluorene, 2 '-bis (2-hydroxyethoxy) -1,1' -binaphthyl, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene and 9, 9-bis [4- (2-hydroxyethoxy) -3-phenyl ] fluorene, the difference in activity between the different monomers being large, block copolymers are easily formed, affecting the optical properties.
Chinese patent CN104769007B describes high refractive index polycarbonates comprising 2,2 '-bis (2-hydroxyethoxy) -1,1' -binaphthyl and 9, 9-bis (4-hydroxy-3-phenylphenyl) fluorene, which have more rigid structures and poorer flowability in the polymer, which is detrimental to the molding process.
Chinese patent CN101805501B describes high refractive polycarbonates comprising 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene, which polymers have a low refractive index and do not meet the current application.
Currently, in the field of mobile phone lenses, the refractive index and flowability of the lens become important factors affecting the development of the lens. Therefore, the polycarbonate with high refraction and good fluidity is developed, so that the light and thin mobile phone lens can be realized, the utilization rate of polymers can be improved, and the development of the mobile phone lens industry is promoted.
Disclosure of Invention
The object of the present invention is to provide copolycarbonates with a high refractive index and high flowability, which at the same time have the advantage of low haze and good transparency.
The invention adopts the following technical scheme:
a copolycarbonate comprising the structure:
1) Structural units derived from a dihydroxy compound represented by formula (I),
wherein X is 1 、X 2 Respectively and independently represents C1-C10 alkylene and C6-C20 arylene, the values of a and b are respectively and independently 0, 1 and 2,
and:
2) Structural units derived from a dihydroxy compound represented by formula (II):
wherein Y is 1 、Y 2 And each independently represents a sulfone group, a sulfoxide group, a thioether bond and an ether bond.
In the source of structural units of the copolycarbonate of the present invention, the molar ratio of the dihydroxy compound represented by formula (I) to the dihydroxy compound represented by formula (II) is 1:99 to 99:1, preferably 35:65 to 70:30, more preferably 55:45 to 60:40.
As a preferable embodiment, the dihydroxy compound represented by formula (I) is 1, 1-bis (2-hydroxyethoxy naphthyl) methanone having the following structural formula:
as a preferable embodiment, the dihydroxy compound represented by formula (II) is m-bis- (4-hydroxyphenoxy) benzene, and its structural formula is as follows:
the polycarbonate of the present invention may further comprise, in addition to the structural units derived from the dihydroxy compounds represented by formulas (I) and (II), one or more structural units derived from the dihydroxy compound represented by formula (V) other than formula (I):
wherein R is 1 、R 2 Each independently represents hydrogen, halogen, C1-C20 alkyl, C4-C20 cycloalkyl or C6-C20 aryl; m and n are independently integers from 0 to 4; w represents a sulfone group, sulfoxide group, ether linkage, carbonyl group, C1-C20 alkylene group, C6-C20 arylene group, C6-C20 alicyclic group or the following groups:
wherein R is 3 And R is 4 Independently of each other, is C1-C20 alkyl, C4-C20 cycloalkyl or C6-C20 aryl;
as a preferable mode, the dihydroxy compound represented by formula (V) is selected from one or more of 1, 1-bis (2-hydroxyethoxy naphthyl) methyl ether, 1-bis (2-hydroxyethoxy naphthyl) methylsulfone, 1-bis (2-hydroxyethoxy naphthyl) methylsulfide, 2, -bis (2-hydroxyethoxy naphthyl) -propane, and alkylated, cycloalkyl-and halogenated compounds thereof;
as another preferred embodiment, the dihydroxy compound represented by formula (V) is one or more selected from 1, 1-bis (2-hydroxyethoxy-6-phenylnaphthyl) methanone, 1-bis (2-hydroxyethoxy-6-phenylnaphthyl) methyl ether, 1-bis (2-hydroxyethoxy-6-phenylnaphthyl) methylsulfone, 1-bis (2-hydroxyethoxy-6-phenylnaphthyl) methylsulfide, 2, -bis (2-hydroxyethoxy-6-phenylnaphthyl) -propane;
as a most preferred embodiment, the dihydroxy compound represented by formula (V) is 1, 1-bis (2-hydroxyethoxy-6-phenylnaphthyl) methanone having the following structural formula:
in the present invention, the amount of the dihydroxy compound represented by formula (V) is 0 to 30% by mol, preferably 10 to 20% by mol, relative to the total molar amount of the dihydroxy compounds of formula (I) and formula (II) constituting the copolycarbonate.
In the present invention, the copolycarbonates may be prepared by melt transesterification, which is well known to those skilled in the art. The melt transesterification method is to prepare polycarbonate by melt reaction of a dihydroxy compound and a carbonic diester in the presence of a basic compound catalyst, a transesterification catalyst or a mixed catalyst composed of the two. Wherein the carbonic acid diester, the catalyst, the reaction conditions and the like are as described in CN103257376A, and preferably, the molar ratio of the carbonic acid diester to the dihydroxy compound is from 0.99 to 1.20, and the molar ratio of the catalyst to the dihydroxy compound is 1X 10 -8 ～1×10 -1 Preferably 1X 10 -7 ～1×10 -3 。
The melt transesterification method is a method of performing polycondensation by transesterification under heating conditions using the above-mentioned raw materials and a catalyst, while removing by-products by the transesterification reaction under normal pressure or reduced pressure. The reaction is generally carried out in two or more stages.
For the transesterification, specifically, the reaction in the first stage is allowed to react at a temperature of 130 to 210 ℃, preferably 170 to 200 ℃ for 0.1 to 5 hours, preferably 2 to 3 hours. Then, the reaction of the dihydroxy compound and the carbonic acid diester is carried out at an elevated temperature while increasing the reduced pressure of the reaction system, and finally, the reaction is carried out at a reduced pressure of 133.32Pa or less and a temperature of 250 to 270 ℃ for 0.1 to 2 hours. Such a reaction may be carried out continuously or batchwise. The reaction apparatus used in the reaction may be a vertical type equipped with an anchor type stirring blade, a MAXBLEND type stirring blade, a ribbon type stirring blade, or the like, may be a horizontal type equipped with a paddle blade, a lattice blade, a spectacle type blade, or the like, may be an extruder type equipped with a screw, or may be preferably implemented by using a reaction apparatus appropriately combined with these in consideration of the viscosity of the polymer.
After the polymerization reaction is completed, the catalyst is removed or deactivated in order to maintain the thermal stability and hydrolytic stability of the polymer. As the catalyst deactivator, there may be used some known acidic substances, preferably esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid, which may be used alone or in combination.
The amount of the catalyst deactivator to be used may be 0.1 to 45 times by mol, preferably 1 to 20 times by mol, and more preferably 2 to 10 times by mol based on the catalyst.
The copolycarbonates prepared according to the invention have a weight average molecular weight of 5000 to 600000 (weight average molecular weight, determined by volume exclusion gel chromatography after pre-calibration with PS or polycarbonate calibration substances), preferably 15000 to 70000, more preferably 20000 to 50000.
The melt index of the copolycarbonate prepared by the invention is 10-70g/10min.
The copolycarbonates of the invention may additionally contain various conventional additives typically added to thermoplastic resins. The proportion of additives is from 0 to 5% by weight, preferably from 0 to 2.5% by weight, particularly preferably from 0 to 2% by weight, based on the total weight of the copolycarbonate. Conventional additives include: mold release agents, flow aids, heat stabilizers, hydrolysis stabilizers, antioxidants, UV absorbers, flame retardants, antistatic agents, pigments, reinforcing fillers.
The copolycarbonates according to the invention and the additives mentioned above can be prepared by compounding. Can be prepared by the following steps: the components are mixed in a known manner and melt compounded and melt extruded at a temperature of 270℃to 330℃in customary devices such as internal mixers, extruders and twin-screw kneaders, and granulated by means of a granulator.
According to the Lorentz-Lorentz equation, the introduction of an aromatic ring structure into the copolymer structure is advantageous for increasing the refractive index of the copolycarbonate. The introduction of the binaphthyl ketone structure can realize the obvious improvement of the refractive index. In addition, the 1, 1-bis (2-hydroxyethoxy naphthyl) ketone can improve the refractive index and the mechanical property of the polymer.
The monomer expressed by the formula (II) is introduced into the copolymerization structure, particularly the m-di- (4-hydroxyphenoxy) benzene molecular chain has good flexibility, the benzene ring can rotate in a large angle range, the rigidity of the copolymerization structure is reduced, and the processability of the polymer can be obviously improved, particularly in the process of manufacturing small-sized articles such as mobile phone lenses and the like. Through the combined design of the structures, the prepared copolycarbonate has high refractive index, high fluidity, low haze, good transparency and good processability.
For the binary copolymerization systems according to the invention containing (I) and (II), preference is given to (III) and (IV), the refractive index can vary from 1.65 to 1.70, depending on the monomer ratio. The transmittance of the copolycarbonate can reach more than 89%, and the Tg of the corresponding copolymer is 120-200 ℃. The binary copolymerization system can combine refractive index and Tg in more ways within the above range by adjusting the structure and content of the dihydroxy compound of formula (V), preferably formula (VI), for example, a higher or lower Tg can be designed at the same refractive index, and thus the heat resistance or processability of the polymer can be adjusted more conveniently.
The invention likewise relates to shaped articles prepared from the copolycarbonates according to the invention or the compositions thereof, and also to solutions formulated from the copolycarbonates according to the invention. By adjusting the comonomer ratio or the content in the composition, the yield of lens molding can be effectively increased.
The copolycarbonate or the composition thereof can be used for preparing any type of molded parts, has good designability, can adapt to molding processes such as injection molding, extrusion, blow molding and the like, and can meet the design requirement of a die.
Preferred applications of copolycarbonates according to the invention or of their compositions are transparent/translucent or coloured injection-molded parts, extrudates such as sheets, film laminates, profiles, semifinished products and cast films made of high molecular weight polycarbonate.
The copolycarbonates according to the invention or their compositions can optionally be blended with other thermoplastic polymers and/or usual additives for processing into arbitrary shaped parts/extrudates, where all known polycarbonates, polyester carbonates and polyesters have already been used.
The other thermoplastic polymer is selected from one or more of bisphenol a copolycarbonate, polymethyl methacrylate, polyethylene terephthalate, acrylonitrile-butadiene-styrene copolymer, polyamide copolymer, and polystyrene.
The invention has the beneficial effects that:
the invention can obtain copolycarbonate with high refractive index, high fluidity, low haze, good transparency and processability by selecting the compounds of the formula (I) and the formula (II) for combination design, and can be applied to the field of mobile phone lenses with high requirements on refractive index and fluidity.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the product of Synthesis example 1 1 H-NMR，
FIG. 2 is a nuclear magnetic resonance spectrum 13C-NMR of the product of monomer synthesis example 1.
Detailed Description
The following examples are intended to illustrate the invention, but the invention is not limited to the scope of the examples, but includes any other modifications within the scope of the claims as claimed.
Raw material sources in examples:
synthesis example 1 of monomer
The synthesis of monomer (III) is carried out in two steps. First, 28.8g (0.72 mol) of sodium hydroxide, 280g (6.09 mol) of absolute ethyl alcohol and 28.8g of beta-naphthol are put into a 1000ml four-necked flask(0.2 mol) and 16ml of 1, 2-dichloroethane are added with shaking. Heated in a water bath at a constant temperature of 55℃and refluxed for 2h under stirring. After the reaction, the reactants in the bottle are poured into a 1000ml flask containing 400ml of crushed ice, and are stirred fully at the same time, and the crystals are completely separated out and filtered by suction. The precipitate was washed twice with 60ml of pure water and filtered off with suction, and the filter cake was naturally dried. Then, 18.8g (0.1 mol) of the dried product was weighed into a 500ml four-necked flask, and 200ml of methylene chloride was added thereto and dissolved by stirring well. After dissolving, adding anhydrous aluminum chloride 1.33X10 - 3 g(1×10 -5 mol) as a catalyst, 9.9g (0.1 mol) of phosgene was introduced at room temperature and stirred thoroughly for 1h. After the reaction is finished, 100ml of n-heptane is added for precipitation, after the precipitation is finished, a centrifuge is used for filtering, a filter cake is collected, and drying is carried out in a constant-temperature oven at 100 ℃ for 24 hours, so that a monomer (III) is obtained, and the nuclear magnetic resonance results of the monomer (III) are shown in figures 1 and 2 and correspond to a hydrogen spectrum and a carbon spectrum respectively.
Synthesis example 2 of monomer
Into a 1000mL three-necked flask, 11.4g (0.1 mol) of m-difluorobenzene, 31g (0.25 mol) of p-methoxyphenol and 20.7g (0.15 mol) of potassium carbonate were charged, the solvent was 250mL of sulfolane, and 80mL of toluene was used as an azeotropic dehydrating agent. And (3) carrying out reaction under the protection of argon, carrying out water at 140 ℃ for 3 hours, then steaming to remove toluene, heating to 220 ℃ for reaction for 6 hours, and discharging in deionized water to obtain gray solid. The residual phenolic monomers are removed by 5% sodium hydroxide solution, and then the mixture is washed to be neutral for a plurality of times, and dried to obtain white solid. Toluene was recrystallized to give a white powder. 12.88g (0.04 mol) of the white powder, 53ml (0.4 mol) of hydroiodic acid and 100ml of glacial acetic acid were taken and heated to reflux under the protection of argon gas, and reacted for 5 hours. After the solution is cooled to room temperature, discharging the solution into deionized water, and filtering and washing the solution to obtain white solid. Toluene was recrystallized to give a white powder, which was the monomer (IV).
Synthesis example 3 of monomer
To a 500ml metal reaction vessel, 10.05g (0.025 mol) of the product (III), 9.4g (0.1 mol) of phenol, 200ml of toluene and 1g of a platinum carbon (Pt/C, the Pt content of the catalyst was 0.5%) catalyst were added, stirring was started, the temperature of the reaction solution was gradually increased from room temperature to 100℃and the rate of increase was controlled to 5℃per minute. After the temperature is raised to 100 ℃, hydrogen chloride is introduced into the kettle, the pressure is maintained at 2MPa, and the reaction is continued for 2 hours. After the reaction, the reaction mixture was cooled to room temperature, neutralized by adding 16wt% sodium hydroxide solution, and the pH was adjusted to 7 to precipitate a crude product, which was obtained by filtration. And finally, flushing the filter cake with toluene, repeatedly filtering for 3 times, and naturally drying the filter cake to obtain the monomer (VI).
Example 1
Copolycarbonates prepared from dihydroxy compounds of formula (III), formula (IV) were synthesized in a molar ratio of 99:1.
397.98g (0.99 mol) of a dihydroxy compound of formula (III), 2.94g (0.01 mol) of a dihydroxy compound of formula (IV), 227.07 (1.06 mol) of diphenyl carbonate and 0.02g (5X 10) -4 mol) sodium hydroxide was added to a reactor with stirring and distillation apparatus and heated to 160℃under normal pressure for 1 hour to melt. Thereafter, the temperature was raised to 200℃over 0.5 hour, and stirring was performed. Then, the pressure was adjusted to 2KPa for 15 minutes, and the reaction was kept at 200℃for 30 minutes under 2KPa to carry out transesterification. Then the temperature is raised to 260 ℃ at the speed of 50 ℃/hour, and the mixture is kept at 260 ℃ for 20 minutes at 2 KPa. Then, the temperature was adjusted to 1KPa for 10 minutes, and the temperature was maintained at 260℃for 1 hour at 1 KPa. Then adjusted to 500Pa for 10 minutes, and maintained at 260℃for 20 minutes at 500 Pa. The pressure was reduced to 133Pa or lower for 30 minutes, and the mixture was stirred at 260℃for 15 minutes under 133Pa or lower to carry out polymerization. After the reaction, butyl benzoate was added in an amount 2 times the amount of the catalyst to deactivate the catalyst, and the catalyst was discharged from the bottom of the reaction tank under nitrogen pressurization, and the mixture was cooled in the water tank and cut with a granulator to obtain granules. The copolycarbonate obtained was the product of the process No. A1 and the weight-average molecular weight 43216.
Example 2
Copolycarbonates prepared from dihydroxy compounds of formula (III), (IV) were synthesized in a molar ratio of 90:10.
A copolycarbonate resin, no. A2, and a weight-average molecular weight 42941 were synthesized according to example 1 except that 361.8g (0.9 mol) of the dihydroxy compound of formula (III) and 29.4g (0.1 mol) of the dihydroxy compound of formula (IV) were used.
Example 3
Copolycarbonates prepared from dihydroxy compounds of formula (III), (IV) were synthesized in a molar ratio of 70:30.
A copolymerized polycarbonate resin, no. A3, and a weight-average molecular weight 41067 were synthesized by referring to example 1, except that 281.4g (0.7 mol) of the dihydroxy compound of the structure of formula (III) and 88.2g (0.3 mol) of the dihydroxy compound of the structure of formula (IV) were used.
Example 4
Copolycarbonates prepared from dihydroxy compounds of formula (III), (IV) were synthesized in a molar ratio of 50:50.
A copolymerized polycarbonate resin, no. A4, and a weight-average molecular weight 41683 were synthesized by the following procedure of example 1, except that 201g (0.5 mol) of the dihydroxy compound of formula (III) and 147g (0.5 mol) of the dihydroxy compound of formula (IV) were used.
Example 5
Copolycarbonates prepared from dihydroxy compounds of formula (III), (IV) were synthesized in a molar ratio of 30:70.
A copolycarbonate resin, no. A5, and a weight-average molecular weight 41365 were synthesized according to example 1 except that 120.6g (0.3 mol) of the dihydroxy compound of formula (III) and 205.8g (0.7 mol) of the dihydroxy compound of formula (IV) were used.
Example 6
Copolycarbonates prepared from dihydroxy compounds of formula (III), (IV) were synthesized in a molar ratio of 10:90.
A copolycarbonate resin, no. A6, and a weight-average molecular weight 42213 were synthesized according to example 1 except that 40.2g (0.1 mol) of the dihydroxy compound of formula (III) and 264.6g (0.9 mol) of the dihydroxy compound of formula (IV) were used.
Example 7
Copolycarbonates prepared from dihydroxy compounds of formula (III), (IV) were synthesized in a molar ratio of 1:99.
A copolymerized polycarbonate resin, no. A7, and a weight-average molecular weight 42983 were synthesized in accordance with example 1, except that 4.02g (0.01 mol) of the dihydroxy compound of the structure of formula (III) and 291.06g (0.99 mol) of the dihydroxy compound of the structure of formula (IV) were used.
Example 8
Ternary copolycarbonates prepared from dihydroxy compounds of formula (III), (IV), (VI) were synthesized in a molar ratio of 70:30:20.
281.4g (0.7 mol) of a dihydroxy compound of formula (III), 88.2g (0.3 mol) of a dihydroxy compound of formula (IV), 110.8g (0.2 mol) of a dihydroxy compound of formula (VI), 272.49g (1.272 mol) of diphenyl carbonate and 0.03g (7.5X10) -4 mol) sodium hydroxide was added to a reactor with stirring and distillation apparatus and heated to 160℃under normal pressure for 1 hour to melt. Thereafter, the temperature was raised to 200℃over 0.5 hour, and stirring was performed. Then, the pressure was adjusted to 2KPa for 15 minutes, and the reaction was kept at 200℃for 30 minutes under 2KPa to carry out transesterification. Then the temperature is raised to 260 ℃ at the speed of 50 ℃/hour, and the mixture is kept at 260 ℃ for 20 minutes at 2 KPa. Then, the temperature was adjusted to 1KPa for 10 minutes, and the temperature was maintained at 260℃for 1 hour at 1 KPa. Then adjusted to 500Pa for 10 minutes, and maintained at 260℃for 20 minutes at 500 Pa. The pressure was reduced to 133Pa or lower for 30 minutes, and the mixture was stirred at 260℃for 15 minutes under 133Pa or lower to carry out polymerization. After the reaction, butyl benzoate was added in an amount 2 times the amount of the catalyst to deactivate the catalyst, and the catalyst was discharged from the bottom of the reaction tank under nitrogen pressurization, and the mixture was cooled in the water tank and cut with a granulator to obtain granules. The copolycarbonate obtained was the product of the following procedure, no. B1 and weight-average molecular weight 43265.
Example 9
Ternary copolycarbonates prepared from dihydroxy compounds of formula (III), (IV), (VI) were synthesized in a molar ratio of 50:40:20.
With the exception of using 201g (0.5 mol) of the dihydroxy compound of formula (III), 117.6g (0.4 mol) of the dihydroxy compound of formula (IV) and 110.8g (0.2 mol) of the dihydroxy compound of formula (VI), a ternary copolycarbonate was synthesized, number B2 and weight average molecular weight 43211, as described in example 8.
Comparative example 1
Copolycarbonates prepared from the dihydroxy compound of formula (III) and bisphenol A in a molar ratio of 70:30.
281.4g (0.7 mol) of a dihydroxy compound of formula (III), 68.49g (0.3 mol) of bisphenol A,227.07 (1.06 mol) diphenyl carbonate and 0.02g (5X 10) -4 mol) sodium hydroxide was added to a reactor with stirring and distillation apparatus and heated to 160℃under normal pressure for 1 hour to melt. Thereafter, the temperature was raised to 200℃over 0.5 hour, and stirring was performed. Then, the pressure was adjusted to 2KPa for 15 minutes, and the reaction was kept at 200℃for 30 minutes under 2KPa, whereby the transesterification reaction was carried out. Then, the temperature was raised to 260℃at a rate of 50℃per hour, and the mixture was kept at 260℃for 20 minutes at 2 Kpa. Then, the temperature was adjusted to 1Kpa for 10 minutes, and the mixture was kept at 260℃for 1 hour at 1 Kpa. Then adjusted to 500Pa for 10 minutes, and maintained at 260℃for 20 minutes at 500 Pa. The pressure was reduced to 133Pa or lower for 30 minutes, and the mixture was stirred at 260℃for 15 minutes under 133Pa or lower to carry out polymerization. After the reaction, butyl benzoate was added in an amount 2 times the amount of the catalyst to deactivate the catalyst, and the catalyst was discharged from the bottom of the reaction tank under nitrogen pressurization, and the mixture was cooled in the water tank and cut with a granulator to obtain granules. The copolycarbonate obtained was No. 1 and had a weight average molecular weight of 41232.
Comparative example 2
Copolycarbonates prepared from the dihydroxy compound of formula (VI) and bisphenol A in a molar ratio of 70:30.
387.8g (0.7 mol) of a dihydroxy compound of the formula (VI), 68.49g (0.3 mol) of bisphenol A, 227.07 (1.06 mol) of diphenyl carbonate and 0.02g (5X 10) -4 mol) sodium hydroxide was added to a reactor with stirring and distillation apparatus and heated to 160℃under normal pressure for 1 hour to melt. Thereafter, the temperature was raised to 200℃over 0.5 hour, and stirring was performed. Then, the pressure was adjusted to 2Kpa for 15 minutes, and the reaction was kept at 200℃for 30 minutes under 2Kpa to carry out transesterification. Then, the temperature was raised to 260℃at a rate of 50℃per hour, and the mixture was kept at 260℃for 20 minutes at 2 Kpa. Then, the temperature was adjusted to 1Kpa for 10 minutes, and the mixture was kept at 260℃for 1 hour at 1 Kpa. Then adjusted to 500Pa for 10 minutes, and maintained at 260℃for 20 minutes at 500 Pa. The pressure was reduced to 133Pa or lower for 30 minutes, and the mixture was stirred at 260℃for 15 minutes under 133Pa or lower to carry out polymerization. After the reaction, butyl benzoate was added in an amount 2 times the amount of the catalyst to deactivate the catalyst, and the catalyst was discharged from the bottom of the reaction tank under nitrogen pressurizationThe mixture is cooled in a water tank and cut by a granulator to obtain granules. The copolycarbonate obtained was found to have a weight average molecular weight of 42387 and a number of 2.
Performance testing
Copolycarbonates were characterized by means of glass transition temperature (Tg), refractive index, transmittance, haze and melt index (MFR) tests. Tg is measured by dynamic differential thermal analysis (DSC) according to ASTM E1356. Refractive index, transmittance, and haze were obtained by measuring copolycarbonate films, refractive index was measured according to ASTM D542. Transmittance and haze were measured according to ASTM D1003. The film was obtained by dissolving a copolycarbonate resin in methylene chloride to prepare a 10wt% solution, and then spin-coating the solution to a thickness of 50. Mu.m.
Melt index measurement
MFR was measured by melt index according to ASTM D1238.
The results of the performance test of the copolycarbonates prepared in examples and comparative examples are shown in Table 1.
TABLE 1
Claims (15)
1. A copolycarbonate comprising the structure:
1) Structural units derived from a dihydroxy compound represented by formula (I):
wherein X is 1 、X 2 Respectively and independently represents C1-C10 alkylene and C6-C20 arylene, the values of a and b are respectively and independently 0, 1 and 2,
and:
2) Structural units derived from a dihydroxy compound represented by formula (II):
wherein Y is 1 、Y 2 And each independently represents a sulfone group, a sulfoxide group, a thioether bond and an ether bond.
2. The copolycarbonate according to claim 1, wherein the dihydroxy compound represented by formula (I) has a structural formula of:
the structural formula of the dihydroxy compound represented by formula (II) is:
3. the copolycarbonate according to claim 1, wherein the molar ratio of the dihydroxy compound represented by formula (I) to the dihydroxy compound represented by formula (II) is 1:99 to 99:1.
4. The copolycarbonate according to claim 1, wherein the molar ratio of the dihydroxy compound represented by formula (I) to the dihydroxy compound represented by formula (II) is 35:65 to 70:30.
5. The copolycarbonate according to claim 1, wherein the molar ratio of the dihydroxy compound represented by formula (I) to the dihydroxy compound represented by formula (II) is 55:45 to 60:40.
6. The copolycarbonate according to any one of claims 1 to 5, wherein the copolycarbonate optionally further comprises structural units derived from a dihydroxy compound represented by formula (V) other than formula (I),
wherein R is 1 、R 2 Each independently represents hydrogen, halogen, C1-C20 alkyl, C4-C20 cycloalkyl or C6-C20 aryl; m and n are independently integers from 0 to 4; w represents a sulfone group, sulfoxide group, ether linkage, carbonyl group, C1-C20 alkylene group, C6-C20 arylene group, C6-C20 alicyclic group or the following groups:
wherein R is 3 And R is 4 Independently of each other, is C1-C20 alkyl, C4-C20 cycloalkyl or C6-C20 aryl.
7. The copolycarbonate according to claim 6, wherein the structural unit of the dihydroxy compound represented by formula (V) is 0 to 30 mol% relative to the total molar amount of the dihydroxy compounds of formulas (I) and (II) constituting the copolycarbonate.
8. The copolycarbonate according to claim 7, wherein the structural unit of the dihydroxy compound represented by formula (V) is 10 to 20mol% relative to the total molar amount of the dihydroxy compounds of formulas (I) and (II) constituting the copolycarbonate.
9. The copolycarbonate according to claim 6, wherein the dihydroxy compound represented by formula (V) is selected from the group consisting of 1, 1-bis (2-hydroxyethoxy naphthyl) methyl ether, 1-bis (2-hydroxyethoxy naphthyl) methylsulfone, 1-bis (2-hydroxyethoxy naphthyl) methylsulfide, 2, -bis (2-hydroxyethoxy-naphthyl) -propane, 1-bis (2-hydroxyethoxy-6-phenylnaphthyl) methanone, 1-bis (2-hydroxyethoxy-6-phenylnaphthyl) methyl ether 1, 1-bis (2-hydroxyethoxy-6-phenylnaphthyl) methylsulfone, 1-bis (2-hydroxyethoxy-6-phenylnaphthyl) methylsulfide, 2, -one or more of bis (2-hydroxyethoxy 6-phenylnaphthyl) -propane.
10. The copolycarbonate according to claim 9, wherein the dihydroxy compound represented by formula (V) is 1, 1-bis (2-hydroxyethoxy-6-phenylnaphthyl) methanone having the structure:
11. the copolycarbonate according to any one of claims 1-5, wherein the copolycarbonate has a refractive index of 1.65-1.70.
12. The copolycarbonate according to any one of claims 1-5, wherein the melt index of the copolycarbonate is 10-70g/10min.
13. The copolycarbonate according to any one of claims 1-5, comprising 0-5wt% of one or two or more of the following components selected from the group consisting of: mold release agents, flow aids, heat stabilizers, hydrolysis stabilizers, antioxidants, UV absorbers, flame retardants, antistatic agents, pigments, reinforcing fillers.
14. A process for the preparation of a copolycarbonate according to any one of claims 1 to 13, characterized in that the process comprises melt transesterification of a dihydroxy compound corresponding to formula (I) and formula (II) with a carbonic acid diester to produce a copolycarbonate.
15. The method of claim 14, wherein the molar ratio of carbonic acid diester to dihydroxy compound is from 0.99 to 1.20.
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| JP2000230044A (en) * | 1999-02-15 | 2000-08-22 | Mitsubishi Gas Chem Co Inc | Copolycarbonate resin |
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| CN105085891A (en) * | 2015-08-21 | 2015-11-25 | 万华化学集团股份有限公司 | High-refractive-index copolycarbonate |
| JP2015212389A (en) * | 2013-02-20 | 2015-11-26 | 帝人株式会社 | Polycarbonate copolymer |
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| KR20140035412A (en) * | 2011-05-19 | 2014-03-21 | 미츠비시 가스 가가쿠 가부시키가이샤 | Polycarbonate copolymer having high fluidity, method for producing aromatic polycarbonate resin having high molecular weight, and aromatic polycarbonate compound |
| JPWO2012157766A1 (en) * | 2011-05-19 | 2014-07-31 | 三菱瓦斯化学株式会社 | High fluidity polycarbonate copolymer, method for producing high molecular weight aromatic polycarbonate resin, and aromatic polycarbonate compound |
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