CN115215998A - Copolycarbonate with high fluidity and high chemical stability resistance, and preparation method and application thereof - Google Patents
Copolycarbonate with high fluidity and high chemical stability resistance, and preparation method and application thereof Download PDFInfo
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- CN115215998A CN115215998A CN202210948713.5A CN202210948713A CN115215998A CN 115215998 A CN115215998 A CN 115215998A CN 202210948713 A CN202210948713 A CN 202210948713A CN 115215998 A CN115215998 A CN 115215998A
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- copolycarbonate
- hydroxide
- acetate
- carbonate
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- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000000126 substance Substances 0.000 title abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 26
- 239000004417 polycarbonate Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 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 claims abstract description 11
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 9
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical group C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 12
- 238000005809 transesterification reaction Methods 0.000 claims description 11
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 4
- 150000007514 bases Chemical class 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 4
- 239000001639 calcium acetate Substances 0.000 claims description 4
- 235000011092 calcium acetate Nutrition 0.000 claims description 4
- 229960005147 calcium acetate Drugs 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 4
- 239000011654 magnesium acetate Substances 0.000 claims description 4
- 235000011285 magnesium acetate Nutrition 0.000 claims description 4
- 229940069446 magnesium acetate Drugs 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- 238000000071 blow moulding Methods 0.000 claims description 3
- 238000001746 injection moulding Methods 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- 125000006833 (C1-C5) alkylene group Chemical group 0.000 claims description 2
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 2
- 125000006835 (C6-C20) arylene group Chemical group 0.000 claims description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 229940112016 barium acetate Drugs 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 2
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 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
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-O triphenylazanium Chemical compound C1=CC=CC=C1[NH+](C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-O 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 8
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229920006026 co-polymeric resin Polymers 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- -1 fatty acid sodium salt Chemical class 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 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
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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
Description
Technical Field
The present invention relates to a copolycarbonate, and more particularly, to a copolycarbonate having high flow and high chemical resistance.
Background introduction
Polycarbonates are known to be stable and transparent thermoplastic resins and have high impact resistance. However, polycarbonates also have a relatively high melt viscosity. Therefore, in order to produce molded products using polycarbonate, relatively high extrusion temperatures and molding temperatures are required. Over the years, considerable efforts have been made to reduce the melt viscosity of polycarbonates while maintaining better physical properties. For this, using a plasticizer, using an aliphatic chain terminator, reducing the molecular weight, or preparing a resin having a long chain aliphatic group when an aliphatic chain terminator is used, fluidity can be easily and correctly obtained, but impact resistance measured using a notched cantilever beam is remarkably deteriorated. Furthermore, brittleness can be problematic. When a bisphenol having an aliphatic long chain is used, an increase in fluidity can be observed. However, this is usually accompanied by a significant reduction in the desired impact strength properties.
Chinese patent CN 112409586A describes a process for preparing high flow polycarbonate by adding excess aqueous sodium hydroxide solution to saturated dibasic fatty acid to prepare saturated dibasic fatty acid sodium salt, mixing saturated dibasic fatty acid sodium salt with bisphenol a, process water and solvent, and introducing phosgene to the mixture to react. The method relates to a highly toxic gas phosgene which has high danger and is difficult to obtain.
Chinese patent CN201711272381.9 describes a high-flow, chemical-resistant polycarbonate and a preparation method thereof, in which a thermoplastic polyester elastomer and ABS are added to the polycarbonate to improve the chemical resistance of the polycarbonate, which is limited to the polycarbonate and has problems of poor compatibility, etc.
Therefore, the invention develops a polycarbonate with high fluidity and high chemical resistance by introducing new monomers from a coalescence structure and controlling the ratio of the monomers and utilizing a melt transesterification process, and can be applied to the fields with both fluidity and chemical resistance.
Disclosure of Invention
In order to overcome the defects of the prior art, the polycarbonate with high heat resistance and high chemical resistance, the preparation method and the application thereof are provided.
In one aspect, the present invention provides a copolycarbonate comprising the structure:
1) Derived from a structural unit of a bisphenol monomer containing a phthalazinone structure shown in a formula (I),
in the formula R 1 And R 2 Independently of one another, represent hydrogen, C1-C10 alkylene or represent a bond only; x represents a single bond, an ether bond or a C1-C5 alkylene group.
Derived from a structural unit represented by formula (II):
in the formula, R 3 And R 4 Each independently represents hydrogen, halogen, C1-C10 alkyl; m and n independently represent an integer of 0 to 5; x represents a single bond, an ether bond, a carbonyl group, a C1-C10 alkylene group, a C6-C20 arylene group, a C6-C20 alicyclic group, or a group represented by the formula:
wherein R is 5 And R 6 Each independently represents a C1-C20 alkyl group, a C4-C20 cycloalkyl group or a C4-C20 aryl group; or R 5 And R 6 Together form a C4-C20 alicyclic ring, which C4-C20 alicyclic ring may be optionally substituted with one or more C1-C20 alkyl, C6-C20 aryl, C7-C21 aralkyl, C5-C20 cycloalkyl groups, or combinations thereof.
Preferably, the structural unit represented by formula (I) is represented by formula (III):
preferably, the structure represented by formula (II) is bisphenol C, bisphenol F or a structural unit represented by formula (IV):
in the source of the structural unit of the copolycarbonate according to the present invention, the molar ratio of the structure of the bisphenol monomer containing a phthalazinone structure represented by formula (I) to the structure of the dihydroxy compound represented by formula (II) is 1:99. 5:95. 10:90. 12:88. 14:86. 15:85.
in the present invention, the molecular weight of the copolycarbonate is not particularly limited, and it is preferable that Mw (weight average molecular weight, measured by GPC after calibration with polystyrene or polycarbonate calibration substances in advance) is 10000 to 60000, preferably 20000 to 40000, and a melt index is 60 to 80g/10min, preferably 70 to 80g/10min.
The copolycarbonates described herein may additionally comprise various conventional additives commonly added to thermoplastic resins. The proportion of additives is from 0 to 3% by weight, relative to the total weight of copolycarbonate, and optional conventional additives include: one or more of a heat stabilizer, an antioxidant, a flame retardant, a mold release agent, a flow aid, and the like.
In another aspect, the present invention also provides a method for preparing copolycarbonates, which method may employ a melt transesterification method known to those skilled in the art to prepare the copolycarbonates of the present invention.
In one embodiment, the melt transesterification process of the present invention comprises the steps of: the polycarbonate is produced by melt-reacting the formula (I) and the formula (II) by a melt transesterification method in the presence of a basic compound catalyst, a transesterification catalyst or a mixed catalyst composed of both.
The basic compound catalyst is selected from lithium hydroxide, sodium hydroxide, potassium hydroxide,Cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, triphenylammonium, diethylamine, and the like, and the transesterification catalyst is one or more selected from magnesium carbonate, cesium carbonate, sodium hydroxide, sodium bicarbonate, tetramethylammonium hydroxide; the catalyst is used in a molar ratio of 3X 10 relative to the sum of the dihydroxy compounds -10 ~3×10 -2 Preferably 3X 10 -8 ~3×10 -4 。
The reaction can be carried out continuously or batchwise. The reaction apparatus for the reaction may be a vertical type equipped with an anchor type paddle, a MAXBLEND type paddle, a ribbon type paddle, or the like, a horizontal type equipped with a paddle blade, a lattice blade, a spectacle-shaped blade, or the like, or an extruder type equipped with a screw, and it is preferable to use a reaction apparatus in which these are appropriately combined in consideration of the viscosity of the polymer.
The prepared copolycarbonate has the melt index of 60-80g/10min by adjusting the monomer ratio of the formula (I) to the formula (II), has good chemical resistance, and has a retention rate of more than 95% of tensile modulus and elongation at break after being soaked in ethyl acetate for 24 hours at normal temperature.
In a specific embodiment, the melt transesterification method is specifically to add the dihydroxy compound represented by the formula (I) and the dihydroxy compound represented by the formula (II), the carbonic diester, the catalyst and the optional auxiliary agent into a reactor, introduce nitrogen into the reactor to sufficiently displace the air in the reactor for 3 to 4 times, and perform the melt transesterification in two stages, wherein the first stage is to raise the temperature to 140 to 250 ℃, preferably 180 to 220 ℃, and keep the temperature for 0.1 to 2 hours, preferably 0.5 to 1 hour under normal pressure within 20 to 60 minutes, preferably 30 to 40 minutes. And starting stirring after the materials are completely in a molten state. The second stage reaction is carried out for 20-80 min, preferably 40-60 min, the temperature of the reactor is increased to 260-340 ℃, preferably 280-320 ℃, and the pressure is reduced along with the temperature increase, wherein the pressure is in the range of 50-1000 pa, preferably 100-300 pa. Then keeping the temperature for 0.1 to 3 hours, preferably 1 to 2 hours. Under the condition, the ester exchange reaction polycondensation reaction is carried out, substances such as small molecular compounds and the like generated in the reaction process can be removed by adopting a distillation mode by reducing the vacuum degree, and finally the target product of the high molecular polycarbonate is obtained.
The invention likewise relates to shaped parts produced from the copolycarbonates according to the invention or the compositions thereof, and to the use of the shaped parts. Solutions of the copolycarbonates according to the invention are also included for applications requiring high heat resistance and high chemical resistance.
The copolycarbonates according to the invention or their compositions can be used to produce shaped parts of any type, which can be produced by injection molding, extrusion and blow molding processes.
The invention has the beneficial effects that the introduction of the bisphenol monomer structure containing the phthalazinone structure can ensure that the polycarbonate has good fluidity and the chemical resistance of the polycarbonate is improved on the basis of ensuring that the polycarbonate has certain mechanical strength, and can be used in some special fields.
Detailed Description
The following examples are intended to illustrate the present invention, and the present invention is not limited to the scope of the examples, but also includes any other changes within the scope of the claims of the present invention.
Raw materials and sources:
bisphenol A: GC from Aladdin reagent Ltd
Bisphenol C: aladdin reagent Gc
Bisphenol F: aladdin reagent Gc
Sodium hydroxide: aladdin reagent Limited AR
Diphenyl carbonate 99% by Aladdin reagent Co., ltd
Other raw materials are all commercially available raw materials unless otherwise specified
Weight average molecular weight test method:
the weight average molecular weight is determined by GPC after calibration beforehand with polystyrene or polycarbonate calibration substances.
Synthesis of bisphenol monomer containing phthalazinone structure
Specifically, refer to the Chinese patent CN 109851563A-a preparation method of bisphenol monomer containing phthalazinone structure example 9.
Example 1
Copolycarbonates prepared according to formula (III) and formula (IV) were synthesized in a molar ratio of 1. 4.36g (0.01 mol) of the compound of the formula (III), 225.72g (0.99 mol) of the compound of the formula (IV), 218.28g (1.02 mol) of diphenyl carbonate and 0.01g (2.5X 10 mol) -4 mol) NaoH is added into a reactor with a stirring and flowing-out device, the first stage reaction is heated to 200 ℃ for 30min under normal pressure and is kept for 1h to melt, after the materials are completely melted, stirring is started, the second stage reaction is started, the temperature of the reactor is increased to 300 ℃ within 50min, the pressure of the reactor is slowly reduced to 150pa while the temperature is increased, and then the ester exchange reaction is carried out for 1h under the temperature and the pressure. After the reaction, 2 times mole of butyl benzoate was added to deactivate the catalyst, and the catalyst was discharged from the bottom of the reaction tank under pressure of nitrogen, cooled in a water tank, and cut with a pelletizer to obtain pellets. The polycarbonate-polyester copolymer resin obtained was designated as P1 and had a weight-average molecular weight of 26523.
Example 2
Copolycarbonates prepared from formula (III), formula (IV) were synthesized in a molar ratio of 5.
A copolycarbonate, no. P2, having a weight average molecular weight of 27231 was synthesized by referring to example 1 except that 21.8g (0.05 mol) of the compound having the structure of the formula (III) and 216.6g (0.95 mol) of the compound having the structure of the formula (IV) were used.
Example 3
Copolycarbonates prepared according to formula (III) and formula (IV) were synthesized in a molar ratio of 10.
A copolycarbonate was synthesized in accordance with example 1, with the exception that 43.6g (0.10 mol) of the compound having the structure of the formula (III) and 205.2g (0.15 mol) of the compound having the structure of the formula (IV) were used, and the number P3 was assigned, and the weight average molecular weight was 28514.
Example 4
Copolycarbonates prepared from formula (III), formula (IV) were synthesized in a 12 molar ratio.
A copolycarbonate, no. P4, having a weight average molecular weight of 29164 was synthesized by referring to example 1 except that 52.32g (0.12 mol) of the compound having the structure of the formula (III) and 200.64g (0.88 mol) of the compound having the structure of the formula (IV) were used.
Example 5
A copolycarbonate prepared from formula (III) and formula (IV) was synthesized in a molar ratio of 14.
A copolycarbonate, no. P5, having a weight average molecular weight of 30581 was synthesized in accordance with example 1 except that 61.04g (0.14 mol) of the compound having the structure of the formula (III) and 196.08g (0.86 mol) of the compound having the structure of the formula (IV) were used.
Example 6
Copolycarbonates prepared from formula (III), formula (IV) were synthesized in a molar ratio of 15.
A copolycarbonate, no. P6, having a weight average molecular weight of 31200 was synthesized by referring to example 1 except that 65.4g (0.15 mol) of the compound having the structure of the formula (III) and 193.8g (0.85 mol) of the compound having the structure of the formula (IV) were used.
Example 7
A copolycarbonate prepared from formula (III), bisphenol C was synthesized in a 5 molar ratio.
A copolycarbonate was synthesized in accordance with example 1 except that 21.8g (0.05 mol) of the compound having the structure of the formula (III) and 243.2g of bisphenol C were used, and the polycarbonate was numbered P7 and had a weight average molecular weight of 27446.
Example 8
A copolycarbonate prepared from formula (III), bisphenol F was synthesized in a 5 molar ratio.
A copolycarbonate was synthesized in accordance with example 1 except that 21.8g (0.05 mol) of the compound having the structure of the formula (III) and 190g of bisphenol F were used, wherein the polycarbonate was numbered P7 and the weight average molecular weight was 27115.
Example 9
Copolycarbonates prepared from formula (III), formula (IV) were synthesized in a molar ratio of 1.
4.36g (0.01 mol) of the compound of the formula (III), 225.72g (0.99 mol) of the compound of the formula (IV), 218.28g (1.02 mol) of diphenyl carbonate and 0.01g (2.5X 10 mol) -4 mol) of NaoH is added into a reactor with a stirring and flowing device, the first stage reaction is heated to 180 ℃ for 30min under normal pressure, the temperature is kept for 1h to melt the NaoH, after the materials are completely melted, stirring is started, the second stage reaction is started, the temperature of the reactor is increased to 280 ℃ within 50min, the pressure of the reactor is slowly reduced to 100pa while the temperature is increased, and then the ester exchange reaction is carried out for 1h under the temperature and the pressure. After the reaction, 2 times mole of butyl benzoate was added to deactivate the catalyst, and the catalyst was discharged from the bottom of the reaction tank under pressure of nitrogen, cooled in a water tank, and cut with a pelletizer to obtain pellets. The resulting polycarbonate-polyester copolymer resin was numbered P10, and had a weight average molecular weight of 26558.
Example 10
Copolycarbonates prepared according to formula (III) and formula (IV) were synthesized in a molar ratio of 1.
4.36g (0.01 mol) of the compound of the formula (III), 225.72g (0.99 mol) of the compound of the formula (IV), 218.28g (1.02 mol) of diphenyl carbonate and 0.01g (2.5X 10 mol) -4 mol) of NaoH is added into a reactor with a stirring and flowing device, the first stage reaction is heated to 220 ℃ for 30min under normal pressure, the temperature is kept for 1h to melt the NaoH, after the materials are completely melted, stirring is started, the second stage reaction is started, the temperature of the reactor is increased to 320 ℃ within 50min, the pressure of the reactor is slowly reduced to 300pa while the temperature is increased, and then the ester exchange reaction is carried out for 1h under the temperature and the pressure. After the reaction, 2 times mole of butyl benzoate was added to deactivate the catalyst, and the catalyst was discharged from the bottom of the reaction tank under pressure of nitrogen, cooled in a water tank, and cut with a pelletizer to obtain pellets. The polycarbonate-polyester copolymer resin obtained was designated as P10 and had a weight-average molecular weight of 26497.
Comparative example 1
Synthesis of a copolycarbonate prepared according to formula (IV).
228g (1 mol) of a compound of the formula (IV), 218.28g (1.02 mol) of diphenyl carbonate and 0.01g (2.5X 10) -4 mol) of NaoH is added into a reactor with a stirring and flowing device, the first stage reaction is heated to 200 ℃ for 30min under normal pressure, the temperature is kept for 1h to melt the NaoH, after the materials are completely melted, stirring is started, the second stage reaction is started, the temperature of the reactor is increased to 300 ℃ within 50min, the pressure of the reactor is slowly reduced to 150pa while the temperature is increased, and then the ester exchange reaction is carried out for 1h under the temperature and the pressure. After the reaction, 2 times the amount of the catalyst was added to deactivate the catalyst by adding butyl benzoate in an amount of 2 moles, discharged from the bottom of the reaction tank under nitrogen pressure, cooled in a water tank, and cut with a pelletizer to obtain pellets. The polycarbonate-polyester copolymer resin obtained was numbered D1, and had a weight average molecular weight of 21865.
Comparative example 2
Copolycarbonates prepared according to formula (III) and formula (IV) were synthesized in a molar ratio of 30.
A copolycarbonate, no. D2, having a weight average molecular weight of 31425 was synthesized by referring to example 1 except that 130.8g (0.30 mol) of the compound having the structure of the formula (III) and 159.6g (0.70 mol) of the compound having the structure of the formula (IV) were used.
Performance testing
The copolycarbonates were characterized by means of melt index MVR, tensile modulus, elongation at break tests, MVR being measured by a melt index apparatus according to ISO 1133.
Tensile modulus
The tensile modulus and the elongation at break are characterized by a universal tester according to ISO527, and the values before and after soaking in ethyl acetate (23 ℃) are respectively tested after soaking in ethyl acetate for 24 hours at normal temperature, and the retention rate is calculated according to the results.
The test results are shown in table 1 below.
TABLE 1
As shown in Table 1, it can be seen that the melt index of the polycarbonate gradually increases as the proportion of the structural monomer of the formula (I) increases. Meanwhile, polycarbonate has good chemical resistance in view of the retention of tensile modulus and elongation at break. It is noted that the monomer ratio is controlled within a certain range to obtain better flowability and chemical resistance.
Claims (9)
1. A copolycarbonate comprising the structure:
1) Derived from a bisphenol monomer structural unit containing a phthalazinone structure shown in a formula (I),
in the formula R 1 And R 2 Independently represent hydrogen, C1-C10 alkylene or represent a bond only; x represents a single bond, an ether bond or a C1-C5 alkylene group.
2) Derived from a structural unit represented by formula (II):
in the formula, R 3 And R 4 Each independently represents hydrogen, halogen, C1-C10 alkyl; m and n independently represent an integer of 0 to 5; x represents a single bond, an ether bond, a carbonyl group, a C1-C10 alkylene group, a C6-C20 arylene group, a C6-C20 alicyclic group, or a group represented by the formula:
wherein R is 5 And R 6 Each independently represents a C1-C20 alkyl group, a C4-C20 cycloalkyl group or a C4-C20 aryl group; or R 5 And R 6 Together form a C4-C20 alicyclic ring, which C4-C20 alicyclic ring may be optionally substituted with one or more C1-C20 alkyl, C6-C20 aryl, C7-C21 aralkyl, C5-C20 cycloalkyl groups, or combinations thereof.
4. the copolycarbonate according to any one of claims 1 to 3, wherein the molar ratio of the bisphenol monomer structure containing a phthalazinone structure represented by formula (I) to the dihydroxy compound represented by formula (II) is in the range of 1 to 99 to 85, preferably including but not limited to 1:99. 5:95. 10:90. 12:88. 14:86. 15:85.
5. the copolycarbonate according to any one of claims 1 to 4, wherein the copolycarbonate further comprises an additive in a proportion of 0 to 3wt% relative to the total weight of the copolycarbonate, the additive comprising one or more selected from the group consisting of a heat stabilizer, an antioxidant, a flame retardant, a mold release agent, a flow aid, and the like.
6. A method for preparing a copolycarbonate, said method comprising the steps of: the polycarbonate is produced by melt-reacting the formula (I) and the formula (II) by a melt transesterification method in the presence of a basic compound catalyst, a transesterification catalyst or a mixed catalyst composed of both.
7. The preparation process according to claim 6A method, wherein the basic compound catalyst is selected from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, triphenylammonium, diethylamine, and the like, and the transesterification catalyst is selected from one or more of magnesium carbonate, cesium carbonate, sodium hydroxide, sodium bicarbonate, tetramethylammonium hydroxide; the catalyst is used in a molar ratio of 3X 10 to the sum of the dihydroxy compounds -10 ~3×10 -2 Preferably 3X 10 -8 ~3×10 -4 。
8. Use of a copolycarbonate according to any one of claims 1 to 5 or prepared by the method according to any one of claims 6 to 7 in the preparation of a molded part by injection molding, extrusion or blow molding.
9. A shaped part which is obtained by injection molding, extrusion or blow molding from a copolycarbonate according to any one of claims 1 to 5 or a copolycarbonate produced by the production method according to any one of claims 6 to 7.
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