CN113929894A - High-temperature-resistant polycarbonate copolymer and preparation method and application thereof - Google Patents
High-temperature-resistant polycarbonate copolymer and preparation method and application thereof Download PDFInfo
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- CN113929894A CN113929894A CN202111473872.6A CN202111473872A CN113929894A CN 113929894 A CN113929894 A CN 113929894A CN 202111473872 A CN202111473872 A CN 202111473872A CN 113929894 A CN113929894 A CN 113929894A
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- bisphenol
- polycarbonate copolymer
- carbonate oligomer
- type carbonate
- resistant polycarbonate
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 143
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 143
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 claims abstract description 94
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 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 description 131
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 84
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 81
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 39
- -1 bisphenol A alkali metal Chemical class 0.000 claims description 30
- 239000012266 salt solution Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims description 20
- 239000004431 polycarbonate resin Substances 0.000 claims description 20
- 229920005668 polycarbonate resin Polymers 0.000 claims description 20
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 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
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000003063 flame retardant Substances 0.000 claims description 6
- 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 4
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 claims description 4
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 239000006082 mold release agent Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-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
- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 238000011437 continuous method Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000004793 Polystyrene Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 239000003643 water by type Substances 0.000 description 10
- 101100094821 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) SMX2 gene Proteins 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- UXUFTKZYJYGMGO-CMCWBKRRSA-N (2s,3s,4r,5r)-5-[6-amino-2-[2-[4-[3-(2-aminoethylamino)-3-oxopropyl]phenyl]ethylamino]purin-9-yl]-n-ethyl-3,4-dihydroxyoxolane-2-carboxamide Chemical compound O[C@@H]1[C@H](O)[C@@H](C(=O)NCC)O[C@H]1N1C2=NC(NCCC=3C=CC(CCC(=O)NCCN)=CC=3)=NC(N)=C2N=C1 UXUFTKZYJYGMGO-CMCWBKRRSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101100094810 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) SMX3 gene Proteins 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 235000000405 Pinus densiflora Nutrition 0.000 description 1
- 240000008670 Pinus densiflora Species 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 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
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002113 nanodiamond Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Images
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
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/24—General preparatory processes using carbonyl halides and phenols
-
- 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
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
- C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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 provides a high-temperature-resistant polycarbonate copolymer, a preparation method and an application thereof, wherein the high-temperature-resistant polycarbonate copolymer comprises a structural unit shown as a formula I and a structural unit shown as a formula II; by adopting a preparation process of a two-step interface phosgene continuous method and regulating and controlling the sequence structures of the structural units shown in the formula I and the formula II in the molecular chain of the high-temperature-resistant polycarbonate copolymer, the effect of preparing the polycarbonate copolymer with higher heat-resistant grade under the condition of using less bisphenol TMC monomers is realized, the preparation cost of the high-temperature-resistant polycarbonate copolymer is reduced, the impact resistance of the high-temperature-resistant polycarbonate copolymer is improved, and the application field of the high-temperature-resistant polycarbonate copolymer is widened.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-temperature-resistant polycarbonate copolymer, and a preparation method and application thereof.
Background
Polycarbonate (PC) is a high molecular polymer containing a carbonate bond in a molecular chain, and specifically can be classified into aliphatic polycarbonate, alicyclic polycarbonate, aliphatic-aromatic polycarbonate, and aromatic polycarbonate; the aromatic polycarbonate has the advantages of excellent mechanical property, heat resistance, electrical insulation property and light transmission property, low creep resistance and water absorption rate, good dimensional stability, excellent dielectric property and the like, can be used as thermoplastic engineering plastic, and is widely applied to the fields of automobiles, electronic equipment, buildings, office supplies, compact discs, sports equipment, medical care, computers, aerospace and the like at present.
However, the conventional PC has some drawbacks, for example, poor heat resistance and further, it cannot be applied to a place where a temperature requirement is high. Therefore, in order to widen the application field of PC, it is required to modify it.
At present, there are two major types of methods for modifying polycarbonate with heat resistance, the first type is a physical blending method, i.e. adding inorganic filler, such as talc powder, silica, graphene, etc., into a polycarbonate resin substrate to improve the heat resistance of the resin substrate. CN110819092A discloses a high-hardness high-flame-retardant polycarbonate composite material, which comprises the following raw materials in parts by weight: 73-85 parts of polycarbonate, 6-13 parts of acrylonitrile-butadiene-styrene, 3-9 parts of brominated polystyrene, 3-9 parts of polyphenylene sulfide powder, 2-7 parts of molybdenum disulfide, 2-9 parts of montmorillonite, 0.5-2 parts of nano diamond powder, 0.3-2 parts of nano silicon dioxide, 3-8 parts of fly ash floating bead, 0.3-0.8 part of polytetrafluoroethylene, 3-11 parts of composite flame retardant, 0.6-3.5 parts of 9, 9-bis (4-hydroxyphenyl) fluorene and 0.8-2 parts of polysiloxane. The high-hardness and high-flame-retardant polycarbonate composite material provided by the invention has the advantages of high hardness, good wear resistance, excellent heat resistance and excellent flame retardant property. However, the addition of inorganic filler can affect the optical properties of the resin, and the blending mode has a limited improvement range on the heat resistance.
The second type is chemical copolymerization modification, and the heat resistance of the polycarbonate is improved by introducing a comonomer into a molecular chain; CN107207718A discloses a melt transesterification process for the preparation of polycarbonate from diaryl carbonate and cycloalkylene diphenol, said process comprising adding a monohydroxyaryl compound in an amount of 5.0 to 20.0 wt.%, based on the total mass of the reaction mixture, the polycarbonate obtained by the process having high heat resistance; however, the method is disadvantageous to the industrial production and application of polycarbonate due to the high addition of the comonomer, which results in high cost.
Therefore, it is an urgent technical problem in the art to develop a polycarbonate copolymer having low cost and excellent high temperature resistance.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant polycarbonate copolymer, a preparation method and application thereof, wherein the high-temperature-resistant polycarbonate copolymer comprises a structural unit shown as a formula I and a structural unit shown as a formula II, is low in preparation cost and has excellent impact resistance and heat resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a high temperature resistant polycarbonate copolymer comprising structural units represented by formula I and structural units represented by formula ii:
the high-temperature-resistant polycarbonate copolymer provided by the invention comprises a structural unit shown in a formula I and a structural unit shown in a formula II, and has high heat resistance and excellent impact strength; the term "high temperature resistance" in the high temperature resistant polycarbonate copolymer of the present invention means that the Vicat softening point of the obtained polycarbonate copolymer is not less than 160 ℃.
Preferably, the high temperature resistant polycarbonate copolymer comprises the general formula:
wherein m is selected from 3 to 15, such as 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, etc., and n is selected from 2 to 20, such as 4, 6, 8, 10, 12, 14, 16 or 18, etc.
Preferably, m is selected from 5-10.
Preferably, n is selected from 3 to 15.
Preferably, the weight average molecular weight of the high temperature resistant polycarbonate copolymer is 20000 to 50000g/mol, 23000g/mol, 26000g/mol, 29000g/mol, 32000g/mol, 35000g/mol, 38000g/mol, 41000g/mol, 44000g/mol or 47000g/mol, and the like, and more preferably 25000 to 40000 g/mol.
Preferably, the content of the structural unit represented by formula I in the high temperature resistant polycarbonate copolymer is 1 to 99% by mass, for example, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%, and more preferably 20 to 80%.
Preferably, the content of the structural unit represented by the formula II in the high-temperature resistant polycarbonate copolymer is 99 to 1% by mass, for example, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20% or 10%, and more preferably 80 to 20%.
The mass percentage of the structural unit shown in the formula II in the high-temperature resistant polycarbonate copolymer provided by the invention can influence the heat resistance and the impact resistance of the polymer.
In a second aspect, the present invention provides a method for preparing the high temperature resistant polycarbonate copolymer according to the first aspect, the method comprising the steps of:
(1) reacting a bisphenol A monomer with phosgene to obtain a bisphenol A type carbonate oligomer; reacting bisphenol TMC monomer with phosgene to obtain bisphenol TMC type carbonate oligomer;
(2) and (2) reacting the bisphenol A type carbonate oligomer obtained in the step (1), the bisphenol TMC type carbonate oligomer, the end-capping reagent and a catalyst to obtain the high-temperature-resistant polycarbonate copolymer.
According to the invention, through the research on the structure-activity relationship of the bisphenol TMC type copolycarbonate, the heat resistance of the bisphenol TMC type copolycarbonate is gradually enhanced along with the increase of the content of the bisphenol TMC structural unit, namely, the content of the comonomer (bisphenol TMC monomer) is increased, so that the polycarbonate resin with higher temperature resistance grade can be obtained; however, the unit price of the bisphenol TMC monomer is very high, and the increase of the content of the bisphenol TMC monomer leads to high preparation cost and is not beneficial to industrial application.
The preparation method provided by the invention is based on the research on the reactivity of bisphenol TMC monomer, bisphenol A type carbonate oligomer and bisphenol TMC type carbonate oligomer, adopts a two-step interface phosgene continuous method preparation process, firstly, the bisphenol TMC monomer is subjected to homopolymerization to obtain bisphenol TMC type carbonate oligomer, the bisphenol A monomer is subjected to homopolymerization to obtain bisphenol A type carbonate oligomer, and the chain segment lengths of the bisphenol TMC type carbonate oligomer and the bisphenol A type carbonate oligomer are controlled; then carrying out copolymerization reaction on the two to prepare a random block copolymer; the preparation method successfully regulates and controls the sequence structure of the polycarbonate chain segment derived from the bisphenol TMC in the finally obtained polycarbonate copolymer chain segment through a two-step method, achieves the effect of obtaining the polycarbonate copolymer with higher heat-resistant grade by using less bisphenol TMC monomers, reduces the preparation cost of the polycarbonate copolymer, and simultaneously has excellent impact resistance, thereby having wider application prospect.
Preferably, the molar ratio of the bisphenol A monomer and the first phosgene in the step (1) is 1 (1.01-1.3), such as 1:1.02, 1:1.04, 1:1.06, 1:1.08, 1:1.1, 1:1.12, 1:1.14, 1:1.16 or 1:1.18, and the like, and more preferably 1 (1.1-1.2).
Preferably, the weight average molecular weight of the bisphenol A type carbonate oligomer of step (1) is 900 to 3000g/mol, such as 1200g/mol, 1400g/mol, 1600g/mol, 1800g/mol, 2000g/mol, 2200g/mol, 2400g/mol, 2600g/mol or 2800g/mol, more preferably 1200 to 2500 g/mol.
Preferably, the molar ratio of the bisphenol TMC monomer and the phosgene in the step (1) is 1 (1.01-1.3), such as 1:1.02, 1:1.04, 1:1.06, 1:1.08, 1:1.1, 1:1.12, 1:1.14, 1:1.16 or 1:1.18, and the like, and further preferably 1 (1.1-1.2).
Preferably, the weight average molecular weight of the bisphenol TMC type polycarbonate oligomer in the step (1) is 500-4000 g/mol, such as 1000g/mol, 1500g/mol, 2000g/mol, 2500g/mol, 3000g/mol, 3500g/mol or 4000g/mol, and the like, and more preferably 1500-3500 g/mol.
Preferably, the reaction of the bisphenol a monomer and phosgene in the step (1) specifically comprises: and reacting the bisphenol A alkali metal salt solution with phosgene in an organic solvent to obtain the bisphenol A type carbonate oligomer.
Preferably, the bisphenol a alkali metal salt solution is obtained by mixing bisphenol a and an aqueous solution of an alkali metal hydroxide.
The mass of the bisphenol A is preferably 150 to 200g, for example 155g, 160g, 165g, 170g, 175g, 180g, 185g, 190g, 195g, etc., more preferably 160 to 170g, based on 1L of the bisphenol A alkali metal salt solution.
Preferably, the reaction of the bisphenol TMC monomer and the phosgene in the step (1) specifically comprises the following steps: reacting bisphenol TMC alkali metal salt solution with phosgene in an organic solvent to obtain the bisphenol TMC type carbonate oligomer.
Preferably, the bisphenol TMC alkali metal salt solution is obtained by mixing bisphenol TMC and an aqueous solution of an alkali metal hydroxide.
Preferably, the mass of the bisphenol TMC is 100-500 g, for example 150g, 200g, 250g, 300g, 350g, 400g or 450g, and more preferably 200-250 g, based on 1L of the bisphenol TMC alkali metal salt solution.
The pH values of the bisphenol A alkali metal salt solution and the bisphenol TMC alkali metal salt solution are preferably 11 to 13, such as 11.2, 11.4, 11.6, 11.8, 12, 12.2, 12.4, 12.6 or 12.8, and more preferably 12 to 12.8.
Preferably, the alkali metal hydroxide comprises any one of potassium hydroxide, lithium hydroxide or cesium hydroxide or a combination of at least two thereof, and further preferably sodium hydroxide.
Preferably, the organic solvent comprises any one or a combination of at least two of dichloromethane, trichloromethane, dichloroethane or trichloroethane, and further preferably dichloromethane.
Preferably, the solid content of the bisphenol A type carbonate oligomer and the bisphenol TMC type polycarbonate oligomer in the step (1) is 5-15% independently, such as 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18% or 19%, and the like, and more preferably 6-10%.
Preferably, the end-capping agent in step (2) comprises any one or a combination of at least two of phenol, p-cumylphenol, p-methylphenol, p-isopropylphenol, p-tert-butylphenol or p-cyanophenol, and is further preferably p-tert-butylphenol and/or p-cumylphenol.
Preferably, the molar ratio of the end-capping agent to the sum of the bisphenol a monomer and the bisphenol TMC monomer in the step (2) is (20-50): 1, for example, 23:1, 26:1, 29:1, 32:1, 35:1, 38:1, 41:1, 44:1 or 47:1, and more preferably (25-40): 1.
Preferably, the catalyst in step (2) comprises any one or a combination of at least two of triethylamine, tetrabutylammonium bromide or tetrabutylammonium chloride, and further preferably triethylamine.
Preferably, the molar ratio of the catalyst in the step (2) to the sum of the bisphenol A monomer and the bisphenol TMC monomer in the step (1) is 1 (100-1000), such as 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, or 1:900, and more preferably 1 (200-500).
Preferably, the reaction in step (2) specifically comprises the following steps:
(2a) mixing the bisphenol A type polycarbonate oligomer obtained in the step (1) with an inert organic solvent to obtain a bisphenol A type polycarbonate oligomer solution; mixing the bisphenol TMC type carbonate oligomer obtained in the step (1) with an organic solvent to obtain a bisphenol TMC type carbonate oligomer solution;
(2b) reacting the bisphenol A type carbonate oligomer solution obtained in the step (2a) with a bisphenol TMC type carbonate oligomer solution to obtain an initial product;
(2c) reacting the initial product obtained in the step (2b), a catalyst solution and an end-capping reagent solution to obtain the high-temperature-resistant polycarbonate copolymer;
preferably, the solid contents of the bisphenol A type carbonate oligomer solution and the bisphenol TMC type polycarbonate oligomer solution in the step (2a) are respectively 1-15%, such as 2%, 4%, 6%, 8%, 10%, 12%, 14% or the like, and more preferably 6-10%.
Preferably, the reaction time in step (2b) is 10-30 min, such as 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min or 28min, and more preferably 10-20 min.
Preferably, the content of the end-capping reagent in the end-capping reagent solution in the step (2c) is 10 to 20% by mass, for example, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26% or 28%, and more preferably 10 to 15%.
Preferably, the mass percentage of the catalyst in the catalyst solution in the step (2c) is 1-10%, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%, and more preferably 2-5%.
Preferably, the reaction time in the step (2c) is 30-90 min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min or 85min, and the like, and more preferably 30-60 min.
Preferably, the method further comprises a post-treatment step after the reaction in the step (2) is finished.
Preferably, the post-treatment comprises the steps of oil-water separation, washing and solvent removal.
Preferably, the washing includes the steps of alkaline washing, acid washing and multiple water washing.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1a) mixing bisphenol A and an aqueous solution of alkali metal hydroxide to obtain a bisphenol A alkali metal salt solution with the pH value of 11-13; mixing bisphenol TMC and an aqueous solution of alkali metal hydroxide to obtain a bisphenol TMC alkali metal salt solution with the pH value of 11-13;
(1b) reacting the bisphenol A alkali metal salt solution obtained in the step (1a) with phosgene in an organic solvent to obtain a bisphenol A type carbonate oligomer with the solid content of 5-15% and the weight average molecular weight of 900-3000 g/mol; reacting the bisphenol TMC alkali metal salt solution obtained in the step (1) with phosgene in an organic solvent to obtain a bisphenol TMC type carbonate oligomer with the solid content of 5-15% and the weight-average molecular weight of 500-4000 g/mol;
(2a) mixing the bisphenol A type carbonate oligomer obtained in the step (1b) with an organic solvent to obtain a bisphenol A type carbonate oligomer solution with a solid content of 1-15%; mixing the bisphenol TMC type carbonate oligomer obtained in the step (2) with an organic solvent for 10-30 min to obtain a bisphenol TMC type carbonate oligomer solution with the solid content of 1-15%;
(2b) reacting the bisphenol A type carbonate oligomer solution obtained in the step (2a) with a bisphenol TMC type carbonate oligomer solution for 10-30 min to obtain an initial product;
(2c) and (3) reacting the initial product obtained in the step (2b), a catalyst solution and an end-capping reagent solution for 30-90 min, performing oil-water separation, taking oil, sequentially performing alkali washing, acid washing and multiple water washing, and removing a solvent to obtain the high-temperature-resistant polycarbonate copolymer.
In a third aspect, the present invention provides a polycarbonate resin composition comprising the high temperature resistant polycarbonate copolymer according to the first aspect in combination with another aromatic polycarbonate.
The term "other aromatic polycarbonates" as used herein means polycarbonates which do not contain structural units derived from bisphenol TMC.
Preferably, the content of the high temperature resistant polycarbonate copolymer in the polycarbonate resin composition is 5 to 100% by mass and is not equal to 100%, for example, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%.
Preferably, the other aromatic polycarbonate includes bisphenol a type homopolycarbonate.
Preferably, the polycarbonate resin composition further comprises an additive.
Preferably, the content of the additive in the polycarbonate resin composition is 0-5% and not equal to 0%, such as 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, or 4.5%.
Preferably, the additive comprises any one of a mold release agent, a flow aid, a heat stabilizer, an antioxidant, a UV absorber, an IR absorber, a flame retardant, an antistatic agent, or a dye, or a combination of at least two thereof.
Compared with the prior art, the invention has the following beneficial effects:
(1) the high-temperature-resistant polycarbonate copolymer provided by the invention comprises a structural unit shown in a formula I and a structural unit shown in a formula II, and has excellent impact resistance and heat resistance.
(2) The high-temperature resistant polycarbonate copolymer provided by the invention adopts a preparation process of a two-step interface phosgene continuous method, and the reaction activity between two monomers is regulated and controlled by controlling the chain lengths of a bisphenol A type carbonate oligomer and a bisphenol TMC type carbonate oligomer in the reaction process, so that the reaction in the copolycondensation stage is mainly controlled by diffusion, the sequence structure in the chain segment of the high-temperature resistant polycarbonate copolymer is regulated and controlled, and the random block copolymer is obtained; and the effect of using less bisphenol TMC monomers to obtain copolycarbonate with higher heat-resistant grade and better impact resistance is realized, the preparation cost is lower, and the method is more suitable for industrial production and application.
(3) The polycarbonate resin composition containing the high-temperature-resistant polycarbonate copolymer provided by the invention also has excellent temperature resistance and impact resistance, and specifically, the polycarbonate resin composition provided by the invention has the notch impact strength (23 ℃) of 650-810J/m, the Vicat softening point of 140-195 ℃, the light transmittance of 89-91 and the haze of 0.88-1.02; the method has potential application value in the fields of car lamps, medical appliances, consumer electronics, solar photovoltaic panels and the like.
Drawings
FIG. 1 is a flow chart of the preparation of the high temperature resistant polycarbonate copolymer provided in example 1
FIG. 2 is a 1H-NMR spectrum of the high temperature resistant polycarbonate copolymer provided in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The bisphenol TMC monomers in the embodiment provided by the invention are all purchased from Japanese pine, and the purity is 99.9%; bisphenol a monomers were purchased from mitsubishi chemical with a purity of 99.5%.
Example 1
A high temperature resistant polycarbonate copolymer, the high temperature resistant polycarbonate copolymer is composed of a structural unit shown as a formula I and a structural unit shown as a formula II:
the preparation method of the high temperature resistant polycarbonate copolymer provided in this example includes the following steps, and its preparation flow chart is shown in fig. 1:
(1) mixing 4566g of bisphenol A (BPA) and an aqueous solution of sodium hydroxide with the mass percentage of 32% in a D1 container to obtain a BPA sodium salt solution with the concentration of 170 g/L; 3058g of bisphenol TMC (BPTMC) and an aqueous solution of 32 mass percent of sodium hydroxide are mixed in a D2 container to obtain a BPTMC sodium salt solution with the concentration of 165 g/L; mixing triethylamine and dichloromethane in a D9 container to obtain a dichloromethane solution of triethylamine with the mass percentage of 5%; in a D10 container, 131g of tert-butyl phenol (PTBP) and dichloromethane are mixed to obtain a dichloromethane solution of PTBP with the mass percentage of 11%;
(2) continuously introducing the BPA sodium salt solution obtained in the step (1), 2277g of phosgene in a container D3 and dichloromethane in a container D5 into a container SMX1 for reaction, ensuring that the excess phosgene rate in the container SMX1 is 15%, and maintaining the pH of a reaction solution at 12-12.5 to obtain a bisphenol A type carbonate oligomer; continuously introducing the bisphenol TMC sodium salt solution obtained in the step (1), 1122g of phosgene in a container D4 and dichloromethane in a container D6 into a container SMX2 for reaction, keeping the excess phosgene rate in the container SMX2 at 15%, and maintaining the pH of the reaction liquid at 12-12.5 to obtain bisphenol TMC type carbonate oligomer;
(3) continuously introducing the bisphenol A type carbonate oligomer obtained in the step (2) and dichloromethane in a container D7 into a container R1 at 30 ℃ for mixing, so that the solid content of the bisphenol A type carbonate oligomer in the container R1 is 10%; continuously introducing the bisphenol TMC type carbonate oligomer obtained in the step (2) and dichloromethane into a container R2 at 25 ℃ for mixing, so that the solid content of the bisphenol TMC type carbonate oligomer in the container R2 is 10%;
(4) introducing the bisphenol A type carbonate oligomer and the bisphenol TMC type carbonate oligomer obtained in the step (3) into a container SMX3 for reaction for 20min to obtain an initial product;
(5) and (3) introducing the initial product obtained in the step (4), the dichloromethane solution of triethylamine (the adding amount of triethylamine is 0.4 percent of the total weight of the finally obtained polymer) obtained in the step (1) and the dichloromethane solution of PTBP into a container R3 to react for 40min, purifying and removing the organic solvent to obtain the high-temperature resistant polycarbonate copolymer.
The molecular weights of the bisphenol A type carbonate oligomer, the bisphenol TMC type carbonate oligomer and the high temperature resistant polycarbonate copolymer obtained in the step (5) obtained in the present example were respectively 1800g/mol, 2000g/mol and 33900g/mol, as measured by a Gel Permeation Chromatograph (GPC) (model No. Waters 1515, solvent tetrahydrofuran, PS as a standard, temperature 30 ℃ and time 45 min); a nuclear magnetic resonance spectrometer (model is AV III HD400MHz of Burker company) is used for testing the high-temperature resistant polycarbonate copolymer obtained in the step (5), a 1H-NMR spectrum of the high-temperature resistant polycarbonate copolymer provided by the embodiment is shown in FIG. 2, as can be seen from FIG. 2, a peak at the position where delta is 1.00ppm is an absorption peak of methyl in a structural unit shown in formula I, and a peak at the position where delta is 1.68ppm is an absorption peak of methyl on a structural unit shown in formula II, and by combining a GPC test result and a Nuclear Magnetic Resonance (NMR) test result, the embodiment proves that the polycarbonate copolymer composed of the structural unit shown in formula I and the structural unit shown in formula II is successfully synthesized; and the molar ratio of the structural unit shown in the formula II in the high-temperature resistant polycarbonate copolymer is 33 percent calculated according to A (delta 1.68)/[ A (delta 1.68) + A (delta 1.0) ]. times.100 percent, wherein A is the integral area.
Example 2
A high temperature-resistant polycarbonate copolymer which differs from example 1 in that, in the production process, the mass of BPTMC in the D2 container of step (1) is 690g, and the mass of PTBP in the D10 container is 91 g; the mass of phosgene in the D4 vessel of step (2) was 253g, and the other compositions, conditions and steps were the same as those of example 1.
The molecular weights of the bisphenol A type carbonate oligomer, the bisphenol TMC type carbonate oligomer and the finally obtained high temperature resistant polycarbonate copolymer obtained in the preparation process of the present example were respectively 1500g/mol, 1600g/mol and 33200g/mol, as measured by a Gel Permeation Chromatograph (GPC) (model No. Waters 1515, solvent tetrahydrofuran, PS as a standard, temperature 30 ℃, time 45 min); and the molar percentage of the repeating unit shown in the formula II in the high-temperature resistant polycarbonate copolymer finally obtained in the embodiment is 10% by adopting a nuclear magnetic resonance spectrometer (model is AV III HD400MHz of Burker company).
Example 3
A high temperature-resistant polycarbonate copolymer which is different from example 1 in that, in the production process, the mass of BPTMC in the D2 container of step (1) is 8230g, and the mass of PTBP in the D10 container is 218 g; the mass of phosgene in the D4 vessel in step (2) was 3018g, and the other compositions, conditions and steps were the same as in example 1.
The molecular weights of the bisphenol A type carbonate oligomer, the bisphenol TMC type carbonate oligomer and the finally obtained high temperature resistant polycarbonate copolymer obtained in the preparation process of the present example were respectively 2000g/mol, 3300g/mol and 33800g/mol, as measured by a Gel Permeation Chromatograph (GPC) (model No. Waters 1515, solvent tetrahydrofuran, PS as a standard, temperature 30 ℃, time 45 min); and the molar percentage of the repeating unit shown in the formula II in the high-temperature resistant polycarbonate copolymer finally obtained in the embodiment is 57% by adopting a nuclear magnetic resonance spectrometer (model is AV III HD400MHz of Burker company).
Example 4
A high temperature-resistant polycarbonate copolymer which is different from example 1 in that, in the production process, the mass of BPTMC in the D2 container of step (1) is 540g, and the mass of PTBP in the D10 container is 89 g; the mass of phosgene in the D4 vessel of step (2) was 198g, and the other compositions, conditions and steps were the same as in example 1.
The molecular weights of the bisphenol A type carbonate oligomer, the bisphenol TMC type carbonate oligomer and the finally obtained high temperature resistant polycarbonate copolymer obtained in the preparation process of the present example were 1900g/mol, 1100g/mol and 33000g/mol, respectively, as measured by a Gel Permeation Chromatograph (GPC) (model No. Waters 1515, solvent tetrahydrofuran, PS as a standard, temperature 30 ℃ C., time 45 min); and the molar percentage of the repeating unit shown in the formula II in the high-temperature resistant polycarbonate copolymer finally obtained in the embodiment is 8% by adopting a nuclear magnetic resonance spectrometer (model is AV III HD400MHz of Burker company).
Example 5
A high temperature resistant polycarbonate copolymer, the high temperature resistant polycarbonate copolymer is composed of a structural unit shown as a formula I and a structural unit shown as a formula II:
the preparation method of the high temperature resistant polycarbonate copolymer provided in this example includes the following steps, and its preparation flow chart is shown in fig. 1:
(1) mixing 4566g of bisphenol A (BPA) and an aqueous solution of sodium hydroxide with the mass percentage of 32% in a D1 container to obtain a BPA sodium salt solution with the concentration of 170 g/L; 2415g of bisphenol TMC (BPTMC) and an aqueous solution of 32 mass percent of sodium hydroxide are mixed in a D2 container to obtain a BPTMC sodium salt solution with the concentration of 165 g/L; mixing triethylamine and dichloromethane in a D9 container to obtain a dichloromethane solution of triethylamine with the mass percentage of 5%; in a D10 container, 120g of tert-butyl phenol (PTBP) and dichloromethane are mixed to obtain a dichloromethane solution of PTBP with the mass percentage of 11%;
(2) continuously introducing the BPA sodium salt solution obtained in the step (1), 2277g of phosgene in a container D3 and dichloromethane in a container D5 into a container SMX1 for reaction, ensuring that the excess phosgene rate in the container SMX1 is 15%, and maintaining the pH of a reaction solution at 12-12.5 to obtain a bisphenol A type carbonate oligomer; continuously introducing the bisphenol TMC sodium salt solution obtained in the step (1), 886g of phosgene in a container D4 and dichloromethane in a container D6 into a container SMX2 for reaction, keeping the excess phosgene rate in the container SMX2 at 15%, and maintaining the pH of the reaction liquid at 12-12.5 to obtain a bisphenol TMC type carbonate oligomer;
(3) continuously introducing the bisphenol A type carbonate oligomer obtained in the step (2) and dichloromethane in a container D7 into a container R1 at 30 ℃ for mixing, so that the solid content of the bisphenol A type carbonate oligomer in the container R1 is 10%; continuously introducing the bisphenol TMC type carbonate oligomer obtained in the step (2) and dichloromethane into a container R2 at 25 ℃ for mixing, so that the solid content of the bisphenol TMC type carbonate oligomer in the container R2 is 10%;
(4) introducing the bisphenol A type carbonate oligomer and the bisphenol TMC type carbonate oligomer obtained in the step (3) into a container SMX3 for reaction for 20min to obtain an initial product;
(5) and (3) introducing the initial product obtained in the step (4), the dichloromethane solution of triethylamine (the adding amount of triethylamine is 0.4 percent of the total weight of the finally obtained polymer) obtained in the step (1) and the dichloromethane solution of PTBP into a container R3 to react for 40min, purifying and removing the organic solvent to obtain the high-temperature resistant polycarbonate copolymer.
The molecular weights of the bisphenol A type carbonate oligomer, the bisphenol TMC type carbonate oligomer and the finally obtained high temperature resistant polycarbonate copolymer obtained in step (2) of this example were 3100g/mol, 1800g/mol and 32900g/mol, respectively, as measured by a Gel Permeation Chromatograph (GPC) (model No. Waters 1515, solvent tetrahydrofuran, PS as a standard, temperature 30 ℃ C., time 45 min); and the molar percentage of the repeating unit shown in formula II in the high temperature resistant polycarbonate copolymer finally obtained in this example was 28% as measured by a nuclear magnetic resonance spectrometer (model number: AV III HD400MHz of Burker Co.).
Example 6
A high temperature-resistant polycarbonate copolymer which differs from example 1 in that, in the production process, the mass of BPTMC in the D2 container of step (1) is 6209g, and the mass of PTBP in the D10 container is 184 g; the mass of phosgene in the D4 vessel of step (2) was 2277g, and the other compositions, conditions and steps were the same as in example 1.
The molecular weights of the bisphenol A type carbonate oligomer, the bisphenol TMC type carbonate oligomer and the finally obtained high temperature resistant polycarbonate copolymer obtained in the preparation process of the present example were 3600g/mol, 2400g/mol and 33700g/mol, respectively, as measured by a Gel Permeation Chromatograph (GPC) (model No. Waters 1515, solvent tetrahydrofuran, PS as a standard, temperature 30 ℃, time 45 min); and the molar percentage of the repeating unit shown in the formula II in the high-temperature resistant polycarbonate copolymer finally obtained in the embodiment is 50% by adopting a nuclear magnetic resonance spectrometer (model is AV III HD400MHz of Burker company).
Example 7
A high-temperature resistant polycarbonate copolymer which is different from example 5 in that in the production process, the mass of PTBP in the D10 vessel of step (1) was 189g, and the other compositions, conditions and steps were the same as those of example 1.
The molecular weights of the bisphenol A type carbonate oligomer, the bisphenol TMC type carbonate oligomer and the finally obtained high temperature resistant polycarbonate copolymer obtained in the preparation process of the present example were 2500g/mol, 1900g/mol and 212000 g/mol respectively, as measured by a Gel Permeation Chromatograph (GPC) (model No. Waters 1515, solvent tetrahydrofuran, PS as a standard, temperature 30 ℃, time 45 min); and the molar percentage of the repeating unit shown in the formula II in the high-temperature resistant polycarbonate copolymer finally obtained in the embodiment is 28% by testing with a nuclear magnetic resonance spectrometer (model: AV III HD400MHz of Burker).
Example 8
A high-temperature resistant polycarbonate copolymer which is different from example 5 in that in the production process, the mass of PTBP in the D10 vessel of step (1) was 80g, and the other compositions, conditions and steps were the same as those of example 1.
The molecular weights of the bisphenol A type carbonate oligomer, the bisphenol TMC type carbonate oligomer and the finally obtained high temperature resistant polycarbonate copolymer obtained in the preparation process of the present example were respectively 1800g/mol, 1800g/mol and 49500g/mol, as measured by a Gel Permeation Chromatograph (GPC) (model No. Waters 1515, solvent tetrahydrofuran, PS as a standard, temperature 30 ℃, time 45 min); and the molar percentage of the repeating unit shown in the formula II in the high-temperature resistant polycarbonate copolymer finally obtained in the embodiment is 28% by testing with a nuclear magnetic resonance spectrometer (model: AV III HD400MHz of Burker).
Example 9
A high-temperature resistant polycarbonate copolymer which is different from example 5 in that in the production process, the solids content of the bisphenol A type carbonate oligomer in the vessel R1 of the step (3) is 8%, the solids content of the bisphenol TMC type carbonate oligomer in the vessel R2 is 8%, and the other composition, conditions and steps are the same as those of example 1.
The molecular weights of the bisphenol A type carbonate oligomer, the bisphenol TMC type carbonate oligomer and the finally obtained high temperature resistant polycarbonate copolymer obtained in the preparation process of the present example were 2100g/mol, 1700g/mol and 33400g/mol, respectively, as measured by a Gel Permeation Chromatograph (GPC) (model No. Waters 1515, solvent tetrahydrofuran, PS as a standard, temperature 30 ℃, time 45 min); and the molar percentage of the repeating unit shown in the formula II in the high-temperature resistant polycarbonate copolymer finally obtained in the embodiment is 28% by testing with a nuclear magnetic resonance spectrometer (model: AV III HD400MHz of Burker).
Example 10
A high-temperature resistant polycarbonate copolymer which is different from example 5 in that in the production process, the content of solids of bisphenol A type carbonate oligomer in the vessel R1 in the step (3) was 12%, the content of solids of bisphenol TMC type carbonate oligomer in the vessel R2 was 12%, and the other composition, conditions and steps were the same as those in example 1.
The molecular weights of the bisphenol A type carbonate oligomer, the bisphenol TMC type carbonate oligomer and the finally obtained high temperature resistant polycarbonate copolymer obtained in the preparation process of the present example were respectively 1300g/mol, 1900g/mol and 33100g/mol, as measured by a Gel Permeation Chromatograph (GPC) (model No. Waters 1515, solvent tetrahydrofuran, PS as a standard, temperature 30 ℃, time 45 min); and the molar percentage of the repeating unit shown in the formula II in the high-temperature resistant polycarbonate copolymer finally obtained in the embodiment is 28% by testing with a nuclear magnetic resonance spectrometer (model: AV III HD400MHz of Burker).
Comparative example 1
A polycarbonate copolymer, commercially available as APEC 1695.
Comparative example 2
One polycarbonate copolymer is commercially available product APEC 1803.
Comparative example 3
One polycarbonate copolymer, commercially available as APEC 2097.
Comparative example 4
A polycarbonate copolymer, which is prepared by a method comprising the steps of:
(1) adding 4566g of bisphenol A (BPA), 3058g of bisphenol TMC (BPTMC), 2793g of sodium hydroxide, 131g of p-tert-butylphenol and 7200g of water into a mixer protected by nitrogen, uniformly mixing, and forming a sodium phenolate brine phase after completely dissolving; in another mixer 3399g of liquid phosgene and 77096g of Methylene Chloride (MC) were added and mixed well;
(2) and (2) putting the sodium phenolate aqueous phase obtained in the step (1) into a polymerization reactor, adding the prepared phosgene solution into the polymerization reactor at a stirring speed of 550rpm, simultaneously dropwise adding a sodium hydroxide aqueous solution with a mass concentration of 32% into the reaction system to keep the pH of the reaction system at 11.4, adding a dichloromethane solution of triethylamine, keeping the temperature of the reaction system at 35 ℃, and after reacting for 2 hours, separating and purifying the reaction system and removing the organic solvent to obtain the polycarbonate copolymer.
Application example 1
A polycarbonate resin composition, which is prepared by a method comprising: will 1000g of high temperature polycarbonate copolymer (example 1), 2277g of Clarnate
General purpose PC resin, 2277g of Clarnate
General purpose PC resin, 6g of antioxidant (Irgafos 168 available from Ciba-Geigy) and 9g of mold release agent (Glycolube)RP-ETS, available from Lonza)) was extruded at 300 ℃ using a coblon CTE35 type extruder, pelletized, and injection molded to obtain the polycarbonate resin composition.
Application examples 2 to 10
A polycarbonate resin composition is different from application example 1 only in that the high-temperature resistant polycarbonate copolymer obtained in examples 2 to 10 is used instead of the high-temperature resistant polycarbonate copolymer obtained in example 1, and other components, use amounts and preparation methods are the same as those of application example 1.
Comparative application examples 1 to 4
A polycarbonate resin composition is different from application example 1 only in that polycarbonate copolymers obtained in comparative examples 1-4 are respectively used to replace the high-temperature resistant polycarbonate copolymer obtained in example 1, and other components, the use amounts and the preparation method are the same as those of application example 1.
And (3) performance testing:
(1) BPTMC ratio: the 1H-NMR of the copolymer was measured by nuclear magnetic resonance measurement, and the absorption peak of methyl group in the BPTMC segment was measured at δ of 1.68ppm, and the molar ratio of the BPTMC, a (δ 1.68)/[ a (δ 1.68) + a (δ 1.0) ] × 100%, where a is the integral area, was calculated to obtain the molar ratio of the structural unit represented by formula ii in the finally obtained polycarbonate copolymer;
(2) vicat softening point: the test was carried out at 50N and 120 ℃ using the ISO 306 standard;
(3) notched impact strength: the determination is carried out according to the Izod impact property detection standard of plastics specified in ASTM D256-1997;
(4) light transmittance and haze: testing was performed according to the test standard provided in ASTM D1003.
The polycarbonate copolymers provided in examples 1 to 10 and comparative examples 1 to 4 were tested according to the above-mentioned test methods (1) to (3), and the test results are shown in Table 1:
TABLE 1
As can be seen from the data in table 1: the high-temperature resistant polycarbonate copolymer provided by the invention can enable the obtained polycarbonate copolymer to achieve higher heat resistance grade under the condition of using less bisphenol TMC monomers, and has higher notch impact strength.
Specifically, the commercially available product APEC1695 (comparative example 1) had a content of BPTMC of 10% and a Vicat softening point of only 159 ℃ which was lower than not only the polycarbonate copolymer obtained in inventive example 2 (the content of BPTMC was 10% and the Vicat softening point was 170 ℃) but also the polycarbonate copolymer obtained in inventive example 6 (the content of BPTMC was only 8% but the Vicat softening point was as high as 161 ℃); and the notched impact strength of the polycarbonate obtained in comparative example 1 was only 500J/m, which is much lower than that of the polycarbonate copolymer provided by the present invention.
Further comparison of example 3 with comparative example 3 revealed that, in the case where the BPTMC ratio was the same (both 57%), the polycarbonate copolymer provided in example 3 of the present invention had a Vicat softening point as high as 213 ℃ and a notched impact strength of 560J/m; whereas the commercial product APEC2097 provided in comparative example 3 has a Vicat softening point of only 200 ℃ lower than that of example 3, and the commercial product APEC2097 provided in comparative example 3 has a notched impact strength of only 400J/m, much lower than that of example 3.
And comparing example 1 with comparative example 4, it can be seen that, under the condition that the proportion of BPTMC is the same (both 33%), the polycarbonate resin prepared by the preparation method provided by the invention has better Vicat softening point, better heat resistance and higher notch impact strength.
The polycarbonate resin compositions provided in the application examples 1 to 10 and comparative application examples 1 to 4 were tested according to the above test methods (2) to (4), and the test results are shown in table 2:
TABLE 2
As can be seen from the data of Table 2, the polycarbonate resin composition comprising the high temperature resistant polycarbonate copolymer provided by the present invention has excellent impact resistance and higher temperature resistance;
specifically, the polycarbonate compositions obtained in application examples 1 to 10 have a notched impact strength (23 ℃) of 650 to 810J/m, a Vicat softening point of 140 to 195 ℃, a light transmittance of 89 to 91, and a haze of 0.88 to 1.02.
The applicant states that the above description is only a specific embodiment of the high temperature resistant polycarbonate copolymer and the preparation method thereof, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A high temperature resistant polycarbonate copolymer, wherein the high temperature resistant polycarbonate copolymer comprises structural units represented by formula I and structural units represented by formula II:
2. the high temperature resistant polycarbonate copolymer of claim 1, wherein the high temperature resistant polycarbonate copolymer comprises the general formula:
wherein m is 3-15, and n is 2-20;
preferably, m is selected from 5-10;
preferably, n is selected from 3-15;
preferably, the weight-average molecular weight of the high-temperature resistant polycarbonate copolymer is 20000-50000 g/mol, preferably 25000-40000 g/mol;
preferably, the mass percentage content of the structural unit shown in the formula I in the high-temperature resistant polycarbonate copolymer is 1-99%, and further preferably 20-80%;
preferably, the mass percentage content of the structural unit shown in the formula II in the high-temperature resistant polycarbonate copolymer is 99-1%, and more preferably 80-20%.
3. A method for preparing the high temperature resistant polycarbonate copolymer of claim 1 or 2, comprising the steps of:
(1) reacting a bisphenol A monomer with phosgene to obtain a bisphenol A type carbonate oligomer; reacting bisphenol TMC monomer with phosgene to obtain bisphenol TMC type carbonate oligomer;
(2) and (2) reacting the bisphenol A type carbonate oligomer obtained in the step (1), the bisphenol TMC type carbonate oligomer, a catalyst and an end-capping reagent to obtain the high-temperature-resistant polycarbonate copolymer.
4. The preparation method according to claim 3, wherein the molar ratio of the bisphenol A monomer and the phosgene in the step (1) is 1 (1.01-1.3), preferably 1 (1.1-1.2);
preferably, the weight average molecular weight of the bisphenol A type carbonate oligomer in the step (1) is 900-3000 g/mol, and more preferably 1200-2500 g/mol;
preferably, the molar ratio of the bisphenol TMC monomer and the phosgene in the step (1) is 1 (1.01-1.3), and more preferably 1 (1.1-1.2);
preferably, the weight average molecular weight of the bisphenol TMC type carbonate oligomer in the step (1) is 500-4000 g/mol, and more preferably 1500-3500 g/mol.
5. The method according to claim 3 or 4, wherein the step (1) of reacting the bisphenol A monomer with phosgene specifically comprises: reacting bisphenol A alkali metal salt solution with phosgene in an organic solvent to obtain bisphenol A type carbonate oligomer;
preferably, the bisphenol a alkali metal salt solution is obtained by mixing bisphenol a and an aqueous solution of an alkali metal hydroxide;
preferably, the mass of the bisphenol A is 150-200 g, more preferably 160-170 g, based on 1L of the bisphenol A alkali metal salt solution;
preferably, the reaction of the bisphenol TMC monomer and the phosgene in the step (1) specifically comprises the following steps: reacting bisphenol TMC alkali metal salt solution with phosgene in an organic solvent to obtain bisphenol TMC type carbonate oligomer;
preferably, the bisphenol TMC alkali metal salt solution is obtained by mixing bisphenol TMC and an aqueous solution of an alkali metal hydroxide;
preferably, the mass of the bisphenol TMC is 100-500 g, and more preferably 200-250 g, calculated by 1L of the bisphenol TMC alkali metal salt solution;
preferably, the pH values of the bisphenol A alkali metal salt solution and the bisphenol TMC alkali metal salt solution are respectively and independently 11-13, and further preferably 12-12.8;
preferably, the alkali metal hydroxide comprises any one or a combination of at least two of potassium hydroxide, lithium hydroxide or cesium hydroxide, further preferably sodium hydroxide;
preferably, the organic solvent comprises any one or a combination of at least two of dichloromethane, trichloromethane, dichloroethane or trichloroethane, and is further preferably dichloromethane;
preferably, the solid contents of the bisphenol A type carbonate oligomer and the bisphenol TMC type polycarbonate oligomer in the step (1) are respectively 5-15% independently, and more preferably 6-10%.
6. The production method according to any one of claims 3 to 5, wherein the end-capping agent in step (2) comprises any one or a combination of at least two of phenol, p-cumylphenol, p-methylphenol, p-isopropylphenol, p-tert-butylphenol, or p-cyanophenol, preferably p-tert-butylphenol and/or p-cumylphenol;
preferably, the molar ratio of the end-capping agent in the step (2) to the sum of the bisphenol A monomer and the bisphenol TMC monomer in the step (1) is (20-50): 1, and more preferably (25-40): 1;
preferably, the catalyst in step (2) comprises any one or a combination of at least two of triethylamine, tetrabutylammonium bromide or tetrabutylammonium chloride, and further preferably triethylamine;
preferably, the molar ratio of the catalyst in the step (2) to the sum of the bisphenol A monomer and the bisphenol TMC monomer in the step (1) is 1 (100-1000), and more preferably 1 (200-500);
preferably, the reaction in step (2) specifically comprises the following steps:
(2a) mixing the bisphenol A type polycarbonate oligomer obtained in the step (1) with an organic solvent to obtain a bisphenol A type polycarbonate oligomer solution; mixing the bisphenol TMC type carbonate oligomer obtained in the step (1) with an organic solvent to obtain a bisphenol TMC type carbonate oligomer solution;
(2b) reacting the bisphenol A type carbonate oligomer solution obtained in the step (2a) with a bisphenol TMC type carbonate oligomer solution to obtain an initial product;
(2c) reacting the initial product obtained in the step (2b), a catalyst solution and an end-capping reagent solution to obtain the high-temperature-resistant polycarbonate copolymer;
preferably, the solid contents of the bisphenol A type carbonate oligomer solution and the bisphenol TMC type carbonate oligomer solution in the step (2a) are respectively 1-15% and more preferably 6-10%;
preferably, the reaction time in the step (2b) is 10-30 min, and more preferably 10-20 min;
preferably, the mass percentage of the end-capping reagent in the end-capping reagent solution in the step (2c) is 10-20%, and more preferably 10-15%;
preferably, the mass percentage of the catalyst in the catalyst solution in the step (2c) is 1-10%, and more preferably 2-5%;
preferably, the reaction time in the step (2c) is 30-90 min, and more preferably 30-60 min.
7. The preparation method according to any one of claims 3 to 6, characterized by further comprising a post-treatment step after the reaction in step (2);
preferably, the post-treatment comprises the steps of oil-water separation, washing and solvent removal;
preferably, the washing comprises the steps of alkaline washing, acid washing and multiple water washing.
8. A polycarbonate resin composition comprising the high temperature resistant polycarbonate copolymer according to claim 1 or 2 in combination with another aromatic polycarbonate.
9. The polycarbonate resin composition according to claim 8, wherein the polycarbonate resin composition comprises 5 to 100% by mass of the high temperature resistant polycarbonate copolymer and is not equal to 100%;
preferably, the other aromatic polycarbonate includes bisphenol a type homopolycarbonate.
10. The polycarbonate resin composition according to claim 8 or 9, further comprising an additive;
preferably, the content of the additive in the polycarbonate resin composition is 0-5% and is not equal to 0%;
preferably, the additive comprises any one of a mold release agent, a flow aid, a heat stabilizer, an antioxidant, a UV absorber, an IR absorber, a flame retardant, an antistatic agent, or a dye, or a combination of at least two thereof.
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