CN113201127B - Polysiloxane-polycarbonate copolymer, method for producing same, and polycarbonate resin - Google Patents
Polysiloxane-polycarbonate copolymer, method for producing same, and polycarbonate resin Download PDFInfo
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- CN113201127B CN113201127B CN202110683748.6A CN202110683748A CN113201127B CN 113201127 B CN113201127 B CN 113201127B CN 202110683748 A CN202110683748 A CN 202110683748A CN 113201127 B CN113201127 B CN 113201127B
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 147
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 137
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 37
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- -1 cyclic siloxane Chemical class 0.000 claims abstract description 115
- 229920001577 copolymer Polymers 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims description 71
- 229920001296 polysiloxane Polymers 0.000 claims description 34
- 125000003118 aryl group Chemical group 0.000 claims description 31
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 19
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 18
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 10
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims description 9
- 239000005770 Eugenol Substances 0.000 claims description 9
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003463 adsorbent Substances 0.000 claims description 9
- 229960002217 eugenol Drugs 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000006082 mold release agent Substances 0.000 claims description 8
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000006096 absorbing agent Substances 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000002216 antistatic agent Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 125000001174 sulfone group Chemical group 0.000 claims description 3
- 125000003375 sulfoxide group Chemical group 0.000 claims description 3
- 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
- ARKAOONWLHWUMJ-UHFFFAOYSA-N 2-hexadecyl-1,3,5,7,9,11,13,15-octaoxa-2,4,6,8,10,12,14,16-octasilacyclohexadecane Chemical compound C(CCCCCCCCCCCCCCC)[SiH]1O[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH2]O[SiH2]O1 ARKAOONWLHWUMJ-UHFFFAOYSA-N 0.000 claims description 2
- KVENFDXDHCWGDV-UHFFFAOYSA-N 2-tetradecyl-1,3,5,7,9,2,4,6,8,10-pentaoxapentasilecane Chemical compound C(CCCCCCCCCCCCC)[SiH]1O[SiH2]O[SiH2]O[SiH2]O[SiH2]O1 KVENFDXDHCWGDV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 66
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 54
- 239000004205 dimethyl polysiloxane Substances 0.000 description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 34
- 238000000034 method Methods 0.000 description 30
- 239000000047 product Substances 0.000 description 25
- 239000007864 aqueous solution Substances 0.000 description 20
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 19
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 238000010517 secondary reaction Methods 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000008188 pellet Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 229920005990 polystyrene resin Polymers 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000012467 final product Substances 0.000 description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000001263 acyl chlorides Chemical group 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000003988 headspace gas chromatography Methods 0.000 description 2
- XKJMJYZFAWYREL-UHFFFAOYSA-N hexadecamethylcyclooctasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XKJMJYZFAWYREL-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VFZRCLLDPCNXPS-UHFFFAOYSA-N 2,2,4,4,6,6,8,8,10,10-decamethyl-1,3,5,7,9,11-hexaoxa-2,4,6,8,10,12-hexasilacyclododecane Chemical compound C[Si]1(C)O[SiH2]O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 VFZRCLLDPCNXPS-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/18—Block or graft polymers
- C08G64/186—Block or graft polymers containing polysiloxane sequences
-
- 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
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a polysiloxane-polycarbonate copolymer, a production method and a polycarbonate resin, wherein the polysiloxane-polycarbonate copolymer main chain comprises a structural unit represented by the formula (I) and a structural unit represented by the formula (II), and is characterized in that the content of cyclic siloxane in the copolymer is 500ppm or less. The polysiloxane-polycarbonate copolymer and the polycarbonate resin containing the polysiloxane-polycarbonate copolymer have good heat distortion temperature resistance and appearance color.
Description
Technical Field
The present invention relates to a polycarbonate copolymer, and more particularly, to a polysiloxane-polycarbonate copolymer, a method for preparing the same, and a polycarbonate resin containing the same.
Background
Polycarbonate is an engineering plastic with excellent performance, has excellent toughness, light transmission and strength, and is widely applied to relevant fields of machinery, electronics, automobiles, buildings, electrical appliances and the like. However, for some special application scenarios, the conventional polycarbonate still has performance limitations, for example, in a low-temperature environment, the polycarbonate is transformed from a strong and tough plastic to a hard and brittle material, and cannot meet the impact resistance requirement under the low-temperature condition.
Researchers have attempted to improve the low temperature resistance of polycarbonate materials by modifying the polycarbonate materials, such as by adding silicon-based modifications and improving the low temperature impact strength of polycarbonate by blending; or the low-temperature resistance of the modified polycarbonate/polysiloxane copolymer is improved by a polycarbonate/polysiloxane copolymerization mode, the method has more reliable and more excellent performance compared with the blending modification mode, the obtained copolymer has outstanding flame retardance, low-temperature impact resistance, chemical corrosion resistance, aging resistance and the like, and the modified polycarbonate/polysiloxane copolymer is widely applied to production of products such as consumer electronic cover plates, sheaths, supports, helmets, new energy automobile charging piles, charging guns and the like.
The special properties of the polysiloxane-polycarbonate copolymer and the resin material thereof, such as flame retardance, low temperature resistance, chemical corrosion resistance, aging resistance and the like, are closely related to the polysiloxane, so that the properties of the polymerized copolymer and the resin material thereof can be obviously influenced by the properties of the polysiloxane during polymerization. In general, in the synthesis of polydimethylsiloxane used for the preparation of the polysiloxane-polycarbonate copolymer, a phenolic hydroxyl group is modified at the end after ring-opening polymerization of a small molecule cyclic siloxane (for example, hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), tetradecamethylcyclopentasiloxane (D7), and hexadecamethylcyclooctasiloxane (D8)), and the cyclic siloxane monomer is not completely converted at the time of ring-opening polymerization, and thus the polysiloxane also contains a small molecule siloxane. The Chinese patent application CN110776640A removes part of cyclic siloxane by rectifying polysiloxane at high temperature, but as the polymerization degree of the cyclic siloxane increases, the boiling point of the cyclic siloxane is higher and higher, which results in poor removal effect of the small molecular cyclic siloxane. Therefore, a certain content of small molecule cyclic siloxane is inevitably present in the copolymer.
In the practical application process of the polysiloxane-polycarbonate copolymer, for example, in the application scene of electronic equipment, the equipment middle frame and the bracket are required to have certain low temperature resistance, but meanwhile, the internal space of the electronic equipment is narrow, and the internal temperature is increased by the heat generated when a large number of components work, so that the situation of heat-resistant deformation occurs.
The applicant found through research that the small molecular weight cyclic siloxane in the polydimethylsiloxane used in the copolymer manufacturing process is a main factor influencing the heat deformation resistance temperature, the content of the small molecular weight cyclic siloxane in the copolymer has a large influence on the heat deformation resistance of the polycarbonate, and excessive siloxane substances existing in the polycarbonate resin can reduce the heat deformation resistance temperature of the polycarbonate resin, so that the molded polycarbonate material is easier to deform, and the invention is completed.
Disclosure of Invention
The comprehensive research on the content of the micromolecular cyclic siloxane in the polysiloxane raw material discovers that the added polysiloxane is pretreated in the synthesis process of the polysiloxane-polycarbonate copolymer, so that the content of the micromolecular cyclic siloxane is reduced to be lower than the specified content, the heat deformation resistance of the copolymer can be improved, and the heat deformation resistance temperature of the copolymer can be increased.
Another object of the present invention is to provide a method for producing such a polysiloxane-polycarbonate copolymer.
It is still another object of the present invention to provide a polycarbonate resin containing such a polysiloxane-polycarbonate copolymer.
In order to realize the purpose, the invention adopts the following technical scheme:
a polysiloxane-polycarbonate copolymer comprises a polycarbonate block structural unit shown in a formula (I) and a polysiloxane block structural unit shown in a formula (II), wherein the content of cyclic siloxane in the polysiloxane-polycarbonate copolymer is less than 500 ppm; preferably, the adding amount of the polysiloxane during the polymerization of the polysiloxane-polycarbonate copolymer accounts for 3-30% of the mass of the copolymer produced after the polymerization; the average polymerization degree of the polysiloxane is 20-80;
in the formula, R 1 And R 2 Each independently selected from hydrogen, halogen, C 1 ～C 20 Alkyl of (C) 4 ～C 20 Cycloalkyl or C 6 ～C 20 Aryl of (a); a and b are independentlyAn integer selected from 0 to 4; x is selected from alkyl, ether linkage, carbonyl, thioether linkage, sulfone group, sulfoxide group, C 1 ～C 20 Alkylene of (C) 6 ～C 20 Arylene of, C 6 ～C 20 Or a group of formula (VI):
wherein R is 5 And R 6 Each independently represents C 1 ～C 20 Alkyl of (C) 4 ～C 20 Cycloalkyl or C 6 ～C 20 Aryl of (a); or R 5 And R 6 Connection forming C 4 ～C 20 C, said C 4 ～C 20 Optionally substituted with one or more C 1 ～C 20 Alkyl of (C) 6 ～C 20 Aryl of (C) 7 ～C 21 Aralkyl radical, C 5 ～C 20 Cycloalkyl or a combination thereof;
R 3 and R 4 Each independently selected from hydrogen, halogen atom or C 1 ～C 6 Alkyl of (C) 1 ～C 6 Alkoxy or C 6 ～C 12 Aryl of (a); y is selected from alkylene groups, containing aliphatic or aromatic organic residues, and may be, for example, methylene, ethylene, phenylene; n is an integer of 20 to 80.
In a specific embodiment, the cyclic siloxane is a cyclic siloxane having the structure of formula (III),
wherein R is 3 And R 4 Each independently selected from hydrogen, halogen atom or C 1 ～C 6 Alkyl of (C) 1 ～C 6 Alkoxy or C 6 ～C 12 Aryl of (a); c represents an integer of 1 to 20.
In a particular embodiment, the structural unit of formula (I) is derived from a polycarbonate prepared from bisphenol A.
In a specific embodiment, R in the structural units represented by the formulae (II) and (III) 3 、R 4 The radicals are simultaneously methyl.
In a specific embodiment, the cyclic siloxane is one or more of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetradecylcyclopentasiloxane, and hexadecmethylcyclooctasiloxane, preferably octamethylcyclotetrasiloxane.
In another aspect of the present invention, the method for producing a polysiloxane-polycarbonate copolymer comprises the steps of:
a) purifying the polysiloxane with the phenolic hydroxyl terminal shown in the formula (IV) by using an adsorbent with micropores;
b) mixing the polysiloxane with the phenolic hydroxyl terminal obtained in the step a) with an organic solvent, adding the mixture into an organic solution of a polycarbonate oligomer generated by the reaction of raw material monomers, and reacting the polysiloxane with the phenolic hydroxyl terminal in the following formula (IV) with the polycarbonate oligomer or phosgene under alkaline conditions;
c) separating the reaction product in the step b) into oil and water, washing, devolatilizing and drying to obtain polysiloxane-polycarbonate copolymer;
wherein R is 3 And R 4 Each independently selected from hydrogen, halogen atom or C 1 ～C 6 Alkyl of (C) 1 ～C 6 Alkoxy or C 6 ～C 12 N is an integer of 20 to 80; z represents a structure represented by the following formula (V):
wherein R is 7 Is represented by C 1 ～C 4 Alkyl of (C) 1 ～C 4 P represents an integer of 0 to 4.
In a specific embodiment, the phenolic hydroxyl group of the polysiloxane terminates with an allylphenol or eugenol.
In still another aspect of the present invention, a polycarbonate resin comprising the aforementioned polysiloxane-polycarbonate copolymer and an aromatic polycarbonate; preferably, any one or more selected from the group consisting 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, a dye, a pigment, and a filler is further contained in an amount of 0 to 5 wt% based on the total amount of the polysiloxane-polycarbonate copolymer and the aromatic polycarbonate.
In a specific embodiment, the polysiloxane-polycarbonate copolymer accounts for 1-50% of the mass of the polycarbonate resin.
In a specific embodiment, the polycarbonate resin has a heat distortion temperature of 120 ℃ or more under a load of 1.8MPa according to ASTM D648.
Compared with the prior art, the invention has the following beneficial effects:
according to the polysiloxane-polycarbonate copolymer disclosed by the invention, the polysiloxane is pretreated, so that the content of the micromolecular cyclic siloxane in the polysiloxane-polycarbonate copolymer is controlled within a certain content, and the polysiloxane-polycarbonate copolymer prepared by the polysiloxane-polycarbonate copolymer is higher in thermal deformation resistance temperature, has good thermal deformation resistance and appearance color tone, and is better in application performance of a resin product prepared by the polysiloxane-polycarbonate copolymer.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
A polysiloxane-polycarbonate copolymer comprises a polycarbonate block structural unit shown in a formula (I) and a polysiloxane block structural unit shown in a formula (II), wherein the content of cyclic siloxane in the polysiloxane-polycarbonate copolymer is less than 500 ppm;
in the formula (I), R 1 And R 2 Each independently selected from hydrogen, halogen, C 1 ～C 20 Alkyl of (C) 4 ～C 20 Cycloalkyl or C 6 ～C 20 Preferably, R 1 And R 2 Each independently selected from hydrogen, halogen (e.g. F, Cl, Br), C 1 ～C 6 Alkyl of (C) 4 ～C 10 Cycloalkyl or C 6 ～C 10 Aryl of (a); a and b are independently selected from integers of 0 to 4, for example from 0, 1, 2, 3 or 4; x is selected from alkyl, ether linkage, carbonyl, thioether linkage, sulfone group, sulfoxide group, C 1 ～C 20 Alkylene of (C) 6 ～C 20 Arylene of, C 6 ～C 20 Or a group of formula (VI): preferably, X is selected from the group consisting of alkyl, ether linkage, carbonyl, thioether linkage, sulfone, sulfoxide, C 1 ～C 10 Alkylene of (C) 6 ～C 10 Arylene of, C 6 ～C 10 Or a group of formula (VI):
wherein R is 5 And R 6 Each independently represents C 1 ～C 20 Alkyl of (C) 4 ～C 20 Cycloalkyl or C 6 ～C 20 Aryl of (2), preferably from C 1 ～C 10 Alkyl of (C) 4 ～C 10 Cycloalkyl or C 6 ～C 10 Aryl of (a); or R 5 And R 6 Connection formation C 4 ～C 20 Alicyclic rings of (2), i.e. R 5 And R 6 Are connected to form a ring, C 4 ～C 20 Optionally substituted with one or more C 1 ～C 20 Alkyl of (C) 6 ～C 20 Aryl of (C) 7 ～C 21 Aralkyl radical, C 5 ～C 20 Cycloalkyl or combinations thereof, preferably substituted by one or more C 1 ～C 8 Alkyl of (C) 6 ～C 8 Aryl of (C) 7 ～C 8 Aralkyl, C 5 ～C 8 Cycloalkyl or a combination thereof;
in the formula (II), R 3 And R 4 Each independently selected from hydrogen, halogen atom or C 1 ～C 6 Alkyl of (C) 1 ～C 6 Alkoxy or C 6 ～C 12 Aryl of (2), preferably from hydrogen, halogen atoms or C 1 ～C 6 Alkyl of (C) 1 ～C 6 Alkoxy or C 6 ～C 12 Aryl of (2), preferably C 1 ～C 4 Alkyl of (C) 1 ～C 4 Alkoxy or C 6 ～C 8 Aryl of (a); y is selected from a single bond, an organic residue containing aliphatic or aromatic groups, and may be, for example, a methylene group, an ethylene group, a phenylene group; n is an integer of 20 to 80.
In a preferred embodiment, a polysiloxane-polycarbonate copolymer comprising a polycarbonate block building block of formula (I) and a polysiloxane block building block of formula (II), wherein:
a) the adding amount of polysiloxane during the polymerization of the copolymer accounts for 3-30% of the mass of the copolymer produced after the polymerization;
b) the average polymerization degree of the polysiloxane is 20-80;
c) the content of cyclic siloxane in the copolymer is 500ppm or less.
Among them, the polycarbonate block represented by the formula (I) in the polysiloxane-polycarbonate copolymer is preferably a structural unit derived from bisphenol a, for example, a structure represented by the formula (VII).
The polysiloxane block represented by formula (II) in the polysiloxane-polycarbonate copolymer is preferably derived from a structural unit of polydimethylsiloxane having a terminal phenolic hydroxyl group, i.e., a structure represented by formula (VIII).
The above-mentioned structural unit derived from polydimethylsiloxane, the structure of the root-terminal phenolic hydroxyl group, is further preferably derived from allylphenol-polydimethylsiloxane, examples thereof include 2-allylphenol-polydimethylsiloxane, 3-allylphenol-polydimethylsiloxane, 4-allylphenol-polydimethylsiloxane, 2-methoxy-5-allylphenol-polydimethylsiloxane, 2-methoxy-6-allylphenol-polydimethylsiloxane, preferably 2-allylphenol-polydimethylsiloxane or 2-methoxy-4-allylphenol-polydimethylsiloxane. The polymerization degree n of the polydimethylsiloxane segment is 20-80, preferably 30-70, and more preferably 40-60.
The cyclic siloxane in the copolymer is the structure described by the formula (III)
Wherein R is 3 And R 4 Each independently selected from hydrogen, halogen atom or C 1 ～C 6 Alkyl of (C) 1 ～C 6 Alkoxy or C 6 ～C 12 Aryl of (2), preferably from hydrogen, halogen atoms or C 1 ～C 4 Alkyl of (C) 1 ～C 4 Alkoxy or C 6 ～C 8 Aryl of (a); c represents an integer of 1 to 20.
In a preferred embodiment, the cyclic siloxane has pendant groups R 3 And R 4 Preferably methyl, and is preferably one or more selected from hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetradecylcoheptasiloxane, and hexadecylcyclooctasiloxane, depending on the degree of polymerization, and is preferably octamethylcyclotetrasiloxane.
In another aspect, a method of making a polysiloxane-polycarbonate copolymer comprises the steps of:
a) purifying the polysiloxane having a phenolic hydroxyl group terminal represented by the above formula (IV), preferably allylphenol-polydimethylsiloxane, by an adsorbent having micropores (for example, an organic adsorption resin);
b) mixing the polysiloxane with the phenolic hydroxyl terminal in the a) with an organic solvent, adding the mixture into an organic solution of a polycarbonate oligomer generated by the reaction of raw material monomers, and reacting the polysiloxane with the phenolic hydroxyl terminal in the following formula (IV) with the polycarbonate oligomer or phosgene under alkaline conditions;
c) separating the reaction product in b) into oil and water, washing, devolatilizing and drying to obtain the polysiloxane-polycarbonate copolymer.
The polydimethylsiloxane in step a) can be synthesized according to the method of chinese patent CN110776640a, i.e., ring-opening polymerization of cyclic siloxane monomers to obtain hydrogen-terminated polydimethylsiloxane, and modification of the hydrogen-terminated polydimethylsiloxane with an allylphenol compound to obtain a crude polydimethylsiloxane having a phenolic hydroxyl group as a terminal, which is well known to those skilled in the art.
For the polycarbonate oligomer in step b), it is an oligomer with a low degree of polymerization formed by reacting a raw material monomer such as bisphenol a or its derivative with an acid chloride, which is well known in the art of polycarbonate preparation, for example, patent CN 102471474B. The polycarbonate oligomer has an acyl chloride group, can be continuously subjected to polymerization reaction with polysiloxane with a phenolic hydroxyl group to introduce a polysiloxane chain segment into the polycarbonate chain segment, or can also be subjected to reaction of the polysiloxane with the phenolic hydroxyl group with phosgene, and the polysiloxane chain segment is introduced into the polycarbonate chain segment by utilizing the reaction between the acyl chloride group and the phenolic hydroxyl group in the phosgene, so that a polycarbonate high polymer is finally generated, namely a final product.
However, the applicant has found that the crude product contains unreacted cyclic siloxane monomer small molecular compounds, and if the crude product is used to directly perform a synthesis reaction of a polysiloxane-polycarbonate copolymer, the cyclic siloxane monomer enters the copolymer, so that the cyclic siloxane monomer remaining in the copolymer reduces the heat resistance of the copolymer, and a molded product is easy to deform, and cannot be used in some thermal fields.
In order to reduce the content of the cyclic siloxane monomer micromolecules in the crude polydimethylsiloxane with the phenolic hydroxyl at the tail end, for example, the cyclic siloxane monomer in the polydimethylsiloxane can be removed by using a high-temperature rectification mode, but the applicant researches and discovers that the boiling point of the cyclic siloxane monomer is gradually increased along with the increase of the polymerization degree of the cyclic monomer, and the temperature required by removal is increased; on the other hand, excessive heating of the terminal phenolic hydroxyl group of polydimethylsiloxane leads to yellowing thereof, and further affects the conversion rate during copolymerization and the appearance of the product after copolymerization.
To this end, the applicants have found that for polydimethylsiloxanes required for polysiloxane-polycarbonates, residual cyclic siloxane monomers can be removed by adsorption to microporous materials. From the viewpoint of effective removal of cyclic small molecules, the adsorbent is required to have an average pore diameter of 100nm or less, more preferably 50nm or less, and still more preferably 25nm or less. As the microporous adsorbent, activated carbon, artificial zeolite, natural zeolite, porous silica, porous alumina, diatomaceous earth, organic resin porous microspheres, and the like can be used, but not limited thereto. The average particle diameter of the adsorbent is 10 μm to 1cm, preferably 100 μm to 500 μm, from the viewpoint of effective separation of the adsorbent from polydimethylsiloxane. The content of cyclic siloxane monomers can be reduced to 1500ppm or less, preferably less than 1000ppm, more preferably less than 500ppm mm by adsorbing the polydimethylsiloxane by the adsorbent.
The polycarbonate oligomer in step b) can be prepared by the known phosgene interfacial process (see, for example, WO2020201180(A1)), in which an aqueous dihydric phenol/alkali solution is reacted simultaneously with phosgene in a given ratio in the presence of an organic solvent, the dihydric phenol being bisphenol A as described above. The organic solvent is preferably methylene chloride, and the polycarbonate oligomer suitable for the present invention preferably has a weight average molecular weight of 1000 to 5000.
In the polysiloxane-polycarbonate copolymer prepared in the step c), the proportion of the dosage of the polydimethylsiloxane to the yield of the final copolymer is 3-30%, and the optimal proportion is 5-20%. When the content of the polydimethylsiloxane is less than 3%, the low-temperature resistance of the copolymer is poor, and when the content of the polydimethylsiloxane is more than 30%, the moldability of the copolymer is greatly reduced. The weight average molecular weight of the copolymer is 10000-40000, preferably 15000-35000, and more preferably 16000-28000.
The residual amount of cyclic siloxane in the copolymer is preferably 1 to 500ppm, more preferably 1 to 400ppm, still more preferably 1 to 200ppm or less, and particularly preferably 1 to 100 ppm.
For the measurement of residual cyclic siloxane monomer in the polysiloxane-polycarbonate copolymer, the copolymer can be precipitated from an organic solvent, the content of cyclic siloxane monomer in part of the solution can be measured using GC/headspace-GC, and converted to the content of cyclic siloxane in the copolymer depending on the amount of copolymer and solution. The specific test steps are as follows:
a) 2g of polysiloxane-polycarbonate are dissolved in 18g of dichloromethane;
b) adding 20g of methanol within 10 min;
c) filtering the mixed system;
d) 5mL of the filtrate was taken and the cyclic siloxane content was measured by GC/headspace-GC.
In still another aspect, the polycarbonate resin of the present invention is a polycarbonate composition resin comprising the polysiloxane-polycarbonate copolymer and an aromatic polycarbonate, wherein the polysiloxane-polycarbonate copolymer is 1 to 50% by mass of the composition resin, and the aromatic polycarbonate is 99 to 50% by mass of the composition resin, and the polycarbonate composition resin is mainly characterized in that the content of a cyclic siloxane monomer is 250ppm or less. The aromatic polycarbonate is a polycarbonate containing no cyclic siloxane monomer, and examples thereof include a bisphenol A type homopolycarbonate produced by a known phosgene interface method and a bisphenol A type homopolycarbonate produced by a melt transesterification method. Both of these methods for the preparation of bisphenol A type homopolycarbonates are well known to those skilled in the art.
In addition, the polycarbonate resin prepared by the present invention may further contain additives known in the art according to the processing requirements, and may contain any one or more selected from the group consisting of mold release agents, flow aids, heat stabilizers, antioxidants, UV absorbers, IR absorbers, flame retardants, antistatic agents, dyes, pigments, and fillers in an amount of 0 to 5 wt% based on the total amount of the polysiloxane-polycarbonate copolymer and the aromatic polycarbonate, which are also well known to those skilled in the art and should be within the scope of the present invention.
The invention is further illustrated, but not limited, by the following more specific examples.
The following examples and comparative examples used the following sources of raw materials:
octamethylcyclotetrasiloxane, dow corning, D4 PMX-0244;
decamethylcyclohexasiloxane, Mingyi silicon, MY D6;
eugenol, alatin;
2-allylphenol, alpha chemical;
polystyrene adsorbent resin NDA-99, Re Bo (Shanghai) Biochemical technology Ltd.
The prepared polycarbonate resin was subjected to a performance test by the following method:
(1) impact strength
Measured at room temperature and-30 ℃ according to ASTM D256;
(2) tensile strength
Measured at room temperature according to ASTM D638;
(3) heat distortion temperature
Measured according to ASTM D648 under a load of 1.8 MPa;
(4) melt index
The measurement was carried out at 300 ℃ under a load of 1.2kg in accordance with ASTM D1238.
EXAMPLE 1 Synthesis of polydimethylsiloxane PDMS-A
1483g of octamethylcyclotetrasiloxane, 30g of 1,1,3, 3-tetramethyldisiloxane and 35g of 86% concentrated sulfuric acid were mixed and stirred at room temperature for 10 hours, the aqueous phase was separated off, 25g of sodium bicarbonate was added to the residue, mixing and stirring were carried out for 1 hour, the solids were removed by filtration, vacuum distillation was carried out at 160 ℃ and 600Pa, the low molecular weight polyorganosiloxanes were removed, and the octamethylcyclotetrasiloxane content was determined to be 10576 ppm. The product after vacuum distillation was passed at a rate of 10g/min to a length of 2 m and a diameter of 10cm and equipped with a polystyrene resin having an average pore diameter of 25nm, and the octamethylcyclotetrasiloxane content of the test effluent was 1568 ppm.
72.2g of eugenol and 0.0014g of platinum chloride-alkoxide complex were mixed, and added to 294g of the adsorbed product, followed by reaction at 100 ℃ for 5 hours. The product was dissolved in 1L of dichloromethane, washed with water, and after water was removed, the polydimethylsiloxane was vacuum distilled at high temperature under vacuum to remove residual eugenol and dichloromethane. The obtained eugenol-polydimethylsiloxane had a degree of polymerization of 48 and a content of octamethylcyclotetrasiloxane of 1354 ppm.
EXAMPLE 2 polydimethylsiloxane PDMS-B Synthesis
According to the method in example 1, the distillation conditions were set at 160 ℃ and 400Pa, and the octamethylcyclotetrasiloxane content before adsorption on the polystyrene resin was 8433ppm and after adsorption was 1263ppm, the polymerization degree of the eugenol-polydimethylsiloxane as the final product was 47 and the octamethylcyclotetrasiloxane content was 1215 ppm.
Example 3 Synthesis of polydimethylsiloxane PDMS-C
According to the method in example 1, the distillation conditions were set to 160 ℃ and 200Pa, and the octamethylcyclotetrasiloxane content before adsorption on the polystyrene resin was 7643ppm and 1146ppm after adsorption were detected, and the degree of polymerization of the final product eugenol-polydimethylsiloxane was 51 and the octamethylcyclotetrasiloxane content was 1015 ppm.
EXAMPLE 4 polydimethylsiloxane PDMS-D Synthesis
According to the method in example 1, the distillation conditions were set at 170 ℃ and 600Pa, and the content of octamethylcyclotetrasiloxane before adsorption on the polystyrene resin was detected to be 9333pm and after adsorption to be 1246ppm, and the polymerization degree of the final product eugenol-polydimethylsiloxane was 50 and the content of octamethylcyclotetrasiloxane was 1163 ppm.
EXAMPLE 5 polydimethylsiloxane PDMS-E Synthesis
According to the method in example 1, the distillation conditions were set to 180 ℃ and 600Pa, and the octamethylcyclotetrasiloxane content before adsorption on the polystyrene resin was 7863pm and 1122ppm after adsorption, and the polymerization degree of the final product eugenol-polydimethylsiloxane was 51 and the octamethylcyclotetrasiloxane content was 986 ppm.
EXAMPLE 6 polydimethylsiloxane PDMS-F Synthesis
According to the method in example 1, the speed of introducing into the polystyrene resin column is set to 5g/min, the octamethylcyclotetrasiloxane content before adsorption by the polystyrene resin is 10576pm and 633ppm after adsorption is detected, the polymerization degree of the final product eugenol-polydimethylsiloxane is 51, and the octamethylcyclotetrasiloxane content is 489 ppm.
Example 7 Synthesis of polydimethylsiloxane PDMS-G
According to the method in example 1, the length of the column passed through the polystyrene resin was set to 3g/min, and the octamethylcyclotetrasiloxane content before adsorption on the polystyrene resin was 10576pm and 864ppm after adsorption were detected, and the polymerization degree of the final product eugenol-polydimethylsiloxane was 50 and the octamethylcyclotetrasiloxane content was 679 ppm.
EXAMPLE 8 polydimethylsiloxane PDMS-H Synthesis
2002.14g of dodecamethylcyclohexasiloxane, 26.82g of 1,1,3, 3-tetramethyldisiloxane and 35g of 86% concentrated sulfuric acid were mixed and stirred at room temperature for 10 hours, the aqueous phase was separated off, 25.2g of sodium bicarbonate was added to the residue, mixed and stirred for 1.5 hours, filtered to remove solids, and vacuum-distilled at 165 ℃ and 600Pa to remove low molecular weight polyorganosiloxanes, which were tested to have a dodecamethylcyclohexasiloxane content of 12140 ppm. The product after vacuum distillation was passed at 10g/min to a length of 2 m and a diameter of 10cm and equipped with a polystyrene resin having an average pore diameter of 25nm, and the test effluent had a dodecamethylcyclohexasiloxane content of 1423 ppm.
82.1g of eugenol and 0.0015g of platinum chloride-alkoxide complex were mixed and added to 300g of the above-adsorbed product, and reacted at 100 ℃ for 5 hours. The product was dissolved in 1L of dichloromethane, washed with water, and after removal of the water the polydimethylsiloxane was vacuum distilled at high temperature under vacuum to remove residual eugenol and dichloromethane. The obtained eugenol-polydimethylsiloxane has the polymerization degree of 50 and the content of dodecamethylcyclohexasiloxane of 1254 ppm.
Example 9 Synthesis of polydimethylsiloxane PDMS-I
The adsorbed product (300 g) obtained in example 1 was taken, and 67.09g of 2-allylphenol and 0.0014g of platinum chloride-alkoxide complex were mixed and added to the adsorbed product, followed by reaction at 100 ℃ for 5 hours. The product was dissolved in 1L of dichloromethane, washed with water, and after removal of the water, the polydimethylsiloxane was vacuum distilled at high temperature under vacuum to remove residual 2-allylphenol and dichloromethane. The degree of polymerization of the resulting 2-allylphenol-polydimethylsiloxane was 49, and the octamethylcyclotetrasiloxane content was 1357 ppm.
EXAMPLE 10 preparation of polysiloxane-polycarbonate copolymer 1
Introducing a bisphenol A (BPA) alkaline aqueous solution (143g/min), phosgene (11.2g/min), dichloromethane (127g/min) and a 32% NaOH aqueous solution (4g/min) into a 3L primary reaction kettle provided with a turbine stirring paddle, a baffle and a constant-temperature jacket, stirring and reacting at 26 ℃, continuously conveying a reaction product from the primary reaction kettle to a 3L secondary reaction kettle provided with the turbine stirring paddle, the baffle and the constant-temperature jacket, and maintaining the liquid level of the primary reaction kettle to be 2.5L.
The siloxane PDMS-F in example 6 was prepared as a 20% mass fraction solution in methylene chloride, premixed with phosgene (1g/min) at a rate of 31.5g/min and added to a secondary reaction vessel, and the reaction product was continuously transferred from the secondary reaction vessel to a 3L tertiary reaction vessel equipped with a turbine paddle, baffles and a constant temperature jacket, maintaining the liquid level of the secondary reaction vessel at 2.5L.
Triethylamine is added into the third-stage reaction kettle at the speed of 0.04g/min, NaOH aqueous solution with the mass fraction of 32% is added into the third-stage reaction kettle at the speed of 4g/min, p-tert-butylphenol is added into the third-stage reaction kettle at the speed of 0.55g/min, reaction products are continuously conveyed into the fourth-stage reaction kettle and the fifth-stage reaction kettle, and the liquid level in the third-stage reaction kettle, the fourth-stage reaction kettle and the fifth-stage reaction kettle is maintained to be 2.5L. And continuously conveying the product in the 5-stage reaction kettle to separation equipment, and removing the water phase to obtain the polysiloxane-polycarbonate copolymer glue solution.
Washing with 0.5% NaOH aqueous solution and 0.4mol/L hydrochloric acid, washing with pure water until the water phase conductivity is below 0.01 μ S/m, concentrating, precipitating, crushing, and drying at 140 deg.C for 6 hr to obtain copolymer powder.
The copolymer was tested for cyclic siloxane residue at 100ppm as described above and found to have a weight average molecular weight of 26753.
Comparative example 1 Synthesis of polydimethylsiloxane PDMS-J
1483g of octamethylcyclotetrasiloxane, 30g of 1,1,3, 3-tetramethyldisiloxane and 35g of 86% concentrated sulfuric acid were mixed and stirred at room temperature for 10 hours, the aqueous phase was separated off, 25g of sodium bicarbonate was added to the residue, mixing and stirring were carried out for 1 hour, the solids were removed by filtration, vacuum distillation was carried out at 190 ℃ and 50Pa, and the low molecular weight polyorganosiloxanes were removed, and the octamethylcyclotetrasiloxane content was determined to be 3276 ppm.
72.2g of eugenol and 0.0014g of platinum chloride-alkoxide complex were mixed and added to 294g of the above-mentioned distilled product, and reacted at 100 ℃ for 5 hours. The product was dissolved in 1L of dichloromethane, washed with water, and after removal of the water the polydimethylsiloxane was vacuum distilled at high temperature under vacuum to remove residual 2-allylphenol and dichloromethane. The polymerization degree of the obtained eugenol-polydimethylsiloxane is 48, and the content of the octamethylcyclotetrasiloxane is 2874 ppm.
Comparative example 2 preparation of polysiloxane-polycarbonate copolymer 2
Introducing a BPA alkaline aqueous solution (143g/min), phosgene (11.2g/min), dichloromethane (127g/min) and a 32% NaOH aqueous solution (4g/min) into a 3L primary reaction kettle provided with a turbine stirring paddle, a baffle and a constant-temperature jacket, stirring and reacting at 26 ℃, continuously conveying a reaction product from the primary reaction kettle to a 3L secondary reaction kettle provided with the turbine stirring paddle, the baffle and the constant-temperature jacket, and maintaining the liquid level of the primary reaction kettle to be 2.5L.
The siloxane in comparative example 1 was prepared as a 20% mass fraction solution in methylene chloride, premixed with phosgene (1g/min) at a rate of 31.5g/min and added to a second-stage reactor, and the reaction product was continuously transferred from the second-stage reactor to a 3L third-stage reactor equipped with a turbine paddle, baffles and a constant temperature jacket, maintaining the liquid level in the second-stage reactor at 2.5L.
Triethylamine is added into the third-stage reaction kettle at the speed of 0.04g/min, NaOH aqueous solution with the mass fraction of 32% is added into the third-stage reaction kettle at the speed of 4g/min, p-tert-butylphenol is added into the third-stage reaction kettle at the speed of 0.55g/min, reaction products are continuously conveyed into the fourth-stage reaction kettle and the fifth-stage reaction kettle, and the liquid level in the third-stage reaction kettle, the fourth-stage reaction kettle and the fifth-stage reaction kettle is maintained to be 2.5L. And continuously conveying the product in the 5-stage reaction kettle to separation equipment, and removing the water phase to obtain the polysiloxane-polycarbonate copolymer glue solution.
Washing with 0.5% NaOH aqueous solution and 0.4mol/L hydrochloric acid, washing with pure water until the water phase conductivity is below 0.01 μ S/m, concentrating, precipitating, crushing, and drying at 140 deg.C for 6 hr to obtain copolymer powder.
The copolymer was tested for cyclic siloxane residue at 550ppm by the method described above and a weight average molecular weight of 25680 was determined.
Comparative example 3 Synthesis of polydimethylsiloxane PDMS-K
1483g of octamethylcyclotetrasiloxane, 30g of 1,1,3, 3-tetramethyldisiloxane and 35g of 86% concentrated sulfuric acid were mixed and stirred at room temperature for 10 hours, the aqueous phase was separated off, 25g of sodium bicarbonate was added to the residue, mixed and stirred for 1 hour, the solid was removed by filtration, vacuum distillation was carried out at 180 ℃ and 100Pa, and the low molecular weight polyorganosiloxanes were removed, and the octamethylcyclotetrasiloxane content was found to be 4083 ppm.
72.2g of eugenol and 0.0014g of platinum chloride-alkoxide complex were mixed and added to 294g of the above-mentioned distilled product, and reacted at 100 ℃ for 5 hours. The product was dissolved in 1L of dichloromethane, washed with water, and after removal of the water the polydimethylsiloxane was vacuum distilled at high temperature under vacuum to remove residual 2-allylphenol and dichloromethane. The obtained eugenol-polydimethylsiloxane has the polymerization degree of 48 and the content of the octamethylcyclotetrasiloxane of 3465 ppm.
Comparative example 4 production of polysiloxane-polycarbonate copolymer 3
Introducing a BPA alkaline aqueous solution (143g/min), phosgene (11.2g/min), dichloromethane (127g/min) and a 32% NaOH aqueous solution (4g/min) into a 3L primary reaction kettle provided with a turbine stirring paddle, a baffle and a constant-temperature jacket, stirring and reacting at 26 ℃, continuously conveying a reaction product from the primary reaction kettle to a 3L secondary reaction kettle provided with the turbine stirring paddle, the baffle and the constant-temperature jacket, and maintaining the liquid level of the primary reaction kettle to be 2.5L.
The siloxane in comparative example 3 was prepared as a 20% mass fraction solution in methylene chloride, premixed with phosgene (1g/min) at a rate of 31.5g/min and added to a second-stage reactor, and the reaction product was continuously transferred from the second-stage reactor to a 3L third-stage reactor equipped with a turbine paddle, baffles and a constant temperature jacket, maintaining the liquid level in the second-stage reactor at 2.5L.
Triethylamine is added into the third-stage reaction kettle at the speed of 0.04g/min, NaOH aqueous solution with the mass fraction of 32% is added into the third-stage reaction kettle at the speed of 4g/min, p-tert-butylphenol is added into the third-stage reaction kettle at the speed of 0.55g/min, reaction products are continuously conveyed into the fourth-stage reaction kettle and the fifth-stage reaction kettle, and the liquid level in the third-stage reaction kettle, the fourth-stage reaction kettle and the fifth-stage reaction kettle is maintained to be 2.5L. And continuously conveying the product in the 5-stage reaction kettle to separation equipment, and removing the water phase to obtain the polysiloxane-polycarbonate copolymer glue solution.
Washing with 0.5% NaOH aqueous solution and 0.4mol/L hydrochloric acid, washing with pure water until the water phase conductivity is below 0.01 μ S/m, concentrating, precipitating, crushing, and drying at 140 deg.C for 6 hr to obtain copolymer powder.
The copolymer was tested for cyclic siloxane residue at 701ppm by the method described above and found to have a weight average molecular weight of 27351.
EXAMPLE 11 preparation of polysiloxane-polycarbonate copolymer 4
Introducing a BPA alkaline aqueous solution (143g/min), phosgene (11.2g/min), dichloromethane (127g/min) and a 32% NaOH aqueous solution (4g/min) into a 3L primary reaction kettle provided with a turbine stirring paddle, a baffle and a constant-temperature jacket, stirring and reacting at 26 ℃, continuously conveying a reaction product from the primary reaction kettle to a 3L secondary reaction kettle provided with the turbine stirring paddle, the baffle and the constant-temperature jacket, and maintaining the liquid level of the primary reaction kettle to be 2.5L.
The siloxane PDMS-H in example 8 was prepared as a 20% mass fraction solution in methylene chloride, premixed with phosgene (1g/min) at a rate of 31.5g/min and added to a secondary reaction vessel, and the reaction product was continuously transferred from the secondary reaction vessel to a 3L tertiary reaction vessel equipped with a turbine paddle, baffles and a constant temperature jacket, maintaining the liquid level of the secondary reaction vessel at 2.5L.
Triethylamine is added into the third-stage reaction kettle at the speed of 0.04g/min, NaOH aqueous solution with the mass fraction of 32% is added into the third-stage reaction kettle at the speed of 4g/min, p-tert-butylphenol is added into the third-stage reaction kettle at the speed of 0.55g/min, reaction products are continuously conveyed into the fourth-stage reaction kettle and the fifth-stage reaction kettle, and the liquid level in the third-stage reaction kettle, the fourth-stage reaction kettle and the fifth-stage reaction kettle is maintained to be 2.5L. And continuously conveying the product in the 5-stage reaction kettle to separation equipment, and removing the water phase to obtain the polysiloxane-polycarbonate copolymer glue solution.
Washing with 0.5% NaOH aqueous solution and 0.4mol/L hydrochloric acid, washing with pure water until the water phase conductivity is below 0.01 μ S/m, concentrating, precipitating, crushing, and drying at 140 deg.C for 6 hr to obtain copolymer powder.
The copolymer was tested for cyclic siloxane residue of 532ppm according to the foregoing procedure and found to have a weight average molecular weight of 25247.
EXAMPLE 12 preparation of polysiloxane-polycarbonate copolymer 5
Introducing a BPA alkaline aqueous solution (143g/min), phosgene (11.2g/min), dichloromethane (127g/min) and a 32% NaOH aqueous solution (4g/min) into a 3L primary reaction kettle provided with a turbine stirring paddle, a baffle and a constant-temperature jacket, stirring and reacting at 26 ℃, continuously conveying a reaction product from the primary reaction kettle to a 3L secondary reaction kettle provided with the turbine stirring paddle, the baffle and the constant-temperature jacket, and maintaining the liquid level of the primary reaction kettle to be 2.5L.
The siloxane PDMS-I in example 9 was prepared as a 20% mass fraction solution in methylene chloride, premixed with phosgene (1g/min) at a rate of 31.5g/min and added to a secondary reaction vessel, and the reaction product was continuously transferred from the secondary reaction vessel to a 3L tertiary reaction vessel equipped with a turbine paddle, baffles and a constant temperature jacket, maintaining the liquid level of the secondary reaction vessel at 2.5L.
Triethylamine is added into the third-stage reaction kettle at the speed of 0.04g/min, NaOH aqueous solution with the mass fraction of 32% is added into the third-stage reaction kettle at the speed of 4g/min, p-tert-butylphenol is added into the third-stage reaction kettle at the speed of 0.55g/min, reaction products are continuously conveyed into the fourth-stage reaction kettle and the fifth-stage reaction kettle, and the liquid level in the third-stage reaction kettle, the fourth-stage reaction kettle and the fifth-stage reaction kettle is maintained to be 2.5L. And continuously conveying the product in the 5-stage reaction kettle to separation equipment, and removing the water phase to obtain the polysiloxane-polycarbonate copolymer glue solution.
Washing with 0.5% NaOH aqueous solution and 0.4mol/L hydrochloric acid, washing with pure water until the water phase conductivity is below 0.01 μ S/m, concentrating, precipitating, crushing, and drying at 140 deg.C for 6 hr to obtain copolymer powder.
The copolymer was tested for cyclic siloxane residue at 670ppm by the method described above and a weight average molecular weight of 26242 was measured.
EXAMPLE 13 preparation of polycarbonate resin a (PC-a) containing polysiloxane-polycarbonate copolymer
1000g of the polysiloxane-polycarbonate copolymer powder of example 10,
2277g of general-purpose PC resin,
2277g of general-purpose PC resin, 6g of antioxidant and 9g of mold release agent were thoroughly mixed, and then extruded and cut into pellets at 280 ℃ by using a Cobelron CTE35 type extruder, and the obtained pellets were characterized by the following conditions after injection molding.
EXAMPLE 14 preparation of polycarbonate resin b containing polysiloxane-polycarbonate copolymer (PC-b)
The procedure of example 13 was followed using the polysiloxane-polycarbonate copolymer of comparative example 2.
EXAMPLE 15 preparation of polycarbonate resin c (PC-c) containing polysiloxane-polycarbonate copolymer
The procedure of example 13 was followed using the polysiloxane-polycarbonate copolymer of comparative example 4.
EXAMPLE 16 preparation of polycarbonate resin d (PC-d) containing polysiloxane-polycarbonate copolymer
500g of the polysiloxane-polycarbonate copolymer powder of example 10,
2277g of general-purpose PC resin,
2277g of general-purpose PC resin, 6g of antioxidant and 9g of mold release agent were thoroughly mixed, and then extruded and cut into pellets at 280 ℃ by using a Cobelron CTE35 type extruder, and the obtained pellets were characterized by the following conditions after injection molding.
EXAMPLE 17 preparation of polycarbonate resin e (PC-e) containing polysiloxane-polycarbonate copolymer
The procedure of example 16 was followed using the polysiloxane-polycarbonate copolymer of comparative example 2.
EXAMPLE 18 preparation of polycarbonate resin f (PC-f) containing polysiloxane-polycarbonate copolymer
The procedure of example 16 was followed using the polysiloxane-polycarbonate copolymer of comparative example 4.
EXAMPLE 19 preparation of polycarbonate resin g (PC-g) containing polysiloxane-polycarbonate copolymer
The procedure of example 16 was followed using the polysiloxane-polycarbonate copolymer of example 11.
EXAMPLE 20 preparation of polycarbonate resin h (PC-h) containing polysiloxane-polycarbonate copolymer
The procedure of example 16 was followed using the polysiloxane-polycarbonate copolymer of example 12.
EXAMPLE 21 preparation of polycarbonate resin i (PC-i) containing polysiloxane-polycarbonate copolymer
240g of the polysiloxane-polycarbonate copolymer powder of example 10,
2277g of general-purpose PC resin,
2277g of general-purpose PC resin, 6g of antioxidant and 9g of mold release agent were thoroughly mixed, and then extruded and cut into pellets at 280 ℃ by using a Cobelron CTE35 type extruder, and the obtained pellets were characterized by the following conditions after injection molding.
EXAMPLE 22 preparation of polycarbonate resin j (PC-j) containing polysiloxane-polycarbonate copolymer
3738g of the polysiloxane-polycarbonate copolymer powder of example 10,
2277g of general-purpose PC resin,
2277g of general-purpose PC resin, 6g of antioxidant and 9g of mold release agent were thoroughly mixed, and then extruded and cut into pellets at 280 ℃ by using a Cobelron CTE35 type extruder, and the obtained pellets were characterized by the following conditions after injection molding.
Comparative example 5 production of polycarbonate resin 1(PC-1) containing polysiloxane-polycarbonate copolymer
1g of the polysiloxane-polycarbonate copolymer powder of example 13,
2277g of general-purpose PC resin,
2277g of general-purpose PC resin, 6g of antioxidant and 9g of mold release agent were thoroughly mixed, and then extruded and cut into pellets at 280 ℃ by using a Cobelron CTE35 type extruder, and the obtained pellets were characterized by the following conditions after injection molding.
Comparative example 6 production of polycarbonate resin 2(PC-2) containing polysiloxane-polycarbonate copolymer
The preparation was carried out according to the method of comparative example 5 using the polysiloxane-polycarbonate copolymer of comparative example 2.
Comparative example 7 production of polycarbonate resin 3(PC-3) containing polysiloxane-polycarbonate copolymer
The preparation was carried out according to the method of comparative example 5 using the polysiloxane-polycarbonate copolymer of comparative example 4.
The polycarbonate resin product performance test data prepared in the foregoing manner are as follows:
from the performance expressions of the examples and the comparative examples in the above table, it can be seen that the polycarbonate resin produced by using the polysiloxane-polycarbonate copolymer of the present invention is advantageous for further increasing the heat distortion temperature thereof while maintaining good impact properties and fluidity when the cyclic siloxane residue in the copolymer is 500ppm or less; and when the cyclic siloxane residue in the copolymer exceeds 500ppm, the more the residue, the lower the heat distortion temperature resistance of the polycarbonate resin, so that the present invention can be applied to various products having a high heat distortion temperature resistance while the products show good appearance color tone.
In addition, in the actual production formulation, it was found that when the cyclic siloxane content is further reduced from 100ppm to less than 1ppm, the polycarbonate resin produced from the polysiloxane-polycarbonate copolymer of the present invention shows less improvement in various properties, but the amount of post-treatment process is significantly increased, and the energy consumption and cost are increased, which is not suitable for actual production.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (12)
1. A polysiloxane-polycarbonate copolymer comprises a polycarbonate block structural unit shown in a formula (I) and a polysiloxane block structural unit shown in a formula (II), wherein the content of cyclic siloxane in the polysiloxane-polycarbonate copolymer is 1-500 ppm; the adding amount of the polysiloxane during polymerization of the polysiloxane-polycarbonate copolymer accounts for 3-30% of the mass of the copolymer produced after polymerization; the average polymerization degree n of the polysiloxane is 20-80;
In the formula, R 1 And R 2 Each independently selected from hydrogen, halogen, C 1 ~C 20 Alkyl of (C) 4 ~C 20 Cycloalkyl or C 6 ~C 20 Aryl of (a); a and b are independently selected from integers of 0-4; x is selected from alkyl, ether linkage, carbonyl, thioether linkage, sulfone group, sulfoxide group, C 1 ~C 20 Alkylene of (C) 6 ~C 20 Arylene of, C 6 ~C 20 Alicyclic group of the formula (A) or
) The group of (a):
Wherein R is 5 And R 6 Each independently represents C 1 ~C 20 Alkyl of (C) 4 ~C 20 Cycloalkyl or C 6 ~C 20 Aryl of (2); or R 5 And R 6 Connection formation C 4 ~C 20 C, said C 4 ~C 20 Optionally substituted with one or more C 1 ~C 20 Alkyl of (C) 6 ~C 20 Aryl of (C) 7 ~C 21 Aralkyl radical, C 5 ~C 20 Cycloalkyl or a combination thereof;
R 3 and R 4 Each independently selected from hydrogen, halogen atom or C 1 ~C 6 Alkyl of (C) 1 ~C 6 Alkoxy or C 6 ~C 12 Aryl of (2); y is selected from alkylene groups comprising aliphatic or aromatic organic residues; n is an integer of 20-80;
the cyclic siloxane is a cyclic siloxane with the structure shown in the formula (III),
Wherein R is 3 And R 4 Each independently selected from hydrogen, halogen atom or C 1 ~C 6 Alkyl of (C) 1 ~C 6 Alkoxy or C 6 ~C 12 Aryl of (a); c represents an integer of 1 to 20.
2. The polysiloxane-polycarbonate copolymer of claim 1, wherein Y is selected from methylene, ethylene, or phenylene.
3. The polysiloxane-polycarbonate copolymer of claim 1, wherein the structural unit of formula (I) is derived from a polycarbonate prepared from bisphenol a.
4. The polysiloxane-polycarbonate copolymer according to claim 1, wherein R in the structural units represented by the formulae (II) and (III) 3 、R 4 The radicals are simultaneously methyl.
5. The polysiloxane-polycarbonate copolymer of claim 1 or 4, wherein the cyclic siloxane is one or more of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetradecylcyclopentasiloxane, and hexadecylcyclooctasiloxane.
6. The polysiloxane-polycarbonate copolymer of claim 5, wherein the cyclic siloxane is octamethylcyclotetrasiloxane.
7. The method for producing a polysiloxane-polycarbonate copolymer according to any one of claims 1 to 6, comprising the steps of:
a) purifying the polysiloxane with the phenolic hydroxyl terminal shown in the formula (IV) by using an adsorbent with micropores;
b) mixing the polysiloxane with the phenolic hydroxyl terminal obtained in the step a) with an organic solvent, adding the mixture into an organic solution of a polycarbonate oligomer generated by the reaction of raw material monomers, and reacting the polysiloxane with the phenolic hydroxyl terminal in the following formula (IV) with the polycarbonate oligomer or phosgene under alkaline conditions;
c) separating the reaction product in the step b) into oil and water, washing, devolatilizing and drying to obtain polysiloxane-polycarbonate copolymer;
Wherein R is 3 And R 4 Each independently selected from hydrogen, halogen atom or C 1 ~C 6 Alkyl of (C) 1 ~C 6 Alkoxy or C 6 ~C 12 N is an integer of 20 to 80; z represents a structure represented by the following formula (V):
Wherein R is 7 Is represented by C 1 ~C 4 Alkyl of (C) 1 ~C 4 P represents an integer of 0 to 4.
8. The method for producing the polysiloxane-polycarbonate copolymer according to claim 7, wherein the phenolic hydroxyl group of the polysiloxane terminates with allyl phenol or eugenol.
9. A polycarbonate resin comprising the polysiloxane-polycarbonate copolymer according to any one of claims 1 to 6 and an aromatic polycarbonate.
10. The polycarbonate resin of claim 9, further comprising 0 to 5 wt% of any one or more selected from the group consisting 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, a dye, a pigment, and a filler, based on the total amount of the polysiloxane-polycarbonate copolymer and the aromatic polycarbonate.
11. The polycarbonate resin according to claim 9 or 10, wherein the polysiloxane-polycarbonate copolymer is 1 to 50% by mass of the polycarbonate resin.
12. The polycarbonate resin of claim 9, wherein the polycarbonate resin has a heat distortion temperature of 120 ℃ or higher under a load of 1.8MPa as measured by ASTM D648.
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