CN117510820A - Polycarbonate with heat resistance, yellowing resistance and precipitation resistance as well as preparation method and application thereof - Google Patents
Polycarbonate with heat resistance, yellowing resistance and precipitation resistance as well as preparation method and application thereof Download PDFInfo
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- CN117510820A CN117510820A CN202311624899.XA CN202311624899A CN117510820A CN 117510820 A CN117510820 A CN 117510820A CN 202311624899 A CN202311624899 A CN 202311624899A CN 117510820 A CN117510820 A CN 117510820A
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- polycarbonate
- dihydric phenol
- phenol compound
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 55
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 55
- 238000001556 precipitation Methods 0.000 title claims abstract description 21
- 238000004383 yellowing Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000004945 emulsification Methods 0.000 claims abstract description 11
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 238000006552 photochemical reaction Methods 0.000 claims abstract description 10
- 238000011282 treatment Methods 0.000 claims abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 phenol compound Chemical class 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 230000001804 emulsifying effect Effects 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 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 13
- 239000000203 mixture Substances 0.000 claims description 8
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 7
- 239000002981 blocking agent Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000003287 optical effect Effects 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
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000003756 stirring 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
- KXIXHISTUVHOCY-UHFFFAOYSA-N 1-propan-2-ylpiperidine Chemical compound CC(C)N1CCCCC1 KXIXHISTUVHOCY-UHFFFAOYSA-N 0.000 claims description 2
- VTDIWMPYBAVEDY-UHFFFAOYSA-N 1-propylpiperidine Chemical compound CCCN1CCCCC1 VTDIWMPYBAVEDY-UHFFFAOYSA-N 0.000 claims description 2
- HJZJMARGPNJHHG-UHFFFAOYSA-N 2,6-dimethyl-4-propylphenol Chemical compound CCCC1=CC(C)=C(O)C(C)=C1 HJZJMARGPNJHHG-UHFFFAOYSA-N 0.000 claims description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 2
- XHASMJXNUHCHBL-UHFFFAOYSA-N 4-(1-phenylethyl)phenol Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=CC=C1 XHASMJXNUHCHBL-UHFFFAOYSA-N 0.000 claims description 2
- KCIVBLNHLBBZFE-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C=2C3=C(C4=CC=CC=C4C3)C=CC=2)=C1 KCIVBLNHLBBZFE-UHFFFAOYSA-N 0.000 claims description 2
- GIXNHONPKYUROG-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phenol Chemical compound C1=CC(O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C12 GIXNHONPKYUROG-UHFFFAOYSA-N 0.000 claims description 2
- JNAUIOQFUDVUJP-UHFFFAOYSA-N 4-cyclododecylphenol Chemical compound C1=CC(O)=CC=C1C1CCCCCCCCCCC1 JNAUIOQFUDVUJP-UHFFFAOYSA-N 0.000 claims description 2
- OAHMVZYHIJQTQC-UHFFFAOYSA-N 4-cyclohexylphenol Chemical compound C1=CC(O)=CC=C1C1CCCCC1 OAHMVZYHIJQTQC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical compound CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- CREVBWLEPKAZBH-UHFFFAOYSA-M hydron;tetraethylazanium;sulfate Chemical compound OS([O-])(=O)=O.CC[N+](CC)(CC)CC CREVBWLEPKAZBH-UHFFFAOYSA-M 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 229960001701 chloroform Drugs 0.000 claims 1
- 150000004679 hydroxides Chemical group 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 11
- 238000005406 washing Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 238000011033 desalting Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 229920005668 polycarbonate resin Polymers 0.000 description 4
- 239000004431 polycarbonate resin Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical group OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method 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
- C08G64/20—General preparatory processes
- C08G64/26—General preparatory processes using halocarbonates
- C08G64/28—General preparatory processes using halocarbonates 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
- C08G64/04—Aromatic polycarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a polycarbonate with heat resistance, yellowing resistance and precipitation resistance, a preparation method and application thereof. The molecular weight distribution coefficient of the polycarbonate is less than or equal to 2.2, the residual quantity of the end capping agent is less than or equal to 1.3ppm, and the hydroxyl end content is less than or equal to 130ppm. The invention carries out emulsification phase inversion on the dihydric phenol photochemical reaction liquid added with the end-capping agent and the alkali liquor, when the weight average molecular weight is increased to a certain range, a proper amount of catalyst is added to continuously complete the polymerization reaction, and then the polycarbonate product is obtained after conventional treatments such as layered desalting, acid washing, water washing, concentration, drying and the like, and has the advantages of good heat resistance, yellowing resistance, few crystal points of a film and the like.
Description
Technical Field
The invention relates to the field of preparation of polycarbonate, in particular to polycarbonate with heat resistance, yellowing resistance and precipitation resistance, and a preparation method and application thereof.
Background
Polycarbonate (PC) is an engineering plastic with excellent performance and is widely applied to the fields of automobiles, electronic equipment, buildings, office supplies, optical discs, sports equipment, medical care, computers, aerospace and the like. In general, when applied to a film material, it is desirable to use a polycarbonate resin having properties such as heat resistance, yellowing resistance, and precipitation resistance.
Japanese patent JP3958634B2 discloses that after the reaction liquid of a carbonate oligomer is emulsified, the reaction liquid is kept standing in a tank without stirring, the emulsified state is maintained to continue the reaction, and at the same time, the reactor is in laminar flow to maintain the emulsified state, and a catalyst is added in the middle of a tubular reactor, so that a polycarbonate resin with few residual chloroformate groups and hydroxyl end groups in the polymer is obtained, and the polycarbonate resin has excellent heat resistance, but since the end-capping agent and the molecular weight distribution are affected by the transfer process of the reaction, significant non-uniformity exists in mass transfer between two phases and in the phases of the laminar flow, the problems of high end-capping agent residue and widening of the molecular weight distribution are caused, and the precipitation resistance is poor. In addition, the invention adopts the tubular reactor, so that huge pressure drop is generated in the production process, and the energy consumption is increased.
Patent CN101195680a continuously synthesizes polycarbonate by using a pipe type high shear dispersing emulsifying machine as a key device for mixing two phases in polycarbonate synthesis by an interfacial phosgene method. The catalyst and the antioxidant are added into a phenol sodium salt solution, a molecular weight regulator is added at the rear part of a first emulsifying machine for end capping, the end hydroxyl number of the generated polycarbonate is reduced, the molecular weight of the polycarbonate is controlled, and a narrow molecular weight distribution product is obtained, but the catalyst is added before emulsification, so that high emulsification occurs in emulsifying equipment, the two phases of reaction liquid are difficult to separate, the end capping agent and other small molecules remain higher due to the fact that an oil phase is easy to carry an aqueous phase, and the yellowing resistance and the precipitation resistance of the final product are poor.
Aiming at the problems existing in the prior art, there is still a need to develop a polycarbonate resin which is suitable for film materials and has the performances of heat resistance, yellowing resistance, precipitation resistance and the like.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a polycarbonate having heat resistance, yellowing resistance and precipitation resistance.
It is another object of the present invention to provide a process for producing the above polycarbonate.
It is a further object of the present invention to provide the use of the polycarbonate.
In order to achieve the above object, the present invention adopts the following technical scheme:
in one aspect, the present invention provides a polycarbonate having heat, yellowing, and precipitation resistance properties, the polycarbonate having a molecular weight distribution coefficient (Mw/Mn) of 2.2 or less, such as 2.2, 2.1, 2.0, 1.8, 1.5, etc., preferably 2.2 to 1.8; the residual amount of the blocking agent is 1.3ppm or less, for example, 1.3ppm, 1.0ppm, 0.8ppm, 0.5ppm, 0.2ppm, 0.1ppm, etc., preferably 1.0 to 0.1ppm; the content of terminal hydroxyl groups is 130ppm or less, for example 130ppm, 120ppm, 100ppm, 50ppm or the like, preferably 130ppm to 100ppm.
In the research on the performance of the polycarbonate, the invention surprisingly discovers that the polycarbonate with the characteristics of narrow molecular weight distribution, low small molecular residue (namely, end capping agent residue) and low-end hydroxyl content can have heat resistance, yellowing resistance and precipitation resistance. It will be understood by those skilled in the art that these properties of the polycarbonates of the present invention are not limited by any method of preparation, and are not relevant to the method by which they are prepared, so long as the above-described features are met and are within the scope of the present invention; it is also understood that the polycarbonate exhibits good heat resistance, yellowing resistance and precipitation resistance as long as it has the above-described characteristics.
In another aspect, the present invention provides a method for preparing the above polycarbonate having heat resistance, yellowing resistance and precipitation resistance, and it should be understood by those skilled in the art that the following preparation method is only an exemplary illustration of the manner in which the polycarbonate product of the present invention having the above characteristics is derived, but not limiting in any way. The polycarbonates according to the invention are also not limited to the preparation methods listed below.
The invention provides a preparation method of polycarbonate with heat resistance, yellowing resistance and precipitation resistance by way of example, the dihydric phenol photochemical reaction liquid added with a blocking agent and alkali liquor is subjected to emulsification phase inversion, when the weight average molecular weight is increased to a certain range, a proper amount of catalyst is added to continue to complete polymerization reaction, and then the polycarbonate product is obtained after conventional treatments such as layered desalting, acid washing, water washing, concentration and drying.
In a preferred embodiment, the method for preparing the polycarbonate with heat resistance, yellowing resistance and precipitation resistance comprises the following steps:
(a) Photochemical stage: continuously introducing alkali solution of dihydric phenol compound, phosgene and inert organic solvent into an photochemical reactor for photochemical reaction to obtain oligomer mixed solution;
(b) Polycondensation stage: the pH value of the oligomer mixture in the step (a) is adjusted to 11-13, such as 11.0, 11.5, 12.0, 12.5, 13.0, preferably 11.5-12.5, a blocking agent is added into the mixture to be uniformly mixed, then the mixture is transferred into an emulsifying machine to be emulsified, then the mixture is transferred into a reaction kettle to be stirred for reaction, and when the weight average molecular weight is increased to 45-70%, such as 45%, 50%, 55%, 60%, 65%, 70%, preferably 50-65%, more preferably 55-60%, of the target molecular weight, a catalyst is added to continue the reaction, so that the polycarbonate is prepared.
In a preferred embodiment, after the reaction of step (b) is completed, a crude product solution containing polycarbonate is prepared, and conventional post-treatment operations such as layered desalting, acid washing, water washing, concentration, drying and the like are further included, for example, the crude reaction product is separated to remove an aqueous phase, and the organic phase is respectively washed, desolventized, dried and the like, so that a person skilled in the art can combine and screen the existing treatment modes according to actual needs, and the invention is not particularly limited.
In a specific embodiment, the alkali solution of the dihydric phenol compound in step (a) is an aqueous solution of the dihydric phenol compound and an alkali, wherein the concentration of the dihydric phenol compound is 14 to 17wt%, such as 14.5wt%, 15.5wt%, 16.5wt%, preferably 15 to 16wt%, and the concentration of the alkali is 5.5 to 6.2wt%, such as 5.6wt%, 5.8wt%, 6.1wt%, preferably 5.7 to 6.0wt%;
wherein the dihydric phenol compound is selected from aromatic phenol compounds, preferably 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A), 4- (1-isopropylidene) bis (2, 6-bisphenol) (tetramethyl bisphenol A), hydroquinone, resorcinol, 1-bis (4-hydroxyphenyl) phenylethane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (3-methyl-4-hydroxyphenyl) cyclohexane one or more of 1, 1-bis (4-hydroxyphenyl) -3, 5-trimethylcyclohexane, 1-bis (4-hydroxyphenyl) cyclododecane, 4 '-dihydroxybiphenyl, 4' -dihydroxydiphenyl ether, 4 '-dihydroxydiphenyl sulfone, 4-dihydroxydiphenylmethane, 4' -dihydroxydiphenyl sulfide, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (3-methyl-4-hydroxyphenyl) fluorene, more preferably 2, 2-bis (4-hydroxyphenyl) propane;
wherein the alkali is selected from alkali metal or alkaline earth metal hydroxide, preferably one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and magnesium hydroxide, more preferably sodium hydroxide.
In a specific embodiment, the inert organic solvent of step (a) is selected from chlorinated aliphatic hydrocarbons, preferably one or more of dichloromethane, chloroform, dichloroethane, trichloroethane, more preferably dichloromethane.
In a specific embodiment, the ratio of the molar flow rate of phosgene fed to the basic solution of dihydric phenol compound in step (a) is from 1 to 1.5:1, such as 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, preferably from 1.1 to 1.2:1, wherein the basic solution of dihydric phenol compound is calculated as the dihydric phenol compound contained.
In a specific embodiment, the ratio of the feed mass flow rate of the inert organic solvent to the feed mass flow rate of the alkali solution of the dihydric phenol compound of step (a) is from 0.3 to 1.2:1, such as from 0.4:1, 0.6:1, 0.8:1, 1.0:1, 1.2:1, preferably from 0.5 to 0.8:1.
In a specific embodiment, the temperature of the photochemical reaction of step (a) is less than or equal to 40 ℃, e.g. 40 ℃, 35 ℃, 30 ℃, 25 ℃, 20 ℃, 15 ℃, 10 ℃,5 ℃, 0 ℃, preferably 19 to 38 ℃, more preferably 26 to 35 ℃; the residence time is from 0.2 to 0.6h, for example from 0.2h, 0.3h, 0.4h, 0.5h, 0.6h, preferably from 0.3 to 0.45h;
preferably, during the photochemical reaction, the pH of the system is maintained at a value of from 10.5 to 13.5, for example from 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, preferably from 11.5 to 12.5, by adjusting the feed ratio of the raw materials.
In a preferred embodiment, the oligomer mixture obtained in step (a) has a weight average molecular weight Mw of 1000 to 5000g/mol, for example 1000g/mol, 2000g/mol, 3000g/mol, 4000g/mol, 5000g/mol, preferably 1500 to 3500g/mol, more preferably 2000 to 3000g/mol.
In a specific embodiment, the end-capping agent of step (b) is selected from one or more of aromatic monophenols, preferably phenol, methylphenol, tert-butylphenol, p-cumylphenol.
In a specific embodiment, the catalyst of step (b) is selected from a tertiary amine compound, a quaternary ammonium compound or a salt thereof, preferably one or more of triethylamine, tributylamine, trioctylamine, N-methylpiperidine, N-ethylpiperidine, N-N-propylpiperidine, N-isopropylpiperidine, tributylbenzyl ammonium, tetraethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium bisulfate, tetraethylammonium tetrafluoroborate, tetrabutylammonium.
In a specific embodiment, the capping agent of step (b) is added in an amount of 1 to 10% by mole of the dihydric phenol compound in the alkaline solution of the dihydric phenol compound of step (a).
In a specific embodiment, the catalyst of step (b) is added in an amount of 0.01 to 10%, such as 0.01%, 0.1%, 0.5%, 1.0%, 2.0%, 4.0%, 6.0%, 8.0%, 10.0%, preferably 0.1 to 1% of the molar amount of dihydric phenol compound in the alkaline solution of dihydric phenol compound of step (a).
In a specific embodiment, step (b) controls the particle size to be 5-25 μm, for example 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, preferably 10-15 μm, by the emulsification operation, so that the emulsified reaction liquid continues to be polymerized in an emulsified form in the tank reactor, reducing the reaction energy consumption, and being more suitable for industrial production;
preferably, the emulsifying device used for the emulsifying operation may be a high-speed emulsifying machine such as a homogenizer, a mixer, a homogenizing mixer, a colloid mill, a jet mixer, etc., or a static emulsifying machine such as a static mixer, a hole mixer, an ultrasonic emulsifying device, etc., preferably a homogenizer is used, and the reaction liquid is phase-inverted from an oil-in-water system to a water-in-oil system by the emulsifying operation.
In a specific embodiment, the reaction of step (b) is carried out at a temperature of 40℃or less, for example 40℃35℃30℃25℃20℃15℃10℃5℃0℃preferably 20 to 39℃more preferably 35 to 38 ℃;
wherein, the reaction time is not particularly limited when the weight average molecular weight is increased to 45-70% of the target molecular weight, wherein the target molecular weight refers to the molecular weight of the polycarbonate end product prepared in the step (b), and the weight average molecular weight Mw ranges from 10000 to 100000g/mol, such as 10000g/mol, 20000g/mol, 40000g/mol, 60000g/mol, 80000g/mol, 100000g/mol, preferably 13000 to 40000g/mol;
wherein, the reaction time of adding the catalyst for continuous reaction is 0.15-0.6 h, such as 0.2h, 0.3h, 0.4h, 0.5h, 0.6h, preferably 0.25-0.4 h;
preferably, the reaction process of step (b) maintains a system pH of 11.5 to 12.5, for example 11.5, 12.0, 12.5, preferably 11.8 to 12.2;
preferably, in the polycondensation stage of step (b), the pH of the system is adjusted by methods conventional in the art, for example by adding an alkali solution, preferably an aqueous alkali hydroxide solution.
The polycarbonate prepared by the preparation method disclosed by the invention has the advantages that the molecular weight distribution is less than or equal to 2.2, the hydroxyl end content is less than or equal to 130ppm, and the residual quantity of the end capping agent is less than or equal to 1.3ppm, so that the polycarbonate product has excellent heat resistance, yellowing resistance and lower precipitation problem.
In still another aspect, the invention also provides an application of the polycarbonate or the polycarbonate prepared by the preparation method, which is suitable for the fields of electronic products, automobiles, medical treatment and the like, and is especially suitable for preparing products such as optical discs, films and the like.
The polycarbonate can be further processed to obtain required molded parts by adding common additives such as a stabilizer, a release agent, a filler or glass fiber and the like before or during processing, and the prepared polycarbonate product has better heat resistance, ground color and processing stability and can be used in the fields of optical discs, films and the like.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1) The polycarbonate has the characteristics of narrow molecular weight distribution, low small molecular residue and low hydroxyl content, and the polycarbonate product with the structural characteristics is not easy to degrade in the processing process, so that the precipitation of small molecules is reduced.
2) In the preparation method, during the polycondensation reaction, the polycarbonate product with narrow molecular weight distribution, low small molecular residue and low hydroxyl end content is obtained by controlling the means of the pH value of the water phase, the particle size of the emulsion after emulsification, the adding time of the catalyst and the like when the end-capping agent is added.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In the examples and comparative examples of the present invention, the performance test parameters and corresponding test methods for polycarbonate products were as follows:
and measuring the pH value of the photochemical reaction liquid and the aqueous phase of the polycondensation reaction liquid by a pH value tester.
The polymer molecular weight (3 separation columns) was measured by Gel Permeation Chromatography (GPC) (apparatus model: agilent Technologies 1260 inches) with methylene chloride as the mobile phase, PS as the standard, flow rate 1mL/min, column temperature and tank temperature of 30 ℃.
Polymer molecular weight was measured by Gel Permeation Chromatography (GPC) (apparatus model number Agilent Technologies 1260 index) methodDistribution coefficient (5 separation columns, separation column model: agilent PLgel)5um 300*7.5mm*2；Agilent PLgel/>5um 300*7.5mm*2；Agilent PLgel/>5um 300 x 7.5mm x 1; ) Dichloromethane is the mobile phase, PS is the standard sample, the flow rate is 1mL/min, and the column temperature and the box temperature are both 30 ℃.
Determination of the polymerization liquid oil phase by nuclear magnetic resonance 1 H-NMR spectrum, the content of terminal hydroxyl groups in the polymerization reaction liquid oil phase was calculated by integration of peaks derived from bisphenol-based compounds.
The low molecular weight (i.e., capping agent) content in the aqueous phase of the polycondensation reaction liquid was tested by high performance liquid chromatography.
YI value of the 3mm test piece obtained by injection molding at 300 ℃ is measured by a color difference meter and reflects the yellowing degree of the sample.
And measuring the background color change of the two test pieces A, B by a color difference meter to obtain a heat-resistant color difference, wherein the test piece A is a 3mm test piece obtained by injection molding at 320 ℃, and the test piece B is a 3mm test piece obtained by injection molding after PC powder stays in an injection molding machine for 10min at 320 ℃ after injection molding of the test piece A is completed.
The precipitation performance is reflected by a method for preparing a film material with a square meter of 1 and counting the number of crystal points.
In each of the examples and comparative examples of the present invention, the main raw materials were obtained by commercially available commercial route, except that other raw materials and reagents were not specifically described as follows:
bisphenol a: industrial grade, trillion self-producing bisphenol A;
bisphenol S: industrial grade, purchased from chemical industry Co., ltd;
bisphenol F: industrial grade, purchased from chemical industry Co., ltd;
tetramethyl bisphenol a: industrial grade, purchased from Ancol Biotechnology Inc., changzhou;
dichloromethane: analytically pure, purchased from the company Miou chemical reagent, inc. of Tianjin, city;
p-tert-butylphenol (PTBP): analytically pure, purchased from Shandong province chemical institute;
phenol: analytically pure, purchased from beijing enoKai technologies Co., ltd;
p-cumylphenol (PCP): analytically pure, purchased from beijing enoKai technologies Co., ltd;
triethylamine: analytically pure, available from the company Miou chemical Co., ltd.
Examples 1 to 9
Polycarbonates of examples 1-9 having heat, yellowing, and precipitation resistance were prepared according to the starting materials and main process conditions in Table 1:
(a) Photochemical stage: continuously introducing NaOH aqueous solution of dihydric phenol compound (the concentration of dihydric phenol compound is 15.5wt%, the concentration of NaOH is 5.85 wt%), phosgene and methylene dichloride into an photochemical reactor for photochemical reaction, wherein the reaction temperature is 30 ℃, the residence time is 0.2-0.6 h, and the pH value of the system is maintained to be 11.5-12.5 in the reaction process to obtain an oligomer mixed solution;
(b) Polycondensation stage: regulating the pH value of the oligomer mixed solution in the step (a) to 11.5-12.5 (C) by adopting a NaOH aqueous solution with the concentration of 32wt%, adding a blocking agent into the oligomer mixed solution, uniformly mixing, then transferring into a homogenizer for emulsification, transferring into a reaction kettle for reaction under stirring, wherein the reaction temperature is 35 ℃, when the weight average molecular weight is increased to 45-70% (E) of the target molecular weight, adding a catalyst triethylamine, wherein the addition amount of the triethylamine is 0.1% of the mole amount of the dihydric phenol compound in the step (a), continuing to react for 0.3h, maintaining the pH value of the system to 11.8-12.2 in the reaction process, separating and removing the aqueous phase after the reaction is completed, washing the organic phase, and removing the dichloromethane solvent to obtain the colorless polycarbonate powder.
In Table 1, A is expressed as the ratio of the molar flow rate of phosgene fed to the molar flow rate of the aqueous NaOH solution of the dihydric phenol compound in step (a), wherein the aqueous NaOH solution of the dihydric phenol compound is calculated as the dihydric phenol compound contained; b is expressed as the ratio of the feed mass flow rate of methylene chloride to the feed mass flow rate of the aqueous NaOH solution of the dihydric phenol compound in step (a); c represents the pH value regulated by the oligomer mixture before adding the end capping agent in the step (b); d is expressed as the amount of the capping agent added in step (b) based on the molar amount of the dihydric phenol compound in step (a); e represents the ratio of the weight average molecular weight to the target molecular weight increase before the end-capping agent is added in step (b).
TABLE 1 types of main raw materials and main process conditions of examples 1 to 9
Comparative example 1
A polycarbonate was produced in substantially the same manner as in example 1 except that: in step (b), the pH was adjusted to 10.8 before the end-capping agent PTBP was added, with other operations and conditions unchanged.
Comparative example 2
A polycarbonate was produced in substantially the same manner as in example 1 except that: adding end capping agent PTBP, mixing uniformly, omitting emulsification step, and keeping other operation and condition unchanged.
Comparative example 3
A polycarbonate was produced in substantially the same manner as in example 1 except that: in the step (b), after the end-capping agent PTBP is added for emulsification, a catalyst triethylamine is directly added for reaction, and other operations and conditions are unchanged.
Comparative example 4
A polycarbonate was produced in substantially the same manner as in example 1 except that: in the step (b), when the weight average molecular weight is increased to 80% of the target molecular weight, triethylamine is added to continue the reaction, and other operations and conditions are unchanged.
The evaluation results of the polycarbonates prepared in each of the examples and comparative examples are shown in Table 2.
Table 2 results of evaluation of polycarbonate in examples and comparative examples
Claims (10)
1. A polycarbonate with heat resistance, yellowing resistance and precipitation resistance is characterized in that the molecular weight distribution coefficient is less than or equal to 2.2, the residual quantity of a blocking agent is less than or equal to 1.3ppm, and the hydroxyl end content is less than or equal to 130ppm.
2. A method for preparing the polycarbonate with heat resistance, yellowing resistance and precipitation resistance according to claim 1, comprising the following steps:
(a) Photochemical stage: continuously introducing alkali solution of dihydric phenol compound, phosgene and inert organic solvent into an photochemical reactor for photochemical reaction to obtain oligomer mixed solution;
(b) Polycondensation stage: and (3) regulating the pH value of the oligomer mixed solution in the step (a) to be 11-13, preferably 11.5-12.5, adding a blocking agent into the oligomer mixed solution, uniformly mixing, then transferring the mixture into an emulsifying machine for emulsification, transferring the mixture into a reaction kettle for reaction under stirring, and adding a catalyst for continuous reaction when the weight average molecular weight is increased to 45-70%, preferably 50-65%, more preferably 55-60% of the target molecular weight, so as to obtain the polycarbonate.
3. The preparation method according to claim 1, wherein the alkali solution of the dihydric phenol compound in step (a) is an aqueous solution of the dihydric phenol compound and an alkali, wherein the concentration of the dihydric phenol compound is 14 to 17wt%, preferably 15 to 16wt%, and the concentration of the alkali is 5.5 to 6.2wt%, preferably 5.7 to 6.0wt%;
preferably, the dihydric phenol compound is selected from the group consisting of aromatic phenol compounds, more preferably 2, 2-bis (4-hydroxyphenyl) propane, 4- (1-isopropylidene) bis (2, 6-bisphenol), hydroquinone, resorcinol, 1-bis (4-hydroxyphenyl) phenylethane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (3-methyl-4-hydroxyphenyl) cyclohexane one or more of 1, 1-bis (4-hydroxyphenyl) -3, 5-trimethylcyclohexane, 1-bis (4-hydroxyphenyl) cyclododecane, 4 '-dihydroxybiphenyl, 4' -dihydroxydiphenyl ether, 4 '-dihydroxydiphenyl sulfone, 4-dihydroxydiphenylmethane, 4' -dihydroxydiphenyl sulfide, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (3-methyl-4-hydroxyphenyl) fluorene, further preferred is 2, 2-bis (4-hydroxyphenyl) propane;
preferably, the base is selected from hydroxides of alkali metals or alkaline earth metals, more preferably one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, further preferably sodium hydroxide.
4. The process according to claim 1, wherein the inert organic solvent of step (a) is selected from one or more of chlorinated aliphatic hydrocarbons, preferably dichloromethane, trichloromethane, dichloroethane, trichloroethane, more preferably dichloromethane; and/or
The ratio of the molar flow rate of phosgene fed to the molar flow rate of the alkaline solution of the dihydric phenol compound in step (a) is 1 to 1.5:1, preferably 1.1 to 1.2:1, wherein the alkaline solution of the dihydric phenol compound is calculated as the dihydric phenol compound contained; and/or
The ratio of the feed mass flow rate of the inert organic solvent to the feed mass flow rate of the alkali solution of the dihydric phenol compound in the step (a) is 0.3 to 1.2:1, preferably 0.5 to 0.8:1.
5. The process according to claim 1, wherein the temperature of the photochemical reaction of step (a) is less than or equal to 40 ℃, preferably 19 to 38 ℃, more preferably 26 to 35 ℃; the residence time is 0.2 to 0.6h, preferably 0.3 to 0.45h;
preferably, the pH of the system is maintained at 10.5 to 13.5, preferably 11.5 to 12.5, during the photochemical reaction.
6. The process according to claim 1, wherein the end-capping agent of step (b) is selected from one or more of aromatic monophenols, preferably phenol, methylphenol, tert-butylphenol, p-cumylphenol; and/or
The catalyst of step (b) is selected from tertiary amine compounds, quaternary ammonium compounds or salts thereof, preferably one or more of triethylamine, tributylamine, trioctylamine, N-methylpiperidine, N-ethylpiperidine, N-N-propylpiperidine, N-isopropylpiperidine, tributylbenzyl ammonium, tetraethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium bisulfate, tetraethylammonium tetrafluoroborate, tetrabutylammonium.
7. The production method according to claim 1, wherein the amount of the blocking agent added in the step (b) is 1 to 10% by mole of the dihydric phenol compound in the alkali solution of the dihydric phenol compound in the step (a). The method comprises the steps of carrying out a first treatment on the surface of the And/or
The catalyst in step (b) is added in an amount of 0.01 to 10%, preferably 0.1 to 1% by mole of the dihydric phenol compound in the alkali solution of the dihydric phenol compound in step (a).
8. The preparation method according to claim 1, wherein step (b) controls the particle size to 5 to 25 μm, preferably 10 to 15 μm, by the emulsification operation;
preferably, the emulsifying device used for the emulsifying operation is a high-speed emulsifying machine, preferably a homogenizer, a mixer, a homogenizing mixer, a colloid mill, a flow jet mixer, or a static emulsifying machine, preferably a static mixer, an orifice mixer, an ultrasonic emulsifying device.
9. The process according to claim 1, wherein the reaction in step (b) is carried out at a temperature of 40 ℃ or less, preferably 20 to 39 ℃, more preferably 35 to 38 ℃;
the reaction time is not particularly limited when the weight average molecular weight is increased to 45-70% of the target molecular weight, wherein the target molecular weight refers to the weight average molecular weight of the polycarbonate product prepared in the step (b);
wherein, the reaction time of adding the catalyst for continuous reaction is 0.15-0.6 h, preferably 0.25-0.4 h;
preferably, the reaction in step (b) maintains a pH of the system of 11.5 to 12.5, preferably 11.8 to 12.2.
10. Use of the polycarbonate according to claim 1 or of the polycarbonate prepared by the preparation method according to claims 2 to 9 in the field of electronics, automobiles, medical applications, in particular for the preparation of optical discs, film products.
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