CN115612084B - Chemical-resistant polycarbonate material and preparation method thereof - Google Patents
Chemical-resistant polycarbonate material and preparation method thereof Download PDFInfo
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- CN115612084B CN115612084B CN202110796484.5A CN202110796484A CN115612084B CN 115612084 B CN115612084 B CN 115612084B CN 202110796484 A CN202110796484 A CN 202110796484A CN 115612084 B CN115612084 B CN 115612084B
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 67
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 59
- 239000000126 substance Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 20
- 239000004408 titanium dioxide Substances 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 17
- 229920002545 silicone oil Polymers 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 claims description 8
- 229940083037 simethicone Drugs 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 9
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000002608 ionic liquid Substances 0.000 abstract description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 5
- 239000012752 auxiliary agent Chemical class 0.000 abstract description 5
- 159000000000 sodium salts Chemical class 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- 238000004383 yellowing Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 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 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000006355 external stress Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 229940008099 dimethicone Drugs 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical group C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- -1 4' -biphenol Chemical compound 0.000 description 1
- LKKXDOSEBJXCFE-UHFFFAOYSA-N CN1N(CCCCCCCCN1)C1CCCCCCCCCC1 Chemical compound CN1N(CCCCCCCCN1)C1CCCCCCCCCC1 LKKXDOSEBJXCFE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000234295 Musa Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 210000003195 fascia Anatomy 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 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
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/24—General preparatory processes using carbonyl halides and phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
- C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
- C08G64/085—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application discloses a chemical-resistant polycarbonate material, which comprises the following raw materials: bisphenol A, dihydric phenol, alkaline agent, catalyst, halogenated alkane, auxiliary agent, siloxane, organic sodium salt, ionic liquid, phosgene and deionized water. According to the application, through accurate raw material selection, compounding and proportion adjustment, and simple melt mixing, the polycarbonate material with good chemical resistance, photoyellowing resistance and mechanical strength is prepared, the overall comprehensive performance of the polycarbonate material is further enhanced, the applicability of the polycarbonate material is improved, and the application field and environment of the polycarbonate material are expanded.
Description
Technical Field
The application relates to the field of IPC classified C08L69, in particular to a chemical-resistant polycarbonate material and a preparation method thereof.
Background
Polycarbonates (PC) are a high molecular polymer containing carbonate groups in the molecular chain, and can be classified into various types depending on the ester groups. Polycarbonate is used as one of amorphous engineering plastics, and has the characteristics of good heat resistance, good transparency and the like, so that the polycarbonate is widely applied to the fields of automobiles, electric appliances and medical care products. At the same time, however, polycarbonate materials also suffer from a number of performance problems, such as notch sensitivity, poor chemical resistance, poor light and yellowing resistance, and susceptibility to cracking, limiting their further application, especially in the healthcare field, where numerous healthcare devices are often in the environment of various medical and medical chemicals, and therefore, higher demands are placed on the corresponding chemical resistance properties of polycarbonate materials.
The prior art (CN 201611178739.7) provides a chemical resistant flame retardant polycarbonate material, which is prepared by simply mixing polycarbonate, oligomeric silsesquioxane, a flame retardant, an anti-dripping agent, a toughening agent and an antioxidant, and is claimed to have good chemical resistance and flame retardant performance, but a simple mixing preparation method is easy to cause problems of additive precipitation and compatibility when adding excessive amounts of functional additives. Meanwhile, the chemical resistance, flame retardance and other properties of the polycarbonate are mainly improved, and the change and improvement of other important characteristic properties such as light resistance, yellowing resistance and hydrophobicity are less.
The prior art (CN 201180063799.3) provides a polycarbonate resin composition having excellent chemical resistance, which mainly adopts aromatic polycarbonate and siloxane-based polycarbonate and syndiotactic polystyrene, and claims to have good chemical resistance and fluidity, but the raw materials of the chemical-resistant polycarbonate material prepared by the composition do not have obvious raw materials capable of inhibiting yellowing and oxidation of the material, which makes the material extremely easy to undergo yellowing and oxidation phenomena under the condition of illumination ultraviolet rays, and simultaneously affects the quality and service life of the polycarbonate material.
It is therefore a significant task to develop a polycarbonate material which has good chemical resistance, and at the same time also has good resistance to light yellowing and hydrophobicity.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present application provides a chemical-resistant polycarbonate material, which comprises the following raw materials: bisphenol A, dihydric phenol, alkaline agent, catalyst, halogenated alkane, auxiliary agent, siloxane, organic sodium salt, ionic liquid, phosgene and deionized water.
In some preferred embodiments, the raw materials comprise at least the following parts by weight: 80-100 parts of bisphenol A, 40-55 parts of dihydric phenol, 30-60 parts of alkaline agent, 1-2 parts of catalyst, 15-25 parts of halogenated alkane, 1-10 parts of auxiliary agent, 40-60 parts of siloxane, 0.1-1 part of organic sodium salt, 1-5 parts of ionic liquid, 110-140 parts of phosgene and 300-500 parts of deionized water.
In some preferred embodiments, the dihydric phenol is at least one of 2,2 '-biphenol, 4' -biphenol, hydroquinone, 2, 6-dihydroxynaphthalene.
In some preferred embodiments, the mass ratio of dihydric phenol to bisphenol a is from 4 to 5: 8-9.
In some preferred embodiments, the dihydric phenol to bisphenol a mass ratio is 4.6:8.5.
in some preferred embodiments, the dihydric phenol is 4,4' -biphenol.
In the application, the chemical resistance of the polycarbonate material is further improved by adding 4,4' -biphenol as a synthesis raw material. The inventors speculate that: the addition of 4,4' -biphenol can cooperate with the process of synthesizing polycarbonate by using o-allylphenol-terminated dimethyl silicone oil and phosgene to form a three-dimensional network structure in order to replace the original straight structure, and the addition of the multi-benzene ring can further improve entanglement strength of long chains and benzene rings in the polycarbonate material, improve crosslinking property and crosslinking density, reduce the number of movable groups in the material and inhibit the flow of internal electrons; meanwhile, the addition of the 4,4' -biphenol can generate stronger connecting force through intermolecular acting force between hydroxyl groups and the surfaces of the titanium dioxide particles, so as to inhibit precipitation of modified particles in the material, wherein the mass ratio of the crosslinking and the titanium dioxide particles to bisphenol A is 4.6: the best is achieved at 8.5; too low an amount of addition significantly reduces the chemical resistance and stability of the polycarbonate material.
In some preferred embodiments, the alkaline agent is at least one of 50wt% aqueous sodium hydroxide solution, 50wt% aqueous sodium bicarbonate solution.
In some preferred embodiments, the alkaline agent is 50wt% aqueous sodium hydroxide.
In some preferred embodiments, the catalyst is triethylamine.
In some preferred embodiments, the haloalkane is at least one of dichloromethane, chloroform.
In some preferred embodiments, the haloalkane is dichloromethane.
In some preferred embodiments, the adjunct is at least one of titanium dioxide, zinc oxide, antimony dioxide, modified titanium dioxide, and modified zinc oxide.
In some preferred embodiments, the adjunct is modified titanium dioxide.
In some preferred embodiments, the modified titanium dioxide has an average fineness of 60 to 80nm.
In some preferred embodiments, the mass ratio of the modified titanium dioxide to bisphenol a is 4 to 8: 80-90.
In some preferred embodiments, the mass ratio of the modified titanium dioxide to bisphenol a is 5:85.
in the application of the application, the mechanical property and the light resistance and yellowing resistance of the polycarbonate material are effectively improved by adding the modified titanium dioxide as an auxiliary agent. The inventors speculate that: the modified titanium dioxide is connected through a metal coordination bond to form an electron flow path with a special PN junction structure, and can gather carriers and electron holes in a valence band and a conduction band of the composite particles under the illumination of visible light, so that the forbidden band distance of the composite ions is reduced, the absorption wavelength of the composite particles under the visible light is improved, the ultraviolet light absorption capacity is further improved, and especially when the mass ratio of the modified titanium dioxide to bisphenol A is 5: at 85, the light resistance of the polycarbonate material is optimal; meanwhile, when the fineness of the modified titanium dioxide is 60-80 nm, the modified titanium dioxide can be most effectively present under the action of external stress, the inside of the generated microscopic crack structure is in filiform tight connection with the polycarbonate material through the active surface and the surface group, and when the modified titanium dioxide is subjected to strong external stress, the modified titanium dioxide can convert cracks into silver cracks, so that microscopic notch formation of the polycarbonate material is prevented, and the penetration of a chemical solvent is further reduced.
In some preferred embodiments, the method of preparing the modified titanium dioxide comprises the steps of: (1) Dissolving succinic anhydride in DMF solution, adding a certain amount of silane coupling agent, heating and stirring for 1 hour at the water bath temperature of 60 ℃; (2) Dropwise adding DMF solution containing titanium dioxide into the reaction solution, and continuously stirring and reacting for 2 hours to obtain pretreated titanium dioxide particles; (3) Dispersing pretreated titanium dioxide particles in deionized water, then adding dimethyl imidazole, cetyl trimethyl ammonium bromide, zinc nitrate and a proper amount of deionized water, rapidly mixing and stirring for 10 minutes, then adding the mixture into a 120 ℃ hydrothermal kettle for reaction for 2-2.5 hours, and after the reaction is completed, vacuum drying at 60 ℃ and grinding to obtain the titanium dioxide.
In some preferred embodiments, the siloxane is at least one of a dimethicone, a hydroxy silicone oil, a hydrogen containing silicone oil.
In some preferred embodiments, the siloxane is an ortho allylphenol terminated dimethicone.
In some preferred embodiments, the weight ratio of the o-allylphenol-terminated simethicone to bisphenol A is from 5 to 6: 8-9.
In some preferred embodiments, the weight ratio of o-allylphenol-terminated simethicone to bisphenol a is 5.8:8.5.
in some preferred embodiments, the ortho allylphenol end capped simethicone has an average molecular weight of 3000 to 3800.
In the application of the application, the chemical solvent resistance and the corresponding mechanical properties of the polycarbonate material are effectively improved by adding the dimethyl silicone oil capped by the o-allylphenol in the synthesis process of the polycarbonate material. The inventors speculate that: adding o-allylphenol-terminated dimethyl silicone oil in the synthesis process, and particularly when the average molecular weight is 3000-3800, and the mass ratio is 5.8:8.5, the o-allylphenol-terminated dimethyl silicone oil can cooperate with bisphenol A and phosgene in the raw materials to form an optimal cyclic low-aggregation structure, so that further condensation reaction is carried out to form a high-molecular-weight polymer material, larger molecular long chains are formed in the polymer material, more internal entanglement points are increased, and disentanglement resistance is improved; in addition, the number of microscopic stress concentration points existing at the low end group in the polycarbonate material can be obviously reduced, and microscopic defects are reduced, so that the formation number of microscopic cracks is greatly reduced when external stress is applied, and the total penetration amount of chemical solvents is reduced.
In some preferred embodiments, the organic sodium salt is sodium gluconate.
In some preferred embodiments, the ionic liquid is at least one of trifluoroethanol, methyltriazabicycloundecane, methylimidazolium.
In some preferred embodiments, the ionic liquid is trifluoroethanol.
In some preferred embodiments, at least one of a flame retardant, an inorganic filler, an organic filler, an anti-drip agent, a heat stabilizer, an antioxidant, and an ultraviolet light absorber may be further added to the chemical-resistant polycarbonate material.
In the application of the application, the modified titanium dioxide is converted from a pure hydrophilic state with 4 hydroxyl groups on the surface into a hydrophobic state with a rough skeleton surface, and then the modified titanium dioxide is synergistic with the dimethyl silicone oil blocked by the o-allylphenol in the raw material, so that the hydrophobic property of the surface of the polycarbonate material is obviously enhanced. When the polycarbonate material is specifically used, the residual time of the chemical water solvent on the surface of the polycarbonate is greatly shortened, so that the cleaning condition of the chemical solvent on the surface of the polycarbonate is improved, and the chemical resistance and environmental applicability of the polycarbonate material are further improved.
In some preferred embodiments, the chemical resistant polycarbonate material is substantially free of non-nanostructured fluoropolymers encapsulated by an encapsulating polymer, preferably substantially free of styrene-acrylonitrile encapsulated non-nanostructured poly (tetrafluoroethylene).
The second aspect of the present application provides a method for preparing the chemical-resistant polycarbonate material, comprising the steps of: (1) Adding deionized water and dihydric phenol into a six-neck flask with a stirrer, a pH meter and a condenser tube, stirring and purging with nitrogen for 5-10 minutes, then adding an alkaline agent, and stirring for 10-15 minutes to dissolve the dihydric phenol; (2) Adding a catalyst and halogenated alkane into another container, and shaking uniformly to prepare a uniform solution; (3) Adding bisphenol A, siloxane, ionic liquid and organic sodium salt into a six-neck flask, then introducing a certain amount of phosgene at a constant speed, simultaneously adding an alkaline agent again to adjust the pH to 9.8-10.2, and continuously stirring for 10-15 minutes; (4) Adding a catalyst and a uniform solution of halogenated alkane into a flask, adding an alkaline agent again in an appropriate amount to keep the pH of the solution at 10-11, and then introducing phosgene at 2-2.4 g/min for 10-12 min, wherein the pH of the solution is kept at 8.7-9.3 continuously by adding the alkaline agent during the process, and adjusting the pH to 8.5 after the introduction of the phosgene is completed; (5) And (3) standing the solution for layering, taking the lower layer of oil phase, adding 0.1N hydrochloric acid with the same volume for washing once, washing with deionized water for four times, adding methanol into the oil phase to precipitate and separate out a product, placing the product in a 100-DEG oven for 6-8 hours for drying, and then adding an auxiliary agent for granulating after melt mixing to obtain the chemical-resistant polycarbonate material.
The third aspect of the present application provides an application of the chemical-resistant polycarbonate material, which is characterized in that: the use of the chemical resistant polycarbonate materials in molded articles, thermoformed articles, extruded films, extruded sheets, substrates for coated articles, and substrates for metallized articles is included.
Further, the chemical resistant polycarbonate material is included in the electronic housing of a game console, game controller, portable game device, cellular telephone, television, personal computer, tablet, laptop, personal digital assistant, portable media player, digital camera, portable music player, appliance, power tool, robot, toy, greeting card, home entertainment system, active speaker, bar-form box, adapter, cell phone, smart phone, GPS device, laptop, tablet, electronic reader, copier or solar device, or the article is an electrical junction box, electrical connector, electric automobile charger, outdoor electrical housing, smart meter housing, smart grid power node, photovoltaic frame, automobile, scooter, and motorcycle exterior or interior components, preferably a panel, rear roof side panel, rocker panel, plaque, fender, battery cover, door, trunk deck lid, trunk lid, engine cover, roof, bumper, fascia, headlights, rear mirror housing, pillar trim, cladding, body side molding, wheel covers, door handles, window covers, tail lights, window frames, roof light, roof side frames, license plates, roof side frames, roof mirror housings, license plates, roof frames, roof light, roof frames.
The beneficial effects are that:
1. according to the application, through accurate raw material selection, compounding and proportion adjustment, and simple melt mixing, the polycarbonate material with good chemical resistance, photoyellowing resistance and mechanical strength is prepared, the overall comprehensive performance of the polycarbonate material is further enhanced, the applicability of the polycarbonate material is improved, and the application field and environment of the polycarbonate material are expanded.
2. In the application of the application, the polycarbonate material with high molecular weight and good crosslinking degree is effectively synthesized by reasonably selecting and preparing the dosage ratio of bisphenol A, the dimethyl silicone oil capped by the o-allylphenol and the biphenol, and the chemical strength and the mechanical property of the polycarbonate material are effectively improved.
3. According to the application, by simply adding the modified titanium dioxide, the light resistance and yellowing resistance of the polycarbonate under visible light are effectively improved, the polycarbonate material has good hydrophobic performance, the tolerance of a chemical solvent is further improved, and the application field and the application environment of the polycarbonate material are widened.
Detailed Description
The following describes the technical solution of the present application in detail by examples, but the scope of protection of the present application is not limited to all the examples described. The raw materials of the present application are all commercially available unless otherwise specified.
Example 1
Example 1 in a first aspect, a chemical resistant polycarbonate material is provided, the raw materials comprising, by weight: 85 parts of bisphenol A, 46 parts of 4,4' -biphenol, 39.3 parts of 50wt% sodium hydroxide aqueous solution, 1.2 parts of triethylamine, 20 parts of methylene dichloride, 5 parts of modified titanium dioxide (average fineness of 75 nm), 58 parts of dimethyl silicone oil (average molecular weight of 3500) capped with o-allylphenol, 0.5 part of sodium alginate, 2 parts of trifluoroethanol, 129.6 parts of phosgene and 400 parts of deionized water.
In this example, the preparation method of the modified titanium dioxide comprises the following steps: (1) 5 parts of succinic anhydride are dissolved in 50 parts of DMF solution, 10 parts of (3-aminopropyl) triethoxysilane are added, and the mixture is heated and stirred for 1 hour at a water bath temperature of 60 ℃; (2) Dropwise adding 50 parts of DMF solution containing 2 parts of titanium dioxide into the reaction solution, and continuously stirring and reacting for 2 hours to obtain pretreated titanium dioxide particles; (3) 1 part of pretreated titanium dioxide particles are dispersed in deionized water, then 10 parts of dimethyl imidazole, 15 parts of 0.01wt% of cetyltrimethylammonium bromide, 2 parts of zinc nitrate and 50 parts of deionized water are added, the mixture is rapidly mixed and stirred for 10 minutes, then the mixture is added into a 120 ℃ hydrothermal kettle for reaction for 2.25 hours, and after the reaction is completed, the mixture is dried in vacuum at 60 ℃ and ground to obtain the titanium dioxide.
In this example, succinic anhydride CAS 108-30-5, (3-aminopropyl) triethoxysilane CAS 919-30-2, dimethylimidazole CAS 693-98-1, cetyl trimethylammonium bromide CAS 57-09-0.
In this example, the titanium dioxide is a model P25 titanium dioxide product sold by Shanghai Michlin corporation.
In this example, bisphenol A is a bisphenol A product sold by Shandong North chemical Co., ltd.
In this example, 4 '-biphenol is a 4,4' -biphenol product sold by Jiangsu Qingquan chemical Co., ltd.
In this example, the o-allylphenol-terminated simethicone was an o-allylphenol-terminated simethicone product sold by Jinan silicon harbor chemical Co.
The second aspect of the present embodiment provides a method for preparing a chemical-resistant polycarbonate material, comprising the steps of: (1) Into a six-neck flask with a stirrer, a pH meter and a condenser tube, 400 parts of deionized water and 46 parts of 4,4 '-biphenol are added, stirred and purged with nitrogen for 8 minutes, then 39.3 parts of 50wt% aqueous sodium hydroxide solution is added, and stirred for 12 minutes to dissolve the 4,4' -biphenol; (2) Adding 1.2 parts of triethylamine and 20 parts of dichloromethane into another container, and shaking uniformly to prepare a uniform solution; (3) 85 parts of bisphenol A, 58 parts of dimethyl silicone oil capped by o-allylphenol, 2 parts of trifluoroethanol and 0.5 part of sodium alginate are added into a six-neck flask, 108 parts of phosgene is introduced at a constant speed, and simultaneously sodium hydroxide solution is added again to adjust the pH to 10, and stirring is continued for 12 minutes; (4) Adding a uniform solution of triethylamine and dichloromethane into a flask, adding a proper amount of sodium hydroxide solution again to keep the pH of the solution at 10.5, and then introducing phosgene at 2.16 parts/min for 10 min, continuously keeping the pH at 9 by adding the sodium hydroxide solution during the period, and adjusting the pH at 8.5 after the phosgene is introduced; (5) And (3) after the solution is still layered, taking the lower layer of oil phase, adding 0.1N hydrochloric acid with the same volume for washing once, washing four times by using deionized water, adding 20 parts of methanol into the oil phase to precipitate a product, placing the product in a 100-DEG C oven for 8 hours for drying, and then adding 5 parts of modified titanium dioxide for granulating by melt mixing to obtain the chemical-resistant polycarbonate material.
Example 2
The specific implementation of this example is the same as example 1, except that: 40 parts of 4,4' -biphenol.
Example 3
The specific implementation of this example is the same as example 1, except that: the modified titanium dioxide is reacted in a hydrothermal kettle for 2.5 hours, and the average fineness of the modified titanium dioxide is 80nm.
Example 4
The specific implementation of this example is the same as example 1, except that: the average molecular weight of the o-allylphenol-terminated simethicone was 3000 and 50 parts by weight.
Comparative example 1
The specific embodiment of this comparative example is the same as example 1, except that: 20 parts of 4,4' -biphenol.
Comparative example 2
The specific embodiment of this comparative example is the same as example 1, except that: the 4,4' -biphenol was 65 parts.
Comparative example 3
The specific embodiment of this comparative example is the same as example 1, except that: the modified titanium dioxide is reacted in a hydrothermal kettle for 4.5 hours, and the average fineness of the modified titanium dioxide is 150nm.
Comparative example 4
The specific embodiment of this comparative example is the same as example 1, except that: 2 parts of modified titanium dioxide.
Comparative example 5
The specific embodiment of this comparative example is the same as example 1, except that: the modified titanium dioxide is replaced by the common P25 type titanium dioxide.
Comparative example 6
The specific embodiment of this comparative example is the same as example 1, except that: the weight of the o-allylphenol-terminated simethicone is 20 parts.
Evaluation of Performance
Spline test: the polycarbonate materials prepared in each example and comparative example were prepared into corresponding ASTM test bars, the surface of the bars was coated with a chemical agent (Banana BOAT Ultra Sport SPF) when a tensile test was performed, the angle of the fixed curved surface stretching was 20 °, and after 15 days, the number of cracks on the surface of the bars was observed to be 3 or less, 6 or less, and 6 or more, C.
Light fastness test: all the polycarbonate materials prepared in examples and comparative examples were prepared into sheets of 3cm x 1cm, sun-dried for 8 hours a day with sufficient sunlight, the yellowing and morphology of the sheets were observed, and the sheets were judged to be unacceptable if there was a significant yellowing, 50 samples were tested in each example and comparative example, 5 or less samples were marked as failed A, 5 or less samples were marked as failed B, 15 or more samples were marked as failed C, and the results of the observations were recorded in Table 1.
Hydrophilicity test: all polycarbonate materials prepared in examples and comparative examples were prepared into 3cm x 1cm flakes, after which the hydrophilic angle of the corresponding flakes was tested by the sitting-drop method, 5 samples were tested in each example comparative example, and the average of the measured values is reported in table 1.
TABLE 1
Examples | Chemical resistance | Light resistance | Hydrophilic (°) |
Example 1 | A | A | 121 |
Example 2 | A | A | 119 |
Example 3 | A | A | 120 |
Example 4 | A | A | 118 |
Comparative example 1 | B | B | 109 |
Comparative example 2 | B | B | 105 |
Comparative example 3 | C | B | 107 |
Comparative example 4 | C | C | 84 |
Comparative example 5 | B | C | 85 |
Comparative example 6 | C | B | 104 |
It can be known from examples 1 to 4, comparative examples 1 to 6 and table 1 that the chemical-resistant polycarbonate material provided by the application has good chemical solvent resistance, mechanical properties, light resistance and hydrophobicity, effectively widens the application field and environment of the polycarbonate material, is suitable for popularization in the field of engineering plastics, and has wide development prospect. Wherein example 1 obtained the best performance index with the best raw material ratio and preparation process.
Finally, it should be understood that the foregoing embodiments are merely preferred embodiments of the present application, and are not intended to limit the application, but are intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (2)
1. A preparation method of a chemical-resistant polycarbonate material is characterized by comprising the following steps: the method comprises the following steps: (1) Into a six-neck flask with a stirrer, a pH meter and a condenser tube, 400 parts of deionized water and 46 parts of 4,4 '-biphenol are added, stirred and purged with nitrogen for 8 minutes, then 39.3 parts of 50wt% aqueous sodium hydroxide solution is added, and stirred for 12 minutes to dissolve the 4,4' -biphenol; (2) Adding 1.2 parts of triethylamine and 20 parts of dichloromethane into another container, and shaking uniformly to prepare a uniform solution; (3) 85 parts of bisphenol A, 58 parts of dimethyl silicone oil capped by o-allylphenol, 2 parts of trifluoroethanol and 0.5 part of sodium alginate are added into a six-neck flask, 108 parts of phosgene is introduced at a constant speed, and simultaneously sodium hydroxide solution is added again to adjust the pH to 10, and stirring is continued for 12 minutes; (4) Adding a uniform solution of triethylamine and dichloromethane into a flask, adding a proper amount of sodium hydroxide solution again to keep the pH of the solution at 10.5, and then introducing phosgene at 2.16 parts/min for 10 min, continuously keeping the pH at 9 by adding the sodium hydroxide solution during the period, and adjusting the pH at 8.5 after the phosgene is introduced; (5) After the solution is static and layered, taking the lower layer of oil phase, adding 0.1N hydrochloric acid with the same volume for washing once, then washing with deionized water for four times, adding 20 parts of methanol into the oil phase to precipitate a product, placing the product in a 100-DEG oven for 8 hours for drying, and then adding 5 parts of modified titanium dioxide for granulating by melt mixing to obtain the chemical-resistant polycarbonate material;
the preparation method of the modified titanium dioxide comprises the following steps: (1) 5 parts of succinic anhydride are dissolved in 50 parts of DMF solution, 10 parts of (3-aminopropyl) triethoxysilane are added, and the mixture is heated and stirred for 1 hour at a water bath temperature of 60 ℃; (2) Dropwise adding 50 parts of DMF solution containing 2 parts of titanium dioxide into the reaction solution, and continuously stirring and reacting for 2 hours to obtain pretreated titanium dioxide particles; (3) Dispersing 1 part of pretreated titanium dioxide particles in deionized water, then adding 10 parts of dimethyl imidazole, 15 parts of 0.01wt% of cetyltrimethylammonium bromide, 2 parts of zinc nitrate and 50 parts of deionized water, rapidly mixing and stirring for 10 minutes, then adding the mixture into a 120 ℃ hydrothermal kettle for reaction for 2.25 hours, and after the reaction is completed, vacuum drying at 60 ℃ and grinding to obtain the titanium dioxide;
the average fineness of the modified titanium dioxide is 75nm;
the average molecular weight of the o-allylphenol end-capped simethicone is 3500;
the titanium dioxide is a P25 titanium dioxide product sold by Shanghai microphone company.
2. Use of a material prepared by the process for the preparation of a chemical resistant polycarbonate according to claim 1, characterized in that: the use of the chemical resistant polycarbonate materials in molded articles, thermoformed articles, extruded films, extruded sheets, substrates for coated articles, and substrates for metallized articles is included.
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