CN112824450A - Low-temperature-resistant high-fluidity flame-retardant PC - Google Patents
Low-temperature-resistant high-fluidity flame-retardant PC Download PDFInfo
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- CN112824450A CN112824450A CN201911149813.6A CN201911149813A CN112824450A CN 112824450 A CN112824450 A CN 112824450A CN 201911149813 A CN201911149813 A CN 201911149813A CN 112824450 A CN112824450 A CN 112824450A
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- Prior art keywords
- bisphenol
- polycarbonate
- polycarbonate copolymer
- retardant
- low temperature
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- 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 title claims abstract description 32
- 239000003063 flame retardant Substances 0.000 title claims abstract description 32
- 239000004417 polycarbonate Substances 0.000 claims abstract description 61
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 claims abstract description 43
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 22
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000155 melt Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- -1 siloxane units Chemical group 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229920006260 polyaryletherketone Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 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 description 5
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000176 sodium gluconate Substances 0.000 description 3
- 229940005574 sodium gluconate Drugs 0.000 description 3
- 235000012207 sodium gluconate Nutrition 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- KCCUBRRTVWFOGF-UHFFFAOYSA-N 2-tritylphenol Chemical compound OC1=CC=CC=C1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 KCCUBRRTVWFOGF-UHFFFAOYSA-N 0.000 description 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical compound CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/18—Block or graft polymers
- C08G64/186—Block or graft polymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/24—General preparatory processes using carbonyl halides and phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to low-temperature-resistant high-fluidity flame-retardant PC. The low-temperature-resistant high-fluidity flame-retardant PC prepared by the invention is prepared from the following raw materials in parts by weight: 10-50 wt% of polysiloxane-bisphenol A polycarbonate copolymer, 5-30 wt% of polyester-bisphenol A polycarbonate copolymer, 10-50 wt% of tetrabromobisphenol A polycarbonate-bisphenol A polycarbonate copolymer and 10-50 wt% of general purpose polycarbonate. The low temperature resistant high flow flame retardant PC prepared by the invention still has impact toughness at-50 ℃, and is measured on a molded NII experimental sample with the thickness of 3.2mm according to ASTM D256-04; a melt volume rate of 15.0-20.5cc/10min at 300 ℃ and a load of 1.2kg and a residence time of 6 minutes, measured according to ASTM D1238-04, of low temperature resistant, high flow flame retardant PC; the flame retardant grade of the low-temperature resistant high-flow flame retardant PC can reach UL 94V 0 grade.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to low-temperature-resistant high-fluidity flame-retardant PC (polycarbonate).
Background
At present, polymer materials are needed in the aspect of our life, and with the progress of science and technology, we have higher and higher requirements on the service performance of the materials, but at present, the polymer materials in the prior art usually have excellent performance in one direction and may have poor performance in the other direction.
The polysiloxane polycarbonate copolymer has excellent ductility retention at low temperatures, but its processing flowability is poor and cannot meet the necessary mold filling requirements. In the prior art, the polymer with processing fluidity is combined with the polysiloxane polycarbonate copolymer, so that the prepared polymer not only keeps the low-temperature impact resistance, but also has good processing stability. Chinese patent CN102227473A discloses a transparent thermoplastic composition having high flow and ductility and articles made therefrom, wherein a polysiloxane-polycarbonate copolymer and a poly (aliphatic ester) -polycarbonate copolymer are combined such that the blend retains 100% ductility at-40 ℃ and a melt volume rate of up to 22cc/10min (at 300 ℃ under a 1.2kg load).
Polyaryletherketone resins have excellent solvent resistance, fire resistance, low wear rate, wear resistance and high strength, but the lower glass transition temperature of polyaryletherketone resins limits their use under load at high temperatures. The Chinese patent CN101802092A is to mix the polyaryl ether ketone resin and the polycarbonate resin copolymer, and the high temperature bearing capacity of the prepared mixture is greatly improved compared with that of the polyaryl ether ketone resin, the polyaryl ether ketone resin has a modulus of 188-204MPa at 160-200 ℃, and the modulus of the mixture of the polyaryl ether ketone resin and the polycarbonate resin at 160-200 ℃ can reach 349-661 MPa.
Therefore, in the field of polymer materials, combining several copolymers to form a mixture, and simultaneously exerting the characteristics of each copolymer in the prepared mixture is a trend of research, but how to combine several polymers overcomes the compatibility problem of the polymers in the mixing process, and the mixture can exert the characteristics of each single polymer is a problem in the research process.
Disclosure of Invention
The invention mixes polysiloxane-polycarbonate copolymer, polyester-polycarbonate copolymer, tetrabromobisphenol A polycarbonate-bisphenol A polycarbonate copolymer and 4 general polycarbonates to prepare the low temperature resistant high flow flame retardant PC.
The technical scheme provided by the invention is as follows:
the low-temperature-resistant high-fluidity flame-retardant PC is prepared from the following raw materials in parts by weight: 10-50 wt% of polysiloxane-bisphenol A polycarbonate copolymer, 5-30 wt% of polyester-bisphenol A polycarbonate copolymer, 10-50 wt% of tetrabromobisphenol A polycarbonate-bisphenol A polycarbonate copolymer and 10-50 wt% of general purpose polycarbonate.
Further, the polysiloxane-bisphenol a polycarbonate copolymer has the following structure:
wherein R and Me are each independently C1-C10 alkyl, C6-C18 aryl, or halogenated or alkoxylated C1-C10 alkyl or C6-C18 aryl;
the weight average molecular weight of the polysiloxane-bisphenol A polycarbonate copolymer is 22000-35000, and the content of siloxane units in the polysiloxane-bisphenol A polycarbonate copolymer is 16-22 wt%.
Further, the structure of the polyester-bisphenol a polycarbonate copolymer is as follows:
wherein m is 8-10;
the weight average molecular weight of the polyester-bisphenol A polycarbonate copolymer was 20000-30000.
Further, the structure of tetrabromobisphenol a polycarbonate-bisphenol a polycarbonate copolymer is as follows:
the weight average molecular weight of the tetrabromobisphenol A polycarbonate-bisphenol A polycarbonate copolymer is 20000-30000.
Further, the general polycarbonate is one or more selected from aromatic polycarbonate.
Further, the content of the siloxane units in the polysiloxane-bisphenol A polycarbonate copolymer is 20 to 22 wt%.
Furthermore, the low-temperature-resistant high-flow flame-retardant PC disclosed by the invention also comprises an auxiliary agent.
Furthermore, the auxiliary agent is one or more of an anti-dripping agent, an antioxidant, an ultraviolet absorbent and a lubricant.
Further, the anti-dripping agent is polytetrafluoroethylene resin anti-dripping agent.
Further, the antioxidant is at least one of a phenolic antioxidant and a phosphite antioxidant;
further, the ultraviolet absorbent is at least one of salicylic acid esters, benzophenones, benzotriazoles, substituted acrylonitriles, triazines and hindered amine ultraviolet absorbents.
Further, the lubricant is fatty acid amide lubricant or dimethyl silicone oil.
Furthermore, the content of the auxiliary agent in the low-temperature-resistant high-flow flame-retardant PC disclosed by the invention is 1-10 wt%.
Furthermore, the polysiloxane-bisphenol A polycarbonate copolymer disclosed by the invention is obtained by random copolymerization of polysiloxane, bisphenol A, alkali metal hydroxide, an inert organic solvent, a catalyst, an end capping agent and phosgene.
Further, the polyester-bisphenol A polycarbonate copolymer disclosed by the invention is obtained by random copolymerization of aliphatic ester, bisphenol A, alkali metal hydroxide, inert organic solvent, catalyst, end capping agent and phosgene.
Furthermore, the tetrabromobisphenol A polycarbonate-bisphenol A polycarbonate copolymer disclosed by the invention is obtained by carrying out random copolymerization on tetrabromobisphenol A, bisphenol A, alkali metal hydroxide, an inert organic solvent, a catalyst, an end capping agent and phosgene.
Further, the alkali metal hydroxide is selected from lithium hydroxide, sodium hydroxide or potassium hydroxide.
Further, the inert organic solvent is selected from the group consisting of dichloromethane, trichloroethylene, 1, 1, 1-trichloroethane, 1, 1, 2-trichloroethane, benzene, toluene, m-/o-/p-xylene and chlorobenzene and mixtures thereof.
Further, the catalyst may be selected from tetrabutylammonium, tributylbenzylammonium, tetraethylammonium hydroxide, chloride, triethylamine, methyltributylammonium chloride or bromide.
Further, the end-capping agent is selected from phenol, p-cumylphenol, p-tert-butylphenol, octylphenol, or tritylphenol.
Further, the low-temperature-resistant high-fluidity flame-retardant PC disclosed by the invention is prepared by adopting the following method: weighing polysiloxane-polycarbonate copolymer, polyester-polycarbonate copolymer, tetrabromobisphenol A polycarbonate-bisphenol A polycarbonate copolymer and an auxiliary agent according to the mass percentage, mixing, adding the mixture into an extruder, extruding and drawing strips, cooling by a water tank, and then cutting into particles to obtain the low-temperature-resistant high-flow flame-retardant PC.
Compared with the prior art, the invention has the beneficial effects that:
the invention blends four polymers of polysiloxane-bisphenol A polycarbonate copolymer, polyester-bisphenol A polycarbonate copolymer, tetrabromobisphenol A polycarbonate-bisphenol A polycarbonate copolymer, universal carbonate and the like to prepare the copolymerized PC. The low-temperature-resistant high-flow flame-retardant PC prepared by the invention still has impact toughness at-50 ℃, and is measured on a molded NII experimental sample with the thickness of 3.2mm according to ASTM D256-04; a melt volume rate of 15.0-20.5cc/10min at 300 ℃ and a load of 1.2kg and a residence time of 6 minutes, measured according to ASTM D1238-04, of low temperature resistant, high flow flame retardant PC; the flame retardant grade of the low-temperature resistant high-flow flame retardant PC can reach UL 94V 0 grade. In addition, the addition agent is added into the PC prepared by the invention, so that the prepared PC can meet the performances, and simultaneously has the performances of oxidation resistance, ultraviolet absorption resistance and the like.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As an embodiment of the invention, the low-temperature-resistant high-flow flame-retardant PC disclosed by the invention comprises the following components:
(1) polysiloxane-bisphenol A polycarbonate copolymer
In the formula, R is methyl, Me is propyl;
the weight average molecular weight of the polysiloxane-polycarbonate copolymer was 26000, wherein the content of siloxane units in the polysiloxane-bisphenol a polycarbonate copolymer was 20 wt%;
the preparation method of the polysiloxane-bisphenol A polycarbonate copolymer comprises the following steps:
907g of bisphenol A is dissolved in 10 percent aqueous solution containing 160g of sodium hydroxide to obtain bisphenol A saline solution; adding the bisphenol A saline solution, 600ml of deionized water, 2500ml of dichloromethane, 3g of phenol, 5.9ml of methyl tributyl ammonium chloride 75% aqueous solution and 1.5g of sodium gluconate into a reactor, uniformly stirring, introducing 450g of phosgene at the speed of 25 g/min for reaction, controlling the reaction temperature to be 32-40 ℃, and adding a sodium hydroxide solution to control the pH value of a reaction system to be 5.3; stirring was continued for 10 minutes, and the sodium hydroxide solution was added to adjust the pH of the system to 11.5. 60g of polysiloxane is dropwise added at a constant speed within 15-20 minutes to carry out random copolymerization, the reaction temperature is 30-40 ℃, the pH value of a reaction system is 11.5, the stirring is continued for 10 minutes, 4.1 ml of triethylamine and 10g of phenol are added, 220g of phosgene is introduced at a speed of 25 g/minute, and the pH value of the solution is kept at 10. And after the reaction is finished, adding dilute hydrochloric acid and deionized water into the organic phase for washing and related subsequent treatment.
(2) Polysebacic acid-bisphenol A polycarbonate copolymer (polyester-bisphenol A polycarbonate copolymer)
Wherein m is 8;
the weight average molecular weight of the polysebacic acid-bisphenol A polycarbonate copolymer is 22000;
the preparation method of the polysebacic acid-bisphenol A polycarbonate copolymer comprises the following steps:
dissolving 400g of sebacic acid in 50% aqueous solution containing 344g of sodium hydroxide to obtain aqueous solution of sebacate; adding the aqueous solution of sebacate, 14L of deionized water, 24L of dichloromethane, 30ml of 2.5% aqueous solution of triethylamine, 10g of sodium gluconate and 4100g of bisphenol A into a reactor, uniformly stirring, introducing 1170g of phosgene at the speed of 80 g/min for reaction, dissolving 180g of p-cumylphenol in 1L of dichloromethane, dropwise adding the p-cumylphenol dissolved in the dichloromethane into the reactor in the phosgene introduction process, adding a sodium hydroxide solution to control the pH value of a reaction system to be 7, introducing 1570g of phosgene, gradually increasing the pH value to 10.2, keeping the pH value of the solution to be 10.2, and introducing 200g of phosgene for reaction. And after the reaction is finished, adding dilute hydrochloric acid and deionized water into the organic phase for washing and related subsequent treatment.
(3) Tetrabromobisphenol A polycarbonate-bisphenol A polycarbonate copolymer
The weight average molecular weight of the tetrabromobisphenol a polycarbonate-bisphenol a polycarbonate copolymer is 24000;
the preparation method of the tetrabromobisphenol A polycarbonate-bisphenol A polycarbonate copolymer comprises the following steps:
adding 100g of sodium hydroxide in 30% aqueous solution into a reactor, adding 12L of deionized water, 16L of dichloromethane, 130mL of triethylamine, 2250g of tetrabromobisphenol A, 2250g of bisphenol A and 10g of sodium gluconate into the reactor, introducing 10% phosgene, adding sodium hydroxide solution, keeping the pH value of the solution in the reactor at 9.8-10.8, starting dropwise adding a p-cumylphenol solution dissolved in dichloromethane (105g of p-cumylphenol dissolved in 250mL of dichloromethane) into the reactor, continuing the reaction by using phosgene, and controlling the pH value to reach 9.5-9.8 at the end of the reaction. And after the reaction is finished, adding dilute hydrochloric acid and deionized water into the organic phase for washing and related subsequent treatment.
(4) The polycarbonate in this embodiment has a molecular weight of 20000-30000 and is produced by Gansu silver light silver chemical Co.
(5) Pure powder type polytetrafluoroethylene resin (anti-dripping agent).
The invention discloses a low-temperature-resistant high-fluidity flame-retardant PC, which is prepared by the following method: weighing polysiloxane-polycarbonate copolymer, polyester-polycarbonate copolymer and tetrabromobisphenol A polycarbonate-bisphenol A polycarbonate copolymer according to mass percent, mixing the raw materials, adding the mixture into an extruder, extruding and drawing strips, cooling by a water tank, and then cutting into particles to obtain the PC. As an embodiment of the invention, the contents of the components in the low temperature resistant high flow flame retardant PC prepared by the invention are shown in Table 1.
TABLE 1 content of each component in the low temperature resistant high flow flame retardant PC
The low-temperature-resistant high-flow flame-retardant PC disclosed by the invention is tested according to the following test standards:
MVR melt volume rate, measured according to ASTM D1238-04 under a load of 300 ℃/1.2kg and with a residence time of 6 minutes, and given in cc/10 min;
notched Izod impact strength (J/m), determined according to ASTM D256-04, on 3.2mm thick molded samples (bars) at a temperature of-50 ℃ reached, wherein the NII impact strength is given in units of joules per meter (J/m);
percent ductility was measured on 3.2mm thick molded NII test specimens according to ASTM D256-04, using impact strength and stress whitening of the fracture surface to determine the presence of ductile fracture.
The glass transition temperature (Tg in ° c) was determined using Differential Scanning Calorimetry (DSC) operating at a ramp rate of 10 ℃/min, and the glass transition temperature was determined using a second heat.
The test results of examples 1 to 4 and comparative examples 1 to 3 are shown in Table 2.
TABLE 2 Low temperature resistant high flow flame retardant PC
In conclusion, the low-temperature-resistant high-flow flame-retardant PC prepared by the invention still has impact toughness at-50 ℃, the melt volume rate at 300 ℃, under the load of 1.2kg and under the residence time of 6 minutes is 15.0-20.5cc/10min, and the flame-retardant grade can reach UL 94V 0 grade.
The present invention has been further described with reference to specific embodiments, but it should be understood that the detailed description should not be construed as limiting the spirit and scope of the present invention, and various modifications made to the above-described embodiments by those of ordinary skill in the art after reading this specification are within the scope of the present invention.
Claims (8)
1. The low-temperature-resistant high-fluidity flame-retardant PC is characterized by being prepared from the following raw materials in parts by weight: 10-50 wt% of polysiloxane-bisphenol A polycarbonate copolymer, 5-30 wt% of polyester-bisphenol A polycarbonate copolymer, 10-50 wt% of tetrabromobisphenol A polycarbonate-bisphenol A polycarbonate copolymer and 10-50 wt% of general polycarbonate; the low temperature resistant high flow flame retardant PC has impact toughness at-50 ℃ as measured on 3.2mm thick molded NII test samples according to ASTM D256-04; the low temperature resistant, high flow flame retardant PC has a melt volume rate of 15.0-20.5cc/10min at 300 ℃ and a load of 1.2kg and a residence time of 6 minutes, measured according to ASTM D1238-04; the flame retardant grade of the low-temperature-resistant high-flow flame-retardant PC reaches UL 94V 0 grade.
2. The PC of claim 1, wherein the polysiloxane-bisphenol A polycarbonate copolymer has the following structure:
wherein R and Me are each independently C1-C10 alkyl, C6-C18 aryl, or halogenated or alkoxylated C1-C10 alkyl or C6-C18 aryl;
the weight average molecular weight of the polysiloxane-polycarbonate copolymer is 22000-35000, and the content of siloxane units in the polysiloxane-bisphenol A polycarbonate copolymer is 16-22 wt%.
3. The PC with low temperature resistance and high flow resistance as claimed in claim 1, wherein the structure of the polyester-bisphenol A polycarbonate copolymer is as follows:
wherein m is 8-10;
the weight average molecular weight of the polyester-bisphenol A polycarbonate copolymer is 20000-30000.
4. The PC with low temperature resistance and high flow resistance and flame retardance of claim 1, wherein the tetrabromobisphenol A polycarbonate-bisphenol A polycarbonate copolymer has the following structure:
the weight average molecular weight of the tetrabromobisphenol A polycarbonate-bisphenol A polycarbonate copolymer is 20000-30000.
5. The PC with low temperature resistance and high flow resistance and flame retardance according to claim 1, wherein the general purpose polycarbonate is one or more selected from aromatic polycarbonate.
6. The PC with low temperature resistance and high flow resistance and flame retardance of claim 1, wherein the siloxane units in the polysiloxane-bisphenol A polycarbonate copolymer are 20-22 wt%.
7. The PC with low temperature resistance and high flow and flame retardance according to claim 1, further comprising an auxiliary agent, wherein the auxiliary agent is one or more of an anti-dripping agent, an antioxidant, an ultraviolet absorber and a lubricant.
8. The PC with low temperature resistance and high flow flame retardance as claimed in claim 7, wherein the content of the auxiliary in the PC with low temperature resistance and high flow flame retardance is 1-10 wt%.
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| CN102227473A (en) * | 2008-11-26 | 2011-10-26 | 沙伯基础创新塑料知识产权有限公司 | Transparent thermoplastic compositions having high flow and ductiliy, and articles prepared therefrom |
| CN103492492A (en) * | 2011-03-31 | 2014-01-01 | 沙特基础创新塑料Ip私人有限责任公司 | Flame retardant polycarbonate compositions, methods of manufacture, and articles formed therefrom |
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| CN102227473A (en) * | 2008-11-26 | 2011-10-26 | 沙伯基础创新塑料知识产权有限公司 | Transparent thermoplastic compositions having high flow and ductiliy, and articles prepared therefrom |
| CN103492492A (en) * | 2011-03-31 | 2014-01-01 | 沙特基础创新塑料Ip私人有限责任公司 | Flame retardant polycarbonate compositions, methods of manufacture, and articles formed therefrom |
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| CN114752052A (en) * | 2022-03-31 | 2022-07-15 | 宁波港智新材料有限公司 | Sebacic acid block copolycarbonate, preparation method and application thereof |
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