CN111205617A - Polycarbonate composition and preparation method thereof - Google Patents
Polycarbonate composition and preparation method thereof Download PDFInfo
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- CN111205617A CN111205617A CN202010115926.0A CN202010115926A CN111205617A CN 111205617 A CN111205617 A CN 111205617A CN 202010115926 A CN202010115926 A CN 202010115926A CN 111205617 A CN111205617 A CN 111205617A
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 149
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 131
- 239000000203 mixture Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 45
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 45
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 42
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 40
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 40
- 239000003063 flame retardant Substances 0.000 claims abstract description 36
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 35
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 239000000314 lubricant Substances 0.000 claims abstract description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- -1 pentaerythritol ester Chemical class 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000008301 phosphite esters Chemical class 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical group C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 229920000638 styrene acrylonitrile Polymers 0.000 claims description 4
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 235000012222 talc Nutrition 0.000 claims description 3
- MFFNRVNPBJQZFO-UHFFFAOYSA-N (2,6-dimethylphenyl) dihydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(O)=O MFFNRVNPBJQZFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000779 smoke Substances 0.000 abstract description 24
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 33
- 229920005989 resin Polymers 0.000 description 33
- 239000011347 resin Substances 0.000 description 33
- 238000001816 cooling Methods 0.000 description 22
- 238000002485 combustion reaction Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 239000002994 raw material Substances 0.000 description 12
- 238000001125 extrusion Methods 0.000 description 11
- 238000005469 granulation Methods 0.000 description 11
- 230000003179 granulation Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- VUFNLQXQSDUXKB-DOFZRALJSA-N 2-[4-[4-[bis(2-chloroethyl)amino]phenyl]butanoyloxy]ethyl (5z,8z,11z,14z)-icosa-5,8,11,14-tetraenoate Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(=O)OCCOC(=O)CCCC1=CC=C(N(CCCl)CCCl)C=C1 VUFNLQXQSDUXKB-DOFZRALJSA-N 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a polycarbonate composition and a preparation method thereof. The polycarbonate composition comprises the following components in parts by weight: 35-72 parts of polycarbonate; 10-20 parts of ABS resin; 12-20 parts of a flame retardant; 1-4 parts of nano silicon oxide; 5-20 parts of superfine talcum powder; 0.1-0.3 part of antioxidant; 0.1-0.3 part of a lubricant; 0.1-0.5 part of anti-dripping agent; the flame retardant comprises a phosphorus-containing flame retardant and potassium perfluorobutyl sulfonate; the polycarbonate includes bisphenol a type aromatic polycarbonate and polysiloxane-polycarbonate. The polycarbonate composition has low smoke density and heat release rate and good flame retardant property.
Description
Technical Field
The invention relates to the field of thermoplastic engineering plastics, in particular to a polycarbonate composition and a preparation method thereof.
Background
Polycarbonate (PC) is a thermoplastic polymer with excellent comprehensive performance, but the flame retardant performance of PC is general, and the flame retardant grade of PC per se can reach the UL94V-2 standard, but because the specific use occasions of polycarbonate all need higher flame retardant performance, the PC generally needs to reach the UL94V-0 standard, and simultaneously needs to have good mechanical properties, thus providing high requirements for the modification of polycarbonate. The modification method can be generally divided into: 1) chemical modification, namely introducing functional groups with flame retardant properties such as halogen, phosphate ester, silicon and the like into a PC main chain structure; 2) blending modification, namely blending and modifying the polycarbonate and the organic or inorganic modified filler by a proper physical method; 3) PC and other polymers are prepared into alloys such as PC/PS alloy, PC/ABS alloy and the like by using silane coupling agent and other compatilizers. PC composites have found wide application in passenger compartments of vehicles such as airplanes, trains, etc., such as luggage rack components, seat components, cart components, air conditioning components, cabinet components, ceilings, siding, dining boards, etc., due to their superior properties. And because the interior cabin space (passenger aircraft cabin, train carriage) of the vehicle has the characteristics of narrow interior space and concentrated personnel, once a fire breaks out, on one hand, the toxic smoke generated by burning can suffocate or die, and on the other hand, a large amount of heat and particles are released by burning, which is also the reason for generating smoke. Therefore, in addition to the requirements for flame retardancy and fire resistance, the PC composite material used in the cabin of a vehicle is also required to have excellent low smoke and low heat release properties.
Currently, the standards for the overall performance of articles used in public transportation cabins are becoming more and more stringent. For example, the fire control standardization for railroad applications adopted in the european union (EN45545) imposes stringent requirements on the heat release, smoke density and toxicity of materials. The federal aviation administration in the United states also establishes standards for flame retardant properties of related materials, and Federal Aviation Regulations (FARs) determine airworthiness standards for flame retardant materials for aviation, with very strict control indexes. China also issues related standards, such as related terms of the airworthiness standard of the China Civil Aviation Administration (CAAC), combustion characteristics of automotive interior materials (GB8410-2006), and technical conditions of motor vehicle operation safety (GB 7258-2012) which all provide corresponding requirements and standards for the flame-retardant and fireproof performance of products in the standards, and the requirements for the performance indexes of the materials and the products tend to be strict. Therefore, the development of a polycarbonate composite material with low heat release, low smoke density, low toxicity, simple processing and low price has important practical significance.
Disclosure of Invention
Based on this, it is an object of the present invention to provide a polycarbonate composition which has a low smoke density and heat release rate and good flame retardancy.
The specific technical scheme is as follows:
a polycarbonate composition comprises the following components in parts by weight:
the flame retardant comprises a phosphorus-containing flame retardant and potassium perfluorobutyl sulfonate;
the polycarbonate includes bisphenol a type aromatic polycarbonate and polysiloxane-polycarbonate.
In some of these embodiments, the polycarbonate composition comprises the following components in parts by weight:
in some of these embodiments, the polycarbonate composition comprises the following components in parts by weight:
in some of these embodiments, the polycarbonate composition comprises the following components in parts by weight:
in some of these embodiments, the ultrafine talc powder has a layered structure and a particle size of 2 to 6 μm, preferably 3 to 5 μm.
In some embodiments, the weight part of the superfine talc powder is 15 to 20 parts, preferably 18 to 20 parts.
In some embodiments, the nano-silica is present in an amount of 2 to 4 parts by weight, and more preferably 3 to 4 parts by weight.
In some of these embodiments, the nano-silica is a layered structure; the thickness of the nano-silica is 8nm to 60nm, further the thickness of the nano-silica is 8nm to 40nm, further 8nm to 30nm, further 8nm to 20nm, further 8nm to 15nm, further 8nm to 12 nm.
In some embodiments, the nano-silica has a particle size of 6nm to 100nm, further 6nm to 50nm, further 6nm to 30nm, further 6nm to 20nm, further 6nm to 15nm, further 6nm to 10 nm.
In some of these embodiments, the phosphorus-containing flame retardant is at least one of triphenyl phosphate, resorcinol-bis (diphenyl phosphate), bisphenol a-bis (diphenyl phosphate), and resorcinol bis [ bis (2, 6-dimethylphenyl phosphate) ].
In some embodiments, the mass ratio of the phosphorus-containing flame retardant to the potassium perfluorobutane sulfonate is 12-16: 0.1 to 0.3, and more preferably 14 to 16: 0.1 to 0.3, and more preferably 16: 0.15 to 0.25.
In some embodiments, the bisphenol A aromatic polycarbonate has a molecular weight of 10000 to 40000, and optionally 10000 to 30000 or 10000 to 20000 or 20000 to 40000.
In some of these embodiments, the polysiloxane-polycarbonate has a molecular weight of 50000 to 80000 and a silicone content of 6 to 10 wt%.
In some embodiments, the ABS resin has a weight average molecular weight of 90000-120000, and the ABS resin has a butadiene content of 20-35 wt%, an acrylonitrile content of 34-50 wt%, and a styrene content of 20-45 wt%.
In some of these embodiments, the lubricant is at least one of a silicone masterbatch, a pentaerythritol ester, and an ethylene bisstearamide.
In some embodiments, the anti-dripping agent is styrene-acrylonitrile coated polytetrafluoroethylene, and the content of the polytetrafluoroethylene in the styrene-acrylonitrile coated polytetrafluoroethylene is 40-60 wt%.
In some of these embodiments, the polycarbonate composition comprises, in parts by weight:
in some embodiments, the antioxidant is a hindered phenol main antioxidant and a phosphite ester auxiliary antioxidant, and the weight ratio of the hindered phenol main antioxidant to the phosphite ester auxiliary antioxidant is 1: 2-1: 4.
Another object of the present invention is to provide a method for preparing the polycarbonate composition, comprising the steps of:
(1) drying the polycarbonate, and mixing with ABS resin, a flame retardant, superfine talcum powder, nano silicon oxide, an antioxidant, a lubricant and an anti-dripping agent to obtain a mixture;
(2) and (2) melting, extruding and granulating the mixture obtained in the step (1).
In some embodiments, the mixture obtained in the step (1) is melted, extruded and granulated by a double-screw extruder; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 210-235 ℃, the temperature of the second zone is 215-245 ℃, the temperature of the third zone is 220-250 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-250 ℃, the temperature of the sixth zone is 240-260 ℃, the temperature of the seventh zone is 240-260 ℃, the temperature of the eighth zone is 230-245 ℃, the temperature of the die head is 230-245 ℃, the rotating speed of the screw is 300-600 rpm, and the ratio of the length L of the screw to the diameter D of the screw is 35: 1-50: 1.
In some embodiments, the mixture obtained in the step (1) is melted, extruded and granulated by a double-screw extruder; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 220-235 ℃, the temperature of the second zone is 230-245 ℃, the temperature of the third zone is 240-250 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-250 ℃, the temperature of the sixth zone is 240-260 ℃, the temperature of the seventh zone is 240-260 ℃, the temperature of the eighth zone is 230-245 ℃, the temperature of the die head is 230-245 ℃, the rotating speed of the screw is 300-600 rpm, and the ratio of the length L of the screw to the diameter D of the screw is 35: 1-50: 1.
In some embodiments, the mixture obtained in the step (1) is melted, extruded and granulated by a double-screw extruder; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 210-220 ℃, the temperature of the second zone is 215-230 ℃, the temperature of the third zone is 220-240 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-250 ℃, the temperature of the sixth zone is 240-260 ℃, the temperature of the seventh zone is 240-260 ℃, the temperature of the eighth zone is 230-245 ℃, the temperature of the die head is 230-245 ℃, the rotating speed of the screw is 300-600 rpm, and the ratio of the length L of the screw to the diameter D of the screw is 35: 1-50: 1.
In some embodiments, the drying of the polycarbonate in step (1) comprises: and drying the polycarbonate at 110-120 ℃ for 4-6 h.
Compared with the prior art, the invention has the following beneficial effects:
the inventor of the invention finds that the flame retardant is compounded by selecting the phosphorus-containing flame retardant and the potassium perfluorobutylsulfonate, and the phosphorus-containing flame retardant and the potassium perfluorobutylsulfonate can play a synergistic effect, so that carbon is formed on the surface of the burning resin more quickly, and the further thermal decomposition of the resin is prevented quickly. On the other hand, the superfine talcum powder has a unique layered structure and particle size, can form a protective layer on the surface of resin, generates a large amount of carbon during combustion, and quickly reduces the heat generated during the combustion of the resin. And thirdly, the nano silicon oxide in the invention can also effectively prevent oxygen from contacting with the resin and obstruct the combustion of the resin and the oxygen, thereby reducing the generation of gas caused by the combustion of the resin and reducing the smoke density of the resin during the combustion. On the basis, the invention further optimizes and matches the types, the use amounts and the specifications of other components such as polycarbonate, ABS resin, antioxidant and the like, and finally obtains the polycarbonate composition with low smoke density and heat release rate and good flame retardant property under the integral action of all the components.
The preparation method of the polycarbonate composition is simple and easy to realize industrial production.
Drawings
FIG. 1 is a flow chart illustrating the preparation of a polycarbonate composition of the present invention.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The embodiment provides a polycarbonate composition, which comprises the following components in parts by weight:
the flame retardant comprises a phosphorus-containing flame retardant and potassium perfluorobutyl sulfonate;
the polycarbonate includes bisphenol a type aromatic polycarbonate and polysiloxane-polycarbonate.
The inventors of the present invention have found in their studies that the shape and size of the ultrafine talc have an important influence on the combustion performance of the polycarbonate composition of the present invention. The superfine talcum powder is layered, the particle size of the superfine talcum powder is controlled to be 2-6 mu m (particularly 3-5 mu m), a protective layer can be formed on the surface of the resin, a large amount of carbon is formed during combustion, and the heat generated during resin combustion is reduced. When the particle size of the superfine talcum powder is too small, bridging is easily generated at a feeding port, and the forming processing is difficult. When the particle size of the superfine talcum powder is too large, the superfine talcum powder is not tightly combined with resin, so that the heat is easily overlarge during combustion, and the heat release rate is high.
In addition, the inventor of the invention also finds that the use amount of the superfine talcum powder and the nano silicon oxide also has a certain influence on the combustion performance of the polycarbonate composition, and when the superfine talcum powder is 10-20 parts, and more preferably 15-20 parts, the smoke density and the heat release rate of the prepared polycarbonate composition are both obviously reduced. On the basis, 2-4 parts of nano silicon oxide is controlled, and 3-4 parts of nano silicon oxide is further preferred, so that the polycarbonate composition with lower smoke density and heat release rate can be prepared.
Furthermore, the shape and size of the nano silicon oxide have certain influence on the combustion performance of the polycarbonate composition, the nano silicon oxide is in a layered form, particularly, the thickness of the nano silicon oxide is further controlled to be 10-60 nm, and the particle size of the nano silicon oxide is controlled to be 6-100 nm, so that the nano silicon oxide can more effectively prevent oxygen from contacting with resin and block the combustion of the resin and oxygen, and therefore, the generation of gas caused by the combustion of the resin is reduced, and the smoke density of the resin during combustion is reduced.
Meanwhile, the type of the flame retardant also has certain influence on the combustion performance of the polycarbonate composition, the phosphorus-containing flame retardant and the potassium perfluorobutylsulfonate are selected for compounding, and particularly, the mass ratio of the phosphorus-containing flame retardant to the potassium perfluorobutylsulfonate is further controlled to be 14-16: 0.1-0.3, the two flame retardants have a synergistic effect, can rapidly form carbon on the surface of the burning resin, and prevent the further thermal decomposition of the resin. When only one of them is selected, the flame retardant does not act synergistically, resulting in a significant increase in both the smoke density on ignition and the rate of heat release of the polycarbonate composition.
The present invention will be described in further detail with reference to specific examples.
The raw materials used in the examples of the present invention were as follows:
bisphenol A aromatic polycarbonate with molecular weight of 20000, selected from Taihua light-emitting Limited liability company;
polysiloxane-polycarbonate, molecular weight 60000, silicon content 9%, selected from Korea Sanzhi resins GmbH;
ABS resin: the weight-average molecular weight is 100000, the acrylonitrile content is 40 wt%, the butadiene content is 30 wt%, and the styrene content is 30 wt%;
flame retardant: resorcinol-bis (diphenyl phosphate) selected from the chemical company ltd, watson, zhejiang;
flame retardant: potassium perfluorobutylsulfonate selected from mitsubishi chemical corporation;
nano silicon oxide: the thickness is 10nm, and the particle size is 8 nm;
superfine talcum powder: the particle size is 3-5 mu m;
ordinary talc powder: the particle size is 15-20 mu m;
antioxidant: the weight portion ratio of the hindered phenol to the phosphite ester antioxidant is 1:2, and the hindered phenol and the phosphite ester antioxidant are selected from Rianlong new material Co., Ltd;
lubricant: silicone masterbatches selected from dow corning corporation;
anti-dripping agent: AS-coated polytetrafluoroethylene having a polytetrafluoroethylene content of 50% by weight, selected from Guangzhou entropy energy materials, Inc.
Example 1
The embodiment provides a polycarbonate composition, which is prepared from the following raw materials in parts by weight:
52 parts of bisphenol A Polycarbonate (PC) resin,
20 parts of polysiloxane-polycarbonate (PC-PC),
10 parts of ABS resin, namely 10 parts of ABS resin,
12 parts of bisphenol A-bis (diphenyl phosphate),
0.3 part of potassium perfluorobutyl sulfonate,
1 part of nano silicon oxide, namely nano silicon oxide,
5 parts of superfine talcum powder, namely 5 parts,
0.1 part of an antioxidant, namely,
0.2 part of a lubricating agent is added,
0.4 part of anti-dripping agent;
the preparation method of the polycarbonate composition comprises the following steps:
(1) and (3) placing the bisphenol A polycarbonate and the polysiloxane-polycarbonate at 120 ℃, drying for 4h, and cooling. Adding the cooled bisphenol A polycarbonate, polysiloxane-polycarbonate, ABS resin, bisphenol A-bis (diphenyl phosphate), potassium perfluorobutylsulfonate, superfine talcum powder, nano silicon oxide, antioxidant, lubricant and anti-dripping agent into a stirrer for mixing;
(2) and (3) adding the mixture mixed in the step (1) into a double-screw extruder through a feeder, and carrying out melting, extrusion, water cooling and granulation. The technological parameters are as follows: the temperature in the first zone was 210 ℃, the temperature in the second zone was 220, the temperature in the third zone was 230 ℃, the temperature in the fourth zone was 235 ℃, the temperature in the fifth zone was 235 ℃, the temperature in the sixth zone was 240 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 235 ℃, the temperature in the die head was 235 ℃ and the screw speed was 500 rpm. The ratio of the screw length L to the diameter D was 40: 1.
Example 2
The embodiment provides a polycarbonate composition, which is prepared from the following raw materials in parts by weight:
41 parts of bisphenol A Polycarbonate (PC) resin,
20 parts of polysiloxane-polycarbonate (PC-PC),
15 parts of ABS resin, namely 15 parts of ABS resin,
12 parts of bisphenol A-bis (diphenyl phosphate),
0.3 part of potassium perfluorobutyl sulfonate,
2 parts of nano silicon oxide, namely 2 parts of nano silicon oxide,
10 parts of superfine talcum powder, 10 parts of,
0.1 part of an antioxidant, namely,
0.2 part of a lubricating agent is added,
0.4 part of anti-dripping agent
The preparation method of the polycarbonate composition comprises the following steps:
(1) and (3) placing the bisphenol A polycarbonate and the polysiloxane-polycarbonate at 120 ℃, drying for 4h, and cooling. Adding the cooled bisphenol A polycarbonate, polysiloxane-polycarbonate, ABS resin, bisphenol A-bis (diphenyl phosphate), potassium perfluorobutylsulfonate, superfine talcum powder, nano silicon oxide, antioxidant, lubricant and anti-dripping agent into a stirrer for mixing;
(2) and (3) adding the mixture mixed in the step (1) into a double-screw extruder through a feeder, and carrying out melting, extrusion, water cooling and granulation. The technological parameters are as follows: the temperature in the first zone was 215 ℃, the temperature in the second zone was 225 ℃, the temperature in the third zone was 235 ℃, the temperature in the fourth zone was 235 ℃, the temperature in the fifth zone was 235 ℃, the temperature in the sixth zone was 240 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 235 ℃, the temperature in the die head was 235 ℃ and the screw speed was 500 rpm. The ratio of the screw length L to the diameter D was 40: 1.
Example 3
The embodiment provides a polycarbonate composition, which is prepared from the following raw materials in parts by weight:
33 parts of bisphenol A Polycarbonate (PC) resin,
15 parts of polysiloxane-polycarbonate (PPC),
20 parts of ABS resin, namely ABS resin,
14 parts of bisphenol A-bis (diphenyl phosphate),
0.2 part of potassium perfluorobutyl sulfonate,
3 parts of nano silicon oxide, namely 3 parts of nano silicon oxide,
15 parts of superfine talcum powder,
0.1 part of an antioxidant, namely,
0.2 part of a lubricating agent is added,
0.4 part of anti-dripping agent;
the preparation method of the polycarbonate composition comprises the following steps:
(1) and (3) placing the bisphenol A polycarbonate and the polysiloxane-polycarbonate at 120 ℃, drying for 4h, and cooling. Adding the cooled bisphenol A polycarbonate, polysiloxane-polycarbonate, ABS resin, bisphenol A-bis (diphenyl phosphate), potassium perfluorobutylsulfonate, superfine talcum powder, nano silicon oxide, antioxidant, lubricant and anti-dripping agent into a stirrer for mixing;
(2) and (3) adding the mixture mixed in the step (1) into a double-screw extruder through a feeder, and carrying out melting, extrusion, water cooling and granulation. The technological parameters are as follows: the temperature in the first zone was 215 ℃, the temperature in the second zone was 225 ℃, the temperature in the third zone was 235 ℃, the temperature in the fourth zone was 235 ℃, the temperature in the fifth zone was 235 ℃, the temperature in the sixth zone was 240 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 235 ℃ and the screw speed was 500 rpm. The ratio of the screw length L to the diameter D was 40: 1.
Example 4
The embodiment provides a polycarbonate composition, which is prepared from the following raw materials in parts by weight:
23 parts of bisphenol A Polycarbonate (PC) resin,
25 parts of polysiloxane-polycarbonate (PPC),
20 parts of ABS resin, namely ABS resin,
14 parts of bisphenol A-bis (diphenyl phosphate),
0.2 part of potassium perfluorobutyl sulfonate,
3 parts of nano silicon oxide, namely 3 parts of nano silicon oxide,
15 parts of superfine talcum powder,
0.1 part of an antioxidant, namely,
0.2 part of a lubricating agent is added,
0.4 part of anti-dripping agent;
the preparation method of the polycarbonate composition comprises the following steps:
(1) and (3) placing the bisphenol A polycarbonate and the polysiloxane-polycarbonate at 120 ℃, drying for 4h, and cooling. Adding the cooled bisphenol A polycarbonate, polysiloxane-polycarbonate, ABS resin, bisphenol A-bis (diphenyl phosphate), potassium perfluorobutylsulfonate, superfine talcum powder, nano silicon oxide, antioxidant, lubricant and anti-dripping agent into a stirrer for mixing;
(2) and (3) adding the mixture mixed in the step (1) into a double-screw extruder through a feeder, and carrying out melting, extrusion, water cooling and granulation. The technological parameters are as follows: the temperature in the first zone was 220 ℃, the temperature in the second zone was 230, the temperature in the third zone was 240 ℃, the temperature in the fourth zone was 240 ℃, the temperature in the fifth zone was 235 ℃, the temperature in the sixth zone was 240 ℃, the temperature in the seventh zone was 240 ℃, the temperature in the eighth zone was 240 ℃, the temperature in the die head was 235 ℃ and the screw speed was 500 rpm. The ratio of the screw length L to the diameter D was 40: 1.
Example 5
The embodiment provides a polycarbonate composition, which is prepared from the following raw materials in parts by weight:
26 parts of bisphenol A Polycarbonate (PC) resin,
20 parts of polysiloxane-polycarbonate (PC-PC),
15 parts of ABS resin, namely 15 parts of ABS resin,
16 parts of bisphenol A-bis (diphenyl phosphate),
0.1 part of potassium perfluorobutyl sulfonate,
3 parts of nano silicon oxide, namely 3 parts of nano silicon oxide,
20 parts of superfine talcum powder, 20 parts of,
0.1 part of an antioxidant, namely,
0.2 part of a lubricating agent is added,
0.4 part of anti-dripping agent;
the preparation method of the polycarbonate composition comprises the following steps:
(1) and (3) placing the bisphenol A polycarbonate and the polysiloxane-polycarbonate at 120 ℃, drying for 4h, and cooling. Adding the cooled bisphenol A polycarbonate, polysiloxane-polycarbonate, ABS resin, bisphenol A-bis (diphenyl phosphate), potassium perfluorobutylsulfonate, superfine talcum powder, nano silicon oxide, antioxidant, lubricant and anti-dripping agent into a stirrer for mixing;
(2) and (3) adding the mixture mixed in the step (1) into a double-screw extruder through a feeder, and carrying out melting, extrusion, water cooling and granulation. The technological parameters are as follows: the temperature in the first zone was 225 ℃, the temperature in the second zone was 230, the temperature in the third zone was 245 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 240 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 245 ℃, the temperature in the eighth zone was 245 ℃, the temperature in the die head was 240 ℃ and the screw speed was 450 rpm. The ratio of the screw length L to the diameter D was 40: 1.
Example 6
The embodiment provides a polycarbonate composition, which is prepared from the following raw materials in parts by weight:
27 parts of bisphenol A Polycarbonate (PC) resin,
20 parts of polysiloxane-polycarbonate (PC-PC),
15 parts of ABS resin, namely 15 parts of ABS resin,
14 parts of bisphenol A-bis (diphenyl phosphate),
0.1 part of potassium perfluorobutyl sulfonate,
4 parts of nano silicon oxide, namely nano silicon oxide,
20 parts of superfine talcum powder, 20 parts of,
0.1 part of an antioxidant, namely,
0.2 part of a lubricating agent is added,
0.4 part of anti-dripping agent;
the preparation method of the polycarbonate composition comprises the following steps:
(1) and (3) placing the bisphenol A polycarbonate and the polysiloxane-polycarbonate at 120 ℃, drying for 4h, and cooling. Adding the cooled bisphenol A polycarbonate, polysiloxane-polycarbonate, ABS resin, bisphenol A-bis (diphenyl phosphate), potassium perfluorobutylsulfonate, superfine talcum powder, nano silicon oxide, antioxidant, lubricant and anti-dripping agent into a stirrer for mixing;
(2) and (3) adding the mixture mixed in the step (1) into a double-screw extruder through a feeder, and carrying out melting, extrusion, water cooling and granulation. The technological parameters are as follows: the temperature in the first zone was 230 ℃, the temperature in the second zone was 240 ℃, the temperature in the third zone was 245 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 240 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 245 ℃, the temperature in the eighth zone was 245 ℃, the temperature in the die head was 240 ℃ and the screw speed was 450 rpm. The ratio of the screw length L to the diameter D was 40: 1.
Example 7
The embodiment provides a polycarbonate composition, which is prepared from the following raw materials in parts by weight:
20 parts of bisphenol A Polycarbonate (PC) resin,
20 parts of polysiloxane-polycarbonate (PC-PC),
20 parts of ABS resin, namely ABS resin,
16 parts of bisphenol A-bis (diphenyl phosphate),
0.2 part of potassium perfluorobutyl sulfonate,
4 parts of nano silicon oxide, namely nano silicon oxide,
20 parts of superfine talcum powder, 20 parts of,
0.1 part of an antioxidant, namely,
0.2 part of a lubricating agent is added,
0.4 part of anti-dripping agent;
the preparation method of the polycarbonate composition comprises the following steps:
(1) and (3) placing the bisphenol A polycarbonate and the polysiloxane-polycarbonate at 120 ℃, drying for 4h, and cooling. Adding the cooled bisphenol A polycarbonate, polysiloxane-polycarbonate, ABS resin, bisphenol A-bis (diphenyl phosphate), potassium perfluorobutylsulfonate, superfine talcum powder, nano silicon oxide, antioxidant, lubricant and anti-dripping agent into a stirrer for mixing;
(2) and (3) adding the mixture mixed in the step (1) into a double-screw extruder through a feeder, and carrying out melting, extrusion, water cooling and granulation. The technological parameters are as follows: the temperature in the first zone was 230 ℃, the temperature in the second zone was 240 ℃, the temperature in the third zone was 245 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 240 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 245 ℃, the temperature in the eighth zone was 245 ℃, the temperature in the die head was 240 ℃ and the screw speed was 450 rpm. The ratio of the screw length L to the diameter D was 40: 1.
Comparative example 1
The comparative example provides a polycarbonate composition, which is prepared from the following raw materials in parts by weight:
31 parts of bisphenol A Polycarbonate (PC) resin,
20 parts of polysiloxane-polycarbonate (PC-PC),
15 parts of ABS resin, namely 15 parts of ABS resin,
14 parts of bisphenol A-bis (diphenyl phosphate),
0.1 part of potassium perfluorobutyl sulfonate,
20 parts of superfine talcum powder, 20 parts of,
0.1 part of an antioxidant, namely,
0.2 part of a lubricating agent is added,
0.4 part of anti-dripping agent;
the preparation method of the polycarbonate composition comprises the following steps:
(1) and (3) placing the bisphenol A polycarbonate and the polysiloxane-polycarbonate at 120 ℃, drying for 4h, and cooling. Adding the cooled bisphenol A polycarbonate, polysiloxane-polycarbonate, ABS resin, bisphenol A-bis (diphenyl phosphate), potassium perfluorobutylsulfonate, superfine talcum powder, antioxidant, lubricant and anti-dripping agent into a stirrer for mixing;
(2) and (3) adding the mixture mixed in the step (1) into a double-screw extruder through a feeder, and carrying out melting, extrusion, water cooling and granulation. The technological parameters are as follows: the temperature in the first zone was 230 ℃, the temperature in the second zone was 240 ℃, the temperature in the third zone was 245 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 240 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 245 ℃, the temperature in the eighth zone was 245 ℃, the temperature in the die head was 240 ℃ and the screw speed was 450 rpm. The ratio of the screw length L to the diameter D was 40: 1.
Comparative example 2
The comparative example provides a polycarbonate composition, which is prepared from the following raw materials in parts by weight:
51 parts of bisphenol A Polycarbonate (PC) resin,
20 parts of polysiloxane-polycarbonate (PC-PC),
15 parts of ABS resin, namely 15 parts of ABS resin,
12 parts of bisphenol A-bis (diphenyl phosphate),
0.3 part of potassium perfluorobutyl sulfonate,
2 parts of nano silicon oxide, namely 2 parts of nano silicon oxide,
0.1 part of an antioxidant, namely,
0.2 part of a lubricating agent is added,
0.4 part of anti-dripping agent;
the preparation method of the polycarbonate composition comprises the following steps:
(1) and (3) placing the bisphenol A polycarbonate and the polysiloxane-polycarbonate at 120 ℃, drying for 4h, and cooling. Adding the cooled bisphenol A polycarbonate, polysiloxane-polycarbonate, ABS resin, bisphenol A-bis (diphenyl phosphate), potassium perfluorobutylsulfonate, superfine talcum powder, nano silicon oxide, antioxidant, lubricant and anti-dripping agent into a stirrer for mixing;
(2) and (3) adding the mixture mixed in the step (1) into a double-screw extruder through a feeder, and carrying out melting, extrusion, water cooling and granulation. The technological parameters are as follows: the temperature in the first zone was 230 ℃, the temperature in the second zone was 240 ℃, the temperature in the third zone was 245 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 240 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 245 ℃, the temperature in the eighth zone was 245 ℃, the temperature in the die head was 240 ℃ and the screw speed was 450 rpm. The ratio of the screw length L to the diameter D was 40: 1.
Comparative example 3
The comparative example provides a polycarbonate composition, which is prepared from the following raw materials in parts by weight:
48 parts of bisphenol A Polycarbonate (PC) resin,
20 parts of ABS resin, namely ABS resin,
14 parts of bisphenol A-bis (diphenyl phosphate),
3 parts of nano silicon oxide, namely 3 parts of nano silicon oxide,
15 parts of superfine talcum powder,
0.1 part of an antioxidant, namely,
0.2 part of a lubricating agent is added,
0.4 part of anti-dripping agent;
the preparation method of the polycarbonate composition comprises the following steps:
(1) and (3) placing the bisphenol A polycarbonate and the polysiloxane-polycarbonate at 120 ℃, drying for 4h, and cooling. Adding the cooled bisphenol A polycarbonate, polysiloxane-polycarbonate, ABS resin, bisphenol A-bis (diphenyl phosphate), superfine talcum powder, nano silicon oxide, antioxidant, lubricant and anti-dripping agent into a stirrer for mixing;
(2) and (3) adding the mixture mixed in the step (1) into a double-screw extruder through a feeder, and carrying out melting, extrusion, water cooling and granulation. The technological parameters are as follows: the temperature in the first zone was 230 ℃, the temperature in the second zone was 240 ℃, the temperature in the third zone was 245 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 240 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 245 ℃, the temperature in the eighth zone was 245 ℃, the temperature in the die head was 240 ℃ and the screw speed was 450 rpm. The ratio L/D of the length L of the screw to the diameter D was 40: 1.
Comparative example 4
The comparative example provides a polycarbonate composition, which is prepared from the following raw materials in parts by weight:
41 parts of bisphenol A Polycarbonate (PC) resin,
polysiloxane-polycarbonate 20 parts
15 parts of ABS resin, namely 15 parts of ABS resin,
12 parts of bisphenol A-bis (diphenyl phosphate),
2 parts of nano silicon oxide, namely 2 parts of nano silicon oxide,
10 parts of common talcum powder,
0.1 part of an antioxidant, namely,
0.2 part of a lubricating agent is added,
0.4 part of anti-dripping agent;
the preparation method of the polycarbonate composition comprises the following steps:
(1) and (3) placing the bisphenol A polycarbonate and the polysiloxane-polycarbonate at 120 ℃, drying for 4h, and cooling. Adding the cooled bisphenol A polycarbonate, polysiloxane-polycarbonate, ABS resin, bisphenol A-bis (diphenyl phosphate), common talcum powder, nano silicon oxide, antioxidant, lubricant and anti-dripping agent into a stirrer for mixing;
(2) and (3) adding the mixture mixed in the step (1) into a double-screw extruder through a feeder, and carrying out melting, extrusion, water cooling and granulation. The technological parameters are as follows: the temperature in the first zone was 230 ℃, the temperature in the second zone was 240 ℃, the temperature in the third zone was 245 ℃, the temperature in the fourth zone was 245 ℃, the temperature in the fifth zone was 240 ℃, the temperature in the sixth zone was 245 ℃, the temperature in the seventh zone was 245 ℃, the temperature in the eighth zone was 245 ℃, the temperature in the die head was 240 ℃ and the screw speed was 450 rpm. The ratio L/D of the length L of the screw to the diameter D was 40: 1.
The performance test method comprises the following steps:
(1) vertical burning performance: test V0 according to UL94, thickness 1.5 mm;
(2) smoke density: test standard ISO5659, test condition 50kw, flameless, smoke density at 4 minutes (Ds (4)), the lower the number the better;
(3) rate of heat release: test standard ISO5659, test condition 50kw, maximum average heat release rate (MARHE), the lower the number the better.
Table 1 examples comparative polycarbonate compositions parts by weight and performance test summary
Wherein, the additive amount of the antioxidant is 0.1 part, the additive amount of the lubricant is 0.2 part, and the additive amount of the anti-dripping agent is 0.4 part.
As is clear from the results in Table 1, the polycarbonate composition of the present invention has a low smoke density and heat release rate and good flame retardancy. From examples 1 to 7, it can be seen that the use amounts of the ultrafine talc powder and the nano silica have a great influence on the performance of the polycarbonate composition; along with the increase of the content of the superfine talcum powder and the addition amount of the nano silicon oxide, the smoke density of the polycarbonate composition is gradually reduced, and the heat release rate is also gradually reduced. As in examples 6 and 7, when the amount of the ultrafine talc was 20 parts and the amount of the nano silica was 4 parts, the heat release rate and the smoke density were significantly improved as compared with those of examples 1 to 5. On the basis of this, by further optimizing the compounding ratio of bisphenol a-bis (diphenyl phosphate) and potassium perfluorobutylsulfonate and the like in the flame retardant, the smoke density and heat release rate of the polycarbonate composition can be further lowered, and as in example 7, the heat release rate and smoke density reach optimum values.
As can be seen from comparison between example 6 and comparative example 1, in which no nano silica was added, failed to form a protective layer on the resin surface, and was liable to burn to generate a large smoke density.
Comparing example 2 with comparative example 2, it can be seen that the absence of the extra fine talc powder in comparative example 2 results in the polycarbonate composition not being able to block oxygen and being easily burned to generate smoke and gas.
As can be seen from comparison between examples 3-4 and comparative example 3, in comparative example 3, no polysiloxane-polycarbonate resin and potassium perfluorobutylsulfonate are added, a protective layer is formed in the resin due to lack of polysiloxane, and the flame retardant cannot play a synergistic role, so that the combustion smoke density and the heat release rate are high due to the combination.
As can be seen from comparison between example 2 and comparative example 4, the larger the particle size of talc powder, the less tight the bonding with the resin and the less strong the coating property, and the more likely the resin is sufficiently burned during burning, resulting in a high heat release rate and a high smoke density.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The polycarbonate composition is characterized by comprising the following components in parts by weight:
the flame retardant comprises a phosphorus-containing flame retardant and potassium perfluorobutyl sulfonate;
the polycarbonate includes bisphenol a type aromatic polycarbonate and polysiloxane-polycarbonate.
2. The polycarbonate composition according to claim 1, wherein the ultrafine talc has a layered structure and a particle size of 2 to 6 μm, preferably 3 to 5 μm.
3. The polycarbonate composition according to claim 1, wherein the superfine talc powder is 15 to 20 parts by weight, preferably 18 to 20 parts by weight; and/or the nano silicon oxide accounts for 2-4 parts by weight, and is further preferably 3-4 parts by weight.
4. The polycarbonate composition according to claim 1, wherein the nano-silica has a layered structure, a thickness of 8nm to 60nm, and a particle size of 6nm to 100 nm.
5. The polycarbonate composition of claim 1, wherein the phosphorus-containing flame retardant is at least one of triphenyl phosphate, resorcinol-bis (diphenyl phosphate), bisphenol a-bis (diphenyl phosphate), and resorcinol bis [ bis (2, 6-dimethylphenyl phosphate) ]; the mass ratio of the phosphorus-containing flame retardant to the potassium perfluorobutylsulfonate is 14-17: 0.1 to 0.3.
6. The polycarbonate composition according to claim 1, wherein the bisphenol A aromatic polycarbonate has a molecular weight of 20000 to 40000; the molecular weight of the polysiloxane-polycarbonate is 50000-80000, and the organosilicon content of the polysiloxane-polycarbonate is 6-10 wt%;
and/or the weight average molecular weight of the ABS resin is 90000-120000; the ABS resin contains 20-35 wt% of butadiene, 34-50 wt% of acrylonitrile and 20-45 wt% of styrene.
7. The polycarbonate composition of any of claims 1-6, wherein the lubricant is at least one of a silicone masterbatch, a pentaerythritol ester, and an ethylene bisstearamide; and/or the anti-dripping agent is styrene-acrylonitrile coated polytetrafluoroethylene, and the content of polytetrafluoroethylene in the styrene-acrylonitrile coated polytetrafluoroethylene is 40-60 wt%; and/or the antioxidant is a hindered phenol main antioxidant and a phosphite ester auxiliary antioxidant, and the weight ratio of the hindered phenol main antioxidant to the phosphite ester auxiliary antioxidant is 1: 2-1: 4.
8. The polycarbonate composition of claim 1, comprising the following components in parts by weight:
9. a method for preparing the polycarbonate composition of any one of claims 1 to 8, comprising the steps of:
(1) drying the polycarbonate, and mixing with ABS resin, a flame retardant, superfine talcum powder, nano silicon oxide, an antioxidant, a lubricant and an anti-dripping agent to obtain a mixture;
(2) and (2) melting, extruding and granulating the mixture obtained in the step (1).
10. The preparation method of claim 9, wherein the mixture obtained in the step (1) is melted, extruded and granulated by a double-screw extruder; the technological parameters of the double-screw extruder are as follows: the temperature of the first zone is 210-220 ℃, the temperature of the second zone is 215-230 ℃, the temperature of the third zone is 220-240 ℃, the temperature of the fourth zone is 230-250 ℃, the temperature of the fifth zone is 230-250 ℃, the temperature of the sixth zone is 240-260 ℃, the temperature of the seventh zone is 240-260 ℃, the temperature of the eighth zone is 230-245 ℃, the temperature of the die head is 230-245 ℃, the rotating speed of the screw is 300-600 rpm, and the ratio of the length L of the screw to the diameter D of the screw is 35: 1-50: 1.
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Cited By (9)
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| CN112266619A (en) * | 2020-11-02 | 2021-01-26 | 广东圆融新材料有限公司 | Polycarbonate composition resistant to wet heat aging and preparation method thereof |
| CN112646343A (en) * | 2020-12-23 | 2021-04-13 | 上海品诚控股集团有限公司 | Low-smoke-density flame-retardant PC composition |
| CN112852139A (en) * | 2021-01-14 | 2021-05-28 | 上海锦湖日丽塑料有限公司 | Low-smoke-density PC/ABS composition and preparation method thereof |
| CN114106417A (en) * | 2021-11-08 | 2022-03-01 | 金发科技股份有限公司 | Silane coupling agent modified halloysite nanotube-loaded antioxidant compound, polycarbonate composition, and preparation method and application thereof |
| CN114181508A (en) * | 2021-12-14 | 2022-03-15 | 安庆会通新材料有限公司 | Ultrathin flame-retardant PC (polycarbonate) film material and preparation method thereof |
| CN114773541A (en) * | 2022-04-24 | 2022-07-22 | 嘉鱼县宇威新材料科技有限公司 | Nano anti-dripping agent and preparation method thereof |
| CN115181407A (en) * | 2022-08-15 | 2022-10-14 | 万华化学（宁波）有限公司 | Halogen-free flame-retardant low-smoke-density polycarbonate material and preparation method and application thereof |
| CN115260731A (en) * | 2022-08-24 | 2022-11-01 | 上海中镭新材料科技有限公司 | Polycarbonate composite material and preparation method and application thereof |
| CN115521600A (en) * | 2022-09-26 | 2022-12-27 | 四川力博为新材料有限公司 | Flame retardant polycarbonate compositions and methods of making articles thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112266619A (en) * | 2020-11-02 | 2021-01-26 | 广东圆融新材料有限公司 | Polycarbonate composition resistant to wet heat aging and preparation method thereof |
| CN112646343A (en) * | 2020-12-23 | 2021-04-13 | 上海品诚控股集团有限公司 | Low-smoke-density flame-retardant PC composition |
| CN112852139A (en) * | 2021-01-14 | 2021-05-28 | 上海锦湖日丽塑料有限公司 | Low-smoke-density PC/ABS composition and preparation method thereof |
| CN114106417A (en) * | 2021-11-08 | 2022-03-01 | 金发科技股份有限公司 | Silane coupling agent modified halloysite nanotube-loaded antioxidant compound, polycarbonate composition, and preparation method and application thereof |
| CN114181508A (en) * | 2021-12-14 | 2022-03-15 | 安庆会通新材料有限公司 | Ultrathin flame-retardant PC (polycarbonate) film material and preparation method thereof |
| CN114773541A (en) * | 2022-04-24 | 2022-07-22 | 嘉鱼县宇威新材料科技有限公司 | Nano anti-dripping agent and preparation method thereof |
| CN115181407A (en) * | 2022-08-15 | 2022-10-14 | 万华化学（宁波）有限公司 | Halogen-free flame-retardant low-smoke-density polycarbonate material and preparation method and application thereof |
| CN115181407B (en) * | 2022-08-15 | 2023-12-19 | 万华化学（宁波）有限公司 | Halogen-free flame-retardant low-smoke-density polycarbonate material and preparation method and application thereof |
| CN115260731A (en) * | 2022-08-24 | 2022-11-01 | 上海中镭新材料科技有限公司 | Polycarbonate composite material and preparation method and application thereof |
| CN115521600A (en) * | 2022-09-26 | 2022-12-27 | 四川力博为新材料有限公司 | Flame retardant polycarbonate compositions and methods of making articles thereof |
| CN115521600B (en) * | 2022-09-26 | 2024-08-23 | 四川力博为新材料有限公司 | Flame-retardant polycarbonate product and preparation method thereof |
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Application publication date: 20200529 |