CN116041931A - Toughening master batch and preparation method and application thereof - Google Patents
Toughening master batch and preparation method and application thereof Download PDFInfo
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- CN116041931A CN116041931A CN202211718122.5A CN202211718122A CN116041931A CN 116041931 A CN116041931 A CN 116041931A CN 202211718122 A CN202211718122 A CN 202211718122A CN 116041931 A CN116041931 A CN 116041931A
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004417 polycarbonate Substances 0.000 claims abstract description 97
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 97
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 43
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 33
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 26
- 239000012745 toughening agent Substances 0.000 claims abstract description 24
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 229920001910 maleic anhydride grafted polyolefin Chemical group 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 22
- 239000003063 flame retardant Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 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 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- -1 small molecule compound Chemical class 0.000 claims description 6
- 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 6
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 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 4
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 11
- 230000000052 comparative effect Effects 0.000 description 19
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 12
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 8
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012963 UV stabilizer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
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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 toughening master batch, a preparation method and application thereof, wherein the preparation raw materials of the toughening master batch comprise polycarbonate containing terminal hydroxyl groups, maleic anhydride grafted polyolefin, siloxane containing epoxy groups, a toughening agent containing epoxy groups and an antioxidant. The polycarbonate composite material formed by the toughening master batch has excellent solvent resistance, flame retardance and toughness, and is suitable for TWS earphone parts.
Description
Technical Field
The invention relates to the technical field of earphone materials, in particular to a toughening master batch, a preparation method and application thereof.
Background
TWS earphone structure is complicated, light and thin and portable, at present, wide application, in order to guarantee better signal, the wall thickness of the product is thinner, and the requirement on the strength and flowability of the material is higher; in order to meet the environmental requirements, spray-free schemes are gradually being used, and the paint or coating can enhance the chemical solvent resistance or cosmetic resistance of the product; after adopting the spraying-free scheme, the chemical resistance of the material is more required; since the lithium battery is built in the earphone, the material is required to have flame retardancy from the viewpoint of safety.
CN109486149a discloses a Polycarbonate (PC) composite material, comprising the following components in parts by weight: 0 to 50 parts of PC, 10 to 20 parts of PC-Si, 20 to 80 parts of PC-Si, 0.5 to 2 parts of toughening agent, 0.1 to 0.5 part of antioxidant, 0.15 to 1.1 parts of UV stabilizer and 0.1 to 0.5 part of release agent; the antioxidant is selected from a mixture of one or two of an antioxidant 168 and an antioxidant 1076 or a high-temperature-resistant antioxidant 412S; the UV stabilizer includes, for example, at least one of benzotriazole such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -benzotriazole, and 2-hydroxy-4-n-octoxybenzophenone, etc. The PC composite material has greatly raised and improved low temperature impact resistance and high transparency. In addition, the material also has the advantages of energy consumption saving and higher cost performance, and can be widely applied to the fields of mobile phone shells, instrument and meter handle shells and the like.
CN103319875a discloses a polycarbonate/acrylonitrile-styrene-butadiene alloy and a preparation method thereof, the disclosed alloy comprises the following components in parts by weight: 70-80 parts of polycarbonate, 3-7 parts of acrylonitrile-styrene-butadiene, 1-10 parts of toughening agent, 1-20 parts of flame retardant, 0.1-5 parts of antioxidant and 1-10 parts of stress cracking resistant agent. The alloy disclosed by the method has good processability and low shrinkage, and ensures high flame retardance, good appearance and low anisotropy, and meanwhile, the impact property of the alloy is greatly enhanced.
However, the chemical resistance of the existing flame-retardant PC alloy material is slightly insufficient, the testing requirement of the TWS earphone is not met, and the PC alloy material with good chemical resistance performance cannot meet the requirements of molding and processing of the TWS earphone and the safety performance requirement.
Therefore, it is necessary to develop a flame retardant alloy material with good chemical resistance, which meets the requirements of TWS headphones.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a toughening master batch, a preparation method and application thereof, and a polycarbonate composite material formed by the toughening master batch has excellent solvent resistance, flame retardance and toughness and is suitable for TWS earphone parts.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a toughening master batch, wherein the raw materials for preparing the toughening master batch comprise polycarbonate containing terminal hydroxyl groups, maleic anhydride grafted polyolefin, siloxane containing epoxy groups, a toughening agent containing epoxy groups and an antioxidant.
In the invention, the polycarbonate contains hydroxyl-terminated groups, the maleic anhydride grafted polyolefin contains carboxyl groups, the siloxane and the toughening agent contain siloxane, the siloxane and the toughening agent react with each other to form a toughening system with a network structure in the polycarbonate, and the formed toughening master batch not only has excellent toughening performance, but also has excellent capability of resisting chemical solvent erosion cracking.
Preferably, the preparation raw materials of the chemical-resistant toughening master batch comprise the following components in percentage by mass, wherein the total mass of the toughening master batch is 100 percent:
in the invention, the components of the toughening master batch are matched for use in a specific proportion, wherein the excessively high proportion of the polycarbonate containing the terminal hydroxyl groups can influence the flowability of the toughening master batch, thereby influencing the toughening effect of the toughening master batch; if the ratio is too low, a network interpenetrating structure is difficult to form, and the toughening effect and chemical solvent resistance of the toughening master batch are affected.
In the present invention, the mass percentage of the polycarbonate containing terminal hydroxyl groups is 30% to 65%, for example, 35%, 40%, 45%, 50%, 55%, 60%, etc.
The mass percent of the maleic anhydride grafted polyolefin is 15% -30%, such as 16%, 18%, 20%, 22%, 24%, 26%, 28%, etc.
The mass percentage of the siloxane containing the epoxy groups is 3% -8%, such as 4%, 5%, 6%, 7% and the like.
The mass percent of the toughening agent containing the epoxy group is 15% -30%, such as 16%, 18%, 20%, 22%, 24%, 26%, 28%, etc.
The mass percentage of the antioxidant is 1% -2%, such as 1.2%, 1.4%, 1.6%, 1.8% and the like.
Preferably, the hydroxyl-terminated polycarbonate has a melt index of 10 to 22g/10min, such as 14g/10min, 16g/10min, 18g/10min, 20g/10min, etc.
In the invention, the test conditions of the melt index are as follows: 260 deg.C, 2.16Kg.
Preferably, the maleic anhydride grafted polyolefin comprises maleic anhydride grafted polyethylene.
Preferably, the maleic anhydride grafted polyolefin has a grafting ratio of 0.5% to 1.0%, such as 0.6%, 0.7%, 0.8%, 0.9%, etc.
Preferably, the mass content of the epoxy group in the epoxy group-containing siloxane is 15% -20%, for example, 16%, 17%, 18%, 19%, etc.
Preferably, the mass content of the epoxy group in the epoxy group-containing toughening agent is 3% -8%, for example, 4%, 5%, 6%, 7%, etc.
In a second aspect, the present invention provides a method for preparing the toughening masterbatch according to the first aspect, the method comprising the steps of:
mixing polycarbonate containing terminal hydroxyl, maleic anhydride grafted polyolefin, siloxane containing epoxy groups, a toughening agent containing epoxy groups and an antioxidant, extruding and granulating to obtain the toughening master batch.
Preferably, the means of mixing comprises a high-speed mixer.
Preferably, the mixing is for a period of time of 1-2min, such as 1.2min, 1.4min, 1.6min, 1.8min, etc.
Preferably, the means for extrusion pelletization comprises a twin screw extruder.
Preferably, the twin screw extruder has an aspect ratio of (40-56): 1, wherein 40-56 can be 42, 44, 46, 48, 50, 52, 54, etc.
Preferably, the temperature of the extrusion granulation is 220-260 ℃, e.g., 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃, 255 ℃, etc.
In a third aspect, the present invention provides a polycarbonate composite comprising polycarbonate, the toughening master batch of the first aspect, a flame retardant, and other adjuvants.
According to the invention, the toughening master batch and the flame retardant are matched with the polycarbonate matrix resin, so that the formed polycarbonate composite material has excellent toughness, flame retardance and chemical solvent resistance, especially the mixed solvent of carbon tetrachloride and alcohol, and is suitable for TWS earphone parts.
Preferably, the polycarbonate composite material comprises the following components in percentage by mass, based on 100% of the total mass of the polycarbonate composite material:
in the invention, the components of the polycarbonate composite material are matched in a specific proportion to achieve better comprehensive performance, for example, the high proportion of toughening master batch can influence the fluidity of a system and further influence the toughening effect; the ratio is too low to meet the toughening requirement, and the chemical solvent resistance is poor.
In the present invention, the mass percentage of the polycarbonate is 70% -85%, for example 72%, 74%, 76%, 78%, 80%, 82%, 84%, etc.
The toughening master batch according to the first aspect has a mass percentage of 6% -15%, for example 8%, 10%, 12%, 14%, etc.
The mass percent of the flame retardant is 8% -12%, such as 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5% and the like.
The mass percentage of the other auxiliary agents is 0.5% -4%, such as 1%, 1.5%, 2%, 2.5%, 3%, 3.5% and the like.
Preferably, the polycarbonate comprises a hydroxyl-terminated polycarbonate.
Preferably, the polycarbonate has a melt index of 10-22g/10min, such as 14g/10min, 16g/10min, 18g/10min, 20g/10min, etc.
Preferably, the flame retardant comprises a combination of a polymeric phosphate and a small molecule compound.
In the invention, the flame retardant comprises a combination of polymer phosphate and a small molecular compound, and the polymer phosphate and the small molecular compound are matched for use, so that on one hand, the flame retardant performance of the system can be ensured, and on the other hand, the flame retardant has a better contribution to the heat resistance of the system.
Preferably, the small molecule compound comprises any one or a combination of at least two of bisphenol a bis (diphenyl phosphate) (BDP), triphenyl phosphate (TPP), or resorcinol bis (diphenyl phosphate) (RDP), wherein typical but non-limiting combinations include: combinations of bisphenol a bis (diphenyl phosphate) and triphenyl phosphate, combinations of triphenyl phosphate and resorcinol bis (diphenyl phosphate), combinations of bisphenol a bis (diphenyl phosphate), triphenyl phosphate and resorcinol bis (diphenyl phosphate), and the like.
Preferably, the mass ratio of the polymer phosphate to the small molecule compound is 1: (1-2), wherein 1-2 may be 1.2, 1.4, 1.6, 1.8, etc.
Preferably, the other auxiliary agents include a weather-resistant agent and/or an antioxidant.
Illustratively, in the present invention, the weathering agent includes any one or a combination of at least two of UV234, UV5411 or UV360, wherein typical but non-limiting combinations include: a combination of UV234 and UV5411, a combination of UV5411 and UV360, a combination of UV234, UV5411 and UV360, and the like.
Illustratively, in the present invention, the antioxidant comprises any one or a combination of at least two of antioxidant 1076, antioxidant 168 or antioxidant 412S, wherein typical but non-limiting combinations include: a combination of antioxidant 1076 and antioxidant 168, a combination of antioxidant 168 and antioxidant 412S, a combination of antioxidant 1076, antioxidant 168 and antioxidant 412S, and the like.
Preferably, the mass percent of the weathering agent is 0.5% -2%, such as 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, etc.
Preferably, the antioxidant is present in an amount of 0.5% -2% by mass, e.g., 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, etc.
In a fourth aspect, the present invention provides a method for preparing the polycarbonate composite material according to the third aspect, the method comprising the steps of:
and mixing the polycarbonate, the toughening master batch, the flame retardant and other auxiliary agents, extruding and granulating to obtain the polycarbonate composite material.
Preferably, the temperature of the extrusion granulation is 240-280 ℃, e.g., 250 ℃,260 ℃, 270 ℃, etc., more preferably 260 ℃.
In a fifth aspect, the present invention provides an earphone, wherein the earphone comprises the polycarbonate composite material according to the third aspect.
Preferably, the earphone comprises a TWS earphone.
Compared with the prior art, the invention has the following beneficial effects:
(1) The polycarbonate composite material formed by the toughening master batch has excellent solvent resistance, flame retardance and toughness, and is suitable for TWS earphone parts.
(2) The polycarbonate composite material formed by the toughening master batch is not cracked after being soaked in a mixed solvent of carbon tetrachloride and alcohol for more than 22 minutes, the flame retardant grade can reach V-0, and the notch impact is more than 356J/M;
in a preferred range, the polycarbonate composite material formed by the toughening master batch is soaked in a mixed solvent of carbon tetrachloride and alcohol (the mass ratio is 1:1) for more than 69 minutes without cracking, the flame retardant grade can reach V-0, and the notch impact strength is more than 510J/M.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a toughening master batch, which comprises the following raw materials in percentage by mass, based on 100% of the total mass of the toughening master batch:
in this example, the melt index of the polycarbonate containing terminal hydroxyl groups was 15g/10min, which was purchased from Japanese emperor under the trademark LV-2225ZS;
the grafting rate of the maleic anhydride grafted polyethylene is 0.8%, and the maleic anhydride grafted polyethylene is purchased from Shenyang Kong Tong, and the brand is KT-12B;
the siloxane containing the epoxy groups has the content of 17.8 percent, is purchased from morning light and has the mark KH560;
the toughening agent containing the epoxy groups has the content of 8 percent, and is purchased from Acomax and has the brand number of AX8900;
the antioxidants are equal-mass antioxidants 1076 and 168.
The toughening master batch is prepared by the following method, and the preparation method comprises the following steps:
mixing polycarbonate containing terminal hydroxyl groups, maleic anhydride grafted polyethylene, siloxane containing epoxy groups, a toughening agent containing epoxy groups and an antioxidant for 1.5 minutes by using a high-speed mixer at 500RPM, extruding and bracing to granulate by using a double-screw extruder with the length-diameter ratio of 50/1 at 240 ℃ to obtain the toughening master batch.
Example 2
The embodiment provides a toughening master batch, which comprises the following raw materials in percentage by mass, based on 100% of the total mass of the toughening master batch:
in this example, the melt index of the hydroxyl-terminated polycarbonate was 10g/10min, purchased from gladiation under the trade designation IR2200;
in the maleic anhydride grafted polyethylene, the grafting rate is 1.0 percent: purchased from Acomax under the brand name 18302N;
the epoxy group-containing siloxane has the epoxy group content of 15.1 percent, is purchased from Kofu le and has the brand of CSF-348;
the epoxy group-containing toughening agent has the epoxy group content of 4 percent and is purchased from Acomax with the brand number of AX8930;
the antioxidant is equal-mass antioxidant 1076, antioxidant 168 and antioxidant 412S.
The toughening master batch is prepared by the following method, and the preparation method comprises the following steps:
mixing polycarbonate containing terminal hydroxyl groups, maleic anhydride grafted polyethylene, siloxane containing epoxy groups, a toughening agent containing epoxy groups and an antioxidant for 1 minute by using a high-speed mixer at 500RPM, extruding a bracing piece by using a double-screw extruder with the length-diameter ratio of 56/1 at 220 ℃, and granulating to obtain the toughening master batch.
Example 3
The embodiment provides a toughening master batch, which comprises the following raw materials in percentage by mass, based on 100% of the total mass of the toughening master batch:
in this example, the melt index of the hydroxyl-terminated polycarbonate was 22g/10min, purchased from light, and brand IR1900;
in the maleic anhydride grafted polyethylene, the grafting rate is 0.5 percent: purchased from Acomax under the trade name 18300;
the epoxy group-containing siloxane has the epoxy group content of 16.9%, is purchased from Kofu le and has the brand of CFS-601;
the epoxy group-containing toughening agent has the epoxy group content of 5 percent and is purchased from Acomax and has the brand number of AX8750;
the antioxidants are antioxidant 1076 and antioxidant 412S with equal mass.
The toughening master batch is prepared by the following method, and the preparation method comprises the following steps:
mixing polycarbonate containing terminal hydroxyl groups, maleic anhydride grafted polyethylene, siloxane containing epoxy groups, a toughening agent containing epoxy groups and an antioxidant for 2 minutes by using a high-speed mixer at 500RPM, extruding a bracing piece by using a double-screw extruder with the length-diameter ratio of 40/1 at 260 ℃ and granulating to obtain the toughening master batch.
Example 4
This example differs from example 1 in that the epoxy group-containing toughening agent is 10% by mass, the hydroxyl group-containing polycarbonate is 63.5% by mass, and the remainder is the same as in example 1.
Example 5
This example differs from example 1 in that the epoxy group-containing toughening agent is 35% by mass, the hydroxyl group-containing polycarbonate is 38.5% by mass, and the remainder is the same as in example 1.
Comparative example 1
This comparative example differs from example 1 in that the hydroxyl-terminated polycarbonate was replaced with an equal mass of hydroxyl-terminated polycarbonate (commercially available from Cangzhou corporation under the designation CH 8105), the remainder being the same as example 1.
Comparative example 2
This comparative example differs from example 1 in that the epoxy group-containing siloxane was replaced with an epoxy group-free siloxane (commercially available from morning light under the designation KH 550), the remainder being identical to example 1.
Comparative example 3
This comparative example differs from example 1 in that the epoxy group-containing toughening agent was replaced with an epoxy group-free toughening agent (available from dupont under the designation 1125 AC), the remainder being identical to example 1.
Application example 1
The application example provides a polycarbonate composite material, which comprises the following components in percentage by mass, based on 100% of the total mass of the polycarbonate composite material:
in the embodiment, the polycarbonate is polycarbonate containing hydroxyl end groups, the melt index is 18g/10min, and the polycarbonate is purchased from Di and has the brand L-1225L;
the mass ratio of the flame retardant is 1:1 (available from FRX under the trade designation HM-1100) and BDP;
the weather-resistant agent is UV234;
the antioxidants are equal-mass antioxidants 1076 and 168.
The polycarbonate composite material is prepared by a method comprising the following steps:
and mixing the polycarbonate, the toughening master batch, the flame retardant and other auxiliary agents, extruding, bracing and granulating at 260 ℃ to obtain the polycarbonate composite material.
Application example 2
The application example provides a polycarbonate composite material, which comprises the following components in percentage by mass, based on 100% of the total mass of the polycarbonate composite material:
in the embodiment, the polycarbonate is polycarbonate containing hydroxyl end groups, the melt index is 10g/10min, and the polycarbonate is purchased from light and has the trade mark of IR2200;
the mass ratio of the flame retardant is 1:2 (available from FRX under the trade designation HM 9000) and TPP;
the weather-resistant agent is UV328;
the antioxidants are antioxidant 1076 and antioxidant 412S with equal mass.
The preparation method of the polycarbonate composite material is the same as that of application example 1.
Application example 3
The application example provides a polycarbonate composite material, which comprises the following components in percentage by mass, based on 100% of the total mass of the polycarbonate composite material:
in the embodiment, the polycarbonate is polycarbonate containing hydroxyl end groups, the melt index is 20g/10min, and the polycarbonate is purchased from Wanhua and has the brand A1220;
the mass ratio of the flame retardant is 1:1.5 Polymer phosphate (commercially available from FRX under the trade designation HM 7000) and RDP;
the weather-resistant agent is UV360;
the antioxidant is equal-mass antioxidant 1076, antioxidant 168 and antioxidant 412s.
The preparation method of the polycarbonate composite material is the same as that of application example 1.
Application examples 4 to 5
Application examples 4 to 5 are different from application example 1 in that the toughening master batches described in example 1 are replaced with the toughening master batches described in example 4 and example 5, respectively, and the rest are the same as application example 1.
Application example 6
The difference between the application example and the application example 1 is that the mass percentage of the toughening master batch is 4%, the mass percentage of the polycarbonate is 83.5%, and the rest is the same as the example 1.
Application example 7
The difference between the application example and the application example 1 is that the mass percentage of the toughening master batch is 20%, the mass percentage of the polycarbonate is 57.5%, and the rest is the same as the example 1.
Application examples comparative examples 1 to 3
The difference between the application examples 1 to 3 and the application example 1 is that the toughening master batches described in example 1 are replaced with the toughening master batches described in comparative examples 1 to 3, respectively, and the rest are the same as in application example 1.
Comparative example 4 was used
The present application comparative example differs from application example 1 in that: the components of the toughening master batch described in example 1 were directly mixed and processed in equal proportions with the other components of application example 1 without mixing in advance and extrusion granulation, and the rest are the same as in application example 1.
Performance testing
The polycarbonate composites described in application examples 1 to 7 and comparative examples 1 to 4 were subjected to the following tests:
(1) Solvent resistance: preparing the polycarbonate composite material into a TWS earphone part, wherein the thickness of the earphone part is 1.0mm, soaking the TWS earphone part in a mixed solvent with the mass ratio of carbon tetrachloride to alcohol being 1:1, and observing the appearance cracking condition.
(2) Flame retardancy: the sample strip was 1.0mm thick as tested in UL 94.
(3) Toughness: cantilever notched impact was tested according to ASTM D256.
The test results are summarized in table 1.
TABLE 1
As shown in an analysis table 1, the polycarbonate composite material formed by the toughening master batch is soaked in a mixed solvent of carbon tetrachloride and alcohol (the mass ratio is 1:1) for more than 22 minutes without cracking, the flame retardant grade can reach V-0, and the notch impact strength is more than 356J/M; the polycarbonate composite material formed by the toughening master batch has excellent solvent resistance, flame retardance and toughness, and is suitable for TWS earphone parts.
In a preferred embodiment, taking application examples 1-3 as an example, the polycarbonate composite material formed by the toughening master batch disclosed by the invention is soaked in a mixed solvent of carbon tetrachloride and alcohol (the mass ratio is 1:1) for more than 69 minutes without cracking, the flame retardant grade can reach V-0, and the notch impact strength is more than 510J/M; the polycarbonate composite material formed by the toughening master batch has excellent solvent resistance, flame retardance and toughness, and is suitable for TWS earphone parts.
Analysis of application comparative example 1 and application example 1 revealed that application comparative example 1 had inferior performance to application example 1, demonstrating that the toughening master batch formed by using the polycarbonate having terminal hydroxyl groups was more advantageous for improving the performance of the polycarbonate composite material.
Analysis of application comparative example 2 and application example 1 revealed that the performance of application comparative example 2 was inferior to that of application example 1, and it was confirmed that the toughening master batch formed by using the epoxy group-containing siloxane was more advantageous for the improvement of the performance of the polycarbonate composite material.
Analysis of application comparative example 3 and application example 1 revealed that the performance of application comparative example 3 was inferior to that of application example 1, and it was confirmed that the toughening master batch formed by using the epoxy group-containing toughening agent was more advantageous for improving the performance of the polycarbonate composite material.
Analysis of application comparative example 4 and application example 1 shows that the performance of application comparative example 4 is not as good as that of application example 1, and the toughening master batch is more beneficial to the improvement of the performance of the polycarbonate composite material.
As can be seen from analysis of application examples 4-5 and application example 1, the performance of application examples 4-5 is not as good as that of application example 1, and it is proved that the toughening master batch formed by controlling 15% -30% of the toughening agent containing the epoxy group in the toughening master batch is more beneficial to improving the performance of the polycarbonate composite material. Other components, such as hydroxyl-terminated polycarbonates, maleic anhydride grafted polyethylenes, and epoxy-containing silicones, also perform better within the scope of the invention.
As can be seen from analysis of application examples 6-7 and application example 1, the performance of application examples 6-7 is inferior to that of application example 1, and the polycarbonate composite material provided by the invention has better performance in the range of 6% -15% by mass of toughening master batch.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The toughening master batch is characterized in that the preparation raw materials of the toughening master batch comprise polycarbonate containing terminal hydroxyl groups, maleic anhydride grafted polyolefin, siloxane containing epoxy groups, a toughening agent containing epoxy groups and an antioxidant.
2. The toughening master batch according to claim 1, wherein the preparation raw materials of the chemical-resistant toughening master batch comprise the following components in percentage by mass, based on 100% of the total mass of the toughening master batch:
3. the toughening masterbatch according to claim 1 or 2, characterized in that the hydroxyl-terminated polycarbonate has a melt index of 10-22g/10min;
preferably, the maleic anhydride grafted polyolefin comprises maleic anhydride grafted polyethylene;
preferably, in the maleic anhydride grafted polyolefin, the grafting rate is 0.5% -1%;
preferably, in the siloxane containing the epoxy groups, the mass content of the epoxy groups is 15-20%;
preferably, in the toughening agent containing the epoxy group, the mass content of the epoxy group is 3-8%.
4. A method of preparing a toughening masterbatch according to any one of claims 1 to 3, comprising the steps of:
mixing polycarbonate containing terminal hydroxyl, maleic anhydride grafted polyolefin, siloxane containing epoxy groups, a toughening agent containing epoxy groups and an antioxidant, extruding and granulating to obtain the toughening master batch.
5. The method of manufacturing according to claim 4, wherein the mixing means comprises a high-speed mixer;
preferably, the mixing time is 1-2min;
preferably, the means for extrusion granulation comprises a twin screw extruder;
preferably, the twin screw extruder has an aspect ratio of (40-56): 1;
preferably, the temperature of the extrusion granulation is 220-260 ℃.
6. A polycarbonate composite comprising a polycarbonate, the toughening masterbatch of any one of claims 1-3, a flame retardant, and other additives.
7. The polycarbonate composite material according to claim 6, wherein the polycarbonate composite material comprises the following components in mass percent, based on 100% of the total mass of the polycarbonate composite material:
8. the polycarbonate composite of claim 6 or 7, wherein the polycarbonate comprises a hydroxyl-terminated polycarbonate;
preferably, the polycarbonate has a melt index of 10-22g/10min;
preferably, the flame retardant comprises a combination of a polymeric phosphate and a small molecule compound;
preferably, the small molecule compound comprises any one or a combination of at least two of bisphenol a bis (diphenyl phosphate), triphenyl phosphate or resorcinol bis (diphenyl phosphate);
preferably, the mass ratio of the polymer phosphate to the small molecule compound is 1: (1-2);
preferably, the other auxiliary agents comprise weather-resistant agents and/or antioxidants;
preferably, the weather-resistant agent accounts for 0.5-2% by mass;
preferably, the antioxidant accounts for 0.5-2% of the total mass of the composition.
9. A method of preparing the polycarbonate composite material of any of claims 6-8, comprising the steps of:
mixing polycarbonate, the toughening master batch according to any one of claims 1-3, a flame retardant and other auxiliary agents, extruding and granulating to obtain the polycarbonate composite material.
10. An earphone characterized in that the earphone comprises the polycarbonate composite material according to any one of claims 6 to 8 as a preparation raw material;
preferably, the earphone comprises a TWS earphone.
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| CN104341760A (en) * | 2013-07-30 | 2015-02-11 | 青岛欣展塑胶有限公司 | Polycarbonate toughened masterbatch with core-shell structure |
| CN104341700A (en) * | 2013-07-30 | 2015-02-11 | 青岛欣展塑胶有限公司 | PC impact-resistant and flame retardant master batch |
| CN104419175A (en) * | 2013-09-05 | 2015-03-18 | 青岛欣展塑胶有限公司 | PC toughening master batch |
| CN113416322A (en) * | 2021-05-06 | 2021-09-21 | 常州大学 | Preparation method and application of polycarbonate low-temperature toughening master batch with compatibilization function |
| CN113637307A (en) * | 2021-08-05 | 2021-11-12 | 金发科技股份有限公司 | Hydrolysis-resistant halogen-free flame-retardant high-toughness PC/ASA alloy material and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104341760A (en) * | 2013-07-30 | 2015-02-11 | 青岛欣展塑胶有限公司 | Polycarbonate toughened masterbatch with core-shell structure |
| CN104341700A (en) * | 2013-07-30 | 2015-02-11 | 青岛欣展塑胶有限公司 | PC impact-resistant and flame retardant master batch |
| CN104419175A (en) * | 2013-09-05 | 2015-03-18 | 青岛欣展塑胶有限公司 | PC toughening master batch |
| CN113416322A (en) * | 2021-05-06 | 2021-09-21 | 常州大学 | Preparation method and application of polycarbonate low-temperature toughening master batch with compatibilization function |
| CN113637307A (en) * | 2021-08-05 | 2021-11-12 | 金发科技股份有限公司 | Hydrolysis-resistant halogen-free flame-retardant high-toughness PC/ASA alloy material and preparation method and application thereof |
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