CN111117168B - Flame-retardant master batch and aromatic polymer composition containing same - Google Patents
Flame-retardant master batch and aromatic polymer composition containing same Download PDFInfo
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- CN111117168B CN111117168B CN201811277353.0A CN201811277353A CN111117168B CN 111117168 B CN111117168 B CN 111117168B CN 201811277353 A CN201811277353 A CN 201811277353A CN 111117168 B CN111117168 B CN 111117168B
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- 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
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- 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
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- 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
- C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
- C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
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Abstract
The invention relates to a flame-retardant master batch and an aromatic polymer composition containing the same, wherein the master batch consists of the following two components in percentage by weight based on the weight of the master batch: 5-40% of hyperbranched polyester and 60-95% of flame retardant; the aromatic polymer composition has the following proportions, based on the weight ratio of the materials: 70-99.5% of aromatic polymer and 0.5-30% of flame-retardant master batch. By adding the flame-retardant master batch, the aromatic polymer composition has excellent flame retardant property, heat resistance, mechanical property and processability, and is suitable for the fields of automobiles, IT, electronic and electric appliances and the like.
Description
Technical Field
The invention relates to a flame-retardant master batch and an aromatic polymer composition containing the same, belonging to the fields of polymer blending and polymer forming.
Background
The aromatic polymer or the composition thereof is widely applied to a plurality of fields such as automobiles, electronic appliances, household appliances and the like by virtue of excellent performance, such as PC/ABS, PC/PBT, ABS alloy, PBT alloy and the like, and is widely applied.
The polycarbonate alloy is widely applied to a plurality of fields such as automobiles, IT, electronic and electric appliances and the like due to excellent mechanical property, heat resistance and processing property. Meanwhile, as people pay more attention to safety, the flame retardant requirement on the polycarbonate alloy is also increased, and a flame retardant is required to be added into the polycarbonate alloy to achieve a high flame retardant effect.
The phosphorus flame retardant system is adopted only, so that the flame retardant effect of the phosphorus flame retardant is limited, and the flame retardant property of the product cannot be greatly improved. On the other hand, the addition amount of the phosphorus flame retardant is large, which causes serious influence on the heat resistance and impact resistance of the product; the sulfonate or silicon flame-retardant system is adopted, the flame-retardant effect is general, the heat resistance and the impact resistance are not greatly influenced, but the product fluidity is poor, and a large-scale thin-wall product is difficult to prepare.
At present, the thin-walled and high-performance requirements of automobile, IT and electronic and electrical products are more and more obvious, and in order to meet the industrial development requirements, polycarbonate alloy enters more application markets, and the flame retardant property, heat resistance and processability of the flame retardant polycarbonate alloy are imperative.
In order to improve the flame retardance and the heat resistance of the polycarbonate alloy, a lot of research works are carried out, and CN 106084717A discloses a high-heat-resistance high-toughness polycarbonate composition and a preparation method thereof, wherein the invention has the following raw material formula: 60-90 parts of polycarbonate, 1-20 parts of butadiene copolymer, 5-25 parts of phosphate homopolymer, 0-8 parts of toughening agent and 0-9.6 parts of other auxiliary agents; the sum of the parts by weight of all the components is 100 parts; according to the invention, the phosphate homopolymer is added into the raw material formula, so that the defect that the heat deformation temperature and the toughness of the polycarbonate can be greatly reduced by using the conventional organic phosphate flame retardant can be well overcome, and the heat resistance and the toughness of the polycarbonate composition are effectively improved. However, the flame retardant grade of the polyphosphate flame retardant is low (only 1.6mmV0), and on the other hand, the polyphosphate homopolymer is expensive and difficult to popularize on a large scale.
CN 103275378A discloses a flame retardant dielectric substrate material for printed circuit, which is composed of the following components in the following ratio: 30-50 parts by weight of a polyethylene elastomer and 30-50 parts by weight of a polyurethane elastomer; 10-30 parts by weight of ethylene propylene diene monomer; 6-15 parts of a flame retardant. The invention adopts the compound of the dendritic organic montmorillonite and the hyperbranched polyphosphate to carry out flame retardant modification, so that the prepared dielectric substrate material not only has excellent flame retardant property and processing property, but also is environment-friendly, but the preparation methods of the hyperbranched polyphosphate and the dendritic montmorillonite are complex and have high cost, and meanwhile, the dendritic montmorillonite can generate larger influence on the system fluidity, and is difficult to prepare thin-wall products.
CN 101333298A discloses a preparation method of a branched polyesteramide and mixed rare earth oxide composite halogen-free flame-retardant plastic master batch and a special resin, wherein the dosage ratio of each component in the flame-retardant master batch is based on 100 parts of matrix resin: base resin 100, BPEA/RE2O3150-200 parts of processing flow assistant and 80-160 parts of calcium carbonate. The special resin for the halogen-free flame-retardant plastic adopting the flame-retardant master batch has higher flame-retardant propertyHowever, the rare earth oxide adopted by the method has poor compatibility with the branched polymer and the resin matrix, so that the method has obvious influence on physical properties, and meanwhile, the synergistic effect between the branched polyesteramide and the rare earth oxide is poor, so that a high-flame-retardant thin-wall product cannot be prepared.
CN107353647A discloses a low-odor and low-emission carrier-free nano flame-retardant master batch, which comprises a main flame retardant, a synergistic flame retardant, an odor adsorbent, hyperbranched polysiloxane, a silane coupling agent, a heat stabilizer and a lubricant, but the flame-retardant master batch also has the problem of poor compatibility with polycarbonate resin.
CN108250566A discloses a low-warpage halogen-free intumescent flame-retardant long glass fiber reinforced polypropylene composite material and a preparation method thereof. The polypropylene composite material is composed of 40-80% of halogen-free flame-retardant master batch and the balance of long glass fiber master batch by mass percentage, the halogen-free flame-retardant master batch comprises a propylene-based elastomer, a nitrogen-phosphorus compound flame retardant, a hyperbranched polymer, active nano zinc oxide and the like, the hyperbranched polymer is multi-stage branched polyester, but the flame-retardant master batch has the problem of poor compatibility with polycarbonate resin.
Therefore, it is necessary to develop a novel polycarbonate alloy material, which has high flame retardancy, high heat resistance, excellent mechanical properties and processability, and meets the environmental protection requirements of related applications.
Disclosure of Invention
The invention aims to provide a flame-retardant master batch and an aromatic polymer composition containing the same, wherein the flame-retardant master batch consisting of hyperbranched polyester and a flame retardant is adopted, so that the flame-retardant performance of the aromatic polymer composition can be effectively improved, and the flame-retardant master batch has excellent heat resistance, mechanical property and processability.
Another object of the present invention is to provide a method for preparing the flame-retardant masterbatch and an aromatic polymer composition containing the masterbatch.
The invention also aims to provide the application of the flame-retardant master batch and the aromatic polymer composition containing the master batch in the fields of automobiles, IT and electronic and electric appliances.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a flame-retardant master batch comprises the following components:
5-40 wt% of hyperbranched polyester; preferably 10-30% wt;
60-95 wt% of flame retardant; preferably 70 to 90 wt%; the wt% is based on the weight of the flame-retardant master batch,
the flame retardant is one or more of sulfonate flame retardant, silicon flame retardant, phosphazene flame retardant, inorganic phosphorus flame retardant and organic phosphorus flame retardant,
preferably, the hyperbranched polyester is one or more of aromatic polyester or aliphatic polyester with the number of terminal hydroxyl functional groups of 24-256, preferably 36-128, and preferably aromatic polyester.
The sulfonate flame retardant can be selected from one or more of potassium perfluorobutyl sulfonate, sodium 2,4, 5-trichlorobenzene sulfonate, potassium diphenyl sulfone sulfonate and the like; the silicon-based flame retardant can be one or more selected from polysilsesquioxane, polydimethylsiloxane and the like; the phosphazene flame retardant may be selected from polyaryloxy phosphazenes and the like; the inorganic phosphorus flame retardant may be selected from red phosphorus flame retardants, and the organic phosphorus flame retardant may be selected from one or more of resorcinol bis (diphenyl phosphate), bisphenol a bis (diphenyl phosphate), resorcinol bis (2, 6-dimethylphenyl) phosphate, and the like.
In the present invention, the flame retardant is preferably an organic phosphorus flame retardant, and more preferably bisphenol a bis (diphenyl phosphate).
In the invention, the preparation method of the flame-retardant master batch comprises the following steps:
the hyperbranched polyester and the flame retardant are weighed in proportion, evenly mixed in mixing equipment, extruded and granulated to prepare the flame-retardant master batch.
The temperature of the cylinder of the extruder is 180-250 ℃, and the rotation speed of the screw is 100-800 RPM.
The present invention further provides an aromatic polymer composition comprising the above flame retardant masterbatch, which comprises:
aromatic polymer and/or aromatic polymer alloy: 70-99.5 wt%; preferably 85-95 wt%;
flame-retardant master batch: 0.5-30 wt%; preferably 5 to 15 wt%;
the wt% is based on the total weight of the aromatic polymer composition.
In the present invention, the aromatic polymer includes: one or more of aromatic polycarbonate, acrylonitrile-butadiene-styrene graft copolymer, polyphenyl ether, aromatic polyamide and aromatic polyester.
The aromatic polymer alloy is one or more of polycarbonate/polyamide, polycarbonate/rubber graft polymer, polycarbonate/polyester, polyphenyl ether/polystyrene, polystyrene/polyamide and polyphenyl thioether/polyamide alloy.
Preferably the aromatic polymer alloy is a polycarbonate/rubber graft polymer alloy.
More preferably, the polycarbonate/rubber graft polymer alloy is prepared in the following proportions, based on the weight of the aromatic polymer:
55-99.5% of polycarbonate resin; preferably 70-85%;
0.5 to 45 percent of rubber graft polymer; preferably 15-30%.
In the invention, the polycarbonate resin is one or more of aromatic polycarbonate resin, aliphatic polycarbonate resin and aromatic-aliphatic polycarbonate resin, bisphenol A type polycarbonate resin is preferred, and the melt index of the polycarbonate resin is 1-65g/10min, preferably 3-50g/10min, more preferably 5-35g/10min under the test condition of 1.2kg at 300 ℃.
In the present invention, the rubber graft polymer is selected from one or more of acrylonitrile-butadiene-styrene graft copolymer and acrylonitrile-styrene-acrylate terpolymer, preferably acrylonitrile-butadiene-styrene graft copolymer (ABS). According to weight percentage, the content of butadiene is 10-40%, the content of acrylonitrile is 15-30%, and the content of styrene is 45-70%.
In the present invention, the material further optionally comprises, in weight percent, based on the total weight sum of the aromatic polymer and the flame-retardant masterbatch:
0-10%, preferably 0.1-5% of plastic additives, wherein the plastic additives comprise one or more of toughening agent, anti-dripping agent, antioxidant and lubricant.
The toughening agent is methyl methacrylate-butadiene-styrene copolymer and/or methyl methacrylate-organic silicon-acrylic acid copolymer, preferably methyl methacrylate-organic silicon-acrylic acid copolymer. The addition amount of the toughening agent accounts for 0.5-10 wt%, preferably 1-5 wt% of the sum of the weight of the aromatic polymer or the composition thereof and the weight of the flame-retardant master batch.
The anti-dripping agent is coated polytetrafluoroethylene and/or pure powder polytetrafluoroethylene, preferably coated polytetrafluoroethylene, and more preferably styrene-acrylonitrile coated polytetrafluoroethylene. The addition amount of the anti-dripping agent accounts for 0-5 wt%, preferably 0.1-2 wt% of the sum of the weight of the aromatic polymer or the composition thereof and the weight of the flame-retardant master batch.
The antioxidant comprises a main antioxidant and an auxiliary antioxidant, wherein the main antioxidant comprises beta- [3, 5-di-tert-butyl-4-hydroxyphenyl ] n-octadecyl propionate, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and the like, and the auxiliary antioxidant comprises tris [2, 4-di-tert-butylphenyl ] phosphite, bis [2, 4-di-tert-butylphenyl ] pentaerythritol diphosphite and the like.
The lubricant is selected from pentaerythritol stearate (PETS) and/or silicone powder.
The sum of the addition amount of the antioxidant and the lubricant accounts for 0-2 wt%, preferably 0.2-1 wt% of the sum of the weight of the aromatic polymer or the composition thereof and the weight of the flame-retardant master batch.
The preparation method of the flame-retardant master batch and the aromatic polymer composition containing the same comprises the following steps:
weighing the flame-retardant master batch, the aromatic polymer and the plastic additive in proportion, and mixing in a mixer. And adding the uniformly mixed substances into a double-screw extruder, and stretching and granulating after the materials are melted and extruded.
Preferably, the barrel temperature of the double-screw extruder is 220-250 ℃, and the screw rotating speed is 100-800 RPM.
The aromatic polymer composition prepared by the method can be used in the fields of charging piles, IT, household appliances and the like.
The invention has the following beneficial effects:
the hyperbranched polyester and the flame retardant are blended and extruded to prepare the flame-retardant master batch, the flame-retardant master batch can exert the synergistic effect of the hyperbranched polyester and the flame retardant, the flame retardant property of the aromatic polymer composition, particularly polycarbonate alloy, can be obviously improved, and the excellent mechanical property and heat resistance of the material are maintained.
Meanwhile, the flame-retardant master batch can endow the aromatic polymer composition with excellent flow processing performance.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Polycarbonate resin: melt index at 300 ℃ of 1.2kg, Vanhua chemical group, Inc. A1105
It was 10g/10 min.
ABS resin: shanghai Gaoqiao 8434, produced by continuous bulk method, with a melt index of 3.8kg at 200 ℃
3.9g/10min。
PBT resin: taiwan Changchun 1100-.
Hyperbranched polymer:
the Wuhan hyperbranched resin branch science and technology Limited company Hyper H30-H304 is aromatic hyperbranched polyester with terminal hydroxyl, and the number of the terminal hydroxyl is 42.
The Wuhan hyperbranched resin branch science and technology Limited company Hyper H30-H303 is aromatic hyperbranched polyester with terminal hydroxyl group, and the number of the terminal hydroxyl groups is 24.
The Wuhan hyperbranched resin branch science and technology Limited company Hyper H30-H301 is aromatic hyperbranched polyester with terminal hydroxyl groups, and the number of the terminal hydroxyl groups is 6.
Organic phosphorus compounds: bisphenol A bis (diphenyl phosphate) (BDP), Inc., of Wangsheng, Zhejiang.
A toughening agent: mitsubishi yang silicon series toughener S-2001.
Anti-dripping agent: guangzhou entropy energy polymer technology Limited SN3300B3, styrene-acrylonitrile coated polytetrafluoroethylene, wherein the mass ratio of styrene-acrylonitrile to polytetrafluoroethylene is 1: 1.
Antioxidant: basf B900, wherein the mass ratio of n-octadecyl beta- [3, 5-di-tert-butyl-4-hydroxyphenyl ] propionate (1076) to tris [2, 4-di-tert-butylphenyl ] phosphite (168) is 1: 4.
Lubricant: american dragon sand PETS.
Example 1
(1) Weighing 0.15kg of Hyper H30-H304 and 1.35kg of BDP, mixing the weighed materials in a high-speed mixer for 5min, adding the mixture into a double-screw extruder, extruding at the temperature of 200 ℃, and performing water-cooling granulation to prepare the flame-retardant master batch after extrusion.
(2) Weighing 6kg of A1105, 2.5kg of 8434, 1.5kg of flame-retardant master batch, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(3) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(4) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set as follows (80 ℃, 220 ℃, 245 ℃, 240 ℃ and 240 ℃. The temperature of the neck ring mold is 240 ℃, the extrusion rotating speed is 300RPM, and the modified material is subjected to water cooling granulation after being extruded from the neck ring mold.
Example 2
(1) Weighing 0.2kg of Hyper H30-H304 and 0.8kg of BDP, mixing the weighed materials in a high-speed mixer for 5min, adding the mixture into a double-screw extrusion stage, extruding at the temperature of 200 ℃, and performing water-cooling granulation to prepare the flame-retardant master batch after extrusion.
(2) Weighing 7kg of A1105, 2kg of 8434, 1kg of flame-retardant master batch, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(3) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(4) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set as follows (80 ℃, 220 ℃, 245 ℃, 240 ℃ and 240 ℃. The temperature of the neck ring mold is 240 ℃, the extrusion rotating speed is 300RPM, and the modified material is subjected to water cooling granulation after being extruded from the neck ring mold.
Example 3
(1) Weighing 0.1kg of Hyper H30-H304 and 0.9kg of BDP, mixing the weighed materials in a high-speed mixer for 5min, adding the mixture into a double-screw extruder, extruding at the temperature of 200 ℃, and performing water-cooling granulation to prepare the flame-retardant master batch after extrusion.
(2) Weighing 7kg of A1105, 2kg of 8434, 1kg of flame-retardant master batch, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(3) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(4) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set as follows (80 ℃, 220 ℃, 245 ℃, 240 ℃ and 240 ℃. The temperature of the neck ring mold is 240 ℃, the extrusion rotating speed is 300RPM, and the modified material is subjected to water cooling granulation after being extruded from the neck ring mold.
Example 4
(1) Weighing 0.3kg of Hyper H30-H304 and 0.7kg of BDP, mixing the weighed materials in a high-speed mixer for 5min, adding the mixture into a double-screw extruder, extruding at the temperature of 200 ℃, and performing water-cooling granulation to prepare the flame-retardant master batch after extrusion.
(2) Weighing 7kg of A1105, 2kg of 8434, 1kg of flame-retardant master batch, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(3) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(4) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set as follows (80 ℃, 220 ℃, 245 ℃, 240 ℃ and 240 ℃. The temperature of the neck ring mold is 240 ℃, the extrusion rotating speed is 300RPM, and the modified material is subjected to water cooling granulation after being extruded from the neck ring mold.
Example 5
(1) Weighing 0.1kg of Hyper H30-H304 and 0.4kg of BDP, mixing the weighed materials in a high-speed mixer for 5min, adding the mixture into a double-screw extruder, extruding at the temperature of 200 ℃, and performing water-cooling granulation to prepare the flame-retardant master batch after extrusion.
(2) Weighing 8kg of A1105, 1.5kg of 8434, 0.5kg of flame-retardant master batch, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(3) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(4) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set at 80 ℃, 220 ℃, 250 ℃, 245 ℃ and 245 ℃. The temperature of the neck ring mold is 245 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then granulated by water cooling.
Example 6
(1) Weighing 0.45kg of Hyper H30-H304 and 1.05kg of BDP, mixing the weighed materials in a high-speed mixer for 5min, adding the mixture into a double-screw extruder, extruding at the temperature of 200 ℃, and performing water-cooling granulation to prepare the flame-retardant master batch after extrusion.
(2) Weighing 8kg of A1105, 0.5kg of 8434, 1.5kg of flame-retardant master batch, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(3) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(4) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set as follows (80 ℃, 220 ℃, 245 ℃, 240 ℃ and 240 ℃. The temperature of the neck ring mold is 240 ℃, the extrusion rotating speed is 300RPM, and the modified material is subjected to water cooling granulation after being extruded from the neck ring mold.
Example 7
(1) Weighing 0.05kg of Hyper H30-H304 and 0.95kg of BDP, mixing the weighed materials in a high-speed mixer for 5min, adding the mixture into a double-screw extruder, extruding at the temperature of 200 ℃, and performing water-cooling granulation to prepare the flame-retardant master batch after extrusion.
(2) Weighing 7kg of A1105, 2kg of 8434, 1kg of flame-retardant master batch, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(3) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(4) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set as follows (80 ℃, 220 ℃, 245 ℃, 240 ℃ and 240 ℃. The temperature of the neck ring mold is 240 ℃, the extrusion rotating speed is 300RPM, and the modified material is subjected to water cooling granulation after being extruded from the neck ring mold.
Example 8
(1) Weighing 0.4kg of Hyper H30-H304 and 0.6kg of BDP, mixing the weighed materials in a high-speed mixer for 5min, adding the mixture into a double-screw extruder, extruding at the temperature of 200 ℃, and performing water-cooling granulation to prepare the flame-retardant master batch after extrusion.
(2) Weighing 7kg of A1105, 2kg of 8434, 1kg of flame-retardant master batch, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(3) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(4) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set as follows (80 ℃, 220 ℃, 245 ℃, 240 ℃ and 240 ℃. The temperature of the neck ring mold is 240 ℃, the extrusion rotating speed is 300RPM, and the modified material is subjected to water cooling granulation after being extruded from the neck ring mold.
Example 9
(1) Weighing 0.3kg of Hyper H30-H304 and 2.7kg of BDP, mixing the weighed materials in a high-speed mixer for 5min, adding the mixture into a double-screw extruder, extruding at the temperature of 200 ℃, and performing water-cooling granulation to prepare the flame-retardant master batch after extrusion.
(2) Weighing 4kg of A1105, 3kg of 8434, 3kg of flame-retardant master batch, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(3) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(4) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set as follows (80 ℃, 200 ℃, 220 ℃, 215 ℃. The temperature of the neck ring die is 215 ℃, the extrusion rotating speed is 100RPM, and the modified material is subjected to water cooling granulation after being extruded from the neck ring die.
Example 10
(1) Weighing 0.4kg of Hyper H30-H304 and 0.55kg of BDP, mixing the weighed materials in a high-speed mixer for 5min, adding the mixture into a double-screw extruder, extruding at the temperature of 200 ℃, and performing water-cooling granulation to prepare the flame-retardant master batch after extrusion.
(2) Weighing 9kg of A1105, 0.05kg of 8434, 0.95kg of flame-retardant master batch, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(3) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(4) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set at 80 ℃, 220 ℃, 250 ℃, 245 ℃ and 245 ℃. The temperature of the neck ring mold is 245 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then granulated by water cooling.
Example 11
(1) Weighing 0.01kg of Hyper H30-H304 and 0.04kg of BDP, mixing the weighed materials in a high-speed mixer for 5min, adding the mixture into a double-screw extruder, extruding at the temperature of 200 ℃, and performing water-cooling granulation to prepare the flame-retardant master batch after extrusion.
(2) Weighing 9kg of A1105, 0.95kg of 8434, 0.05kg of flame-retardant master batch, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(3) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(4) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set at 80 ℃, 220 ℃, 250 ℃, 245 ℃ and 245 ℃. The temperature of the neck ring mold is 245 ℃, the extrusion rotating speed is 800RPM, and the modified material is extruded from the neck ring mold and then granulated by water cooling.
Example 12
(1) Weighing 0.6kg of Hyper H30-H304 and 2.4kg of BDP, mixing the weighed materials in a high-speed mixer for 5min, adding the mixture into a double-screw extruder, extruding at the temperature of 200 ℃, and performing water-cooling granulation to prepare the flame-retardant master batch after extrusion.
(2) Weighing 5kg of A1105, 2kg of 8434, 3kg of flame-retardant master batch, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(3) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(4) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set as follows (80 ℃, 220 ℃, 245 ℃, 240 ℃ and 240 ℃. The temperature of the neck ring mold is 240 ℃, the extrusion rotating speed is 300RPM, and the modified material is subjected to water cooling granulation after being extruded from the neck ring mold.
Example 13
(1) Weighing 0.2kg of Hyper H30-H304 and 0.8kg of BDP, mixing the weighed materials in a high-speed mixer for 5min, adding the mixture into a double-screw extruder, extruding at the temperature of 200 ℃, and performing water-cooling granulation to prepare the flame-retardant master batch after extrusion.
(2) Weighing 7kg of A1105, 2kg of 1100-211M, 1kg of flame-retardant master batch, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(3) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(4) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set as follows (80 ℃, 220 ℃, 240 ℃, 235 ℃). The temperature of the neck ring mold is 235 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then is granulated by water cooling.
Example 14
(1) Weighing 0.2kg of Hyper H30-H303 and 0.8kg of BDP, mixing the weighed materials in a high-speed mixer for 5min, adding the mixture into a double-screw extruder, extruding at the temperature of 200 ℃, and performing water-cooling granulation to prepare the flame-retardant master batch after extrusion.
(2) Weighing 7kg of A1105, 2kg of 1100-211M, 1kg of flame-retardant master batch, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(3) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(4) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set as follows (80 ℃, 220 ℃, 240 ℃, 235 ℃). The temperature of the neck ring mold is 235 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then is granulated by water cooling. Comparative example 1
(1) Weighing 8kg of A1105, 1.2kg of 8434, 0.8kg of BDP, 0.3kg S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the material is added into a double-screw extruder, the temperature of each section of the extruder is set as shown in the specification (from a feeding port to a machine head) that the temperature is 80 ℃, 220 ℃, 250 ℃, 245 ℃ and 245 ℃, the temperature of a neck ring is 245 ℃, the extrusion speed is 300RPM, and the modified material is extruded from the neck ring and then water-cooled and granulated. Comparative example 2
(1) Weighing 7kg of A1105, 2kg of 1100-211M, 1kg of BDP, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set as follows (80 ℃, 220 ℃, 240 ℃, 235 ℃). The temperature of the neck ring mold is 235 ℃, the extrusion rotating speed is 300RPM, and the modified material is extruded from the neck ring mold and then is granulated by water cooling. Comparative example 3
(1) Weighing 6kg of A1105, 2.5kg of 8434, 0.15kg of Hyper H30-H304, 1.35kg of BDP, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(2) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(3) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set as follows (80 ℃, 220 ℃, 245 ℃, 240 ℃ and 240 ℃. The temperature of the neck ring mold is 240 ℃, the extrusion rotating speed is 300RPM, and the modified material is subjected to water cooling granulation after being extruded from the neck ring mold. Comparative example 4
(1) Weighing 0.2kg of Hyper H30-H301 and 0.8kg of BDP, mixing the weighed materials in a high-speed mixer for 5min, adding the mixture into a double-screw extruder, extruding at the temperature of 200 ℃, and performing water-cooling granulation to prepare the flame-retardant master batch after extrusion.
(2) Weighing 7kg of A1105, 2kg of 8434, 1kg of flame-retardant master batch, 0.3kg of S-2001, 0.03g of SN3300B3, 0.02kg of B900 and 0.03kg of PETS;
(3) mixing the weighed materials in a high-speed mixer for 5min, and discharging;
(4) the material was fed into a twin-screw extruder, and the temperatures of the extruder stages (from the feed port to the head) were set as follows (80 ℃, 220 ℃, 245 ℃, 240 ℃ and 240 ℃. The temperature of the neck ring mold is 240 ℃, the extrusion rotating speed is 300RPM, and the modified material is subjected to water cooling granulation after being extruded from the neck ring mold.
The polycarbonate alloys prepared in examples 1 to 13 and comparative examples 1 to 4 were tested according to ISO Standard ISO 1133, ISO180-A, ISO306 for flow properties, impact properties, heat resistance and flame retardancy according to the American Electrical Association UL94 standards, and the results are shown in tables 1 and 2.
Table 1 results of performance testing
Table 2 results of performance testing
Compared with the comparative example, the flame retardant performance of the product in the example is obviously improved after the flame retardant master batch is added, and the product also has excellent heat resistance, mechanical property and processability. However, it should be noted that the excessive addition of the flame-retardant master batch has a negative effect on the impact properties and heat resistance of the material.
Claims (23)
1. A flame retardant masterbatch for use in an aromatic polymer composition comprising, based on the weight of the flame retardant masterbatch:
10-40% of hyperbranched polyester;
60-90% of flame retardant;
the flame retardant is one or more of sulfonate flame retardant, silicon flame retardant, phosphazene flame retardant, inorganic phosphorus flame retardant and organic phosphorus flame retardant,
the hyperbranched polyester is one or more of aromatic polyester or aliphatic polyester with the number of terminal hydroxyl functional groups of 36-256;
the content of the flame-retardant master batch in the aromatic polymer composition is 5-30%.
2. The flame retardant masterbatch according to claim 1, comprising, based on the weight of the flame retardant masterbatch:
10-30% of hyperbranched polyester;
70-90% of flame retardant.
3. The flame retardant masterbatch according to claim 1, wherein the hyperbranched polyester is one or more of aromatic polyester or aliphatic polyester with 36-128 hydroxyl-terminated functional groups.
4. The flame retardant masterbatch according to any one of claims 1-3, wherein the hyperbranched polyester is an aromatic polyester.
5. The flame retardant masterbatch according to any one of claims 1-3, wherein the flame retardant is an organophosphorus flame retardant.
6. The flame retardant masterbatch according to claim 5, wherein said flame retardant is bisphenol A bis (diphenyl phosphate).
7. The method of preparing the flame retardant masterbatch of any one of claims 1-6, wherein the method comprises:
the hyperbranched polyester and the flame retardant are weighed in proportion, evenly mixed in mixing equipment, extruded and granulated to prepare the flame-retardant master batch.
8. The method as claimed in claim 7, wherein the barrel temperature of the extruder is 180-250 ℃ and the screw rotation speed is 100-800 RPM.
9. An aromatic polymer composition comprising, based on the weight of the polymer composition:
70-99.5% of aromatic polymer and/or aromatic polymer alloy;
the flame retardant masterbatch of any one of claims 1-6 in the range of 5-30%.
10. The aromatic polymer composition of claim 9, comprising, based on the weight of the polymer composition:
85-95% of aromatic polymer and/or aromatic polymer alloy;
the flame retardant masterbatch of any one of claims 1-6 in the range of 5-15%.
11. The aromatic polymer composition according to claim 9 or 10,
the aromatic polymer is selected from aromatic polycarbonate, acrylonitrile-butadiene-styrene graft copolymer, polyphenyl ether, aromatic polyamide and aromatic polyester;
the aromatic polymer alloy is selected from one or more of polycarbonate/polyamide, polycarbonate/rubber graft polymer, polycarbonate/polyester, polyphenyl ether/polystyrene, polystyrene/polyamide and polyphenyl thioether/polyamide alloy.
12. The aromatic polymer composition of claim 11, wherein the aromatic polymer alloy is a polycarbonate/rubber graft polymer alloy.
13. The aromatic polymer composition of claim 12, wherein the polycarbonate/rubber graft polymer alloy comprises: 55-99.5% of polycarbonate resin; 0.5 to 45 percent of rubber graft polymer based on the weight of the polycarbonate/rubber graft polymer alloy;
the polycarbonate resin is one or more of aromatic polycarbonate resin and aromatic-aliphatic polycarbonate resin, and the melt index of the polycarbonate resin is 1-65g/10min under the test condition of 1.2kg at 300 ℃.
14. The aromatic polymer composition of claim 13, wherein the polycarbonate/rubber graft polymer alloy comprises: 70-85% of polycarbonate resin; 15-30% of rubber graft polymer, based on the weight of the polycarbonate/rubber graft polymer alloy.
15. The aromatic polymer composition according to claim 13, wherein the polycarbonate resin is a bisphenol a polycarbonate resin.
16. The aromatic polymer composition according to claim 13, wherein the polycarbonate resin has a melt index of 3 to 50g/10min under a test condition of 1.2kg at 300 ℃.
17. The aromatic polymer composition according to claim 13, wherein the polycarbonate resin has a melt index of 5 to 35g/10min under a test condition of 1.2kg at 300 ℃.
18. The aromatic polymer composition of claim 12, wherein the rubber graft polymer is selected from one or more of acrylonitrile-butadiene-styrene graft copolymer, acrylonitrile-styrene-acrylate terpolymer.
19. The aromatic polymer composition of claim 18, wherein the rubber graft polymer is an acrylonitrile-butadiene-styrene graft copolymer (ABS); according to weight percentage, the content of butadiene is 10-40%, the content of acrylonitrile is 15-30%, and the content of styrene is 45-70%.
20. The aromatic polymer composition according to claim 9 or 10, wherein the aromatic polymer composition further optionally comprises, in weight percent, based on the total weight of the aromatic polymer composition and the flame retardant masterbatch:
0-10% of plastic additives, wherein the plastic additives are selected from one or more of toughening agents, anti-dripping agents, antioxidants and lubricants.
21. The aromatic polymer composition of claim 20, further comprising 0.1 to 5% by weight of a plastic additive, based on the total weight of the aromatic polymer composition and the flame retardant masterbatch.
22. The method of making the aromatic polymer composition of any of claims 9-21, comprising the steps of:
weighing the aromatic polymer, the flame-retardant master batch and the plastic additive in proportion, and mixing in a mixer; adding the uniformly mixed substances into a double-screw extruder, and granulating after melting and extruding the materials;
the barrel temperature of the double-screw extruder is 220-250 ℃, and the screw rotating speed is 100-800 RPM.
23. Use of the aromatic polymer composition of any one of claims 9 to 21 in automotive, IT or electronic appliances.
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| JP2009256502A (en) * | 2008-04-18 | 2009-11-05 | Dic Corp | Styrene-based resin composition |
| CN105315481A (en) * | 2015-11-30 | 2016-02-10 | 赤峰富龙市政公用工程有限责任公司 | Method for preparing flame-retardant phenolic resin low temperature foam material |
| CN107353647A (en) * | 2016-05-10 | 2017-11-17 | 合肥杰事杰新材料股份有限公司 | A kind of low smell, low distribute carrier-free nano flame-proof agglomerate and preparation method thereof |
| CN108117735A (en) * | 2018-01-17 | 2018-06-05 | 北京濮源新材料技术研究院(普通合伙) | High-performance halogen-free flame retardant makrolon material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2009256502A (en) * | 2008-04-18 | 2009-11-05 | Dic Corp | Styrene-based resin composition |
| CN105315481A (en) * | 2015-11-30 | 2016-02-10 | 赤峰富龙市政公用工程有限责任公司 | Method for preparing flame-retardant phenolic resin low temperature foam material |
| CN107353647A (en) * | 2016-05-10 | 2017-11-17 | 合肥杰事杰新材料股份有限公司 | A kind of low smell, low distribute carrier-free nano flame-proof agglomerate and preparation method thereof |
| CN108117735A (en) * | 2018-01-17 | 2018-06-05 | 北京濮源新材料技术研究院(普通合伙) | High-performance halogen-free flame retardant makrolon material and preparation method thereof |
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