CN116333428A - Polymer composition, polymer masterbatch composition and sheet comprising or made therefrom - Google Patents

Polymer composition, polymer masterbatch composition and sheet comprising or made therefrom Download PDF

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Publication number
CN116333428A
CN116333428A CN202111603038.4A CN202111603038A CN116333428A CN 116333428 A CN116333428 A CN 116333428A CN 202111603038 A CN202111603038 A CN 202111603038A CN 116333428 A CN116333428 A CN 116333428A
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weight
parts
antioxidant
polymer
polymer composition
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孙毅明
周宏杰
辛菲
帕特里克·雅各布斯
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Lanxess Chemical China Co ltd
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Lanxess Chemical China Co ltd
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Priority to CN202111603038.4A priority Critical patent/CN116333428A/en
Priority to PCT/CN2022/141554 priority patent/WO2023116907A1/en
Publication of CN116333428A publication Critical patent/CN116333428A/en
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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
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0038—Use of organic additives containing phosphorus
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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J9/0066—Use of inorganic compounding ingredients
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/142—Compounds containing oxygen but no halogen atom
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    • C08K3/34—Silicon-containing compounds
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
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    • C—CHEMISTRY; METALLURGY
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    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
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    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
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Abstract

The present invention provides polymer compositions, polymer masterbatch compositions, and plaques containing or made therefrom. The polymer composition comprises: 90 to 99 parts by weight of a polymer matrix; 1 to 10 parts by weight of a flame retardant; 0.1 to 0.5 parts by weight of an acid-binding agent; 0.1 to 0.5 parts by weight of an antioxidant; and 0.2 to 5 parts by weight of a synergist, the parts by weight being based on 100 parts by weight of the total weight of the polymer composition. By applying the polymer composition, the polymer masterbatch composition and the board comprising or made of the same according to the invention, an improved stability at high temperatures is achieved, as well as a balance of flame retardancy and mechanical properties.

Description

Polymer composition, polymer masterbatch composition and sheet comprising or made therefrom
Technical Field
The invention relates to the field of polymer processing, in particular to a polymer composition, a polymer master batch composition and a plate containing the polymer composition or prepared from the polymer composition.
Background
Polymers exhibit some unique properties that metals or ceramics typically do not possess, including low density, high toughness and impact resistance, and optical clarity. One of the drawbacks of polymers with excellent properties is their lack of flame retardancy. Flame retardancy is achieved in the prior art by adding flame retardants to the polymer.
In order to achieve a flame retardant effect in polymers, small molecule Hexabromocyclododecane (HBCD) is typically used as a flame retardant additive to the polymer. However, in a number of applications and experiments, HBCD was found to be somewhat biotoxic, capable of accumulating in vivo, and environmentally non-degradable. Therefore, in order to reduce environmental pollution and biological pollution, various novel macromolecular (polymeric) flame retardants have been developed in the polymer industry, such as Emerald Innovation (EI 3000) type flame retardants of lang Cheng Huaxue. The polymeric flame retardant has a higher molecular weight and increases migration, extraction and evaporation resistance, thereby reducing the risk of release of the flame retardant from the polymer into the environment. In addition, polymeric flame retardants have a higher molecular weight relative to small molecule flame retardants, and thus they are not easily decomposed and absorbed by the digestive tract, reducing the availability of organisms thereto, and adverse effects on the ecological environment.
However, in the case of using the polymeric flame retardant, it was found that it was degraded at a temperature of 190 ℃ to adversely affect its flame retardant properties. In addition, since acidic substances are generated during the degradation of the polymeric flame retardant, the mechanical properties of the polymer product will also be affected by it. Accordingly, there remains a need to develop polymer compositions that have stability at high temperatures and are capable of balancing the flame retardant properties and mechanical properties of polymer products.
Disclosure of Invention
The main object of the present invention is to provide a polymer composition, a polymer masterbatch composition and a board comprising or made from the same, which solves the problem of instability of the polymer composition at high temperatures in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a polymer composition comprising: 90 to 99 parts by weight of a polymer matrix; 1 to 10 parts by weight of a flame retardant; 0.1 to 0.5 parts by weight of an acid-binding agent; 0.1 to 0.5 parts by weight of an antioxidant; and 0.2 to 5 parts by weight of a synergist, the parts by weight being based on 100 parts by weight of the total weight of the polymer composition.
Further, in the above polymer composition, the acid-binding agent includes tetrabromobisphenol a diglycidyl ether, dipentaerythritol, brominated epoxy resin, or any combination of two or more thereof.
Further, in the above polymer composition, the antioxidant includes a primary antioxidant and a secondary antioxidant, and wherein the primary antioxidant includes a hindered phenol antioxidant, an amine antioxidant, a thioether antioxidant, a triazine antioxidant, or any combination of two or more thereof, and the secondary antioxidant includes a phosphite antioxidant, a triazine antioxidant, or a combination thereof.
Further, in the above polymer composition, the synergist comprises a zinc compound, expanded graphite, dicumyl (i.e., 2, 3-dimethyl-2, 3-diphenylbutane), or any combination of two or more thereof.
Further, in the above polymer composition, the flame retardant is a brominated butadiene-styrene block copolymer, and wherein the brominated butadiene-styrene block copolymer comprises brominated 1, 2-butadiene blocks, brominated 1, 4-butadiene blocks, or a combination thereof; the amount of the brominated 1, 2-butadiene block is in the range of 50 to 90 parts by weight and the amount of the brominated 1, 4-butadiene block is in the range of 10 to 50 parts by weight based on 100 parts by weight of the brominated butadiene block in the brominated butadiene-styrene block copolymer.
Further, in the above polymer composition, the weight ratio of the flame retardant to the synergist is in the range of 1:1 to 10:1.
Further, in the above polymer composition, the weight ratio of the acid-binding agent to the antioxidant is in the range of 0.5:1 to 5:1.
According to another aspect of the present invention, there is provided a polymer masterbatch composition characterized by comprising: a first masterbatch comprising 5 to 20 parts by weight of a synergist and 80 to 95 parts by weight of a polymer matrix based on 100 parts by weight of the total weight of the first masterbatch; the second masterbatch comprises 40 to 60 parts by weight of a flame retardant, 2 to 5 parts by weight of an acid-binding agent, 2 to 3.75 parts by weight of an antioxidant, and 30 to 60 parts by weight of a polymer matrix based on 100 parts by weight of the total weight of the second masterbatch, and the weight ratio of the first masterbatch to the second masterbatch is in the range of 1:2 to 1:4.
According to another aspect of the present invention there is provided a sheet comprising the polymer composition as hereinbefore described.
According to another aspect of the present invention, there is provided a sheet prepared from the polymer composition described hereinbefore or the polymer masterbatch composition described hereinbefore.
By applying the polymer composition, the polymer masterbatch composition and the board comprising or made of the same according to the invention, an improved stability at high temperatures is achieved, as well as a balance of flame retardancy and mechanical properties.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments in the present application may be combined with each other. The present invention will be described in detail with reference to examples. The following examples are illustrative only and are not intended to limit the scope of the invention.
As noted in the background, the polymer compositions of the prior art are unstable at high temperatures, are prone to decomposition and adversely affect the final polymer product. In view of the problems of the prior art, one exemplary embodiment of the present invention provides a polymer composition comprising: 90 to 99 parts by weight of a polymer matrix; 1 to 10 parts by weight of a flame retardant; 0.1 to 0.5 parts by weight of an acid-binding agent; 0.1 to 0.5 parts by weight of an antioxidant; and 0.2 to 5 parts by weight of a synergist, the parts by weight being based on 100 parts by weight of the total weight of the polymer composition.
After extensive experimentation by the inventors of the present invention, it has surprisingly been found that the oxygen index of a polymer system can be effectively increased when 1 to 10 parts by weight of a flame retardant is added simultaneously with 0.2 to 5 parts by weight of a synergist to the polymer composition. The inventors have found that when the flame retardant and the synergist are added to the polymer system in the above parts by weight, the synergist can effectively react with substances formed by decomposition of the flame retardant at high temperature, for example, when a halogen-containing compound is used as the flame retardant, the synergist will react with hydrogen halide or active halogen element generated at high temperature, thereby reducing the generation of volatile combustible gas and generating carbide which can isolate heat and play a role in shielding, and further thermal decomposition of the polymer system is protected. After limiting oxygen index (LOI index) testing by ASTM D2863-97, it was found that with the polymer compositions of the present application, the LOI index was increased by at least 5% as compared to polymer systems without any flame retardant and synergist.
In the prior art, some flame retardants, while effective in imparting the desired flame retardancy to the final polymer, polymer systems containing only flame retardants generally exhibit undesirable decreases in mechanical and thermal conductivity properties, such as thermal conductivity and compression properties. However, in the case of using the polymer composition of the present invention, the flame retardant property and mechanical property of the polymer product can be effectively balanced, and the product can still maintain good thermal conductivity and compression property while improving the flame retardancy of the product.
In some embodiments of the invention, the acid-binding agent comprises tetrabromobisphenol a diglycidyl ether, dipentaerythritol, a brominated epoxy resin, an epoxy resin, or any combination of two or more thereof. In an embodiment of the present invention, the acid-binding agent of the characteristics described above is selected to effectively achieve the effect of neutralizing the acidic species (hydrogen bromide) in the polymer system, thereby inhibiting the autocatalytic decomposition of the brominated butadiene-styrene block copolymer. Among the above acid-binding agents, the preferred acid-binding agent is an epoxy resin. The epoxy resin acid-binding agent comprises epichlorohydrin-cresol formaldehyde epoxy resin, epoxy phenol formaldehyde resin, bisphenol a type epoxy resin, bisphenol a-epichlorohydrin epoxy resin, a mixture of bisphenol F type epoxy resin and bisphenol a type epoxy resin, or any combination of two or more thereof. When the acid-binding agent is used, the acid-binding agent can play a synergistic effect with the flame retardant, effectively improve the thermal decomposition temperature of the flame retardant, further improve the high-temperature stability of the polymer composition and inhibit the generation of hydrogen bromide.
In some embodiments of the invention, the antioxidants comprise a primary antioxidant and a secondary antioxidant, and wherein the primary antioxidant comprises a hindered phenolic antioxidant, an amine antioxidant, a thioether antioxidant, a triazine antioxidant, or any combination of two or more thereof, and the secondary antioxidant comprises a phosphite antioxidant, a triazine antioxidant, or a combination thereof. In some embodiments, the flame retardant composition of the present invention may comprise only a single class of antioxidants, such as hindered phenolic antioxidants, aminic antioxidants, phosphite antioxidants, thioether antioxidants, or triazine antioxidants. In a preferred embodiment, the flame retardant composition of the present invention comprises only triazine-based antioxidants. In other embodiments, the flame retardant composition of the present invention comprises a combination of a primary antioxidant and a secondary antioxidant. In the case of using two or more antioxidants, it is preferable to use a hindered phenol antioxidant as the primary antioxidant and a phosphite antioxidant as the secondary antioxidant in combination.
In some particular embodiments of the present invention, the primary antioxidant comprises pentaerythritol tetrakis [ β - (3.5-di-tert-butyl, 4-hydroxyphenyl) propionate ], pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, pentaerythritol 2, 6-di-tert-butyl-p-cresol, 4-hydroxymethyl-2, 6-di-tert-butylphenol, 2, 6-di-tert-butyl- α -dimethylaminophenol, N-cyclohexyl-N ' -phenyl-p-phenylenediamine, N ' -diphenyl-p-phenylenediamine, dilaurate thiodipropionate, 2, 4-bis (dodecylthiomethyl) -6-methylphenol, 6- (4-hydroxy-3, 5-di-tert-butylphenylamino) -2, 4-bis (octylthio) -1,3, 5-triazine, 2-N-octylthio-4, 6-bis (4 ' -hydroxy-3, 5-di-tert-butylphenoxy) -1,3, 5-triazine, or any combination of two or more thereof.
In some particular embodiments of the present invention, the secondary antioxidant comprises tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-butylphenyl) pentaerythritol diphosphate, bisphenol A phosphite, tributyl phosphite, 6- (4-hydroxy-3, 5-di-tert-butylanilino) -2, 4-bis (octylthio) -1,3, 5-triazine, 2-n-octylthio-4, 6-bis (4' -hydroxy-3, 5-di-tert-butylphenoxy) -1,3, 5-triazine, or any combination of two or more thereof.
In some particular embodiments of the present invention, the synergist in the polymer compositions of the present application comprises a zinc compound, expanded graphite, co-dried (i.e., 2, 3-dimethyl-2, 3-diphenylbutane), or any combination of two or more thereof. In a further preferred embodiment, the synergist comprises expanded graphite, zinc stannate, zinc borate, zinc oxide, dicumyl (i.e., 2, 3-dimethyl-2, 3-diphenylbutane), or any combination of two or more thereof. In the case of using the above-mentioned synergist, a synergistic effect can be generated with the flame retardant, thereby effectively increasing the oxygen index of the polymer composition.
In some embodiments of the present invention, the brominated butadiene-styrene block copolymer comprises 10 to 40 parts by weight of a styrene block and 60 to 90 parts by weight of a brominated butadiene block based on 100 parts by weight of the brominated butadiene-styrene block copolymer. In a preferred embodiment, the brominated butadiene-styrene block copolymer comprises 15 to 35 parts by weight of a styrene block and 65 to 85 parts by weight of a brominated butadiene block based on 100 parts by weight of the brominated butadiene-styrene block copolymer. Specifically, in some embodiments of the present invention, the minimum value of the styrene block should be greater than 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, or 20 parts by weight, and the maximum value thereof should be less than 40 parts by weight, 39 parts by weight, 38 parts by weight, 37 parts by weight, 36 parts by weight, 35 parts by weight, 34 parts by weight, 33 parts by weight, 32 parts by weight, 31 parts by weight, or 30 parts by weight, based on 100 parts of the brominated butadiene-styrene block copolymer. And in some embodiments, the minimum value of the brominated butadiene block should be greater than 60 parts by weight, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight, or 75 parts by weight, and the maximum value thereof should be less than 90 parts by weight, 89 parts by weight, 88 parts by weight, 87 parts by weight, 86 parts by weight, 85 parts by weight, 84 parts by weight, 83 parts by weight, 82 parts by weight, 81 parts by weight, 80 parts by weight, 79 parts by weight, 78 parts by weight, 77 parts by weight, or 76 parts by weight, based on 100 parts of the brominated butadiene-styrene block copolymer.
Specifically, the amount of the styrene block may be in the following range, based on 100 parts by weight of the brominated butadiene-styrene block copolymer: 10 to 40 parts by weight, 11 to 39 parts by weight, 12 to 38 parts by weight, 13 to 37 parts by weight, 14 to 36 parts by weight, 15 to 35 parts by weight, 16 to 34 parts by weight, 17 to 33 parts by weight, 18 to 32 parts by weight, 19 to 31 parts by weight, 20 to 30 parts by weight, 10 to 20 parts by weight, 10 to 30 parts by weight, 20 to 40 parts by weight, or 30 to 40 parts by weight. And the amount of the brominated butadiene block may be in the following range based on 100 parts by weight of the brominated butadiene-styrene block copolymer: 60 to 90 parts by weight, 61 to 89 parts by weight, 62 to 88 parts by weight, 63 to 87 parts by weight, 64 to 86 parts by weight, 65 to 85 parts by weight, 66 to 84 parts by weight, 67 to 83 parts by weight, 68 to 82 parts by weight, 69 to 81 parts by weight, 70 to 80 parts by weight, 70 to 90 parts by weight, 80 to 90 parts by weight, 60 to 80 parts by weight, or 60 to 70 parts by weight.
In some embodiments of the present invention, the amount of brominated 1, 2-butadiene blocks is in the range of 50 to 90 parts by weight and the amount of brominated 1, 4-butadiene blocks is in the range of 10 to 50 parts by weight, based on 100 parts by weight of brominated butadiene blocks in the brominated butadiene-styrene block copolymer.
In some embodiments of the present invention, the amount of brominated 1, 2-butadiene blocks is in the range of 60 to 85 parts by weight and the amount of brominated 1, 4-butadiene blocks is in the range of 15 to 40 parts by weight, based on 100 parts by weight of brominated butadiene blocks in the brominated butadiene-styrene block copolymer. In some embodiments of the present invention, the brominated butadiene-styrene block copolymer may comprise both brominated 1, 2-butadiene blocks and brominated 1, 4-butadiene blocks, such as styrene-brominated 1, 2-butadiene-brominated 1, 4-butadiene triblock copolymers, styrene-brominated 1, 2-butadiene-brominated 1, 4-butadiene-styrene tetrablock copolymers, as described previously. In some embodiments, where both brominated 1, 2-butadiene blocks and brominated 1, 4-butadiene blocks are included, the minimum value of the brominated 1, 2-butadiene block should be greater than 60 parts by weight, greater than 61 parts by weight, greater than 62 parts by weight, greater than 63 parts by weight, greater than 64 parts by weight, greater than 65 parts by weight, greater than 66 parts by weight, greater than 67 parts by weight, greater than 68 parts by weight, greater than 69 parts by weight, or greater than 70 parts by weight, and the maximum value thereof should be less than 85 parts by weight, less than 84 parts by weight, less than 83 parts by weight, less than 82 parts by weight, less than 81 parts by weight, less than 80 parts by weight, less than 79 parts by weight, less than 78 parts by weight, less than 77 parts by weight, less than 76 parts by weight, or less than 75 parts by weight, based on 100 parts by weight of the brominated butadiene blocks in the brominated butadiene-styrene block copolymer. And in some embodiments, the minimum value of the brominated 1, 4-butadiene block should be greater than 15 parts by weight, greater than 16 parts by weight, greater than 17 parts by weight, greater than 18 parts by weight, greater than 19 parts by weight, greater than 20 parts by weight, greater than 21 parts by weight, greater than 22 parts by weight, greater than 23 parts by weight, greater than 24 parts by weight, or greater than 25 parts by weight, and the maximum value thereof should be less than 40 parts by weight, less than 39 parts by weight, less than 38 parts by weight, less than 37 parts by weight, less than 36 parts by weight, less than 35 parts by weight, less than 34 parts by weight, less than 33 parts by weight, less than 32 parts by weight, less than 31 parts by weight, or less than 30 parts by weight, based on 100 parts of the brominated butadiene block in the brominated butadiene-styrene block copolymer.
Specifically, the amount of brominated 1, 2-butadiene blocks is within the following range, based on 100 parts by weight of the brominated butadiene block in the brominated butadiene-styrene block copolymer: 60 to 85 parts by weight, 61 to 84 parts by weight, 62 to 83 parts by weight, 63 to 82 parts by weight, 64 to 81 parts by weight, 65 to 80 parts by weight, 66 to 79 parts by weight, 67 to 78 parts by weight, 68 to 77 parts by weight, 69 to 76 parts by weight, 70 to 75 parts by weight, 60 to 80 parts by weight, 60 to 75 parts by weight, 60 to 70 parts by weight, 60 to 65 parts by weight, 65 to 85 parts by weight, 70 to 85 parts by weight, 75 to 85 parts by weight, or 80 to 85 parts by weight. And the amount of brominated 1, 4-butadiene blocks is within the following range, based on 100 parts by weight of the brominated butadiene block in the brominated butadiene-styrene block copolymer: 15 to 40 parts by weight, 16 to 39 parts by weight, 17 to 38 parts by weight, 18 to 37 parts by weight, 19 to 36 parts by weight, 20 to 35 parts by weight, 21 to 34 parts by weight, 22 to 33 parts by weight, 23 to 32 parts by weight, 24 to 31 parts by weight, 25 to 30 parts by weight, 20 to 40 parts by weight, 25 to 40 parts by weight, 30 to 40 parts by weight, 35 to 40 parts by weight, 15 to 35 parts by weight, 15 to 30 parts by weight, 15 to 25 parts by weight or 15 to 20 parts by weight.
In some embodiments of the invention, the brominated butadiene-styrene block copolymer has a weight average molecular weight of 100,000 to 160,000 g/mole as measured by Gel Permeation Chromatography (GPC) using bisphenol a homopolycarbonate standards. Preferably, the brominated butadiene-styrene block copolymer has a weight average molecular weight of 120,000 to 150,000 g/mole. In some embodiments of the invention, regardless of the particular structure, the weight average molecular weight of the brominated butadiene-styrene block copolymer may be greater than or equal to 100,000 g/mole greater than or equal to 110,000 g/mole, greater than or equal to 120,000 g/mole, greater than or equal to 130,000 g/mole, greater than or equal to 140,000 g/mole, or greater than or equal to 150,000 g/mole and less than or equal to 160,000 g/mole, less than or equal to 150,000 g/mole, less than or equal to 140,000 g/mole, less than or equal to 130,000 g/mole, or less than or equal to 120,000 g/mole. In some embodiments of the invention, the molecular weight may also be determined by Gel Permeation Chromatography (GPC) using polystyrene standards according to ASTM D5296-11. In some embodiments, 1-chloronaphthalene may be used as a solvent at 220℃using a high temperature GPC method, e.g., as determined according to ASTM D6474-11.
In some embodiments of the present invention, the weight ratio of flame retardant to synergist in the polymer composition of the present invention is in the range of 1:1 to 10:1. In a preferred embodiment, the weight ratio of flame retardant to synergist is in the range of 3:1 to 7:1. When the weight ratio of the flame retardant to the synergist is less than 1:1, the flame retardant effect cannot be effectively achieved due to the too small content of the flame retardant. When the weight ratio of the flame retardant to the synergist is more than 10:1, the content of the flame retardant is excessive, so that the synergist is insufficient to perform synergistic effect with the flame retardant, and the effect of increasing the oxygen index is difficult to realize.
Specifically, in some embodiments of the present invention, the weight ratio of flame retardant to synergist is within the following range: 1:1 to 10:1, 2:1 to 10:1, 3:1 to 10:1, 1:1 to 9:1, 1:1 to 8:1, 1:1 to 7:1, 2:1 to 9:1, 2:1 to 8:1, 2:1 to 7:1, 3:1 to 9:1, 3:1 to 8:1, or 3:1 to 7:1).
In some embodiments of the invention, the weight ratio of acid-binding agent to antioxidant is in the range of 0.5:1 to 5:1, preferably the weight ratio of acid-binding agent to antioxidant is in the range of 1:1 to 2:1. In the invention, the acid-binding agent and the antioxidant have synergistic effect and can simultaneously thermally stabilize the flame retardant, so that the weight ratio of the acid-binding agent to the antioxidant is required to be in the range of 0.5:1 to 5:1 so as to realize the effect of jointly promoting the thermal stability of the flame retardant in high-temperature (above 300 ℃). In a specific embodiment, the weight ratio of the acid binding agent to the antioxidant may be in the following range: 1:1.5 to 4.5:1, 1:1.4 to 4:1, 1:1.3 to 3.5:1, 1:1.2 to 3:1, 1:1.1 to 2.5:1, or 1:1 to 2:1.
In some embodiments of the invention, the weight ratio of the total amount of acid-binding agent and antioxidant to the amount of brominated butadiene-styrene block copolymer in the flame retardant composition is in the range of 1:20 to 1:3. Preferably, the weight ratio of the total amount of acid-binding agent and antioxidant to the amount of brominated butadiene-styrene block copolymer is in the range of 1:12 to 1:5. More preferably, the weight ratio of the total amount of acid-binding agent and antioxidant to the amount of brominated butadiene-styrene block copolymer is in the range of 1:8 to 1:10.
In the invention, the acid-binding agent and the antioxidant are used as additives for stabilizing the flame retardant, when the weight ratio of the total amount of the acid-binding agent and the antioxidant to the amount of the brominated butadiene-styrene block copolymer is less than 1:20, the effect of stabilizing the flame retardant cannot be effectively achieved due to the excessively small addition amount, so that the flame retardant cannot effectively maintain the flame retardant property in the high-temperature processing process.
When the weight ratio of the total amount of the acid-binding agent and the antioxidant to the amount of the brominated butadiene-styrene block copolymer is greater than 1:3, the total amount of the acid-binding agent and the antioxidant is excessive, which will adversely affect the mechanical properties of the polymer system.
Specifically, in some embodiments of the present invention, the weight ratio of the total amount of acid binding agent and antioxidant to the amount of brominated butadiene-styrene block copolymer in the flame retardant composition is within the following range: 1:20 to 1:3, 1:18 to 1:3.5, 1:16 to 1:4, 1:14 to 1:4.5, 1:12 to 1:5, 1:10 to 1:5.5, 1:8 to 1:6, 1:8 to 1:10, 1:6 to 1:6.5, 1:4 to 1:7, 1:2 to 1:7.5, or 1:1 to 1:8.
In some embodiments of the invention, the weight ratio of primary antioxidant to secondary antioxidant is in the range of 1:0.5 to 1:5; preferably, the weight ratio of primary antioxidant to secondary antioxidant is in the range of 1:1 to 1:2. Specifically, in some embodiments of the present invention, the weight ratio of primary antioxidant to secondary antioxidant is within the following range: 1:0.75 to 1:4.5, 1:1 to 1:4, 1:1.25 to 1:3.5, 1:1.5 to 1:3, 1:1.75 to 1:2.5, 1:1 to 1:2, 1:1 to 1:3, or 1:1 to 1:5.
In some embodiments of the present invention, the polymer matrix in the polymer composition of the present invention is not particularly limited, and any known thermoplastic material may be used. In a preferred embodiment, the polymer matrix comprises polystyrene, polyetherimide, acrylic, fluorocarbon, polyamide, polyethylene, polyester, polypropylene, polycarbonate, polyurethane, polyetheretherketone, polyphenylene sulfide, and polyetherketoneketone, or a mixture or copolymer of two or more thereof.
In a specific embodiment of the present invention, the amount of the polymer matrix ranges from 90 to 99 parts by weight based on 100 parts by weight of the total weight of the polymer composition. In a preferred embodiment, the amount of the polymer matrix may be in the following range, based on 100 parts by weight of the total weight of the polymer composition: 90.5 to 98.5 parts by weight, 91 to 98 parts by weight, 91.5 to 97.5 parts by weight, 92 to 97 parts by weight, 92.5 to 96.5 parts by weight, 93 to 96 parts by weight, 93.5 to 95.5 parts by weight, 94 to 95 parts by weight, 97 to 98 parts by weight, 95 to 96 parts by weight, or 91 to 92 parts by weight.
The amount of the flame retardant ranges from 1 to 10 parts by weight based on 100 parts by weight of the total weight of the polymer composition. In a preferred embodiment, the amount of flame retardant may be in the following range, based on 100 parts by weight of the total weight of the polymer composition: 1 to 10 parts by weight, 2 to 9 parts by weight, 3 to 8 parts by weight, 4 to 6 parts by weight, 1 to 9 parts by weight, 1 to 8 parts by weight, 1 to 7 parts by weight, 1 to 6 parts by weight, 1 to 5 parts by weight, 2 to 10 parts by weight, 3 to 10 parts by weight, 4 to 10 parts by weight, 5 to 10 parts by weight, 2 to 6 parts by weight, 2 to 4 parts by weight, 3 to 5 parts by weight, 4 to 6 parts by weight, or 5 to 7 parts by weight.
The amount of the acid-binding agent ranges from 0.1 to 0.5 parts by weight based on 100 parts by weight of the total weight of the polymer composition. In a preferred embodiment, the amount of the acid-binding agent may be in the following range, based on 100 parts by weight of the total weight of the polymer composition: 0.1 to 0.5 part by weight, 0.15 to 0.45 part by weight, 0.2 to 0.4 part by weight, 0.25 to 0.35 part by weight, 0.1 to 0.2 part by weight, 0.1 to 0.15 part by weight, 0.15 to 0.2 part by weight, 0.2 to 0.28 part by weight, 0.3 to 0.35 part by weight, or 0.35 to 0.4 part by weight.
The amount of the antioxidant ranges from 0.1 to 0.5 parts by weight based on 100 parts by weight of the total weight of the polymer composition. In a preferred embodiment, the amount of antioxidant may be in the following range, based on 100 parts by weight of the total weight of the polymer composition: 0.1 to 0.5 part by weight, 0.15 to 0.45 part by weight, 0.2 to 0.4 part by weight, 0.25 to 0.35 part by weight, 0.1 to 0.2 part by weight, 0.1 to 0.15 part by weight, 0.15 to 0.2 part by weight, 0.2 to 0.28 part by weight, 0.3 to 0.35 part by weight, or 0.35 to 0.4 part by weight.
In embodiments where the antioxidant comprises a primary antioxidant and a secondary antioxidant, the amounts of primary and secondary antioxidants may range from 0.05 to 0.20 parts by weight, respectively, based on 100 parts by weight of the total weight of the polymer composition. In a preferred embodiment, the amounts of the primary and secondary antioxidants may be within the following ranges, respectively, based on 100 parts by weight of the total weight of the polymer composition: 0.05 to 0.20 parts by weight, 0.06 to 0.19 parts by weight, 0.07 to 0.18 parts by weight, 0.08 to 0.17 parts by weight, 0.09 to 0.16 parts by weight, 0.1 to 0.15 parts by weight, 0.11 to 0.14 parts by weight, 0.12 to 0.13 parts by weight, 0.05 to 0.07 parts by weight, 0.08 to 0.1 parts by weight, 0.1 to 0.13 parts by weight, 0.15 to 0.17 parts by weight, or 0.18 to 0.20 parts by weight.
The amount of the synergist ranges from 0.2 to 5 parts by weight based on 100 parts by weight of the total weight of the polymer composition. In a preferred embodiment, the amount of the synergist may be in the following range, based on 100 parts by weight of the total weight of the polymer composition: 0.2 to 5 parts by weight, 0.25 to 4.5 parts by weight, 0.3 to 4 parts by weight, 0.35 to 3.5 parts by weight, 0.4 to 3 parts by weight, 0.45 to 2.5 parts by weight, 0.5 to 2 parts by weight, 0.5 to 1.5 parts by weight, 0.75 to 1.25 parts by weight, 0.4 to 0.7 parts by weight, 0.8 to 1 part by weight, 1 to 1.2 parts by weight, 1.2 to 1.4 parts by weight, or 1.3 to 1.6 parts by weight.
In a preferred embodiment of the present invention, the polymer composition of the present invention comprises or consists of the following substances based on 100 parts by weight of the total weight of the polymer composition of the present invention: 91.5 to 97.5 parts by weight of a polymer matrix, 2 to 6 parts by weight of a flame retardant, 0.2 to 0.3 parts by weight of an acid-binding agent, 0.2 to 0.3 parts by weight of an antioxidant, and 0.5 to 1.5 parts by weight of a synergist.
In embodiments where the antioxidant comprises a primary antioxidant and a secondary antioxidant, the polymer composition of the present invention comprises or consists of, based on 100 parts by weight of the total weight of the polymer composition of the present invention: 90 to 99 parts by weight of a polymer matrix, 1 to 10 parts by weight of a flame retardant, 0.1 to 0.5 part by weight of an acid-binding agent, 0.05 to 0.20 part by weight of a primary antioxidant, 0.05 to 0.20 part by weight of a secondary antioxidant, and 0.2 to 5 parts by weight of a synergist.
In a preferred embodiment, the polymer composition of the present invention comprises or consists of the following substances based on 100 parts by weight of the total weight of the polymer composition of the present invention: 91.5 to 97.5 parts by weight of a polymer matrix, 2 to 6 parts by weight of a flame retardant, 0.2 to 0.3 parts by weight of an acid-binding agent, 0.1 to 0.15 parts by weight of a primary antioxidant, 0.1 to 0.15 parts by weight of a secondary antioxidant, and 0.5 to 1.5 parts by weight of a synergist.
In other embodiments of the present application, the polymer composition of the present invention further comprises 0.02 parts by weight to 0.1 parts by weight of a blowing agent. In particular embodiments of the present invention, the amount of blowing agent may be within the following range, based on 100 parts by weight of the total weight of the polymer composition: 0.02 to 0.1, 0.03 to 0.09, 0.04 to 0.08, or 0.05 to 0.07 parts by weight.
In other embodiments of the present application, the polymer composition of the present invention further comprises 0.001 parts by weight to 0.03 parts by weight of a nucleating agent. In particular embodiments of the present invention, the amount of nucleating agent may be in the following range, based on 100 parts by weight of the total weight of the polymer composition: 0.001 to 0.03, 0.003 to 0.025, 0.005 to 0.02, 0.008 to 0.015, or 0.01 to 0.02 parts by weight.
In another exemplary embodiment of the present invention, a polymeric masterbatch composition is provided that includes a first masterbatch and a second masterbatch. In the first masterbatch, 5 to 20 parts by weight of a synergist and 80 to 95 parts by weight of a polymer matrix based on 100 parts by weight of the total weight of the first masterbatch; and in the second masterbatch, 40 to 60 parts by weight of a flame retardant, 2 to 5 parts by weight of an acid-binding agent, 2 to 3.75 parts by weight of an antioxidant, and 30 to 60 parts by weight of a polymer matrix are included based on 100 parts by weight of the total weight of the second masterbatch, and the weight ratio of the first masterbatch to the second masterbatch is in the range of 1:2 to 1:4. In the case of using the above polymer masterbatch composition, it is possible to effectively increase the limiting oxygen index of the polymer and to effectively balance the flame retardant properties and mechanical properties of the polymer finished product. The synergists, polymer matrices, flame retardants, acid scavengers, and antioxidants used in this embodiment may be selected from those previously described and will not be repeated here. In one embodiment, the first masterbatch and the second masterbatch are a blend. In another embodiment, the first masterbatch and the second masterbatch are independent of each other and are not blended together.
In some embodiments of the present invention, the weight ratio of flame retardant to synergist in the polymer composition of the present invention is in the range of 1:1 to 10:1. In a preferred embodiment, the weight ratio of flame retardant to synergist is in the range of 3:1 to 7:1. When the weight ratio of the flame retardant to the synergist is less than 1:1, the flame retardant effect cannot be effectively achieved due to the too small content of the flame retardant. When the weight ratio of the flame retardant to the synergist is more than 10:1, the content of the flame retardant is excessive, so that the synergist is insufficient to perform synergistic effect with the flame retardant, and the effect of increasing the oxygen index is difficult to realize.
Specifically, in some embodiments of the present invention, the weight ratio of flame retardant to synergist is within the following range: 1:1 to 10:1, 2:1 to 10:1, 3:1 to 10:1, 1:1 to 9:1, 1:1 to 8:1, 1:1 to 7:1, 2:1 to 9:1, 2:1 to 8:1, 2:1 to 7:1, 3:1 to 9:1, 3:1 to 8:1, or 3:1 to 7:1).
In some embodiments of the invention, the weight ratio of acid-binding agent to antioxidant is in the range of 0.5:1 to 5:1, preferably the weight ratio of acid-binding agent to antioxidant is in the range of 1:1 to 2:1. In the invention, the acid-binding agent and the antioxidant have synergistic effect and can simultaneously thermally stabilize the flame retardant, so that the weight ratio of the acid-binding agent to the antioxidant is required to be in the range of 0.5:1 to 5:1, thereby realizing the effect of jointly promoting the thermal stability of the flame retardant in high-temperature (above 300 ℃). In a specific embodiment, the weight ratio of the acid binding agent to the antioxidant may be in the following range: 1:1.5 to 4.5:1, 1:1.4 to 4:1, 1:1.3 to 3.5:1, 1:1.2 to 3:1, 1:1.1 to 2.5:1, or 1:1 to 2:1.
In some embodiments of the invention, the antioxidants include a primary antioxidant and a secondary antioxidant. The weight ratio of the primary antioxidant to the secondary antioxidant is in the range of 1:0.5 to 1:5; preferably, the weight ratio of primary antioxidant to secondary antioxidant is in the range of 1:1 to 1:2. Specifically, in some embodiments of the present invention, the weight ratio of primary antioxidant to secondary antioxidant is within the following range: 1:0.75 to 1:4.5, 1:1 to 1:4, 1:1.25 to 1:3.5, 1:1.5 to 1:3, 1:1.75 to 1:2.5, 1:1 to 1:2, 1:1 to 1:3, or 1:1 to 1:5.
In some embodiments of the present invention, the polymer matrix in the polymer composition of the present invention is not particularly limited, and any known thermoplastic material may be used. In a preferred embodiment, the polymer matrix comprises polystyrene, polyetherimide, acrylic, fluorocarbon, polyamide, polyethylene, polyester, polypropylene, polycarbonate, polyurethane, polyetheretherketone, polyphenylene sulfide, and polyetherketoneketone, or a mixture or copolymer of two or more thereof.
In another exemplary embodiment of the present invention, a sheet comprising the polymer composition of the present invention is provided. Because of the inclusion of the polymer composition of the invention as described hereinbefore, the sheet comprising it will have the desired balance of flame retardancy, high limiting oxygen index, and excellent flame retardancy and mechanical properties.
In another exemplary embodiment of the present invention, a sheet prepared from the polymer composition of the present invention or the polymer masterbatch composition of the present invention is provided. By using the polymer composition of the present invention or the polymer masterbatch composition of the present invention, the produced sheet comprises an effective amount of flame retardant, acid binding agent, antioxidant and synergist. Accordingly, the sheet material prepared by using the polymer composition of the present invention or the polymer masterbatch composition of the present invention has excellent flame retardancy and mechanical properties.
Examples
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
The components used in the examples below are listed in table 1 below, along with a brief description and source of these components.
Table 1 brief description and sources of the components used in the examples
Figure BDA0003432480270000101
Figure BDA0003432480270000111
Preparation of polymer foam
Using a two-stage extrusion process, a 85200 type extruder combination from Han Plastic, which includes a twin-screw extruder and a single-screw extruder, was used, and the individual components were fed into the twin-screw extruder via different feeders in the amounts shown in Table 2 below. In the first stage of the extruder combination (twin-screw extruder), the screw diameter of the twin-screw extruder was 85mm and the heating stage temperature thereof was 190℃to 220 ℃. After passing through the twin-screw extruder, the obtained mixture was introduced into the second stage of the extruder combination (single-screw extruder) in which the screw diameter of the single-screw extruder was 200mm, 13.5kg of a foaming agent (carbon dioxide and alcohol) (commercially available from Shanghai Biyang) was introduced together into the single-screw extruder, and passed through the single-port dry extruder at a temperature of 70℃to 120℃to obtain a foamed sheet through a die and a molding apparatus.
The data units in examples 1 to 14 and comparative example 1 below are kg/h, and the total throughput of the extruder combination is 300kg/h.
TABLE 2 compositions and contents of the polymer foam materials of examples 1 to 14 and comparative example 1
Figure BDA0003432480270000112
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Figure BDA0003432480270000121
Note that: compound 1: is a styrene-brominated butadiene diblock copolymer having 10 to 30 parts by weight of a styrene block, a weight average molecular weight of 10,000 to 13,000 g/mole, 50 to 60 parts by weight of a 1, 2-butadiene block, and 40 to 50 parts by weight of a 1, 4-butadiene block;
compound 2: is a styrene-brominated butadiene-styrene triblock copolymer having 25 to 40 parts by weight of a styrene block, a weight average molecular weight of 14,000 to 16,000 g/mol, 50 to 90 parts by weight of a 1, 2-butadiene block, and 10 to 50 parts by weight of a 1, 4-butadiene block.
Both compound 1 and compound 2 described above are commercially available from the langerhans group of germany.
Performance test of foaming Material
The foamed materials prepared by examples 1 to 14 and comparative example 1 were tested by the following test conditions of table 3, respectively:
table 3 test items and test criteria for each example
Figure BDA0003432480270000122
Figure BDA0003432480270000131
The test results are shown in table 4 below.
Table 4 test results of the tests performed on the various embodiments
Figure BDA0003432480270000132
From the above experimental results, it can be seen that the polymer of the present invention can achieve an effective increase in LOI of 19.7% for pure PS (comparative example 1) and an effective increase in LOI for all of examples 1-14 of the present invention. From the results of the horizontal burn test, it can be seen that the polymer compositions of the present invention are capable of achieving a horizontal burn rating of HF 1.
In addition, the test experiment results of the material density, the heat conductivity and the compression strength show that the flame retardant property and the mechanical property of the polymer foam material can be effectively balanced under the condition of preparing the foam board by using the polymer composition, and the finished product can still keep good heat conductivity and compression property under the condition of improving the flame retardant property of the finished product. The material density results by densitometer showed that the density, thermal conductivity and compressive strength of the foams of examples 1-14 were all close to those of comparative example 1 (pure PS foam). The foaming material prepared from the polymer composition is similar to a pure PS foaming material in mechanical property, so that the polymer composition can effectively improve the flame retardant effect and realize balance with mechanical property.
Other embodiments
Specific example 1. A polymer composition comprising:
90 to 99 parts by weight of a polymer matrix;
1 to 10 parts by weight of a flame retardant;
0.1 to 0.5 parts by weight of an acid-binding agent;
0.1 to 0.5 parts by weight of an antioxidant; and
0.2 to 5 parts by weight of a synergist,
the parts by weight are based on 100 parts by weight of the total weight of the polymer composition.
Specific example 2. The polymer composition according to specific example 1, the acid-binding agent comprises tetrabromobisphenol a diglycidyl ether, dipentaerythritol, brominated epoxy resin, or any combination of two or more thereof.
Specific example 3. The polymer composition according to specific example 1, the acid-binding agent comprises epichlorohydrin-cresol novolac epoxy resin, epoxy phenol novolac resin, bisphenol a type epoxy resin, bisphenol a-epichlorohydrin epoxy resin, a mixture of bisphenol F type epoxy resin and bisphenol a type epoxy resin, and any combination thereof.
Specific example 4. The polymer composition according to specific example 1 or 2, the antioxidant comprises a primary antioxidant and a secondary antioxidant, and wherein the primary antioxidant comprises a hindered phenolic antioxidant, an amine antioxidant, a thioether antioxidant, a triazine antioxidant, or a combination thereof, and the secondary antioxidant comprises a phosphite antioxidant, a triazine antioxidant, or a combination thereof.
Specific example 5. Flame retardant composition according to specific example 4, the primary antioxidant comprises tetrakis [ beta- (3.5-di-tert-butyl, 4-hydroxyphenyl) propionate ] pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, pentaerythritol tetrakis (3, 5-di-tert-butyl-p-methylphenol, 4-hydroxymethyl-2, 6-di-tert-butylphenol, 2, 6-di-tert-butyl-alpha-dimethylaminophenol, N-cyclohexyl-N ' -phenyl-p-phenylenediamine, N ' -diphenyl-p-phenylenediamine, thiodipropionate dilaurate, 2, 4-di (dodecylthio) -6-methylphenol, 6- (4-hydroxy-3, 5-di-tert-butylphenylamino) -2, 4-bis (octylthio) -1,3, 5-triazine, 2-N-octylthio-4, 6-bis (4 ' -hydroxy-3, 5-di-tert-butylphenoxy) -1,3, 5-triazine, or any combination thereof.
Specific example 6. Flame retardant composition according to specific example 4, the secondary antioxidant comprises tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-butylphenyl) pentaerythritol diphosphate, bisphenol A phosphite, tributyl phosphite, 6- (4-hydroxy-3, 5-di-tert-butylphenyl) -2, 4-bis (octylthio) -1,3, 5-triazine, 2-n-octylthio-4, 6-bis (4' -hydroxy-3, 5-di-tert-butylphenoxy) -1,3, 5-triazine, or any combination thereof.
Example 7. The polymer composition according to example 1 or 2, the synergist comprises a zinc compound, expanded graphite, co-dried or any combination thereof.
Example 8. The polymer composition of example 7, the synergist comprises expanded graphite, zinc stannate, zinc borate, zinc oxide, or any combination thereof.
Specific example 9. The polymer composition of specific example 1 or 2, the flame retardant is a brominated butadiene-styrene block copolymer, and wherein the brominated butadiene-styrene block copolymer comprises brominated 1, 2-butadiene blocks, brominated 1, 4-butadiene blocks, or a combination thereof; the amount of the brominated 1, 2-butadiene block is in the range of 50 to 90 parts by weight and the amount of the brominated 1, 4-butadiene block is in the range of 10 to 50 parts by weight based on 100 parts by weight of the brominated butadiene block in the brominated butadiene-styrene block copolymer.
Specific example 10. The polymer composition according to specific example 9, the brominated butadiene-styrene block copolymer comprises 10 to 40 parts by weight of a styrene block and 60 to 90 parts by weight of a brominated butadiene block based on 100 parts by weight of the brominated butadiene-styrene block copolymer; and the brominated butadiene-styrene block copolymer has a weight average molecular weight of 100,000 to 160,000 g/mole as measured by gel permeation chromatography using bisphenol a homopolycarbonate standard.
Specific example 11. The polymer composition according to specific example 1 or 2, the ratio of flame retardant to synergist is in the range of 1:1 to 10:1.
Example 12. The polymer composition according to example 11, the ratio of flame retardant to synergist is in the range of 3:1 to 7:1.
Specific example 13. The polymer composition according to specific example 1 or 2, the mass ratio of acid binding agent to antioxidant is in the range of 0.5:1 to 5:1.
Specific example 14. The polymer composition according to specific example 4, the weight ratio of primary antioxidant to secondary antioxidant is in the range of 1:0.5 to 1:5.
Embodiment 15. The polymer composition of embodiment 1 or 2, the polymer matrix comprises polystyrene, polyetherimide, acrylic, fluorocarbon, polyamide, polyethylene, polyester, polypropylene, polycarbonate, polyurethane, polyetheretherketone, polyphenylene sulfide, polyetherketoneketone, or any combination thereof.
Example 16. The polymer composition according to example 1 or 2, comprises:
91.5 to 97.5 parts by weight of a polymer matrix;
2 to 6 parts by weight of a flame retardant;
0.2 to 0.3 parts by weight of an acid-binding agent;
0.2 to 0.3 parts by weight of an antioxidant; and
0.5 to 1.5 parts by weight of a synergist,
the parts by weight are based on 100 parts by weight of the total weight of the polymer composition.
Example 17 the polymer composition according to example 4, comprising:
90 to 99 parts by weight of a polymer matrix;
1 to 10 parts by weight of a flame retardant;
0.1 to 0.5 parts by weight of an acid-binding agent;
0.05 to 0.20 parts by weight of a primary antioxidant;
0.05 to 0.20 parts by weight of an auxiliary antioxidant; and
0.2 to 5 parts by weight of a synergist,
the parts by weight are based on 100 parts by weight of the total weight of the polymer composition.
Example 18. The polymer composition according to example 16, comprises:
91.5 to 97.5 parts by weight of a polymer matrix;
2 to 6 parts by weight of a flame retardant;
0.2 to 0.3 parts by weight of an acid-binding agent;
0.1 to 0.15 parts by weight of a primary antioxidant;
0.1 to 0.15 parts by weight of an auxiliary antioxidant; and
0.5 to 1.5 parts by weight of a synergist,
the parts by weight are based on 100 parts by weight of the total weight of the polymer composition.
Example 19. The polymer composition according to example 1 or 2, the polymer composition further comprises:
0.02 to 0.1 parts by weight of a foaming agent.
Example 20. The polymer composition according to example 1 or 2, the polymer composition further comprises:
and (3) from 0.001 to 0.03 parts by weight of a nucleating agent.
Example 21A polymeric masterbatch composition comprising
A first masterbatch comprising 5 to 20 parts by weight of a synergist and 80 to 95 parts by weight of a polymer matrix based on 100 parts by weight of the total weight of the first masterbatch;
the second masterbatch comprises 40 to 60 parts by weight of a flame retardant, 2 to 5 parts by weight of an acid-binding agent, 2 to 3.75 parts by weight of an antioxidant, and 30 to 60 parts by weight of a polymer matrix based on 100 parts by weight of the total weight of the second masterbatch,
the weight ratio of the first masterbatch to the second masterbatch is in the range of 1:2 to 1:4.
Specific example 22. The polymer masterbatch composition of specific example 21, the acid-binding agent comprises tetrabromobisphenol a diglycidyl ether, dipentaerythritol, brominated epoxy resin, an epoxy resin, or any combination of two or more thereof.
Example 23. The polymer masterbatch composition of example 21, the antioxidant includes a primary antioxidant and a secondary antioxidant, and wherein the primary antioxidant comprises a hindered phenolic antioxidant, an amine antioxidant, a thioether antioxidant, a triazine antioxidant, or a combination thereof, and the secondary antioxidant comprises a phosphite antioxidant, a triazine antioxidant, or a combination thereof.
Example 24. The polymer masterbatch composition of example 21, the synergist comprises a zinc compound, expanded graphite, co-dried, or any combination thereof.
Embodiment 25. The polymer masterbatch composition of embodiment 21, the flame retardant is a brominated butadiene-styrene block copolymer, and wherein the brominated butadiene-styrene block copolymer comprises brominated 1, 2-butadiene blocks, brominated 1, 4-butadiene blocks, or a combination thereof; the amount of the brominated 1, 2-butadiene block is in the range of 50 to 90 parts by weight and the amount of the brominated 1, 4-butadiene block is in the range of 10 to 50 parts by weight based on 100 parts by weight of the brominated butadiene block in the brominated butadiene-styrene block copolymer.
Example 26. The polymer masterbatch composition of example 21, the ratio of flame retardant to synergist is in the range of 1:1 to 10:1.
Example 27. The polymer masterbatch composition of example 21 has a ratio of flame retardant to synergist in the range of 3:1 to 7:1.
Example 28. The polymer masterbatch composition of example 21, the mass ratio of acid-binding agent to antioxidant is in the range of 0.5:1 to 5:1.
Example 29. The polymer masterbatch composition of example 23, the weight ratio of primary to secondary antioxidants being in the range of 1:0.5 to 1:5.
Example 30. The polymer masterbatch composition of example 21, the polymer matrix comprises polystyrene, polyetherimide, acrylic, fluorocarbon, polyamide, polyethylene, polyester, polypropylene, polycarbonate, polyurethane, polyetheretherketone, polyphenylene sulfide, polyetherketoneketone, or any combination thereof.
Embodiment 31 a sheet comprising the polymer composition of any one of embodiments 1 to 20.
Embodiment 32 a sheet made from the polymer composition of any one of embodiments 1 to 20 or the polymer masterbatch composition of any one of embodiments 21 to 30.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A polymer composition comprising:
90 to 99 parts by weight of a polymer matrix;
1 to 10 parts by weight of a flame retardant;
0.1 to 0.5 parts by weight of an acid-binding agent;
0.1 to 0.5 parts by weight of an antioxidant; and
0.2 to 5 parts by weight of a synergist,
the parts by weight are based on 100 parts by weight of the total weight of the polymer composition.
2. The polymer composition of claim 1, wherein the acid-binding agent comprises tetrabromobisphenol a diglycidyl ether, dipentaerythritol, brominated epoxy resin, or any combination of two or more thereof.
3. The polymer composition of claim 1 or 2, wherein the antioxidant comprises a primary antioxidant and a secondary antioxidant, and wherein the primary antioxidant comprises a hindered phenolic antioxidant, an amine antioxidant, a thioether antioxidant, a triazine antioxidant, or any combination of two or more thereof, and the secondary antioxidant comprises a phosphite antioxidant, a triazine antioxidant, or a combination thereof.
4. The polymer composition of claim 1 or 2, wherein the synergist comprises a zinc compound, expanded graphite, co-dried, or any combination of two or more thereof.
5. The polymer composition of claim 1 or 2, wherein the flame retardant is a brominated butadiene-styrene block copolymer, and wherein the brominated butadiene-styrene block copolymer comprises brominated 1, 2-butadiene blocks, brominated 1, 4-butadiene blocks, or a combination thereof; the amount of the brominated 1, 2-butadiene block ranges from 50 to 90 parts by weight, and the amount of the brominated 1, 4-butadiene block ranges from 10 to 50 parts by weight, based on 100 parts by weight of the brominated butadiene block in the brominated butadiene-styrene block copolymer.
6. The polymer composition according to claim 1 or 2, characterized in that the weight ratio of the flame retardant to the synergist is in the range of 1:1 to 10:1.
7. The polymer composition according to claim 1 or 2, characterized in that the weight ratio of the acid binding agent to the antioxidant is in the range of 0.5:1 to 5:1.
8. A polymer masterbatch composition comprising:
a first masterbatch comprising 5 to 20 parts by weight of a synergist and 80 to 95 parts by weight of a polymer matrix based on 100 parts by weight of the total weight of the first masterbatch;
The second masterbatch comprises 40 to 60 parts by weight of a flame retardant, 2 to 5 parts by weight of an acid-binding agent, 2 to 3.75 parts by weight of an antioxidant, and 30 to 60 parts by weight of the polymer matrix based on 100 parts by weight of the total weight of the second masterbatch,
the weight ratio of the first masterbatch to the second masterbatch is in the range of 1:2 to 1:4.
9. A sheet comprising the polymer composition of any one of claims 1 to 7.
10. A sheet prepared from the polymer composition of any one of claims 1 to 7 or the polymer masterbatch composition of claim 8.
CN202111603038.4A 2021-12-24 2021-12-24 Polymer composition, polymer masterbatch composition and sheet comprising or made therefrom Pending CN116333428A (en)

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