WO2021243836A1 - Mélange maître d'agent ignifuge, son procédé de préparation et son application - Google Patents

Mélange maître d'agent ignifuge, son procédé de préparation et son application Download PDF

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WO2021243836A1
WO2021243836A1 PCT/CN2020/106195 CN2020106195W WO2021243836A1 WO 2021243836 A1 WO2021243836 A1 WO 2021243836A1 CN 2020106195 W CN2020106195 W CN 2020106195W WO 2021243836 A1 WO2021243836 A1 WO 2021243836A1
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flame
retardant
parts
flame retardant
retardant masterbatch
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Chinese (zh)
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王忠卫
武军
尹淑君
于青
侯计金
曾冲
段好东
王庆坤
马玉涵
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山东科技大学
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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
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
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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
    • 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
    • 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
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • 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
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • 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
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5397—Phosphine oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Definitions

  • the present invention relates to the field of polymer materials, in particular to a flame-retardant masterbatch and a preparation method and application thereof.
  • polymer materials can be used in different fields such as fibers, containers, films, coatings, engineering plastics, rubber, etc. However, most polymers All materials have a certain degree of flammability. With the improvement of fire safety requirements, higher and higher flame retardant and comprehensive performance requirements are put forward for polymer materials in electronic and electrical, automotive, textiles and other applications. Adding flame retardants to polymer materials is one of the effective methods to improve the flame retardancy of polymer materials.
  • the commonly used polymer material flame retardants are mainly reactive flame retardants and additive flame retardants.
  • the reactive flame retardant is added to the molecular chain of the resin as a third monomer reaction during the resin synthesis process. It is a permanent flame retardant modification method, but it has disadvantages such as high cost and easily affecting the degree of resin polymerization.
  • Additive flame retardant means that with the addition of the flame retardant, it will not cause the flame retardant to react with the polymer matrix, but use the flame retardant properties of the flame retardant itself to improve the flame retardancy of the polymer material, because it has The advantages of flexible formula and good effect occupy a major position.
  • the flame retardant effect is not ideal.
  • the purpose of the present invention is to provide a flame-retardant masterbatch and a preparation method and application thereof.
  • the flame-retardant masterbatch provided by the present invention shows good compatibility when applied to resin products, and has a good flame-retardant effect.
  • the present invention provides a flame-retardant masterbatch, which includes the following components in parts by weight: 10 to 70 parts by weight of carrier resin, 10 to 80 parts of diphenyl phosphine oxide derivatives, 1 to 10 parts of antioxidant and synergistic resistance Burning agent 0 ⁇ 70 parts;
  • the diphenylphosphine oxide derivative has a chemical structure shown in formula I:
  • n is a positive integer
  • R 1 and R 2 are independently one of H, a C 1 ⁇ C 6 alkyl group, and an aromatic group;
  • the melting point of the diphenylphosphine oxide derivative is 200°C to 340°C.
  • the flame-retardant masterbatch includes the following components by weight: 20-60 parts of carrier resin, 20-70 parts of diphenyl phosphine oxide derivative, 3-8 parts of antioxidant, and 5 parts of synergistic flame retardant. ⁇ 60 servings.
  • the diphenylphosphine oxide derivative has a chemical structure shown in formula II:
  • the diphenylphosphine oxide derivative has a chemical structure shown in formula III:
  • the antioxidant is tris[2.4-di-tert-butylphenyl] phosphite, tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester and At least one of bis(2,4-dicumylphenyl)pentaerythritol diphosphite.
  • the antioxidant is tris[2.4-di-tert-butylphenyl] phosphite, tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester and Two kinds of bis(2,4-dicumylphenyl) pentaerythritol diphosphite are compounded.
  • the synergistic flame retardant is one of metal oxides, metal salts, natural minerals, carbon-based free radical initiators, and organic flame retardants containing at least one of the three elements of phosphorus, nitrogen and silicon. At least one.
  • the metal oxide is at least one of titanium dioxide, zinc oxide and aluminum oxide.
  • the natural mineral is at least one of montmorillonite, hydrotalcite and clay.
  • the metal salt is at least one of zinc borate and zinc stannate.
  • the carbon-based free radical initiator is at least one of 2,3-dimethyl-2,3-diphenylbutane and 2,3-dimethyl-2,3-dinaphthylbutane A sort of.
  • the organic flame retardant containing at least one element among the three elements of phosphorus, nitrogen and silicon is zinc diethylphosphinate, polysiloxane, cage silsesquioxane, and hexaphenoxy Cyclotriphosphazene, diphenyl sulfone phenylphosphonate, 1-benzene-1,2-bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide)ethane, P-xylylene bis (9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide), p-xylylene bis (diphenyl phosphine oxide), melamine cyanurate, At least one of melamine polyphosphate, melamine hydrobromide, tris(2,3-dibromopropyl) isocyanurate, aluminum diphenylphosphinate, and aluminum diethylphosphinate.
  • the carrier resin is at least one of polyester, polyamide and polyolefin.
  • the present invention also provides a method for preparing the flame-retardant masterbatch according to the above technical scheme, which includes the following steps:
  • the present invention also provides the application of the flame-retardant masterbatch according to the above-mentioned technical solution or the flame-retardant masterbatch prepared by the preparation method according to the above-mentioned technical solution in resin products.
  • the synergistic flame retardant in the flame retardant masterbatch is polyphenyl diphenyl phosphonate, zinc diethyl phosphinate, and hexaphenoxy ring three.
  • Phosphononitrile, 1-benzene-1,2-bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide)ethane, caged silsesquioxane and montmorillonite At least one of.
  • the synergistic flame retardant in the flame retardant masterbatch is 1-benzene-1,2-bis(9,10-dihydro-9-oxo-10-phosphine At least one of phenanthrene-10-oxide) ethane, titanium dioxide and clay.
  • the synergistic flame retardant in the flame retardant masterbatch is tris (2,3-dibromopropyl) isocyanurate, 2,3-di Methyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-dinaphthylbutane and 1-benzene-1,2-bis(9,10-dihydro-9- At least one of oxy-10-phosphaphenanthrene-10-oxide) ethane.
  • the synergistic flame retardant in the flame retardant masterbatch is melamine cyanurate, melamine polyphosphate, melamine hydrobromide, aluminum diphenylphosphinate, and diphenylphosphinate. At least one of aluminum ethyl phosphinate, zinc oxide, zinc borate, and hydrotalcite.
  • the synergistic flame retardant in the flame retardant masterbatch is p-xylylene bis (diphenyl phosphine oxide), 1-benzene-1,2-bis( 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide)ethane, p-xylylene bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10 -At least one of oxide), polysiloxane and cage silsesquioxane.
  • the present invention provides a flame-retardant masterbatch, which includes the following components in parts by weight: 10 to 70 parts by weight of carrier resin, 10 to 80 parts of diphenyl phosphine oxide derivatives, 1 to 10 parts of antioxidant and synergistic resistance Burning agent 0 ⁇ 70 parts; the diphenyl phosphine oxide derivative has the chemical structure shown in formula I:
  • n is a positive integer, and R 1 and R 2 are independently one of H, C 1 -C 6 alkyl and aromatic groups; the melting point of the diphenyl phosphine oxide derivative is 200° C. ⁇ 340°C.
  • the present invention uses the diphenyl phosphine oxide derivative with the structure of formula I, which has the characteristics of high phosphorus content and good flame retardancy, as the main flame retardant, and at the same time uses its appropriate melting point to improve its dispersibility in the polymer processing process And reduce the influence of flame retardants on melt fluidity; use antioxidants to prevent high molecular polymers from becoming sticky, discolored, brittle or broken due to decomposition; use resins as diphenyl phosphine oxide derivatives and antioxidants
  • the carrier resin is used to realize the loading of p-diphenyl phosphine oxide derivatives and antioxidants, while improving the dispersibility and compatibility of diphenyl phosphine oxide derivatives and antioxidants; finally, the carrier resin, two The combination of phenyl phosphine oxide derivatives and antioxidants improves the flame retardant effect.
  • Figure 1 is a TGA thermogravimetric loss analysis diagram of the phosphorus-containing flame retardant of structural formula II prepared in Example 1;
  • Example 2 is a DSC melting point analysis chart of the phosphorus-containing flame retardant of structural formula II prepared in Example 1;
  • Example 3 is a TGA thermogravimetric loss analysis diagram of the phosphorus-containing flame retardant of structural formula III prepared in Example 2;
  • Example 4 is a DSC melting point analysis chart of the phosphorus-containing flame retardant of structural formula III prepared in Example 2.
  • the present invention provides a flame-retardant masterbatch, which includes the following components in parts by weight: 10 to 70 parts by weight of carrier resin, 10 to 80 parts of diphenyl phosphine oxide derivatives, 1 to 10 parts of antioxidant and synergistic resistance Burning agent 0 ⁇ 70 parts;
  • the diphenylphosphine oxide derivative has a chemical structure shown in formula I:
  • n is a positive integer
  • R 1 and R 2 are independently one of H, a C 1 ⁇ C 6 alkyl group, and an aromatic group;
  • the melting point of the diphenylphosphine oxide derivative is 200°C to 340°C.
  • the raw materials used are all conventional commercial products in the field.
  • the flame-retardant masterbatch provided by the present invention includes 10 to 70 parts of carrier resin, preferably 20 to 60 parts, and more preferably 50 parts.
  • the weight parts of the carrier resin may specifically be 60 parts, 40 parts, 20 parts or 50 parts.
  • the amount of the carrier resin is controlled within the above range, and the good fluidity of the carrier resin during the melting process can be used to achieve the uniform dispersion effect of the components in the flame-retardant masterbatch and improve the flame-retardant masterbatch.
  • the flame-retardant properties of the pellets can't evenly disperse other ingredients when the dosage is small, and excessive dosage will result in waste of raw materials.
  • the carrier resin is preferably at least one of polyester, polyamide and polyolefin, more preferably PET polyethylene terephthalate, PBT polybutylene terephthalate, PETG poly At least one of ethylene terephthalate-1,4-cyclohexanedimethanol, polypropylene, SEBS, and PA66 polyhexamethylene adipamide.
  • the type of the carrier resin may specifically be PET, PA66, polypropylene or SEBS.
  • the carrier resin serves as a carrier for the diphenyl phosphine oxide derivative and the antioxidant, and improves the dispersibility and compatibility of the diphenyl phosphine oxide derivative and the antioxidant.
  • the flame-retardant masterbatch provided by the present invention includes 10 to 80 parts of diphenyl phosphine oxide derivatives, preferably 20 to 70 parts, more preferably 20 to 60 parts.
  • the parts by weight of the diphenylphosphine oxide derivative may specifically be 40 parts, 30 parts, 60 parts or 12.5 parts.
  • the diphenylphosphine oxide derivative has a chemical structure shown in formula I:
  • n is a positive integer, preferably a positive integer from 1 to 5, more preferably 2 or 3; in the formula I, R 1 and R 2 are independently H, C 1 ⁇ C 6 alkyl And an aromatic group; preferably one of H and a C 1 -C 6 alkyl group, more preferably H.
  • the diphenyl phosphine oxide derivative when n is 2 or 3, and R 1 and R 2 are H, the diphenyl phosphine oxide derivative has the chemical structure shown in formula II:
  • the diphenyl phosphine oxide derivative when n is 2 or 3, and R 1 and R 2 are H, the diphenyl phosphine oxide derivative has the chemical structure shown in formula III:
  • the melting point of the diphenylphosphine oxide derivative is 200°C to 340°C, preferably 210°C to 330°C, more preferably 230 to 300°C, more preferably 250 to 280°C.
  • the melting point of the diphenylphosphine oxide derivative may specifically be 272°C or 263°C.
  • the present invention adopts the diphenyl phosphine oxide derivative with the above structure and melting point to solve the problems of uneven dispersion and hygroscopicity of conventional flame retardants, and the halogen-free flame retardant has high phosphorus content and good flame retardant effect. Good compatibility, with a higher melting point that is slightly lower than that of polyester and high-temperature nylon processing, it can be in a molten state in polymer materials, which further improves the compatibility of flame retardants in polymer materials.
  • the present invention has no special regulations on the synthesis method of the diphenyl phosphine oxide derivative, as long as the synthesis method well known to those skilled in the art is adopted.
  • the method for synthesizing the diphenyl phosphine oxide derivative is preferably the polymerization reaction of diphenyl phosphine oxide and the corresponding chlorinated hydrocarbon under alkaline conditions, which is well known to those skilled in the art.
  • the flame-retardant masterbatch provided by the present invention includes 1-10 parts of antioxidant, preferably 3-8 parts, more preferably 5 parts.
  • the antioxidant effect will not be achieved.
  • the antioxidant will directly interact with molecular oxygen to form free radicals, resulting in a pre-oxidation effect and accelerating the aging process.
  • the concentration is too high, The negative impact of this advanced oxidation effect will offset the stabilizing effect of antioxidants.
  • the anti-oxidation effect is the best in the above-mentioned dosage range.
  • the antioxidant is preferably tris[2.4-di-tert-butylphenyl] phosphite (antioxidant 168), tetra[ ⁇ -(3,5-di-tert-butyl-4-hydroxybenzene) (Base) propionic acid] pentaerythritol ester (antioxidant 1010) and at least one of bis(2,4-dicumylphenyl) pentaerythritol diphosphite (antioxidant S9228), more preferably antioxidant 168, antioxidant
  • 1010 and antioxidant S9228 there are two combinations of 1010 and antioxidant S9228, the most preferred is the combination of antioxidant 1010 and antioxidant S9228, or the combination of antioxidant 1010 and antioxidant 168.
  • the compound dosage of the antioxidant is specifically a 2:3 compound by weight ratio of 1010 and S9228; a 2:1 compound by weight ratio of 168 and 1010; or a weight ratio of 168 and 1010 1:1 compounding.
  • the use of the above-mentioned compound antioxidant and the above-mentioned amount can more effectively prevent the high molecular polymer from becoming sticky, discolored, brittle or broken.
  • the flame retardant masterbatch provided by the present invention includes 0 to 70 parts of a synergistic flame retardant, more preferably 5 to 60, and most preferably 10 to 50 parts.
  • the weight parts of the synergistic flame retardant may specifically be 6 parts, 10 parts, 50 parts, 40 parts or 52.5 parts.
  • the present invention has no special regulations on the addition of synergistic flame retardant. When the material requires higher flame retardant effect, synergistic flame retardant is added, but the amount of synergistic flame retardant cannot exceed the above range, otherwise it will cause the material The mechanical properties decrease.
  • the synergistic flame retardant is preferably a metal oxide, a metal salt, a natural mineral, a carbon-based free radical initiator, and an organic flame retardant containing at least one element among the three elements of phosphorus, nitrogen and silicon At least one of the agents.
  • the metal oxide is preferably at least one of titanium dioxide, zinc oxide and aluminum oxide.
  • the natural mineral is preferably at least one of montmorillonite, hydrotalcite and clay.
  • the metal salt is preferably at least one of zinc borate and zinc stannate.
  • the carbon-based free radical initiator is preferably 2,3-dimethyl-2,3-diphenylbutane and 2,3-dimethyl-2,3-dinaphthylbutane At least one of them.
  • the organic flame retardant containing at least one element among the three elements of phosphorus, nitrogen and silicon is preferably zinc diethylphosphinate, polysiloxane, cage silsesquioxane, six Phenoxy cyclotriphosphazene, polyphenyl phosphonate diphenyl sulfone ester, 1-benzene-1,2-bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide) Ethane, p-xylylene bis (9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide), p-xylylene bis (diphenyl phosphine oxide), melamine cyanuride At least
  • the type of the synergistic flame retardant can be specifically zinc diethylphosphinate, polysiloxane, titanium dioxide, aluminum diphenylphosphinate, melamine cyanurate, para Xylylene bis (diphenyl phosphine oxide), melamine hydrobromide, melamine cyanurate, or a synergist (2,3-dimethyl-2,3-diphenylbutane).
  • the flame-retardant masterbatch made by selecting the above-mentioned synergistic flame retardant can exhibit a good flame-retardant synergistic effect when applied to resin products.
  • the flame-retardant masterbatch provided by the present invention uses the diphenyl phosphine oxide derivative with the structure of formula I, which has the characteristics of high phosphorus content and good flame retardancy, as the main flame retardant, and at the same time, uses its low melting point to improve its performance Dispersibility during polymer processing; using antioxidants to prevent polymer from becoming sticky, discolored, brittle or broken; using carrier resin to achieve the loading of p-diphenyl phosphine oxide derivatives and antioxidants, and at the same time improve the two The dispersibility and compatibility of phenyl phosphine oxide derivatives and antioxidants; finally, under the combined action of carrier resin, diphenyl phosphine oxide derivatives and antioxidants, the compatibility and resistance of flame retardants are improved. Burning effect.
  • the present invention also provides a method for preparing the flame-retardant masterbatch according to the above technical solution, which includes the following steps:
  • the carrier resin, the diphenyl phosphine oxide derivative, the antioxidant and the synergistic flame retardant are mixed to obtain the mixture.
  • the present invention has no special regulations on the mixing operation, as long as the obtained dry raw materials are uniformly mixed.
  • the carrier resin, diphenyl phosphine oxide derivative, antioxidant and synergistic flame retardant are preferably mixed before the mixing of the carrier resin, diphenyl phosphine oxide derivative, antioxidant and synergistic flame retardant. Dry it.
  • the present invention does not have special regulations on the drying method.
  • the drying method well known to those skilled in the art can be used to remove the moisture absorbed by the above-mentioned materials during storage and some volatile substances, so as to prevent the resin from being volatile due to moisture or volatile
  • the presence of substances causes the resin to decompose during processing, and at the same time avoid bubbles in the resin processing process.
  • the present invention granulates the mixture to obtain a flame-retardant masterbatch.
  • the present invention has no special regulations on the granulation method, and the granulation method well known to those skilled in the art can be used.
  • the granulation device is preferably a component with a twin screw.
  • the temperature of the twin screw is preferably 210 to 300°C, more preferably 210 to 275°C, and most preferably 220 to 270°C.
  • the temperature of the twin screw may specifically be 270°C, 260°C, 200°C, or 220°C.
  • the present invention adopts the above-mentioned temperature to prevent the carrier resin from being unable to be processed into a plastic state when the temperature is too low, and at the same time avoids the material sticking in the thread groove due to the high temperature due to the high temperature, and also avoids the decomposition of the raw material.
  • the granulated product is preferably cooled and dried in sequence to obtain the flame-retardant masterbatch.
  • the present invention has no special regulations on the cooling method, and the cooling method well known to those skilled in the art can be used.
  • the present invention has no special regulations on the drying method, and the drying method well known to those skilled in the art can be used to remove the moisture absorbed by the masterbatch during the production process and the volatile substances that have not been volatilized.
  • the purpose of drying the masterbatch in the present invention is to improve the stability of the masterbatch during storage.
  • the preparation method provided by the invention is easy to operate, low in cost, and very suitable for rapid and large-scale production.
  • the present invention also provides the flame-retardant masterbatch described in the above technical solution and the application of the flame-retardant masterbatch prepared by the preparation method described in the above technical solution in resin products.
  • the synergistic flame retardant in the flame-retardant masterbatch is preferably polyphenyl diphenyl phosphonate, zinc diethyl phosphinate, and hexaphenoxy Cyclotriphosphazene, 1-benzene-1,2-bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide)ethane, cage silsesquioxane and montan At least one of the soil removal.
  • the synergistic flame retardant in the flame retardant masterbatch may specifically be zinc diethylphosphinate.
  • the flame retardant formula can maintain the better transparency and spinning performance of the fiber film, and give full play to the phosphorus-phosphorus synergistic effect and the phosphorus-silicon synergistic effect (the gas phase flame retardant mechanism and the solid phase flame retardant mechanism cooperate with each other).
  • Different flame retardants participate in the combustion process of polyester at different temperatures when the polyester is decomposed.
  • the synergistic formula system can improve the flame retardant efficiency and reduce the amount of flame retardant added.
  • the specific phosphorus-silicon-mineral synergistic effect Can improve the dripping performance of polyester.
  • the synergistic flame retardant in the flame retardant masterbatch is preferably 1-benzene-1,2-bis(9,10-dihydro-9-oxy-10 -Phosphaphenanthrene-10-oxide) at least one of ethane, titanium dioxide and clay.
  • the synergistic flame retardant in the flame retardant masterbatch may specifically be titanium dioxide.
  • the flame retardant formula can not only maintain the excellent spinnability of the fiber, but also exert the phosphorus and phosphorus synergy between the selected flame retardants, and the selected titanium dioxide and clay can be oxidized with diphenyl in a certain amount of addition.
  • the synergistic effect of the phosphine derivative flame retardant can significantly promote the carbonization of nylon, further increase the oxygen index of the flame retardant nylon, and at the same time achieve the flame retardant effect of V-0.
  • the synergistic flame retardant in the flame retardant masterbatch is preferably tris (2,3-dibromopropyl) isocyanurate, 2, 3-Dimethyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-dinaphthylbutane and 1-benzene-1,2-bis(9,10-dihydro) -9-oxo-10-phosphaphenanthrene-10-oxide) at least one of ethane.
  • the synergistic flame retardant in the flame retardant masterbatch may specifically be 2,3-dimethyl-2,3-diphenylbutane.
  • the flame retardant formula is a fusible flame retardant, which does not affect the spinning performance of polypropylene fiber. At the same time, it can exert the synergistic effect of phosphorus and bromine.
  • the addition of a carbon-based free radical initiator can further accelerate the decomposition of polypropylene. The heat is dripping and the ratio of the three is optimized, so that the polypropylene can reach V-2 level when the flame retardant content is 1-2%, and the oxygen index is above 26%.
  • the synergistic flame retardant in the flame retardant masterbatch is preferably melamine cyanurate, melamine polyphosphate, melamine hydrobromide, and diphenylphosphinic acid. At least one of aluminum, aluminum diethylphosphinate, zinc oxide, zinc borate, and hydrotalcite.
  • the synergistic flame retardant in the flame retardant masterbatch may specifically be aluminum diethylphosphinate.
  • the flame retardant formula can fully utilize the synergistic mechanism between the gas phase flame retardant and solid phase flame retardant between phosphorus nitrogen flame retardant elements and the phosphorus-metal ion of metal oxides by introducing nitrogen-based flame retardants. Synergistically catalyze the formation of charcoal to achieve excellent flame retardant effect.
  • the synergistic flame retardant in the flame retardant masterbatch is p-xylylene bis (diphenyl phosphine oxide), 1-benzene-1,2- Bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide)ethane, p-xylylene dimethyl bis(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide) -10-oxide), at least one of polysiloxane and cage silsesquioxane.
  • the synergistic flame retardant in the flame retardant masterbatch may specifically be polysiloxane.
  • the synergistic formula system of selected organophosphorus-silicon flame-retardant elements added to the flame-retardant formula exerts the synergistic effects of phosphorous and phosphorous and silicon, and improves the flame retardant efficiency.
  • the flame retardant masterbatch derived from organic DPO has good compatibility with polymer resin materials, reducing inorganic flame retardancy
  • polar flame retardants such as chemical agents minimizes the influence of the flame retardant system on the electrical properties, so that the flame retardant polymer materials maintain better dielectric properties and lower water absorption.
  • the present invention does not have special regulations on the application process of flame-retardant masterbatch in resin products. According to the preparation process of resin products well known to those skilled in the art, the resin product preparation process needs to be added to improve its flame retardancy. The flame-retardant components of, can be directly replaced with the flame-retardant masterbatch prepared by the present invention.
  • the carrier resin of the flame-retardant masterbatch and the resin component selected in the preparation process of the resin-based product may be the same or different, and are preferably the same.
  • the same resin is selected, the problem of different processing parameters due to different resins can be further avoided, and the compatibility of the resin selected in the preparation process of the flame retardant masterbatch and resin products can be improved, thereby further improving the resistance of the material. Combustion performance.
  • the preferred polyphenylene ether is poly-2,6-dimethyl-1,4-phenylene ether, modified polyphenylene ether terminated with epoxy structure
  • the carrier added to the masterbatch is polypropylene, vinyl elastomer, styrene-butadiene copolymer
  • the flame retardant masterbatch of at least one of hydrogenated styrene-butadiene copolymer and maleic anhydride styrene-butadiene copolymer can solve the flame retardant performance of the material and can give the material better mechanical properties.
  • the flame-retardant masterbatch provided by the invention shows good compatibility when applied to resin products, and the flame-retardant effect can reach V-0 level.
  • the vertical combustion test is tested in accordance with the GB/T2408-2008 method, the sample size (mm) (125 ⁇ 5) ⁇ (13.0 ⁇ 0.5) ⁇ (3.2/1.6 ⁇ 0.25); the oxygen index (LOI) test is in accordance with GB/T2406.1 -2008: Specimen size (mm)(80 ⁇ 5) ⁇ (6.5 ⁇ 0.5) ⁇ (3 ⁇ 0.25); tensile strength and elongation at break are tested according to GB/T1040-2006 method, type I, Tensile speed 500mm/min; dielectric constant (Dk), (1GHz) microwave induction analyzer measurement; drop weight impact test, ISO ImpactTester, install the sample as required, fix the drop weight at a height of 20mm, so that The free fall hits the material, and the clearer the cross cracks produced by the falling hammer hitting the material, the better the toughness of the material.
  • Dk dielectric constant
  • ISO ImpactTester ISO ImpactTester
  • TGA test results of the prepared compound EDPO with the structure of formula II are shown in Figure 1. Its weight loss is 5% at 372.2°C, which has high thermal stability, and the final carbon residue is 3.97%; its DSC melting point test is shown in Figure 2, and its melting point is 272°C.
  • the raw materials EDPO and BDPO involved in Examples 3-29 were all obtained by the preparation method provided in Example 1 or 2.
  • the mixed raw materials are fed into the screw extruder for melting and extrusion, the screw extruder is the highest Set the temperature to 275°C, cool and pelletize after extrusion, the flame-retardant polyester composition is colorless and transparent, then dried, take it out and fill it in the mold, press it into a tablet at 270°C, and let it cool. After cutting the sample test.
  • the screw extruder is the highest Set the temperature to 275°C, cool and pelletize after extrusion, the flame-retardant polyester composition is colorless and transparent, dry, take it out and fill it in the mold, press and shape it on a flat plate vulcanizer at 270°C, and wait for it to cool down Cut sample test.
  • the flame-retardant masterbatch is dried, and the weight ratio of the flame-retardant masterbatch FRM-1 to the PET polyester chip is 10:90.
  • the mixed raw materials are fed into the screw extruder for melting and extrusion, the screw extruder is the highest Set the temperature to 275°C, cool and pelletize after extrusion, the flame-retardant polyester composition is colorless and transparent, dry, take it out and fill it in the mold, press and shape it on a flat plate vulcanizer at 270°C, and wait for it to cool down Cut sample test.
  • the screw extruder is the highest The temperature was set to 275°C, after extrusion, it was cooled and pelletized, dried, taken out and filled in a mold, and pressed into a tablet at a 270°C flat vulcanizer. After cooling, the sample was cut and tested.
  • the screw extruder is the highest Set the temperature to 235°C, cool and pelletize after extrusion, the flame-retardant polyester composition is colorless and transparent, dried, take it out and fill it in a mold, press and shape it on a flat vulcanizer at 240°C, and wait for it to cool down Cut sample test.
  • the flame-retardant masterbatch is dried and mixed according to the weight ratio of the flame-retardant masterbatch FRM-2 and PETG chips at a ratio of 10:90.
  • the mixed raw materials are fed into the screw extruder for melting and extrusion.
  • the maximum temperature of the screw extruder is set Set the temperature to 230°C, cool and pelletize after extrusion, the flame-retardant polyester composition is colorless and transparent, dry, take it out and fill it in a mold, press and shape it on a plate vulcanizer at 230°C, and cut the sample after cooling. test.
  • the mixed raw materials are fed into the screw extruder to melt and extrude.
  • the maximum temperature of the screw extruder is set to 280°C. After extrusion, it is cooled and pelletized, dried, taken out and filled in the mold, and pressed into a tablet at 280°C on a plate vulcanizing machine. After cooling, the sample is cut for testing.
  • the raw materials are fed into the screw extruder for melting and extrusion.
  • the maximum temperature of the screw extruder is set to 280°C. After extrusion, it is cooled and pelletized, dried, taken out and filled in the mold, and pressed into a vulcanizing machine at 280°C. After forming, let it cool down and cut samples for testing.
  • the mixed raw materials are fed into the screw extruder for melting and extrusion, The highest temperature of the machine is set to 280°C. After extrusion, it is cooled and pelletized, dried, taken out and filled in a mold, and pressed into a tablet at a 280°C plate vulcanizing machine. After cooling, the sample is cut for testing.
  • the mixed raw materials are fed into the screw extruder for melting and extrusion.
  • the maximum temperature of the screw extruder is set to 280°C. After extrusion, it is cooled and pelletized, dried, taken out and filled in the mold, and pressed into a tablet at 280°C on a plate vulcanizing machine. After cooling, the sample is cut for testing.
  • the prepared flame-retardant polyester reaches 1.6mm V-0 level, the LOI is increased to 34.5%, and the flame retardant
  • the flame retardant effect of the reinforced polyester to 0.8mmV-0 is because the compound flame retardant system can give full play to the phosphorus-phosphorus synergistic effect and the phosphorus-silicon synergistic effect (the gas phase flame retardant mechanism and the solid phase flame retardant mechanism cooperate with each other).
  • the flame-retardant masterbatch After the flame-retardant masterbatch is dried, it is mixed according to the weight ratio of the flame-retardant masterbatch FRM-4 and PA6 of 10:90, and the mixed raw materials are fed into the screw extruder for melting and extrusion, and the maximum temperature of the screw extruder is set The temperature is 240°C, after extrusion, cooling and pelletizing, the flame-retardant PA6 resin composition is translucent, dried, taken out and filled into a mold, and pressed into a tablet at 240°C on a flat plate vulcanizer. After cooling, the sample is cut and tested.
  • the weight ratio is 20:80.
  • the mixed raw materials are fed into the screw extruder for melting and extrusion.
  • the maximum temperature of the screw extruder is set to 270°C, and it is cooled after extrusion.
  • the mixed raw materials are fed into the screw extruder for melting and extrusion, and the maximum temperature of the screw extruder is set to 320 °C, after extrusion, cool and granulate, without agglomerated powder, dry, take it out and fill it in a mold, press and shape it on a plate vulcanizer at 320°C, and cut samples after cooling.
  • the mixed raw materials are fed into the screw extruder to melt and extrude, and the screw is extruded.
  • the maximum temperature of the machine is set to 320°C. After extrusion, it is cooled and granulated. There is no agglomerated powder, dried, taken out and filled in the mold, and pressed into a tablet at 320°C. After cooling, the sample is cut and tested.
  • the mixed materials are fed into the screw extruder for melting and extrusion.
  • the maximum temperature of the screw extruder is set to 220 °C, and then cooled after extrusion.
  • the mixed raw materials are fed into the screw extruder for melting and extrusion.
  • the maximum temperature of the screw extruder is set to 220 °C, and then cooled after extrusion.
  • the mixed materials are fed into the screw extruder for melting and extrusion, and the maximum temperature of the screw extruder is set The temperature is 250°C. After extrusion, it is cooled and granulated. There is no agglomerated powder. It is dried, taken out and filled in a mold. It is pressed into a tablet on a 250°C flat-plate vulcanizer. After cooling, the sample is cut and tested.
  • toluene solution of the composition is a resin varnish with a concentration of 55%.
  • the resin composition is attached to the glass fiber cloth by impregnation or coating, and then heated and baked into a semi-cured state to obtain a prepreg. Take four prepregs and two copper foils prepared above, stack them in the order of copper foil, four prepregs, and copper foil, and then laminate them under vacuum conditions at 200°C for 1.5 hours to form a copper foil substrate. The physical properties of copper-containing substrates and copper-free substrates after etching are measured.
  • the flame-retardant masterbatch prepared by the present invention has a good flame-retardant effect when added to pure PA6, PA66 and PPA.
  • flame retardant masterbatch 4 prepared by a combination of DPO derivative flame retardant and titanium dioxide
  • 10% when 10% is added, the vertical combustion of PA6 reaches V-2 level, the oxygen index reaches 29.5%, and the oxygen index increases significantly.
  • the flame-retardant masterbatch can be used in the melt spinning of flame-retardant nylon, excellent flame retardant effect can be spun Strong performance; when used in a glass fiber reinforced nylon system, the diphenyl phosphine oxide derivative defined by the present invention and the commonly used phosphorus nitrogen flame retardant and metal oxide prepared in a certain proportion of flame retardant masterbatch 5 can make poly
  • the amide material achieves a 1.6mm V-0 flame retardant effect, and the oxygen index is further increased to more than 35%, while maintaining good mechanical properties and low water absorption.
  • the introduction of other specific phosphorus-based flame retardants and nitrogen-based flame retardants in the compound system can give full play to the synergistic mechanism between the gas phase flame retardant and solid phase flame retardant between the phosphorus nitrogen flame retardant elements, and the selected titanium dioxide
  • the synergy with phosphorus-based flame retardants can significantly promote the formation of carbon from polyamides, further increase the oxygen index of flame-retardant polyamides, and at the same time achieve the flame retardant effect of V-0.
  • diphenyl phosphine oxide derivatives defined in the present invention can also produce obvious phosphorus-bromine synergistic flame retardant effects with brominated flame retardants, and adding a small amount of carbon-based free radical initiators can further promote the decomposition of polypropylene Accelerate the drop of heat, so as to achieve an excellent flame retardant effect.
  • the flame retardant system can be used in polypropylene molding compounds and polypropylene fiber films.
  • the flame-retardant masterbatch 6 prepared by the present invention was added to ordinary polyphenylene ether, and the addition of 10% can make the glass fiber reinforced PPO reach the V-0 level and the oxygen index 36.9%.
  • polyphenylene ether has extremely low dielectric constant, dielectric loss and water absorption, excellent heat resistance, good dimensional stability, and excellent adhesion to copper foil, it has a very large In the application space, the polyphenylene ether structure itself has certain flame retardancy, but due to the introduction of reactive groups such as vinyl and the reduction of molecular weight, the flame retardant performance is significantly reduced, vertical combustion is not graded, and the oxygen index drops to about 21%. After cross-linking and curing, there are problems such as insufficient toughness.
  • the flame-retardant masterbatch provided by the present invention is especially a resin varnish obtained from modified PPO with active group end caps, flame-retardant masterbatch, solvent, and crosslinking accelerator to make the resin composition adhere to the resin composition by impregnation or coating.
  • the particles have good thermal decomposition matching properties with the polymer resin material, fully exerting the synergistic effect of phosphorous and phosphorous and silicon, and improving the flame-retardant efficiency.
  • the flame retardant masterbatch can reduce the use of polar flame retardants such as inorganic flame retardants, and minimize the influence of the flame retardant system on the dielectric properties and water absorption of the laminate, and the polyolefin carrier resin is non-polar
  • the synergistic combination of resin and various influencing factors ultimately enables the flame-retardant PPO laminate to maintain better dielectric properties and lower water absorption.

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Abstract

La présente invention se rapporte au domaine des matériaux polymères et concerne un mélange maître d'agent ignifuge. Un dérivé d'oxyde de diphénylphosphine présentant une structure spécifique et une grande stabilité thermique est utilisé en tant qu'agent ignifuge et présente également un point de fusion similaire à celui d'une résine, de telle sorte que la dispersibilité du dérivé d'oxyde de diphénylphosphine dans un procédé de transformation des polymères est améliorée et que l'effet de l'agent ignifuge sur la fluidité à l'état fondu est réduit. Un antioxydant est utilisé pour empêcher un polymère de devenir collant, décoloré, fragilisé ou fragmenté en raison de sa décomposition. Le chargement du dérivé d'oxyde de diphénylphosphine et de l'antioxydant est réalisé au moyen d'une résine de support et, parallèlement, la dispersibilité et la compatibilité du dérivé d'oxyde de diphénylphosphine et de l'antioxydant sont améliorées. Les résultats des modes de réalisation montrent que le mélange maître d'agent ignifuge selon la présente invention présente une bonne compatibilité lorsqu'il est appliqué à des produits en résine, et son effet ignifugeant peut atteindre le niveau V-0.
PCT/CN2020/106195 2020-06-03 2020-07-31 Mélange maître d'agent ignifuge, son procédé de préparation et son application WO2021243836A1 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114134592A (zh) * 2021-12-17 2022-03-04 石狮市益明染织有限公司 一种耐阻燃的涤纶丝及其制备方法
CN115011087A (zh) * 2022-07-18 2022-09-06 华润化学材料科技股份有限公司 一种阻燃聚酯泡沫板及其制备方法
CN115042497A (zh) * 2022-08-16 2022-09-13 杭州和顺科技股份有限公司 一种双向拉伸阻燃聚酯薄膜及其制备方法
CN115160758A (zh) * 2022-06-30 2022-10-11 湖北合聚新材料有限公司 一种用于汽车零部件的六方氮化硼改性无卤阻燃pc/abs材料及其制备方法和应用
CN115466385A (zh) * 2022-10-31 2022-12-13 中化学科学技术研究有限公司 一种聚酰胺膜及制备方法、电子器件
CN115594915A (zh) * 2022-09-20 2023-01-13 道恩周氏（青岛）复合包装材料有限公司（Cn） 一种固碳减排塑料母粒及其制备方法及应用
CN115819961A (zh) * 2022-11-30 2023-03-21 江苏集萃先进高分子材料研究所有限公司 尼龙6阻燃复合材料制备方法
CN116041893A (zh) * 2023-01-28 2023-05-02 山东旭锐新材股份有限公司 高热稳定性溴化sbs阻燃母粒、制备方法和xps材料
CN115011087B (zh) * 2022-07-18 2024-05-17 华润化学材料科技股份有限公司 一种阻燃聚酯泡沫板及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111440424A (zh) * 2020-06-03 2020-07-24 山东科技大学 一种阻燃母粒及其制备方法和应用
CN112679933A (zh) * 2020-12-17 2021-04-20 浙江旭森非卤消烟阻燃剂有限公司 一种环保型阻燃透明聚酯材料
CN112679539B (zh) * 2021-01-05 2024-02-13 李萍萍 一种含有双二苯基次膦氧结构的化合物及其制备方法
CN114230906B (zh) * 2021-11-30 2023-05-09 天津金发新材料有限公司 一种低烟密度阻燃聚丙烯复合材料及其制备方法和应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3370030A (en) * 1966-03-14 1968-02-20 American Cyanamid Co Flame-retardant compositions for plastics
JP2005170964A (ja) * 2003-12-05 2005-06-30 National Institute Of Advanced Industrial & Technology 難燃性ポリアミド組成物
CN103849042A (zh) * 2012-12-04 2014-06-11 青岛三利中德美水设备有限公司 一种用于改性聚乙烯的无卤阻燃抗静电母粒
CN105238000A (zh) * 2014-07-10 2016-01-13 中山台光电子材料有限公司 一种低介电复合材料及其积层板和电路板
CN105713312A (zh) * 2014-12-05 2016-06-29 台光电子材料(昆山)有限公司 芳香族四官能乙烯苄基树脂组成物及其应用
CN108456397A (zh) * 2017-02-17 2018-08-28 联茂电子股份有限公司 具有低介电损耗的无卤素环氧树脂组成物
CN110760163A (zh) * 2019-11-21 2020-02-07 山东科技大学 一种无卤阻燃环氧树脂组合物及其应用
CN111440424A (zh) * 2020-06-03 2020-07-24 山东科技大学 一种阻燃母粒及其制备方法和应用

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3370030A (en) * 1966-03-14 1968-02-20 American Cyanamid Co Flame-retardant compositions for plastics
JP2005170964A (ja) * 2003-12-05 2005-06-30 National Institute Of Advanced Industrial & Technology 難燃性ポリアミド組成物
CN103849042A (zh) * 2012-12-04 2014-06-11 青岛三利中德美水设备有限公司 一种用于改性聚乙烯的无卤阻燃抗静电母粒
CN105238000A (zh) * 2014-07-10 2016-01-13 中山台光电子材料有限公司 一种低介电复合材料及其积层板和电路板
CN105713312A (zh) * 2014-12-05 2016-06-29 台光电子材料(昆山)有限公司 芳香族四官能乙烯苄基树脂组成物及其应用
CN108456397A (zh) * 2017-02-17 2018-08-28 联茂电子股份有限公司 具有低介电损耗的无卤素环氧树脂组成物
CN110760163A (zh) * 2019-11-21 2020-02-07 山东科技大学 一种无卤阻燃环氧树脂组合物及其应用
CN111440424A (zh) * 2020-06-03 2020-07-24 山东科技大学 一种阻燃母粒及其制备方法和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DU, CHAOJUN ET AL., ISBN:978-7-5509-1754-5; SYNTHESIS AND STUDY ON THE PROPERTIES OF NOVEL PHOSPHOROUS-NITROGEN-CONTAINING FLAME RETARDANTS, ISBN:978-7-5509-1754-5, THE YELLOW RIVER WATER CONSERVANCY PRESS, 1ST EDITION, 31 May 2017 (2017-05-31) *
STACKMAN, ROBERT W.: "Phosphorus based additives for flame retardant polyester. 1. Low molecular weight additives", INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, AMERICAN CHEMICAL SOCIETY, US, vol. 21, no. 2, 1 June 1982 (1982-06-01), US , pages 328 - 331, XP009135578, ISSN: 0196-4321, DOI: 10.1021/i300006a027 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114134592A (zh) * 2021-12-17 2022-03-04 石狮市益明染织有限公司 一种耐阻燃的涤纶丝及其制备方法
CN115160758B (zh) * 2022-06-30 2023-10-27 湖北合聚高分子材料有限公司 一种用于汽车零部件的六方氮化硼改性无卤阻燃pc/abs材料及其制备方法和应用
CN115160758A (zh) * 2022-06-30 2022-10-11 湖北合聚新材料有限公司 一种用于汽车零部件的六方氮化硼改性无卤阻燃pc/abs材料及其制备方法和应用
CN115011087A (zh) * 2022-07-18 2022-09-06 华润化学材料科技股份有限公司 一种阻燃聚酯泡沫板及其制备方法
CN115011087B (zh) * 2022-07-18 2024-05-17 华润化学材料科技股份有限公司 一种阻燃聚酯泡沫板及其制备方法
CN115042497A (zh) * 2022-08-16 2022-09-13 杭州和顺科技股份有限公司 一种双向拉伸阻燃聚酯薄膜及其制备方法
CN115594915A (zh) * 2022-09-20 2023-01-13 道恩周氏（青岛）复合包装材料有限公司（Cn） 一种固碳减排塑料母粒及其制备方法及应用
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CN116041893A (zh) * 2023-01-28 2023-05-02 山东旭锐新材股份有限公司 高热稳定性溴化sbs阻燃母粒、制备方法和xps材料

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