WO2014098341A1 - Composition de résine thermoplastique ignifuge, et articles moulés à partir de celle-ci - Google Patents

Composition de résine thermoplastique ignifuge, et articles moulés à partir de celle-ci Download PDF

Info

Publication number
WO2014098341A1
WO2014098341A1 PCT/KR2013/006944 KR2013006944W WO2014098341A1 WO 2014098341 A1 WO2014098341 A1 WO 2014098341A1 KR 2013006944 W KR2013006944 W KR 2013006944W WO 2014098341 A1 WO2014098341 A1 WO 2014098341A1
Authority
WO
WIPO (PCT)
Prior art keywords
flame retardant
substituted
ether
unsubstituted
thermoplastic resin
Prior art date
Application number
PCT/KR2013/006944
Other languages
English (en)
Korean (ko)
Inventor
배수학
주민정
박동민
신승식
최동길
Original Assignee
제일모직 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 제일모직 주식회사 filed Critical 제일모직 주식회사
Publication of WO2014098341A1 publication Critical patent/WO2014098341A1/fr

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides

Definitions

  • the present invention relates to a flame retardant thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a flame-retardant thermoplastic resin composition having excellent flame retardancy, thermal stability and long-term durability and environmentally friendly flame retardant thermoplastic resin composition and molded articles formed by applying a polymerized phosphorus compound having a specific structure as a flame retardant.
  • Styrene-based resins which are used as exterior materials for electronic products, are applied to almost all electronic products due to their excellent processability and mechanical properties.
  • the styrene resin itself has a property that combustion can easily occur and is not resistant to fire. Therefore, the styrene-based resin can be easily burned by the external ignition source, and may serve to further spread the fire. Accordingly, in order to guarantee the safety of fire of electronic products, the United States, Japan, Europe and the like regulate the law to use only polymer resin satisfying the flame retardant standard as an exterior material.
  • halogen-based compounds may damage the mold and have a fatal effect on the human body due to the hydrogen halide gas generated during processing.
  • polybrominated diphenyl ethers which are mainly halogen-based flame retardants, are highly likely to generate very toxic gases such as dioxins and furans during combustion, attention has been focused on flame-retardant methods that do not apply halogen-based compounds.
  • blends that can be flame retarded using a phosphorus compound include a blend of polycarbonate and acrylonitrile-butadiene-styrene copolymer, a blend of rubber-reinforced styrene resin and polyphenylene ether resin, and the like.
  • Korean Patent No. 2002-007813 discloses a method of using a mixture of carboxy phosphonic acid and phosphoric acid or a derivative compound as a flame retardant in a polystyrene resin or the like, and studies similar to the present patent have been actively conducted.
  • the patent and the like have excellent flame retardancy when using a halogen-based flame retardant or a phosphate ester flame retardant, but may not bond to a material that requires long-term durability such as a solar material.
  • thermoplastic resin composition In order to solve the problems of the conventional flame-retardant thermoplastic resin, the present inventors apply a polymeric phosphonate flame retardant to the thermoplastic resin, while excellent in environmental stability and fire safety, excellent heat resistance and excellent long-term durability compared to existing products It is early to develop a thermoplastic resin composition.
  • Another object of the present invention is to provide an environmentally friendly flame retardant thermoplastic resin composition and a molded article formed therefrom without using a halogen-based flame retardant.
  • Still another object of the present invention is to provide a flame retardant thermoplastic resin composition and a molded article formed therefrom which can be used as an internal / exterior material such as electronic products due to relatively excellent thermal stability, mechanical strength and fluidity.
  • the flame retardant thermoplastic resin composition may include 100 parts by weight of a basic resin comprising (A) about 10 to about 49% by weight of an aromatic vinyl resin and (B) about 51 to about 90% by weight of a polyphenylene ether resin; And (C) about 0.1 to about 30 parts by weight of a polyphosphonate comprising a unit represented by Formula 1 below:
  • A is a single bond, C1-C5 alkylene group, C2-C5 alkylidene group, C5-C6 cycloalkylidene group, -S- or -SO 2-
  • R 1 is substituted or unsubstituted A substituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a C6-C20 substituted or unsubstituted aryloxy group
  • R 2 and R 3 are each independently substituted or unsubstituted C1-
  • a and b are each independently an integer of 0 to 4
  • n is 1 to It is an integer of 500.
  • the polyphosphonate (C) may include at least one polyphosphonate including a unit represented by the following formula (2).
  • a and B are each independently a single bond, an alkylene group of C1-C5, an alkylidene group of C2-C5, a cycloalkylidene group of C5-C6, -S- or -SO 2- , A and B are not the same as each other, R 1 and R 4 are each independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group or C6-C20 substituted or unsubstituted Is an aryloxy group, R 2 , R 3 , R 5 and R 6 are each independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6 -C12 is an aryl group or a halogen atom, a, b, c and d are each
  • the sum of m and n may be 3 to 600.
  • the aromatic vinyl-based resin (A) comprises a monomer mixture comprising about 1 to about 30 weight percent of a rubbery polymer having an average particle diameter of about 0.1 to about 3 ⁇ m and about 70 to about 99 weight percent of an aromatic vinyl monomer. It may be a polymer.
  • the polyphenylene ether resin (B) may be poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, Poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4 -Phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dimethyl Copolymer of -1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether, and poly (2,6-dimethyl-1,4-phenylene) ether It may contain one or more of the copolymers of poly (2,3,6-triethyl-1,4-phenylene)
  • the flame retardant thermoplastic resin composition has a tensile strength of about 610 to about 800 kgf / according to ASTM D-638 after exposure at a temperature of about 135 ° C. for about 3,000 hours. may be 2 mm.
  • the flame retardant thermoplastic resin composition may further comprise an additive comprising at least one flame retardant, lubricant, plasticizer, heat stabilizer, anti-drip agent, antioxidant, compatibilizer, light stabilizer, pigment, dye and inorganic additives. have.
  • Another aspect of the invention relates to a molded article.
  • the molded article is formed from the flame retardant thermoplastic resin composition.
  • the present invention is excellent in flame retardancy, thermal stability and long-term durability, environmentally friendly by not using a halogen-based flame retardant, relative to thermal stability, mechanical strength and fluidity, flame retardant thermoplastic resin that can be used as an interior / exterior material such as electronic products It has the effect of providing the composition and the molded article formed therefrom.
  • the flame retardant thermoplastic resin composition according to the present invention comprises 100 parts by weight of a base resin comprising about 10 to about 49 wt% of an aromatic vinyl resin and about 51 to about 90 wt% of a polyphenylene ether resin; And about 0.1 to about 30 parts by weight of a polyphosphonate including a unit represented by Formula 1 below.
  • the aromatic vinyl resin (A) used in the present invention is a polymer of an aromatic vinyl monomer (monomer), a copolymer with another monomer copolymerizable with an aromatic vinyl monomer, or a polymer of a monomer mixture containing the aromatic vinyl monomer and a rubbery polymer. Phosphorus rubber-modified aromatic vinyl resin.
  • the aromatic vinyl monomers may include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, and the like. These can be used individually or in mixture of 2 or more types.
  • the other copolymerizable monomer may be acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, or the like. These can be used individually or in mixture of 2 or more types.
  • the rubbery polymers include butadiene type rubbers, copolymers of butadiene and styrene, diene rubbers such as poly (acrylonitrile-butadiene) and saturated rubbers hydrogenated with the diene rubber, isoprene rubber, acrylic rubber and ethylene-propylene- Diene terpolymer (EPDM) and the like can be used.
  • diene rubbers such as poly (acrylonitrile-butadiene) and saturated rubbers hydrogenated with the diene rubber
  • isoprene rubber acrylic rubber and ethylene-propylene- Diene terpolymer (EPDM) and the like
  • EPDM ethylene-propylene- Diene terpolymer
  • polybutadiene, a copolymer of butadiene and styrene, isoprene rubber, alkyl acrylate rubbers, and the like can be used.
  • the content of the rubbery polymer may be about 1 to about 30% by weight, for example, about 5 to about 15% by weight of the monomer mixture.
  • the content of the aromatic vinyl monomer may be about 70 to about 99% by weight, for example about 85 to about 95% by weight of the monomer mixture. It is possible to obtain a good balance of physical properties of the impact strength and mechanical properties in the above range.
  • the average particle diameter of the rubbery polymer may be about 0.1 to about 3 ⁇ m, for example, about 0.25 to about 2.5 ⁇ m in Z-average.
  • the rubber-modified aromatic vinyl resin and the polyphenylene ether resin blend in the above range can exhibit appropriate physical properties.
  • examples of the aromatic vinyl resin (A) include polystyrene (PS), high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer resin (ABS), acrylonitrile-styrene copolymer resin (SAN), acrylonitrile-styrene-acrylate copolymer resin (ASA), etc.
  • PS polystyrene
  • HIPS high impact polystyrene
  • ABS acrylonitrile-butadiene-styrene copolymer resin
  • SAN acrylonitrile-styrene copolymer resin
  • ASA acrylonitrile-styrene-acrylate copolymer resin
  • HIPS high impact polystyrene
  • HIPS high impact polystyrene
  • the method for producing the aromatic vinyl resin (A) is well known by those skilled in the art to which the present invention pertains, and is easy to purchase commercially.
  • the aromatic vinyl resin (A) may be polymerized by thermal polymerization without an initiator or polymerized in the presence of an initiator.
  • an initiator at least one of peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, cumene hydroperoxide, and azo initiators such as azobis isobutyronitrile may be selected and used.
  • peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, cumene hydroperoxide
  • azo initiators such as azobis isobutyronitrile
  • the aromatic vinyl resin (A) may be prepared using a bulk polymerization, suspension polymerization, emulsion polymerization or a mixture thereof, and among these polymerization methods, a bulk polymerization method may be preferably used.
  • the aromatic vinyl resin (A) may have a weight average molecular weight of about 50,000 to about 200,000 g / mol, for example, about 100,000 to about 200,000 g / mol, measured by gel permeation chromatography (GPC), but is not limited thereto. .
  • the aromatic vinyl resin (A) constitutes a base resin in the flame retardant thermoplastic resin composition of the present invention, and is about 10 to about 49 wt% of the base resin consisting of (A) + (B), for example, about 15 to about 45 weight percent, specifically about 20 to about 40 weight percent. If the content of the aromatic vinyl-based resin (A) is less than about 10% by weight of the base resin, there is a risk that the impact strength, fluidity, etc. may be lowered, and when it exceeds 49% by weight, long-term durability may be lowered. .
  • the polyphenylene ether resin (B) used in the present invention is for increasing flame retardancy and heat resistance.
  • a common polyphenylene ether resin used in a flame retardant thermoplastic resin composition can be used, for example, poly (2,6-dimethyl-1,4-phenylene) Ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1, 4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6 -Diphenyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether Copolymers, copo
  • poly (2,6-dimethyl-1,4-phenylene) ether or poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1, Copolymers of 4-phenylene) ether may be used, and specifically, poly (2,6-dimethyl-1,4-phenylene) ether may be used.
  • the degree of polymerization of the polyphenylene ether resin (B) is not particularly limited, but considering the thermal stability and workability of the resin composition, the intrinsic viscosity when measured in a chloroform solvent at 25 ° C. is about 0.2 to about 0.8 dl. / g may be used.
  • the polyphenylene ether-based resin (B) constitutes a base resin in the flame retardant thermoplastic resin composition of the present invention, and is about 51 to about 90% by weight of the base resin consisting of (A) + (B), for example, about 55 To about 85% by weight, specifically about 60 to about 80% by weight. If the content of the polyphenylene ether resin (B) is less than about 51% by weight of the basic resin, there is a fear that long-term durability, flame retardancy and heat resistance is lowered, and when it exceeds about 90% by weight, impact strength and the like There is a risk of deterioration.
  • Polyphosphonate (C) used in the present invention includes a unit represented by the following formula (1).
  • A is a single bond, C1-C5 alkylene group, C2-C5 alkylidene group, C5-C6 cycloalkylidene group, -S- or -SO 2-
  • R 1 is substituted or unsubstituted A substituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a C6-C20 substituted or unsubstituted aryloxy group
  • R 2 and R 3 are each independently substituted or unsubstituted C1-
  • a and b are each independently an integer of 0 to 4
  • n is 1 to 500, for example, an integer from 4 to 500.
  • the polyphosphonate (C) may include at least one polyphosphonate including a unit represented by the following formula (2).
  • a and B are each independently a single bond, an alkylene group of C1-C5, an alkylidene group of C2-C5, a cycloalkylidene group of C5-C6, -S- or -SO 2- , A and B are not the same as each other, R 1 and R 4 are each independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group or C6-C20 substituted or unsubstituted Is an aryloxy group, R 2 , R 3 , R 5 and R 6 are each independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6 -C12 is an aryl group or halogen atom, a, b, c and d are each independently an independently an
  • the sum of m and n may be 3 to 600. More excellent flame retardancy can be provided in the above range.
  • the polyphosphonates (C) are, for example, polyphosphonates in the form of homopolymers, polyphosphonates in the form of copolymers, respectively, or polyphosphonates in the form of homopolymers and polyphosphes in the form of copolymers. Phonates may be used together, but are not limited thereto.
  • the polyphosphonate (C) is prepared by reacting a diol including one or more of a diol represented by the following Chemical Formula 3 and a diol represented by the following Chemical Formula 4 and a phosphonic dichloride represented by the following Chemical Formula 5. can do.
  • A, B, R 2 , R 3 , R 5 , R 6 , a, b, c and d are as defined in Formula 2 above.
  • diol examples include 4,4'-dihydroxybiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl) -2- Methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5 -Dichloro-4-hydroxyphenyl) -propane and the like, and may be used alone or in combination of two or more thereof.
  • 4,4'-dihydroxybiphenyl alone or 4,4'-dihydroxybiphenyl and 2,2-bis- (4-hydroxyphenyl) -propane may be applied.
  • the ratio between diols may be appropriately adjusted according to the physical properties to be expressed.
  • the molar ratio of 4,4′-dihydroxybiphenyl and 2,2-bis- (4-hydroxyphenyl) -propane may be from about 5 to about 95: about 95 to about 5. More excellent flame retardancy can be provided in the above range.
  • each R is independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a C6-C20 substituted or unsubstituted aryloxy group.
  • the phosphonic dichloride represented by Formula 5 may use two kinds of compounds in which R is not the same, and R in Formula 5 corresponds to R 1 and R 4 in Formulas 1 and 2.
  • the phosphonic dichloride can be reacted dropwise with a solution containing a diol, a catalyst, and an end capping agent, and about 1 equivalent of the total diol can be reacted with about 1 equivalent of the phosphonic dichloride.
  • the reaction of the diol and phosphonic dichloride can be carried out by a conventional polymerization method under a Lewis acid catalyst.
  • a Lewis acid catalyst for the polymerization, for example, solution polymerization may be used.
  • the Lewis acid catalyst aluminum chloride, magnesium chloride, or the like may be used, but is not limited thereto.
  • the catalyst may be applied in an amount of about 0.01 to about 10 equivalents, such as about 0.01 to about 1 equivalents, specifically about 0.01 to about 0.1 equivalents, based on about 1 equivalent of the total diol.
  • the reaction may be carried out in the presence of an end capping agent.
  • an end capping agent C1-C5 alkyl group-containing phenol may be preferably applied.
  • phenol, 4-t-butylphenol, or 2-t-butylphenol may be used.
  • the end capping agent may be used in an amount of about 1 equivalent or less, such as about 0.01 to about 0.5 equivalents, based on about 1 equivalent of the total diol.
  • the reaction may be completed and then washed with an acid solution.
  • Phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, etc. may be applied as the acid solution, for example, phosphoric acid or hydrochloric acid.
  • the acid solution may be in a concentration of about 0.1 to about 10%, for example about 1 to about 5%. Thereafter, washing and filtration may give a polyphosphonate in the form of a white solid.
  • the polyphosphonate (C) may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 1,000 to about 50,000 g / mol. For example, about 1,000 to about 20,000 g / mol, specifically about 1,000 to about 10,000 g / mol. More excellent flame retardancy can be provided in the above range.
  • Mw weight average molecular weight measured by gel permeation chromatography
  • the polyphosphonate may have an acid value of about 0.005 to about 4 KOH mg / g, for example, about 0.01 to about 1 KOH mg / g. Decomposition of the thermoplastic resin does not occur in the above range.
  • the polyphosphonate may have a polydispersity index (PDI) of about 1 to about 3.5, for example about 1.5 to about 2.5. In the above range, physical properties such as flame retardancy and fluidity, impact strength, heat resistance, and the like may be excellent.
  • PDI polydispersity index
  • the polyphosphonate may have a glass transition temperature of about 75 to about 90 °C, for example about 78 to about 87 °C.
  • the processability of the resin composition may be excellent in the above range.
  • the polyphosphonate (C) may have an acid value change rate of about 0.005 to about 6, for example, about 0.01 to about 5, by the following Formula 1. In the above range, decomposition of the thermoplastic resin may not occur. In embodiments, the rate of change of the acid value of the polyphosphonate (C) may be about 0.05 to about 1.
  • ⁇ AV represents an acid value change rate
  • AVa represents an acid value after about 10 g of polyphosphonate is left at about 280 ° C. for about 1 hour
  • AVb represents an initial acid value of polyphosphonate.
  • the polyphosphonate (C) is about 0.1 to about 30 parts by weight, for example about 1 to about 25 parts by weight, specifically about 10 to about 100 parts by weight of the base resin consisting of (A) + (B) About 25 parts by weight. If the content of the polyphosphonate (C) is less than about 0.1 part by weight based on 100 parts by weight of the base resin, there is a risk that the flame resistance, heat resistance, and the like may be lowered. When the content of the polyphosphonate (C) exceeds about 30 parts by weight, fluidity, impact strength, Physical properties such as flame retardancy and heat resistance, and long-term durability may be lowered.
  • the flame-retardant thermoplastic resin composition according to the present invention has a tensile strength of about 610 to about 800 kgf / mm measured under the condition of about 5 mm / min after exposure to about 3,000 hours at a temperature of about 135 °C according to ASTM D-638 2 , for example, about 620 to about 750 kgf / mm 2 , the tensile strength change rate according to the following formula 2 is about 10% or less, the long-term durability is particularly excellent.
  • ⁇ TS (TS 0 -TS 3,000 ) ⁇ 100 / TS 0
  • Equation 1 TS 0 is tensile strength before high temperature exposure, and TS 3,000 is tensile strength after about 3,000 hours of exposure at high temperature.
  • the flame retardant thermoplastic resin composition of the present invention may further include additives such as flame retardant aids, lubricants, plasticizers, heat stabilizers, anti-drip agents, antioxidants, compatibilizers, light stabilizers, pigments, dyes, inorganic additives, and the like, if necessary. These can be used individually or in mixture of 2 or more types.
  • the additive may include about 0.1 to about 10 parts by weight based on 100 parts by weight of the base resin, but is not limited thereto.
  • the flame retardant thermoplastic resin composition may be prepared by pelletizing after melt-extrusion in an extruder after mixing the components and other additives at the same time.
  • the prepared pellets may be manufactured into various molded articles through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding.
  • Another aspect of the present invention provides a molded article formed from the thermoplastic resin composition.
  • the molded article is excellent in impact resistance, fluidity, flame retardancy, etc. can be widely applied to parts, exterior materials, automobile parts, sundries, structural materials of electrical and electronic products.
  • Poly (2,6-dimethyl-phenylether) (trade name: LXR-035C) from China Buluta Chemical was used.
  • the resin is in the form of a pale yellow powder having an average particle diameter of several tens of micrometers to several mm.
  • biphenyl polyphosphonate represented by Chemical Formula 1a manufactured by Cheil Industries was used as the flame retardant.
  • n 4.
  • polyphosphonate represented by Chemical Formula 2a manufactured by Cheil Industries was used as the flame retardant.
  • the pellets were prepared by extruding in a temperature range of 200 to 280 °C in a conventional twin screw extruder.
  • the prepared pellet was dried at 80 ° C. for 3 hours, and then injected into a mold at a temperature of 180 to 280 ° C. and a mold temperature of 40 to 80 ° C. in a 6 Oz injection machine to prepare a flame retardant specimen.
  • the physical properties of the prepared specimens were evaluated by the following method.
  • Izod impact strength (unit: kgf ⁇ cm / cm): Notch was evaluated by making an Izod specimen having a thickness of 1/8 "by the evaluation method specified in ASTM D256.
  • ⁇ TS (TS 0 -TS 3,000 ) ⁇ 100 / TS 0
  • Equation 1 TS 0 is tensile strength before high temperature exposure, and TS 3,000 is tensile strength after 3000 hours of exposure at high temperature.
  • VST Low heat resistance
  • Comparative Example 4 Even when the fonate (C-1) is applied, when the polyphenylene ether resin (B) content is low, it can be seen that long-term durability is lowered at 110 ° C or higher. Comparative Examples 5 and 6, in which the polyphosphonate (C) was not applied as the flame retardant, showed that the heat resistance and the flame retardancy were similar to those of the examples, but the long-term durability (long-term heat resistance) was significantly reduced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine thermoplastique ignifuge qui est caractérisée en ce qu'elle comprend : (A) environ 10 à 49 % en poids de résine à base de vinyle aromatique ; (B) 100 parties en poids de résine de base comprenant environ 51 à 90 % en poids de résine à base d'éther de polyphénylène ; et (C) environ 0,1 à 30 parties en poids de polyphosphonates comprenant des motifs exprimés par la formule chimique 1 selon la revendication 1. La résine thermoplastique ignifuge présente d'excellentes propriétés de résistance aux flammes, stabilité thermique et durabilité sur le long terme, et est respectueuse de l'environnement.
PCT/KR2013/006944 2012-12-17 2013-08-01 Composition de résine thermoplastique ignifuge, et articles moulés à partir de celle-ci WO2014098341A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020120147858A KR20140090290A (ko) 2012-12-17 2012-12-17 난연성 열가소성 수지 조성물 및 이로부터 형성된 성형품
KR10-2012-0147858 2012-12-17

Publications (1)

Publication Number Publication Date
WO2014098341A1 true WO2014098341A1 (fr) 2014-06-26

Family

ID=50978627

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2013/006944 WO2014098341A1 (fr) 2012-12-17 2013-08-01 Composition de résine thermoplastique ignifuge, et articles moulés à partir de celle-ci

Country Status (2)

Country Link
KR (1) KR20140090290A (fr)
WO (1) WO2014098341A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109867942A (zh) * 2019-01-30 2019-06-11 中国科学院宁波材料技术与工程研究所 一种阻燃微发泡聚苯醚复合材料的制备方法及其产品

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4350793A (en) * 1980-01-26 1982-09-21 Bayer Aktiengesellschaft Flame-retardant composition of polyphenylene ether, polystyrene resin and polyphosphonate
KR20020005237A (ko) * 2000-07-04 2002-01-17 안복현 난연성 열가소성 수지 조성물
KR20090072936A (ko) * 2007-12-28 2009-07-02 제일모직주식회사 난연성 열가소성 수지 조성물 및 그 제조방법
KR20100065901A (ko) * 2008-12-09 2010-06-17 제일모직주식회사 새로운 인계 화합물, 그 제조방법 및 이를 이용한 난연성 열가소성 수지 조성물
KR20120078586A (ko) * 2010-12-30 2012-07-10 제일모직주식회사 폴리포스포네이트, 그의 제조 방법 및 이를 포함하는 난연성 열가소성 수지 조성물

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4350793A (en) * 1980-01-26 1982-09-21 Bayer Aktiengesellschaft Flame-retardant composition of polyphenylene ether, polystyrene resin and polyphosphonate
KR20020005237A (ko) * 2000-07-04 2002-01-17 안복현 난연성 열가소성 수지 조성물
KR20090072936A (ko) * 2007-12-28 2009-07-02 제일모직주식회사 난연성 열가소성 수지 조성물 및 그 제조방법
KR20100065901A (ko) * 2008-12-09 2010-06-17 제일모직주식회사 새로운 인계 화합물, 그 제조방법 및 이를 이용한 난연성 열가소성 수지 조성물
KR20120078586A (ko) * 2010-12-30 2012-07-10 제일모직주식회사 폴리포스포네이트, 그의 제조 방법 및 이를 포함하는 난연성 열가소성 수지 조성물

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109867942A (zh) * 2019-01-30 2019-06-11 中国科学院宁波材料技术与工程研究所 一种阻燃微发泡聚苯醚复合材料的制备方法及其产品
CN109867942B (zh) * 2019-01-30 2021-06-29 中国科学院宁波材料技术与工程研究所 一种阻燃微发泡聚苯醚复合材料的制备方法及其产品

Also Published As

Publication number Publication date
KR20140090290A (ko) 2014-07-17

Similar Documents

Publication Publication Date Title
EP1651718B1 (fr) Composition de resine thermoplastique ignifuge
KR100778010B1 (ko) 비할로겐계 난연성 스티렌계 수지 조성물
KR20100004848A (ko) 난연 및 충격 개선제, 그 제조방법 및 이를 포함하는 열가소성 수지 조성물
EP2143754B1 (fr) Modificateur d'impact et ignifuge, procédé de préparation associé, et composition de résine thermoplastique le contenant
WO2019132584A1 (fr) Composition de résine thermoplastique et produit moulé formé à partir de celle-ci
WO2012086867A1 (fr) Composition de résine copolymère acrylique
WO2021020741A1 (fr) Composition de résine thermoplastique et article moulé formé à partir de celle-ci
WO2017057904A1 (fr) Composition de résine thermoplastique et produit moulé la comprenant
WO2018124790A2 (fr) Composition de résine de polyoléfine et article moulé l'utilisant
WO2010067926A1 (fr) Nouveaux composés de phosphate, leur procédé de préparation, et compositions de résine thermoplastique ignifuges utilisant de tels composés
KR20060041303A (ko) 난연성 고무강화 폴리스티렌 수지 조성물
WO2019132575A1 (fr) Composition de résine thermoplastique et article moulé fabriqué à partir de celle-ci
WO2018043930A1 (fr) Copolymère à base de vinyle aromatique, son procédé de préparation et composition de résine thermoplastique comprenant celui-ci
WO2017105007A1 (fr) Copolymère greffé à base de vinyle modifié par du caoutchouc et composition de résine thermoplastique le contenant
WO2014098341A1 (fr) Composition de résine thermoplastique ignifuge, et articles moulés à partir de celle-ci
WO2018117438A1 (fr) Composition de résine et produit moulé fabriqué à partir de cette composition de résine
WO2022211458A1 (fr) Composition de résine thermoplastique et article fabriqué à l'aide de celle-ci
WO2022005181A1 (fr) Composition de résine polyphosphonate et produit moulé fabriqué à partir de celle-ci
KR100850802B1 (ko) 비할로겐계 난연성 수지 조성물
WO2022025409A1 (fr) Composition de résine thermoplastique et article moulé formé à partir de celle-ci
WO2010074384A1 (fr) Nouveaux phosphonates et compositions de résine styrénique ignifugeantes les incluant
WO2013100295A1 (fr) Composition de résine thermoplastique ignifuge et produit moulé fabriqué à partir de celle-ci
WO2012091300A1 (fr) Composition de résine thermoplastique, et article moulé comprenant celle-ci
KR100815992B1 (ko) 난연성 열가소성 수지 조성물
WO2016052821A1 (fr) Composition de résine thermoplastique ignifuge et produit moulé comprenant cette dernière

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13864102

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13864102

Country of ref document: EP

Kind code of ref document: A1