WO2013100296A1 - Copolymère polyphosphonate, son procédé de préparation et composition de résine thermoplastique ignifugeante comprenant celui-ci - Google Patents

Copolymère polyphosphonate, son procédé de préparation et composition de résine thermoplastique ignifugeante comprenant celui-ci Download PDF

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WO2013100296A1
WO2013100296A1 PCT/KR2012/005505 KR2012005505W WO2013100296A1 WO 2013100296 A1 WO2013100296 A1 WO 2013100296A1 KR 2012005505 W KR2012005505 W KR 2012005505W WO 2013100296 A1 WO2013100296 A1 WO 2013100296A1
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copolymer
flame retardant
formula
thermoplastic resin
polyphosphonate
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PCT/KR2012/005505
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English (en)
Korean (ko)
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이선애
고창홍
이민수
안성희
장승우
홍상현
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제일모직 주식회사
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Priority claimed from KR1020110147851A external-priority patent/KR101469270B1/ko
Priority claimed from KR1020110147852A external-priority patent/KR101447275B1/ko
Application filed by 제일모직 주식회사 filed Critical 제일모직 주식회사
Publication of WO2013100296A1 publication Critical patent/WO2013100296A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

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  • the present invention relates to a polyphosphonate copolymer, a method for preparing the same, and a flame retardant thermoplastic resin composition comprising the same. More specifically, the present invention develops a polymerized phosphorus compound having a specific structure in which two or more repeating units are introduced into the main chain, and uses it as a flame retardant to provide environmentally friendly flame retardancy, as well as transparency, heat resistance, impact strength, appearance, and the like.
  • the present invention relates to a polyphosphonate copolymer, a method for producing the same, and a thermoplastic resin composition including the same, which have excellent physical properties and are environmentally friendly.
  • phosphorus flame retardant is phosphoric acid ester, and monomolecular phosphorus flame retardants such as triphenyl phosphate and resorcinol bisphenol phosphate are mainly used.
  • Such a monomolecular phosphorus flame retardant has a low molecular weight may be volatilized at a high molding temperature during plastic molding to reduce the appearance of the plastic, and when the product is used, the monomolecular phosphorus flame retardant may be extracted naturally to cause environmental pollution.
  • polyphosphonates which are polymerized phosphorus-based flame retardants.
  • the polyphosphonate in the polymer form is superior in flame retardancy, mechanical properties, heat resistance and transparency to the monomolecular phosphorus flame retardant, and is particularly suitable for application to resins requiring high heat resistance and high transparency such as polycarbonate resins.
  • the polyphosphonates developed so far are still not satisfactory in impact strength, heat resistance and appearance, and may deteriorate some of the thermoplastic resins due to their structural properties.
  • the compatibility with the thermoplastic resin is not sufficient and the dispersibility is not good.
  • An object of the present invention is to introduce a polyphosphonate copolymer and a method for producing the same, by introducing two or more repeating units into the main chain to improve compatibility with the resin and increase dispersibility of the phosphorus polymer compound in the resin. It is to provide.
  • Another object of the present invention is to provide a polyphosphonate copolymer having excellent balance of physical properties such as flame retardancy and appearance while being an environmentally friendly flame retardant.
  • Still another object of the present invention is to provide a polyphosphonate copolymer having excellent balance of physical properties such as flame retardancy, heat resistance, impact strength, and the like, and a method of manufacturing the same, by adjusting the content of the repeating unit.
  • Still another object of the present invention is to provide a flame retardant thermoplastic resin composition having excellent balance of physical properties such as transparency, heat resistance, impact strength, appearance, etc. by applying the polyphosphonate copolymer as a flame retardant.
  • Still another object of the present invention is to provide an environment-friendly flame retardant thermoplastic resin composition without problems such as gas generation or decomposition.
  • the polyphosphonate copolymer has a repeating unit represented by the following formula (1):
  • a and B are each independently a single bond, C1-C5 alkylene, C1-C5 alkylidene, C5-C6 cycloalkylidene, -S- or -SO 2- , A and B are not identical to each other, and R 5 and R 6 are each independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C6-C20 Is an aryloxy group, R 1 , R 2 , R 3 and R 4 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 and b are each independently an integer of 0 to 4, n and
  • the sum of n and m may be 3 to 600.
  • the polyphosphonate copolymer may have a weight average molecular weight of about 1,000 to about 50,000 g / mol.
  • the polyphosphonate copolymer may have a glass transition temperature of about 75 to about 90 °C.
  • the polyphosphonate copolymer may have an acid value change rate of about 0.005 to about 5 according to Formula 1:
  • ⁇ AV represents an acid value change rate
  • AVa represents an acid value after 10 g of the copolymer is left at 280 ° C. for 1 hour
  • AVb represents an initial acid value of the copolymer
  • the polyphosphonate copolymer can contain from about 1 to about 99 mole percent of the total copolymer.
  • Another aspect of the present invention relates to a method of preparing a polyphosphonate copolymer.
  • the method is characterized in that it comprises the step of reacting the diol represented by the formula (2-1), the diol represented by the formula (2-2) and the phosphonic dichloride represented by the formula (3):
  • a and B are each independently a single bond, alkylene of C1-C5, alkylidene of C1-C5, cycloalkylidene of C5-C6, -S- or- SO 2- , provided that A and B are not identical to each other, and R 1 , R 2 , R 3 and R 4 are each independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C3-C6 A cycloalkyl group, a substituted or unsubstituted C6-C12 aryl group or a halogen atom, and a and b each independently represent an integer of 0 to 4);
  • R is each 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 flame retardant thermoplastic resin composition may be a polyphosphonate copolymer having a repeating unit represented by Formula 1; And thermoplastic resins.
  • the flame retardant thermoplastic resin composition includes about 100 parts by weight of the base resin including the thermoplastic resin, and about 0.1 to about 30 parts by weight of the polyphosphonate copolymer having a repeating unit represented by Chemical Formula 1.
  • the base resin may include a polycarbonate resin.
  • the base resin may include about 30 to about 100 wt% of a polycarbonate resin and about 0 to about 70 wt% of a rubber-modified aromatic vinyl polymer.
  • the rubber modified aromatic vinyl polymer may include about 10 to about 100% by weight of the graft copolymer resin and about 0 to about 90% by weight of the copolymer resin.
  • the graft copolymer resin is about 5 to about 65 weight percent rubbery polymer, about 34 to about 94 weight percent aromatic vinyl monomer and about 1 to about 30 weight percent monomer copolymerizable with the aromatic vinyl monomer Graft polymerized copolymers.
  • the copolymer resin may be a copolymer of about 60 to about 90 wt% of an aromatic vinyl monomer and about 10 to about 40 wt% of a monomer copolymerizable with the aromatic vinyl monomer.
  • the flame retardant thermoplastic resin composition further comprises at least one additive selected from the group consisting of flame retardant aids, lubricants, plasticizers, heat stabilizers, anti-drip agents, antioxidants, compatibilizers, light stabilizers, pigments, dyes, inorganic additives can do.
  • 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 introduces two or more repeating units into the main chain to improve compatibility with the resin, increase the dispersibility of the phosphorus polymer compound in the resin, and is an environmentally friendly flame retardant and excellent in balance of physical properties such as flame retardancy and appearance. And, by adjusting the content of the repeating unit, it has the effect of providing a polyphosphonate copolymer excellent in the balance of physical properties such as flame retardancy, heat resistance, impact strength and the like for a thermoplastic resin and a method for producing the same.
  • the polyphosphonate copolymer as a flame retardant, not only flame retardancy, but also excellent balance of physical properties such as transparency, heat resistance, impact strength, appearance, and the like, there is no problem of gas generation or decomposition, and an eco-friendly flame retardant thermoplastic resin composition. Provided has the effect of the invention.
  • the polyphosphonate copolymer according to the present invention has a repeating unit represented by the following formula (1).
  • a and B are each independently a single bond, C1-C5 (alkyl having 1 to 5 carbon atoms), C1-C5 alkylidene, C5-C6 cycloalkylidene, -S- or -SO 2
  • R 5 and R 6 are each independently a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C6-C20 aryl group or C6-C20
  • R 1 , R 2 , R 3 and R 4 are each independently a substituted or unsubstituted C 1 -C 6 alkyl group, a substituted or unsubstituted C 3 -C 6 cycloalkyl group, a substituted or It is an unsubstituted C6-C12 aryl group or a halogen atom
  • a and b are each independently an unsubstituted C6-C12
  • the sum of n and m may be 3 to 600, preferably 5 to 550.
  • the post-treatment process is easy in the above range, there is an advantage that the dispersion is well in the resin.
  • the polyphosphonate copolymer may have a weight average molecular weight of about 1,000 to about 50,000 g / mol, preferably about 1,100 to about 20,000 g / mol, more preferably about 1,200 to about 10,000 g / mol. More excellent flame retardancy can be provided in the above range.
  • the polyphosphonate copolymer may have an acid value of about 0.005 to about 4 KOH mg / g, preferably about 0.01 to about 3 KOH mg / g. Decomposition of the thermoplastic resin does not occur in the above range.
  • the polyphosphonate copolymer may have a polydispersity index (PDI) of about 1.5 to about 3.5, preferably about 1.8 to about 3.4. It is possible to impart excellent flame retardancy in the above range.
  • PDI polydispersity index
  • the polyphosphonate copolymer may have a glass transition temperature of about 75 to about 90 °C, preferably about 78 to about 87 °C. It is excellent in workability with resin excellent in the said range.
  • the polyphosphonate copolymer may have an acid value change rate of about 0.005 to about 5, preferably about 0.01 to about 4, based on Equation 1 below. Decomposition of the thermoplastic resin does not occur in the above range.
  • ⁇ AV represents an acid value change rate
  • AVa represents an acid value after 10 g of the copolymer is left at 280 ° C. for 1 hour
  • AVb represents an initial acid value of the copolymer
  • the polyphosphonate copolymer may contain from about 1 to about 99 mol%, preferably from about 1 to about 50 mol%, of the biphenyl units in the total copolymer. It is possible to impart excellent flame retardancy in the above range.
  • the polyphosphonate copolymer does not cause decomposition of the thermoplastic resin to be mixed and may be preferably applied as a flame retardant.
  • Another aspect of the present invention relates to a method of preparing a polyphosphonate copolymer.
  • Method for producing a polyphosphonate copolymer according to the present invention is to react the diol represented by the formula (2-1), the diol represented by the formula (2-2), and the phosphonic dichloride represented by the formula (3) Steps.
  • A, B, R 1 , R 2 , R 3 , R 4 , a and b are the same as defined in Formula 1 above, and in Formula 3, R is substituted or unsubstituted A 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 3 may use two kinds of compounds in which R is not the same, and R in Formula 3 corresponds to R 5 and R 6 in Formula 1.
  • 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 can be exemplified, and two or more thereof can be selected and used.
  • 4,4'-dihydroxybiphenyl and 2,2-bis- (4-hydroxyphenyl) -propane can be used.
  • the ratio between the two diols is not particularly limited, but may be appropriately adjusted according to the physical properties to be expressed. For example, about 40 to about 60 mole%: about 60 to about 40 mole%, preferably 4,4'-dihydroxybiphenyl and 2,2-bis- (4-hydroxyphenyl) -propane About 45 to about 55 mole%: about 55 to about 45 mole%. It is possible to obtain the optimum flame retardancy and impact strength in the above range.
  • the polyphosphonate copolymer is prepared by polymerizing the two diols (Formula 2-1 and 2-2) and the phosphonic dichloride (Formula 3) by a conventional polymerization method in the presence of a catalyst.
  • the reaction may be performed by dropwise addition of phosphonic dichloride to a solution in which the two diols, the catalyst, and the end capping agent are mixed.
  • a conventional polymerization catalyst may be used.
  • a Lewis acid catalyst may be used, and the polymerization may be preferably solution polymerization.
  • the Lewis acid catalyst may be used, such as aluminum chloride, magnesium chloride, but is not limited thereto.
  • the phosphonic dichloride can be reacted in about 1 equivalent, and the catalyst is from about 0.01 to about 10 equivalents, preferably about 0.02, relative to 1 equivalent of total diol To about 1 equivalent, more preferably about 0.03 to about 0.1 equivalent.
  • C1-C5 alkyl group-containing phenol may be used.
  • 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, preferably about 0.01 to about 0.5 equivalents, based on 1 equivalent of the total diol.
  • the method for producing a polyphosphonate copolymer according to the present invention may further include washing and filtering the polymerization product after the polymerization reaction is completed.
  • the washing may be by water such as an acid solution and distilled water
  • the acid solution may be an aqueous solution of phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, and the like, and preferably an aqueous solution of phosphoric acid or hydrochloric acid may be used.
  • the concentration of the acid solution may be, for example, about 0.1 to about 10%, preferably about 1 to about 5%.
  • the polyphosphonate copolymer prepared by the method of the present invention is linear and has flame retardancy, heat resistance and transparency, it can be preferably applied to resins requiring high heat resistance, high transparency and high impact.
  • the flame retardant thermoplastic resin composition according to the present invention includes a polyphosphonate copolymer having a repeating unit represented by Chemical Formula 1, and a thermoplastic resin.
  • thermoplastic resin examples include polycarbonate resin, styrene resin, polyamide, polyester, polyvinyl chloride, styrene copolymer resin, (meth) acrylic resin, polyphenylene ether resin, and the like. It is not limited to this.
  • the flame-retardant thermoplastic resin composition is about 0.1 to about 30 parts by weight, preferably 100 parts by weight of a base resin containing the thermoplastic resin, and a polyphosphonate copolymer having a repeating unit represented by the formula (1) About 1 to about 25 parts by weight, more preferably about 3 to about 20 parts by weight. It is excellent in the physical properties such as flame retardancy and fluidity, impact strength, heat resistance in the above range.
  • the base resin may include polycarbonate resin, and preferably, about 30 to about 100 wt% of (A) polycarbonate resin and (B) about 0 to about 70 of rubber-modified aromatic vinyl polymer It may be to include a weight percent.
  • the polycarbonate resin (A) used in the present invention may be a conventional thermoplastic polycarbonate resin, for example, diols (diphenols) represented by the formula (2-1), phosgene, carbonate ester or a combination thereof Can be prepared by reaction.
  • diphenols used in the production of the polycarbonate resin include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane ("bisphenol-A "), 2,4-bis (4-hydroxyphenyl) -2-methylbutane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2- Bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxy Phenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, bis (4 -Hydroxyphenyl) ether, etc.
  • 2,2-bis (4-hydroxyphenyl) propane 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) cyclo Hexane can be used, more preferably 2,2-bis (4-hydroxyphenyl) propane.
  • the polycarbonate resin (A) may be a copolymer in which two or more kinds of diphenols represented by the formula (2-1) are combined to form a repeating unit of the polycarbonate resin, a mixture thereof, and the like.
  • the polycarbonate resin (A) may be in the form of linear polycarbonate, branched polycarbonate, polyester carbonate copolymer resin.
  • Examples of the linear polycarbonate may include bisphenol-A-based polycarbonate, and the branched polycarbonate may be prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride and trimellitic acid with diphenols and carbonates. It can illustrate that.
  • the polyfunctional aromatic compound may be included in an amount of about 0.05 to about 2 mol% based on the total amount of the branched polycarbonate.
  • As said polyester carbonate copolymer resin what was manufactured by making bifunctional carboxylic acid react with diphenols and a carbonate can be illustrated.
  • As the carbonate a diaryl carbonate such as diphenyl carbonate, ethylene carbonate, or the like may be used.
  • the polycarbonate resin (A) may have a weight average molecular weight of about 15,000 to about 25,000 g / mol, for example, about 16,000 to about 23,000 g / mol. There is a high flame retardancy in the above range.
  • the polycarbonate resin (A) may have a melt flow index (MFR, 300 ° C., 1.2 kg) of about 45 to about 80 g / 10 min.
  • the content of the polycarbonate resin (A) is about 30 to about 100% by weight, preferably about 40 to about 90% by weight, more preferably about 50 to about 80% by weight, most preferably based on the total base resin Is about 60 to about 77 weight percent. Within this range, excellent balance of physical properties of flame retardancy and mechanical properties can be obtained.
  • the rubber-modified aromatic vinyl polymer (B) used in the present invention is a polymer in which a rubbery polymer is dispersed and present in a particle form in a matrix (continuous phase) made of an aromatic vinyl polymer.
  • Non-limiting examples of the rubber-modified aromatic vinyl copolymer resin (B) include acrylonitrile-butadiene-styrene copolymer resin (ABS resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer resin (AES resin), Acrylonitrile-acryl rubber-styrene copolymer resin (AAS resin) etc. can be illustrated.
  • the rubber-modified aromatic vinyl polymer (B) may be obtained by polymerizing a rubbery polymer and an aromatic vinyl monomer. If necessary, the rubber-modified aromatic vinyl polymer (B) may be further polymerized by further adding a monomer copolymerizable with the aromatic vinyl monomer. .
  • the rubber-modified aromatic vinyl polymer (B) may be prepared by a known polymerization method such as emulsion polymerization, suspension polymerization, or bulk polymerization, for example, (B1) graft copolymer resin alone, or (B1) graft. It can be produced using a copolymer resin and (B2) copolymer resin.
  • (B1) and / or (B2) can be produced by a bulk polymerization method (one-step reaction step) in which the resin is mixed and extruded, and preferably mixed in consideration of their compatibility.
  • the graft copolymer resin (B1) used in the present invention can be obtained by graft copolymerizing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer to a rubbery polymer, and, if necessary, provide processability and heat resistance. Monomers may be further included.
  • the rubbery polymer examples include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), saturated rubbers hydrogenated to the diene rubber, isoprene rubber, and polybutylacrylic acid.
  • diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), saturated rubbers hydrogenated to the diene rubber, isoprene rubber, and polybutylacrylic acid.
  • Acrylic rubber, ethylene-propylene-diene monomer terpolymer (EPDM), mixtures thereof, and the like can be used.
  • EPDM ethylene-propylene-diene monomer terpolymer
  • diene rubber more preferably butadiene rubber can be used.
  • the content of the rubbery polymer may be about 5 to about 65% by weight, preferably about 10 to about 60% by weight, more preferably about 20 to about 50% by weight, based on the total weight of the graft copolymer resin (B1). . 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 size (Z-average) of the rubbery polymer (rubber particles) may be about 0.1 to about 6 ⁇ m, preferably about 0.15 to about 4 ⁇ m, and more preferably about 0.25 to about 3.5 ⁇ m. Excellent impact strength and appearance in the above range.
  • the aromatic vinyl monomer may be graft copolymerized to the rubbery copolymer, for example, styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, para t-butylstyrene, ethyl styrene, vinyl Xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, and the like may be used, and preferably, styrene may be used, but is not limited thereto.
  • the content of the aromatic vinyl monomer is about 34 to about 94% by weight, preferably about 36 to about 80% by weight, more preferably about 40 to about 60% by weight, based on the total weight of the graft copolymer resin (B1). Can be. It is possible to obtain a good balance of physical properties of the impact strength and mechanical properties in the above range.
  • the monomer copolymerizable with the aromatic vinyl monomer for example, vinyl cyanide compounds such as acrylonitrile, unsaturated nitrile compounds such as ethacrylonitrile, methacrylonitrile, and the like can be used. It can mix and use the above.
  • the content of the monomer copolymerizable with the aromatic vinyl monomer is about 1 to about 30% by weight, preferably about 4 to about 29% by weight, more preferably about 10 to about 10% by weight of the total weight of the graft copolymer resin (B1). 28 weight percent. It is possible to obtain a good balance of physical properties of the impact strength and mechanical properties in the above range.
  • Examples of the monomer for imparting processability and heat resistance may include, but are not limited to, acrylic acid, methacrylic acid, maleic anhydride, N-substituted maleimide, and the like.
  • the content of the monomer for imparting processability and heat resistance may be about 0 to about 15 wt%, preferably about 0.1 to about 10 wt% of the total weight of the graft copolymer resin (B1). In the above range, workability and heat resistance can be imparted without deterioration of other physical properties.
  • the copolymer resin (B2) used in the present invention may be prepared using a monomer mixture except for rubber (rubber polymer) among the components of the graft copolymer resin (B1), and the ratio of the monomer may vary depending on compatibility and the like. Can be.
  • the copolymer resin (B2) may be obtained by copolymerizing an aromatic vinyl monomer and a monomer copolymerizable with an aromatic vinyl monomer, and may further include a monomer that imparts workability and heat resistance, if necessary.
  • the content of the aromatic vinyl monomer may be about 60 to about 90% by weight, preferably about 70 to about 80% by weight of the total weight of the copolymer resin (B2). It is possible to obtain a good balance of physical properties of the impact strength and mechanical properties in the above range.
  • the content of the monomer copolymerizable with the aromatic vinyl monomer may be about 10 wt% to about 40 wt%, preferably about 20 wt% to about 30 wt% of the total weight of the copolymer resin (B2). It is possible to obtain excellent balance of physical properties of impact strength and mechanical properties in the above range.
  • the content of the monomer for imparting the processability and heat resistance may be about 0 to about 30% by weight, preferably about 0.1 to about 20% by weight of the total weight of the copolymer resin (B2). In the above range, workability and heat resistance can be imparted without deterioration of other physical properties.
  • the content of the graft copolymer resin (B1) is about 10 to about 100% by weight, preferably about 15 to about 90% by weight
  • the content of the copolymer resin (B2) is about 0 to about 90% by weight, preferably about 10 to about 85% by weight. It is possible to obtain excellent balance of physical properties of impact strength and mechanical properties in the above range.
  • the content of the graft copolymer resin (B1) is about 55 to about 90% by weight, preferably about 60 to about 80% by weight, and the content of the copolymer resin (B2) is about 10 to About 45% by weight, preferably about 20 to about 40% by weight. In the above range, in particular, there is an advantage of excellent impact strength.
  • the content of the graft copolymer resin (B1) is about 15 to about 50% by weight, preferably about 20 to about 40% by weight, and the content of the copolymer resin (B2) is about 50 to About 85% by weight, preferably about 60 to about 80% by weight. In the above range, in particular, there is an advantage of excellent rigidity and chemical resistance.
  • the content of the rubber-modified aromatic vinyl copolymer resin (B) used in the present invention is about 0 to about 70% by weight, preferably about 10 to about 60, based on the total base resin ((A) + (B)). Weight percent, more preferably about 20 to about 50 weight percent, and most preferably about 23 to about 40 weight percent. Within this range, excellent balance of physical properties of flame retardancy and mechanical properties can be obtained.
  • thermoplastic resin composition according to the present invention may further include additives such as flame retardant aids, lubricants, plasticizers, heat stabilizers, antidrip agents, antioxidants, compatibilizers, light stabilizers, pigments, dyes, inorganic additives, and the like, as necessary. These can be used individually or in mixture of 2 or more types.
  • the thermoplastic resin composition may be melt-extruded in an extruder after mixing the respective components to form a pellet.
  • the pellet may be manufactured into various molded articles through various molding methods such as injection molding, extrusion molding, vacuum molding, casting molding, and the like.
  • the molded article is formed from the flame retardant 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.
  • Weight average molecular weight (unit: g / mol): After dissolving 0.01 g of the sample in 2 mL of MC using GPC, dilute about 10 mL of THF, and filter the dissolved sample using a 0.45 ⁇ m syringe filter to gel permeation. The weight average molecular weight was measured by chromatography (GPC).
  • Heat loss It was measured using Thermogravimetric data TGA (device name: METTLER TOLEDO).
  • ⁇ AV represents an acid value change rate
  • AVa represents an acid value after 10 g of the copolymer is left at 280 ° C. for 1 hour
  • AVb represents an initial acid value of the copolymer
  • a flame retardant was added to 100 parts by weight of polycarbonate resin (PANLITE L-1250W) according to Table 2, and the specimen was prepared by extrusion at a temperature range of 200 to 280 ° C. in a conventional twin screw extruder.
  • the prepared specimens were evaluated for physical properties according to the following method. The evaluation results are shown in Table 2.
  • VST Heat resistance
  • Izod impact strength A notch was made in an Izod specimen according to ASTM D-256 (1/8 ", notched) and evaluated at room temperature (unit: kgfcm / cm).
  • Flame retardancy was measured according to UL94 V flame retardancy regulations for each of 2 mm, 1.5 mm and 1/8 "thick specimens.
  • Comparative Examples 5 to 10 to which the monomolecular flame retardant is applied are inferior in impact and heat resistance to Comparative Examples 2 to 4 to which the polyphosphonate (Comparative Example 1) is applied.
  • thermoplastic resin composition of Examples 2 to 4 to which the polyphosphonate copolymer (Example 1) according to the present invention is applied is Comparative Examples 2 to 4 to which a polyphosphonate (Comparative Example 1) containing only bisphenol units is applied. It can be confirmed that the thermoplastic resin composition having more excellent impact strength and transparency.
  • Copolymer latex 50 parts by weight of butadiene rubber latex, 36 parts by weight of styrene polymerized monomer, 14 parts by weight of acrylonitrile, and 150 parts by weight of deionized water in a mixture of 1.0 parts by weight of potassium oleate and cumenehydr 0.4 parts by weight of loper oxide, 0.2 parts by weight of mercaptan-based chain transfer agent, 0.4 parts by weight of glucose, 0.01 parts by weight of iron sulfate hydrate, and 0.3 parts by weight of pyrophosphate sodium salt were added to maintain 75 ° C for 5 hours to complete the reaction.
  • Copolymer latex was prepared.
  • 0.4 parts by weight of sulfuric acid was added to the resulting resin composition solids and solidified to prepare a graft copolymer resin (G-ABS) in powder form.
  • the weight average molecular weight of the prepared polymer (C-2) was 3,400 g / mol, PDI was 1.9, the acid value was 0.01 KOH mg / g.
  • the acid value change rate according to the above formula 1 was 0.69.
  • C-3 Phosphate ester flame retardant CR-741S (brand name) of Daihachi, Japan was used.
  • the components were added according to the following Tables 3 and 4, and extruded in a conventional twin screw extruder at a temperature range of 200 to 280 °C to prepare a pellet. After drying the pellet at 70 °C for 2 hours, the specimen was prepared using a 10 oz injection machine at a molding temperature of 180 to 280 °C, a mold temperature of 40 to 80 °C. The prepared specimens were evaluated for physical properties according to the following method. The evaluation results are shown in Table 3.
  • Flame retardant Flame retardancy was measured according to UL94 VB flame retardant regulations for 1/8 "thick specimens.
  • VST Heat resistance
  • Izod impact strength A notch was made in an Izod specimen according to ASTM D-256 (1/8 ", notched) and evaluated at room temperature (unit: kgf ⁇ cm / cm).
  • Comparative Examples 14 to 19 to which the monomolecular flame retardant is applied are inferior in impact strength and heat resistance compared to Comparative Examples 11 to 13 to which the polyphosphonate is applied.
  • thermoplastic resin compositions of Examples 5 to 7 to which the polyphosphonate copolymer (C-1) according to the present invention is applied are comparative examples 10 to 12 to which polyphosphonates (C-2) containing only bisphenol units are applied. And compared with the thermoplastic resin composition of 19, it can be confirmed that it has more excellent impact strength.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un copolymère polyphosphonate comprenant un motif récurrent spécifique, et une composition de résine thermoplastique ignifugeante comprenant le copolymère. Selon la présente invention, un composé phosphoré polymérisé ayant une structure spécifique, dans laquelle deux types de motifs récurrents sont introduits dans une chaîne principale, est utilisé comme agent ignifugeant, et ainsi, la présente invention concerne une composition de résine thermoplastique ignifugeante qui est respectueuse de l'environnement et qui présente un bon équilibre en termes de propriétés physiques telles que la transparence, la résistance thermique, la résistance aux chocs, l'apparence ainsi que l'ininflammabilité.
PCT/KR2012/005505 2011-12-30 2012-07-11 Copolymère polyphosphonate, son procédé de préparation et composition de résine thermoplastique ignifugeante comprenant celui-ci WO2013100296A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR1020110147851A KR101469270B1 (ko) 2011-12-30 2011-12-30 폴리포스포네이트 공중합체, 그 제조 방법 및 이를 포함하는 난연성 열가소성 수지 조성물
KR1020110147852A KR101447275B1 (ko) 2011-12-30 2011-12-30 난연성 열가소성 수지 조성물
KR10-2011-0147851 2011-12-30
KR10-2011-0147852 2011-12-30

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004217784A (ja) * 2003-01-15 2004-08-05 Teijin Chem Ltd 難燃性熱可塑性樹脂組成物
US20040167284A1 (en) * 2003-02-24 2004-08-26 Michael Vinciguerra Branched polyphosphonates that exhibit an advantageous combination of properties, and methods related thereto
JP2010006965A (ja) * 2008-06-27 2010-01-14 Toray Ind Inc 難燃性熱可塑性ポリエステル樹脂組成物
KR20110079480A (ko) * 2009-12-30 2011-07-07 제일모직주식회사 중합형 인계 화합물을 포함하는 열가소성 수지 조성물, 상기 조성물로부터 성형된 플라스틱 성형품 및 중합형 인계 화합물의 제조방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004217784A (ja) * 2003-01-15 2004-08-05 Teijin Chem Ltd 難燃性熱可塑性樹脂組成物
US20040167284A1 (en) * 2003-02-24 2004-08-26 Michael Vinciguerra Branched polyphosphonates that exhibit an advantageous combination of properties, and methods related thereto
JP2010006965A (ja) * 2008-06-27 2010-01-14 Toray Ind Inc 難燃性熱可塑性ポリエステル樹脂組成物
KR20110079480A (ko) * 2009-12-30 2011-07-07 제일모직주식회사 중합형 인계 화합물을 포함하는 열가소성 수지 조성물, 상기 조성물로부터 성형된 플라스틱 성형품 및 중합형 인계 화합물의 제조방법

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