WO2013100296A1 - Polyphosphonate copolymer, method for preparing same and flame retardant thermoplastic resin composition including same - Google Patents

Abstract

The present invention relates to a polyphosphonate copolymer having a specific recurring unit, and to a flame retardant thermoplastic resin composition comprising the copolymer. According to the present invention, a polymerized phosphor-based compound having a specific structure in which at least two kinds of recurring units are introduced into a main chain is used as a flame retardant, and thus, the present invention provides a flame retardant thermoplastic resin composition which is eco-friendly and has a good balance of physical properties such as transparency, heat resistance, impact strength, and appearance as well as flame retardance.

Description

Polyphosphonate copolymer, preparation method thereof and flame retardant thermoplastic resin composition comprising same

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.

With the growing interest in environmental issues, regulations on existing halogen flame retardants are gradually tightening in each country. Therefore, research on non-halogen flame retardants to dash the halogen-based flame retardant has been made, and in particular, research on phosphorus-based flame retardants has been intensively made. The most widely used phosphorus flame retardant is phosphoric acid ester, and monomolecular phosphorus flame retardants such as triphenyl phosphate and resorcinol bisphenol phosphate are mainly used. However, 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. . Accordingly, there is an increasing interest in 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.

However, 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. In addition, there is a disadvantage that the compatibility with the thermoplastic resin is not sufficient and the dispersibility is not good.

SUMMARY OF THE INVENTION 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 above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the invention relates to polyphosphonate copolymers. The polyphosphonate copolymer has a repeating unit represented by the following formula (1):

[Formula 1]

(In 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 m are an integer of 1 to 500).

In embodiments, the sum of n and m may be 3 to 600.

In embodiments, the polyphosphonate copolymer may have a weight average molecular weight of about 1,000 to about 50,000 g / mol.

In embodiments, the polyphosphonate copolymer may have a glass transition temperature of about 75 to about 90 ℃.

In embodiments, the polyphosphonate copolymer may have an acid value change rate of about 0.005 to about 5 according to Formula 1:

[Equation 1]

(In Formula 1, ΔAV 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, and AVb represents an initial acid value of the copolymer).

In an embodiment, 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):

[Formula 2-1]

[Formula 2-2]

(In Formula 2-1 and Formula 2-2, 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);

[Formula 3]

(In Formula 3, 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.).

Another aspect of the invention relates to a flame retardant thermoplastic resin composition comprising the polyphosphonate copolymer. The flame retardant thermoplastic resin composition may be a polyphosphonate copolymer having a repeating unit represented by Formula 1; And thermoplastic resins.

In an embodiment, 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.

In an embodiment, the base resin may include a polycarbonate resin.

In some embodiments, 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.

In embodiments, 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.

In embodiments, 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.

In an embodiment, 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.

In embodiments, 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. In addition, by applying 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.

1 is an NMR spectrum of a polymer prepared in Example 1. FIG.

Hereinafter, the present invention will be described in detail.

The polyphosphonate copolymer according to the present invention has a repeating unit represented by the following formula (1).

[Formula 1]

In 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 Provided that 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 C6-C20 A substituted or unsubstituted aryloxy group, 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 integer of 0-4, n and m are an integer of 1-500.

In embodiments, 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.

The polyphosphonate copolymer may have a glass transition temperature of about 75 to about 90 ℃, preferably about 78 to about 87 ℃. 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.

[Equation 1]

In Formula 1, ΔAV 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, and 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.

[Formula 2-1]

[Formula 2-2]

[Formula 3]

In Formulas 2-1 and 2-2, 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. Here, 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.

Specific examples of the diol 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. Preferably 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. For example, 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.

As the catalyst, a conventional polymerization catalyst may be used. For example, a Lewis acid catalyst may be used, and the polymerization may be preferably solution polymerization. In addition, the Lewis acid catalyst may be used, such as aluminum chloride, magnesium chloride, but is not limited thereto.

In an embodiment, with respect to 1 equivalent of total diol, 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.

As the end capping agent, C1-C5 alkyl group-containing phenol may be used. For example, 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, and 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%.

Through the washing and filtration steps, a polyphosphonate copolymer in the form of a white solid can be obtained.

Since 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.

Another aspect of the invention relates to a flame retardant thermoplastic resin composition comprising the polyphosphonate copolymer. 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.

Examples of the thermoplastic resin may 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.

In embodiments, 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.

In some embodiments, 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.

(A) polycarbonate resin

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.

Specific examples of the 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. can be illustrated. Preferably 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. In addition, 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.

In addition, 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.

(B) rubber modified aromatic vinyl polymer

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.

For example, 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. Preferably, (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.

(B1) graft copolymer resin

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.

Examples of the rubbery polymer 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. Acrylic rubber, ethylene-propylene-diene monomer terpolymer (EPDM), mixtures thereof, and the like can be used. Preferably, 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 μm, preferably about 0.15 to about 4 μm, and more preferably about 0.25 to about 3.5 μm. Excellent impact strength and appearance in the above range.

The aromatic vinyl monomer may be graft copolymerized to the rubbery copolymer, for example, styrene, α-methylstyrene, β-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.

As 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.

(B2) copolymer resin

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. For example, 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.

In the copolymer resin (B2), 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.

In addition, 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.

In the rubber-modified aromatic vinyl copolymer resin (B) used in the present invention, 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.

In one embodiment, 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.

In another embodiment, 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.

The 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.

Another aspect of the invention relates to a molded article. 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.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, the following examples are provided to help the understanding of the present invention, and the scope of the present invention is not limited to the following examples. Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

EXAMPLE

Example 1: Preparation of Polyphosphonate Copolymer

As diols, 7.18 kg (38.54 mol) of biphenol (manufactured by Songwon Industries) and 8.80 kg (38.54 mol) of 2,2-bis- (4-hydroxyphenyl) -propane (manufactured by Kumho), 4 5.79 kg (38.54 mol) of -t-butylphenol (manufactured by TCI) and 0.51 kg of aluminum chloride were added to 100 kg of chlorobenzene (manufactured by Samjeon Chemical), and then dissolved at 145 ° C. 15.45 kg (77.08 mol) of phenylphosphonic acid dichloride (manufactured by IDB) was slowly added dropwise to this mixed solution, followed by stirring for 8 hours. After washing with aqueous hydrochloric acid solution and distilled water, this process was repeated twice, and then the organic layer was collected, dehydrated, and precipitated in hexane (manufactured by Samjeon Chemical) to obtain a polyphosphonate copolymer as a white solid. The NMR (Briker AVANCE III & Ultrashield Magnet, 300 MHz) data of the prepared copolymer are shown in FIG. 1. In addition, the physical properties of the prepared polyphosphonate copolymers were evaluated according to the following method. The number average molecular weight was 2,100 g / mol, the weight average molecular weight was 4,400 g / mol, the PDI was 2.1, and the glass transition temperature was 82 ° C.

Comparative Example 1: Preparation of Polyphosphonate Copolymer

As a diol, the same procedure as in Production Example 1 was conducted except that 77.08 mol of 2,2-bis- (4-hydroxyphenyl) -propane (manufactured by Kumho) was used instead of the biphenol. Was performed.

Property evaluation method

(1) 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 μm syringe filter to gel permeation. The weight average molecular weight was measured by chromatography (GPC).

(2) Acid value (unit: KOH mg / g): Dissolve 1-20 g of sample in dimethyl sulfoxide (50 ml), add 0.03-0.2 ml of BTB (bromothmol blue) solution, and titrate with 0.1 N NaOH solution. Measured.

Acid value = ((0.1N-NaOH solution consumption ml) * (0.1N-NaOH solution Factor) * 5.61) / sample amount (g)

(3) Heat loss (Heat loss): It was measured using Thermogravimetric data TGA (device name: METTLER TOLEDO).

(4) Hydrolysis resistance: After stirring 75g of the sample and 25g of distilled water under the conditions of 93 ° C. × 48h, the acid values before and after were compared.

(5) Thermal resistance: After 100 g of the sample was left at 280 ° C. for 1 hour, the acid value was compared before and after leaving, and the acid value change rate was calculated according to the following Formula 1.

[Equation 1]

(In Formula 1, ΔAV 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, and AVb represents an initial acid value of the copolymer).

Table 1

		Example 1	Comparative Example 1	C1	C2
Acid value increment		0.90	0.91	0.91	2.20
Heat resistance	thermal resistance (△ AV)	0.64	0.69	0.89	1.19
Heat loss	200 ℃	0.2	0.4	1.0	0.4
	250 ℃	0.6	0.7	1.6	0.7
	300 ℃	1.9	2.0	4.1	4.2
	350 ℃	3.9	4.2	17.6	19.5
Initial Acid Value (KOH mg / g)		0.01	0.01	0.01	0.01

* (C1) monomolecular flame retardant 1: CR-741S (brand name) of Daihachi, Japan was used.

* (C2) monomolecular flame retardant 2: PX-200 (brand name) by Daihachi, Japan was used.

Examples 2-4 and Comparative Examples 3-10: Preparation of Thermoplastic Resin Composition

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.

(1) Heat resistance (VST): It measured on 5 kg and 50 degreeC / HR conditions by ISO R 306 (unit: degreeC).

(2) 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).

(3) Flame retardancy: Flame retardancy was measured according to UL94 V flame retardancy regulations for each of 2 mm, 1.5 mm and 1/8 "thick specimens.

(4) Transparency and Haze: Total light transmittance (TT) and Haze were measured with the Haze meter (manufacturer: NIPPON DENSOHKU KOGYO).

(5) Appearance: Pinhole and silver were measured by 6 inch X 6 inch sized specimen.

TABLE 2

		Example			Comparative example
		2	3	4	2	3	4	5	6	7	8	9	10
Polycarbonate		100	100	100	100	100	100	100	100	100	100	100	100
Flame retardant	Example 1	5	10	15	-	-	-	-	-	-	-	-	-
	Comparative Example 1	-	-	-	5	10	15	-	-	-	-	-	-
	C1	-	-	-	-	-	-	5	10	15	-	-	-
	C2	-	-	-	-	-	-	-	-	-	5	10	15
Heat resistance degree (℃)		142	138	134	143	139	136	130	119	107	130	120	111
Impact strength		60.1	11.2	8.1	53.2	10.2	7.8	10	5.4	4.8	9.0	6.0	4.8
Flame retardancy	2 mm	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0	V-0
	1.5mm	V-0	V-0	V-0	V-0	V-0	V-0	V-1	V-0	V-0	V-0	V-0	V-0
	1/8 "	V-0	V-0	V-0	V-0	V-0	V-0	V-2drip	V-1	V-0	V-0	V-0	V-0
Transparency (%)		89.5	89.5	89.3	89.3	86.7	64.7	89.5	89.7	89.6	88.4	88.0	87.9
Haze		1.23	1.43	1.60	1.8	1.8	2.70	2.06	2.34	2.71	2.76	3.53	3.91
Exterior		0	0	0	0	0	0	0	0	One	0	0	0

From the results of Table 2, it can be seen that 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. In addition, the 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.

Hereinafter, the specification of each component used in the Example and the comparative example is as follows.

(A) Polycarbonate resin: PANLITE L-1250W of Teijin, Japan was used as a bicarbonate (PC) of bisphenol-A type | mold whose weight average molecular weight is 25,000 g / mol.

(B) rubber modified aromatic vinyl polymer:

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.

(C) flame retardant

(C-1) Polyphosphonate Copolymer: The polyphosphonate copolymer of Example 1 was used.

(C-2) Bisphenol group containing polyphosphonate:

1 equivalent of Bisphenol A (manufactured by Songwon Industrial Co., Ltd.), 0.2 equivalent of 4-t-butylphenol, and 0.01 equivalent of aluminum chloride were added to chlorobenzene 6 times more than the biphenol content, and the temperature was raised to 131 ° C, and phenyl The reaction was started by dropwise addition of 1 equivalent of phosphonic acid dichloride (Phenylphosphonic dichloride) (manufactured by Acros). After the addition was completed, the reaction was terminated after further stirring for 2 hours. After completion of the reaction, the temperature was lowered to 80 ° C., washed with 10% aqueous hydrochloric acid solution, and then washed twice with water. After washing, the water layer was removed, and the organic layer was removed through reduced pressure distillation to obtain a bisphenol group-containing polyphosphonate (C-2). 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.

(C-4) Phosphate ester flame retardant: PX-200 (brand name) of Daihachi Japan, was used.

Examples 5-7 and Comparative Examples 11-19: Preparation of Thermoplastic Resin Composition

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 ℃ to prepare a pellet. After drying the pellet at 70 ℃ for 2 hours, the specimen was prepared using a 10 oz injection machine at a molding temperature of 180 to 280 ℃, a mold temperature of 40 to 80 ℃. The prepared specimens were evaluated for physical properties according to the following method. The evaluation results are shown in Table 3.

Property evaluation method

(1) Flame retardant: Flame retardancy was measured according to UL94 VB flame retardant regulations for 1/8 "thick specimens.

(2) Heat resistance (VST): It measured on 5 kg and 50 degreeC / HR conditions by ISO R306 (unit: degreeC).

(3) 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).

TABLE 3

		Example			Comparative example
		5	6	7	11	12	13	14	15	16	17	18	19
(A) PC		80	80	80	80	80	80	80	80	80	80	80	80
(B) G-ABS		20	20	20	20	20	20	20	20	20	20	20	20
Flame retardant	(C-1)	5	10	15	-	-	-	-	-	-	-	-	-
	(C-2)	-	-	-	5	10	15	-	-	-	-	-	-
	(C-3)	-	-	-	-	-	-	5	10	15	-	-	-
	(C-4)	-	-	-	-	-	-	-	-	-	5	10	15
Flame retardancy		V-0	V-0	V-0	V-0	V-0	V-0	V-1	V-0	V-0	V-0	V-0	V-0
Heat resistance degree (℃)		122	118	110	115	109	104	98	87	77	100	89	80
Izod impact strength		69	65	41	68	65	40	61	52	26	67	63	37

From the results of Table 3, it can be seen that 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. In addition, the 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.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments and can be manufactured in various forms, and a person of ordinary skill in the art to which the present invention pertains has the technical idea of the present invention. However, it will be understood that other specific forms may be practiced without changing the essential features. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (15)

1. Polyphosphonate copolymer having a repeating unit represented by the formula (1):

   [Formula 1]

   

   (In 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 m are an integer of 1 to 500).
2. The polyphosphonate copolymer of claim 1, wherein the sum of n and m is 3 to 600.
3. The polyphosphonate copolymer of claim 1, wherein the polyphosphonate copolymer has a weight average molecular weight of about 1,000 to about 50,000 g / mol.
4. The polyphosphonate copolymer of claim 1, wherein the polyphosphonate copolymer has a glass transition temperature of about 75 to about 90 ° C.
5. The polyphosphonate copolymer of claim 1, wherein the polyphosphonate copolymer has an acid value change rate of about 0.005 to about 5 according to Equation 1 below:

   [Equation 1]

   

   (In Formula 1, ΔAV 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, and AVb represents an initial acid value of the copolymer).
6. The polyphosphonate copolymer of claim 1, wherein the polyphosphonate copolymer contains from about 1 to about 99 mole percent of the total copolymer.
7. To the diol represented by the formula (2-1), the diol represented by the formula (2-2) and the phosphonic dichloride represented by the following formula (3) of the polyphosphonate copolymer Manufacturing Method:

   [Formula 2-1]

   

   [Formula 2-2]

   

   (In Formula 2-1 and Formula 2-2, 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);

   [Formula 3]

   

   (In Formula 3, 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.).
8. A polyphosphonate copolymer according to any one of claims 1 to 6; And

   Flame retardant thermoplastic resin composition comprising a thermoplastic resin.
9. The flame retardant thermoplastic resin composition of claim 8, wherein the flame retardant thermoplastic resin composition comprises 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.
10. The flame retardant thermoplastic resin composition of claim 9, wherein the base resin comprises a polycarbonate resin.
11. The flame retardant thermoplastic resin composition of claim 9, wherein the base resin comprises about 30 to about 100 wt% of a polycarbonate resin and about 0 to about 70 wt% of a rubber-modified aromatic vinyl polymer.
12. 12. The flame retardant thermoplastic resin composition of claim 11, wherein the rubber modified aromatic vinyl polymer comprises about 10 to about 100 weight percent of graft copolymer resin and about 0 to about 90 weight percent of copolymer resin.
13. The graft copolymer resin of claim 12, wherein the graft copolymer resin is about 5 wt% to about 65 wt% rubbery polymer, about 34 wt% to about 94 wt% aromatic vinyl monomer, and about 1 wt% to about 30 wt% monomer copolymerizable with the aromatic vinyl monomer. % Is a graft polymerized copolymer;

    The copolymer resin is a flame retardant thermoplastic resin composition, characterized in that the copolymer of about 60 to about 90% by weight aromatic vinyl monomer and about 10 to about 40% by weight monomer copolymerizable with the aromatic vinyl monomer.
14. The method of claim 8, wherein the flame retardant thermoplastic resin composition 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. A flame retardant thermoplastic resin composition further comprising.
15. A molded article formed from the flame retardant thermoplastic resin composition according to any one of claims 8 to 14.

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