KR20130078739A - Polyphosphonate copolymer, method for preparing thereof and flame retardant thermoplastic resin composition comprising the same - Google Patents

Abstract

PURPOSE: A polyphosphate copolymer is provided to improve flame retardancy, transparency, thermal resistance, impact strength, heat resistance, impact strength, and the exterior appearance. CONSTITUTION: A polyphosphate copolymer includes a repeating unit represented by chemical formula 1. In chemical formula 1, A and B is a single bond, a C1-5 alkylene, a C1-5 alkylidene, a C5-6 cycloalkylidene, -S-, or -SO2-; R5 and R6 is a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C6-20 aryl group, or a C6-20 substituted or unsubstituted aryloxy group; each of R1, R2, R3, and R4 is a substituted or unsubstituted C1-6 alkyl group, a substituted or unsubstituted C3-6 cycloalkyl group, a substituted or unsubstituted C6-12 aryl group, or halogen; each of a and b is an integer from 0-4; and each of n and m is an integer from 1-500.

Description

POLYPHOSPHONATE COPOLYMER, METHOD FOR PREPARING THEREOF AND FLAME RETARDANT THERMOPLASTIC RESIN COMPOSITION COMPRISING THE SAME

The present invention relates to a polyphosphonate copolymer, a method for producing 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 capable of expressing a balance of physical properties, a method for producing the same, and a thermoplastic resin composition comprising the same.

With the growing interest in environmental issues, regulations on halogenated flame retardants in existing countries are being tightened. Therefore, research on non-halogen flame retardants is active and research on phosphorus-based flame retardants has been made more intensive as an alternative. The most widely used phosphorus flame retardant is a monomolecular phosphorus flame retardant such as triphenyl phosphate and resorcinol bisphenol phosphate. 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 increasing interest in polyphosphonates, which are polymerized phosphorus-based flame retardants. Polymeric polyphosphonates have superior flame retardancy, mechanical properties, heat resistance and transparency than monomolecular phosphorus-based flame retardants, and are particularly suitable for resins requiring high heat resistance and high transparency such as polycarbonate resins.

Polyphosphonates developed so far are still not satisfactory in impact strength, heat resistance and appearance, and due to their structural properties, some of the thermoplastic resins may be decomposed to cause deterioration of physical properties. In addition, there was a disadvantage that the compatibility with the resin is not sufficient and the dispersibility is not good.

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyphosphonate copolymer capable of increasing the dispersibility of a phosphorus-based high molecular compound in a resin by introducing two or more repeating units into the main chain to improve compatibility with the resin, and a method for preparing the same. will be.

Another object of the present invention is to provide a polyphosphonate copolymer and a method for producing the same, which are environmentally friendly flame retardants and which can express excellent physical balance such as flame retardancy and appearance.

Still another object of the present invention is to provide a polyphosphonate copolymer and a method for producing the same, which can provide excellent physical properties such as flame retardancy, heat resistance, impact strength, and the like to a thermoplastic resin by adjusting the repeating unit content.

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 is characterized by being represented by the following formula (1)

[Formula 1]

Wherein A and B are each independently a single bond, C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -S- or -SO 2- Provided that A and B are not identical to each other, and R5 and R6 are each independently a substituted or unsubstituted C ₁ -C ₆ alkyl group, a substituted or unsubstituted C ₆ -C ₂₀ aryl group or C ₆ -C ₂₀ Is 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 unsubstituted group A ring C ₆ -C ₁₂ aryl group or a 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 1,000 to 50,000 g / mol.

The polyphosphonate copolymer may have a glass transition temperature of 75 to 90 ℃.

The polyphosphonate copolymer may have an acid value change rate of 0.005 to 5 according to Formula 1 below:

 [Formula 1]

(In the above, ΔAV is the acid value change rate, AVa is the acid value after leaving 10g of the copolymer at 280 ℃, 1 hour, AVb is the initial acid value of the copolymer).

The polyphosphonate copolymer may contain 1 to 99 mol% of the biphenyl units in the entire 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, a cycloalkyl C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C ₅ -C ₆ of vinylidene , -S- or -SO2-, provided that A and B are not identical to each other, and R1, R2, R3 and R4 are each independently a substituted or unsubstituted C ₁ -C ₆ alkyl group, a substituted or unsubstituted C _{A 3} -C ₆ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₁₂ aryl group or a halogen atom, a and b are each independently an integer of 0 to 4);

(3)

(In Formula 3, R is each independently a substituted or unsubstituted C ₁ -C ₆ alkyl group, a substituted or unsubstituted C ₆ -C ₂₀ aryl group or C ₆ -C ₂₀ substituted or unsubstituted aryl jade Period).

Another aspect of the invention relates to a flame retardant thermoplastic resin composition comprising the polyphosphonate copolymer. The flame retardant thermoplastic resin composition is the polyphosphonate copolymer; And thermoplastic resins.

The present invention can improve the compatibility with the resin by introducing two or more repeating units in the main chain to increase the dispersibility of the phosphorus-based polymer compound in the resin, it is an environmentally friendly flame retardant and can exhibit excellent physical properties such as flame retardancy, appearance The present invention provides a polyphosphonate copolymer capable of providing excellent physical property balance such as flame retardancy, heat resistance and impact strength to a thermoplastic resin by controlling the content of a repeating unit, and a method of manufacturing the same.

NMR spectrum of the polymer prepared in Preparation Example 1.

The polyphosphonate copolymer of the present invention is represented by the following general formula (1):

[Formula 1]

Wherein A and B are each independently a single bond, C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -S- or -SO 2- Provided that A and B are not identical to each other, and R5 and R6 are each independently a substituted or unsubstituted C ₁ -C ₆ alkyl group, a substituted or unsubstituted C ₆ -C ₂₀ aryl group or C ₆ -C ₂₀ Is 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 unsubstituted group A ring C ₆ -C ₁₂ aryl group or a 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. 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 be prepared by reacting a diol represented by the following Chemical Formula 2-1, a diol represented by the following Chemical Formula 2-2, and a phosphonic dichloride represented by the following Chemical 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, a cycloalkyl C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C ₅ -C ₆ of vinylidene , -S- or -SO2-, provided that A and B are not identical to each other, and R1, R2, R3 and R4 are each independently a substituted or unsubstituted C ₁ -C ₆ alkyl group, a substituted or unsubstituted C _{A 3} -C ₆ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₁₂ aryl group, or a halogen atom, a and b are each independently an integer from 0 to 4).

remind Examples of diols 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 two or more of them may be selected and used. In the embodiment, 4,4'-dihydroxybiphenyl and 2,2-bis- (4-hydroxyphenyl) -propane may be preferably applied. The ratio between these two diols can be appropriately adjusted according to the physical properties to be expressed. In the specific example, the molar ratio between 4,4'-dihydroxybiphenyl and 2,2-bis- (4-hydroxyphenyl) -propane is used in a ratio of 40 to 60 mol%: 60 to 40 mol%. Optimum flame retardancy and impact strength can be obtained in the above range.

(3)

(In Formula 3, R is each independently a substituted or unsubstituted C ₁ -C ₆ alkyl group, a substituted or unsubstituted C ₆ -C ₂₀ aryl group or C ₆ -C ₂₀ substituted or unsubstituted aryl jade Period).

In embodiments, the phosphonic dichloride may be added dropwise to a solution in which two diols, a catalyst, and an end capping agent are mixed.

In an embodiment one equivalent of phosphonic dichloride may be reacted relative to one equivalent of total diol.

The reaction of the diol and phosphonic dichloride may be carried out by a conventional polymerization method under a Lewis acid catalyst. Solution polymerization may be preferably used.

In an embodiment, aluminum chloride, magnesium chloride, or the like may be used as the Lewis acid catalyst, but is not necessarily limited thereto. The catalyst may be applied in an amount of 0.01 to 10 equivalents, preferably 0.01 to 0.1 equivalents based on 1 equivalent of the total diol.

The reaction can also be carried out in the presence of an endcapping agent. The end capping agent may be preferably a C1-5 alkyl group-containing phenol, for example, phenol, 4-t-butylphenol, 2-t-butylphenol may be used. The end capping agent may be used in an amount of 1 equivalent or less, preferably 0.01 to 0.5 equivalents, based on 1 equivalent of the total diol.

In embodiments, the reaction may be completed, followed by washing with an acid solution. The acid solution may be applied phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, and the like, preferably phosphoric acid or hydrochloric acid. At this time, the acid solution is preferably 0.1 to 10%, preferably 1 to 5% concentration.

Thereafter, the washing and filtration steps may yield a polyphosphonate copolymer in the form of a white solid. The polyphosphonate copolymers thus prepared are linear.

The polyphosphonate copolymer may have a weight average molecular weight of 1,000 to 50,000 g / mol. Preferably 1,000 to 20,000 g / mol, more preferably 1,000 to 10,000 g / mol. It is possible to impart better flame retardancy in the above range.

The polyphosphonate copolymer may have an acid value of 0.005 to 4 KOH mg / g, preferably 0.01 to 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 1.5 to 3.5, preferably 1.8 to 3.5. It is possible to impart excellent flame retardancy in the above range.

The polyphosphonate copolymer may have a glass transition temperature of 75 to 90 ℃.

The polyphosphonate copolymer may have an acid value change rate of 0.005 to 5 according to Formula 1 below:

 [Formula 1]

(In the above, ΔAV is the acid value change rate, AVa is the acid value after leaving 10g of the copolymer at 280 ℃, 1 hour, AVb is the initial acid value of the copolymer).

The polyphosphonate copolymer may contain 1 to 99 mol% of the biphenyl units in the entire copolymer.

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

The kind of the said thermoplastic resin is not specifically limited. For example, styrene resin, polyamide, polycarbonate, polyester, polyvinyl chloride, styrene copolymer resin, (meth) acrylic resin, polyphenylene ether resin and the like may be applied, but is not necessarily limited thereto.

In an embodiment, the polyphosphonate copolymer may be used in an amount of 1 to 30 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the thermoplastic resin.

Since the polyphosphonate copolymer prepared by the method of the present invention has flame retardancy, heat resistance and transparency, it can be preferably applied to resins requiring high heat resistance, high transparency and high impact.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. However, the following examples are provided to aid 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

Preparation Example 1 Preparation of Polyphosphonate Copolymer

Biphenol (manufactured by Songwon Industry) 7.18 kg (38.54 mol), 2,2-bis- (4-hydroxyphenyl) -propane (Kumho) 8.80 kg (38.54 mol), 4-t-butylphenol (manufactured by TCI) 5.79 kg (38.54 mol) 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 the mixed solution, followed by stirring for 8 hours. After washing with aqueous hydrochloric acid and distilled water and repeating this process twice, the organic layer was collected and 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 polymer is shown in FIG. 1. In addition, the physical properties of the prepared polyphosphonate copolymer 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, PDI was 2.1, and the glass transition temperature was 82 ° C.

Manufacturing example  2 : Of polyphosphonates  Produce

Diol was used in the same manner as in Preparation Example 1 except that 77.08 mol of 2,2-bis- (4-hydroxyphenyl) -propane (Kumho) was applied without using biphenol.

Property evaluation method

(1) Weight average molecular weight: After dissolving 0.01 g of sample in 2 mL of MC using GPC, diluted about 10 mL of THF, and filtering the dissolved sample using 0.45 μm syringe filter to determine the weight average molecular weight by gel permeation chromatography (GPC). It was measured (unit: g / mol).

(2) Acid value (KOH mg / g): 1 ~ 20g of sample was dissolved in dimethylsulfoxide (50ml), 0.03ml ~ 0.2ml of BTB solution was added, and titrated with 0.1N NaOH solution.

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

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

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

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

 [Formula 1]

(In the above, ΔAV is the acid value change rate, AVa is the acid value after leaving 10g of the copolymer at 280 ℃, 1 hour, AVb is the initial acid value of the copolymer).

Preparation Example 1 Production Example 2 C1 C2 Hydrolysis resistance
(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 ° C 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 1 to 3 and Comparative Examples 1 to 6: Preparation of the thermoplastic resin composition

A flame retardant was added to 100 parts by weight of polycarbonate resin (PANLITE L-1250W) according to the following Table 2 and extruded at a temperature range of 200 ~ 280 ℃ in a conventional twin screw extruder to prepare a specimen. 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 by 5 kg and 50 degreeC / HR conditions by ISO R306. (Unit: ℃)

(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: kgf · cm / cm).

(3) Flame retardancy: Flame retardancy was measured according to the UL94 V flame retardant regulations for each of the specimens of 2mm and 1.5mm thickness.

(4) Transparency: The total light transmittance (TT) was measured with a Haze meter (manufacturer: NIPPON DENSOHKU KOGYO).

(5) Appearance: The pinhole and silver were measured by 6 inch x 6 inch size specimen.

Example Comparative example One 2 3 One 2 3 4 5 6 7 8 9 Polycarbonate 100 100 100 100 100 100 100 100 100 100 100 100 I
year
My Preparation Example 1 5 10 15 - - - - - - - - - Production Example 2 - - - 5 10 15 - - - - - - C1 - - - - - - 5 10 15 - - - C2 - - - - - - - - - 5 10 15 Heat resistance degree (VST) 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 2mm 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 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 Exterior 0 0 0 0 0 0 0 0 One 0 0 0

As shown in Table 2, Comparative Examples 4 to 9 to which the monomolecular flame retardant is applied may be inferior in impact and heat resistance to Comparative Examples 1 to 3 to which the polyphosphonate is applied. In addition, it can be confirmed that Examples 1 to 3 to which the polyphosphonate copolymer of the present invention is applied have better impact strength and transparency than the polyphosphonates of Comparative Examples 1 to 3 containing only bisphenol units.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

Claims (8)

Polyphosphonate copolymer having a repeating unit of formula
[Formula 1]

Wherein A and B are each independently a single bond, C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -S- or -SO 2- Provided that A and B are not identical to each other, and R5 and R6 are each independently a substituted or unsubstituted C ₁ -C ₆ alkyl group, a substituted or unsubstituted C ₆ -C ₂₀ aryl group or C ₆ -C ₂₀ Is 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 unsubstituted group A ring C ₆ -C ₁₂ aryl group or a halogen atom, a and b are each independently an integer of 0 to 4, n and m are an integer of 1 to 500).
The polyphosphonate copolymer of claim 1, wherein the sum of n and m is 3 to 600.
The polyphosphonate copolymer of claim 1, wherein the polyphosphonate copolymer has a weight average molecular weight of 1,000 to 50,000 g / mol.
The polyphosphonate copolymer of claim 1, wherein the polyphosphonate copolymer has a glass transition temperature of 75 to 90 ° C.
The polyphosphonate copolymer of claim 1, wherein the polyphosphonate copolymer has an acid value change rate of 0.005 to 5 according to the following Formula 1:
[Formula 1]

(In the above, ΔAV is the acid value change rate, AVa is the acid value after leaving 10g of the copolymer at 280 ℃, 1 hour, AVb is the initial acid value of the copolymer).
The polyphosphonate copolymer of claim 1, wherein the polyphosphonate copolymer contains 1 to 99 mol% of the biphenyl units in the total copolymer.
A polyol represented by the following Chemical Formula 1, comprising reacting a diol represented by the following Chemical Formula 2-1, a diol represented by the following Chemical Formula 2-2, and a phosphonic dichloride represented by the following Chemical Formula 3. Process for preparing phosphonate copolymer:
[Formula 1]

Wherein A and B are each independently a single bond, C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -S- or -SO 2- Provided that A and B are not identical to each other, and R5 and R6 are each independently a substituted or unsubstituted C ₁ -C ₆ alkyl group, a substituted or unsubstituted C ₆ -C ₂₀ aryl group or C ₆ -C ₂₀ Is 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 unsubstituted group A ring C ₆ -C ₁₂ aryl group or a halogen atom, a and b are each independently an integer of 0 to 4, n and m are integers of 1 to 500;
[Formula 2-1]

[Formula 2-2]

(In Formula 2-1 and Formula 2-2, A and B are each independently a single bond, a cycloalkyl C ₁ -C ₅ alkylene, C ₁ -C ₅ alkylidene, C ₅ -C ₆ of vinylidene , -S- or -SO2-, provided that A and B are not identical to each other, and R1, R2, R3 and R4 are each independently a substituted or unsubstituted C ₁ -C ₆ alkyl group, a substituted or unsubstituted C _{A 3} -C ₆ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₁₂ aryl group or a halogen atom, a and b are each independently an integer of 0 to 4);
(3)

(In Formula 3, R is each independently a substituted or unsubstituted C ₁ -C ₆ alkyl group, a substituted or unsubstituted C ₆ -C ₂₀ aryl group or C ₆ -C ₂₀ substituted or unsubstituted aryl jade Period).
The polyphosphonate copolymer of any one of claims 1 to 6; And
Thermoplastic resin;
Flame retardant thermoplastic resin composition comprising a.

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