NL2007946A - Polyphosphonate, method of preparing the same, and flame retardant thermoplastic resin composition including the same. - Google Patents

Polyphosphonate, method of preparing the same, and flame retardant thermoplastic resin composition including the same. Download PDF

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NL2007946A
NL2007946A NL2007946A NL2007946A NL2007946A NL 2007946 A NL2007946 A NL 2007946A NL 2007946 A NL2007946 A NL 2007946A NL 2007946 A NL2007946 A NL 2007946A NL 2007946 A NL2007946 A NL 2007946A
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polyphosphonate
substituted
unsubstituted
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group
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Min Soo Lee
Chang Hong Ko
Seon Ae Lee
Sang Hyun Hong
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Cheil Ind Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus

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Description

POLYPHOSPHONATE, METHOD OF PREPARING THE SAME, AND FLAME RETARDANT THERMOPLASTIC RESIN COMPOSITION INCLUDING THE SAME
Field of the Invention
The present invention relates to polyphosphonate and a flame retardant thermoplastic resin composition including the same. More specifically, the present invention relates to polyphosphonate which has an improved acid value by postprocessing with an alkylene oxide in manufacture of polyphosphonate, and a thermoplastic resin composition using the same as a flame retardant.
Description of the Related Art
To impart flame retardancy without use of halogen flame retardants, phosphorus flame retardants are used. Conventionally, monomolecular phosphorus flame retardants, such as triphenyl phosphate and resorcinol bisphenol phosphate, are used. However, such monomolecular phosphorus flame retardants have a low molecular weight and thus volatilize at a high molding temperature in molding plastic, causing appearance deterioration of the plastic. Further, monomolecular phosphorus flame retardants can escape to the external environment during use of products containing the same, causing environmental contamination. Thus, polyphosphonate receives increasing attention as a polymerizable phosphorus flame retardant. Polyphosphonate in a polymer form exhibits excellent flame retardancy, mechanical properties, heat resistance, and transparency, as compared with monomolecular phosphorus flame retardants, and thus is suited to resins requiring high heat resistance and high transparency, particularly, to polycarbonate resins.
Such polyphosphonate may be prepared by deoxidation of a diol and phosphonic dichloride. However, phosphonic dichloride has a strong tendency to hydrolyze into phosphonic acid, thereby causing decomposition of a polycarbonate resin and decomposition of polyphosphonate.
Polyphosphonate may be polymerized through solution polymerization (US Patent Nos. 2534252; 3946093; 3919363), interfacial polymerization (US Patent Publication No. 2002/0058779) and melt polymerization (US Patent Nos. 3719727; 3829405; 3830771; 4229552). Particularly, melt polymerization uses phosphonic dialkyl or aryl instead of phosphonic dichloride and thus does not cause hydrolysis. However, this method requires specialized equipment to remove by-products and requires strict polymerization conditions. Solution polymerization and interfacial polymerization can cause hydrolysis due to the presence of phosphonic chloride at a polymer terminal.
A method of endcapping using an alcohol has been developed to prevent hydrolysis of terminal phosphonic chloride. However, if an excessive amount of an endcapping agent is used, an acid value can increase and a polycarbonate resin can be decomposed due to the remaining endcapping agent. Moreover, it is not easy to remove the hydrolyzed phosphonic acid.
Conventionally, neutralization using a base containing an alkali metal is used to reduce an acid value. In this case, however, alkali metal ions can remain in the polycarbonate thus decomposing the polycarbonate.
Thus, there is a need for a flame retardant for polycarbonate which has a low acid value and does not allow an agent used for reducing an acid value to remain.
Summary of the Invention
Aspects of the present invention provide polyphosphonate which has a remarkably low acid value without using an endcapping agent, and a method of preparing the same. Using the polyphosphonate as a flame retardant, a flame retardant thermoplastic resin composition exhibiting excellent flame retardancy and heat resistance without causing deterioration in other physical properties may be provided.
An aspect of the invention provides polyphosphonate. The polyphosphonate has an acid value of about 5.5 mg KOH/g or less and is represented by Formula 1: [Formula 1]
Figure NL2007946AD00031
where A represents a single bond, C1 to C5 alkylene, C1 to C5 alkylidene, C5 to C6 cycloalkylidene, -S- or -S02-, R represents a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C6 to C20 aryloxy group, and R2 each independently represent a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C3 to C6 cycloalkyl group, a substituted or unsubstituted C6 to C12 aryl group or a halogen atom, a and b each independently represent an integer from about 0 to about 4, and n represents an integer from about 1 to about 500.
In one embodiment, the polyphosphonate may be post-treated with alkylene oxide.
In one embodiment, the polyphosphonate may have an acid value of 4.5 mg KOH /g or less and have a structure represented by Formula 1-1: [Formula 1-1]
Figure NL2007946AD00041
where R represents a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C6 to C20 aryloxy group, R^ and R2 each independently represent a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C3 to C6 cycloalkyl group, a substituted or unsubstituted C6 to C12 aryl group or a halogen atom, a and b each independently represent an integer from about 0 to about 4, and n represents an integer from about 1 to about 500.
Another aspect of the present invention provides a method of preparing the polyphosphonate. The method includes reacting a diol represented by Formula 2 with phosphonic dichloride represented by Formula 3, and treating the reaction product with alkylene oxide: [Formula 2]
Figure NL2007946AD00042
where A represents a single bond, C1 to C5 alkylene, C1 to C5 alkylidene, C5 to C6 cycloalkylidene, -S- or -S02-, R^ and R2 each independently represent a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C3 to C6 cycloalkyl group, a substituted or unsubstituted C6 to C12 aryl group or a halogen atom, and a and b each independently represent an integer from about 0 to about 4; and [Formula 3]
Figure NL2007946AD00043
where R represents a C6 to C20 aryl group or C6 to C20 aryloxy group.
The alkylene oxide may be represented by Formula 4: [Formula 4]
Figure NL2007946AD00051
where R2 represents hydrogen, a C1 to C6 alkyl group, a C6 to C20 aryl group, a C6 to C20 alkyl substituted aryl group, or a C6 to C20 aralkyl group.
In one embodiment, the alkylene oxide may be added in an equivalent of about 2 to 7 of the acid value of the reaction product.
In another embodiment, the reaction product may be treated with the alkylene oxide after reaction with 4-cumylphenol to adjust a terminal group.
A further aspect of the present invention provides polyphosphonate prepared by the method and having an acid value of about 5.5 mg KOH/g or less.
Yet another aspect of the present invention provides a flame retardant thermoplastic resin composition including the polyphosphonate. The composition may include about 0.1 to about 30 parts by weight of the polyphosphonate based on 100 parts by weight of polycarbonate resin.
Further, the flame retardant thermoplastic resin composition may have a number average molecular weight of about 12,000 to 20,000 g/mol, a weight average molecular weight of about 23,000 to 40,000 g/mol, and a heat distortion temperature of about 90 to 180°C according to ASTM D648 (1/4, 18.6 kg).
Detailed description of the Invention
Polyphosphonate in accordance with an aspect of the invention has an acid value of about 5.5 mg KOH /g and is represented by Formula 1: [Formula 1]
Figure NL2007946AD00052
where A represents a single bond, C1 to C5 alkylene, C1 to C5 alkylidene, C5 to C6 cycloalkylidene, -S- or -S02-, R represents a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C6 to C20 aryloxy group, and R2 each independently represent a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C3 to C6 cycloalkyl group, a substituted or unsubstituted C6 to C12 aryl group or a halogen atom, a and b each independently represent an integer from about 0 to about 4, and n represents an integer from about 1 to about 500.
In one embodiment, the polyphosphonate may have an acid value of 4.5 mg KOH/g or less and have a structure represented by Formula 1-1: [Formula 1-1]
Figure NL2007946AD00061
where R represents a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C6 to C20 aryloxy group, R^ and R2 each independently represent a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C3 to C6 cycloalkyl group, a substituted or unsubstituted C6 to C12 aryl group or a halogen atom, a and b each independently represent an integer from about 0 to about 4, and n represents an integer from about 1 to about 500.
The polyphosphonate may be prepared by reaction of a diol with phosphonic dichloride.
In one embodiment, the polyphosphonate may be prepared by reacting a diol represented by Formula 2 with phosphonic dichloride represented by Formula 3 and by treating the reaction product with alkylene oxide: [Formula 2]
Figure NL2007946AD00062
where A represents a single bond, C1 to C5 alkylene, C1 to C5 alkylidene, C5 to C6 cycloalkylidene, -S- or -S02-, R^ and R2 each independently represent a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C3 to C6 cycloalkyl group, a substituted or unsubstituted C6 to C12 aryl group or a halogen atom, and a and b each independently represent an integer from about 0 to about 4.
Examples of the diol may 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, and 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane.
[Formula 3]
Figure NL2007946AD00071
where R represents a C6 to C20 aryl group or C6 to C20 aryloxy group.
Specifically, the phosphonic dichloride may be reacted with the diol in an equivalent ratio of 1 to 1.
In one embodiment, the reaction of the diol and the phosphonic dichloride may be conducted by a general method in the presence of a Lewis acid as a catalyst. For example, aluminum chloride and magnesium chloride may be used as a catalyst, without being limited thereto. The catalyst may be reacted with the diol in an equivalent ratio of about 0.01 or more to 1, preferably about 0.01 ~ about 0.1 to 1.
In one embodiment, after the reaction terminates, the product may be washed with an acid solution. The acid solution may be phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, and the like, preferably phosphoric acid or hydrochloric acid. Here, the acid solution may have a concentration of about 0.1 to about 10 %, preferably about 1 to about 5 %.
The reaction product washed with the acid solution is reacted with the alkylene oxide represented by Formula 4. In one embodiment, dehydration for removal of water is conducted before reaction with the alkylene oxide, thereby stably conducting the reaction.
[Formula 4]
Figure NL2007946AD00072
where R2 represents hydrogen, a C1 to C6 alkyl group, a C6 to C20 aryl group, a C6 to C20 alkyl substituted aryl group or a C6 to C20 aralkyl group.
In one embodiment, R2 may be a C1 to C6 alkyl group.
In one embodiment, the alkylene oxide may be added in an equivalent of about 2 to 7, preferably about 3 to 5, of the acid value of the reaction product. Within this range, excellent balance between physical properties can be obtained.
The reaction of the reaction product with the alkylene oxide may be conducted for about 1 minute to about 24 hours, preferably about 1 to about 20 hours. Reaction temperature may be about 30 to about 150°C.
In the present invention, due to use of the alkylene oxide, an acid value may decrease and the alkylene oxide is entirely washed out in washing. Thus, when the polyphosphonate is applied to a polycarbonate resin, metal ions do not remain in the resin.
Alternatively, before the reaction with the alkylene oxide, the reaction product may further be subjected to endcapping by a general method. In one embodiment, the reaction product may be reacted with 4-cumylphenol to adjust a terminal group and then be treated with the alkylene oxide.
After reaction of the reaction product with the alkylene oxide, washing and filtering may further be carried out.
The polyphosphonate prepared as above may have an acid value of about 5.5 mg KOH/g or less, preferably about 4.5 mg KOH/g or less, and more preferably about 0.01 to about 3 mgKOH/g.
In particular, if polyphosphonate contains a biphenyl group, the polyphosphonate may have an acid value of about 1 mg KOH/g or less, preferably about 0.5 mg KOH/g or less, and more preferably about 0.001 to about 0.3 mgKOH/g.
As such, the polyphosphonate has a considerably low acid value, which does not cause decomposition of a thermoplastic resin to be mixed and is suited to use as a flame retardant.
Another aspect of the present invention relates to a flame retardant thermoplastic resin composition including the polyphosphonate.
There is no particular restriction as to the kind of the thermoplastic resin. Examples of the thermoplastic resin may include styrene resins, polyamide, polycarbonate, polyester, polyvinyl chloride, styrene copolymer resins, (meth)acrylic resins, and polyphenylene ether resins, without being limited thereto.
The polyphosphonate prepared by the method according to the present invention has a low acid value and exhibits flame retardancy, heat resistance and transparency and thus may be properly applied to resins requiring high heat resistance and high transparency.
In one embodiment, the flame retardant thermoplastic resin composition may include about 0.1 to about 30 parts by weight, preferably about 1 to about 15 parts by weight of the polyphosphonate based on 100 parts by weight of a polycarbonate resin.
The flame retardant thermoplastic resin composition does not cause decomposition of polycarbonate and may have a number average molecular weight of about 12,000 to 20,000 g/mol, a weight average molecular weight of about 23,000 to 40,000 g/mol, and a heat distortion temperature of about 90 to 180°C according to ASTM D648 (1/4, 18.6 kg).
Next, the present invention will be explained in more detail with reference to the following examples. These examples are provided for illustrative purposes only and are not to be in any way construed as limiting the present invention.
Examples
Preparation of polyphosphonate
Examples 1 to 5: Preparation of polyphosphonate 1 equivalent of bisphenol A (Kumho Co., Ltd.) and 0.01 equivalents of aluminum chloride were added to dichlorobenzene (Samchun Chemical Co., Ltd.) and thoroughly mixed through stirring while heating to 140°C. When the temperature reached 140°C, a mixture of 1 equivalent of phenyldichloride phosphonate (Acros Co., Ltd.) with dichlorobenzene (Samchun Chemical Co., Ltd.) was dropped thereinto, thereby initiating reaction. After completion of dropping, the product was further stirred for 8 hours, and then the reaction terminated. Then, the product was washed with a 30 % or less hydrochloric acid solution, followed by elimination of a water layer, elimination of dichlorobenzene through vacuum distillation, and then measurement of an acid value. Toluene and 5 equivalents of propylene oxide (Aldrich Co., Ltd.) of the acid value were added to the product, which was heated to 130°C, followed by stirring for a period of time listed in Table 1. Temperature was lowered to room temperature, and the product was washed with water twice and deposited in normal hexane, thereby obtaining a final product.
Examples 6 to 8: Preparation of polyphosphonate containing biphenyl group 1 equivalent of biphenol (Songwon Industrial Co., Ltd.) and 0.01 equivalents of aluminum chloride were added to dichlorobenzene (Samchun Chemical Co., Ltd.) and thoroughly stirred while heating to 140°C. When the temperature reached 140°C, a mixture of 1 equivalent of phenyldichloride phosphonate (Acros Co., Ltd.) with dichlorobenzene (Samchun Chemical Co., Ltd.) was dropped thereinto, thereby initiating reaction. After completion of dropping, the product was further stirred for 8 hours, and then the reaction terminated. Then, the product was washed with a 30 % or less hydrochloric acid solution, followed by elimination of a water layer, elimination of dichlorobenzene through vacuum distillation, and then measurement of an acid value. Toluene and 6 equivalents of propylene oxide (Aldrich Co., Ltd.) of the acid value were added to the product, which was heated to 130°C, followed by stirring for a period of time listed in Table 2. Temperature was lowered to room temperature, and the product was washed with water twice and deposited in normal hexane, thereby obtaining a final product.
Comparative Example 1
The same process as in Example 1 was carried out except that treatment with propylene oxide was not conducted.
Comparative Example 2
The same process as in Example 6 was carried out except that treatment with propylene oxide was not conducted.
The polyphosphonates prepared in Examples 1 to 8 and Comparative Examples 1 and 2 were evaluated as to acid value and yield by the following method, and results are listed in Tables 1 and 2.
Acid value (mg KOH/g): 1 to 20 g of a sample was dissolved in dimethyl sulfoxide (50ml) and 0.03 to 0.2 ml of a BTB solution was added thereto, after which the Consumed amount of 0.1N-NaOH solution was measured by titration with a 0.1 N NaOH solution. The acid value of the mixture was calculated by the following equation 1: [Equation 1]
Acid value = ((Consumed amount of 0.1N-NaOH solution (ml)) * (0.1N-NaOH solution Factor) * 5.61) / amount of sample (g)
Table 1
Figure NL2007946AD00111
In Table 1, it can be seen that Examples 1 to 5 employing the method of the present invention exhibit a remarkably low acid value as compare with Comparative Example 1.
Table 2
Figure NL2007946AD00112
Preparation of thermoplastic resin composition
Polyphosphonate prepared in each of Examples 1 to 8 and Comparative Examples 1 and 2 was added to 100 parts by weight of polycarbonate and extruded into pellets using a general biaxial extruder at 200 to 280°C. 0.01 to 0.015 g of these pellets was dissolved in a 2 ml MC, and the solution was diluted with about 10 ml of THF and then filtered through a 0.45 pm syringe filter. Molecular weight was measured by gel permeation chromatography (GPC) and flame retardancy at a thickness of 1/8" was measured according to UL94 VB standards. Heat resistance (unit: °C) was measured according to ASTM D648 (1/4, 18.6 kg).
Comparative Example 3
The same process as above was carried out except that phosphate ester (PX-200, Daihachi Co., Ltd.) was used as a flame retardant in 100 parts by weight of polycarbonate having a number average molecular weight of 12,700 g/mol and weight number average molecular weight of 24,300 g/mol.
Table 3
Figure NL2007946AD00121
Table 4
Figure NL2007946AD00122
As shown in Tables 3 and 4, the polyphosphonate prepared by the method according to the present invention did not cause decomposition of polycarbonates, and thus the polycarbonate had a high molecular weight. Further, the resin compositions have remarkably excellent heat resistance as compared with those in Comparative Examples 3 and 4, which used a monomolecular phosphorus flame retardant.
Although some embodiments have been disclosed herein, it should be understood that these embodiments are provided by way of illustration only, and that various modifications, changes, and alterations can be made without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be limited only by the accompanying claims and equivalents thereof.

Claims (12)

1. Polyfosfonaat met een zuurwaarde van 5,5 mg KOH/g of minder en weergegeven door formule 1: [formule 1]A polyphosphonate with an acid value of 5.5 mg KOH / g or less and represented by formula 1: [formula 1]
Figure NL2007946AC00141
Figure NL2007946AC00141
 waarin A weergeeft een enkelvoudige binding, C1 tot C5-alkyleen, C1 tot C5-alkylideen, C5 tot C6-cycloalkylideen, -S- of -S02-, R weergeeft een al of niet gesubstitueerde C6 tot C20-arylgroep of een al of niet gesubstitueerde C6 tot C20-aryloxigroep, R^ en R2 geven elk onafhankelijk een al of niet gesubstitueerde C1 tot C6-alkylgroep, een al of niet gesubstitueerde C3 tot C6-cycloalkylgroep, een al of niet gesubstitueerde C6 tot C12-arylgroep of een halogeenatoom weer, a en b geven elk onafhankelijk weer een geheel getal van 0 tot 4, en n geeft een geheel getal van 1 tot 500 weer.wherein A represents a single bond, C 1 to C 5 alkylene, C 1 to C 5 alkylidene, C 5 to C 6 cycloalkylidene, -S- or -SO 2 -, R represents a C 6 to C 20 aryl group optionally substituted or unsubstituted or unsubstituted or substituted substituted C6 to C20 aryloxy group, R1 and R2 each independently represent a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C3 to C6 cycloalkyl group, a substituted or unsubstituted C6 to C12 aryl group, or a halogen atom , a and b each independently represent an integer from 0 to 4, and n represents an integer from 1 to 500. 2. Polyfosfonaat volgens conclusie 1, waarbij de polyfosfonaat wordt nabehandeld met alkyleenoxide.The polyphosphonate of claim 1, wherein the polyphosphonate is post-treated with alkylene oxide. 3. Polyfosfonaat volgens conclusie 1, waarbij de polyfosfonaat een structuur bezit weergegeven door formule 1-1: [formule 1-1]The polyphosphonate of claim 1, wherein the polyphosphonate has a structure represented by formula 1-1: [formula 1-1]
Figure NL2007946AC00142
Figure NL2007946AC00142
 waarin R weergeeft een al of niet gesubstitueerde C6 tot C20-arylgroep of een al of niet gesubstitueerde C6 tot C20 aryloxigroep, R^ en R2 geven elk onafhankelijk weer een al of niet gesubstitueerde C1 tot C6-alkylgroep, een al of niet gesubstitueerde C3 tot C6-cycloalkylgroep, een al of niet gesubstitueerde C6 tot C12-arylgroep of een halogeenatoom, a en b geven elk onafhankelijk weer een geheel getal van 0 tot 4, en n geeft een geheel getal van 1 tot 500 weer.wherein R represents an optionally substituted C6 to C20 aryl group or an optionally substituted C6 to C20 aryloxy group, R1 and R2 each independently represent an optionally substituted C1 to C6 alkyl group, an optionally substituted C3 to C6 alkyl C 6 cycloalkyl group, an optionally substituted C 6 to C 12 aryl group or a halogen atom, a and b each independently represent an integer from 0 to 4, and n represents an integer from 1 to 500. 4. Polyfosfonaat volgens conclusie 1, waarbij de polyfosfonaat een zuurwaarde van 4,5 mg KOH/g of minder bezit.The polyphosphonate of claim 1, wherein the polyphosphonate has an acid value of 4.5 mg KOH / g or less. 5. Werkwijze ter bereiding van een door formule 1 weergegeven polyfosfonaat, omvattende: het in reactie brengen van een door formule 2 weergegeven diolverbinding met een door formule 3 weergegeven fosfondichloride; en het behandelen van het reactieproduct met alkyleenoxide: [formule 1]A process for the preparation of a polyphosphonate represented by formula 1, comprising: reacting a diol compound represented by formula 2 with a phosphorous dichloride represented by formula 3; and treating the reaction product with alkylene oxide: [formula 1]
Figure NL2007946AC00151
Figure NL2007946AC00151
 waarin A weergeeft een enkelvoudige binding, C1 tot C5-alkyleen, C1 tot C5-alkylideen, C5 tot C6-cycloalkylideen, -S- of -S02-, R weergeeft een al of niet gesubstitueerde C6 tot C20-arylgroep of een al of niet gesubstitueerde C6 tot C20-aryloxigroep, R^ en R2 geven elk onafhankelijk een al of niet gesubstitueerde C1 tot C6-alkylgroep, een al of niet gesubstitueerde C3 tot C6-cycloalkylgroep, een al of niet gesubstitueerde C6 tot C12-arylgroep of een halogeenatoom weer, a en b geven elk onafhankelijk weer een geheel getal van 0 tot 4, en n geeft een geheel getal van 1 tot 500 weer; [formule 2]wherein A represents a single bond, C 1 to C 5 alkylene, C 1 to C 5 alkylidene, C 5 to C 6 cycloalkylidene, -S- or -SO 2 -, R represents a C 6 to C 20 aryl group optionally substituted or unsubstituted or unsubstituted or substituted substituted C6 to C20 aryloxy group, R1 and R2 each independently represent a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C3 to C6 cycloalkyl group, a substituted or unsubstituted C6 to C12 aryl group, or a halogen atom , a and b each independently represent an integer from 0 to 4, and n represents an integer from 1 to 500; [formula 2]
Figure NL2007946AC00152
Figure NL2007946AC00152
 waarin A weergeeft een enkelvoudige binding, C1 tot C5-alkyleen, C1 tot C5-alkylideen, C5 tot C6-cycloalkylideen, -S- of -S02-, R^ en R2 geven elk onafhankelijk weer een al of niet gesubstitueerde C1 tot C6-alkylgroep, een al of niet gesubstitueerde C3 tot C6-cycloalkylgroep, een al of niet gesubstitueerde C6 tot C12-arylgroep of een halogeenatoom, en a en b geven elk onafhankelijk weer een geheel getal van 0 tot 4; en [formule 3]wherein A represents a single bond, C 1 to C 5 alkylene, C 1 to C 5 alkylidene, C 5 to C 6 cycloalkylidene, -S or -SO 2 -, R 1 and R 2 each independently represent a C 1 to C 6 substituted or unsubstituted alkyl group, an optionally substituted C3 to C6 cycloalkyl group, an optionally substituted C6 to C12 aryl group or a halogen atom, and a and b each independently represent an integer from 0 to 4; and [formula 3]
Figure NL2007946AC00161
Figure NL2007946AC00161
 waarin R weergeeft een C6 tot C20-arylgroep of een C6 tot C20-aryloxigroep.wherein R represents a C6 to C20 aryl group or a C6 to C20 aryloxy group. 6. Werkwijze volgens conclusie 5, waarbij de alkyleenoxideverbinding wordt weergegeven door formule 4: [formule 4]The method of claim 5, wherein the alkylene oxide compound is represented by formula 4: [formula 4]
Figure NL2007946AC00162
Figure NL2007946AC00162
 waarin R2 weergeeft waterstof, een C1 tot C6-alkylgroep, een C6 tot C20-arylgroep, een C6 tot C20-alkyl gesubstitueerde arylgroep of een C6 tot C20-aralkylgroep.wherein R 2 represents hydrogen, a C 1 to C 6 alkyl group, a C 6 to C 20 aryl group, a C 6 to C 20 alkyl substituted aryl group or a C 6 to C 20 aralkyl group. 7. Werkwijze volgens conclusie 5, waarbij de alkyleenoxideverbinding wordt toegevoegd in een equivalent van 2 tot 7 van de zuurwaarde van het reactieproduct.The method of claim 5, wherein the alkylene oxide compound is added in an equivalent of 2 to 7 of the acid value of the reaction product. 8. Werkwijze volgens conclusie 5, waarbij het reactieproduct wordt behandeld met de alkyleenoxideverbinding na reactie met 4-cumylfenol om een eindstandige groep in te stellen.The method of claim 5, wherein the reaction product is treated with the alkylene oxide compound after reaction with 4-cumylphenol to establish a terminal group. 9. Polyfosfonaat verkregen door de werkwijze volgens een of meer van de conclusies 5 tot 8 en in het bezit van een zuurwaarde van 5,5 mg KOH/g of minder.A polyphosphonate obtained by the method according to one or more of claims 5 to 8 and having an acid value of 5.5 mg KOH / g or less. 10. Vlam vertragende thermoplastische harssamenstelling, omvattende de polyfosfonaatverbinding volgens conclusie 9.A flame retardant thermoplastic resin composition comprising the polyphosphonate compound of claim 9. 11. Vlam vertragende thermoplastische harssamenstelling volgens conclusie 9, waarbij de samenstelling 0.01 tot 30 gewichtsdelen polyfosfonaat omvat, op basis van 100 gewichtsdelen polycarbonaathars.The flame-retardant thermoplastic resin composition according to claim 9, wherein the composition comprises 0.01 to 30 parts by weight of polyphosphonate, based on 100 parts by weight of polycarbonate resin. 12. Vlam vertragende thermoplastische harssamenstelling volgens conclusie 11, waarbij de vlam vertragende thermoplastische harssamenstelling een getalgemiddeld molecuulgewicht van 12.000 tot 20.000 g/mol, een gewichts-gemiddeld molecuulgewicht van 23.000 tot 40.000 g/mol en een warmtedistortie-temperatuur van 90 tot 180°C, volgens ASTM D648 (1/4, 18,6 kg), bezitThe flame retardant thermoplastic resin composition according to claim 11, wherein the flame retardant thermoplastic resin composition has a number average molecular weight of 12,000 to 20,000 g / mol, a weight average molecular weight of 23,000 to 40,000 g / mol and a heat distortion temperature of 90 to 180 ° C according to ASTM D648 (1/4, 18.6 kg)
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