JP2009144042A - Phosphorus-containing polymer and method for producing it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phosphorus-containing polymer greatly increasing bleed-out resistance of a composition added to a thermoplastic rein during use at a high temperature, causing less deterioration in physical properties by addition, and having a flame-retardant effect. <P>SOLUTION: The phosphorus-containing polymer is obtained by performing polycondensation of a phosphorus-containing compound having a 9,10-dihydro-9-oxa-10-phosphaphenanthrene skeleton, ethylene glycol, and dihydric alcohol represented by a structural formula 4. In the formula, -A- is -O-, -S-, -SO-, -SO<SB>2</SB>-, -CO-, a 1-20C alkylene group, or a 6-20C alkylidene group; each of R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>, R<SP>6</SP>, R<SP>7</SP>and R<SP>8</SP>is a hydrogen atom, a halogen atom, or a 1-5C monovalent hydrocarbon group; and both of R<SP>9</SP>and R<SP>10</SP>are 1-5C bivalent hydrocarbon groups and may be the same or different. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel phosphorus-containing polymer, a flame retardant containing the polymer as a main component, and a method for producing the same.

  Engineering plastics are widely used in electrical and electronic parts, automobile parts and the like because of their excellent characteristics. In recent years, particularly in home appliances, electricity, and OA-related parts, there are many examples in which flame retardancy is required in order to ensure safety against fire, and therefore, various flame retardant formulations have been studied.

  As a method for flame-retarding a resin, a method in which a halogen-based flame retardant represented by brominated polystyrene or the like and an antimony-based flame retardant aid represented by antimony trioxide or the like are conventionally added, There is a suspicion of generating toxic gas at the time of combustion, regulations on resin compositions containing halogenated flame retardants are becoming stricter, and development of non-halogen flame retardants has been activated.

  Examples of a method for making a resin composition flame retardant without using a halogen-based flame retardant include a method using a metal oxide and a method using a phosphorus compound. In the method using a metal oxide, it is difficult to obtain desired flame retardant properties unless used in a large amount, and when it is used in a large amount, there is a problem that the properties inherent to the resin are deteriorated.

  As a method for flame-retarding a resin using a phosphorus compound, a method using an organic phosphate ester compound is conventionally known, but a relatively low molecular weight organic phosphate ester is volatile, sublimable, and heat resistant. In addition, there is a problem that the flame retardant bleeds out when the resin composition is used at a high temperature for a long time. Furthermore, there has been a problem that the low molecular weight organic phosphorus compound acts as a plasticizer for the resin and reduces the heat resistance of the composition.

  Structural formula (1) which is one of the constituent components of the compound of the present application

The technology (Patent Documents 1 and 2) relating to a resin composition comprising an organophosphorus flame retardant and a thermoplastic resin having the same structure is disclosed, but there is room for improvement in compatibility depending on the resin type, In some cases, delamination occurred in the molded body made of the resin composition.
JP-A-53-128195 International Publication WO2007 / 040075

  In view of the current situation as described above, the object of the present invention is to enhance the compatibility with thermoplastic resins, particularly engineering plastics, and to improve the bleed-out resistance of the composition added to the resin when used at high temperatures. It is to obtain a phosphorus-containing polymer that is enhanced and has a small decrease in physical properties due to addition, and further to obtain a flame retardant containing the phosphorus-containing polymer as a main component.

  As a result of intensive studies to achieve the above object, the present inventors have made the two types of structural units shown below present in the molecule at the same time, thereby increasing the compatibility with the thermoplastic resin and adding it to the resin. As a result, the present inventors have found a phosphorus-containing polymer that has a high bleed-out resistance when used under high temperature and a small decrease in physical properties. Further, the present inventors have found that the phosphorus-containing polymer is useful as an efficient production method for efficiently obtaining the phosphorus-containing polymer and further as a flame retardant, and completed the present invention.

  That is, the first of the present invention is the following structural formula (1) in the main chain.

And structural formula (2)

(Wherein, -A- is, -O -, - S -, - SO -, - SO 2 -, - CO-, an alkylene group or alkylidene group having 6 to 20 carbon atoms, having 1 to 20 carbon atoms , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are all a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group having 1 to 5 carbon atoms. , R ⁹ and R ¹⁰ are each a divalent hydrocarbon group having 1 to 5 carbon atoms, which may be the same or different, and m and n are the number of repeating units of the oxyalkylene group. And 2 ≦ m + n ≦ 50.) In the same molecule, the present invention relates to a phosphorus-containing polymer.

  The second of the present invention relates to a flame retardant comprising the above-described polymer as a main component.

  The third of the present invention is the structural formula (3)

And a phosphorus-containing compound represented by the formula (4)

2. The method for producing a phosphorus-containing compound according to claim 1, wherein the dihydric alcohol represented by the formula (2) is polycondensed.

  The fourth of the present invention is a structural formula (3) as a further preferred embodiment of the production method.

Structural formula (5) obtained by polycondensation of a phosphorus-containing dicarboxylic acid represented by

In the compound represented by the structural formula (4)

(Wherein, -A- is, -O -, - S -, - SO -, - SO 2 -, - CO-, an alkylene group or alkylidene group having 6 to 20 carbon atoms, having 1 to 20 carbon atoms , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are all hydrogen atoms, halogen atoms, or monovalent hydrocarbon groups having 1 to 5 carbon atoms, R ⁹ and R ¹⁰ are each a divalent hydrocarbon group having 1 to 5 carbon atoms, and they may be the same or different, and m and n represent the number of repeating units of the oxyalkylene group. 2 ≦ m + n ≦ 50). The method for producing a phosphorus-containing polymer according to claim 1, wherein a dihydric alcohol represented by 2) is allowed to act to cause a deethylene glycol reaction.

  The phosphorus-containing polymer of the present invention is highly compatible with a thermoplastic resin, does not cause delamination when added to the resin, and is suitable as a flame retardant with little deterioration in properties inherent to the resin. It can be used and is industrially useful.

  The phosphorus-containing polymer of the present invention increases the compatibility with the thermoplastic resin, suppresses the bleed-out of the composition added to the thermoplastic resin at a high temperature, and further reduces the physical properties of the original thermoplastic resin. In order to suppress, the following structural formula (1)

Structural unit and structural formula (2)

(Wherein, -A- is, -O -, - S -, - SO -, - SO 2 -, - CO-, an alkylene group or alkylidene group having 6 to 20 carbon atoms, having 1 to 20 carbon atoms , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are all a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group having 1 to 5 carbon atoms. , R ⁹ and R ¹⁰ are each a divalent hydrocarbon group having 1 to 5 carbon atoms, which may be the same or different, and m and n are the number of repeating units of the oxyalkylene group. And 2 ≦ m + n ≦ 50.) In the same molecule.

Here, including the structural units of the structural formulas (1) and (2) in the same molecule means that the two kinds of structural units each have at least one unit in one molecular chain. . In a mixture of a phosphorus-containing polymer consisting only of a single structural unit, the phosphorus-containing polymer consisting only of the structural formula (1) lacks compatibility, and thus causes delamination in the molded body. It is clear that the two kinds of structural units are contained in the same molecule by measuring the glass transition temperature (T _g ) of the phosphorus-containing polymer with a differential scanning calorimeter (DSC). If, in a mixture of phosphorus-containing polymer consisting of a repeating unit of the sole, so that the two T _g of appears.

The lower limit of the weight average molecular weight (M _w ) of the phosphorus-containing polymer of the present invention is preferably 3000, more preferably 4000, and still more preferably 5000 in terms of polystyrene by gel permeation chromatography (GPC). When the weight-average molecular weight (M _w ) of the phosphorus-containing polymer is less than 3000, when added to the resin, bleeding out tends to occur or mechanical strength tends to decrease. On the other hand, the upper limit value of the weight average molecular weight (M _w ) of the phosphorus-containing polymer is not particularly specified, but if the molecular weight is excessively increased, the dispersibility and the like may be adversely affected. Therefore, the upper limit of _Mw is preferably 50000, more preferably 40000, and still more preferably 30000.

  The proportions of the structural formulas (1) and (2), which are the structural units of the phosphorus-containing polymer of the present invention, are the structural formulas when the total number of structural units of the structural formulas (1) and (2) is 100. The lower limit of the proportion of (1) is preferably 5, more preferably 10, and even more preferably 15. When the lower limit of the ratio of the structural formula (1) is smaller than 5, the phosphorus content must be excessively added to the resin as a flame retardant, possibly reducing the properties inherent in the resin. There is. As an upper limit of the ratio of Structural formula (1), 95 is preferable, 93 is more preferable, and 90 is still more preferable. When the upper limit is larger than 95, the effect of increasing the compatibility with the thermoplastic resin is reduced, and there is a possibility that problems such as delamination of the layered product may occur.

The constitutional ratio of the repeating unit is clarified by measuring ¹ H-NMR of the produced phosphorus-containing polymer.

  In the present invention, the following structural formula (3) is used as the dicarboxylic acid component.

As a diol component, ethylene glycol and the following structural formula (4)

The dihydric alcohol shown by these is used.

Here, in the structural formula (4), -A- is, -O -, - S -, - SO -, - SO 2 -, - CO-, an alkylene group having 1 to 20 carbon atoms or carbon atoms 6, Among these, isopropylidene group is preferable from the viewpoints of availability, ease of handling, and the like. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are all hydrogen atoms, halogen atoms, or monovalent hydrocarbon groups having 1 to 5 carbon atoms. In general, a hydrogen atom is preferred. R ⁹ and R ¹⁰ are each a divalent hydrocarbon group having 1 to 5 carbon atoms, and they may be the same or different, but —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ - are common. m and n represent the number of repeating units of the oxyalkylene group.

The lower limit value of m + n is preferably 2. If m + n is less than 2, one or both ends have a phenolic hydroxyl group, which may cause a problem that the esterification reactivity decreases. The upper limit of m + n is preferably 40, more preferably 30, and still more preferably 20. When the number of repeating units of oxyalkylene group is too large, by the T _g decreases, or the handling property is lowered, by the phosphorus content is lowered, no longer has to be a large amount added as a flame retardant tends There is.

  The phosphorus-containing polymer of the present invention can be obtained by a condensation reaction with a dicarboxylic acid or an ester-forming derivative thereof and a diol.

  That is, structural formula (3)

A phosphorus-containing compound represented by the formula: ethylene glycol and structural formula (4)

It can be produced by polycondensation of a dihydric alcohol represented by

  More specifically, structural formula (6)

9 and 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and an equimolar amount or more of itaconic acid are heated and mixed in a temperature range of 150 to 200 ° C. in a nitrogen gas atmosphere. Subsequently, after reducing the reaction temperature to about 120 ° C., ethylene glycol and the dihydric alcohol of the structural formula (4) are converted into a theoretical composition ratio (structural formula (1) / (2) in the phosphorus-containing polymer to be produced. ) Is added to a desired ratio, and the mixture is heated at 120 to 200 ° C. and stirred. Next, a metal catalyst such as antimony trioxide, zinc acetate, germanium oxide, etc. is added and maintained at 220 ° C. under a vacuum pressure of 1 Torr or less to obtain a target phosphorus-containing polymer by polycondensation reaction. it can.

  However, when two or more kinds of diol components are used, depending on the type of diol component, the selectivity of the reaction may be biased due to the difference in reactivity, and as a result, the composition ratio of the obtained polymer is different from the desired one, which is desired. There is a possibility that a polymer cannot be obtained or the degree of polymerization does not increase.

  In this case, the production by the following method is more preferable because two kinds of diol components can be contained in the phosphorus-containing polymer at a desired ratio.

  That is, the phosphorus-containing polymer of the present invention has the structural formula (3)

Structural formula (5) obtained by polycondensation of a phosphorus-containing compound represented by

In the compound represented by the structural formula (4)

(Wherein, -A- is, -O -, - S -, - SO -, - SO 2 -, - CO-, an alkylene group or alkylidene group having 6 to 20 carbon atoms, having 1 to 20 carbon atoms , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are all a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group having 1 to 5 carbon atoms. , R ⁹ and R ¹⁰ are each a divalent hydrocarbon group having 1 to 5 carbon atoms, which may be the same or different, and m and n are the number of repeating units of the oxyalkylene group. And 2 ≦ m + n ≦ 50.) Can be produced by a method in which a dihydric alcohol represented by 2) is allowed to act to cause a deethylene glycol reaction.

  The production method shown above is not particularly defined except for the reaction sequence, but can be produced by the following method.

  That is, the following structural formula (6)

In an amount of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide represented by the formula, an equimolar amount of itaconic acid and an itolonic acid amount of 2 times the molar amount of ethylene glycol are mixed. In a nitrogen gas atmosphere, the mixture is heated at 120 to 200 ° C. and stirred. Next, a metal catalyst such as antimony trioxide, zinc acetate, germanium oxide, etc. is added and maintained at 220 ° C. under a vacuum pressure of 1 Torr or less, and a polycondensation reaction is carried out while distilling ethylene glycol. 5)

Is obtained. The compound is usually a glassy solid having a molecular weight of 4000 to 12000 and a phosphorus content of around 8%.

  Next, the reaction temperature is lowered to about 150 ° C., and a desired amount of the structural formula (4) with respect to the compound represented by the structural formula (5).

Are added, and the mixture is gradually heated to 150 to 230 ° C. and stirred under a nitrogen gas atmosphere. Next, the target phosphorus-containing polymer can be obtained by performing a transesterification while distilling ethylene glycol while maintaining the temperature at 250 ° C. under a vacuum pressure of 1 Torr or less.

  The phosphorus-containing polymer of the present invention can be suitably used as a flame retardant for thermoplastic resins.

  The target thermoplastic resin is not particularly limited. For example, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polyamide resins, polycarbonate resins, polyphenylene oxide resins, polyphenylene sulfide resins, and polyacetals. Examples thereof include resins, polyolefin resins, polystyrene resins, ABS resins, and polyacrylic resins.

  Among these, it is useful as a flame retardant for engineering plastics such as polyethylene terephthalate resin, polybutylene terephthalate resin, polyamide resin, polycarbonate resin, polyphenylene oxide resin in that the bleed-out during high temperature use is reduced. is there.

  When the phosphorus-containing polymer of the present invention is used as a flame retardant, the lower limit of the amount added to the thermoplastic resin varies depending on the resin, but is preferably 1 part by weight with respect to 100 parts by weight of the thermoplastic resin. Is more preferable, and 5 parts by weight is even more preferable. If the amount added is less than 1 part by weight, sufficient flame retardancy may not be obtained. The upper limit is preferably 80 parts by weight, more preferably 75 parts by weight, and even more preferably 70 parts by weight. When the addition amount exceeds 80 parts by weight, there is a possibility that the mechanical strength is lowered or the moldability is deteriorated.

  Next, the present invention will be specifically described with reference to specific examples, but the present invention is not limited thereto.

The raw materials used in the production examples, examples and comparative examples are shown below.
Phosphorus-containing compound (A1): 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., HCA)
Phosphorus-containing compound (A2): synthesized in Production Example 1.
Phosphorus-containing polymer (A3): synthesized in Production Example 2.
Phosphorus-containing polymer (A4): synthesized in Production Example 3.
Phosphorus-containing polymer (A5): synthesized in Production Example 4.
Phosphorus-containing polymer (A6): synthesized in Production Example 5.
Phosphorus-containing polymer (A7): synthesized in Production Example 6.
Phosphorus-containing polymer (A8): synthesized in Production Example 7.
Dihydric alcohol (C1): Structural formula (7) below; manufactured by Toho Chemical Co., Ltd., Bisol 4EN

Dihydric alcohol (C2): Structural formula (8) below; Bishool 18EN, manufactured by Toho Chemical Industries

Thermoplastic resin (D): Polycarbonate resin (Teflon A2200, manufactured by Idemitsu Kosan Co., Ltd.)
Stabilizer (E1): Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionate; Ciba Specialty Chemicals, IRAGANOX 1010)
The evaluation method in this production example is as follows.

<Weight average molecular weight (M _w )>
The _Mw of the obtained phosphorus-containing polymer was measured by GPC using chloroform as a solvent and determined by polystyrene conversion. GPC measurement was performed at 35 ° C. using a GPC measurement device (column: K-804 and K-802.5, manufactured by Showa Denko KK) manufactured by Water (sampler: 717 plus, pump: 515).

<Glass transition temperature (T _g )>
T _g of the resultant phosphorus-containing polymer, was determined using DSC. The DSC measurement was performed using a DSC-220C manufactured by Seiko Instruments Inc. at a temperature rising rate of 10 ° C./min and under a nitrogen stream.

<Constitution ratio in phosphorus-containing polymer (ratio of structural formula (1) and general formula (2))>
The composition ratio in the obtained phosphorus-containing polymer was calculated from signals derived from hydrogen on the p-phenylene hydrogen and phosphaphenanthrene rings in the dihydric alcohol of the structural formula (4) in ¹ H-NMR [peak: 6.62-6.82, 7.02-7.07 (based on p-phenylene hydrogen) and 7.07-8.00 ppm (based on hydrogen on the phosphaphenanthrene ring)].
¹ H-NMR measurement was performed in deuterated chloroform using a Varian Gemini 300.

<Phosphorus content>
The phosphorus content of the obtained phosphorus-containing polymer was determined by high frequency plasma emission spectroscopy (ICP-AES). ICP-AES was subjected to microwave decomposition using Milestone's ETHOS in accordance with US EPA METHOD 3052 as a pretreatment, and ICPS-8100 made by Shimadzu Corporation was used.

    The evaluation method in the present example is as follows.

<Flame retardance>
The obtained pellets were dried at 120 ° C. for 3 hours, and then injection-molded using an injection molding machine (JS36SS clamping pressure: 35 tons) under conditions of a cylinder set temperature of 250 to 280 ° C. and a mold temperature of 60 ° C. A test piece of 127 mm × 12.7 mm × thickness 1/16 inch was obtained. In accordance with the UL94 standard V-0 test, flammability was evaluated using the obtained 1/16 inch thick bar-shaped test piece.

<Tensile strength and elongation at break>
The obtained pellets were dried at 120 ° C. for 3 hours, and then an injection molding machine (IE-75E-2A (clamping pressure: 75 tons) manufactured by Toshiba Machine Co., Ltd.) was used. Injection molding was performed under the conditions of a mold temperature of 60 ° C. and an injection rate of 30 cm ³ / sec or 80 cm ³ / sec to produce a dumbbell test piece according to ASTM D-638.
Using the obtained test specimen, a tensile test was performed according to ASTM D-638, and the tensile strength and elongation at break at 23 ° C. were measured.

<Layered peeling state of molded product>
The broken dumbbells after the tensile test were observed to examine the presence or absence of delamination.
○: No delamination occurred.
Δ: Delamination occurred in the sample formed by increasing the injection rate (80 cm ³ / sec).
X: Delamination has occurred.

<Bleed-out evaluation>
The dumbbell used for the tensile test was heated in an oven at 120 ° C. for 1 hour, and the absorbent cotton was pressed against the heated molded article to examine whether the absorbent cotton adhered to the molded article.
○: There is no bleed-out of the phosphorus-containing compound, and absorbent cotton does not adhere to the molded body.
X: There is a bleed-out of a phosphorus-containing compound, and absorbent cotton adheres to the molded body.

(Production Example 1)
In a vertical polymerization vessel having a distillation tube, a rectification tube, a nitrogen introduction tube and a stirring group, 100 parts by weight of the phosphorus-containing compound (A1), 60 parts by weight of itaconic acid equimolar to (A1), and itaconic acid 160 parts by weight of ethylene glycol having a molar amount of 2 times or more was added, and the temperature was gradually raised to 120 to 200 ° C. in a nitrogen gas atmosphere, followed by stirring for about 10 hours.
Next, 0.1 parts by weight of antimony trioxide and zinc acetate were added, and the polycondensation reaction was performed while distilling ethylene glycol while maintaining the temperature at 220 ° C. under a vacuum pressure of 1 Torr or less. About 5 hours later, the distillation amount of ethylene glycol was extremely reduced, and thus the reaction was considered to be completed. Properties of the obtained phosphorus-containing compound (A2) are shown in Table 1.

(Production Example 2)
100 parts by weight of the phosphorus-containing compound (A2) obtained in Production Example 1 in a vertical polymerization vessel having a distillation tube, a rectification tube, a nitrogen introduction tube and a stirring group, the theoretical composition ratio in the produced phosphorus-containing polymer 26.2 parts by weight of dihydric alcohol (C1), 0.13 parts by weight of stabilizer (E1) and 0.05% by weight of antimony trioxide so that (Structural Formula (1) / (2)) is 75/25. The temperature was gradually raised to 120 to 230 ° C. in a nitrogen gas atmosphere and stirred for about 5 hours.
Subsequently, the ester exchange reaction was carried out while distilling ethylene glycol while maintaining the temperature at 250 ° C. under a vacuum pressure of 1 Torr or less. About 6 hours later, when the charged dihydric alcohol (C1) and an equimolar amount of ethylene glycol flowed out, the reaction was considered to be completed.
Table 1 shows the properties of the obtained phosphorus-containing polymer (A3).

(Production Example 3)
Production Example 2 except that 52 parts by weight of (C1) is used as the dihydric alcohol so that the theoretical composition ratio (structural formula (1) / (2)) in the produced phosphorus-containing polymer is 50/50. The reaction was carried out in the same manner as above. Table 1 shows the properties of the obtained phosphorus-containing polymer (A4).

(Production Example 4)
Production Example 2 except that 79 parts by weight of (C1) is used as the dihydric alcohol so that the theoretical composition ratio (structural formula (1) / (2)) in the produced phosphorus-containing polymer is 25/75. The reaction was carried out in the same manner as above. Table 1 shows the properties of the obtained phosphorus-containing polymer (A5).

(Production Example 5)
Production Example 2 except that 39 parts by weight of (C2) is used as the dihydric alcohol so that the theoretical composition ratio (structural formula (1) / (2)) in the produced phosphorus-containing polymer is 25/75. The reaction was carried out in the same manner as above. Table 1 shows the properties of the obtained phosphorus-containing polymer (A6).

(Production Example 6)
Production Example 2 except that 105 parts by weight of (C1) is used as the dihydric alcohol so that the theoretical composition ratio (structural formula (1) / (2)) in the produced phosphorus-containing polymer is 25/75. The reaction was carried out in the same manner as above. Table 1 shows the properties of the obtained phosphorus-containing polymer (A7).

(Production Example 7)
100 parts by weight of phosphorus-containing compound (A1) and 60 parts by weight of equimolar itaconic acid with respect to (A1) are charged into a vertical polymerization vessel having a distillation tube, a rectification tube, a nitrogen introduction tube and a stirring group, The temperature was gradually raised to 150 ° C. to 200 ° C., followed by stirring for 3 hours. After lowering the temperature to 120 ° C., 22 parts by weight of ethylene glycol and (C1) so that the theoretical composition ratio (structural formula (1) / (2)) in the resulting phosphorus-containing polymer is 75/25. 47 parts by weight was added, and the temperature was gradually raised to 120 to 190 ° C. in a nitrogen gas atmosphere, followed by stirring for about 5 hours.
Subsequently, dehydration polycondensation was performed while maintaining the temperature at 250 ° C. under a vacuum pressure of 1 Torr or less. About 6 hours later, when the outflow of water and unreacted diol components disappeared, the reaction was considered to be completed. Table 1 shows the properties of the obtained phosphorus-containing polymer (A8).

(Examples 1-5)
In accordance with the raw materials and blending composition (unit: parts by weight) shown in Table 2, dry blending was performed in advance. Using a vent type 44mmφ same-direction twin screw extruder (manufactured by Nippon Steel Works Co., Ltd., TEX44), the mixture is supplied from the hopper hole, melt kneaded at a cylinder set temperature of 250 to 280 ° C, and pelletized. It was.
The obtained pellet was injection-molded under the above conditions to obtain a test piece, and an experiment was performed using the evaluation method described above.
Table 2 shows the evaluation results in Examples 1 to 5.

(Comparative Examples 1-3)
According to the blending composition shown in Table 2 (unit: parts by weight), pelletization and injection molding were carried out in the same manner as in Examples 1 to 5 to obtain test pieces, and experiments were conducted using the same evaluation method.
The evaluation results in Examples 5 to 6 are shown in Table 2.

  From the comparison of the examples and comparative examples, by including the phosphorus-containing polymer of the present invention in the resin composition as a flame retardant, the delamination of the molded product is improved, the bleed-out is less even after high temperature exposure, and the tensile It is clear that the decrease in mechanical properties such as strength and tensile elongation is small.

  The phosphorus-containing polymer of the present invention can be suitably used as a flame retardant for thermoplastic resins.

Claims (4)

In the main chain, the following structural formula (1)

And structural formula (2)

(Wherein, -A- is, -O -, - S -, - SO -, - SO 2 -, - CO-, an alkylene group or alkylidene group having 6 to 20 carbon atoms, having 1 to 20 carbon atoms , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are all hydrogen atoms, halogen atoms, or monovalent hydrocarbon groups having 1 to 5 carbon atoms, R ⁹ and R ¹⁰ are each a divalent hydrocarbon group having 1 to 5 carbon atoms, and they may be the same or different, and m and n represent the number of repeating units of the oxyalkylene group. 2 ≦ m + n ≦ 50.)
The phosphorus containing polymer which has the structural unit represented by these in the same molecule | numerator. A flame retardant comprising the compound according to claim 1 as a main component. Structural formula (3)

Phosphorus-containing compound represented by the formula: ethylene glycol and structural formula (4)

Characterized by polycondensation of a dihydric alcohol represented by
The manufacturing method of the phosphorus containing compound of Claim 1. Structural formula (3)

Obtained by polycondensation of a phosphorus-containing compound represented by formula (II) with ethylene glycol.

In the compound represented by the formula (4)

(Wherein, -A- is, -O -, - S -, - SO -, - SO 2 -, - CO-, an alkylene group or alkylidene group having 6 to 20 carbon atoms, having 1 to 20 carbon atoms , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are all hydrogen atoms, halogen atoms, or monovalent hydrocarbon groups having 1 to 5 carbon atoms, R ⁹ and R ¹⁰ are each a divalent hydrocarbon group having 1 to 5 carbon atoms, and they may be the same or different, and m and n represent the number of repeating units of the oxyalkylene group. 2. The process for producing a phosphorus-containing polymer according to claim 1, wherein a dihydric alcohol represented by 2 ≦ m + n ≦ 50 is allowed to act to cause a deethylene glycol reaction.