JPH05163288A - Phosphonate compound, resin-compounding agent and flame-retardant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the subject new compound capable of giving a flame- retardant thermoplastic resin composition having high flame-retardance, low volatility at a high temperature and high heat-resistance and bleeding resistance and useful as a resin-compounding agent to impart flame-retardance to a thermoplastic resin. CONSTITUTION:The phosphonate compound of formula (R and R' are aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group), e.g. pentaerythritol diphenylphosphonate. The compound is produced by reacting 1mol of pentaerythritol with 2-3mol of a phosphonic acid halide such as methylphosphonic acid dichloride and phenylphosphonic acid dichloride in the presence of a dehalogenation catalyst (e.g. pyridine) in a solvent (e.g. dioxane) at 50-250 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel phosphonate compound, a resin compounding agent comprising the compound, and a flame-retardant thermoplastic resin composition containing the resin compounding agent. More specifically, the present invention relates to a novel phosphonate compound having a spiro ring, a resin compounding agent comprising this compound, and
The present invention relates to a flame-retardant thermoplastic resin composition comprising a thermoplastic resin and this resin compounding agent.

[0002]

BACKGROUND OF THE INVENTION Organic phosphorus compounds have been used as flame retardants for thermoplastic resins. Examples of the organic phosphorus compound include phosphate compounds such as triphenyl phosphate, trixylenyl phosphate and polyphosphate ester.

However, when these phosphate compounds are blended with a thermoplastic resin, the heat resistance and physical properties of the resin may deteriorate. Further, this phosphate compound has a problem that at least a part of the phosphate compound is lost from the resin by volatilization or bleeding when the resin is heated to a high temperature. As described above, regarding the flame retardant method of the thermoplastic resin, there is currently no satisfactory organic phosphorus compound, and the physical properties of the resin are not deteriorated by blending, and further, it is lost by volatilization and bleeding during blending. There is a strong demand for the development of a new phosphorus-based compounding agent that does not have any of these.

[0004]

OBJECTS OF THE INVENTION The present invention provides novel phosphonate compounds. Another object of the present invention is to provide a novel compounding agent which imparts flame retardancy to a thermoplastic resin. Further, the present invention also aims to provide a flame-retardant thermoplastic resin composition comprising a thermoplastic resin and the phosphonate compound.

[0005]

SUMMARY OF THE INVENTION The phosphonate compound of the present invention is represented by the following formula [I].

[0006]

[Chemical 4]

[I] However, in the above formula [I], R and R'each independently represent a group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. Indicates the selected group,
These groups may have a halogen atom or another substituent.

The resin compounding agent of the present invention is characterized by comprising a phosphonate compound represented by the above formula [I]. Furthermore, the flame-retardant thermoplastic resin composition of the present invention comprises a thermoplastic resin and 1 to 30 parts by weight of the phosphonate compound represented by the above formula [I] per 100 parts by weight of the thermoplastic resin. It is characterized by

The present invention provides novel phosphonate compounds. By blending this phosphonate compound with a thermoplastic resin, flame retardancy of the thermoplastic resin can be achieved. The thermoplastic resin composition containing the phosphonate compound does not deteriorate the properties such as heat resistance and impact resistance due to the addition of the flame retardant, and the phosphonate compound which is the flame retardant during kneading is It is not lost from the resin due to evaporation or bleeding.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below. First, the phosphonate compound of the present invention will be described.

The phosphonate compound of the present invention can be represented by the following formula [I].

[0012]

[Chemical 5]

[I] However, in the above formula [I], R and R ′ are each independently selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. The selected group is shown.
Further, these groups may have a halogen atom or other substituent.

Examples of the aliphatic hydrocarbon group include alkyl groups having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms. Specific examples of this alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, tert-butyl group, n-amyl group, n-hexyl group and n-octyl group. Can be mentioned.

Examples of the alicyclic hydrocarbon group include groups having an alicyclic structure having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms. A specific example of this group is:
Mention may be made of cyclopropyl groups and cyclohexyl groups.

Further, examples of the aromatic hydrocarbon group include:
An aromatic hydrocarbon group having 6 to 18 carbon atoms can be mentioned. Specific examples of this group include a phenyl group, a naphthyl group and an anthracenyl group.

These groups mentioned above may have a halogen atom or other substituents. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a bromine atom is preferable. Moreover, a hydroxyl group, an alkyl group, and an alkoxy group can be mentioned as an example of another substituent.

Specific examples of the phosphonate compound represented by the above formula [I] include pentaerythritol dimethylphosphonate, pentaerythritol diethylphosphonate, pentaerythritol dicyclohexylphosphonate, pentaerythritol diphenylphosphonate, pentaerythritol di (methylphenyl) phosphonate. , Pentaerythritol di (dimethylphenyl) phosphonate and pentaerythritol di (tert-butylphenyl) phosphonate. Among these, compounds in which R and R ′ in the formula [I] are aromatic hydrocarbon groups, preferably compounds having a phenyl group, can be produced in high yield and are useful as flame retardants. Is high.

The phosphonate compound of the present invention can be synthesized by reacting pentaerythritol with a halide of phosphonic acid having a group corresponding to R and R '.

As the phosphonic acid halide having a group corresponding to R and R ', a chloride is usually used. Specifically, examples of this chloride include methylphosphonic acid dichloride, ethylphosphonic acid dichloride, cyclohexylphosphonic acid dichloride, phenylphosphonic acid dichloride, methylphenylphosphonic acid dichloride,
Examples thereof include dimethylphenylphosphonic acid dichloride, tert-butylphenylphosphonic acid dichloride dichloride, and naphthylphosphonic acid dichloride.

These phosphonic acid halides are usually used in an amount of 2 mol or more, preferably 2 to 3 mol, based on 1 mol of pentaerythritol. The reaction between the halide of phosphonic acid and pentaerythritol is a dehydrohalogenation reaction, and therefore the reaction is carried out in the presence of a dehydrohalogenation catalyst. Examples of dehydrohalogenation catalysts used herein include basic substances such as pyridine and sodium methoxide.

The reaction between the halide of phosphonic acid and pentaerythritol is usually carried out in a reaction solvent. Here, as the reaction solvent, an organic polar solvent such as dioxane can be used.

The above reaction usually proceeds under heating. The heating temperature is usually 50 to 250 ° C. A spiro ring is formed in the phosphonate compound obtained as described above. The resin compounding agent of the present invention comprises a phosphonate compound represented by the above formula [I], and the resin becomes flame-retardant by incorporating this phosphonate compound.

This resin compounding agent has a phosphorus content of 10% by weight.
The above phosphonate compound is preferable,
Phosphonate compounds having a phosphorus content in the range of 12 to 25% by weight are especially preferred. Phosphonate compounds having a phosphorus content of less than 10% by weight have to be added in a large amount in order to make the thermoplastic resin flame-retardant, which is not economical.

As the resin compounding agent of the present invention, the phosphonate compounds represented by the above formula [I] can be used alone or in combination. Among these phosphonate compounds having a spiro ring, pentaerythritol diphenyl is used. It is preferable that the phosphonate alone or the main component is pentaerythritol diphenylphosphonate.

The flame-retardant thermoplastic resin composition of the present invention comprises the above-mentioned resin compounding agent (ie, the phosphonate compound represented by the formula [I]) and a thermoplastic resin. The thermoplastic resin used in the present invention is a melt-moldable resin, and specific examples of such a thermoplastic resin include polycarbonate resin, polyester resin, polyamide resin, polyphenylene ether resin, and polyolefin. Examples thereof include resin based resins, cyclic olefin based resins and polystyrene based resins. These resins are used alone or in combination. Further, these thermoplastic resins may form an alloy with the above resin or a resin other than the above resin. By forming the alloy in this way, physical properties such as impact resistance, heat resistance, and chemical resistance are generally improved.

The composition of the present invention contains the above phosphonate compound in an amount of 1 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the thermoplastic resin. By containing the phosphonate compound in the amount as described above, the composition has good flame retardancy,
It is possible to effectively prevent deterioration of the physical properties of the resin due to the inclusion of the phosphonate compound.

The flame-retardant thermoplastic resin composition of the present invention can be applied with various methods generally employed when blending a plasticizer, a stabilizer, a colorant or a filler. For this blending, a general mixer such as an extruder or a plastomill can be used.

The flame-retardant thermoplastic resin composition of the present invention comprises a thermoplastic resin and a specific phosphonate compound as described above, but other additives such as, for example, Reinforcing agent such as glass fiber, filler,
A filler, a stabilizer, a plasticizer, a lubricant, an antistatic agent, a foaming agent and the like can be used in combination. It also does not interfere with blending of other polymers, if desired.

The flame-retardant thermoplastic resin composition of the present invention is used for a wide range of applications from household products to industrial products, for example, electric parts, electronic parts, automobile parts, machine mechanism parts, synthetic fibers and the like.

[0031]

The present invention provides a novel phosphonate compound. This phosphonate compound can be used as a resin compounding agent for obtaining a flame-retardant thermoplastic resin composition.

The flame-retardant thermoplastic resin of the present invention containing the phosphonate compound is a thermoplastic resin,
Since it is composed of a specific phosphonate compound having a spiro ring, it has both high flame retardancy and low volatility at high temperature, heat resistance, bleed resistance and the like.

[0033]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0034]

Example 1 Synthesis of pentaerythritol diphenylphosphonate In a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 39 g of phenylphosphonic acid dichloride was added.
(0.2 mol), 13.6 g of pentaerythritol (0.1 mol).
1 mol), 1,4-dioxane (500 ml) and pyridine as a dehydrochlorination catalyst (31.6 g) were added, and the mixture was reacted at a reaction temperature of 60 to 80 ° C. for 3 hours and then at a temperature of 145 to 150 ° C. for 1 hour.

The reaction mixture was cooled, and the reaction mixture was gradually added to 1 liter of methanol while stirring to obtain white crystals. The crystals were separated by filtration, washed with methanol, purified, and dried to obtain 30.2 g of white crystals. The melting point of this white crystal measured by DSC was 267 ° C.

The ¹ H-NMR spectrum of this white crystal was measured. The chart of this ¹ H-NMR spectrum is shown in FIG. From the results of the above analysis, this white crystal was identified as pentaerythritol diphenylphosphonate. Yield: 80% From the result of elemental analysis, the phosphorus content rate in the obtained pentaerythritol diphenylphosphonate is 1
It was 6.9% by weight.

Preparation of Resin Composition As a thermoplastic resin, a bisphenol A-based polycarbonate (having an intrinsic viscosity of 0.50 dl / g measured in a dichloromethane solvent at 20 ° C.) (A), and a phosphonate compound having a spiro ring as described above. Pentaerythritol diphenylphosphonate (melting point 267
(° C, phosphorus content analysis value 16.9%) (B) was used.

100 parts by weight of (A) and 5 parts by weight of (B) were mixed together and then mixed with an extruder having a screw diameter of 40 mm to obtain 280 parts.
The mixture was kneaded at ℃ and pelletized. From the pellets, using an injection molding machine with a mold clamping force of 50 tons, at an injection temperature of 300 ° C,
Combustion test specimens and various physical property test specimens were prepared. The prepared test piece had good transparency, and neither foaming nor coloring was observed.

Table 1 shows the results of various physical properties measured using these test pieces. Various physical properties were measured under the following conditions. Flammability: UL-94 standard, sample thickness 1 /
32-inch oxygen index: measured according to JIS K7201.

Impact strength: JIS K710
0, notched Izod impact strength was measured. Flexural strength, flexural modulus: Measured according to JIS K7203.

Heat distortion temperature: JIS K720
2 was measured under the condition of a load of 18.6 kg / cm ² .

[0042]

Example 2 A test piece was prepared in the same manner as in Example 1 except that the compounding amount of the phosphorus compound (B) was changed to 10 parts by weight, and the test piece was subjected to the same conditions as in Example 1. The test was conducted at. The results are shown in Table 1.

[0043]

Comparative Example 1 A test piece was prepared in the same manner as in Example 1 except that the phosphorus compound (B) was not added, and this test piece was tested under the same conditions as in Example 3.
The results are shown in Table 1.

[0044]

Comparative Example 2 A test piece was prepared in the same manner as in Example 1 except that 10 parts by weight of trixylenyl phosphate was added instead of the phosphorus compound (B), and the test piece was prepared. The test was conducted under the same conditions as in Example 3. The results are shown in Table 1.

[0045]

[Table 1]

[0046]

Example 3 As a thermoplastic resin, nylon-66 (30
(C) 100 parts by weight was used, and 5 parts by weight of the phosphorus compound (B) synthesized in the above Example 1 was used as the phosphorus compound. They were used and mixed, and then kneaded at 280 ° C. using an extruder having a screw diameter of 40 mm to form pellets.

From the pellets, a test piece for combustion test and a test piece for various physical property tests were prepared at an injection temperature of 280 ° C. using an injection molding machine having a mold clamping force of 50 tons. No foaming or coloring was observed in the prepared test piece.

Table 2 shows the results of various physical properties measured using these test pieces.

[0049]

Example 4 A test piece was prepared in the same manner as in Example 3 except that the compounding amount of the phosphorus compound (B) was changed to 10 parts by weight, and the test piece was subjected to the same conditions as in Example 3. The test was conducted at. The results are shown in Table 2.

[0050]

Comparative Example 3 A test piece was prepared in the same manner as in Example 3 except that the phosphorus compound (B) was not added, and this test piece was tested under the same conditions as in Example 3.
The results are shown in Table 2.

[0051]

[Comparative Example 4] A test piece was prepared in the same manner as in Example 3 except that 10 parts by weight of trixylenyl phosphate was added instead of the phosphorus compound (B). The test was conducted under the same conditions as in Example 3. The results are shown in Table 2.

[0052]

[Table 2]

[0053]

Example 5 Poly (2,6-dimethyl-1,4-phenylene) having an intrinsic viscosity of 0.51 dl / g (measured in chloroform at 25 ° C.)
46 parts by weight of ether and high impact polystyrene (Asahi Dow
Manufactured by KK, 475D) 54 parts by weight and phosphorus compound (B)
3 parts by weight were melt mixed and pelletized at 250 ° C. using a twin-screw extruder having a screw diameter of 45 mm.

From the pellets, a test piece for combustion test and a test piece for various physical property tests were prepared at an injection temperature of 260 ° C. using an injection molding machine having a mold clamping force of 50 tons. Table 3 shows the results of various physical properties measured using these test pieces.

[0055]

Example 6 A test piece was prepared in the same manner as in Example 5 except that the compounding amount of the phosphorus compound (B) was changed to 5 parts by weight, and the test piece was subjected to the same conditions as in Example 5. The test was conducted at. The results are shown in Table 3.

[0056]

Comparative Example 5 A test piece was prepared in the same manner as in Example 5 except that the phosphorus compound (B) was not added, and this test piece was tested under the same conditions as in Example 5.
The results are shown in Table 3.

[0057]

Comparative Example 6 A test piece was prepared in the same manner as in Example 5 except that 5 parts by weight of trixylenyl phosphate was added instead of the phosphorus compound (B), and this test piece was used. The test was conducted under the same conditions as in Example 5. The results are shown in Table 3.

[0058]

[Table 3]

[0059]

Example 7 Ethylene / tetracyclododecene copolymer (ethylene content 60 mol%, load 2.16 kg, 260
Melt flow index measured at ℃ 35g / 10
Min) 100 parts by weight, and 5 parts by weight of the phosphorus compound (B) were mixed and melt-mixed at 260 ° C. and pelletized by an extruder having a screw diameter of 45 mm.

Using these pellets, test pieces for combustion tests and various physical property tests were prepared in the same manner as in Example 1. Table 4 shows the results of various physical properties measured using these test pieces.

[0061]

Example 8 A test piece was prepared in the same manner as in Example 7, except that the compounding amount of the phosphorus compound (B) was changed to 10 parts by weight, and the test piece was subjected to the same conditions as in Example 7. The test was conducted at. The results are shown in Table 4.

[0062]

Comparative Example 7 A test piece was prepared in the same manner as in Example 7 except that the phosphorus compound (B) was not added, and this test piece was tested under the same conditions as in Example 7.
The results are shown in Table 4.

[0063]

Comparative Example 8 A test piece was prepared in the same manner as in Example 7 except that 10 parts by weight of trixylenyl phosphate was added instead of the phosphorus compound (B), and this test piece was used. The test was conducted under the same conditions as in Example 7. The results are shown in Table 4.

[0064]

[Table 4]

[0065]

Example 9 100 parts by weight of polyethylene terephthalate (having an intrinsic viscosity of 0.80 dl / g measured in an o-chlorophenol solvent at 25 ° C.) was used as a thermoplastic resin, and 5 parts by weight of (B) was used as a phosphorus compound. Use, mix both,
Using an extruder with a screw diameter of 40 mm, the mixture was kneaded at 280 ° C. and pelletized.

From the pellets, test pieces for combustion test and various physical property tests were prepared at an injection temperature of 280 ° C. by using an injection molding machine having a mold clamping force of 50 tons. No foaming or coloring was observed in the prepared test piece.

Table 5 shows the results of measurements of various physical properties using these test pieces.

[0068]

Example 10 A test piece was prepared in the same manner as in Example 9 except that the compounding amount of the phosphorus compound (B) was changed to 10 parts by weight, and the test piece was subjected to the same conditions as in Example 9. The test was conducted at. The results are shown in Table 5.

[0069]

Comparative Example 9 A test piece was prepared in the same manner as in Example 9 except that the phosphorus compound (B) was not added, and this test piece was tested under the same conditions as in Example 9.
The results are shown in Table 5.

[0070]

Comparative Example 10 A test piece was prepared in the same manner as in Example 9 except that 10 parts by weight of trixylenyl phosphate was added instead of the phosphorus compound (B), and this test piece was used. The test was conducted under the same conditions as in Example 9. The results are shown in Table 5.

[0071]

[Table 5]

[0072]

Example 11 Polypropylene (2
Melt flow rate at 30 ° C is 4.5 g / 10 minutes) 10
0 parts by weight and 10 parts by weight of (B) were used as a phosphorus compound, and both were mixed and then kneaded at 230 ° C. using an extruder having a screw diameter of 40 mm to form pellets.

Test pieces for combustion test and various physical property tests were prepared from the pellets at an injection temperature of 230 ° C. by using an injection molding machine having a mold clamping force of 50 tons. No foaming or coloring was observed in the prepared test piece.

Table 6 shows the results of various physical properties measured using these test pieces.

[0075]

Example 12 A test piece was prepared in the same manner as in Example 11 except that the compounding amount of the phosphorus compound (B) was changed to 10 parts by weight, and the test piece was subjected to the same conditions as in Example 11. The test was conducted at. The results are shown in Table 6.

[0076]

Comparative Example 11 A test piece was prepared in the same manner as in Example 11 except that the phosphorus compound (B) was not added, and this test piece was tested under the same conditions as in Example 11. The results are shown in Table 6.

[0077]

Comparative Example 12 A test piece was prepared in the same manner as in Example 11 except that 10 parts by weight of trixylenyl phosphate was added instead of the phosphorus compound (B).
This test piece was tested under the same conditions as in Example 11. The results are shown in Table 6.

[0078]

[Table 6]

[Brief description of drawings]

FIG. 1 is a chart of ¹ H-NMR spectrum of pentaerythritol diphenylphosphonate.

Claims (10)

[Claims] 1. A phosphonate compound represented by the following formula [I]: ... [I] [In the formula [I], R and R ′ each independently represent a group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. , These groups may have halogen atoms or other substituents]. 2. In the formula [I], R and R ′ are
Is an aromatic hydrocarbon group, The phosphonate compound according to claim 1, wherein 3. In the above formula [I], R and R '.
Is a phenyl group, The phosphonate compound according to claim 2, wherein 4. A resin compounding agent comprising a phosphonate compound represented by the following formula [I]: ... [I] [In the formula [I], R and R ′ each independently represent a group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. , These groups may have halogen atoms or other substituents]. 5. In the above formula [I], R and R '.
Is an aromatic hydrocarbon group, The resin compounding agent according to claim 4, characterized in that. 6. In the above formula [I], R and R '.
Is a phenyl group, The resin compounding agent according to claim 5, wherein 7. A thermoplastic resin and the thermoplastic resin 100.
Flame-retardant thermoplastic resin composition comprising 1 to 30 parts by weight of phosphonate compound represented by the following formula [I] with respect to parts by weight; ... [I] [In the formula [I], R and R ′ each independently represent a group selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. , These groups may have halogen atoms or other substituents]. 8. In the above formula [I], R and R '.
Is an aromatic hydrocarbon group, The flame-retardant thermoplastic resin composition according to claim 7, wherein. 9. In the above formula [I], R and R '
Is a phenyl group, The flame-retardant thermoplastic resin composition according to claim 8. 10. The thermoplastic resin is at least one resin selected from the group consisting of polycarbonate resins, polyester resins, polyamide resins, polyphenylene ether resins, polyolefin resins, cyclic olefin resins and polystyrene resins. The flame-retardant thermoplastic resin composition according to any one of claims 7 to 9, wherein