JPH021762A - Bis(pentabromophenoxy)diphenylsilane-blended flame-retardant high polymer composition - Google Patents

Abstract

PURPOSE:To obtain a flame-retardant high polymer composition having excellent compatibility with high polymer, heat resistance and water resistance and containing bis(pentabromophenoxy)diphenylsilane as a flame retardant capable of exhibiting high flameretardant effect by a small amount of addition thereof. CONSTITUTION:The aimed flame-retardant high polymer composition obtained by blending (A) 100 pts.wt. high polymer (e.g., polyethylene, epoxy resin or styrene-butadiene rubber) with (B) 3-100 pts.wt., preferably 10-50 pts.wt. bis(pentabromophenoxy)diphenylsilane expressed by the formula obtained by reaction of pentabromophenol with a dihalogenodiphenylsilane and as necessary flame-retardant auxiliary (e.g., antimony trioxide), other flame retardant and other additives (e.g., antioxidant, filler and crosslinking agent), having excellent flame retardance and free from breed-out of flame retardant in molding or long-term storage.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a flame-retardant polymer composition containing bis(pentabromophenoxy)diphenylsilica.

(Prior Art) Various halogen-containing flame retardants, phosphorus-containing flame retardants, phosphorus-containing halogen-containing flame retardants, inorganic compounds, and the like have been known as flame retardants for polymers. As highly heat-resistant polymers have been developed in recent years, the processing and use temperatures of polymers have also increased, and flame retardants that are stable even at high temperatures have been required.

However, there are still few flame retardants with excellent heat resistance, and they have drawbacks such as corrosion of the molding tank due to thermal decomposition of the flame retardant during polymer molding. Furthermore, when a flame retardant is added to a polymer, there is a problem in that the inherent properties of the polymer are deteriorated, such as a decrease in the mechanical properties and electrical properties of the polymer. In addition, in recent years, laws and regulations regarding flame retardation have become more stringent, both domestically and internationally.For example, exported products to the United States must pass UL standards, and the most stringent standards are UL94-VO. There are many things that are strongly required to be achieved. In order to meet the above demands, it is necessary to develop a flame retardant that exhibits a high flame retardant effect even when added in a small amount and has excellent heat resistance.

In order to solve these problems, the use of various flame retardants has been proposed. For example, U.S. Patent No. 4.476.267
No. 4,476.268 discloses a flame-retardant resin composition in which bis(tribromophenoxy)dimethylsilane (hereinafter abbreviated as TBMS) is blended with polystyrene and ABS resin to improve resin physical properties such as impact resistance. things are disclosed. Also, in U.S. Patent No. 3,546,267, bis(pentabromophenoxy)dimethylsilane (hereinafter abbreviated as PBMS)
, describes a method for producing bis(tribromophenoxy)diphenylsilane (hereinafter abbreviated as TBPS), and describes that it is useful as a flame retardant.

However, these compounds still have unsatisfactory heat resistance as measured by a 5% heating weight loss temperature of 350°C or less, and when added to a resin, the flame retardant bleeds out onto the resin surface, resulting in poor appearance. It had the disadvantage that a significant decrease in In addition, these flame retardants have poor water resistance, and when exposed to high-temperature steam, they decompose and reduce electrical insulation.

(Problems to be Solved by the Invention) The purpose of the present invention is to overcome the drawbacks of the prior art and to incorporate a flame retardant that has excellent compatibility with polymers, has improved heat resistance and water resistance, and has an excellent flame retardant effect. An object of the present invention is to provide a polymer composition comprising:

(Means for Solving the Problems) In view of the above circumstances, the present inventors synthesized various compounds and found them suitable as flame retardants having excellent flame retardancy, high heat resistance, and good compatibility with polymers. As a result of intensive studies on compounds that can be used, we found that bis(pentabromophenoxy)diphenylsilane (hereinafter abbreviated as PBPS) satisfies the above conditions and imparts a significantly high flame retardant effect when blended with a high molecular weight polymer. They discovered this and arrived at the present invention.

That is, the present invention is based on 1 part by weight of 100 polymers,
This is a flame-retardant polymer composition characterized by containing 3 to 100 parts by weight of bis(pentabromophenoxy)diphenylsilane represented by Formula 1.

This will be explained in more detail below. The bis(pentabromophenoxy)diphenylsilane of the present invention can be obtained by a commonly known reaction such as a reaction between pentabromophenol and dihalogenodiphenylsilane.

In the present invention, target polymers for blending the compound of formula (1) as a flame retardant for polymers are not particularly limited, but include polyethylene, polypropylene, polybutene, ethylene-vinyl acetate, etc. Polymer, ethylene-ethyl acrylate copolymer, ethylene propylene copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate-grafted vinyl chloride copolymer, ethylene-ethyl Acrylate-grafted vinyl chloride copolymer, ethylene propylene-grafted vinyl chloride copolymer, chlorinated polyethylene, chlorinated polyethylene-grafted vinyl chloride copolymer, polyamide, acrylic resin, polyethylene, polycarbonate, polybutylene terephthalate, Thermoplastic resins or elastomers such as polyethylene terephthalate, acrylonitrile-butadiene-styrene copolymer, thermosetting resins such as polyester, polyurethane, epoxy resin, phenolic resin, melamine resin, urea resin, and butyl rubber, chlorobrasion rubber, nitrile rubber, Natural rubber, silicone comb, chlorosulfosinated polyethylene, styrene butadiene rubber, polyester
Examples include ether elastomer. These polymers may be used alone or in combination of two or more.

When the compound represented by formula (1) is used as a flame retardant for polymers, the amount added is 3 to 10 parts per 100 parts by weight of the polymer.
0 parts by weight, preferably 10 to 50 parts by weight are selected. The reason for this is that if it is less than 1 part by 3 weight, the flame retardant effect is insufficient, and if it exceeds 1 part by 100 weight, the effect of increasing the amount is hardly seen.

When the compound represented by formula (1) is used as a flame retardant for polymers, the method of adding it to the polymer is not particularly specified, but for example, a method of kneading and blending the polymer and the flame retardant, a method of melt-molding the mixture, etc. , a method in which the flame retardant is added at the final stage of polymerization of the polymer, or a method in which the polymer and the flame retardant are each brought into a solution state and then mixed, and then reprecipitated with a poor solvent or the solvent is evaporated.

In addition, when the compound represented by formula (1) is used as a flame retardant for polymers, it is also possible to use a flame retardant aid (for example, antimony trioxide) or other known flame retardants in order to enhance the flame retardant effect. good. Other known additives (for example, colorants, ultraviolet absorbers, antioxidants, fillers, lubricants, surfactants, crosslinking agents, etc.) may be added as necessary.

(Effects of the Invention) As shown in Table 1, the PBPS of the present invention has significantly better heat resistance and hot water resistance than the already disclosed silane compounds such as TBMS, TBPS, and PBMS.

The polymer composition containing the compound of the present invention has an extremely high flame retardant effect even with the addition of a small amount of I, and has excellent heat resistance, and no fleet-out phenomenon is observed during molding or long-term storage.

(Examples) Hereinafter, the present invention will be explained in more detail according to Examples, but the present invention is not limited only by these examples.

Example 1 Synthesis of bis(pentabromophenoxy)diphenylsilane Dimethylacetamide (750 ml) and pentabromophenol 2 were placed in a 21 round bottom four rotorable flask equipped with a calcium chloride tube, a power stirrer, and a continuous condenser.
00.0g (0,410mof), pyridine 32.2g
(0,410m0+) was added one after another and stirred to make a homogeneous solution. Then dichlorodiphenylsilane 5
1.6 g (0,205 mol) was added, and the mixture was refluxed at 80°C for 3 hours.

After cooling, 400 rnl of methanol was added and the resulting precipitate was filtered. After washing the precipitate with methanol 10100O,
White crystals were obtained by drying at 10°C for 4 hours. Melting point 280.2°, yield ft 141.99, yield 60.0%
Met. Also, the elemental analysis values are C: 24.7%, H: 0.
9%, Br: 68.9%, (calculated value C: 24.89%,
H: 0.88%, Br: 69.05%) and were in direct agreement. Further, it was confirmed to be pure by high performance gel permeation liquid chromatography analysis using a TSK GEL G-10008 (manufactured by Tosoh Corporation) column (eluent: tetrahydrofuran). From the above, it was confirmed that the compound of formula (1) was synthesized.

Comparative Example 1 Synthesis of bis(tribromophenoxy)dimethylsilane Dimethylacetamide (1500 ml) and tribromophenol 3 were placed in a 41 round bottom separable flask equipped with a calcium chloride tube, a power stirrer, and a continuous condenser.
00.0g (0,907mol), pyridine 71.2g
(0,907 mol) were sequentially added and stirred to form uniform droplets. Then dichlorodimethylsilane 56. Add tg (0,453 mol) and heat at 800C for 3
Refluxed for an hour. After cooling, the solution was concentrated and diluted with ethanol (10
00ml). The resulting precipitate was filtered, washed with 10,100 O ethanol, and then dried at 110°C for 4 hours to obtain white crystals. Melting point 116-118°C1
The total amount was 155.4 g, and the yield was 48.4%. Also, the elemental analysis values are C: 23.5%, H: 1.5%, Br: 66
．． 6%, (calculated value C: 23.40%, H: 1.40%,
Br: 66.80%) and were in agreement. Also TSK
It was confirmed to be pure by high performance gel permeation liquid chromatography analysis using a GEL G-1000H (manufactured by Tosoh Corporation) column (eluent: tetrahydrofuran). From the above, it was confirmed that TBMS was synthesized.

Comparative Example 2 Synthesis of bis(tribromophenoxy)diphenyl Shirashi Dimethylacetamide (1500 ml) and tribromophenol 3 were placed in a 41 round-bottomed 4-rose Paraflu flask equipped with a calcium chloride tube, a power stirrer, and a reflux condenser.
00.0g (0,907mol), pyridine 71.2g
(0,907 mol) were sequentially added and stirred to form a homogeneous solution. Then dichlorodiphenylsilane 1
Add 14.1g (0,453mol) and heat at 80°C.
Refluxed for an hour.

After cooling, the solution was concentrated and poured into ethanol (1000 ml). Filter the resulting precipitate and add ethanol 1010
White crystals were obtained by washing at 0O and drying at 110°C for 4 hours. Melting point 165-170'C2 yield 157.
6g, yield 48.4%. Also, the elemental analysis value is C:
34.5%, H: 1.5%, Br: 56.7%, (calculated value C: 34.20%, H: 1.68%, Br: 56.
96%) and were in agreement. Also TSK GEL G
-10008 (manufactured by Tosoh Corporation) column (eluent: tetrahydrofuran), analysis by high performance gel permeation liquid chromatography confirmed that the product was pure. From the above, it was confirmed that TBPS was synthesized.

Comparative Example 3 Synthesis of bis(pentabromophenoxy)dimethylsilane Dimethylacetamide (1500 ml) and pentabromophenol 200.0 g (0.0 , 410 mol), pyridine 32.2
g (0,410 m0I) were sequentially added and stirred to obtain a homogeneous solution. Then dichlorodimethylsilane 2
6.5 g (0.205 mof) was added and refluxed at 80° for 3 hours.

After cooling, 800 ml of methanol was added and the resulting precipitate was filtered. After washing the precipitate with 1000ml of methanol,
White crystals were obtained by drying at 0°C for 4 hours. Melting point 2
03-220°C1 yield 143.2g, yield 67.6%
Met. Also, the elemental analysis values are C: 16.4%, H: 0.
6%, Br near 7.1%, (calculated value C: 16.27%
, H: 0.59%, Br near: 7.33%) and were in agreement. Further, it was confirmed to be pure by high performance gel permeation liquid chromatography analysis using a TSK GEL G-1000H (manufactured by Tosoh Corporation) column (eluent: tetrahydrofuran). From the above, it was confirmed that PBPM was synthesized.

The thermal stability of the compounds obtained in Example 1 and Comparative Examples 1 to 3 was analyzed by TGA under the following conditions, and the results are shown below.The hot water resistance of the crystals was also examined under the following conditions. Crystal 5.09 to 1
The suspension was suspended in 00ml of water and refluxed. After 6 hours, the crystals were filtered and the purity was measured by analysis by high performance gel permeation liquid chromatography using a TSK GEL G-10008 (manufactured by Tosoh Corporation) column (eluent: tetrahydrofuran). The results are summarized in Table 1. In addition, if sublimate (tribromophenol) was attached to the reflux condenser, it was described as having an attached substance.

Examples 2 to 5 Boppropyregi (Chisso 7014, impact resistant grade)
The pellets were roll-kneaded with the compounds in the proportions (parts by weight) shown in Tables 2-1 and 2-2 at 180°C for 12 minutes. Regarding the roll kneading properties, those with no adhesion of resin or flame retardant to the roll and no decomposition of the flame retardant were rated as good. Items that may cause adhesion to rolls or decomposition of flame retardants were allowed. Kneaded material at 200°C
Heat press (100kg/cm2) for 2 minutes at L, 30
It was cooled for 5 minutes under pressure (100 kg/cm2) at 1°C to obtain a sheet with a thickness of 3 mm. The sheet JISK-7
201-1972, a test piece for measuring 01 (oxygen index) was prepared, and a UL94 flammability test piece with a thickness of 3 mm was prepared, and a vertical combustion test was conducted on each.

Furthermore, the 3 mm thick sheet after press molding was left at 160°C for 100 hours, and the heat resistance was evaluated by measuring the ΔE value (color difference) after being left. If the resin was severely cracked and the resin turned black, making it impossible to measure, it was judged as impossible. Regarding fleet-out, the surface condition of the molded sheet was visually judged after being left for 30 days. The above results are summarized in Table 2-1 and Table 2-2. Further, the relationship between the number of blended parts of flame retardant and the oxygen index is shown in FIG.

Comparative Examples 4 to 14 Polypropylene (Chisso 7014, impact resistant grade)
The pellets alone or the compounds in the proportions shown in Tables 2-1 and 2-2 were kneaded on a roll at 180°C for 12 minutes. Heat press the mixed wire material at 200'C for 2 minutes (100k
g/cm2) t, under 30°C2 pressure (100kg/cm2)
cm2) for 5 minutes to obtain a sheet with a thickness of 3 mm. The results of evaluation using the same method as Examples 2 to 5 are shown in Tables 2-1 and 2-2, and in FIG.

Examples 6 to 9 High impact resistant polystyrene resin (Idemitsu styrene HT 5
0 (hereinafter abbreviated as HIPS), the composition shown in Table 3 (each part by weight) was extruded into pellets at an extrusion temperature of 220°C using a D20-25 extruder at Toyo Seiki Seisakusho Labo Blast Mill. The pellets were heated at 230'C for 5 minutes (100 kg/cm2) and cooled for 5 minutes at 30'C under pressure (100 kg/cm2) to obtain a sheet with a thickness of 3 mm. The sheet JIS K-7201-
1972, a test piece for 01 (oxygen index) measurement was prepared, and a 3 mm thick test piece for UL94 flammability test was prepared, and a vertical combustion test was conducted on each. In addition, a 3 mm thick sheet after press molding was heated at 120°C for 50 minutes.
The heat resistance was evaluated by leaving it for a time and measuring the ΔE value (color difference) after leaving it. Regarding bleed-out, the surface condition of the molded sheet after being left for 30 days was visually determined. The above results are summarized in Table 3.

Comparative Examples 15 to 19 HIPS (Idemitsu Styrofoam HT-50) alone or the composition shown in Table 3 was extruded at 220° using a D20-25 extruder at Toyo Seiki Seisakusho Labo Plastomill.
It was extruded into pellets using C. Thereafter, the results were evaluated in the same manner as in Examples 6 to 9, and the results are shown in Table 3.

[Brief explanation of the drawing]

FIG. 1 shows the relationship between the number of blended parts of flame retardant and the oxygen index of each sheet obtained in Examples 2 to 5 and Comparative Examples 4 to 14. Number of parts (Phr)

Claims (1)

[Claims] 3 to 100 parts by weight of bis(pentabromophenoxy)diphenylsilane represented by formula 1 ▲Mathematical formula, chemical formula, table, etc.▼(1) is blended with 100 parts by weight of the polymer. A flame-retardant polymer composition characterized by: