JPS6214531B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to 1,1-dihalo-2-(polybromophenoxymethyl)cyclopropane, its production method, and its uses. Various flammable materials such as synthetic resins, synthetic fibers, paper, and wood contain halogen-containing compounds, phosphorus-containing compounds,
It is widely known that flame retardants such as nitrogen-containing compounds are added to make flame retardant. Although a wide variety of compounds are known as flame retardants, halogen-containing compounds or compounds containing halogen and phosphorus are particularly effective. However, it is not enough for a flame retardant to simply have a high flame retardant effect; it is also required to have many properties such as not deteriorating the chemical and physical properties of the material to be flame retardant. Conventional flame retardants are not necessarily satisfactory in all respects, and new types of flame retardants have been required. The present inventor conducted various research studies on new flame retardants, and as a result, discovered a new compound having a dihalocyclopropane ring. The present invention is a novel 1,1-dihalo-2-(polybromophenoxymethyl)cyclopropane represented by the following general formula. X: Cl or Br n: An integer of 1 to 5 As described later, the compound of the present invention is effective as a flame retardant for synthetic resins and the like. Furthermore, known compounds similar to the compounds of the present invention, such as

Since [Formula] is known as a fungicide (see US Pat. No. 3,012,079), there is a possibility that the compound of the present invention can also be used as a biologically active agent such as a fungicide or insecticide, or as a raw material thereof. are doing. When used as a flame retardant, it is thought that the higher the halogen content, and the higher the flame softening effect of bromine than chlorine.
It is preferable that n be larger, but usually n is 4 to 5.
Since it is difficult to produce compounds of 1 to 3, compounds of 1 to 3 are suitable. The compounds of the present invention can be produced in a variety of ways, including:
Methods that can be used on an industrial scale can be roughly divided into the following two methods, focusing on the formation reaction of a dihalocyclopropane ring. The first is polybromophenyl allyl ether This is a method for producing 1,1-dihalo-2-(polybromophenoxymethyl)cyclopropane of the present invention by reacting dihalocarbene (:CX 2 ) with dihalocarbene (:CX ₂ ). The second method uses allyl halide (CH ₂ = CH
-CH ₂ Z, Z: Cl or Br) is reacted with dihalocarbene to produce 1,1-dihalo-2-halomethyl-cyclopropane.

Manufacture [formula] and add it to Polybromophenol

[Formula] is reacted to form the 1,1-dihalo-2- of the present invention.
(Polybromophenoxymethyl)cyclopropane. The production method of the present invention uses polybromophenyl allyl ether, allyl halide and dihalocarbene as raw materials, and uses a combination of halogenation, etherification and cyhalopropane ring formation reactions. The important reactions here are the formation of dihalocarbenes and the addition of these to α,β-unsaturated groups. Various methods are conventionally known for producing dihalocarbenes. For example, methods of reacting alkali metal alcoholates with haloforms, thermal decomposition of trihaloacetates, cleavage reactions of trichloroacetic acid alkyl esters, reactions of BrCCl ₃ with alkali metal hydrocarbons, decomposition of φHgCX ₃ , etc. are known. There are, but
Although these methods are possible on a laboratory scale, they are difficult to use on an industrial scale. Currently, dihalocarbenes, which can be used on an industrial scale, are formed by reacting haloform with aqueous alkali metal hydroxide in the presence of a catalyst. This reaction method is also applied to the production method of the present invention. That is,
A dihalocarbene is formed by reacting haloform with an aqueous alkali metal hydroxide solution in the presence of a phase transfer catalyst, particularly a quaternary ammonium salt, and at this time, a compound containing an α,β unsaturated group is present in the system. A dihalocyclopropane ring is thereby formed. Haloform is chloroform or bromoform. Preferred alkali metal hydroxides are sodium hydroxide or potassium hydroxide, with sodium hydroxide being most suitable on an industrial scale. A phase transfer catalyst is a catalyst that can move between an aqueous phase and an organic phase, and quaternary ammonium salts, quaternary phosphonium salts, and the like are known, but quaternary ammonium salts are preferred. Specific examples of quaternary ammonium salts include triethylbenzylammonium chloride, trimethylcetylammonium bromide, methyltricaprylylammonium chloride, tetrabutylammonium bromide, dodecyltrimethylammonium chloride, tetrapropylammonium chloride, n-hexadecyltributylammonium Examples of quaternary phosphonium salts include n-hexadecyltributylphosphonium bromide. By adding an aqueous alkali metal hydroxide solution in the presence of a phase transfer catalyst to the coexistence of haloform and an α,β-unsaturated group-containing compound, the dihalocarbenes formed immediately add to the α,β-unsaturated groups and di- Forms a halocyclopropane ring. Usually, haloform is used in excess to form an organic phase, which is then
-Dissolve or disperse unsaturated group-containing compounds. After adding a phase transfer catalyst to this organic phase, an aqueous alkali metal hydroxide solution is added. At this time, the amount of alkali metal hydroxide added is usually in excess of the α,β-unsaturated group-containing compound. Although the concentration of the alkali metal hydroxide aqueous solution is not particularly limited,
Since the yield decreases at low concentrations, it is preferably 10% by weight or more, particularly 20 to 60% by weight. Although the reaction temperature is not particularly limited, 5 to 90°C is used, and 20 to 60°C is suitable. The product is dissolved or dispersed in the organic phase and isolated by distillation or other methods. Etherification can be carried out by reacting halophenol and 1,1-dihalo-2-halomethyl-cyclopropane in the presence of an alkali. The present invention further relates to the use of this 1,1-dihalo-2-(halofenoxymethyl)cyclopropane as a flame retardant. In this case, in order to improve the flame retardant effect as mentioned above, Y is
Br is preferred, and n is suitably 1-3. The flame retardant of the present invention can be used alone or in combination with a flame retardant aid or other flame retardants. There are various flame retardant aids such as antimony compounds, tin compounds, and boron compounds, but antimony compounds such as antimony trioxide are preferred. Other flame retardants include halogen-containing compound flame retardants, phosphorus-containing compound flame retardants, nitrogen-containing compound flame retardants, and flame retardants containing halogen, phosphorus, or both are particularly preferred. A particularly effective system is a combination of the flame retardant of the invention and antimony dioxide. The flame retardant of the present invention is effective in making various combustible materials flame retardant, such as synthetic resins, synthetic fibers, paper, and wood. It is particularly effective as an additive flame retardant for synthetic resins or synthetic fibers. Synthetic resins that can be made flame retardant by adding the flame retardant of the present invention include thermoplastic synthetic resins and thermosetting synthetic resins. Thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, and polybutylene; polystyrene resins such as polystyrene, ABS, and AS; polyester resins such as polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate;
Polyamide resins such as nylon 66 and nylon 6, acrylic resins such as polymethyl methacrylate and polymethyl acrylate, polyvinyl chloride resins such as polyvinyl chloride, vinyl chloride-ethylene copolymer, polycarbonate resins, cellulose acetate, etc. There are cellulose resins, polyurethane resins, and various other thermoplastic resins. In particular, thermoplastic resins that can be effectively made flame retardant by adding the flame retardant of the present invention include polyolefin resins, polystyrene resins, polyester resins,
They are polyamide resin and polycarbonate resin. Thermosetting resins for which the flame retardant of the present invention is effective include phenolic resins, unsaturated polyester resins, epoxy resins, vinyl ester resins, allyl resins, and other thermosetting resins. Furthermore, as synthetic fibers that can be effectively made flame retardant, fibers of the above-mentioned synthetic resins are effective, and in addition to synthetic fibers, natural fibers such as cellulose are also effective. Various additives other than the flame retardant of the present invention may be added to the synthetic resin or other flame retardant material. Additives include plasticizers, fillers, stabilizers,
These include coloring agents, reinforcing materials, lubricants, hardening agents, foaming agents, flame retardant aids, and flame retardants other than those of the present invention. The amount of the flame retardant of the present invention added to the material to be flame retardant is not particularly limited, but usually 5 to 40% by weight based on the material to be flame retardant (including additives) is appropriate. When a flame retardant other than a flame retardant is used in combination, the amount may be further reduced. The method of adding the flame retardant of the present invention to the material to be flame retardant is not particularly limited, and various methods such as screw kneading or other kneading, impregnation, coating, and dissolution in a solution of the material to be flame retardant can be used. Since the flame retardant of the present invention has a high bromine content and a high flame retardant effect, an excellent flame retardant material can be obtained even when used in a relatively small amount. Moreover, the physical and chemical properties of the material containing the flame retardant of the present invention are less likely to deteriorate, making it particularly suitable for flame retardant synthetic resin molding materials. For example, thermoplastic resins containing the flame retardant of the present invention have little decrease in strength, and hardly cause any build-up or deterioration in weather resistance. In addition, the flame retardant of the present invention has good affinity or solubility with these resins and can be easily mixed and kneaded, and is particularly suitable for making foamed resins flame retardant. EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples. Example 1 An aqueous solution consisting of 41.2 parts of sodium hydroxide and 300 parts of water was added to a solution of 330.8 parts (by weight, same hereinafter) of 2,4,6-tribromophenol in 800 parts of methanol, and then 84.2 parts of allyl chloride was added at 45°C. was dripped. After refluxing for 4 hours and cooling, the precipitated crystals were thoroughly washed with a 1% by weight NaOH aqueous solution and then with water to obtain white needle crystals with a melting point of 77°C.
4,6-tribromophenylyl ether
Obtained 295 copies. Add 0.66 parts of tricaprylylmethylammonium chloride to a solution of 55.7 parts of 2,4,6-tribromophenyl-allyl ether and 67 parts of chloroform, and while stirring at 50°C, prepare an aqueous solution consisting of 46.5 parts of NaOH and 100 parts of water. added. After reacting at 50-55°C for 3 hours, 200 parts of water was added. The extract was extracted twice with 35 parts of chloroform, thoroughly washed, and then dried over anhydrous sodium sulfate. After chloroform was distilled off, 28.2 parts of a colorless viscous liquid was obtained by distilling off ether from the ether-soluble portion of the residue. This was thought to be 1,1-dichloro-2-(2,4,6-tribromophenoxymethyl)cyclopropane, and its properties were as follows. IR: Figure 1 NMR: Figure 2 C ₁₀ H ₇ Br ₃ Cl ₂ O (453.8) Calculated value: C26.47%, H1.55%, Br52.83% Cl15.63% Actual value: C26.32% , H1.38% Br52.69% Cl15.60% Example 2 1,1-dichloro-2-bromomethylcyclopropane was first prepared by a method known in [J.AmChem.Soc. 87 , 4256 ('65)]. Synthesized. 2.3 parts of triethylbenzylammonium chloride was added to a solution of 121 parts of allyl bromide and 119 parts of chloroform, and while stirring at 50°C, an aqueous solution consisting of 160 parts of sodium hydroxide and 160 parts of water was added. After reacting at 50°C for 2 hours, 500 parts of water was added. The extract extracted twice with chloroform was thoroughly washed with water and then dried over anhydrous sodium sulfate. After chloroform was distilled off, the residue was distilled under reduced pressure to obtain 155 parts of a compound believed to be 1,1-dichloro-2-bromomethylcyclopropane, with a molecular weight of 204 and a yield of 76%. An aqueous solution consisting of 31 parts of water-solubilized sodium and 60 parts of water was added to a solution of 121 parts of m-bromophenol and 550 parts of methanol, and 143 parts of 1,1-dichloro-2-bromomethylcyclopropane was added dropwise under reflux. After refluxing for 10 hours, 1500 parts of water was added, and 125 parts of ether were added.
Extraction was performed. The ether layer was washed twice with 350 parts of a 2% aqueous sodium hydroxide solution and then with 700 parts of water. After drying over anhydrous sodium sulfate, the ether was distilled off, and the residue was distilled under reduced pressure to obtain 179.2 parts of a colorless and transparent liquid. From the analysis results below, it was confirmed that this was 1,1-dichloro-2-(m-bromophenoxymethyl)cyclopropane. C ₁₀ H ₉ Cl ₂ Br0 (295.0) Calculated value: C 40.68 H3.05 Cl23.72 Br 27.12 Actual value: C 40.61 H2.85 Cl23.81 Br 27.08 Example 3 Commercially available polystyrene produced in Example 1 above Add 1,1-dichloro-2-(2,4,6-tribromophenoxymethyl)cyclopropane and antimony trioxide, respectively, to the total composition.
1,1-dichloro-2-(2,4,6-tribromophenoxymethyl)cyclopropane was mixed at 14.0% by weight and antimony trioxide at 4% by weight. A test piece was produced from this composition using an extruder and an injection molding machine, and its flame retardant effect was measured according to JIS K7201. As a result, it was found that the limiting oxygen index was 27.0 and that it was self-extinguishing. For comparison, a test piece made of resin alone was similarly tested, and the limiting oxygen index was 19.0. Example 4 1,1-dichloro-2-(2,4,6-tribromophenoxymethyl)cyclopropane and antimony trioxide produced in Example 1 were mixed with the resin shown in Table 1, A test piece was molded using a conventional method. Using this test piece, a test similar to JIS K7201 was conducted to measure the limiting oxygen index. For comparison, test pieces made of resin alone were molded in the same manner.
These test pieces were also measured for oxygen index, and the results are also shown in Table 1.

[Table] Example 5 11, - for 100 parts of expandable polystyrene particles
Add 5.0 parts of cyclo-2-(2,4,6-tribromophenoxymethyl)cyclopropane and stir well in a beaker at room temperature to uniformly coat the surface of the polystyrene particles with the flame retardant compound. After the surface-treated polystyrene grains are expanded by heating at 100°C steam pressure for 10 minutes, this pre-foamed product is left at room temperature for at least 5 hours, then placed in a mold and heated with heated steam at 10 atmospheres for 90 seconds. Thereafter, it was cooled to room temperature to obtain the desired flame-retardant foamed polystyrene molded article. This molded article was subjected to a combustion test in accordance with "JIS A-9511-1965" flammability test method for foam polystyrene insulation materials. The results are shown in Table 2.

[Table] Example 6 1,1-dichloro-2- prepared in Example 2 was added to 100 parts of a commercially available epoxy resin (Epicote 828).
(m-bromophenoxymethyl)cyclopropane
Add 12.0 parts and 7 parts of amine curing agent, 20 to 40 parts
Mixed at °C. The composition was cured at 100°C for 1 hour and then at 150°C for 4 hours. After cooling, a test piece was cut out and its flame retardant effect was measured according to JIS K7201. As a result, it was found that the limiting oxygen index was 32.0 and that it was self-extinguishing. For comparison, a test piece made of resin alone was similarly tested, and the limiting oxygen index was 24.0. Example 7 The resin shown in Table 3 was mixed with 1,1-dichloro-2-(m-bromophenoxymethyl)cyclopropane and antimony trioxide prepared in Example 2, and a test piece was prepared by a conventional method. was molded. Using this test piece, the limiting oxygen index was measured in a test similar to JIS K7201. For comparison, test pieces made of resin alone were molded in the same manner.
The oxygen index was also measured for these test pieces, and the results are also shown in Table 3.

【table】 [Brief explanation of the drawing]

FIG. 1 shows 1,1 manufactured in Example 1.
FIG. 2 is a diagram showing an IR spectrum of -dichloro-2-(2,4,6-tribromophenoxymethyl)cyclopropane, and FIG. 2 is a diagram also showing an NMR spectrum.

Claims (1)

[Claims] 1 1,1-dihalo-2 represented by the following general formula
-(Polybromophenoxymethyl)cyclopropane. 1,1-dihalo-2-(polybromophenoxymethyl)cyclopropane according to claim 1, characterized in that X: C1 or Br n: an integer 2 of 1 to 5; n is 1 to 3; 3 Polybromophenyl allyl ether 1,1-dihalo-2-(polybromophenoxymethyl)cyclopropane ([ [Formula] X: C1 or Br, n: an integer from 1 to 5). 4 Allyl halide (CH ₂ = CH−CH ₂ Z Z: Cl
or Br) and haloform in the presence of a phase transfer catalyst by adding an aqueous alkali metal hydroxide solution to produce 1,1-dihalo-2-halomethyl-cyclopropane [Formula], and then The 1,1-dihalo-2-halomethyl-
1,1-dihalo-2-(polybromophenoxymethyl)cyclopropane ([formula]) characterized by reacting cyclopropane with polybromophenol [formula] ([formula] X: Cl or Br, n: 1-5 manufacturing method (an integer of ). 5 1,1-dihalo-2 represented by the following general formula
-A flame retardant consisting of (polybromophenoxymethyl)cyclopropane. The flame retardant according to claim 5, wherein: X: Cl or Br n: an integer 6 of 1 to 5; n is 1 to 3. 7. The flame retardant according to claim 5, wherein the flame retardant is a flame retardant for synthetic resins.