JPS591308B2 - Nannenzaisoseibutsu - Google Patents

Description

[Detailed description of the invention] FIELD OF THE INVENTION The present invention relates to flame retardant compositions.

Recently, with the rapid development of industry, a wide variety of organic synthetic polymer substances have come to be used in ornaments, building materials, daily necessities, buildings, structures, electrical appliances, and the like. However, organic synthetic polymer substances generally have flammable properties,
Once it ignites and burns, the danger is beyond imagination.

Therefore, combustible resins are required to retain their original excellent properties and be free from flammability, and research on making flammable resins flame retardant is being conducted in various fields.
For example, in Japanese Patent Publication No. 37-5739, 1, 1, 2,
2,-tetrabromoethane, 1,2-dichloro-1 ・
2, 3, 4-tetrachloroethane, 1, 2,
-Dibromemen, Special Publication No. 41-20216 has 2-
Halogenated hydrocarbons such as chloro-1, 2, 3, and 4-tetrapromratane are described, and in Japanese Patent Publication No. 7089/1989, acetals or ethers of 2,3-dibromopropanol-1 are used as thermoplastic resins. It is known as a flame retardant.

However, these have industrial drawbacks.

In other words, these flame retardants must be added in large amounts to the resin and meet the UL standards (Underwriters
Items that are difficult to pass the 94V-O or 94V-L test of Household Goods Standards (hereinafter referred to as UL) of Laboratories, Inc., have poor weather resistance and discolor and deteriorate over time after molding. Some products are produced, some are not suitable for practical use in terms of price, some flame retardants are mixed into the resin, and the softening point of the homogeneous composition is lower than that of the original resin, and the impact value of the resin is reduced. It is difficult to obtain a perfect product. As a result of various studies regarding flame retardant compositions, the present inventors have found that they do not have any of the drawbacks mentioned above, do not impair the physical properties inherent to the resin, and are different from the above-mentioned known substances. This led to the discovery of a flame retardant composition.

That is, a flame retardant characterized by comprising a polymer (111 and halogenated polyolefin, or polymer m) obtained by polymerizing the monomers represented by general formula (I), a halogenated polyolefin, and antimony trioxide. It is a composition. (In the formula, X is a chlorine or bromine atom, and n is 1 to 5.) The monomer represented by the general formula (1) thus obtained is subjected to general polymerization such as bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization. The polymer of the present invention can be obtained by using a method.

The polymer of the present invention can also be obtained by dissolving polystyrene in a solvent that is inert to halogens and dissolving polystyrene, and adding bromine or chlorine to halogenate the phenyl groups. General formula (1)
Examples of industrially useful monomers include dibromostyrene, tribromostyrene, pentabromostyrene, dichlorostyrene, trichlorostyrene, benzchlorostyrene, and the like. Methods for polymerizing the polymer according to the present invention include bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization, and commonly used solution polymerization methods are as follows.

100 parts of the compound represented by the general formula (1) is dissolved in an aromatic solvent, and a radical catalyst such as azobisisobutyronitrile or benzoyl peroxide is added to the monomer at 0.00 parts.
01 to 1.0% by weight is added, and the polymerization reaction is carried out at a reaction temperature of 80 to 100° C. for several hours under a nitrogen gas atmosphere.

After the reaction, the reactant is added to an alcohol solvent that is a non-solvent for the polymer to precipitate the polymer.

Then, the solvent and the polymer are separated, and the polymer is dried. In addition, the method for halogenating polystyrene is to dissolve polystyrene in a halogenated carbon solvent, and the reaction temperature is 60~60℃.
The reaction is carried out at 100°C by gradually adding bromine or chlorine.

Hydrogen chloride generated during this reaction is taken out of the system. *An integer) The polymer used in the present invention can be produced by dehydrohalogenating an alkylbenzene halide with an alkali or amine in a suitable solvent as shown in the following formula.

After the reaction is completed, since the reaction solution is acidic, it is sufficiently neutralized with alkaline water and then washed. After washing, the solvent is distilled off or the reactant is added to an alcohol solvent as a non-solvent.
The polymer of the present invention is obtained by precipitating the polymer.

Further, the halogenated polyolefin used in the present invention includes chlorinated paraffin, brominated paraffin, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene,
Brominated polypropylene, polyvinyl chloride, etc., and the halogen content in these compounds is at least 20%. The flame retardant composition obtained according to the present invention is effective when the halogen content is 2 to 50% by weight based on the resin used. Preferably, for example, 8 to 2 for polystyrene resin.
0% by weight is optimal. As the content of logen in the resin increases, it loses its organic characteristics and becomes inorganic, making it impossible to maintain the original characteristics of the resin.
However, in the above flame retardant composition, the halogenated polyolefin is 15 parts or less, preferably 1 part or less, per 100 parts of resin.
0 parts or less, antimony trioxide is 15 parts per 100 parts of resin.
part or less, preferably 1 to 105 parts.

Although the polymer (n) used in the present invention can easily make the resin flame retardant, it is difficult to maintain the same impact value of the resin as the original resin.

However, it is possible to maintain the impact value by using a halogenated polyolefin in combination.

If the amount of halogenated polyolefin used exceeds the above range, the properties of the resin will be lost and the properties of the halogenated polyolefin will change.

Similarly, if the amount of antimony trioxide used exceeds the above range, mineralization of the resin will proceed. The flame retardant composition obtained in the present invention has a much larger molecular weight than monomeric compounds such as tetrabromobutane and hexabromobenzene that are currently commonly used as flame retardants.

Since the polymeric substance according to the present invention is polymerized or copolymerized, its molecular weight is thought to be at least 10,000 or more. Therefore, when added to a highly crystalline resin such as polypropylene resin, it has good compatibility with the resin, and even if the resin is left at high temperatures for a long time, the flame retardant does not bleed onto the resin surface. Even if the amount is slightly increased, the impact value of the resin will not be extremely reduced. but,
Hexabromobenzene, tetrabromobutane, etc. have good flame retardancy the moment they are added to the resin, but if the resin is left at high temperatures for a long time as described above, the flame retardant will be liberated on the resin surface, and the flame retardant will become flame retardant. Flammability also decreases. Moreover, it extremely lowers the impact test value of the resin. The flame retardant effect according to the UL-94 law, which is attracting attention in particular to prevent flammability of electrical products, i.e., UL94V-0 or UL-94
When trying to find V-1, it is necessary to add a considerable amount of bromine or chlorine atoms to the resin used.
This requires the addition of significant flame retardants to the resin, as mentioned above. Tetrabromobutane, hexabromobenzene, etc., which are commonly used today, have a UL-94V-0 or UL-94V-1 rating even when added to resin in large quantities.
is actually impossible to obtain. This is because when a large amount of such flame retardant is added to resin, the resin becomes plasticized by the flame retardant and becomes easily softened, and at the same time, the compatibility of the flame retardant with the resin is poor, and the impact value of the resin becomes extremely low. The current situation is that the desired results cannot be easily obtained.

On the other hand, even when the flame retardant composition of the present invention is added to a resin, it does not plasticize the resin body at all, and moreover, when the resin is burned, it is in a carbonized state, and is UL-94V-
1 or V-0 standards can be easily passed. The resins into which the flame retardant composition of the present invention is kneaded include thermosetting resins such as phenolic resin, area resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, diallyl phthalate resin, silicone resin, and urethane foam. and urethane resins, and thermoplastic resins include polyethylene, polystyrene, A
These include S resin, ABS resin, polypropylene, polybutene, petroleum resin, methacrylic resin, vinyl chloride resin, polyamide resin, polycarbonate resin, polyphenylene oxide resin, and the like.

Additionally, additives such as stabilizers and lubricants that are usually added to resins and rubbers may be added. In addition, it can be reinforced with glass fiber or other fibers, or it can be made into a foaming agent by adding a foaming agent.
It is also possible to add customary fillers, etc. Next, the present invention will be explained with reference to examples, but it would be cumbersome to enumerate and explain each compound that can be used, and in view of the fact that almost the same effects can be obtained, typical A few examples will be given as examples. In addition, in the present invention, "part" means "
"Parts by weight" and "%" refer to "% by weight." Example 1 Into a five-piece flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube, 100 parts of beaten styrene,
200 parts of toluene solution and 0.1 part of benzoyl peroxide as a catalyst are added, and polymerization is carried out at a reaction temperature of 90 to 100° C. for 10 hours while introducing nitrogen gas.

After the polymerization is completed, the polymerization solution is transferred to 100 parts of methanol to precipitate a white powdery polymer. Then, the solvent and the polymer are separated, and the polymer is thoroughly dried. Furthermore, this polymer was kneaded into 100 parts of high-impact polystyrene resin using a hot roll with a roll temperature of 150 DEG C., a test piece was prepared according to the test method of ASTM-D-635, and a combustion test was conducted.

The results are shown in Table 1. Example 2 The polymer obtained in Example 1, halogenated polyolefin, and antimony trioxide were mixed and kneaded into 100 parts of various resins using a heated roll to prepare a test piece.
4 combustion tests, impact tests, heat resistance tests, and bleed tests were conducted.

The results are shown in Table 2. In the halogenated polyolefin, the Cl content of the chlorinated paraffin is 70%, and the Cl content of the chlorinated polyethylene is 40%. As a comparative example, the results of using hexabromocyclododecane and tetrabromobutane as flame retardants are also shown. Example 3 Polystyrene 5 with a molecular weight of 1000 was placed in a five-point flask equipped with a stirrer, a reflux condenser, a thermometer, and a bromine dropping device.
0 parts, add 200 parts of carbon tetrachloride solution, and raise the reaction temperature to 50~
230 parts of bromine is slowly added dropwise at 60°C.

Since hydrogen bromide is generated at the same time as the dropping, this is taken out of the system. After the reaction, the reactant is neutralized with alkaline water, and after neutralization and washing, the reactant is added to 1000 parts of methanol solvent to precipitate a white powdery polymer.

The polymer and the solvent are separated and the polymer is dried. Analysis of the polymer revealed that the bromine content was 70.1%. This polymer, chlorinated polyethylene (Cl content: 40%), and antimony trioxide were mixed and kneaded into 100 parts of polystyrene resin, and a UL-94 combustion test was conducted.

The results are shown in Table 3. Example 4 10 parts of the polymer obtained in Example 3 and chlorinated paraffin (Cl content 70%) 5 parts to 100 parts of unsaturated polyester resin
1 part, 0.5 part of cobalt naphthenate aqueous solution and 1 part of t-butyl peroxide were added and mixed uniformly, and the resin liquid was poured onto a molded plate.

12.7 x 1.27 x 0 according to ASTM-D-635
．． A test piece of 15c7rL was prepared. ASTM-D-6
The combustion result with No. 35 was non-flammable.

Claims (1)

[Claims] 1 A polymer (II) obtained by polymerizing monomers represented by general formula (I) and a halogenated polyolefin, or a polymer (II), a halogenated polyolefin, and antimony trioxide A flame retardant composition characterized by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
) (wherein X is a chlorine or bromine atom, and n is an integer from 1 to 5).