JPS5920686B2 - Method for producing flame retardant resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a flame retardant resin having excellent flame retardant properties.

In order to make flammable resins such as polyethylene and polypropylene nonflammable, various nonflammable agents are mixed into these resins.

For example, halogenated aliphatic compounds such as chlorinated paraffin and chlorinated polyethylene, and halogenated aromatic compounds such as hexabromobenzene and decabromodiphenyl ether are known as flame retardants, but in general, the latter halogen It is said that the most effective method is the incorporation of aromatic compounds.

However, due to their molecular structure, halogenated aromatic compounds have poor compatibility with resins, so they may bloom on the resin surface during long-term use or volatilize at high temperatures. It tends to lead to variations in flame retardant properties.

The object of the present invention is to provide an advantageous flame-retardant resin that does not cause the flame-retardant to bloom or volatilize unlike conventional resins, and therefore can maintain stable flame-retardant properties over a long period of time. The purpose of this invention is to provide a new method for producing this type of resin.

That is, the present invention applies the general formula Ar to a resin to be imparted with flame retardancy.
A nonflammable agent represented by mo0-CH2CH=CH2)n (wherein Ar is a ring halogen-substituted aromatic ring residue substituted or not substituted with another substituent, n is 1 or 2) is added, and to this The present invention relates to a method for producing a flame-retardant resin, which is characterized by subjecting it to a free radical generation treatment. The resin to be imparted with the above-mentioned flame retardancy is not particularly limited as long as it is a crosslinked resin that does not disintegrate due to the treatment for generating free radicals.

Specifically, olefin polymers such as polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer are mainly used.

It is not possible to use a resin that is made into a cross-linked type by adding multi-toxic monomers such as trimethylolpropane trimethacrylate or polyethylene glycol dimethacrylate to a type of collapsible resin such as polyvinyl chloride. There is no difference.

Examples of ring halogen-substituted aromatic ring residues substituted with or unsubstituted with other substituents corresponding to Ar in the general formula of the flame retardant include benzene, naphthalene, diphenyl, diphenyl ether, diphenylmethane, diphenyl sulfide, benzophenone, With salicylanilide etc. as the skeleton,
Examples include those in which an appropriate number of hydrogen atoms in the aromatic nucleus are replaced with halogens.

In most cases, the halogen is bromine, and the value of n in the general formula is limited to an integer of 2 or less due to synthesis problems and the need to ensure Ar bond that contributes to flame retardant properties.

Specifically, 1-oxylyl-2,3,4,5,6-pentabromobenzene, 1,4-dioxyallyl-2,3,
5,6-tetrabromobenzene, 2,4,3',5'-
Tetrabromo-2'-oxyallyl salicylanilide, 4-oxyallyl 2,3,6,2',3',6'-hexabromodienyl 4,l-dioxyallyl-3,5,
3', 5'-tetrapromodiphenyl, 4, 1-dioxyallyl 3, 5, 3ζ 5'-tetrapromodiphenyl ether, 4, 1-dioxyallyl-3, 5, 3', 5'
-tetrapromodiphenylmethane, 4,41-dioxyallyl-3,5,3ζ5'-tetrapromodiphenylpropane, 4,4'-dioxyallyl-3,5,3',5
'-Tetrapromodiphenyl sulfone, 4,4'-dioxyallyl-3,5,3',5'-tetrapromodiJ
G Nylsulfide, 4,4'-dioxyallyl-2,
3,5,6,2',3',5',6'-octapromodiphenyl, 4,4'-dioxyallyl2,3,5,6,
2', 3', 5', 6'-octapromophenyl ether, 4, 4'-dioxyallyl-2, 3, 5, 6, 2'
・3', 5', 6'-diphenylmethane, etc. are used as nonflammable agents. Such a flame retardant can be prepared by dissolving phenol in acetone, adding sodium carbonate or potassium carbonate to the solution, and then dissolving allyl bromide (BrCH2).
CH=CH2) or by dropping allyl chloride.

The amount of these flame retardants mixed is in the range of 10 to 60 parts by weight per 100 parts by weight of the resin at the lower limit to ensure good flame retardant properties and at the upper limit to ensure the elongation characteristics and flexibility of the resin. It is preferable.

Specific means for free radical generation treatment include dicumyl peroxide, 1,3-bis(t-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(t-butylperoxide). Even if an organic peroxide such as oxy)hexine-3 is mixed, heating or irradiation with radiation such as β rays, γ rays, and electron beams can be considered.

Free radical generation treatment by mixing polyfunctional monomers such as trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate, triallylisocyanurate, etc. is preferable in terms of work efficiency, regardless of whether the resin is semi-degradable or not. That's true.

Further, it is preferable to add inorganic fillers such as antimony trioxide and aluminum hydroxide from the viewpoint of flame retardant properties, and there is no problem in adding pigments, lubricants, stabilizers, etc.

Examples of synthesis of the flame retardant used in the present invention will be explained below.

Synthesis Example 1 Synthesis of 1-oxyallyl-2,3,4,5,6-pentapromobenzene 48.97 g of pentapromophenol and 12 f7 of sodium carbonate were dissolved in 300 d of acetone.

While refluxing this, 13.37 g of allyl bromide was added dropwise and continued for 20 hours. After the reaction was completed, the resulting precipitate was filtered and washed with 100 ml of acetone. The filtrate and washing solution were cooled on ice, and the resulting precipitate was filtered out and washed with 50 d of acetone. Furthermore, the filtrate and washing liquid were concentrated, cooled on ice, the resulting precipitate was separated by filtration, and similarly washed with acetone.
These products were further washed with hot water and dried. Synthesis Example 2 Synthesis of 2,4,3',5'-tetrabromo-2'-oxyallylsalicylanilide 2,4,3',5'-tetrabromo-2'-hydroxysalicylanilide52.
9y, sodium carbonate 12y1 allyl bromide 13.
The procedure was the same as in Synthesis Example 1 except that 37 was used as the raw material.

Synthesis example 3 4,4'-dioxyallyl-2,3,5,6,2ζ3'
・Synthesis of 5', 6'-octapromodiphenyl ether 4, 4'-dihydroxy-2, 3, 5, 6, 2', 3'
・5ζ6'octapromodiphenyl ether 76.2y
1 Sodium carbonate 247, allyl bromide 26.67
The procedure was the same as in Synthesis Example 1 except that .

Synthesis Example 4 Synthesis of 4,4'-dioxyallyl-3,5,3',5'-tetrapromodiphenyl 4,4'-dihydroxy-3
- The procedure was the same as in Synthesis Example 1 except that 5,3',5'-tetrapromodiphenyl 437 and sodium carbonate 24y1 allyl bromide 26.67 were used as raw materials.

Synthesis Example 5 Synthesis of 1,4-dioxyallyl-2,3,5,6-tetrabromobenzene Tetrabromohydroquinone 42,67
, sodium carbonate 24f, allyl bromide 26.61
The procedure was the same as in Synthesis Example 1 except that .

In order to confirm the structure of the nonflammable agents obtained in Synthesis Examples 1 to 5, nuclear magnetic resonance spectroscopy was performed and the results are shown in the table below.

Next, examples of the manufacturing method of the present invention will be described.

In each of the following examples, the unit of amount of each component is parts by weight. In addition, each component was uniformly kneaded using a hot roll at 120°C, and then heated and pressed for 10 minutes using a hot press at 180°C.
It will be done.

Example 1 Molded into a 17n1L thick sheet Example 2 Example 3 .

Ethylene-vinyl acetate copolymer 100 (vinyl acetate bond amount: 30% by weight).

4 ・4'-dioxyallyl- 2 ・ 3 ・ 5
・ 6 ・ 2' ・ 3' ・ 5' ・ 6'-
Octapromodiphenyl ether 25.

Antimony trioxide 20.

2,6-di-tert-butylphenol 0.5.

Dicumyl peroxide 2 Example 4 〇Polyethylene 100 〇4・4'-dioxyallyl-3・5・3
'・5'-Tetrabromodiphenyl 30.

Antimony trioxide 2002.6 Di-t-butylphenol 0.50 Dicumyl peroxide 2 Example 5 Ethylene-propylene copolymer 100 (propylene bond amount 40% by weight) 1.4-dioxyallyl-2.3. 5.6. Tetra Promobe 3.

Antimony trioxide 20 〇2.6-di-t-butylphenol 0.5.

Dicumyl peroxide 2 Reference example 1 〇 Polyethylene 100 0 Hexabromobenzene 30 0 Antimony trioxide 20 0 2.6-di-t-butylphenol 0.50 Dicumyl peroxide 2 Reference example 2 0 Polyethylene 100 02. 4 . 3 '・5'-Tetrapromosalicylanilide O antimony trioxide 20 02.6-di-t-butylphenol 0.5.

Dicumyl peroxide reference example 3 0 polyethylene 100 〇3・5・3'・5'-tetrabromo30 Sifueninore o Antimony trioxide 20 02.6-di-t-butylphenol 0.5 nore .

Dicumyl peroxide Second, the properties of the sheets obtained in each of the above examples are shown in the table below.

(Notes) (1) For the bloom test, place the sheet in a constant temperature bath at 80℃ for 9
The sample was left to stand for 6 hours, and then allowed to cool to room temperature, and the presence or absence of bloom was observed.

(2) Anti-inflammatory time is ASTM. D. 635-63, and the extinguishing time before and after heating in the above-mentioned bloom test was displayed, respectively.

(3) Gel fraction was measured under conditions of immersion in xylene at 110°C for 18 hours.

As is clear from the above characteristics, the present invention can provide an excellent flame retardant resin that does not cause bloom or volatilization of the flame retardant by mixing a specific flame retardant, and its industrial value is extremely high. There is something big.

Claims (1)

[Scope of Claims] 1. A resin to which flame retardancy is to be imparted has the general formula Ar O-CH_2CH=CH_2)n (wherein Ar is a ring halogen-substituted aromatic ring residue which is substituted or unsubstituted with other substituents). A method for producing a flame-retardant resin, which comprises adding a flame-retardant represented by (group) and subjecting it to free radical generation treatment.