JPS626565B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel halogenated acenaphthylene polymer. The polymer of the present invention has properties that can be incorporated into various flammable resins to make the resins flame retardant and radiation resistant. Therefore, the present invention further relates to a flame retardant and a radiation resistance imparting agent comprising a halogenated acenaphthylene polymer. Today, various flame retardants are mixed into flammable resins such as polyethylene, polypropylene, and ethylene-propylene rubber for the purpose of making these resins flame retardant. Known flame retardants include, for example, halogenated aliphatic compounds such as chlorinated paraffin and chlorinated polyethylene, and halogenated aromatic compounds such as hexabromobenzene and decabromodiphenyl ether. However, the former has poor compatibility with resins and can only be used in very limited materials such as polyethylene. Furthermore, since the latter halogenated aromatic compound has a low molecular weight, it may bloom onto the resin surface during long-term use or volatilize at high temperatures, which tends to cause a change in the flame retardant properties of the resin. Furthermore, it has recently become essential for electric wires, cables, and various equipment used in nuclear reactors, breeder reactors, ionizing radiation generators, etc., to be flame retardant for safety reasons. Therefore, the various resin compositions used in these products, such as insulating materials for electric wires and cables, various electrical insulating materials, packing, sealing materials, frames, and hoses, are required to have both flame retardancy and radiation resistance. . As a result of intensive research, the present inventors have discovered a novel halogenated acenaphthylene polymer having the following general formula for resins to which flame retardancy and radiation resistance are desired to be imparted: (However, in the formula, X is a chlorine or bromine atom; n and
n' is an integer of 2 to 6; R is an alkyl group, alkoxy group, or alkyl ester group having 1 to 4 carbon atoms; m and m' are integers of 0 to 4; n+m≦6,
and n'+m'≦6; when m or m' is 2 or more, R may be the same or different; k and l have the relationship of l≧0, K≠0, K≧l, K+l≧2. By blending and molding a flame retardant and/or a radiation resistance imparting agent (N represents an integer satisfying 2 to 30), the flame retardant will not bloom or volatilize, and therefore, It has been discovered that it is possible to provide a resin molded article that can maintain stable flame retardant properties and/or radiation resistance over a long period of time. Therefore, the main object of the present invention is to provide a new halogenated acenaphthylene polymer. Another object of the invention is to provide flame retardants comprising such polymers. Furthermore, another object of the present invention is to provide a radiation resistance imparting agent comprising such a polymer. Other objects and advantages of the present invention will be made clear in the following. The halogenated acenaphthylene polymer of the present invention is represented by the following formula; (However, in the formula, X is a chlorine or bromine atom; n and
n' is an integer of 2 to 6; R is an alkyl group, alkoxy group, or alkyl ester group having 1 to 4 carbon atoms; m and m' are integers of 0 to 4; n+m≦6,
and n'+m'≦6; when m or m' is 2 or more, R may be the same or different; k and l have the relationship of l≧0, K≠0, K≧l, K+l≧2. Integer (N represents 2 to 30) N represents the degree of polymerization. It is to be understood that this general formula represents both homopolymers and copolymers.
Although X in the general formula is chlorine or bromine, chlorine and bromine may coexist in the same molecule. When the number of substitutions in each acetinaphthylene unit is n=1, the flame retardant effect is not so great, and it is necessary to have substitutions with n=2 or more. As shown in the general formula, the flame retardant effect is significantly enhanced by containing a large amount of acenaphthylene units in which halogen atoms are directly bonded to carbon atoms in the main chain. In addition, the compatibility between the halogenated acenaphthylene polymer and the resin is good even when this polymer has no hydrocarbon group (R _n ), but in order to further increase the compatibility between them, it is necessary to This is achieved by introducing an alkyl group, a methoxy group, a methyl ester group, etc. This improves the processability during kneading and molding, and the property of not volatilizing or exuding during high temperature and long-term use of the molded product. Those with more than 4 alkyl groups are difficult to synthesize, and long-chain alkyl groups beyond the limit reduce flame retardancy and radiation resistance, and tend to cause voids in the composition. Therefore, it must be avoided. The substitution position of R _n in the acenaphthylene unit when m and m'≠0 is, for example, 3-
Methyl, 5-methyl, 3-ethyl, 5-ethyl,
3,5-dimethyl, 3,5-diethyl, 5,6-
Examples include dimethyl, 5-butyl, 3-methoxy, 5-methoxy, 5-ethoxy, 5-butoxy, 5-methylcarboxylate, 3.5-di(methylcarboxylate), and the like. Examples of resinous materials whose flame retardance is improved according to the present invention include polyethylene, polypropylene,
Polybutene, ethylene-vinyl acetate copolymer, 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, polyurethane, polyamide, polyester, acrylic resin, butyl rubber, chloroprene rubber, nitrile rubber, natural rubber, silicone rubber,
Examples include chlorosulfonated polyethylene, styrene-butadiene rubber, styrene-butadiene-acrylonitrile copolymer, acrylonitrile-styrene copolymer, and polyester-ether elastomer. The blending amount of the polymer of the present invention in these polymers is at the lower limit to ensure good flame retardant properties, and at the upper limit to ensure resin elongation properties, flexibility, etc. It is preferably in a range of about 150 parts by weight. Note that radiation resistance has already been observed in compositions containing 0.5 parts by weight or more of acenaphthylene polymer, and the greater the amount, the more effective the effect. When molding a resin composition containing the polymer of the present invention, a so-called "thermal method" in which an organic peroxide such as dicumyl peroxide is mixed and heated, or β-ray, γ-ray, Cross-linking treatment by irradiation with ionizing radiation such as electron beams is effective depending on the type of resin. Free radical generation treatment by mixing polyfunctional monomers such as trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate, and triallyl isocyanurate may be preferable in terms of work efficiency. Furthermore, in addition to the polymer of the present invention, it is preferable to add inorganic fillers such as antimony trioxide, aluminum hydroxide, and talc to the resin from the viewpoint of flame retardant properties. Alternatively, there is no problem in adding light stabilizers, radiation resistance aids, etc. Next, the present invention will be explained in more detail with reference to Examples and Reference Examples. In each of the following examples, the unit of amount of each component is parts by weight. Moreover, after the main components other than the free radical generator were uniformly kneaded with a hot roll at 120°C, the free radical generator was further added at 20 to 70°C. Further, these were heated under pressure in a hot press at 160°C for 30 minutes and formed into sheets with a thickness of 1 mm or 3 mm. The degree of polymerization of the halogenated acenaphthylene polymer used in each example was measured using a gel permeation chromatograph (Waters Inc.).
model ALC/GPC-202/R401, column 10 ⁴ ,
10 ³ , 5×10 ² , 10 ² Å, the polymerization degree distribution measured by the solvent tetrahydrofuran method. Note that Example 1 is for confirming the production of the polymer of the present invention, and Examples 2 to 9 are for confirming the effect of the polymer of the present invention as a flame retardant and radiation resistance imparting agent. Reference Examples 1 to 3 are intended to demonstrate the effects of conventional flame retardants and radiation resistance imparting agents. Example 1 O-xylene 150c.c. in a glass ampoule, 1
(2) 30 g of 3,5-tribromoacenaphthylene and 6 g of dicumyl peroxide were taken, frozen and degassed repeatedly to remove dissolved air, and then sealed. Subsequently, it was immersed in an oil constant temperature bath at 115°C for 24 hours to polymerize. The yield of polymer after fractionating unreacted monomers was 14.4 g (yield 48%). The attached FIGS. 1 and 2 are gel permeation chromatograms measured for the raw monomer and the solution after polymerization treatment, respectively. As is clear from FIG. 3, the average degree of polymerization is approximately 5. Figures 3 and 4 are proton NMR spectra of monomers and polymers.
The absorptions at 1.95 _ppm and 7.12 ppm are due to acetone and _C6D6 , respectively (reference sample). In the monomer, deep absorption was observed at 7.40ppm and 7.47ppm, but these disappeared in the polymer. It is believed that the above absorption in the monomer is due to H existing at the 1 or 2 position of the brominated acenaphthylene. On the other hand, a broad absorption around 4 ppm was observed in the polymer, which was not observed in the monomer.
This is because the double bonds at positions 1 and 2 are cleaved by polymerization, resulting in H(~CH-CBr
~) seems to be the cause. From these things, 1
(2).3.5-tribromoacenaphthylene is 1.
It is thought that radical polymerization occurred due to cleavage of the 2-bond. The broad peak centered at 2.2 ppm in Figure 4 is thought to be due to initiator fragments incorporated into the polymer. In Examples 2 to 7 and Reference Examples 1 to 3, molding resin compositions were prepared by blending the blending examples shown on the left at the blending ratios shown on the right. Example 2 Polyethylene (Mitsubishi Yuka KK.ZG-30) 100 Chlorinated polyethylene (chlorine content 40%) 35 1,3,5-tribromoacenaphthylene polymer 30 Antimony trioxide 20 2,6-di-t-butylphenol 0.5 Dicumyl peroxide 3 Example 3 Polyethylene (Mitsubishi Yuka KK.ZF-30) 100 Chlorinated polyethylene (chlorine content 40%) 35 5-butoxy, 1・3,6,8-tetrabromoacenaphthylene polymer 50 Antimony trioxide 25 2,6-di-t-butylphenol 0.5 Dicumyl peroxide 5 Example 4 Ethylene-vinyl acetate copolymer (Mitsubishi Yuka KK. Yucalon Eva 25K) 100 1,3,5,6-tetrachlor Acenaphthylene polymer 35 Antimony trioxide 15 2,6-di-t-butylphenol 0.5 Dicumyl peroxide 3 Example 5 Ethylene-propylene-diene copolymer (Japan Synthetic Rubber KK.EP-21) 100 1, 3, 5, 6- Tetrabromoacenaphthylene polymer 30 Antimony trioxide 20 2,6-di-t-butylphenol 0.5 Dicumyl peroxide 3 Talc 100 Example 6 Ethylene-propylene-diene copolymer (Japan Synthetic Rubber KK.EP-21) 100 1.3.6. 8-tetrachloro-5-methoxyacenaphthylene polymer 40 Antimony trioxide 25 2,6-di-t-butylphenol 0.5 Dicumyl peroxide 4 Talc 100 Example 7

[Table] Reference example 1 Polyethylene (Mitsubishi Yuka KK.ZF-30) 100 Chlorinated polyethylene (chlorine content 40%) 35 2, 4, 3', 5'-tetrabromosalicylanilide 30 Antimony trioxide 20 2,6-di-t-butylphenol 0.5 Dicumyl peroxide 3 Reference example 2 Ethylene-propylene copolymer (Japan Synthetic Rubber)
KK.EP-21) 100 3,5,3',5'-tetrabromodiphenyl 30 Antimony trioxide 10 2,6-di-t-butylphenol 0.5 Dicumyl peroxide 3 Reference example 3 Ethylene-propylene copolymer (Japan Synthetic Rubber)
KK.EP-21) 100 3,5,3',5'-tetrachlordiphenyl 30 Antimony trioxide 10 2,6-di-t-butylphenol 0.5 Dicumyl peroxide 3 Next, the above Example 2~ Table 2 shows the properties of the sheets obtained using the molding resin compositions of No. 7 and Reference Examples 1 to 3.

[Table] Examples 8 and 9 A 2 mm thick sheet of flame retardant polyethylene having the composition of Example 2 and flame retardant ethylene-propylene-diene copolymer having the composition of Example 5 was heated at 100 Mrad in air at room temperature. The radiation resistance was evaluated by irradiating with gamma rays and measuring the mechanical property values before and after. The results are in the table-
2, and as is clear from the comparison with the similar test results of Reference Examples 1 and 2, the method of the present invention has a large residual elongation rate and has excellent radiation resistance. It can be seen that a flammable resin composition is obtained.

【table】

【table】 [Brief explanation of the drawing]

FIGS. 1 and 2 are gel permeation chromatograms measured for the raw monomer and the solution after polymerization treatment, respectively. Figures 3 and 4 are proton NMR spectra of monomers and polymers.

Claims (1)

[Scope of Claims] 1. A halogenated acenaphthylene polymer having the following general formula. (However, in the formula, X is a chlorine or bromine atom; n and
n' is an integer of 2 to 6; R is an alkyl group, alkoxy group, or alkyl ester group having 1 to 4 carbon atoms; m and m' are integers of 0 to 4; n+m≦6,
and n'+m'≦6; when m or m' is 2 or more, R may be the same or different; k and l have the relationship of l≧0, K≠0, K≧l, K+l≧2. A satisfying integer: N represents 2 to 30) 2. A radiation resistance imparting agent comprising a halogenated acenaphthylene polymer having the following general formula. (However, in the formula, X is a chlorine or bromine atom; n and
n' is an integer of 2 to 6; R is an alkyl group, alkoxy group, or alkyl ester group having 1 to 4 carbon atoms; m and m' are integers of 0 to 4; n+m≦6,
and n'+m'≦6; when m or m' is 2 or more, R may be the same or different; k and l have the relationship of l≧0, K≠0, K≧l, K+l≧2. (N represents 2 to 30) 3 A flame retardant comprising a halogenated acenaphthylene polymer having the following general formula. (However, in the formula, X is a chlorine or bromine atom; n and
n' is an integer of 2 to 6; R is an alkyl group, alkoxy group, or alkyl ester group having 1 to 4 carbon atoms; m and m' are integers of 0 to 4; n+m≦6,
and n'+m'≦6; when m or m' is 2 or more, R may be the same or different; k and l have the relationship of l≧0, K≠0, K≧l, K+l≧2. Integer that satisfies; N represents 2 to 30)