JPS6150502B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilized polyphenylene oxide resin composition, and in particular to a stabilizer that exhibits an excellent effect in preventing polyphenylene oxide from deteriorating under various effects of heat and atmospheric conditions. The present invention relates to a blended polyphenylene oxide resin composition. Polyphenylene oxides are susceptible to oxidative deterioration due to heat, atmospheric oxygen, ozone, and various other influences, and the aging process causes a decrease in mechanical strength.
This results in a decrease in molecular weight, loss of electrical insulation, and often a change in color. When putting polyphenylene oxides into practical use, in order to prevent such deterioration, for example, acid anhydrides, 2-mercaptobenzimidazoles, hydrazine derivatives, boric acid derivatives, phenol compounds, phosphite compounds, etc. are used. Although methods have been proposed, not only are they not always sufficiently effective, but they often cause staining and discoloration of the appearance. The object of the present invention is to stabilize polyphenylene oxides against oxygen-induced deterioration under the action of light and heat without the drawbacks mentioned above. As a result of repeated research, the inventor has found the following general formula ()
It was revealed for the first time that a polyphenylene oxide resin composition stabilized against the effects of heat, light, oxygen, etc. can be obtained by blending the phosphite compound represented by the following formula. _{( wherein , _} Alkyl, arylalkyl, alkyl, cycloalkyl, aryl, alkylaryl, alkoxyaryl, cycloalkylaryl groups having an ether bond, or polyhydric alcohol and polyhydric phenol residues, or groups whose hydroxyl groups are substituted with phosphite esters ) In the general formula (), examples of the hydrocarbon-substituted methylene group include groups such as isopropylidene, butylidene, octylidene, nonylidene, benzylidene, isopropylbenzylidene, and cyclohexylidene. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tertiary-butyl, amyl, tertiary-amyl, isoamyl, hexyl, isohexyl, heptyl, octyl, isooctyl, 2-ethylhexyl. , decyl, isodecyl, lauryl, tridecyl, _C12-15 mixed alkyl, stearyl, eicosyl and the like _. Examples of cycloalkyl groups include groups such as cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, and 4-methylcyclohexyl. Examples of aryl groups are phenyl, naphthyl,
Examples include groups such as phenyl and phenyl. Examples of arylalkyl groups are benzyl,
β-phenylethyl, γ-phenylpropyl,
Mention may be made of groups such as β-phenylpropyl. Examples of alkylaryl groups include tolyl, xylyl, ethyl phenyl, butylphenyl, tert-butylphenyl, octylphenyl, isooctyl phenyl, tert-octylphenyl, nonylphenyl, 2,4-di-tert-butylphenyl, etc. It will be done. Ether bond-containing alkyl groups include furfuryl, tetrahydrofurfuryl, 5-methylfurfuryl and α-methylfurfuryl groups, 3-methoxybutyl groups, or methyl, ethyl, isopropyl, butyl, isobutyl, and hexyl. --,
Cyclohexyl-, phenyl cellosolve residue; methyl-, ethyl-, isopropyl-, butyl-,
Isobutyl carbitol residue; triethylene glycol monomethyl ether, -monoethyl ether, -monobutyl ether residue; glycerin-
1,2-dimethyl ether, -1,3-dimethyl ether, -1,3-diethyl ether, -1-
Ethyl-2-propyl ether residue; examples include nonylphenoxypolyethoxyethyl and lauroxypolyethoxyethyl groups. Further, as the alkoxyaryl group, 4-methoxyphenyl, 4-ethoxyphenyl, 3-lauroxyphenyl, 2-methoxy-4-methylphenyl, 2-t-butyl-4-methoxyphenyl,
Examples include groups such as 4-benzyloxyphenyl and 3,4-methylenedioxyphenyl. Examples of the cycloalkylaryl group include groups such as 2-cyclohexylphenyl and 2,4-di-cyclohexylphenyl. Examples of polyhydric phenol and polyhydric alcohol residues include hydroquinone, 2,5-di-tert-butylhydroquinone, 2,3,6-trimethylhydroquinone, 2-methylresorcin, 2,6-di-tert-butylresorcin, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,
2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-n-butylidenebis(4, 6-di-methylphenol), bis-1,1-(2'-hydroxy-3',5'-di-methylphenyl)-3,
5,5-trimethylhexane, 2,2'-cyclohexylidene bis(4-ethyl-6-tert-butylphenol), 2,2'-isopropylbenzylidene-bis(4-ethyl-6-tert-butylphenol) , 2,2'-thiobis(4-tert-butyl-6-
methylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2,2'-thiobis(4,6-di-tert-butylphenol),
4,4'-methylenebis(2-methyl-6-tert-butylphenol), bisphenol A, 4,4'-
Isopropylidene bis(2-phenylethylphenol), 4,4'-n-butylidene bis(3-methyl-6-tert-butylphenol), 4,4'-cyclohexylidene bisphenol, 4,4'-cyclohexylphenol Cylidene bis (2-tert-butylphenol), 4,4'-cyclohexylidene bis (2-cyclohexylphenol), 4,4'-benzylidene bis (2-tert-butyl-5-methylphenol), 4, 4'-oxobis(3-methyl-6-isopropylphenol), 4,4'-thiobis(3
-methyl-6-tert-butylphenol), 4,
4'-sulfobis(3-methyl-6-tert-butylphenol), bis(2-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, 1,
1,3-tris(2'-methyl-4'-hydroxy-
5'-tert-butylphenyl)butane, 2,2-bis(3'-tert-butyl-4'-hydroxyphenyl)-
4-(3″,5″-di-tert-butyl-4″-hydroxyphenyl)butane, ethylene glycol, diethylene glycol, triethylene glycol,
1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, thiodiethylene glycol,
1,6-hexanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4
Examples include residues such as -cyclohexanedimethanol, 1,4-phenyldimethanol, hydrogenated bisphenol A, glycerin, trimethylolmethane, trimethylolethane, and tris-(2-hydroxyethyl)isocyanurate. It is also used to produce the phosphite compound of the present invention.

Typical bisphenol compounds represented by the formula include 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,
2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-isobutylidenebis(4,6-dimethylphenol), 2,2'-methylenebis(4-methyl-6-t- nonylphenol), 2,2'-methylenebis(4-methyl-6-
α-methylcyclohexylphenol), 2,
2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,2'-thiobis(4,6-di-t-butyl) phenol),
2,2'-thiobis(4-t-octylphenol), 2,2'-thiobis(4-isopropyl-5
-methylphenol), 2,2'-methylenebis(4-styryl-4-cyclohexylphenol), 2,2'-butylidenebis(4,6-dimethylphenol), 2,2'-octylidenebis(4
-methylphenol), 2,2'-isononylidene bis (4,6-dimethylphenol), 2,2' benzylidene bis (4-methyl-6-t-butylphenol), 2,2'-isopropylbenzylidene bis (4-ethyl-6-t-butylphenol), 2,2'-cyclohexylidenebis(4-ethyl-6-t-butylphenol), and the like. Next, typical phosphite compounds represented by the general formula () are shown in Table 1. The amount of these phosphite compounds added is 0.01 parts by weight per 100 parts by weight of polyphenylene oxide resin.
-5 parts by weight, particularly preferably 0.05-3 parts by weight. Various additives commonly used for polyphenylene oxide resins can be added to the composition of the present invention. These other additives include 2,6-di-tert-butyl-p-cresol, 4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol), 1,1,3- Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3,5- di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, β
-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid and monohydric to tetrahydric alcohol {e.g. methanol, decanol, stearyl alcohol, ethylene glycol, thiodiethylene glycol, 1,6-hexanediol, tris (2-hydroxyethyl)isocyanurate, phenolic antioxidants such as esters with pentaerythritol}, organic sulfides such as dilauryl-, dimyristyl- or distearylthiodipropionate, pentaerythritol tetra (lauryl mercaptopropionate) antioxidants, acid anhydrides such as phthalic anhydride and benzoic anhydride, Ca,
Carboxylate salts such as Mg, Ba, and Zn, hydrazine, hydrazine derivatives such as adipic acid dihydrazide, boric acid, boric acid anhydride, boric acid derivatives such as boric acid ester, organotin compounds, alkanolamines, and amines such as diphenylamine. , 2-hydroxybenzophenones, 2-hydroxyphenylbenzotriazoles, nickel chelate, hindered piperidyl compounds, and other light stabilizers, pigments, dyes, flame retardants, fillers, antistatic agents, antifouling agents, etc. can be given. In the present invention, the stabilized polyphenylene oxide resin has the formula (In the formula, Ra represents a hydrogen atom, an alkyl group, an alkoxy group, a haloalkyl group, or a haloalkoxy group, Rb, Rd, and Re represent the group represented by Ra or a halogen atom, and Rc represents a hydrogen atom or a halogen atom. Polymers produced by oxidative polycondensation of phenols shown in Graft copolymers or copolymers obtained by oxidative coupling of the above phenols in the presence of other polymers such as polystyrene, styrene copolymers, polycarbonates, polysulfones, nylons, polyolefins and rubbery polymers, and the above polymers or copolymers. Examples include blends of the polymer and other polymers mentioned above. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 50 parts by weight of poly(2,6-dimethyl-1,4-phenylene oxide) with an intrinsic viscosity of 0.56 dl/g (in chloroform at 25°C), 47.5 parts by weight of polystyrene,
2.5 parts by weight of polycarbonate, 3.0 parts by weight of titanium oxide, and 0.5 parts by weight of a stabilizer were added, thoroughly mixed in a Henschel mixer, pelletized in an extruder, and then injection molded to prepare a test piece. This sample was heated in a gear oven at 125°C for 100 hours, and the elongation and Izod impact value retention were measured. The results are shown in Table 2.

[Table] Example 2 0.3 parts by weight of a stabilizer was blended with 100 parts by weight of poly(2,6-dimethyl-1,4-phenylene oxide) having an intrinsic viscosity of 0.60 dl/g (in chloroform at 25°C), and a sufficient After mixing, the mixture was pressed at 300°C to prepare a test piece. Using this test piece, the temperature was 160℃ in an oxygen stream.
The mixture was heated for 3 hours and the amount of oxygen absorbed was measured. The results are shown in Table 3.

【table】

【table】

【table】

Claims (1)

[Scope of Claims] 1. A stabilized polyphenylene oxide resin composition containing at least one phosphite compound represented by the following general formula (). _{( wherein , _} , alkyl, arylalkyl, alkyl having an ether bond, cycloalkyl, aryl, alkylaryl, alkoxyaryl, cycloalkylaryl group, or polyhydric alcohol and polyhydric phenol residue, or their hydroxyl group is substituted with a phosphite ester (indicates the group)