JPS634589B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a copolymer obtained by graft polymerizing an alkenyl aromatic monomer onto (a) polyphenylene oxide or polyphenylene oxide and an alkenyl aromatic polymer, and (b) an ethylene-α-olefin-polyene terpolymer. This composition is characterized by adding (c) poly α-olefin to a composition containing a polymer, and particularly relates to a composition having excellent heat resistance, weather resistance, and impact resistance. Although polyphenylene oxide is a resin with excellent properties such as heat resistance, chemical resistance, and mechanical and electrical properties, it has drawbacks such as poor moldability and low impact resistance. In order to improve these drawbacks, a method of blending alkenyl aromatic polymers that are compatible with polyphenylene oxide to improve moldability, and a method of blending and dispersing rubber to improve impact resistance. It is well known how to do this. In particular, when a rubber-modified alkenyl aromatic polymer is blended, it is advantageous because moldability and impact resistance can be improved at the same time. However, alkenyl aromatic polymers modified with this rubber generally contain diene rubber as a rubber component, so they have the disadvantage that they rapidly become brittle when exposed to high temperatures or outdoors for long periods of time. , has become a problem. This point can be improved by using a copolymer obtained by graft polymerizing an alkenyl aromatic monomer to an ethylene-α-olefin-polyene terpolymer rubber. Regarding this point, the
Proposed in 43174, 43290. however,
This composition has the disadvantage that the impact resistance at low temperatures is greatly reduced compared to systems containing diene rubber. The inventors of the present invention conducted extensive studies aimed at further improving the physical properties, including this point, and surprisingly found that polyα-
The present inventors have discovered that by adding olefin, the impact resistance at low temperatures is improved, and the impact resistance at room temperature is improved, resulting in a composition having excellent properties, and has thus arrived at the present invention. That is, the present invention comprises graft polymerizing an alkenyl aromatic monomer onto (a) polyphenylene oxide or polyphenylene oxide and an alkenyl aromatic polymer, and (b) an ethylene-α-olefin-polyene terpolymer. In the copolymer, the weight ratio of ethylene-α-olefin-polyene terpolymer part/alkenyl aromatic monomer polymer part is 1/20 to 20/
A composition comprising a graft copolymer within the range of 1.
The present invention relates to a polyphenylene oxide composition characterized in that 0.5 to 10 parts by weight of (c) poly-α-olefin is added to 100 parts by weight. Regarding the effects of the present invention, even if polyphenylene oxide or polyphenylene oxide and alkenyl aromatic polymer, which is component (a), are added, the compatibility is poor, so only those with low impact strength can be obtained. In contrast, polyα-olefin is used in combination with a copolymer obtained by graft polymerizing an alkenyl aromatic monomer to the ethylene-α-olefin-polyene terpolymer (component (b)). As a result, a composition having higher impact strength than the compositions of components (a) and (b) was obtained for the first time, something that could not have been predicted using conventional techniques. Hereinafter, embodiments of the present invention will be specifically described. The polyphenylene oxide of component (a) used in the present invention has the general formula A polymer having a unit structure represented by n is 50 or more. R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, halogen, a hydrocarbon group or a substituted hydrocarbon group, a hydrocarbon oxy group or a substituted hydrocarbon oxy group. Specific examples of R ₁ , R ₂ , R ₃ and R ₄ include hydrogen; halogen atoms such as chlorine, bromine, and iodine; methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, allyl, phenyl, benzyl, and methylbenzyl and substituted hydrocarbon groups such as chloromethyl and bromomethyl; hydrocarbon oxy groups such as methoxy, ethoxy, phenoxy and chloroethoxy, and substituted hydrocarbon oxy groups. Specifically, poly-2,6-dimethyl-1,4-phenylene oxide, poly-2,6-diethyl-1,4-
Phenylene oxide, poly-2,6-dipropyl-1,4-phenylene oxide, poly-2-methyl-6-isopropyl-1,4-phenylene oxide, poly-2,6-dimethoxy-1,4- Phenylene oxide, poly-2,6-diphenyl-
1,4-phenylene oxide, poly-2,6-dichloro-1,4-phenylene oxide, poly-
Polymers such as 2,5-dimethyl-1,4-phenylene oxide, 2,6-dimethylphenol and 2,
3,6-trimethylphenol copolymer, 2,
Examples include copolymers such as a copolymer of 6-dimethylphenol and 3-methyl-6-tert-butylphenol. Furthermore, the polyphenylene oxide of the present invention also includes modified products of the above polymers or copolymers. For example, in the presence of an ethylene-propylene-polyene terpolymer, the formula

Oxidative polymerization of [Formula], formula in the presence of polystyrene

[Formula] is oxidatively polymerized, styrene is polymerized in the presence of polyphenylene oxide polymer or copolymer, polyphenylene oxide polymer or copolymer and styrene are kneaded together with peroxide in an extruder. Examples include those made by reacting with water. Component (a) of the present invention also includes a case where an alkenyl aromatic polymer is added to the polyphenylene oxide described above. Here, the alkenyl aromatic polymer has the general formula

[Formula] (R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen, halogen, hydrocarbon group or substituted hydrocarbon group, hydrocarbon oxy group, substituted hydrocarbon oxy group, R ₆ is hydrogen, A lower alkyl group having 1 to 4 carbon atoms. Specific examples of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ include hydrogen; halogen atoms such as chlorine and iodine; methyl,
ethyl, propyl, vinyl, allyl, benzyl,
Included are hydrocarbon groups such as methylbenzyl; substituted hydrocarbon groups such as chloromethyl and bromomethyl; hydrocarbon oxy groups or substituted hydrocarbon oxy groups such as methoxy, ethoxy, phenoxy, and monochloromethoxy. Further, specific examples of R ₆ include hydrogen; lower alkyl groups such as methyl and ethyl. Polymers and copolymers of alkenyl aromatic monomers include polystyrene, polychlorostyrene,
Poly-α-methylstyrene, styrene-acrylonitrile copolymer, styrene-α-methylstyrene copolymer, styrene-p-methylstyrene copolymer, styrene-maleic anhydride copolymer, styrene-methyl methacrylate copolymer Among them, polystyrene is particularly preferred.
Furthermore, the alkenyl aromatic polymers of the present invention include modified diene rubbers. The diene rubber herein means a rubber-like polymer containing a diene component such as butadiene, isoprene, chlorobutadiene, etc., and includes homopolymers thereof or copolymers with various monomers. Specifically, polybutadiene, polyisoprene, polychlorobutadiene, butadiene-styrene copolymer, isoprene-styrene copolymer,
Examples include butadiene-acrylonitrile copolymers, copolymers of isobutylene and butadiene or isoprene, and the like. The method for modifying alkenyl aromatic polymers with this diene-based rubbery polymer is as follows:
Various methods are known, and any method may be used. For example, there are mechanical mixing methods, solution blending methods, etc., but in particular, the method of dissolving rubber in alkenyl aromatic monomer and polymerizing it is commonly used industrially, and commercially available products are easily available and useful. . Specific examples of such materials include butadiene rubber-modified polystyrene commercially available as impact-resistant polystyrene, styrene-butadiene rubber-modified polystyrene, and acrylonitrile-butadiene-styrene copolymer commercially available as ABS resin. When the alkenyl aromatic polymer described above is used in combination with polyphenylene oxide, it is preferable to use the polyphenylene oxide/alkenyl aromatic polymer at a weight ratio of 1/10 or more. Next, in the present invention, ethylene-
A copolymer obtained by graft polymerizing an alkenyl aromatic monomer to an α-olefin-polyene terpolymer is used. The α-olefin used as the second monomer in the ethylene-α-olefin-polyene terpolymer in which the alkenyl aromatic monomer is grafted may be a hydrocarbon compound having 3 to 20 carbon atoms. Either is fine. Specific examples of these α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, styrene, p-isopropylstyrene, and vinylcyclohexane, but propylene is particularly important. . Further, as the polyene compound which is the third monomer in the ethylene-α-olefin-polyene terpolymer in which the alkenyl aromatic monomer is grafted, 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6
-Methyl-1,5-heptadiene, 7-methyl-
1,6-octadiene, 11-ethyl-1,11-tridecadiene, 9-ethyl-1,9-undecadiene, isoprene, 1,4-pentadiene, 1,
3-pentadiene, 1,4,9-decatriene,
myrcene, 1-phenyl-1,3-butadiene,
p-diallylbenzene, p-bromoallylbenzene, 4-vinyl-1-cyclohexene, 1,3,
5-Trivinylcyclohexane, trans-1,
2-divinylcyclobutane, 1,5-cyclooctadiene, 1,3,5-cycloheptatriene,
1,5,9-cyclododecatriene, 1,4-cycloheptadiene, cyclopentadiene, 2,
2'-dicyclopentenyl, 1,4-bis(cyclopenten-2-yl)butane, 4,7,8,9-
Tetrahydroindene, 6-methyl-4,7,
8,9-tetrahydroindene, bicyclo(3,
3,0)-octadiene-2,6, dicyclopentadiene, 2-methyl-2,5-norbornadiene, 5-methylene-2-norbornene, 5-tylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-isopropenyl-2-
Norbornene, 5-(2'-methyl-1'-propenyl)-2-norbornene, 5-(1',2'-dimethyl-1'-propenyl)-2-norbornene, 5-
(2'-butenyl)-2-norbornene, 6-methyl-5-(2'-butenyl)-2-norbornene,
It may be any of 6-(3'-cyclohexenyl)-2-norbornene, tricyclopentadiene, 6-chloromethyl-5-isopropenyl-2-norbornene, and the like. The terpolymer used in the method of the present invention has a content of ethylene, α-olefin and polyene compound of 40 to 90 mol%, respectively.
A well-known composition of 10 to 60 mol% of α-olefin and 0.3 to 20 mol% of polyene compound, preferably 60 to 85 mol% of ethylene, 15 to 35 mol% of α-olefin, and 1 to 5 mol% of polyene compound is used. is preferred, but in addition to this, those containing a polyene compound of 20 mol% or more can also be used.
Furthermore, the content of ethylene and α-olefin may also be outside this range. The method of the present invention also includes the use of, for example, a chlorinated terpolymer instead of the terpolymer described above. The alkenyl aromatic monomer to be polymerized in the present invention has the general formula (Here, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen,
It is either a halogen, a hydrocarbon, a substituted hydrocarbon group, a hydrocarbon oxy group, or a substituted hydrocarbon oxy group, and R ₆ is hydrogen or a lower alkyl group having 1 to 4 carbon atoms. ). Specific examples of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ in the above formula include hydrogen; halogen atoms such as chlorine, bromine and iodine; methyl, ethyl, propyl, vinyl, allyl, benzyl, methyl Hydrocarbon groups such as benzyl; substituted hydrocarbon groups such as chloromethyl and bromomethyl; hydrocarbon oxy groups or substituted hydrocarbon oxy groups such as methoxy, ethoxy, phenoxy, and monochloromethoxy. Further, specific examples of R ₆ include hydrogen; methyl,
Examples include lower alkyl groups such as ethyl. Specific examples of alkenyl aromatic monomers include styrene, 2,4-dichlorostyrene, p-methoxystyrene, p-methylstyrene, p-phenylstyrene, p-divinylbenzene, p-(chloromethoxy)- Styrene, α-methylstyrene, o
-Methyl-α-methylstyrene, m-methyl-α
Examples include -methylstyrene, p-methyl-α-methylstyrene, and p-methoxy-α-methylstyrene. These may be used alone or in combination of two or more. The alkenyl aromatic monomer is grafted onto the ethylene-α-olefin-polyene terpolymer used in the present invention by suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization (using a polymerization tank). It can be produced by any known polymerization method, including a method using an extruder. In this case, ethylene-α-olefin-
The amount of alkenyl aromatic monomer to be graft-polymerized to the polyene terpolymer is such that the weight ratio of ethylene-α-olefin-polyene terpolymer/alkenyl aromatic monomer is 1/20 to 20/1. Used within a range. If this ratio is less than 1/20 or more than 20/1, the effect as a graft polymer will be less than that of alkenyl aromatic monomer or ethylene-α-olefin-polyene terpolymer alone, respectively. In particular, it is preferable that this ratio is in the range of 1/3 to 3/1 because it is very well compatible with and dispersed in polyphenylene oxide, and the effect of improving impact resistance is extremely large. The ratio of component (a) and component (b) used in the present invention is (a)
It is preferable to use component (b) in an amount of 1 to 100 parts by weight per 100 parts by weight of component. In particular, this addition amount is 5 to 50
Optimal effects can be obtained when used within the range of parts by weight. In the present invention, in addition to the above components (a) and (b), poly-α-olefin is added as component (c). Poly-α-olefin has 2 to 20 carbon atoms and a carbon at the end.
Any polymer of hydrocarbon compounds having carbon unsaturated double bonds may be used. These poly α-
Specific examples of olefins include polyethylene (high, medium, and low density polyethylene), polypropylene, polybutene, poly-4-methyl-1-pentene, random and block copolymers of ethylene and propylene, copolymers of ethylene and 1-butene, etc. Polyethylene is particularly important. Commercially available poly-α-olefins can be used. In the present invention, the amount of component (c) added is in the range of 0.5 to 10 parts by weight per 100 parts by weight of the total amount of components (a) and (b). If this amount is less than 0.5 parts by weight, the effect of improving impact resistance will hardly be expressed, and if it exceeds 10 parts by weight, even if the amount added is increased further, there will be no effect of improving impact resistance. The heat resistance of the oxide decreases. In addition, in the present invention, commonly used additives such as heat stabilizers, flame retardants, pigments, fillers, plasticizers, lubricants, and ultraviolet absorbers may be added to the extent that the physical properties do not change significantly. Furthermore, fiber reinforcing agents such as glass fiber, asbestos fiber, carbon fiber, alumina fiber, etc. can also be added. The method of mixing these components (a), (b), and (c) of the present invention with various additives as necessary is a mechanical method using a mixer such as a roll mill, Banbury mixer, extruder, or kneader. Any method of mixing, mixing in a solution or suspension state can be used. Next, the present invention will be explained using specific examples, but these are illustrative and do not limit the present invention. Production example of graft copolymer A Ethylene-propylene-ethylidene norbornene terpolymer (manufactured by Sumitomo Chemical Co., Ltd., Esplen)
505) crushed into particles within 5 mm square, 40 g;
Pour 200g of water into a 500c.c. glass autoclave and add benzoyl peroxide to it while stirring.
A solution of 0.2 g dissolved in 40 g of styrene and a solution of 1.2 g of polyvinyl alcohol (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., Gohsenol GL-05) dissolved in 40 g of water as a dispersion stabilizer were added in this order, and stirring was continued for 1 hour. Styrene was impregnated into ethylene-propylene-ethylidene norbornene terpolymer particles. Next, the reaction was carried out at 90°C for 6 hours and at 115°C for 2 hours, and after the reaction was completed, filtration, water washing and vacuum drying were performed to obtain 77.0 g of graft copolymer pellets. Production example of graft copolymer B: 20 g of the same ethylene-propylene-ethylidene norbornene terpolymer as in production example A and 140 g of water.
Pour into a 500 c.c. glass autoclave and add 0.2 g of benzoyl peroxide dissolved in 40 g of styrene while stirring, and as a dispersion stabilizer, add 0.9 g of the same polyvinyl alcohol as in Production Example A to 40 g of water.
were added in order, and impregnation and reaction were carried out under the same conditions as in Production Example A. After the reaction is complete, filter, wash with water,
Graft copolymer pellets by vacuum drying 55.5
I got g. Table 1 shows the analysis results of the graft copolymers produced in Production Examples A and B.

[Table] Example 1 Comparative Example 1 Concentration in chloroform of 0.5 g/dl and temperature obtained by oxidative polymerization of 2,6-dimethylphenol
80 parts of polyphenylene oxide having a reduced viscosity of 0.59 at 25°C, 20 parts of the graft copolymer of Production Example A,
A mixture consisting of 3 parts of low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., Sumikasen F210-7), 6 parts of triphenyl phosphate, and 0.5 parts of Sumilizer MDP as a stabilizer was heated at 250°C for 10 minutes using a Brabender Plastograph. Kneaded. This is 250℃, 290℃
When press-molded and measured for Izot impact strength, they were 51 kg/cm/cm and 50 kg/cm/cm, respectively. For comparison, a composition containing no polyethylene (Comparative Example 1) was kneaded and molded in the same manner, and its Izot impact strength was measured. The results are shown in Table 2. As is clear from the table, the composition of Example 1 containing the polyethylene of the present invention had significantly improved impact resistance compared to the composition of Comparative Example 1 which did not contain it.

[Table] Example 2, Comparative Example 2 The same polyphenylene oxide as in Example 1, the graft copolymer of Production Example A, polyethylene, triphenyl phosphate, Sumilizer MDP and high-impact polystyrene (manufactured by Nippon Polystyrene Co., Ltd.) , S-Brite 500AS) were kneaded at 250° C. for 10 minutes using a Brabender Plastograph at various blending ratios shown in Table 3. This was press-molded at 250°C and 290°C, and the Izot impact strength was measured. As is clear from Table 3, the composition of Example 2 containing the polyethylene of the present invention had greatly improved impact resistance compared to the composition not containing it (Comparative Example 2). Example 3, Comparative Example 3 The 250°C press molded products of Example 2 and Comparative Example 2 were measured for Izot impact strength at -30°C. The results are shown in Table 4. As is clear from the table, the impact resistance at low temperatures was improved by adding polyethylene.

【table】

[Table] Examples 4 and 5, Comparative Examples 4 and 5 2,6-dimethylphenol/3-methyl-6
- Polyphenylene oxide with a reduced viscosity of 0.60 at a concentration of 0.5 g/dl in chloroform and a temperature of 25°C obtained by oxidative polymerization with tert-butylphenol = 96/4 (molar ratio), impact-resistant polystyrene ( Made by Nippon Polystyrene Co., Ltd., S-Bright
500A, S-Bright 500AS), the graft copolymers of Production Examples A and B, low-density polyethylene (Sumikasen F210-7 manufactured by Sumitomo Chemical Co., Ltd.), triphenyl phosphate, and Sumilizer MDP in various formulations shown in Table 5. 250 using Brabender Plastograph
The mixture was kneaded for 10 minutes at ℃. This was press-molded at 250°C and 290°C, and the Izot impact strength was measured. From Table 5, it is clear that the impact resistance is improved by adding the polyethylene of the present invention.

[Table] Examples 6 and 7 Same polyphenylene oxide as in Example 2, graft copolymer of Production Example A, high-impact polystyrene, polyethylene, triphenyl phosphate,
Sumilizer MDP was kneaded at 250° C. for 10 minutes using a Brabender Plastograph at the mixing ratio shown in Table 6. This was press-molded at 250°C and 290°C, and the Izot impact strength was measured. It is clear from the table that the addition of polyethylene significantly improves impact resistance.

【table】

Claims (1)

[Claims] 1. (a) polyphenylene oxide or polyphenylene oxide and an alkenyl aromatic polymer; and (b) an ethylene-α-olefin-polyene terpolymer grafted with an alkenyl aromatic monomer. In the polymerized copolymer, the weight ratio of ethylene-α-olefin-polyene terpolymer portion/alkenyl aromatic monomer polymer portion is 1/20 to 20/
A composition comprising a graft copolymer within the range of 1.
A polyphenylene oxide composition characterized in that (c) 0.5 to 10 parts by weight of polyα-olefin is added to 100 parts by weight.