DE2057107A1 - Process for the production of modified polyphenylene oxides - Google Patents

Description

This invention relates to a method for Manufacture of modified polyphenylene oxides with excellent Properties.

Polyphenylene oxides are widely known as resins which have excellent properties such as heat resistance, chemical resistance, and mechanical and electrical Properties. On the other hand, however, they have a high Softening point and poor flowability and therefore have the disadvantage of relatively poor machinability on. To improve machinability and deformability of polyphenylene oxides without impairing their excellent

MQndllch · Agreement n. Inabesomloiii by phone. t < <usually written confirmation

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BATH

Neten properties are proposed methods τ / orden, at which are a styrene compound in the presence of polyphonylene oxides is polyiaerized (Japanese patent specification 22 O69 / C7, Dutch patent applications 66-17 395 and C6-17 520 as well as the French patent specification 1 551 503). Furthermore are for this purpose processes have been proposed in which a large amount of styrene is contained in an aqueous dispersion of suspension type in the presence of a polyphenylene oxide and a rubber component is polymerized (Dutch patent application 66-17 529 and French patent specification 1,551,503).

In the event that a styrene pre-bond is polymerized in the presence of a polyphenylene oxide as in the above-mentioned process, the polyphenylene oxide prohibits or inhibits the polymerization of the styrene compound, whereby the polymerisation yield of the styrene compound is lowered and, in particular, if the polyphenylene oxide is used When used in large quantities, there are some cases where the polynomialization does not progress at all. Accordingly, nan'reino v: e sent lent polymerization can take place unless the polyphenylene · :: ·; / ·. "Is used in as small an amount as possible in order to increase the I / O concentration of the styrene compound ? rrscheir.ür.- ;: is also observed in the case of v / o a Styrolvorbindur.g in v; äßriger dispersion in Anv / esenheit a polyphenylene le no: yd ur.ii a Kautschukkomponcnten is polymerized from the o.. For reasons, use Japanese patent specification 22 069/67, clio

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BAD ORfGiNAL

Dutch patent application 66-17 529 and French patent specification 1 551 503 the styrene compound in nine times or more than eight times or 3/5 times the amount of polyphenylene oxide '. Also give the Dutch Patent applications 66-17 395 and 66-17 529 as well as the French patent specification 1 551 503 indicate that the styrene in a suspension type aqueous dispersion system in the presence of a polyphenylene oxide is polymerized, and the Dutch patent application 66-17 529 as well as the French U.S. Patent 1,551,503 uses rubber or acrylonitrile in addition to styrene. However, in all of the above mentioned Process that uses styrene in larger quantities than the polyphenylene oxide and therefore the processes mentioned should be addressed as techniques which rather involve modification of styrene as the modification of polyphenylene oxides. According to the above-mentioned method, the styrene content of the polymerization product, it is therefore necessary to lower the polymerization yield.

However, in the case where the polymerization takes place in a suspension system is carried out, a phenomenon is observed that even if the styrene content is intentionally reduced of the polymerization product with a reduction in the polymerization yield, a large amount of unreacted styrene remains in the polymerization product because the polymerization product is in the form of pearls. That not implemented, relatively high-boiling monomers, which are contained in such pearls

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is difficult to remove by drying, with the result that a molded article obtained from the polymerization product has a badly deteriorated appearance and also has deteriorated physical properties.

In short, when polymerizing a styrene compound in the presence of a polyphenylene oxide, it is necessary that the styrene compound is used in a larger amount to the polymerization prohibiting or inhibiting effect of the Exclude polyphenylene oxide. As a result, the graft conversion of the styrene compound onto the polyphenylene oxide becomes low and the polymerization product is essentially a mixture of the polyphenylene oxide and a polymer of Is styrene compound. It is well known that such a mixture varies widely in its physical properties is of a graft polymer of high graft efficiency. On the other hand, in the case where the polymerization yield remains is lowered in order to reduce the styrene content of the polymerization product, unreacted monomer s in the polymerization product, whereby a molded article obtained therefrom deteriorates physical properties owns.

In the applicant's Japanese patent applications 56 501/68 and 525/69, methods are proposed in which a styrene compound in the presence of a polyphenylene oxide

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or in the presence of a polyphenylene oxide and a rubbery one Polymer is polymerized to enable a high polymerization yield and a high graft conversion to reach"

A further object is to provide a method for producing a by graft polymerization with a styrene compound to find modified polyphenylene oxide, the modified polyphenylene oxide having a higher graft conversion and has higher molecular weight of the polystyrene part.

According to the invention, a method is now to be created in which a “relatively small amount of a styrene compound is essentially completely graft polymerized on a polyphenylene oxide or on a mixture of a polyphenylene oxide and a rubbery polymer. Further, in such a method, the graft polymerization should proceed more smoothly by causing a Distillation during the graft polymerization to remove any excess To remove part of the styrene compound, the remainder continuing to be graft polymerized. This method is said to be able to produce a modified one composed of fine pearls with excellent surface condition To produce polyphenylene oxide. The graft polymer of a styrene compound on a polyphenylene oxide produced in this way, is said to have a high graft conversion of the styrene compound

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and a graft polymer portion of the styrene compound of a high molecular weight.

The above-mentioned objects are achieved according to the invention by, in an aqueous dispersion which has a Suspension stabilizer and a radical initiator contains 0.4 to 3 parts by weight of a styrene compound in the presence from one part by weight of a polyphenylene oxide, or from 15 to 69 parts by weight of a styrene compound in the presence polymerized from 85 to 31 parts by weight of a mixture, the latter from 74 to 96 weight percent of one Polyphenylene oxide and 26 to 4 wt .-% of a rubbery polymer. In this way a relative small amount of styrene can be smoothly graft polymerized onto a polyphenylene oxide with a high graft efficiency and with high polymerization yield.

In order to carry out the polymerization reaction more efficiently and more smoothly, it is preferred that it be in excess initially provided in the polymerization system via the amount of styrene compound contained in the finished graft polymer becomes, and that unreacted styrene compound in the form of an azeotropic mixture with water by distillation is removed in the course of the polymerization, leaving the desired amount of styrene in the system, and the reaction is carried out to complete the polymerization,

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In this way, a bead-shaped graft polymer can be obtained obtained, which has an excellent surface resistance and has a smaller diameter.

According to the invention is the amount of residual unreacted Monomers contained in the polymerization product are so small that the appearance of a deformed object, which is obtained by subjecting the polymerization product to extrusion or injection molding, Is not affected at all.

It is also possible according to the invention to produce a graft polymer which has a high graft conversion Styrene compound and has a high molecular weight graft polymer part of styrene compound. When the graft transformation the styrene compound is high, the obtained graft polymer is more excellent in modulus, flowability, creep, Tension-relaxation, tension modulus, flexural modulus, Vicat softening point and transparency, as a mere mixture of a polyphenylene oxide with a polymer of a styrene compound, or as a modified polyphenylene oxide with low graft conversion of the styrene compound, and is excellent in the temperature dependence of the physical properties and in the machinability. These properties are of Importance in considering the fact that the poly: phenylene oxide has the properties of a polymer, which

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is used at elevated temperature. Furthermore, that is high Molecular weight of the grafted. Polystyrene part is remarkably preferable in view of tensile strength and the like properties.

The Styrofoam compound / which in the present Er invention is polymerized is a styrene of the formula:

I ₀ a CH ά

f ~ \

in which R '■ <»R' ₂ > ^R * 3 ' ^{R <} 4 ^{and R>} 5 independently of one another, a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, a hydroxyl group, a carboxyl group, or a hydrocarbon group or respectively is a halogen-substituted or a cyano-substituted hydrocarbon group having 12 or fewer carbon atoms, or a hydrocarbon foxy group or a halogen-substituted or hydrocarbonoxy-substituted hydrocarbonoxy group in which the number of carbon atoms is 12 or less; or a mixture of this styrene with an alpha-substituted styrene of the formula:

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in which R ^1. , R ^1. , ^Rl ₃ f ^{R <} 4 and R 'have the above meaning and R'g is a hydrocarbon group in which the number of carbon atoms is 12 or less.

As examples of R ¹ ^, R ', R ¹ -, R' and R * ₅ in the above formula, which represents the styrene compound used in the invention, may be mentioned; Hydrogen; Halogen atoms such as chlorine, bromine and iodine atoms; Cyano groups; Nitro groups; Amino groups; Carboxyl groups; Hydrocarbon groups such as methyl, ethyl, propyl, heptyl, dodecyl, vinyl, allyl, benzyl and methylbenzyl groups; halogen-substituted or cyano-substituted hydrocarbon groups such as chloromethyl, bromomethyl and cyanoethyl groups; and hydrocarbon oxy groups and halogen-substituted or hydrocarbon oxy-substituted hydrocarbon oxy groups such as methoxy, ethoxy, phenoxy, monochloromethoxy and (methoxy) methoxy groups.

Examples of R ' _g are methyl, ethyl, propyl, pentyl, nonyl, undecyl and phenyl groups *

Typical examples of styrene include: styrene, 2,4-chlorostyrene, p-methoxystyrene, p-nitrostyrene, p-methyl- ' styrene, 3,4-dimethylstyrene, m-tert.-butylstyrene, p-dodecylstyrene, p-phenylstyrene, p-acetoxystyrene, divinylbenzene, p-aminostyrene, p- (chloromethoxy) -styrene, m-cyanogen styrene, p-vinylbenzoic acid and o-hydroxystyrene? and typical examples

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of the alpha-substituted styrene count; alpha-methylstyrene, alpha-propylstyrene, alpha-undecylstyrene, o-methyl-alpha-methy1-styrene, m-methyl-alpha-methylstyrene, p-methyl-alpha-methylstyrene, p-methoxy-alpha-methylstyrene , p ~ cyano- alpha ~ methyl styrene, m-bromo-alpha-methylstyrene, p-chloro-alpha-methylstyrene and 1,1-diphenylethylene. These styrenes or alpha-substituted styrenes can be used either alone or in a mixture of two or more.

For examples of the rubbery polymer which used in the present invention include: polybutadiene, polyisoprene (including natural rubber) Polychloroprene, butadiene-styrene copolymers, butadiene-styrene block copolymers, Polybutadiene-styrene graft copolymers, polyisoprene-styrene graft copolymers, Isoprene-styrene copolymers, isobutylene-isoprene copolymers, polybutadiene-acrylonitrile-styrene graft copolymers, Butadiene-acrylonitrile copolymers, polybutadiene-styrene-alpha-methylstyrene graft copolymers, Polybutadiene-styrene-methyl methacrylate ~ graft copolymers, Poly (butadiene-styrene) -styrene graft copolymers, poly (butadiene-styrene) -styrene-acrylonitrile graft copolymers, Polychloroprene-styrene graft copolymers, Poly (butadiene-acrylonitrile) -styrene graft copolymers and ethylene-styrene copolymer.

The polyphenylene oxide used in this invention has the general formula:

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in related R-, R ₃ , R ₃ and R / is, independently of one another, a hydrogen atom, a halogenated, a hydrocarbon group or halogen or cyano-substituted carbon group with 12 or less carbon atoms, cclcr a hydrocarbonoxy group or is a halogen- or cyano-substituted hydrocarbonoxy group having 12 or fewer carbon atoms, and η indicates the degree of polymerization and is an integer greater than 50.

As examples for R.,

and R. are named-:

Hydrogen, chlorine? Bromine and iodine atoms, and "ethyl, ethyl, Propyl, allyl, phenyl, benzyl, methylbenzyl, chloromethyl, Bromomethyl, 2-chloroethyl * cyanoethyl, methoxy, monochloromethoxy, Ethoxy and phenoxy,

Typical examples of the polyphenylene oxide counter ·. 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-methy1-6- allyl, 4-phenylene oxide, poly-2,6-diraethoxy-l ^ -phenylerioxy:!, poly-2,6-dichloromethyl-1,4-phenyleneoxy, poly-2, G-dibrorninetliyI 1,4-phenylene oxide, poly-2 _# 6-ai (2-chloroethyl) -1,4-phenyler o _i: -; yd, poly-2, 6-ditolyl-l, 4-phenyler _i c :: yd, poly-2, fi dichloro-1,4-phoiv, · - lenoxvd, poly-2 _r 6-diphenyl-l, 4-phi2nylenoxvd and POLV-2 .5-di "

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BATH ORIGINAL

methyl ~ 1,4-phenylene oxide.

The catalysts used in the present invention are organic or inorganic radical initiators, which are commonly used as polymerization catalysts for styrenic compounds. Of these, the organic ones Peroxides are preferred in view of the physical properties of the resulting graft polymers.

Typical examples of catalysts include: decanoyl peroxide, benzoyl peroxide, laurel peroxide, octanoyl peroxide, Steamer peroxide, 3,5,5-trimethylhexanoyi peroxide, tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl perpivalate, Diisopropylbenzene, hydroperoxide, 2,5-dimethyl-2,5-di-tert-butyl-peroxyhexane, Di-tert-butyl peroxide, cyclohexanone peroxide, Dicumyl peroxide, alpha, alpha'-azobisisobutyronitrile, tert.-butylperoxyisobutyrate, and tert-butyl peroxylaurate.

These radical initiators are preferably those catalysts which decompose at high temperature, or they are used in the form of a combination of two or more catalysts, for example a combination one type of catalyst decomposing at low temperature with one type decomposing at high temperature Catalyst type. In the case where the combination of a low temperature decomposing catalyst with

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When a catalyst which decomposes at high temperature is used, the polymerization is effected initially at below about 90 C and after a certain amount Polymerization yield has been achieved, the temperature of the system is increased to initiate the polymerization at a high temperature-essentially complete.

To preferred catalyst combinations / which according to the invention used include the combinations of: lauroyl peroxide with dicumyl peroxide; Lauroyl peroxide with di-tert-butyl peroxide; Lauroyl peroxide with tert-butyl peroxybenzoate; Laurayi peroxide with 2,5-dimethyl-2,5-di-tert-butylperoxyhexane; Lauroyl peroxide with benzoyl peroxide; 3,5,5-trimethylhexanoyl peroxide with dicumyl peroxide; 3,5,5-trimethylhexanoyl peroxide with tert-butyl peroxybenzoate; 3,5,5-trimethylhexanoyl peroxide with benzoyl peroxide; 3,5,5-trimethylhexanoyl peroxide with di-tert-butyl peroxide; tert-butyl peroxypivalate with di-tert-butyl peroxide; tert-butyl peroxypivalate with dicumyl peroxide; tert-butyl peroxy pivalate with tert-butyl peroxybenzoate; 2,4-dichlorobenzoyl peroxide with tert-butyl peroxybenzoate; 2,4-dichlorobenzoyl peroxide with dicumyl peroxide; 2,4-dichlorobenzoyl peroxide with di-tert-butyl peroxide; 2,4-dichlorobenzoyl peroxide with 2,5-dimethyl-2,5-di-tert-butylhexane; Octanoyl peroxide with dicumyl peroxide; and octanoyl peroxide with di-tert-butyl peroxide.

To increase the rate of polymerization, you can use a redox catalyst, which thereby

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is prepared that one of the aforementioned radical initiators is combined with a reducing agent. For examples such reducing agents include dimethylaniline, p-chlorobenzenesulfinic acid, Benzoin and acetoin.

In the present invention, the catalyst can be used in an amount sufficient for polymerization the styrene compound is suitable. To exercise appropriately According to the invention, the catalyst is based on an amount of from 0.01 to 10% by weight, preferably from 0.3 to 10% by weight based on the weight of the styrene compound fed. This preferred amount of the catalyst used in accordance with the invention is greater than the amount of a catalyst which is usually used for the polymerization of S ty ro ^ .verbindungen will. However, this is likely to be due to the fact that the polyphenylene oxide is a polymerisaticnsverbietende shows or inhibitory effect, as explained above. It is well known that when using a Polymerization catalyst in a large amount, the molecular weight of the resulting polymer tends to be low to become. Nevertheless, the molecular weight of the polystyrene grafted part obtained by the present invention is high. This point is therefore an essence of the present invention, although the reason for it cannot be clearly recognized at present is. Such a fact one has before this one

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Invention never presented.

The amount of water used in this invention can be any amount as long as the suspension state of the reaction system is kept favorable. Generally this will But water in an amount of at least 0.7 parts by weight, preferably 1 to 10 parts by weight, per part by weight of the mixture of polyphenylene oxide, rubber-like polymer and Styrofoam compound applied.

The aqueous dispersion used in the present invention contains a dispersion stabilizer. Examples of such Dispersion stabilizers include: polyvinyl alcohol, gelatin, agar-agar, starch, glycerin, sodium salt of polyacrylic acid and of polymethacrylic acid, polyethylene glycol, ethylene glycol. Polyacrylamide and the 1: 1 copolymer of styrene and maleic ahydride. The use of the dispersion stabilizer is not always required when the following mentioned surface-active agents or the anti-adhesion agent Agent is used, but its application successfully stabilizes the dispersion. The amount of to use Dispersion stabilizer is not particularly limited, but it is usually 0.0001 to 3% by weight, preferably 0.001 up to 1.5% by weight, and in particular 0.01 to 1.5% by weight, based on the weight of the water used. If further such cationic, anionic or non-ionic surfactants such as hydroxyethyl cellulose, carboxymethyl

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cellulose, methyl cellulose, resin soap, sodium glycolate, sodium dodecylbenzenesulfonate, sodium stearate, polyoxyethylene monooleate, polyoxyethylene distearate, polyoxyethylene lauryl ether or lauryl trimethylainmonium chloride is used in combination with the dispersion stabilizer, so that such effects can be achieved in a stabilized dispersion system and the surface of the beads of the polymer being formed becomes smooth. The amount of the surfactant to be used is 0.00005 to 0.5% by weight, preferably 0.0005 to 0.5% by weight based on the weight of the water used, although it is used in the case of using the dispersion stabilizer is not particularly required. In addition, a water-insoluble inorganic compound such as a carbonate, silicate, sulfate or phosphate of calcium, magnesium, lead or barium can be used as a so-called anti-adhesion agent; an oxide such as clay, bentonite, talc, clay, titanium oxide or lead oxide; or a silicate, which further increases the stability of the pearls. The use of such an anti-adhesion agent is not always necessary. ¹ When it is desired to use the adhesion preventive agent, the amount thereof is preferably about 0.01 to 5% by weight based on the weight of water, although the amount is not particularly limited. In addition, water-soluble inorganic salts, for example sodium sulfate, can also be added to enable the polymerization

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progresses smoothly. The addition of these inorganic salts also gives the effect that the dispersion before an emulsification due to fine granulation is preserved. These dispersion stabilizers can either be used individually or can be used in a mixture of two or more. When these dispersion stabilizers are used, there are some Cases where during the distillation of the excess styrene compound foaming takes place which interferes with the operation. However, if a suitable defoaming agent is used beneficial effects can be expected. As such a defoaming agent, octyl alcohol and silicone oil are used, for example.

Furthermore, plasticizers, lubricants, coloring agents and stabilizers can be previously added to the system unless there is a particular adverse effect on the polymerization the styrene compound is brought about.

In the case where the content of the polymer is the styrene compound in the polymer beads obtained according to the present invention is to be controlled, the composition can of course be controlled at the time of feeding. The above However, according to the two-step process, the objective can be easily achieved by leaving the excess of the unreacted Monomers distilled off during the polymerization.

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: ORIGINAL INSPECTED

According to the present invention, in order to carry out the polymerization reaction more smoothly, it is preferred that the initial Styrene compound added to the system in excess, in the form of an azeotropic mixture with water, in the course the polymerization is removed by distillation to give the composition of a desired modified polyphenylene oxide and then the polymerization is completed (this process is hereinafter referred to as the two-step process designated).

In the two-stage process according to the invention, the styrene compound initially fed is not limited in terms of quantity. However, if the styrene compound is in excess, the amount of the monomer to be distilled off is to adjust the styrene compound to a final composition / undesirably large. Accordingly, it is preferred the styrenic compound in an amount less than 20 parts by weight per part by weight of the polyphenylene oxide or a mixture of which to be used with a rubbery polymer.

According to the two-step process of the invention, not only unreacted styrene can be distilled off at a low temperature by taking advantage of its azeotropic distillation with water, which is a dispersion medium, but that itself The resulting modified polyphenylene oxide is also made from fine Composed of pearls, which have a favorable surface condition

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: .OBlGlNAU INSPECTEC

own. The modified polyphenylene oxide found in Obtaining the form of such fine pearls enables additives such as stabilizers, lubricants, plasticizers and coloring agents at the time of post-treatment such as water removal and at the time of molding, uniform to disperse.

Steps in the two-stage process according to the invention the polymerization reaction in aqueous dispersion precedes and In the course of this reaction, excess styrene compound distilled off. In the case of a coarse distribution, this procedure can be used according to any of those ways of working like those be carried out from an aqueous dispersion which prepares was made by dispersing oil droplets of a polyphenylene oxide and a styrene compound in water in the presence or the absence of a rubbery polymer, with (1) excess monomer distilling off in the stage v / o the styrene compound has not been polymerized or has been sparsely polymerized, and (2) the excess Monomers is distilled off at the time where the polymerization has progressed to some extent.

To remove this excess of unreacted styrene compound, its azeotropic distillation is used exploited as much as possible with water. This distilling off can not only at atmospheric pressure, but-

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can also be carried out under pressure. It should be noted that in the case where the excess fees are in accordance with the working method (2) distilled off x ^ should be the initial polymerization yield the styrene compound is preferably controlled to a low level in order to improve the grafting efficiency to increase the styrene compound. If one takes this point into consideration, then the distilling off of excess styrene compound can and the polymerization are carried out in parallel with each other.

Furthermore, there is a close relationship between the time of distilling off the excess styrene compound (i.e. the initial polymerization yield of the styrene compound), the dispersion stabilizer and the catalyst.

For example, there is a method in which the excess monomer is distilled off after polymerize to some extent below about 90 ° C using a catalyst system has caused the latter to have a low decomposition temperature catalyst in combination with a high decomposition temperature catalyst, and then the remainder Substantially completely polymerizes monomers at a higher temperature; or there is a procedure which the polymerization from the beginning using a catalyst high decomposition temperature at a high

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BATH ORIGINAL

Temperature is effected, and unreacted monomer is distilled off in the course of the polymerization and then the polymerization is terminated at a higher temperature. However, a method using a catalyst system can also be used present, the latter consisting of a low decomposition temperature catalyst in combination with a Catalyst high decomposition temperature exists, with excess monomer being distilled off in the initial stage of the polymerization and the polymerization is initially determined at below about 90 ° C. up to a polymerization yield To a large extent, and then stopped at a higher temperature? or a process in which only one catalyst high decomposition temperature is used, with excess monomer in the initial stage of the polymerization distilled off, and then the polymerization is completed.

The above does not mean that the present invention is lower using only one catalyst Decomposition temperature could not be carried out. Even if a low decomposition temperature catalyst is used alone, the present invention can be successfully practiced if the amount of the catalyst is increased will.

The present invention is in the manner and order of adding the polyphenylene oxide, the rubbery type Polymers, the styrene compound, from chiodancr dispers

BADORIGfNAL

sion stabilizers and other additives, no restriction subject. However, it is preferred that the catalyst and / or the rubbery polymer be previously in the styrene compound or the polyphenylene oxide solution in styrene compounds has been dissolved or dispersed to distribute them uniformly.

In the present invention, when the styrofoam compound has been used in a small amount and therefore has been supplied at around room temperature, the GeTr ₁ ISCh of polyphenylene oxide and styrene cannot be made into the form of a solution but is in the form of a wet :: powder before. Therefore, for the polymerization reaction of the present invention to proceed smoothly, it is desirable that the polyphenylene oxide is sufficiently wetted with the styrene compound. Even in such a state, if the temperature is raised to melt the mixture, the reaction mixture may be brought into a homogeneous suspension. Such a phenomenon has not been described because the amount of the styrene compound is small. It appears that this phenomenon is peculiar to the polyphenylene oxides.

In the case, for example, where a shockproof modified Polyphenylene oxide according to the invention. Process is to be generated, it is preferred in some cases,

that the rubber component participates in the graft polymerization reaction participates while keeping a clenched state of particles, which latter have a suitable particle diameter. A preferred particle diameter is 0.1 to 10 microns.

The polymerization reaction of the present invention is in view of the reaction temperature is not particularly limited, provided that the water, which is a dispersing medium, present in pom of a liquid. The reaction can not can be carried out only under normal pressure and under pressure, but also under reduced pressure.

In the invention, the molecular weight of the grafted on the polyphenylene oxide or the rubbery polymers Styrene compound can be controlled by the temperature, the amount and the type of styrene compound, of polyphenylene oxide, the rubbery polymer and the catalyst varies. However, one can also control the molecular weight by using a chain terminator which is used in an ordinary polymerization reaction. 2u such chain terminators include mercaptans, alcohols, etc. When the molecular weight and number of branches of the grafted styrene compound controlled / so the physical properties of the resulting grafted po-

lyphenylenoxyds can be varied, ".,", ",",

^{XL 2} - ORIGINAL BATHROOM

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Have graft polymers prepared according to the invention not only improved flowability without regard to aor properties peculiar to polyphenylene oxides to be changed, but they also have increased resistance to oxidation and shock resistance. Even if, for example the free hydroxyl groups of the polyphenyls used: '.- oxides have not been treated at all, they still have the resulting graft polymers have less color non-variation and high resistance to oxidation at elevated temperatures. This is likely to be attributed to the fact that the process according to the invention leads to a much higher graft conversion of styrene compound than the previous ones Procedure.

The present invention is described below with reference to ve. " Embodiments explained in more detail, these examples saying nothing about the scope of the invention and numerous further modifications within the scope of the invention possible are.

The reviews of the polymers and the physical Properties are in the manner described below. The test piece used for the evaluation of the physical properties was prepared from a sheet, which one obtained by kneading a sample at 220 ° C. for 5 minutes by means of rollers and then kneading the sample at 240 ° C. for 10 minutes

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presses below 100 kg / cm.

Styrene plug conversion:

The graft conversion is evaluated in the following manner :

A polymer sample is extracted under reflux with acetone a: c, the latter containing 20% by weight of cyclohexane. After filtering off at elevated temperature / the extract is charged with fresh, 20 wt .-% CyclohGxan containing acetone and then subjected to extraction. This operation is repeated 10 times and the extraction treatment 30 For hours. The extraction residue is a graft polymer. From the yield of the graft polymer, the Styrene graft conversion calculated according to the following equation:

In the case where no rubbery polymer is used:

(Weight of the graft (weight of the styrene graft polymer) th Polvohe

conversion (%} ~ " ~ ΓΤΤ I TTTZ 7 " Z. ",

Waxed the supplied styrene

In the case where a rubbery polymer is used will:

Gev; icht des Zug- ku <.; ^ I.;,. to do (Weight of the! Led Polvphc> ~ + kcioL ^ üv.r -:.:

Weight of the supplied styrene

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ORIGlNAL BATHROOM

Note: ^τ in the second step process, this refers to the styrene weight in the second step.

Molecular weight of the grafted styrene:

The extract, which was obtained to calculate the graft conversion of styrene by extraction with a cyclohexarene: solution, is reprecipitated using He than o i ■ ·.;.: .. ·· and the intrinsic viscosity / yj / des The resulting homopolystyrene is v / ird in benzene at 25 C geiv.esso :; «From this intrinsic viscosity // Vj / vnx your mean molecule c.r weight Hn according to the equation of FR Mayo:

Mn = 1.67 χ 10 ⁵ / InJ ^{X '37}

calculated and this average molecular weight v / ird £ ils the. Considered the molecular weight of the grafted styrene.

Content of unreacted styrene in the plug olvmer pearls:

The content of unreacted styrene is measured by G: ^ chromatography and given in S by weight.

Tensile strength and modulus of tension:

These are measured at room temperature at eirwn: Anspannv.:;^.· speed of 10 ram jo Hinute gcm'iß JIS-o74 ^r ) (Japarij.r, ü Industrial Standard).

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Notched impact strength:

measured at 20 ° C with notch according to JIS-6745,

Vicat softening point:
measured according to ASTH D-1525-65T.

Degree of color:

Coloring of a film 1 mm thick, produced by A sample is pressed for 10 minutes at 100 kg / cm "and 270 ° C., the color being assessed by visual inspection.

In the examples, all parts and percentages relate to weight, unless otherwise stated is. Poly-2,6-dimethy1-1,4-phenylene oxide is hereinafter referred to as PPO called.

example 1

In a 500 cm barrel, pressure-resistant flask for polymerization, which is equipped with Thermcr.eter, nitrogen inlet and magnetic stirrer, are no.n fixed amounts of poly (2,6-dimethy1-1,4-phenylene oxide) {ßjj - 0.65 , measured in chloroform at 2 5 ° C), which according to polymerization by means of oxidative coupling using a catalyst made of manganese (II) chloride-ria-

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- 23 -

Triummethylat, styrene, LauroyIperoxyd and DicumyIperoxyd obtained became. The compounds are stirred thoroughly to create a mixed system.

Then an aqueous solution containing polyvinyl alcohol (degree of polymerisation 2000, degree of saponification LC

up to 89 mol%) and sodium dodecylbenzene sulfate eivJ '.. \;.;,.

added, and the system stirred at 620 U / Hin. In this Trap nitrogen gas is introduced, and the oxygen to be adequately replaced and excluded in the system. Huh Complete replacement with nitrogen will polymerize. tion reaction first at 90 C and then at 130 C while continuing Stirring is carried out and a product is obtained which consists of beads of substantially uniform diameter consists. The product is collected by filtration, washed with water and air dried and then dried the physical properties of the product are measured. The results obtained are shown in Table I.

The table shows the ratios of styrene / PPO and of water / styrene as weight ratios; the amounts of polyvinyl alcohol and sodium dodecylbenzenesulfonate are given as% by weight, based on the weight of the Water; and the amounts of the catalysts LauroyIperoxide and Dicumyl peroxide are given in% by weight, based on weight of the styrene monomer.

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O

0— ·

r-!

C \!

δ I

C-O

~ ί ITv O

Ci—

VO

'.ΐ- O LPv

O Cl

LTi LPi

A " tr. 6

6 "

VO O

CvI r-!

O <~. O Ov

ο—

VO

ο- O OH

O

O Ϊ-'Υ

¹ w

YY-

OJ

O
Ö

ri
O

o-O

^Γ ϋ

O O ! "• ι I. X Γ "; Π D. - '. ■> f-i -P ρ I Ό C, Ch ί-ί * -V3 .; * * 1ί "A. r'-i r-i 4-) N ^ ν _% ■ Η •! r-i ^> ₍ GJ <- { \ λ ϊ * 0 V) 0 JL \ t;) M. C) ^ j [! j r-i 'J υ Υ ** σ) ¹ C y * O <? ί • Η pi E-J ► 1 Cl ' ' * *

O H

-P 'ij *
f ../ • rl -P 0 CO egg K - ' 4.} ta (/1 r. 0 O Il ., 4 m ω -r-i • r ·! ■: i C) Ii r-l'ü O o - Pm Ai

M. O O .U O i " ¹ b ^ ~. -P to Γ-i ■ O -. ^ t; · Tj r; ή-, ^r j ■ β r-i C. .; J Γ "'ί to • i-i ™ / C, \\ ■; 0 'r' Ul r. r-i r "-i .'_! O 0 f <* (P ; ι H r ... ! · ■! el r " Oj ι- ί f "Si Ci φ

BATH ORIGINAL

109823/2023

lrsaUz No.

I - '. Molecular weight of grafted styrene

32,000 76,000 74,000 72,000

Bexugsbeisüiel

4 5 000

O cc CC

Physical Properties

Tensile strength (kg / cm)

Tension module (kg / cm)

Vicat-ri'v / üichurig.sptmkt (C) 151.0

Degree of coloration

800 900 1,000 1,200 1 310 12,000 13,000 14,000 14 500 14 6OO 151.0 155.3 16O, 3 104.1 ■ 163.8 pale pale pale pale pale yellow yellow yellow yellow yellow

The Bezugsbeisniel shows the case where styrene under the same conditions _e n v / ie in Annatz Mr. 1 horaopolymerisiert v; urde.

20571

Example 2

Example 1 is repeated with the exception that instead of using styrene alone / the styrene in combination with a mixture of p-methyl-alpha-methylstyrene and m-methyl-alpha-methylstyrene. (Ilol ratio of the p-derivative 3 to the m-derivative 4/6) is applied. The results obtained are shown in Table II.

BATH 109823/2023

■ j'r'jol.lo YT

CN

Approach Ur.

A goGet2 i; e S LoΓf e Sfcyrol / PPO

Water / styrofoam!

Styrene / o- and p-riethyl-

-methy! styrenes 2.5

Polyvinyl alcohol (%) ο, 5

Sodium dodecylbenzene

sulfonate (%) 0.01

Lauroyl peroxide (%) 0.6

Dicumyl peroxide (%) 0.3

Polymerization time (hours) 2

90

Polymerization ^{temperature (0} C)

Polymerization product

Unreacted amount of styrene (%) in the beads 0.10

Graft conversion 32.0

Physical properties Tensile strength (kg / cm ² ) Tension modulus (kg / ση) 12100 Vicat calibration point

Degree of coloration pale

yellow

4th
0.5

1.5
5

O, 5

6th
0.5

0.01 O, Ol 0.01
0.6 O, 6 0.6
0.3 0.4 0.4

1.3 5

0.5

0.01

0.6

0.6

2 10 3 12 3 12 4 15 130 90 130 90 130 90 130

0.10 0.15 0.15 0.20 00.3 89.3 87.2 92.1

pale yellow

930 1000
141C0 14500

1200 14 600

1.3

6 0.5

0.01

0.6

0.6

4 90

0.20 92.8

14800 163.8 161.6 171.8 165.0

pale-pale-pale-pale yellow yellow yellow yellow

2Θ57107

Example 3

Example 1 is repeated with the exception that the catalyst and the reaction conditions can be varied » The results obtained are shown in Table III.

109823/2023

Table III

"• ν. IO O

Γ sentence no.

Styrene / PPO "water / styrene

Polyvinyl alcohol (%)

Natriuifidodec "! benriolsulf c. ;

-·;;, gate

Kai: -I · '·:;, tor Art

! '. close (%)

PolynoriFsa gen (setting)

Temperature (° C) Time (hours)

1 2 1 3 j
4th 5 ί - 8th 1 5 1 3 0 ^ 01 1 _? 5 1.3 1.5 i
1
1.5 .IjO 0.5 5 tert-
Btttyl
peroxy 5 5 5 5 -
- "t 5 ■ J. 01
ί 0.0
t 0.5 0.5 Oc. 5 0.5 Oo 5
I. tert-
Butyl
j.ercxy-
benzoate 0.01 OjOl 0.01 0 ^ 01
/ 0.6 no di-tert-
Butyl
peroxide di-tert-
Butyl 2 _f 6-
Dichloro -
bcnzoyl
peroxide Ji ~? I !? **
Trirethyl
rsroxyd thing-
yiuerisa- 15th 0.8 γ 1.5 I _; r 2.0 110 10 130 130 00 S3 -. -, -, 150 15th 17th 5 -, ->, ", O

ι
ir>

oa tζ No. \ 1

T- ■ jlyranrisatir.p.product

not rea <" ^!
Styrene ^ .en · .- '.O _r .O3 den Per'.on (ϊ,)' Pfro (7i; i.iiav; and- δδίΟ lung 'U) ^τ

Mobku lorgew.
of the grafted Shyro ls

79 500

Physical Properties

Tensile strength

ugfest
(kg / cm

G
)

^b 1,000

S ρ annun g smo-

dul (kg / cm2) M 000

Vicat expansion point ( ⁰ C)

Coloring
Degree

16O ₉ O

pale yellow

pale yellow

OolO
87 _r 0

77,000

1,000
14 300

162 ^ 0

pale yellow

OnIO

90c0 75 COO

1 2C0 14 600

165 »3

pale yellow

o: o

0.30

. 73 OCO

000

160 * 0

pale yellow

IA OCO

16IyO

pale yellow

Ο «15

88.0

72,000

1 OCO
14,000

169 = 0

pale yellow

O ₁ IO

0 co:

14 5c:

170 ^ 0

pale yellow

Example 4

Poly (2,6-dimethyl- 1,4-phenylene oxide) {/ JIJ - 0.65, measured in chloroform at 25 ° C.), which was obtained by polymerization (by means of oxidative coupling), is placed in the same reaction _{vessel as in Example I 7} ) using a catalyst made from manganese (II) chloride and sodium methylate. Water is added to the reaction vessel and the compound is dispersed therein by stirring. Then a Ctyrollösuiig is added with violent stirring, which contains lauroyl peroxide and dicumyl peroxide and which is absorbed uniformly in the polyphenylene oxide. In this system, polyvinyl alcohol is grounded. (Degree of polymerization 2000; degree of saponification 86 to 89% Hol) and sodium dodec / 1-benzenesulfonate dissolved and the oxygen in the system is sufficiently replaced by nitrogen gas. After complete replacement by nitrogen, a polymerization reaction is carried out with stirring, first at 90 ° C., and then a polymerization reaction is carried out at 130 ° C. and a product is obtained which consists of beads of essentially uniform diameter. The product is through. ⁷ Nbfiltration recovered, washed with water and air dried and then the properties of the product are measured. The measurement results are shown in Table IV.

109823/2023

Approach no.

Substances used

Styrene / PPO
What s er / StyroI Polyvinyl alcohol (%) Sodium dodecylbenzenesulfonate

2 , 5 10 '3 1 , 5 1 12th 5 , 01 130 90 5 30th O / 6 O , 5 O , 3 O .0 /O O 0 / 4 2 90

Lauroyl Peroxide (%) Dicumyl peroxide (%)

Polymerization time (hours) Polymerization temperature (C)

Amount of polymerization product not converted, styrene

monomers in the beads (%) 0.10 0.10

Graft Conversion (%) 83.0 90.0

Molecular weight of the

grafted styrene 82 000 76 OGO

Physical Properties Tensile Strength (kg / cm) Tension Module (kg / cm) Vicat reaching point (° C) degree of coloration

800 1 COO 12,000 Ii 000 151.0 160.0 pale yellow pale galb

Example 5

In a pressure-resistant polymerisation with a capacity of 500 cm reaction vessel with round 3ode, v / elches with thermometer,

Nitrogen inlet tube and magnetic stirrer is provided, 'are poly (2,6-dimethyl-1,4-phenylene oxide) {£ ~ VJ = 0.65, measured in chloroform at 25 ° C), which according to the polymerization by oxidative coupling using oinea man-

109823/2023

BATH

2 Q 5 71 O 7

gan (II) chloride sodium methylate catalyst, Lauroy! peroxy ά, Dicumy! Peroxide and a styrene solution obtained vmrcie, in valcher a rubber-like polymer is contained in dissolved form. The compounds are used to prepare a mixed. Systems thoroughly stirred.

Then an aqueous solution containing polyvinyl alcohol (degree of polymerization 2000; degree of saponification 86 to 89 mol%) and sodium dodecylbenzenesulfonate are added and the system is stirred at 620 rpm. In this case, nitrogen gas is introduced to remove the oxygen i ;;; Sufficiently replace and exclude the system. After complete replacement by nitrogen, SO ¹ * C and dar.r. polymerized at 130 ° C. while continuing the stirring, and a product is obtained which consists of beads of substantially uniform diameter. The product is purified by .b:? ^R may iltrieren GeV /, washed with V7asser and air-dried, and then the physical properties of the product are measured. The results obtained are compiled in Tabollo V.

The rubbery polymer was a polymer which by graft polymerizing styrene onto polybutadiene boron, and it had a styrene / butadiene ratio of -i / ö, ur ;; \ its amount is given in weight ", based on c; as weight ......

109823/2023

resulting polymers, the amounts of suspension stabilizers, i.e. polyvinyl alcohol and sodium dodecylbenzenesulfonate, are given in Gev; .-%, based on Gev; not aas v7ai: - SQTSr and the amounts of catalysts are given in Gov. '. _-ΐ; based on the weight of the styrene monomer.

109823/2023

T from ο 11 η V

Approach no. 1 2 3 4th substances used Styrene / PPO 2 1.8 Ι / 5 1.3 Water / styrene 5 5 5 5 rubbery poly
meres (%) 5 5 5 5 Polyvinyl alcohol (%) 0.5 0.5 0.5 0.5 Sodium dodecylbenzene
sulfonate (%) 0.01 0.01 0.01 0.01 Lauroyl Peroxide (%) 0.6 0.6 0.6 0.6 Dicumyl peroxide (%) 0.3 0.3 0.4 0.6 Polymerisation time (hrs) 2 10 2 10 3 12 4 15

Polymerization ^{temperature (0} C)

9O

130

90

130

Polymerization product

Amount of unreacted styrene monomer in the beads (%)

Graft conversion (%)

Molecular weight of the graft polymer mean diameter of the polymer beads (rom)

Physical Properties Tensile Strength (kg / cm ² )

90

0.04 0.08 0.10 0.15 CD 83.1 87.0 85.8 91.9 cn 81,000 80,000 75,000 74,000 0.8 0.9 1.0 1.1 790 800 820 850

Voltage module 12

Vicat Softening Point (C) 149.3

■ Charpy impact value (kg.cra / cra ^) 15.0 Degree of coloration pale

yellow

11 500 11 800 2,200 153.0 157 i.59 17.0 18.0 19.0 pale
yellow pale
yellow pale
yellow

O CO OD

Example 6

Example 5 is repeated with the exception
that instead of styrene, a mixture of p-methyl-alrhair.ethylstyrene and m-methyl-alpha-ethylstyrene (molar ratio of the p-derivative to the m-derivative 4/5} is used in combination with styrene. The results obtained are in Table VI shown.

109823/2023

^ h: 'Hf

Approach Ur.

Substances used styrene / PPO water / StyroI Styrene / n- and p-methyl- ^ methylstyrenes

Polyvinyl alcohol (%) sodium dodecylbenzenesulfonate (%) lauroyl peroxide (%) dlcumyl peroxide (%) ca rubbery polymer (%)

ι Polymerization time (Stä.) Polymerization temperature ( ⁰ C)

Polymerization product

Amount of unreacted styrofoam monomer in the Pearls (£)

Graft conversion (%) mean bead diameter (mm)

Physical Properties

Tensile strength (kg / cm)

2 Modulus of tension (kg / cm) Vicat warming point ( ⁰ C) Charpy basket impact (kg.cm/cm ") Degree of coloration

2 , X 2 1.8 3 1 r.5 12th 4th 1.3 15th 3 , 01 90 3 90 3 , 01 130 90 3 130 3 , 6 3 3 , 6 3 0 , 3 0.05 0 , 4 0.5 0 0.001 0 0.005 0 10 0.6 0 0.6 0 130 0.3 0 0.6 5 5 ' 5 5 2 10 90 130

0.10

0.10

0.10

0.15

80.9 88.2 88.0 89.8 IS® 0.7 0.8 1.0 1.2 CD 780 790 800 820 cn 12,000 11 500 11,000 12 900 159 160 162 3 64 18th 17th 17th 18th b3 ate-yellow pale yellow pale yellow pale yellow

_ 44 Example 7

Example 5 v / ill be repeated, varying with the exception Cs..ί the type of the rubbery polymer. The results obtained are shown in Table VII.

109823/2023 _0RtGWM .

νχΐ

Approach no.

deployed scoffs

Styrene / PpO

V ⁷ as ser / S tyro 1

rubbery polymer Art

Lot (%)
'' Polyvinyl alcohol (%)

Sodium dodecylbenzenesulfonate lauroyl peroxide (%)
Dicumylperojiyd (%)

Polymerization time (hours)

Polymeric ion temperature (C) Polymerization ^ product

Amount of η! .Ent converted Stvrolaonoraeren in the pearls ■ (%)

Graft conversion (%)
Molecular weight of the grafted styrofoam
medium pearl urchraes scr

1.5 5

Polybutadiene CD

• 90

0.5

0.01

0.6

0.4

(well)

0.10 87

75,000 1.1

Physical properties Tensile strength (kg / cm ² !
Stress module (kg / cm ² )
Vicat softening point ( ⁰ C) _ ",, ^. Charpy impact four (kg.cm/cm) 16.0 degree of coloration "pale yellow

800

12,000 157.0

1.5

Butadiene- * Gtyro1-Conolymeres (2)

0.5

0.01

0.6

0.4

3 12 90 130

0.10 87

-75,000 1.3

79Ο

11 800 159.0 17.0

pale yellow

1.5 1.5 5

Butadiene- polybu-acrylonitrile- tadiene copolymer (3) (4)

5

0.5 0.5

0.01 0.01

0.6 0.6

0.4 0.4

12 3 130 90

0.10
88

000

810

000
160.0
18.0
pale yellow

1.5 5

natural rubber (5)

0.5 0.01 0.6 0.4

0.10 86

1.0

820

158.5 18.0 pale yellow

0.10

88

76 Upper Austria 1.0

800

12 100 159.5 17.0

pale yellow

Remarks:

(1) = JSR 0700 manufactured by Japan Synthetic

Rubber Co., Ltd.

(2) = JSR 1500 manufactured by Japan Synthetic

Rubber Co., Ltd.

(3) = N 24OS manufactured by Japan Synthetic P.

Co., Ltd.

(4) = NF 35Λ, manufactured by Asahi 'Kasei Kogyo

Kabushiki Kalsha

(5) = RSS, No. 1

Example 3

Example 5 is repeated with the exception . you
the catalyst and the polymerization conditions vary:
v / earth. The results obtained are shown in Table VIII together
set.

109823/2023 bad

ITr.

substances used

Styrene / PPO 1.5

Water / styrene 5 Amount of rubbery

Polymers (%) 5

Γοΐννίη "·!, Alcohol {3) 0.5 Sodium dodecylbenzenesulfpnate 0.01

Catalyst (w _{n Λ r> J} _ ,.

Art

.1.5
5

1.5
5

Lot (%)

Polymerization Conditionson. Temperature ( ⁰ C)
Time (hours)

Polymerization product

Amount of unreacted styrene monomer in the beads (%)

Graft conversion (%)
Molecular weight of the grafted styrene
mean bead diameter (mm)

Physical properties Tensile strength (kg / cm ² ) Modulus of tension (kg / cm 2) Vicat softening point (C) Charpy impact value

(kg.cm/cm)
Degree of coloration

2,4-Di eh.Io rbonsoyl peroxide 1.5.

70

0.10 80.0

70

8OO

12,000 159.0

17.0

pale yellow 1.5
5

5 5

0.5 0.5 0.5

0.01 0.01 0.01

tort, -Butyl- Di-tort.- Di-tert, -

peroxypivabutylper- butyl perlate oxide

1.5 0.8 0.1

1.0
5

0.5

0.01

Dicurayl peroxide

1.0

0.5

0.01

.Dicumyl peroxide

1.0

2.0

0.15
84.0

000
1.2

820

800
160.0

18.0

130

20th

0.15
87.0

000
1.2

810

100
158.0

19.0

130
25th

0.25
84.0

500

1.4

830

000
155.0

15.0

130
10

0.15
85.0

000
1.5

340

000
161.0

15.0

130
10

0.10 88.0

70 1.5

850

100 162.0

15.0

pale yellow pale yellow pale yellow pale yellow pale-c ^ b

Ö on • »J

Example 9

Poly (2,6-dimethyl- 1,4-phenylene oxide) {fj] J- 0.65, measured in Chloroform at 25 C) obtained according to Polymerisation dui ": oxidative coupling using a manganese (II) chloride-sodium methylate catalyst, styrene, lauroyl peroxide and dicumyl peroxide. The compounds are thoroughly stirred to prepare a mixed system. On the other hand In the same manner as above, a mixed system is also prepared in which a rubber-like polymer is dissolved, then an aqueous solution is added which contains polyvinyl alcohol (degree of polymerization 2000; degree of saponification 85 to 89 mol%), and the system is at In this case nitrogen is introduced in order to adequately replace and exclude the oxygen in the system Complete replacement by nitrogen, the polymerization is carried out in a first stage while continuing the T <"': \ ~ rens at 90 C, and then the styrene and the hater are azeotropically removed by steam distillation at 94 ° C in order to To withdraw a lot of styrene from the system. A second polymerization reaction stage is then carried out at 130 ° C. and a product is obtained which consists of beads of substantially uniform diameter. The product is filtered off

109 * 2 3/2023 _B ao

gex * / onnen, washed with water and air-dried, and then the physical properties of the product are measured. The results obtained are shown in Table IX.

The rubbery polymer used was a polybutadiene-styrene-Pfropfcopolyir.eres which was obtained by graft polymerizing styrene on polybutadiene and which had a styrene / butadiene ratio of 4/6, the amount in wt .-% based on the weight of the polymer produced. The amounts of dispersion stabilizers, ie polyvinyl alcohol and sodium dodecylbenzenesulfonate, are given in% by weight, based on the weight of the water, and the amounts of the catalyst are given in% by weight, based on the weight of the initial amount of styrene.

109823/2023 _{BAD 0R1G1NAL}

Approach ilr.

LD

Substances used styrene / PPO

Water / Styrofoam rubber-like polymer Art

!! close (%) polyvinyl alcohol (%) sodium dodecy! benzo isulfonate

Lauroyl peroxide (%) Dicurayl peroxide (%)

Polymerization conditions styrene / PPO in the second reaction stage Time (hours)

Polymerization product Amount of unreacted styrene monomer in the beads (%) Graft conversion (%) Molecular weight of the grafted styrene

Physical property ^; -.en tensile strength (kg / cm ² )

4th
3

0.5

0.01 0.30 0.15

first second stage stage 1 10

O ₁ .

Modulus of tension (kg / cm ^κ ) Vicat softening point ("C) Charpy impact value

■ (kg. Cn / cm ')

O , 05 84 ,1 72 000 850 14th 300 161 , 6

4th
4th

Polybutadiene styrene graft Copolvmeres 5 0.2

0.01 0.30 0.15

first second level level 0.4

0.08 87.3

72

790

13 158.9

18th

3 6

0.05

0.005

0.35

0.15

3 3.

Polybutadiene

Styrene graft

Copolymores

0.1.

0.01 0.35 0.15

1

first second / first second

Level level level level

1.5 10 1.0

0.09 89.8

70

960 13

164.4

0 , 12 94 ,1 70 000 780 14th 000 160 , 2

cn

18th

CD

Example 10

Example 9 is repeated, with the exception that instead of styrene, a mixture of p-methyl-O-C-methylstyrene is used and m-methyl- oC-methylstyrene (molar ratio of the p-derivative to the m-derivative 4/6), used in combination with styrene. the The results obtained are shown in Table X.

103823/2023

Table X

Anaatz No.

ΓΙ

O CD OO

Substances used styrene / PPO water / styrene s ty ro l / m- and p-methyl- ^ - methylstyrenes polyvinyl alcohol (%) sodium dodecylbenzenesulfonate (%) lauryl peroxide (%) dicumyl peroxide (%) rubber-like polymer Art

Amount (%) Polymerization Time (hours)

Polymerization product

Amount of unreacted styrene in the pearls (%) Graft conversion (%)

Physical properties Tensile strength (kg / cm ^) Modulus of tension (kg / cm ^) Vicat softening point (° C) Charpy impact value (kg.cm/cm)

3
5 in in co in 4th
5 5
O, O5
0.0Ol
0.35
0.15 5
0.5
0.01
0.35
0.15 4th
0.1
0.005
0.35
0.15 4th
0.5
0.01
0.35
0.15 Polybuta
service (1) Butadiene-sty-
rol graft
copolymeres ( Butadiene
S ty ro 1-
2) graft
polymer
(3) first second
Level level
2 10 5
first second
Level level
0.4 11 5
first second
Level level
0.15 15 5
first second
Level level
1 14 0.10
79.8 O, IO
78.0 0.10
90.1 0.15
83.8 980
14 500
166.0
5 86O
12 700
161.8
18th 880
11 900
163.2
19th 920
12 0OO
164.1
19th 2057 107

Remarks:

(1) β JSR 0700 manufactured by Japan Synthetic

Rubber Co., Ltd.

(2) = JSR 1500 made by Japan Synthetic

Rubber Co., Ltd.

(3) = The rubbery one used in Example 9

Polymers.

Example 11

Example 9 is repeated with the exception that
the kind of the rubbery polymer is varied. The results obtained are shown in Table XI.

109823/2023

Table XI

Approach no.

O CO GO K.1 CO ■ χ. KS O IvJ CO

Substances used styrene / PPO water / styrene rubbery polymer

Art 3
3

Polybutadiene (1)

3
3

Butadiene-styrene copolymer (2)

Lot (%)

Polyvinyl alcohol (%) _t sodium dodecylbenzenesulfonate (%)

Lauryl peroxide (%) S Dicumyl peroxide (%)

ι Styrene / PPO polymerization conditions in the second Reaction stage

Time (hours)

Polymerization product

Amount of unreacted styrenes in the beads (%) Graft conversion {%) Molecular weight of the grafted styrene

Physical Properties Tensile Strength (kg / cm ² )

Tension modulus (kg / cm ^) Vicat softening point {C)

Charpy impact value (kg.cm/cm) O ₇ Ol
0.35
0.15

0.01
0.35
0.15

3
3

Butadiene-acrylonitrile copolymer (3)

0.1
0.01 0.35 0.15

3 3

Polybutadiene (4)

0.1 0.01 0.35 0.15

first second
Level level
1 10 , 10
, 0 first
step
1 second
step
10 first
step
1 second
step
10 first
step
1 second
step
10 O ₁
9O ₁ 000 0
91 , Io
, 0 0
92 , 12
, 0 O,
90 15th
0 70 71 000 70 0OO 71 5OO 77Ο 700
, 5 770 790 780 13th
158, 13th
161 9OO
, 0 13th
160 700
, 0 14th
162, 000 °
⁰ p 18th 17th 16 19th

Remarks:

(1) = JSR 0700 manufactured by Japan Synthetic

Rubber Co., Ltd.

(2) = JSR 1500 made by Japan Synthetic

Rubber Co., Ltd.

(3) = N 42OS, manufactured by Japan Synthetic

Rubber Co », Ltd.

(4) = NF-35A manufactured by Asahi Kasei Kogyo

Kabushiki Kaisha

Example 12

Example 9 is repeated with the exception that
the catalyst and the polymerization conditions vary
will. The polybutadiene-styrene copolymer of Example 9 is used as the rubber-like polymer. The results obtained are shown in Table XII.

109823/2023

Table XII

VD in

O CO OO

Approach no. 1 2 3 4th substances used Styrene / PPO 3 3 3 3 Water / styrene 3 3 3 3 Amount of rubbery polymer (%) 5 5 5 5 Polyvinyl alcohol (%) 0.1 0.1 0.1 Sodium dodecylbenzenesulfonate (%) 0.01 0.01 0, ol 0.01 Catalysts Type and quantities (%) Octanoyl 2, 4-dichlorobene 3,5,5-trimethyl tert-Bu peroxide zoyl peroxide hexanoyl peroxide ty lperoxy 0.3 0.3 0.3 pivalate 0.3 di-tert.- tert-butyl per- tert-butyl per- Dicurayl Butyl peroxide oxybenzoate oxybenzoate peroxide 0.3 0.3 0.5 0.5

Polymerization conditions styrene / PPO in the second reaction stage

Time (hours)

Polymerization product

Amount of unreacted styrofoam in the pearls (% by weight) graft conversion (%) Molecular weight of the grafted s ty ro is

Physical Properties Tensile Strength (kg / cm ² )

Tension modulus (kg / cm) Vicat softening point (° C) Charpy impact value (kg.cm/cm ² )

first second
Level level
1 15 first second
Level level
0.5 10 first
step
1 second
step
5 first
step
0.5 second
step
10 000 O
f η 0.10
90.0 0.15
89.0 0
38 , 15 0.10
92.0 KJ \
800 -Y 70,000 71,000 70 000 70 , 0 _ο 780 770 780 790 14,000 14 1OO 14th 000 13th 16O, 5 160.2 160 , 2 160, 17th 18th 17th 18th

Example 13

Example 1 is repeated with the exception that different polyphenylene oxides, catalysts and dispersants can be applied and the reaction conditions are those of the previous case. The results obtained are compiled in Table XIXI.

109823/2023

Table XIII

CO

Approach no.

Substances used polyphenylene oxide styrene / PPO

Water / styrene dispersion _{stabilizer +++} surfactant catalyst Art

Lot {%)

Polymerization Temperature (C) time (hrs

Polymerization product

Amount of unreacted styrene in the beads (%) graft conversion (%> Molecular weight of the grafted styrene

Physical Properties Vicat Softening Point {C) A
0.6

5.0.

O, O1 ^e '

1.0
5.0
0.03

b)

0.001

f)

C.
1.2

³ ' ⁷ c)
0.12 ^CJ

0.004

gi

D. 0.7

⁵ '° d) 0.3O'

0.002 ^nj

E 1.1

² '° 0.10

t-butyl per-cyclohexa-di-isopropyl-benzoyl chlorobenzoate nonperoxide benzene hydroperoxide

peroxide

1.1

2.0

1.2

0.001

Dicumyl peroxide

1.0

14O
5 , 02
, 0 140
10 , 03
, 0 120
15th , 12
, 0 100
14th , 09
, 0 140
5 14th
6th 0
89 000 0
91 000 0
79 ooo 0
93 000 O,
90 000 66 62 71 63 69 148 152 147 144 151

Polyphenylene oxide

(A) Poly-2,6-dichloro-1,4-phenylene oxide

(B) Poly-2,6-dl (2-chloroethyl) -1,4-phenylene oxide

(C) Poly-2,6-dimethoxy-1,4-phenylene oxide

(D) Poly-2-allyl-6-methyl-1,4-phenylene oxide

(E) poly-2,6-dibromoethoxy-1,4-phenylene oxide Dispersion stabilizer

(a) Sodium salt of polymethacrylic acid

(b) gelatin

(c) sodium salt of the copolymer of styrene and
Maleic anhydride

(d) polyacrylamide

yy y _n

surfactant

(e) polyoxyethylene monooleate

(f) sodium stearate

(g) resin soap

(h) carboxymethyl cellulose sodium salt

Example 14

Example 1 is repeated with the exception that
different styrenes, dispersants and catalysts are used and the reaction conditions are those of the previous case. The results obtained are shown in Table XIV.

109823/2023

Table XIV
Approach no. 1 2

(1) (2) (3) (4) (5) (6) 1.5 1.5 1.5 1.5 1.5 1.5 - 2 1.5 4.0 4.5 5.0 5.0 4.5 5.0 0.4 ο, ι 0.2 0.01 O, 05 O, 08 Ο, ΟΟΙ 0.01 0.005 0.10 O, O3 0.05 0.5 0.1 0.9 ο, ι Ο, ΙΟ 0.5 0.9 ■ "1.5 0.5 1.0 2.0 2.0 10 ι δ 1 10 1 10 1 8 1 15

Substances used styrenes
Styrenes / PPO
Styrenes / 0c-alkyl styrene water / monomeric polyvinyl alcohol (%) methyl cellulose (%) benzoyl peroxide (%) dicumyl peroxide (%)

Polymerization time (hours) Polymerization temperature

( ⁰ C) 90 130 90 13Ο 90 130 90 130 9O 140 90 130

ι Polymerization product ο Amount of unreacted ^ω styrene in the pearls ι Graft conversion (%)

Physical Properties - * Tensile Strength (kg / cm ² )

cd Vicat softening point

^ J ⁺ styrenes

ο (1) p-methylstyrene

¹ ^ (2) p -chlorostyrene

(3) p-chloromethoxystyrene

(4) p-methoxystyrene

(5) m-bromo-et-methyls tyro I + styrene ^

(6) p-methoxy- d -methylstyrene + p-methylstyrene cn

h) 0.10
88.0 0.15
85.0 Ο, ΙΟ
82.0 0.05
87.0 0.18
85, O 0.19
88.0 * n
910 820 - - - 930 ( ⁰ C) 162.5 161.3 159.2 154.1 167.1 164.3

Claims (9)

Claims 1. A process for the preparation of modified polyphenylene oxides, characterized by polymerizing (1) 0.4 to 3 parts by weight of a styrene compound of the formula: CH ₂ = CH ■ / J ^E '5 ■ "' ♦ in which R '^ / ^R * 2'^R> 3 ' ^R * 4 ^{and RI} 5' independently, a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, a hydroxyl group, a carboxyl group, a hydrocarbon group or halogen - or cyano-substituted hydrocarbon groups with 12 or fewer carbon atoms, or a -hydrocarbon-oxy group or halogen- or hydrocarbon-oxysubstituted hydrocarbon-oxy group with 12 or fewer carbon atoms, are4 or a mixture of this styrene compound with a «^ -substituted styrene of the formula: R ¹ OH ₂ in which R ¹ ^, R ' ₂ , R * ₃ , R' ₄ and R ' _{5 have} the above meaning and R'- is a hydrocarbon group of 12 or less 109823/2023 Is carbon atoms; in an aqueous dispersion which contains a suspension stabilizer and a radivalinitiator , in the presence of 1 part by weight of a polyphenylene oxide of the mold in which R ₁ , R, »R ₃ and R., independently of one another, a hydrogen atom, a halogen atom, a hydrocarbon group or halogen- or cyano-substituted hydrocarbon group with 12 or fewer carbon atoms, or a hydrocarbon oxy group or halogen or cyano-substituted hydrocarbon oxy group having 12 or less carbon atoms and η denotes the degree of polymerization and is an integer greater than 50; or by polymerizing (2) from 15 to 69 parts by weight of a styrene compound as defined above or a mixture of this styrene compound with an oC-substituted styrene as defined above, in the presence of 85 to 31 parts by weight of a mixture which consists of 74 to 94 parts by weight % of a polyphenylene oxide as defined above and 26 to 4% by weight of a rubbery polymer. ' 2. The method according to claim 1, characterized in that a reaction temperature of 40 to 150 ° C is maintained. IUUB Ί 3/2 T 2 3 3. The method according to claim 1, characterized in that that the styrene compound styrene, 2,4-dichlorostyrene, p-methoxystyrene, p-nitrostyrene, p-methylstyrene, 3,4-dimethylstyrene, m-tert-butylstyrene, p-dodecylstyrene, p-phenylstyrene, p-acetoxystyrene, Divinylbenzene, p-aminostyrene, p- (chloromethoxy) styrene, m-Cyaiö'styrene, vinyl benzoic acid, o-hydroxystyrene or mixtures two or more of these compounds are used. 4. The method according to claim 1, characterized in that the oü-substituted styrene compound 06-methylstyrene., <A- ρ ropy Is ty ro 1, o (-undecylstyrene, o-methyl- ot-methylstyrene, m-methyl- oV-methylstyrene, p-methyl-oC-methylstyrene, p-methoxyo (-methylstyrene, p-Cyano-CA-methylstyrene, m-bromo- ^ methylstyrene, p-chloro-oC-methylstyrene, 1,1-diphenylethylene, or mixtures two or more of these compounds are used. 5. The method according to claim 1, characterized in that that the polyphenylene oxide is 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-ally1-1,4-phenylene oxide, poly-2,6-diraethoxy-1,4-phenylene oxide, Poly-2,6-dichloromethy1-1,4-phenylene oxide, poly-2,6-dibromomethyl-1,4-phenylene oxide, poly-2,6-ditoIy1-1,4-phenylene oxide, Poly-2,6-dichloro-1,4-phenylene oxide, Poly-2,6-dipheny1-1,4-phenylene oxide or poly-2, S-dimethyl-1,4-phenylene oxide used. 6. The method according to claim 1, characterized in that 10 9823/2023 that the rubber-like polymer is polybutadiene, polyisoprene, Polychloroprene, a butadiene-styrene copolymer, a butadiene-styrene block copolymer, a polybutadiene-styrene graft copolymer, Polyisoprene-styrene graft copolymer, an isoprene-styrene copolymer, an isobutylene-isoprene copolymer, a polybutadiene-acrylonitrile-styrene graft copolymer, a butadiene-acrylonitrile copolymer, a polybutadiene-styrene-C ^ -Methylstyrene graft copolymer, a polybutadiene-styrene-methyl methacrylate graft copolymer, poly (butadiene-styrene) -styrene graft copolymer, a poly (butadiene-styrene) -styrene-acrylonitrile graft copolymer, a poly (butadiene-acrylonitrile) -styrene graft copolymer or a ethylene-styrene copolymer is used. 7 1 method according to claim 1, characterized in that an organic peroxide is used as the radical initiator. 8. The method according to claim 1, characterized in that the organic peroxide is decanoyl peroxide, benzoyl peroxide, Lauroyl peroxide, octanoyl peroxide, stearoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl perpivalate, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di-tert-butyl peroxide, di-tert-butyl peroxide, Cyclohexanone peroxide, Dlcumylperoxid, O (, Ol'-Azobisisobutyronitril, tert-butyl peroxyisobutyrate, or tert-butyl peroxylaurate used. 109823/2023 9. The method according to claim 1, characterized in that the styrene compound or its mixture with the o (-substituted Styrene in an amount of 0.4 to 20 parts by weight per part by weight of the polyphenylene oxide or its mixture with adds to the rubbery polymer to be unreacted Styrene compound and oC-substituted styrene in the course of the The reaction is distilled off, the styrene compound remaining and the remaining {^ -substituted in the polymerization system Styrene adjusts to the composition of the desired, modified polyphenylene oxide, and then the polymerization finished. 109823/2023