SU470968A3 - Method for producing modified polyphenylene oxides - Google Patents

Description

rubber) , poly- (butadiene styrene) -methyl methacrylate graft copolymer, poly- (butadiene styrene) -styrene graft copolymer, poly (butadiene styrene) styrene acrylonitrile graft-sonolimer, polychloro prenstirolny graft copolymer and poly - (butadienakrilonitril) - styrene graft copolymer. These resinous polymers are used in an amount of 0.01-2, mostly 0.01-1 weight. h. pa 1 wt. including polyphenylene oxides. The compounds of the alpha-methylstyrene type used in the invention are represented by the formulas K, R,. or RC; In Ig-, R (. Where RI-Rs is a hydrogen atom, a halogen atom, a hydroxy group, a C 1 -C 3 hydrocarbon group, a C 1 -C 5-halo-substituted hydrocarbon group, a C 1 -C alkoxy group or a GI-C 5-halo-substituted alkoxy group. Specifically RI-Rs are any of the atoms hydrogen, chlorine, bromine and iodine, hydroxy, methyl, ethyl, propyl, allyl, phenyl, benzyl, methylbenzyl, chloromethyl, bromomethyl, methoxy, ethoxy, and chloromethoxy. Specific examples of styrene compounds and alpha methylstyrene compounds types include styrene, 2,4-dichlorosti ol, o-oxystirol, i-methoxystyrene, methoxystyrene, d-phenylstyrene, i-oxystirol, 0-divinylbenzene, p-divinylbenzene, a-methylstyrene, p-methoxy-cc-methylstyrene, / g-methyl-ss-methylstyrene, W-methyl-methylstyrene, o-methyl-a-methylstyrene. The aqueous medium used in the invention contains a surface-active agent, a free-radical initiator, a solvent, and may sometimes contain a dispersing stabilizer. Radical initiators include octanoyl peroxide, decanoyl peroxide, stearoyl peroxide, lauryl peroxide, 2, b-dimethyl-2,5di- (t; C er-butyl roxie) hexane, 3,6 -butane, cyclohexapaper peroxide, methyl ethyl ketope peroxide, dicum.peroxide, a, aazobpsisobutyronitrile, hydrogen peroxide, potassium persulfate, ammonium persulfate and sodium perborate. These radical initiators can be used in combination of two or more. In order to achieve sufficiently high polymerization rates at low temperatures, it is sometimes advantageous to use redox initiators of the type prepared by adding reducing agents to the radical initiator. Commonly used reducing agents include glucose, fructose, ammonium ferrous sulphate, acidic sulphite, soda, K, N-dimethylaniline, tetraethylenepentamine, parachlorobenzenesulphinic acid, benzoin, acetoin, glyceraldehyde, and dioxnacetone. These initiators can be used in a mixture of two or more and can be added with additives such as sodium pyrophosphate, sodium hydrogen phosphate. Initiators are used in an amount of 0.01-5. weight. ,% based on the amount of styrene compound. Surface-active agent is selected from anionic, cationic and non-ionic surface-active agents. Preferred surfactants are alkali metal salts of higher fatty acids, alkali metal salts of alkyl benzene sulfonic acids, fatty acid esters of polyoxyethylene, and polyoxyethylene thiol esters. Specific examples of particularly effective surface-active agents include sodium stearate, potassium stearate, sodium oleate, sodium palmitate, sodium myristate, sodium laurate, potassium laurate, sodium dodecylbenzenesulfonate, polyoxyethylene mono-oleate, polyoxyethylene distearate, and polyethylene, and you can also apply, and you can also apply and you will not apply. . These surface active agents can be used in combination with two or more, in an amount of 0.01-5 weight. % based on the amount of water. When these surfactants are used in combination with dispersion stabilizers such as polyvinyl alcohol, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, starch, agar, sodium glycolate, calcium carbonate, calcium phosphate, magnesium carbonate, talc, bentonite, it is achieved that the aqueous dispersion system is stabilized. Solvents use any polyphenylene oxide dissolving, insoluble in water and inert to the polymerization reaction. They do not need to be good solvents for the resinous polymers used. Benzene, toluene, xylene, and similar aromatic hydrocarbons are used as solvents; chlorobenzene, nitrobenzene or nitrosubstituted derivatives of aromatic hydrocarbons; chloroform, hydrocarbon tetrachloride and similar halogenated hydrocarbons. These solvents are used in 0.5 to 20 times, preferably 1 to 10 times the amount compared to the weight of polyphenylene oxide.

Water can be used in an arbitrary amount, but usually it is used in 0.5-10 times, preferably 1-fold, as compared with the total weight of nofenfenylene oxide, elastomer, styrene-type compound, and solvent.

In the invention, the order of addition of polyphenylene oxide, elastomer, styrene type compound, surface active agent, initiator, and other reactive agents is not limited. For example, a styrene-type compound is added to a solution containing nolyphenylene oxide and an elastomer, and then an aqueous solution containing an initiator and surface-active agents is charged to the resulting mixture; or the styrene compound is loaded into water, and then a solution containing polyphenylene oxide and an elastomer is added to the resulting mixture, and then the initiator and surface-active agent.

The elastomer can be used in the form of a solution or latex. The elastomer can be added at the initial stage of the reaction or it can be added at a suitable stage during the polymerization reaction in order to vary the degree of influence of the elastomer on the graft polymerization, taking into account the property of the resulting polyphenylene oxide. This is decided depending on the wall gelatinization, molecular weight and other physical properties or the amount of elastomer added.

When producing, for example, a high impact modified polyphenylene oxide according to the invention, it is desirable for the elastomer to participate in the graft polymerization, while maintaining the state of molecules having a suitable particle diameter. The preferred diameter of the parts of the elastomer is 0.1 to 10 microns.

Polymerization reaction temperature 40-150 ° C. The reaction can be carried out not only under normal pressure, but also under pressure or under reduced pressure ...,:

If oxygen is present in the reaction system, the rate of polymerization, the utilization rate, during graft polymerization, and others. The indicators are subject to adverse effects. It is desirable to carry out the reaction in an inert gas atmosphere or at a reduced pressure. This, however, does not mean that oxygen must be completely removed during the polymerization reaction.

According to the invention, the molecular weight of the styrene type compound grafted onto the polyphenylene oxide and the elastomer can be controlled by varying the concentrations of the styrene type compound, polyphenylene oxide, elastomer and initiator. Molecular weight can be controlled by adding a non-transfer agent, used in a conventional polymerization reaction. Such chain transfer agents include mercanthans and alcohols. By adjusting the molecular weight of the styrene-type graft compound and the number of graft chains,

physical properties of grafted polyphenylene oxide.

After the reaction has been sealed, the reaction mixture or the oily layer alone, separated by salting out the reaction mixture,

is loaded into a solvent that is poor in the ratio of the polymer, or this solvent is added to the peaKiuioHiTOU mixture or to the oil layer to precipitate the polymer, followed by. The polymer can be separated off directly by HVTCM drying with hot air or dissolving the reaction mixture or oil layer.

Graft polymers obtained in accordance with the invention have improved properties

yield strength and new resistance to oxidation and impact without any significant change in properties, npiicynuix oxide and polyfentylene oxide. According to the invention, without any treatment of free hydroxyl groups of polyphennylene oxides, graft polymers that do not substantially change in color shade during heating and are superior in impact resistance and extended in oxidation stability.

at higher temperatures than polyphenylene oxide.

Example 1. In a volumetric flask with a capacity of 500 ml, equipped with a thermometer, tube

for introducing nitrogen into a condenser, 16 g of poly-2, b-dimethyl-1,4-feshtlene oxide (65 dl / g in chloroform at 25 ° C) obtained by oxidation using a coupling reaction using manganese chloride (I) - methylate on three

As a catalyst, it is dissolved in 48 g of technical xylene, and then 1.6 g of polybutadiene, prepared by salting out the JSR0700 latex, is dissolved in the resulting solution.

To this solution (g) 16 styrene, 192 distilled water, 3,4 sodium stearate as a surface-active agent and a mixture of 0.2 benzoyl peroxide and 0.074 glucose as a catalyst are added. Then in

The flask was injected with nitrogen gas while dispersing the mixture with energy movement (620 revolutions per minute) to eliminate the oxygen present in the system. The mixture then reacts as you move.

at 80 ° C for 5 hours

After completion of the reaction, the reaction product is demulsified. add 4 ml of concentrated hydrochloric acid. Thereafter, the organic layer is loaded into 500 ml of methanol, and the resulting precipitate is isolated by filtration, giving 31.2 g of a white polymer.

The polymer thus obtained is extracted for 30 hours with hot acetone containing 15-20% by weight of cyclohexane, 29.2 g of acetone containing 15-20% by weight of cyclohexane with an insoluble part are obtained. From these data, the data of such physical properties are calculated, such as the graftpolymerization depth of styrene, the utilization rate of styrene in graft polymerization, the amount of bound styrene per whole polymer, and others. The data obtained are given in table. 2

In tab. Figure 1 compares the physical properties of the graft polymer with the mixture prepared by mixing in a solution of 55.2 wt. including polyphenylene oxide (l 0.65 DL / g in chloroform at 25 ° C) and 5.0 weight. including polybutadiene (both compounds were used in the above reaction) and 39.8 wt. hours of polystyrene (mol. weight 270 000).

Table I

The test pieces were prepared by rolling at 220–230 ° C for 5 min, and then by hot pressing at 220 ° C under a pressure of 100 kg / cm for 10 min.

The angularity was determined in accordance with JIS 6745 at 20 ° C. Wick point was measured according to ASTM. . The tensile test was carried out according to JIS 6745 at a strain rate of 10 mm / min / 20 ° C.

Example 2. Example 1 is repeated, except that 2.6 g of polybutadiene latex JSR 0700 (solid content 60%) is used as polybutadiene, to obtain 34.0 g of a white polymer.

The polymer thus obtained is treated as in Example 1. The characteristics of the polymerization and the physical properties of the polymer are given in table. 3

Example 3. Example 1 is repeated except that 2.6 g of polybutadiene latex (JSR0700, solid content 60%) is added to the reaction system after 4 hours and 30 minutes from the start of the heating reaction, 31.7 g of a white polymer are obtained.

The polymer thus obtained is treated as in Example 1. The polymerisation characteristics and physical properties of the polymer are summarized in Table 2. 2

Example 4. Examples 1-3 are repeated, except that a mixture of 0.2 g of potassium persulphate and 0.3 g of sodium hydrogen sulphite is used as a catalyst, to obtain 31.2 29.3 and 31.2 g of white polymers, respectively .

The polymers thus obtained are treated as in Example 1. The full-dimensioning characteristics and physical properties of the individual polymers are summarized in table. 2, columns 4-1, 4-2 and 4-3, respectively.

Example 5. Examples 1-3 are repeated except that a mixture of 0.164 g of 3,5,5-trimethylhexanoyl peroxide and 0.088 g of peroxybenzoic acid treg-butyl ester is used instead of benzoyl peroxide, to obtain white polymers.

The polymers thus obtained are treated as in Example 1. The results are summarized in Table 2. 2, respectively, the columns 5-; 1, 5-2 and 5-3.

Example 6. Example 1 is repeated, except that 3.0 g of polystyrene graft copolymer latex (solid content. 60%, bound styrene 25%) and a mixture of 10 g styrene and 6 g cc are used as resinous polymer. methyl p-methylstyrene is used instead of 16 g of styrene, get

10 Results are reported in

oily polymer table. 2

Example 7. Example 1 is repeated, except that instead of polybutadiene, 1.9 g of a polybutadiene-styrene graft copolymer is used (bound styrene content is 25%). The results are given in Table. 2

Example 8. Examples 2 and 3 are repeated.

except that 3.0 g of polybutadiene styrene graft copolymer latex (solid content 60%. bound styrene content 25%) is used instead of polybutadiene latex. The results are given in Table. 2, respectively, columns 8-1 and 8-2.

Example 9. Example 2 is repeated, except that a mixture of 8 g of styrene and 8 g of p-methoxy styrene is used instead of 16 g

styrene. The results are given in Table. 2

Example 10 Example 2 is repeated, except that instead of poly-2,6-dimethyl-1, 4-phenylene, a mixture of poly2,6-diethyl-1,4-phenylene is used, having a molecular weight of 70,000. . 2

Example 11. Example 2 is repeated with the exception that each of the compounds listed in Table. 3. used as a surface-active agent. The results are shown in Table. 3

Table 3