JPS59500771A - Polyphenylene ether compositions and methods - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Polyphenylene ether composition and method SUMMARY DESCRIPTION OF THE INVENTION The present invention relates to polyphenylene ether, also known as polyphenylene oxide. high impact polystyrene (HIPS) and aromatic phosphate flame retardants; from low molecular weight polymers selected from polyolefin glycols or polyamides. Regarding the composition, the composition contains a substantial amount of polyolefin such as polyethylene. Do not include or exclude amounts. When molded, the composition is easy to paint and has no paint contact. Use of polio, such as polyethylene, as a mold release agent, which is known to have a negative effect on between paint and molded compositions, as distinguished from compositions containing refins. Shows a high degree of adhesion. Furthermore, parts molded from the new composition can be molded without losing mold releasability. The product uses a composition that does not contain any of the above polymers from which polyethylene has been removed. There is no resistance to removal from the molding machine during injection molding, as in the case of molding.

Additionally, the new compositions exhibit good or improved Izodt and Gardner impact strength. and in the case of polyolefin glycol polymers such as polyethylene glycol increases the mutual solubility of the components of the composition and provides increased resistance to environmental stress. There is a reduction in the phenomenon known as juicing. aromatic phosphate In addition to imparting the above properties to the flame-retardant PPO/HIPS blend, The addition of polyethylene glycol polymer acts as a compatibilizer and improves the ) In addition to providing improved blend homogeneity, it increases the solvent resistance of the blend.

The present invention also relates to a method for producing and molding a new composition, and a molded article obtained therefrom. related.

Background technique Polyphenylene ether resin is a well-known engineering material in the field of polymer technology. A group of thermoplastic resins.

These polymers are prepared by various catalysts from the corresponding phenols or their reactive derivatives. It can be made by catalytic and non-catalytic methods. To illustrate, the types of polyphenylene consisting of Ether is described in Hay U.S. Pat. No. 3,306,874 and 3,306,875; No. 3,257,357 and No. 3,257,358 to Bistamatov. It is. In Hay's patent, polyphenylene ether is a combination of phenol and metal. Oxidative coupling consisting of passing an oxygen-containing gas into the reaction solution of an amine complex catalyst made using the Google method. Craft copolymerization of styrenic compounds and polyphenylene ether Other descriptions of methods for producing polyphenylene ether resins containing U.S. Patent No. 3,356,761 to X: British Patent No. 1,291,609 to Sumitomo Bussink, U.S. Pat. No. 3,337,499; Blancyard et al., U.S. Pat. No. 3' No. 219,626: U.S. Pat. No. 3,342,892 to Laakso et al.: U.S. Pat. No. 3,344,166; Poly et al., U.S. Pat. No. 3,384,619; Fauloth et al. No. 3,440,217; and based on amine-free metals. Concerning catalysts (3) No. 3,442,885 (Controlled Amidine) by Wieden et al. U.S. Pat. No. 3,573,257 to Shio et al. ); patents such as U.S. Pat. No. 3,445,880 (cobalt chelate) by Kobayashi et al. Known from Huh. In Stamatov's patent, polyphenylene ether is , peroxide salts, acid peroxides, hypohalogenates, etc. in the presence of complexing agents. It is made by reacting an initiator such as the following with a corresponding amount of ferrite ion. lead dioxide, acid A description of non-catalytic methods such as oxidation with silver oxide etc. is provided by Price et al., US Pat. No. 3,382. It is described in 212 calyx. Chitzek's U.S. Patent No. 3,383,485 Phenylene ether-styrene resin compositions are described. All patents mentioned above The description is incorporated herein by reference.

The term “polystyrene resin” includes styrene, α-methylstyrene, chlorostyrene, polymers and copolymers such as rubber, and rubber-modified polystyrene. impact-resistant polystyrene known to those skilled in the art (published May 23, 1980) , Science Vol. 208, p. 817).

In the conventional technology, rubber-modified styrenic resins are made with compositions with modified properties. It is mixed with polyphenylene ether resin to form. U.S. Patent for Chitsueku No. 3383435 D is such that the rubber component is a polymer or copolymer of butadiene. Rubber-modified styrene resin - polyphenylene ether resin, which is an unsaturated rubber component A composition is described. This (4) The physical properties of these compositions are improved, with many of the properties of styrene resins being improved and It appears that improved moldability of nylene ether is realized.

The product name of the modified high-impact polystyrene is AMOCO 6H6. FG-834 from Foster Grants Company, and Monosanto.com It is available in the market under the name Bunnykara HT-91. These are generally polybutadiene It is polystyrene modified with rubber. Preferred HIPS is Amoco 6H6 .

U.S. Pat. No. 3,737,479 describes polyphenylene oxide or polyphenylene oxide. Len oxide-polystyrene blend, preferably rubber-modified high-impact polystyrene The addition of silicone oil to the lens (see Example 1) improves Gardner impact strength. However, it is stated that the Izot impact strength is not affected. This patent no. Column 6, lines 48 to 54 states that ``In a preferred embodiment of the invention, the composition Incorporate polyolefin. This allows for Izots collisions without degrading other properties. Increases impact strength and improves workability.

Suitable polyolefins↓ are polyethylene and polyisoprene.

and ethylene-propylene copolymers, polyisoprene, polyisobutylene Also included. ” is written. Example 1 describes polyethylene.

In U.S. Pat. No. 4,226,761, polyethylene has a polyphenylene ether composition. contained in things.

Polyphenylene ether (ppo), high impact polystyrene (HIPS), Compositions containing aromatic flame retardants and polyethylene (PE) have good physical They have properties such as lacquer/paint coating and PPO/HIPS/fragrance. As a result of poor adhesion between group phosphates/PE substrates, in injection molded form It has proven difficult to paint.

Is the paint adhesion a PPO/HIPS/aromatic phosphate)/PE composition or composite? This can be easily improved by removing the PE from the injection molding. This adversely affects not only the releasability of the mold but also the impact performance.

PE can be substituted with a low molecular weight polyamide or a low molecular weight polyolefin glycol such as If substituted with ethylene glycol or polypropylene glycol, mold release properties will be lost. ie, the molded part does not resist being removed from the molding machine during injection molding. It has now been found that paint adhesion is significantly improved. The new composition is also good. or improved Izod and Gardner impact strength, and polyolefins Mutual solubility of each component of the composition when replacing polyethylene with a glycol polymer increased resistance to environmental stress and known as juicing This will lead to a reduction in the number of phenomena that occur. Acts as a compatibilizer and improves blend uniformity In addition to providing properties, polyolephic refill polymers also improve the solubility resistance of new compositions. Increases drug properties.

Disclosure of invention The above-mentioned advantages and objects and others will be readily apparent to those skilled in the art by the compositions described below. It will be. The preferred form is ((6) (by weight): 1-1 about 20 to about 80 parts of polyphenylene ether resin (PPO), and (about 0 to about 80 parts of bl high impact polystyrene (HIPS) resin, and (C1 aromatic phosphate flame retardant from about 0 to about 25 parts, and (dl polyolefin from about 0.1 to about 5 parts of a low molecular weight polymer selected from glycols or polyamides. The composition includes a thermoplastic resin composition consisting of a polyolefin, such as a polyester resin. Excludes or contains no substantial content of tyrene.

The composition may also include pigments such as titanium dioxide, carbon black, and pigment colors such as For example, Flora Yellow, which is a trademark of a pigment owned by DuPont Compat. -908 and Flora Orange 909 may also be included.

High impact polystyrene (HIPS) is made by dissolving rubber into styrene monomers and then For example, styrene monomer is polymerized in the presence of polybutadiene rubber. Make it by matching it.

Polystyrene resin formula (In the formula, R' and R2 are a group consisting of hydrogen or a lower alkyl group having 1 to 6 carbon atoms. and R3 and R4 are chlorine, bromine, hydrogen and lower atom of 1 to 6 carbon atoms. A group consisting of rukyl group (7) R5 and R6 are selected from groups having 1 to 6 carbon atoms and /Xrogen, Alternatively, R6 and R6 may be combined with a hydrocarbyl group to form a naphthyl group. ) should have at least 25% of its units derived from styrene monomers. .

Specific examples of styrene monomers include styrene, bromo-butylene, chlorostyrene and Contains σ-methylstyrene.

Examples of polystyrene resins include homopolystyrene and monochloropolystyrene. Homopolymers such as styrene and styrene-chlorostyrene co-i11, styrene - Bromostyrene copolymer and α-alkylstyrene copolymer such as kystyrene Contains copolymers.

Preferred polyphenylene ethers have the formula (wherein one unit of the oxygen ether atom is connected to the benzene nucleus of the next adjacent unit, n is a positive integer, and at least 5 0, and each Q is hydrogen, halogen, hydrocarbon group not containing a tertiary α-carbon atom, halo halohydrocarbon group having at least 2 carbon atoms between the gen atom and the phenyl nucleus , a hydrocarbon oxy group, and at least two atoms between the halogen atom and the phenyl nucleus A monovalent substituent selected from the group consisting of halohydrocarbonoxy groups having a carbon atom. It is a polyphenylene ether of

(8) Examples of polyphenylene ethers corresponding to the above formula are the Heiyaku and Stamatofu mentioned above. can be found in patents. Particularly preferred is poly(2,6-cymethyl-1, 4-phenylene) ether. The intrinsic viscosity of polyphenylene ether is 30℃ measured in CHCl, and ranges from approximately 0.37 to 0.65 dt/y. be able to.

The polyamide may contain repeating aromatic and/or refers to condensation products containing aliphatic amide groups; such products are generally referred to as It is known as ``N''. These have at least 2 groups between the ami7 group and the carboxylic acid group. Polymerization of monoaminomonocarboxylic acids or their internal lactams having 5 carbon atoms or with at least 2 carbon atoms between the dicarboxylic acid and the amine 7 group. By polymerizing substantially equimolar proportions of the diamines contained, Monoaminocarboxylic acids or monoaminocarboxylic acids such as those mentioned above together with can be obtained by polymerizing its internal lactam. dicarboxylic acid can be used in the form of its functional derivatives, such as esters.

The term “substantially equimolar proportions” (of diamines and dicarboxylic acids) refers to strict equimolar proportions of diamines and dicarboxylic acids. included in the prior art to stabilize the molar proportion and viscosity of the polyamide formed. It is used to include both proportions that are slightly different from the above.

Examples of the above-mentioned monoaminomonocarboxylic acids or lactams thereof include amide 7 groups and carboxylic acids. Compounds containing 2 to 6 carbon atoms between the carboxylic acid groups may be mentioned; In the case of a lactam, the elementary atoms form a ring with the -CO.NH- group. Aminocarboxylic acid and specific examples of lactams such as aminocaproic acid, butyrolactam, and Vivalola. lactam, caprolactam, capryllactam, enantholactam, -undecano Mentioning lactams, dodecanolactam and 3- and 4-aminobenzoic acids Can be done.

Examples of the above diamines include the general formula H, N(CH2)nNH2 (where n is an integer of 2 to 16). There are diamines with a number of Amine, pentamethylene diamine, octamethylene diamine, decamethylene diamine amine, dodecamethylene diamine, hexadecamethylene diamine, and especially hexane There is methylene diamine.

Another example is a C-alkylated diamine, such as 2,2-dimethylpentamethylene diamine. amines, and 2.2.4- and 2,4.4-)dimethylhexamethylenedia There is Min.

Other diamines that may be mentioned by way of example include aromatic diamines, e.g. Nylene diamine, 4,4'-diaminodiphenylsulfony/,4,4'-dia minodiphenyl ether, and 4,4'-diaminodiphenylmethane, and Alicyclic diamines include diaminodicyclohexylmethane.

The dicarboxylic acids may be aromatic such as isophthalic acid and terephthalic acid. can. Preferred dicarboxylic acids have the formula HOOC, Y-COOH, where Y is at least also contains 2 carbon atoms (10) is a dicarboxylic acid (representing a divalent aliphatic group), and an example of such an acid is cepatine. Acid, octadecadicarboxylic acid, speric acid, azelaic acid, undecadicarboxylic acid acids, glutaric acid, pimelic acid, and especially adipic acid. Oxalic acid is also a preferred acid. be.

In particular, the following polyamides may be incorporated into the thermoplastic polymer blend of the present invention. : Polyhexamethylene adipamide (nylon 6:6) polypyrrolidone (nylon 4) ) Polycaprolactam (nylon 6) Polyhebutlactam (nylon 7) Polycaprylactam (nylon 8) Poly7 nanolactam (nylon 9) Polyundecanolactam (Nylon 11) Poly7 Nanolactam (Nylon 22) Polyhexamethylene azelaamide (nylon 6:9) polyhexamethylene azelaamide Min (nylon 6:10) polyhexamethylene isophthalamide (nylon 6: iP) Polymethaxylene adipamide (nylon MXD: 5) nylon Copolymers can also be used, for example: Hexamethylene adipamide/caprolactam (nylon 6:6/6) (11) Hexamethylene adipamide/hexamethylene-isophthalimide (nylon a: 6/6ip) 1 Hexamethylene adipamide/hexamethylene terephthalimide (nylon 6: 6/yT) Adipamide/Hexamethylene-Azelaamide (Nylon O: 6) /6.9) Also useful is nylon 6:3 made by Dynamid Novell. child The polyamide is composed of dimethyl ester of terephthalic acid and the isomer trimethylhexamethylene. The product is a mixture of diamines. Other useful nylons include nylon base. There is DuPont's Zeitel ST which is a Sualloy.

The average molecular weight of the polyamide used in the present invention ranges from about 1000 to 10000. Ru.

A preferred polyamide is Uniret 2621D, which is made of dimerized tall fat. Composed of fatty acids, primarily amides of oleic acid and linoleic acid. This polyamide Available from Nion Camp Company.

Polyglycols useful in the present invention have molecular weights ranging from about 150 to about 25,000. I can say something. Polyethylene glycol with a molecular weight of 6000 is preferred. stomach. Also very effective is polypropylene glycol with a molecular chain of 4,000. It is le.

Aromatic and/or alkyl (12) that also acts as plasticizer II Examples of aromatic phosphate flame retardants include triarylbosphate and isopropylene. triaryl phosphates such as triphenyl phosphate and isopropylene There is pylated triphenyl phosphate. They range from about 2 to about 20 parts by weight. and generally in an amount effective to render the composition flame retardant. preferred ho Sulfate is triphenyl phosphate. Particularly preferred is Hood Mashi. such as Chronitex 50, supplied by Nalley Corporation. Mixed tria with one or more inglovyl groups on some or all of the aryl rings It is a composition consisting of lyal phosphate.

The composition of the present invention is prepared by homogeneously mixing each component to form a premix; The extruder, e.g. a twin-screw Worker Pfeidler at a high temperature below about 450 to about 600 It can be formed through a screw extruder. The extrudate is e.g. Injection molding in an injection molding machine such as a Newbury injection molding machine at a temperature in the range below about 600°C. By shaping, it can be molded into a desired shape. The composition can be used in molded parts, such as automobile parts. various types such as Urbenz grills, and radio and television cabinets. Cabinets and other moldings where it is desired to enhance the surface appearance by painting It can be used to make goods. Molded articles made from the novel composition of the present invention Paints versus plastics as distinct from compositions containing refins, e.g. polyethylene. High degree of paint-to-plastic adhesion, especially for acrylic lacquer paints. have

Preferred form for carrying out the invention The following examples are presented to further illustrate the invention and are not intended to limit the invention. It should not be thought of as something that

Parts are parts by weight.

Examples 1 to 5 0.49d7 when measured in chloroform at 30C! has an intrinsic viscosity of /y Poly(2,6-dimethyl-1,4-phenylene)x-te/l/(PPO) 50 Department, M? 50 parts of fi-impact polystyrene (Amoco 6H5, HIPs), inpropylene 13 parts of triphenyl phosphate (G, MC Clonitex 50), low molecular weight Quantity Polyamide (Union Camp Shizu Niret 2621D) 1.5F115, f　/　/L/0.5 parts of diphenylphoscite, 0.15 parts of zinc sulfide, zinc oxide 0.15 g of lead, 0.5 part of the following pigment titanium dioxide, and 0.5 part of carbon black. 18 parts, 0.6 parts of Flora Yellow 908, 1 part of Flora Orange 909 ．． Mix 0 parts and place in a 28-tone water heater set at 500'F with a 5 inch mercury exhaust vacuum. It was extruded in a Nar Preidler twin screw extruder. 40Z new under 460 A molded article was obtained using a single-burry injection molding machine.

For comparison, similar compositions, i.e. low molecular weight polyamide, polyethylene or low One that does not use any of the child polyolefin glycols, and o95.1 o and 1.5 parts of polyethylene (available from Allied Chemical Company). Three compositions were made containing the available polyethylene Ac6). these pairs as well as low molecular weight boria (14) Compositions containing mido and their properties are shown in Table 1 below.

3 Po! J Echi 1z71.0 19r 4,1. v-o 2.6 5, 4.34 Polyethylene 1.5 20 4.1. V-02, 81, 2, 2 notes (Channel length (in) molded at 1,110,000 psi.

The data in Table I are: (contains no 11PE and contains 15 parts (about 100 parts) of low molecular weight polyamide) Good paint/plastic adhesion is obtained for compositions with (15) (Even at concentrations as low as 210,5 parts (about 100 parts) (below 0,5 parts) Mold releasability is also unsatisfactory (unsatisfactory), the presence of PE has a negative effect on paint adhesion, (31 The physical properties of compositions containing low molecular weight polyamides are those of PE compositions. Comparable It is shown that.

In these examples, each formulation was as described in Examples 4 and 5, except that Shil Q in mercury exhaust vacuum, 53 throat warner set at 500 to 520 below. It was scaled up to 25'Olba using a Prydler extruder. Molded products are carried out Obtained as in Examples 4 and 5. Properties are shown in Tables ■A and ■B.

(16) Table ■B-Enlarged PPO/HIPS/Chronitex 50/Modified 8 Polyethylene 1. 5’3. :3,2,1,1,0,0.1 11 notes Stress whitening areas on the surface of a given injection molded product have poor release properties from the molding machine. This was evidence that The larger the number of these stress whitening defects, the more The mold release ability of the parts will be poor.

Scaling data for Table 1IA and IB: (1) Contains low molecular weight polyamide Good solid paint/plastic adhesion is obtained for the composition (all PE-containing (much better than the control case) (2) the mold release properties of polyamide compositions are comparable to those of comparable amounts of PE; (3) polyamide compositions have The physical properties of the mido composition are also comparable to those of the counter-dose PK. It is shown that.

Examples 10-19 In these examples, 15 parts (18) of low molecular weight polyamide Four parts were mixed in the same manner as in Examples 1 to 5 except that 1.5 parts were used. Control example (Example 10) used 1.5 parts of polyethylene. Each formulation is shown in Table 1. IIA and extruded, molded and tested in the same manner under the same conditions as in IB. "strange The number under "Sexual Agent" indicates the molecular weight. Union Carbo polyethylene glycol under the trade name Carbowax from Ido Corporation, and from Dow Chemical. It is commercially available under the trade name Polyglycol E from Kompany. polypropylene Recall is available from Dow Chemical Co. under the trade name Polyglycol P. Ru.

The properties of each composition are shown in Table 3.

(19) (20) The data in Table ■ shows that when compared with the polyethylene control example (Example 10), Glycol 600o has excellent paintability, excellent mold release properties, and has the same impact strength. It shows that. Polypropylene glycol 4000 is also an excellent coating material. This indicates that the material exhibits wearability and appropriate impact resistance. Other polyolefin glycos The paint also shows excellent paintability, but there are some changes in other properties.

Obviously other modifications of the invention are possible. The preferred polyethylene oxide is having a molecular weight of 300,000 but excluding high molecular weight polyethylene oxide. of polyphenylene ether resin and polystyrene resin when compared to the composition. The Izot impact strength and Gardner impact strength of the composition were determined using high molecular weight polyethylene resin. oxide was observed to increase. However, the paintability of the composition is low molecular weight. Paintability approaching that achieved with polyamides and polyolefin glycols There is no such thing.

The patents and/or publications mentioned above are hereby incorporated by reference. defined in the scope of claims. In each of the above-described embodiments, which are fully within the contemplation of the invention as defined above, It should be understood that modifications may be made.

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Claims (1)

[Claims] 1. IA + Holophenylene F Lem Fat, Tbl Optional Ingredients Impact-resistant polystyrene hmm, (C1 optional aromatic phosphate flame retardant, and (dl polyolefin glyco Low molecular weight polymers selected from polymers or polyamides a composition comprising a substantial amount of polyolefin; No or excluded composition. 2 On a weight basis, (the amount of Al is about 20 to about 80 parts, (the amount of BL is about 0 to about 20 parts) , (C) in an amount of about 0 to about 20 parts and (di) in an amount of about 0 to about 5 parts. A composition according to scope 1. 3. The composition according to claim 1, wherein the polymer is a low molecular weight polyamide. 4. The composition according to claim 1, wherein the polymer is a polyolefin glycol. 5 Aromatic phosphate is triaryl phosphate or isopropylated tri- The composition according to claim 1, which is an aryl phosphate. 6. Claim 5, wherein the aromatic phosphate is triphenyl phosphate. composition. 7 Claim that the aromatic phosphate is isopropylated triphenyl phosphate The composition according to item 5. 8. Low molecular weight polyamide polymers are combined with oleic acid and oleic acid on dimerized tall oil fatty acids. The composition according to claim 1, which is a resin comprising an amide of linoleic acid and linoleic acid. 9. The polyolefin glycol has a molecular weight ranging from about 150 to about 25,000. The composition 10 according to claim 1, wherein the polyolefin glycol is 6000% The composition according to claim 9, which is a polyethylene glycol having a molecular weight. 11. Polyprene glyco whose polyolefin glycol has a molecular weight of 4000 10. The composition according to claim 9, which is a polymer. 12. Polyphenylene ether resin formula (in the formula, one unit of oxygen ether atom is connected to the benzene nucleus of the next adjacent unit, n is a positive integer, and at least 5 0, each Q is a hydrocarbon group containing no hydrogen, halogen, or tertiary α-carbon atom, Halohydrocarbon having at least 2 carbon atoms between the halogen atom and the phenyl nucleus At least 2 atoms between a hydrogen atom, a hydrocarbon oxy group, and a halogen atom and a phenyl nucleus] a monovalent substituent selected from the group consisting of halohydrocarbonoxy groups having 5 carbon atoms; The composition according to claim 1, wherein the composition is selected from the following compounds. 13. Claim 1, wherein the impact-resistant polystyrene is rubber-modified polystyrene. composition. 14. Polyphenylene ether is poly(2,6-dimethyl-(23) A composition according to claim 1, which is 1,4-phenylene) ether. 15. Weight: about 40 parts of poly(2,6-dimethyl-phenylene) ether, Approximately 60 parts of high impact polystyrene, approximately 13 parts of isopropylated triphenyl phosphate and 1.5 parts of low molecular weight polyamide. . 16. About 40 parts by weight of poly(2,6-dimethyl-phenylene) ether, Approximately 60 parts high-impact polystyrene, approximately 1 part isopropylated triphenyl phosphate 3 parts and about 1.5 parts of polyethylene glycol having a molecular weight of about 6000 The composition according to claim 1, comprising: 17. About 40 parts by weight of poly(2,6-dimethyl-phenylene) ether, Approximately 60 parts of high impact polystyrene, approximately 13 parts of isopropylated triphenyl phosphate parts, and about 1.5 parts of polypropylene glycol having a molecular weight of about 4000 The composition according to claim 1, comprising: 18. The high degree of Molded composition with paint adhesion. 19゜(al　1　(bl　I　fcl　and A method for producing a composition according to claim 1, characterized in that: 20 The blended product is molded into the desired shape, and the molded product becomes a highly advanced paint. 20. The method according to claim 19, which has adhesive properties.