NL8102634A - THERMOPLASTIC, POLYPHENYLENE ETH RESIN CONTAINING COMPOSITIONS. - Google Patents

Description

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S 2348-1129 P & c

Thermoplastic, polyphenylene ether resin containing compositions.

The polyphenylene ether resins include a known group of polymers that can be prepared by a variety of catalytic and non-catalytic processes, such as, for example, described in U.S. Pat. Nos. 3,306,874, 3,306,875, 3,257,357, 3,257,258, 3,356,761 , 5 3,337,499, 3,219,626, 3,384,619, 3,440,217, 3,442,885, 3,573,257, 3,455,880, and 3,382,212.

U.S. Patent 3,383,435 describes compositions of polyphenylene ether resins and styrene resins, including halogenated styrene resins. US patent 3,887,646 describes compositions containing a polyphenylene ether resin and a chlorostyrene resin. U.S. Patent 3,639,506 describes polyphenylene ether resin compositions containing styrene resins, phosphates and halogenated flame retardants.

Compositions of a polyphenylene ether resin and a rubber-modified copolymer of styrene and bromine styrene have been found to have better physical properties, namely, an improved deformation temperature and impact strength, better burning properties, and better stability to ultraviolet rays than rubber-modified compositions. styrene, in which the same bromine concentration is present in the form of representative low molecular weight brominated flame retardants.

The compositions of the invention contain: (a) a polyphenylene ether resin; and (b) a rubber-modified styrene-bromostyrene copolymer.

The polyphenylene ether resins are polymers according to formula (1) of the formula sheet, wherein Q is a hydrogen atom, hydrocarbon group, halogen hydrocarbon group with at least two carbon atoms between the halogen atom and the phenyl core, hydrocarbon oxy group or halohydrocarbon oxy group with at least two carbon atoms between the halogen atom and the phenyl core; each of the symbols Q 'and Q "have the same meanings as given above for Q and may further represent a halogen atom, provided that Q and Q' are both free of tertiary carbon atoms; and n a number with a value of at least 50 is.

The preferred polyphenylene ether resin is poly (2.6-35 dimethyl-1,4-phenylene) ether with an intrinsic viscosity of about 0.40-0.60 dl / g, determined in chloroform at 30 ° C.

The rubber-modified copolymers of styrene and bromostyrene can be prepared from styrene and bromostyrene and a rubber. Instead of this, isomeric mixtures of bromostyrene may be used, which mixtures may contain para, meta and ortho-bromostyrene. In general, the weight ratio of styrene to bromostyrene in the copolymer can range from 15:85 to 85:15; preferably this ratio is 30: 70-85: 15. The reason for these ratios is that phase separation can take place using 100% bromostyrene at a 50:50 polyphenylene ether / bromostyrene ratio. A bromo styrene copolymer with a ratio of 85:15 is compatible in a composition with a ratio between polyphenylene ether and bromostyrene copolymer of 75:25, while in a composition with a ratio between polyphenylene ether and bromostyrene copolymer of 50:50 a copolymer with a ratio of Bromine styrene and styrene of 85:15 or 100: 0 is not compatible. A copolymer with a bromostyrene-styrene ratio of 70:30 is compatible in all proportions with polyphenylene ether resins, as are bromostyrene-styrene copolymers with a bromostyrene-styrene ratio of less than 70:30. The same degree of compatibility for the bromostyrene-styrene copolymers is to be expected at the lower part of the concentration range. 80-10 parts by weight can be used. of the copolymer of styrene and bromostyrene in combination with 20-90 parts by weight. use polyphenylene ether-20 resin.

The copolymers of styrene and bromostyrene can be modified with rubbers such as polybutadiene rubber by copolymerizing styrene monomer, bromostryene monomer and the polybutadiene rubber to form a graft polymer containing small, discrete rubber particles partially cross-linked and grafted to the styrene bromine styrene units. Furthermore, other rubbers such as EPDM rubbers, polysulfide rubbers, ethylene-propylene copolymers, etc. may be used. Also, in the compositions of the invention, 1-15 parts by weight can be used. of a thermoplastic rubber, e.g. an ABA or AB block copolymer. Suitable ABA block copolymers 30 are the Kraton or Kraton G polymers described in U.S. Pat. No. 3,646,162 and U.S. Pat. No. 3,595,942, respectively.

If desired, reinforcing amounts of reinforcing fillers can be added to the compositions in an amount of 5-40% by weight of the total composition. Glass fibers or other reinforcing agents, such as quartz, mica, wollastonite or carbon fibers, can be used as reinforcing fibers. Non-reinforcing fillers can also be used.

If the amount of bromine in the composition of the invention is insufficient to obtain the desired degree of flame retardancy, 8102634 * t - 3 - a small amount of a phosphorus compound, i.e., 0.1-7.5 wt. parts. phosphorus compound, calculated as elemental phosphorus, per 100 parts by weight. of the total composition.

Generally, the preferred phosphorus containing materials can be selected from elemental phosphorus and organic phosphonic acids, phosphonates, phosphinates, phosphonites, phosphinites, phosphine oxides, phosphines, phosphites and phosphates. An example of this is triphenylphosphine oxide. These materials may or may not be used in combination with antimony oxides.

Representative examples of the preferred phosphorus compounds according to the invention are those of the general formula (2) of the formula sheet, wherein each of the symbols O, which may represent the same or different groups, is a hydrocarbon group (eg alkyl, cycloalkyl aryl, alkyl-substituted aryl or aryl-substituted alkyl), a halogen atom, a hydrogen atom or combinations thereof, with the proviso that at least one of the groups Q is an aryl group. Representative examples of suitable phosphates are phenyl bis-dodecyl phosphate, phenylethyl hydrophosphate, ethyl diphenyl phosphate, 2-ethylhexyl di (p-tolyl) phosphate, diphenyl hydrophosphate, tricresyl phosphate, triphosphyl, triethyl propylphenyl.

The preferred phosphates are those available commercially, such as Kronitex-50, a mixture of isomers of tri-propylphenylphosphate.

The compositions can be prepared by the components in the form of powder, pearls or extruded granules, with or without suitable reinforcing agents, stabilizers, pigments, non-reinforcing fillers, eg 5-50% by weight (based on the total weight of the composition) to mix clay, talc, flame retardants, plasticizers or extruders by tumbling them. The compositions can be prepared by extruding the ingredients into continuous strands, cutting the strands into tablets or granules, and shaping the granules into a desired shape.

Preferred embodiments Example I

A rubber-modified copolymer of styrene and bromostyrene was prepared by dissolving cis-trans-poly (butadiene) rubber in a mixture of styrene and bromostyrene and polymerizing the mixture of styrenes with stirring to obtain a graft polymer of rubber , styrene and bromostyrene, which contained separate small rubber particles 81 0 2 6 34 * - 4 - which were partially cross-linked and grafted to the styrene-bromostyrene copolymer. Optical microscopy shows that the rubber particles had an average diameter of about 2.3 microns. The terpolymer contained 17.1% bromine (about 40 wt% bromostyrene) and 7.5% rubber. The terpolymer contained 17% toluene-insoluble rubbery gel with a toluene swelling index of 9.2. The styrene-bromostyrene copolymer, which was separated from the rubber phase by extraction with methyl ethyl ketone, had an intrinsic viscosity of 0.77 dl / g in chloroform at 30 ° C.

A mixture of 80 parts by weight. poly (2,6-dimethyl-1,4-phenyl) ether [PPO, 10 a product of Genèral Electric Company, with an IV value of about 0.5 in CHCl 3 at 30 ° C] and 20 parts by weight . of the rubber-modified styrene-butadiene copolymer (Composition A) was extruded in a single screw extruder and then molded into standard specimens with a screw injection molding machine. For comparison, a mixture (composition B) was also extruded and molded in which the bromostyrene terpolymer was replaced with an equal weight of a rubber-modified polystyrene (Monsanto HT-91), a graft copolymer of cis-trans-poly (butadiene) with polystyrene containing 20% toluene insoluble gel, swelling index 7.7. Another mixture (composition C) was prepared from poly (2,6-dimethyl-1,4-phenylene) ether and a mixture of a copolymer of styrene and bromostyrene with 27% bromine, polystyrene homopolymer (Dylene 8G) and a styrene-butadiene block copolymer (Kraton 1101), the amounts being adjusted so that the bromine concentration, the rubber concentration and the ratio of poly (2,6-dimethyl-1,4-phenylene) ether and polystyrene were the same as in composition A .

The properties are summarized in Table A. The styrene-bromostyrene-rubber graft polymer composition had a higher deformation temperature and a higher Izod impact strength than the other two. This composition had the rating VR-1 for flammability, while the composition, which contained the same amount of bromine in the form of a styrene-boron aastrene copolymer, had the rating V-1 and a significantly longer average burning time.

81 0 2 6 3 4 * * i

- 5 -Table A

Composition * ^ Izod impact-resistant Deformation _ OL 94_ (Joule / cm temperature rating average _ notch_ (° C) _ _ burning time A 0.96 153 V-0 4.9 sec.

B2) 0.80 145 V-1 15.0 sec.

C2) _ 0.59 147 V-1 6.5 sec.

Each composition also contained 3 parts by weight. triphenyl phosphate per 100 parts by weight. resin, 1 part by weight. diphenyl decyl phosphite per 100 parts by weight. resin, 1.5 parts by weight. polyethylene per 100 parts by weight. resin, 0.15 parts by weight. zinc sulfide and zinc oxide per 100 parts by weight. resin.

2 ^ Control

Example II

A mixture of 60 parts by weight. poly (2,6-dimethyl-1,4-fcinylene) ether, 40 parts by weight. of the bromostyrene terpolymer described in Example I, 1 part by weight. diphenyldecylphosphite, 1.5 parts by weight. polyethylene, 0.15 parts by weight. zinc sulfide and 0.15 parts by weight. zinc oxide was extruded in the manner described in Example I. and shaped. Another mixture was prepared from 60 wt. parts. poly (2,6-dimethyl-3,4-phenylene) ether, 40 parts by weight. rubber-modified polystyrene (Monsanto HT-91) and the other additives mentioned above and with the addition of 8.9 parts by weight. decabromophenyl ether (DBDFE) so that the boron concentration in the two mixtures was equal. Two other mixtures were prepared in the same manner, but 3 parts by weight in each mixture (TFF). triphenylphosphate. The properties of the molded material are summarized in Table B. The compositions prepared with styrene-bromostyrene-rubber terpolymer had a higher Izod impact strength and a higher deformation temperature than the corresponding compositions with the same amount of bromine in the form of tetrabromodiphenyl ether. Bromine in the form of bromostyrene terpolymer was also more effective as a flame retardant than in the form of the brominated low molecular weight additive. Both compositions with the terpolymer had a rating of V-0 for flammability, while those with decabromodiphenyl ether had a rating of V-1 and a longer average burn time (determined by the burning test of Bulletin 94 of Underwriters' Laboratory) 8102634 - 6 -

Table B

2) 2)

Composition TFP DBDFE Izod impact-resistant Deformation UL-94 ___ (Joule / cm temperature Rating Average notch) (° C) the fire ___ __________________________________ time (sec) D none none 1.28 148 V-0 4.4 EX) none 8.9 0.85 131 Vl 6.2 F 3 none 1.12 130 V-0 3.8 GX) 3 8.9 0.80 124 Vl 5.7 - 1)

Check 2 ^ parts by weight. per 100 parts by weight. resin

Example III

Mixtures of 40 parts by weight. poly (2,6-dimethyl-1,4-phenylene ether and 60 parts by weight of rubber-modified polystyrene (Monsanto HT-91) or the styrene-bromostyrene-rubber graft polymer described in Example I were extruded and formed as described in Example I. To some of the blends containing rubber-modified polystyrene, a sufficient amount of a representative brominated flame retardant additive was added to make the total bromine concentration the same as that of the bromostyrene terpolymer blend, each composition also containing 3 wt. parts of triphenylphosphate, 0.5 parts of zinc sulfide, 0.5 parts of zinc oxide and 3 parts of titanium dioxide The properties of the formed compositions are given in Table C. The composition prepared with the bromostyrene terpolymer had greater impact strength and a higher deformation temperature than that contained the brominated flame retardant additive, as well as better color and improved fire properties.

Table c

Composition Poly- Additive Izod impact- Distorted UL-94_ Styrene firmness Minging rating Average- Yellow- (Joule / cm perature partial notch) (° C) Fire index ___ ___'__ time _ „. no 1.17 118 Vl 5.5 sec v ”21.7 H bromine- styrene terpolymer 1) I HT-91 none 0.85 109 not satisfactory 36 sec 21.0 1) J" decabromo-0, 69 107 does not suffice 11.2 sec 26.4 diphenyl ether K1} "1,2-bis. 0.64 98 V-1 6.3 sec 29.0 (PéntaBromo-, phenoxy) ethane 8102634 5 -i - 7 -

Together- Poly- Additive Izod-stroke- Distort- OL-94_Yellow position styrene firmness mingstem- _- (Joule / cm perature 3 index S * yard) <° C> brafd- _ ________ __________ ___time 1) L HT-91 Hexabromo-0.64 100 is not satisfactory 13.6 24.8 biphenyl sec.

1) M Pentabromo-0.53 102 is not satisfactory 16.7 3) 10 phenyl carbons.

naat 1) Control 2) The rating for flammability and the average burning time were strongly influenced by one sample with a long burning time. Repeating with a second group of samples gave the rating V-0 for the flammability and an average burning time of 2.1 sec.

3) Strongly discolored, dark gray.

EXAMPLE IV

A solution of 10 g of a butadiene-styrene di-block copolymer 20 (Solprene 308) and 143 g of polybutadiene (Takten 1202) in 620.5 g of bromostyrene monomer (according to IR analysis 27% ortho, 70% para and 3% meta) and 926.5 g of styrene monomer along with 0.9 g of azo-bis (isobutyronitrile) and 0.9 g of dicumyl peroxide were transferred to a 3.78 L reactor. The mixture was stirred at 82 ° C for 6 hours (750 revolutions per minute) to a styrene conversion of 32% and suspended with 1500 ml of water containing 4.5 g of poly (vinyl alcohol) in 3.3 g of gelatin. The mixture was stirred at 100 ° C for 5 hours, at 120 ° C for 5 hours and finally at 140 ° C for 6 hours. The product in the form of large beads was filtered off, washed with hot water and dried. It was found to contain 22.1% insoluble gel in toluene 30, swelling index 8.9.

A composition of 50 parts by weight of rubber-modified styrene-bromostyrene copolymer, 50 parts by weight of poly (2,6-dimethyl-1,4-phenylene) ether resin, 1 part by weight of diphenyldecylphosphite, 1.5 parts by weight of polyethylene, 3 parts by weight of triphenylphosphate, 0.15 parts by weight of zinc sulfide and 0.15 parts by weight of zinc oxide were extruded in a twin screw extruder (28 mm) and formed into test pieces in a screw injection molding machine. The same composition was prepared for comparison, except that instead of the rubber-modified copolymer of bromostyrene, a rubber-modified polystyrene of high impact strength (Foster 40 Grant 834) was used. The properties of the molded parts were as follows: 8102634 * V * * Γ - 8 -

Rubber Modified rubber Modified bromine styrene-polystyrene · styrene and copolymer of high impact - with high resistance to slack 5 Properties of strength *) strength__

Elongation (%) 66 48

Strain limit (kPa) 66200 70300

Tensile strength (kPa) 57200 62000

Izod impact strength (Joule / cm notch) 2.24 2.03 10 Gardner impact strength (Joule) 11.3 11.3

Gloss (45 °) 44.1 48.3

Distortion temperature (° C) 114 124 UL94 (rating) is not satisfactory V-0 UL94 (average burn time, sec.) 35 3.6 15 1) Check

EXAMPLE V

A solution of 100 g of EPDM rubber (Epcar 387) in 400 g of styrene and 600 g of bromostyrene (27% ortho, 70% para and 3% meta) was placed together with 1.0 g of t-butyl peracetate in a stainless steel reactor and stirred. The reactor was purged with nitrogen and the mixture heated at 120 ° C for 14 hours. The product contained 17% toluene insoluble gel, swelling index 9.9. The bromine content was 25.7%.

A composition was prepared using 50 parts by weight of a rubber-modified copolymer of bromostyrene and styrene, the preparation of which is described above; 50 parts of poly (2,6-dimethyl-1,4-phenylene) ether resin; 1 part by weight of diphenyldecylphosphite; 1.5 parts of polyethylene; 3 parts of triphenylphosphate; 0.16 parts by weight of zinc sulfide; and 0.16 parts by weight of zinc oxide, by extrusion with a twin screw extruder.

The extrudate was comminuted into granules which were molded into test pieces in a screw injection molding machine. The product had an Izod notch impact value of 1.87 Joule / cm notch, a deformation temperature of 128 ° C and in a section of 0.16 cm the rating V-0 according to UL-94 with an average burning time of 2.0 sec.

EXAMPLE VI

A solution of 90 g of polybutadiene rubber (Taktene 12Q2) in 607 g of bromostyrene monomer and 303 g of styrene monomer was introduced into a stainless steel reactor with 0.5 g of dicumyl peroxide, 0.5 g of benzoyl peroxide and 0.5 g of tert-dodecyl mercaptan. The mixture was heated to 135 ° C under nitrogen and with vigorous stirring for 7 hours. The rubber modified copoly-40 beads were filtered, washed and dried; the bromine content was 26.8%. 8102634 * - 9 -

A composition of 50 parts by weight of this copolymer, 50 parts by weight of poly (2,6-dimethyl-1,4-phenylene) ether resin and 3 parts by weight of triphenylphosphate was extruded and formed as described in Example IV. The molded part had a good surface appearance and a gloss value (45 °) of 59.4, an Izod impact strength of 1.44 Joule / cm notch, a Gardner impact resistance of 19.8 Joule, a deformation temperature of 134 ° C and the rating V-0 for the flammability according to UL-94 and an average burning time of 1.5 sec.

EXAMPLE VII

A solution of 7 g of butadiene-styrene-diblock copolymer (Solprene 308) and 95 g of polybutadiene rubber (Taktene 1202) in 906 g of bromostyrene and 227 g of styrene was transferred with 0.6 g of azo-bis (isobutyronitrile) to a stirrer reactor, stirred at 82 ° C for 5 hours and suspended in 2000 ml of water containing 4.5 g of gelatin and 8 g of poly (vinyl alcohol). The suspension was heated at 100 ° C for 5 hours, at 120 ° C for 5 hours and then at 140 ° C for 8½ hours. The polymer beads were filtered off, washed with water and dried.

EXAMPLE VIII

A solution of 162 g of polybutadiene rubber (Taktene 1202) in 545 g of styrene and 1093 g of bromostyrene (isomer mixture) was mixed with 0.9 g of dicumyl peroxide, 0.9 g of benzoyl peroxide and 0.9 g of tert-dodecyl mercaptan in one of a stirrer provided stainless steel reactor. The reactor was purged with nitrogen and heated to 90 ° C for 7 hours. The product was suspended in 2000 ml of hot water containing 4.5 g of gelatin and 6.0 g of poly (vinyl alcohol) and heated at 135 ° C for 14 hours. The mixture was cooled and the polymer beads were filtered off, washed with hot water and dried. The product contained 29.8% toluene insoluble gel, swelling index 4.7. The bromine content was 26.7%.

A mixture of 50 parts of the product, 50 parts of poly (2,6-di-30-methyl-1,4-phenylene) ether, 3 parts of triphenyl phosphate, 1 part of diphenyl decyl phosphite, 1. 5 parts of polyethylene, 0.15 parts of zinc sulfide and 0.15 parts of zinc oxide were extruded and formed as described in Example IV.

The formed composition had satisfactory physical properties and excellent flame resistance.

81 02 6 34 tf - 10 -

Strain limit 72400 kPa

Elongation at break 48%

Izod impact resistance 1.44 Joule / cm notch

Distortion temperature 134 ° C

5 Gloss (45 °) 59.4

Gardner impact resistance 19.8 Joule

Flammability (UL-94) V-0

Average burn time 1.5

EXAMPLE IX

The following compositions were prepared from poly (2,6-dimethyl-1,4-phenylene) ether and modified with 9% polybutadiene rubber (Taktene 1202) 2) copolymers of styrene and bromostyrene according to the procedure of Example IV; the compositions had the properties listed below: 15-Bromo-Poly (2,6-Izod-impact-resistant-Impact-resisting Styrene dimethyl moiety in copoly-1,4-phenylene) - (Joule / cm according to temperature (wt%) ether: copolymer) Gardner nature,

more of sty- (Joule) ° C

20 _ reen bromostyrene _____________ _______ _______ 0 ^ -94 01J 50:50 1.65 11.3 109.5 V-0 (33.0) 40 50:50 1.81 19.8 126 V-0 (3, 6) 67 50:50 1.81 11.3 133 V-0 (1.4) 80 50:50 0.37 0.56 130.5 V-0 (0.6) 25 100 50:50 0.27 0.56 125.5 V-0 (0.9) 01} '75:25 1.23 11.3 144 Vl (12.6) 40 75:25 1.49 33.9 153 V-0 (3, 1) 67 75:25 1.87 28.2 154.5 V-0 (1.3) 80 75:25 2.24 19.8 157 V-0 (1.3) 30 100 75:25 0.56 0.56 159.5 V-0 (1.0) 1) Rubber modified polystyrene of high impact strength.

2) Each composition also contained 3 parts by weight of triphenyl phosphate per 100 parts by weight. parts of resin, 1 part of diphenyldecyl phosphite per 100 parts of resin, 1.5 parts of polyethylene per 100 parts of resin, 0.15 parts of zinc sulfide per 100 parts of resin and 0.15 parts zinc oxide per 100 parts by weight of resin.

3) Average burn time in seconds.

81 0 2 6 3 4

Claims (10)

Flame retardant thermoplastic molding material, characterized by; (a) a polyphenylene ether resin, and (b) a rubber-modified styrene-bromostyrene graft copolymer. Material according to claim 1, characterized in that the polyphenylene ether resin is a compound according to formula (1), wherein Q is a hydrogen atom, hydrocarbon group, halohydrocarbon group with at least 2 carbon atoms between the halogen atom and the phenyl core, hydrocarbon oxy group or halohydrocarbon oxy group with represents at least 2 carbon atoms between the halogen atom and the phenyl core, each of the symbols Q 'and Q "have the same meanings as given above for Q and may further represent halogen, provided that Q and Q' are both free from tertiary carbon atoms , and n is a number with a value of at least 50. Material according to claim 2, characterized in that the groups Q "are hydrogen. Material according to claim 2, characterized in that the polyphenylene ether resin is poly (2,6-dimethyl-1,4-phenylene) ether resin. 5. Material according to claims 1-4, characterized in that the weight ratio between styrene and bromostyrene in the copolymer is 85; 15 - 15:85. 6. Material according to claims 1-5, characterized in that the material «also contains a reinforcing filler. 7. Material according to claims 1-6, characterized by 20 - 90 parts by weight of polyphenylene ether and 80 - 10 parts by weight of the copolymer. Material according to claims 1-7, characterized in that the rubber in the copolymer is a diene rubber. Material according to claims 1-8, characterized in that the material further contains a phosphate as a flame retardant. 10. Material as claimed in claims 1-9, characterized by an ABA block copolymer as thermoplastic rubber. 8102634 —--... ---- --- w ---- · *. > »General Electric Company of Schenectady, New York, United States of America Q" Q "-" w i 0 I • I! (2) QO-P-OQ OQ 8102634