FR2483443A1 - COMPOSITION OF POLY (OXYPHENYLENE) AND STYRENE BROMOSTYRENE COPOLYMER - Google Patents

Abstract

COMPOSITION WITH BETTER PHYSICAL PROPERTIES. IT INCLUDES: A. POLY RESIN (OXYPHENYLENE); AND B. A RUBBER-MODIFIED STYRENE-BROMOSTYRENE COPOLYMER. MOLDING APPLICATION.

Description

The term "poly (oxyphenylene) resin" characterizes a group of

  well-known polymers that can be prepared by various catalytic or non-catalytic processes, such as

  describe them, for example, the United States patents

  Nos. 3,306,874, 3,306,875, 3,257,357, 3,257,358, 3,356,761,

  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 No. 3,383,435 discloses

  poly (oxyphenylene) resin compositions and resins-

  of styrene, comprising halogenated styrene resins. The

  U.S. Patent No. 3,887,646 discloses composites

  which include a polyphenylene oxide resin and a chlorostyrene resin. The patent of the United States of America

  No. 3,629,506 discloses compositions of a poly (oxy) resin.

  phenylene) which comprise styrene resins, phospha-

  halogenated flame retardants. -

  Compositions of a poly (oxyphenylene) resin and a styrene-bromostyrene copolymer have been found

  rubber-modified have better physical properties.

  that is to say a better sag temperature under load and better impact resistance; better fire behavior and better light stability

  that the compositions prepared with polystyrene

  rubber-modified rene with the same concentration of

  bromine present in the form of conventional brominated flame retardants -

of low molar mass.

  The compositions of the invention comprise: a. a poly (oxyphenylene) resin; and B. a modified styrene-bromostyrene copolymer

rubber.

  Poly (oxyphenylene) resins include

  whose reasons match the formula:

Qi Qi -

<9 S n

Q "Q

  wherein Q is selected from the group consisting of

  hydrocarbon radicals, hydrocarbon radicals,

  halogenated animals having at least two carbon atoms between

  the halogen atom and the phenyl ring, the oxyhydro-

  carbon and halogenated oxyhydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl ring, Q 'and QI' may represent the same radicals as Q, and in addition a halogen, provided that Q and Q be

  both lack a tertiary carbon atom and n represent

  an integer of at least 50.

  The most preferred poly (oxyphenylene) resin is poly (2,6-phenylmethyl-1,4-phenylene) resin having a viscosity limit of between about 0.40 dl / g and

  about 0.60 dl / g measured in chloroform at 30 C.

  The copolymers of styrene and

  rubber-modified mostyrene from styrene and

  mostyrene and rubber. We can still use mixes

  isomeric bromostyrene salts that include para-, meta- and ortho-bromostyrene. In general, the weight ratio of styrene to bromostyrene in the copolymer can vary between 15:85 and 85:15, and will preferably be included

  between 30:70 and 85:15. These reports are specified because a separate

  phase ration can occur if 100% bromostomy-

  for a poly (oxyphenylene): bromostyrene ratio of 50:50.

  A 85:15 bromostyrene copolymer is compatible with a

  poly (oxyphenylene) 75:25 composition: polymer copolymer

  mostyrene, whereas a 50:50 composition of poly (oxyphenyl)

  lene): bromostyrene copolymer with a bromostyrene ratio:

  styrene 85:15 or 100: 0 in the copolymer is incompatible.

  A 70:30 bromostyrene: styrene copolymer is compatible in all proportions with the poly (oxyphenylene) resins as are all bromostyrene: styrene copolymers which have a bromostyrene: styrene ratio of less than 70:30. The same degree of compatibility is expected for bromostyrene-styrene copolymers at the lower end

  of the concentration range. We can use from 80 to 10 par-

  by weight of the styrene-bromostyrene copolymer in combination with

  naison with 20 to 90 parts by weight of the poly resin

(Polyphenylene ether).

  The styrene-bromostyl copolymers can be modified

  rubbers with, for example, polybutadiene rubber by copolymerizing the styrene monomer, bromostyrene monomer and polybutadiene rubber for

  form a grafted terpolymer that contains small particles

  the discrete partially crosslinked and grafted rubber

  with styrene-bromostyrene units. We can still use from

  very rubbers, such as EPDM rubbers, polysulfide rubbers, ethylene-propylene copolymers, etc. We

  can also use from 1 to 15 parts by weight of a rubber

  In the compositions of the invention, the thermoplastic copolymers such as an ABA or AB block copolymer are suitable. Among the suitable ABA block copolymers are the Kraton or Kraton-G polymers which are described respectively in the US Pat.

  United States of America Nos. 3,646,162 and 3,595,942.

  If desired, we can add

  forcing the composition, in an effective amount of between 40% and 40% by weight of the total composition. Glass fibers or other reinforcing agents such as quartz, mica, wollastonite or carbon fiber can be used as fillers

  de-strengthening. It is also possible to use non-renewable

  forçatrices. If the amount of bromine present in the compositions of the invention does not make it possible to attain the desired degree of fire resistance, a small amount of a compound of the invention can be added.

  phosphorus, that is to say from 0.1 to 7.5 parts by weight of a

  posed phosphorus, calculated as elemental phosphorus,

  per 100 parts by weight of the total composition.

  In general, we can choose the compounds

  phosphorus recommended in the group consisting of phosphorus

  elemental phosphorus or phosphonic acids, phosphonates

  phosphinates, phosphonites, phosphinites, phosphine oxides, phosphines, phosphites and

  phosphates. For example, triphenyl ether may be used.

  phosphine. They can be used alone or with

monk.

  Among the phosphorus compounds recommended,

  conventional compounds which can be used in this invention are compounds of the general formula:

QO -P- OQ

OQ

  wherein the Q groups are the same or different and

  represent radicals among which we can cite

  hydrocarbon radicals such as alkyl, cycloalkyl, aryl, aryl radicals substituted by alkyl groups, aryl-substituted alkyls; halogens; hydrogen and their combinations, provided that at least one of the groups

  Q represents an aryl radical. We can cite as a classic example

  Suitable phosphates include phenyl phosphate and bisdocecyl phosphate. Phenyl Phosphate, Ethyl Phosphate, Ethyl Phosphate, Ethyl Phosphate, Ethyl Phosphate, Ethyl Phosphate

  hexyl and di (p-tolyl), diphenyl phosphate and hydro-

  gene, tricresyl phosphate, triphenyl phosphate, tri-isopropylphenyl phosphate, chloro-2

  ethyl and diphenyl, and diphenyl and hydrogen phosphate

  gene. We recommend among the phosphates, those found

  in the trade, like Kronitex-50, which is a mixture of i-

  somersaults of tri-isopropylphenyl phosphate.

  The compositions can be prepared by tumbling extruded powders, beads or pellets of the components with or without reinforcing agents, stabilizers, pigments, non-reinforcing fillers and the like. suitable, and for example from 50% of the total weight of the composition of clays and talcs, added flame retardants, plasticizers or extrusion aids. The compositions can be prepared by extruding the components into continuous core yarns, by cutting the base yarns into pellets and molding the pellets to the desired shape.

EXAMPLE 1

  A bromostyrene-styrene copolymer was prepared

  rubber-modified by dissolving polybutary rubber

  cis-trans diene in a mixture of styrene and bromostyrene

  and polymerizing the styrenic mixture with stirring to obtain

  a grafted terpolymer of rubber, styrene and

  mostyrene containing small, discrete particles of rubber

  partially crosslinked and grafted onto the styrene bromostyrene copolymers. Rubber particles, measured

  optical microscopy showed a mean diameter of

  Viron 2-3 microns. The terpolymer contained 17.1% bromine

  (about 40% by weight bromostyrene) and 7.5% rubber.

  It contained 17% of rubber gel insoluble in toluene,

  with a swelling index of 9.2 in toluene. The copoly-

  styrene bromostyrene, separated from the rubber phase by extraction with methyl ethyl ketone,

  viscosity limit of 0.77 dl / g in chloroform at 30 C.

  A mixture of 80 parts of poly (oxidized

  2,6-phenylphenylene-1,4) *, 20 parts of the styrene-copolymer

  rubber-modified bromostyrene (composition A) in a

  single-screw extruder, and then molded in the form of

  conventional test pieces with a molding machine

screw injection.

  For comparative purposes a mixture (composition B) was also extruded and molded, in which the bromostyrene terpolymer was replaced by an equal weight of a rubber-modified polystyrene (Monsanto HT-91), a cis-polybutadiene graft copolymer -trans with polystyrene that contains 20% of

  insoluble gel in toluene with a swelling index of 7.7.

  * PPO, General Electric Company with a limit index of

  viscosity of about 0.5 in CHCl 3 at 30 C.

  Another mixture (Composition C) was prepared from

  poly (2,6-oxydimethylphenylene-1,4) and a mixture of a

  styrene and bromostyrene monomer containing 27% bromine, a polystyrene homopolymer (Diene 8G) and a block copolymer of styrene-butadiene (Kraton 1101), adjusting the proportions to obtain the same concentrations of

  bromine, rubber concentration and poly (oxydimethyl)

  2,6-phenylene-1,4) -polystyrene, than for Composition A. The properties are summarized in Table 1. The composition

  containing the grafted terpolymer of styrene-bromostyrene rubber

  rubber exhibited a lower load deflection temperature and Izod impact strength than the other two. It received the classification of fire behavior V-O, while the composition containing the same amount of bromine in the form of a styrene-bromostyrene copolymer received the classification V-1, with an average burning time clearly

higher.

TABLE 1

  Composition Temperature Resistance of UL 94

  shocks Izod sagging Ranking Time of com

  N0 * (joules / cm) under load (C) medium boiling A 0.96 153 VO 4.9 s B ** 0, 80 145 V-1 15.0 s C ** 0.59 147 V-1 6, 5s

  * Each composition also contained three parts per cent of phosphorus

  triphenyl lighthouse, 1 part percent diphenyl and decyl phosphite, 1.5 part polyethylene, 0.15 part per cent

  zinc sulphide and zinc oxide.

** witness.

EXAMPLE 2

  A mixture of 60 parts of poly (2,6-dimethylphenylphenyl), 40 parts of the bromostyrene terpolymer described in Example 1, 1 part of diphenyl decyl phosphite, was extruded and molded. Part of polyethylene, 0.15 parts of zinc sulfide and 0.15 part of zinc oxide, as described in Example 1. Another mixture was prepared from -60 parts of poly (2,6-oxydimethylphenylene-1,4),

  parts of rubber-modified polystyrene (Monsanto HT-

  91), with the other additives indicated above, and adding 8.9 parts of decabromodiphenyl oxide (DBOPE) so that the bromine concentration is the same in both mixtures. Two other mixtures were prepared in the same manner but adding 3 parts of triphenyl phosphate (TPP) to each mixture. The properties of the molded material-are summarized

  in Table 2. Compositions prepared with terpoly-

  styrene-bromostyrene-rubber had a resistance

  Izod impact strength and a higher load deflection temperature than the corresponding compositions which contained the same amount of bromine oxide

  decabromodiphenyl. Bromine added in the form of terpoly-

  mother of bromostyrene was also more-effective as igni-

  only in the form of the low molecular weight brominated additive. The two compositions containing the terpolymer received the VO fire rating, while the compositions containing decabromodiphenyl oxide were rated V-1, with longer average burning times, determined by the test. Fire behavior of the newsletter

94 of Underwriter's Laboratory.

TABLE 2

  Compo - TPP DBDPE Resistance Temperature UL 94 sition (parts (parts at bending shocks - Classification time of N for for Izod - combustion under one hundred) hundred) (joules / cm) load (C) medium (s)

D O O 1.28 148 V-O 4.4

E * O 8.9 0.85 131 V-1 6.2

F 3 0 1.12 130 V-O 3.8

G * 3 8.9 0.80 124 V-1 5.7

* witness.

2483443-

EXAMPLE 3

  Mixtures of 40 parts of

  poly (2,6-oxydimethyl-1,4-phenylene) and 60 parts polysaccharide

  rubber modified tyrene (Monsanto HT-91) or terpoly-

  styrene-bromostyrene-rubber grafted mother described in Example 1, as described in Example 1. To some of the mixtures containing rubber-modified polystyrene,

  a sufficient quantity of several fire additives has been added

  conventional brominated fugents to achieve the same overall bromine concentration as in the mixture containing the bromostyreene terpolymer. Each of the compositions also contained 3 parts of triphenyl phosphate, 0.5 part of zinc sulfide, 0.5 part of zinc oxide and 3 parts of titanium dioxide. The properties of the molded compositions were reported in Table 3. The composition prepared with the bromostyrene terpolymer had higher impact strength and sag temperature under load than

  compositions containing the brominated flame retardant additive, thus -

  better color and improved fire behavior.

(see table 3 on page 9).

EXAMPLE 4

  a solution of 10 g of di-type copolymer was

  sequenced butadiene-styrene (Solprene 308) and 143g poly-

  butadiene (Taktene 1202) in 620.5 g of bromostyl monomer.

  rene1 and 926.5g of styrene monomer in a 4.543 liter reactor with 0.9g of azobis (isobutyronitrile) and 0.9g of dicumyl peroxide. The mixture was stirred (750 rpm) for six hours at 82 ° C until a styrene conversion of 32% was obtained and suspended with 1500 ml of water containing 4.5 g of polyvinyl alcohol and 3.3 g of gelatin. The mixture was stirred for five hours at 1.5 hours at 120.degree. C. and finally at 140.degree. C. for six hours.

  separates the product by filtration, in the form of large

  they were washed in hot water and dried. It was found to contain 22.1% toluene-insoluble gel with a hint

swelling of 8.9.

  1. 27% ortho; 70% of para; 3% meta by I.R. analysis

TABLE 3

  Composition N Polystyrene Izod impact strength (joules / cm Notch additive) Load deflection temperature (C) UL 94 Classification Average burn time

Index of.

  yellowing terpolymer bromostyrene None HT-91 None

decabromodiphenyl

diphenyl 1.17 0.85 0.69

bis (penta-

bromophenoxy) -1.2 ethane 0.64

hexabromo-

biphenyl carbonate

of pentabro-

  mophenyl 0.64 0.53 * Control ** Classification and average combustion time very affected prolonged combustion. The repetition of this test with classification of fire behavior V-O, with a time

  *** Poor color change, dark gray.

  by a single test piece having a time of a second group of test pieces leads to a mean combustion pressure of 2.1 seconds. Co U4 L> 4 H 1 * V-1 bad bad V-1 bad bad, 5s ** 36 s 11.2 s 6.3 s 13.6 s 21.7 21.0 26.4 29.0 24, 16.7 s A composition comprising 50 parts of rubber-modified styrene-bromostyrene copolymer was extruded; 50 parts of poly (2,6-oxydimathylphenylene-1,4) resin; 1 part of diphenyl and decyl phosphite; 1.5 parts of polyethylene; 3 parts of triphenyl phosphate; 0.15 parts zinc sulphide and 0.15 parts zinc oxide in a 28 mm twin-screw extruder and molded as test specimens in a molding apparatus by injection screw. For comparative purposes, a composition was prepared,

  which except for the replacement of the bromostyrene copolymer

  rubber-modified with rubber-modified polystyrene

  high shock resistance (Foster Grant 834), was similarly

  tick to the previous one. The molded parts presented the

following properties: Copolymer of

Polystyrene mono-polybromostyrene

  rubber-modified rubber-resistant rubber resistant to high tensile strength High * high impact Tensile elongation (%) 66 48 Tensile yield strength (daN / mm2) 6.614 7.028 Tensile strength (daN) / mm2) 5,719 6,201 Impact resistance Izod (joules / cm notch) 2.24 2.03 Impact strength Gardner (joules) 11, 30 11.30 Gloss (450) 44.1 48.3 Bending temperature under load (C) 114 124 UL-94 (classification) bad VO UL-94 (average burn time, seconds) 35- 3.6 * control

EXAMPLE 5

  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 in a steel reactor.

  stainless with 1.0 g of tert-butyl peracetate, with stirring.

  The reactor was purged with nitrogen and the mixture was heated for 14 hours at 120 C. The product contained 17% gel

  insoluble in toluene, with a swelling index of 9.9.

  It had a bromine content of 25.7%. A composition was prepared using 50 parts of a rubber modified bromostyrene / styrene copolymer, the preparation of which was described previously; 50 parts of poly (2,6-dimethyl-2,6-phenylphenyl) resin; 1 part of

  diphenyl and decyl phosphite; 1.5 parts of polyethylene

  lene; 3 parts of triphenyl phosphate; 0.16 parts of zinc sulfide and 0.16 part of zinc oxide, extruding in a twin-screw extruder. The extrudate was cut into pellets which were molded in the form of test specimens in a screw injection molding apparatus. The product

  had a Izod impact strength on a test piece

  1.87 joules / cm of notch, a bending temperature of

  under load of 128 C, and received from UL-94 the V-O rating for a section of 1.587 mm, with a burn time

average of 2.0 seconds.

EXAMPLE 6

  A solution of 90g of polybutary rubber was placed

  diene (Taktene 1202) in 607 g of bromostyrene monomer and

  303 g of styrene monomer in a stainless steel reactor

  ble with 0.5g of dicumyl peroxide; 0.5 g of benzene peroxide

  Zoile; and 0.5 g of tertododecyl sulfide. The mixture was heated under nitrogen, stirring vigorously for seven hours at 135 ° C. The rubber-modified copolymer beads were filtered off, washed and dried;

  they had a bromine content of 26.8%.

  A composition comprising 50 parts was extruded and molded.

  of this copolymer, 50 parts of poly (oxydimethyl)

  2,6-phenylene-1,4) and 3 parts of triphenyl phosphate as described in Example 4. The molded part had a

  good surface appearance with a 459 gloss of 59.4; a resistance

  Izod impact strength of 1.44 joule / cm notch; a resistance

  Gardner shocks of 19.77 joules; a bending temperature

  under load of 134 C; and received from UL-94 the fire behavior rating V-O, with an average burn time

1.5 seconds.

EXAMPLE 7

  A solution of 7 g of disulfide copolymer was

  of butadiene-styrene (Solprene 308) and 95 g of polybutadiene rubber (Taktene 1202) in 906 g of bromostyrene and 227 g of styrene in a reactor, with stirring with 0.6 g of azobis (isobutyronitrile) and stirred for 5 hours at 82 ° C. and then suspended in 2000 ml of water containing 4.5 g of gelatin and 8 g of polyvinyl alcohol. The solution was heated for 5 hours at 1000 ° C. for 5 hours at 120 ° C. and then

  8 1/2 hours at 140 C. The polymer beads were separated by

  filtered, washed with water and dried.

EXAMPLE 8

  A solution of 162 g of polybutadiene rubber (Taktene 1202) was transferred into 545 g of styrene and 1093 g of bromostyrene (isomeric mixture) in a stainless steel reactor with stirring, with 0.9 g of dicumyl peroxide, 0, 9g

  of benzoyl peroxide and 0.9 g of tert-dodecyl sulfide.

  The reactor was purged with nitrogen and heated for seven hours at 90 ° C. The product was suspended in 2000 ml.

  of water containing 4.5g of gelatin and 6.0g of polyvinyl alcohol

  and we heated it for fourteen hours at 135 degrees Celsius.

  cool the mixture and separate the poly-

  mother by filtration, they were washed with hot water and dried.

  The product contained 29.8% toluene insoluble gel with a swelling index of 4.7. It had a content

bromine 26.7%.

  A mixture comprising 50 parts of the product, 50 parts of poly (2,6-oxy-2,6-dimethylphenylene), 3 parts of triphenyl phosphate, 1 part of diphenyl and decyl phosphite was extruded and molded. 1.5 part of polyethylene, 0.15 part of zinc sulfide and 0.15 part of zinc oxide, as described in Example 4. The molded composition had satisfactory physical properties and strength. excellent fire resistance: tensile yield strength 7.235 daN / mm2 elongation at break 48% impact resistance Izod 1.44 joule / cm notch sagging temperature under load 134 C gloss (45) 59.4 impact resistance Gardner 19.77 joules Fire behavior (UL 94) VO Average burn time 1.5

EXAMPLE 9

  The following compositions were prepared from poly (2,6-oxy-2,6-phenylene-1,4-phenylene) and copolymers of

  styrene and bromostyrene2modified with polybutary rubber

  diene (Taktene 1202) at 9% according to the method of Example 4, and found to have the following properties:% by weight

bromosty-

rene in the copolymer

- 01

80

80

poly (oxydimé-

2.6-thyl phenol

1,4-nylene) & copolymer of

styrene

  bromostyrene: 50: 50: 50: 50: 50: 25: 25: 25: 25: 25 Izod impact strength (joules / cm notch 1.65 1.81 1.81 0.37 0.27 1.23 1.49 1.87 2.24 1, 01 Resistance to shocks Gardner joules 11.30 19.77 11.30 0.56 0.56 11.30 33.90 28.25

19 ', 77

0.56

tempera-

ture of

fléchisse-

under load C UL-94 *

V-O (33.0)

V-0 (3.6)

* v-o (1.4) V-o (0.6) v-o (0.9)

V-1 (12.6)

* V-o- (3.1) v-o (1.3)

V- (1.3)

v-o C 1.3)

159 V-O (1.0)

  1. Rubber modified polystyrene of high impact resistance.

  2 each composition also contained (percent by weight resin) 3 parts

  triphenyl phosphate, 1 part by weight of diphenyl and decyl phosphite, 1.5 part by weight of polyethylene, 0.15 part by weight of zinc sulphide and 0.15 part per cent

by weight of zinc oxide.

  * Average burn time in seconds.

Claims (10)

  1. Thermoplastic molding composition fireproof, characterized in that it consists essentially of: a. a poly (oxyphenylene) resin; and B. a styrene-bromostyrene graft copolymer modified attached to rubber.   2. Composition according to claim 1, characterized in that the poly (oxyphenylene) resin comprises units corresponding to the formula: Q "Q   wherein Q is selected from the group consisting of hydro-   hydrocarbon radicals, halogenated hydrocarbon radicals having at least 2 carbon atoms between the halogen atom and the phenyl nucleus, oxyhydrocarbon radicals and halogenated oxyhydrocarbon radicals having at least two carbon atoms between the atom halogen and the phenyl ring, Q 'and Q "may represent the same radicals as Q, and in addition a halogen, provided that Q and Q" are both   without a tertiary carbon atom, and n represents a whole number not less than 50.   3. Composition according to claim 2, characterized   in that the Q "groups represent hydrogen.   4. Composition according to claim 2, characterized in that the poly (oxyphenylene) resin is a resin of   poly (2,6-oxydimethyl-1,4-phenylene).   5. Composition according to.any of the claims   in that the copolymer contains styrene and bromostyrene in a weight ratio of between 248344.3 : 15 and 15:85.   6. Composition according to any one of the claims   tions, characterized in that it still includes a reinforcing load.   7. Composition according to any one of the preceding claims, characterized in that it comprises, by weight, from 20 to 90 parts of a poly (oxyphenylene) and from 80 to parts of the copolymer.   8. Composition according to any one of the claims   in that in the copolymer   rubber is a diene rubber.   9. Composition according to any one of the claims   tions, characterized in that it still includes a flame retardant phosphate.   10. Composition according to any one of the claims   preceding, characterized in that the thermoplastic rubber   that is an ABA block copolymer.