DE2906035A1 - FLAME-RETARDANT POLYSTYRENE PLASTIC PREPARATIONS - Google Patents

Description

DR. BERG DIPL.-ING. STAPF DIPL.-ING. SCHWABE DA. DR. SANDMAIR

PATENTANWÄLTE PO Box 8602 45 8000 Munich 86

Attorney's file: 29 707 .1 rs. Fob, 1979

VELSICOL CHEMICAL CORPORATION CHICAGO, ILLINOIS / USA

Flame-retardant polystyrene plastic preparations

VCC -

P (089) 988272 Telegrams: Bank accounts: Hypo-Banlc Munich 4410122850

988273 BERGSTAPFPATENT MUnchen (BLZ 70020011) Swift Code: HYPO DE MM

988274 TELEX: 9θ98 ^ Α / ΠζίϊΙ! Bayec Vereinsbank Munich 453100 (BLZ 70020270) 983310 0524560BERGd ^www - ^ «■>" * / VOQQ Post check Munich 65343-808 (BLZ 70010080)

description

The invention relates to a polystyrene plastic preparation, which contains a three-component flame retardant system.

US Pat. No. 3,658,63M discloses a fiber with a sheath-core structure described, which consists of a thermoplastic shell polymer and a thermoplastic core polymer (both are either polyester or polyamide as described). The core polymer contains a fire retardant system from two components, namely from

a) a halogenated aromatic fire retardant of the general formula _, Xm

'Yn
where X is bromine or chlorine and Y-R ', -OR' or -OR "is OR ¹ (where R 'is alkyl, aryl, aralkyl, alkaryl and halogenated derivatives thereof, and R" is an alkylene radical having 1 to 6 carbon atoms), furthermore η and m are integers which correspond to the formula 6>m> 1.5 ^ η - ^ 0; and

b) an organophosphorus compound. Bisphenoxyalkanes are described as useful flame retardants in this patent.

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Japanese Patent Publication 72/14500 describes a flame-retardant polyester preparation which is polyethylene terephthalate and a compound of the formula

ORO

contains, where X is bromine or chlorine, m and η each represent integers from 1 to 5, and R is a halogen-free alkylene, phenylene or R ¹ 0R ' ^r R "' group in which R ¹ , R" and R " ^{1 are} alkyl or phenyl groups.

US Pat. No. 3,383,435 describes a thermoplastic preparation comprising a polyphenylene ether and a styrene resin contains.

In US-PS 3,717,609 a flame retardant polymer is shown, the propylene and a flame retardant two-component additive of an organotin compound and a bromophenyl contains.

In GB-PS 1 416 5 85 and the German patent publication 2 32 8520 polystyrene preparations are described, which contain certain bisbromophenoxyalkane flame retardants and, optionally, promoters such as antimony trioxide. The described While bisphenoxy compounds are generally excellent flame retardants for polystyrene, they are

-/8th

908884/0555

however, less useful if the flame retardant Riymer should have a relatively high deformation temperature (heat distortion temperature), since these bisphenoxy compounds generally impart a relatively low deformation temperature to the polymer system.

Also of interest in connection with the present invention are U.S. Patents 3,717,609, 3,403,036, 3,819,761, 3 887 846, 3 883 613, 3 663 654, 3 660 531 and 3 639 506.

Polystyrene and its uses are known; see, for example, "Polystyrene", W.C. Teach and G.C. Kiessling (Reinhold Plastics Applications Series, Reinhold Publishing Corporation, New York, 1960) and "Modern Plastics Encyclopedia" 1972-1973, Vol. 49: No. 10A, October, 1972, pp. 97-99, 161 and 261-272.

There was also a need for flame retardant polystyrenes recognized, as for example in US-PS 3 34-7 882 and 3 442 048, as well as in the "Modern Plastics Encyclopedia" page 221, and 456-458.

In the previous knowledge it is expressly pointed out that polymer systems are both in their flammability as also differ significantly from one another in their material properties, and that no prediction is made in

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Regarding the individual systems can be made. As stated in the publication by Norris et al., "Toxicological and Environmental Factors Involved in the Selection of Decabromodiphenyl Oxide as a Fire Retardant Chemical " , Applied Polymer Symposium Mon. 22, 195-219 (1973): "The growing awareness of the high number of deaths caused annually by fire, leads to ever more stringent regulations with regard to many fields of application the flammability of plastic polymers. Economic Constraints as well as the need to make flame retardant polymers without sacrificing existing manufacturing processes have to be completely replaced by new processes lead to the fact that one generally has an increased Seeks to achieve flame resistance by incorporating a fire retardant chemical into the final product. Such a Substance is usually based on bromine, chlorine, phosphorus or nitrogen, and can either be chemically reacted with the product or mechanically mixed with it. Since polymer systems differ in their flammability as well as in their material properties differ significantly from each other, the choice of a suitable flame retardant depends on one Number of factors affecting the number of usable substances very narrow ".

"... Some of the most important criteria for a usable flame retardant are:

1. It has to be as effective as possible at both cost

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and to keep the effect on the polymer properties as small as possible. The proportions used can make up to 15%.

2. It must be stable enough to withstand the conditions encountered during polymer processing and use. During processing (mixing, extruding and molding) temperatures of over 300 ^° C. often occur. The flame retardant must not decompose or volatilize under these conditions. The hydrolytic stability and oxidative degradation must also be taken into account, especially in the case of prolonged use at high temperatures.

3. It must be compatible with the base polymer and must have minimal adverse effect on properties that are important for the polymer. These critical properties include tensile strength, impact strength, Deformation temperature, shear force and flexural modulus.

M-. Finally, the flame retardant is allowed to look and shape of the desired product.

Because of the extremely strict requirements with regard to thermal stability, only very few compounds could be found which meet the necessary criteria

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in terms of performance and economy ".

Among the disadvantages of using various known substances as flame retardants for plastic preparations occur, include factors such as migration under the influence of heat, heat and light instability, the impossibility they biodegrade, toxicity, discoloration, the large amounts needed for sufficient effectiveness as well as the unpredictable end results that one gets when one uses the same substance other plastic used. For example, in the Modern Plastics Encyclopedia, page 650, the use of octabromobiphenyl shown as flame retardants in polyolefins, but not in the other 27 preparations listed.

The above considerations apply particularly to the flame retardancy of polystyrene plastics. It is important that, in addition to maintaining good material properties, three characteristics of rystyrene are kept within certain limits in order to obtain a functional product; These are the flame retardancy (eg measured according to UL 9Ό, the heat stability (measured eg with certain ASTM tests for decomposition and migration) and the deformation temperature.

It is known that possible flame retardants must be assessed on a case-by-case basis, since when an additive is incorporated into a

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.909834 / 05SS

Polymer system the results are unpredictable. For example, US Pat. No. 3,658,634 states that "... the as Compounds to be used fire retardants, which contain chlorine or bromine atoms, generally sublime, see above that the fire retardant during the process of making fire retardant polymers or in post-treatment processes sublimate or get lost. The cases in which the fire retardancy is decreased or difficulties occur during use predominate.

The previous problem, a flame-retardant polystyrene preparation Manufacture with the desired chemical, physical and mechanical properties is essential solved by the present invention.

It has been found that by adding a certain poly (brominated Phenylene oxide) to a polystyrene preparation containing a bisphenoxyalkane compound, a preparation is obtained in which all the excellent material properties of a preparation that only contains these bisphenoxy compounds contains, are retained, while in addition a significant increase in the deformation temperature of this Preparation is achieved.

The invention relates to a flame-retardant plastic preparation, which contains the following components:

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a polystyrene polymer, a flame retardant amount of a bis phenoxy compound of the formula

0 alkylene

wherein alkylene has a straight chain hydrocarbon group 1 to 6 carbon atoms means a flame retardant agent (promoter), as well as a poly (brominated Phenylene oxide) condensation product obtained from a brominated Phenol obtained from the group tribromophenol, tetrabromophenol and pentabromophenol. This condensation product has a repeating structural unit of the formula

(Br)

where a is an integer from about 0 to U, b is an integer from about 0 to 2, c is an integer from about 1 to 5, a plus b plus c is equal to 5, Q is a monovalent bond between a carbon atom in the aromatic ring of the repeating structural unit and an oxygen atom bonded to an aromatic ring, and the polymer units, which contain the repeating structural unit make up at least 80% by weight of said product; this flame retardant condensation product contains about 17 to 31 weight percent elemental carbon, about 0 to 1.0

909884/0555

% By weight of elemental hydrogen, about 3 to 8% by weight of elemental Oxygen and at least about 60 weight percent elemental bromine; it has a molecular weight of at least about 750, and a or more polymer units containing at least four aromatic rings per unit make at least about 80% by weight of the product.

The group of bis-tribromophenoxy compounds found in Preparations according to the invention are used, has the Formula I.

Alkylene

wherein alkylene is a straight-chain hydrocarbon group with 1 to 6 carbon atoms and, inter alia, groups such as -Ch ₂ -, - <CH ₂ ) ₂ -, - <CH ₂ ) ₃ -, - (CH ₂ -) ^ -, - (CH ₂ > ₅ - and - (CH ^ includes.

All compounds which correspond to the formula I and the above definition are here generally referred to as "bis-tribromophenoxyverbs indungen ".

Examples of compounds of the formula I include 1,1-bis (2,4,6-tribromophenoxy) methane, 1,2-bis (2,4,6-tribromophenoxy) ethane, 1,3-bis (2,4,6-tribromophenoxy) propane, 1,4-bis- (2,4,6-tribromophenoxy) -butane, 1,5-bis- (2,4,6-tribromophenoxy) -pentane, 1,6-bis (2,4,6-tribromophenoxy) hexane,

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- ψ-

1,1-bis- (3, if, 5-tribromophenoxy) methane, 1,2-bis (3,4,5-tribromophenoxy) ethane, 1,3-bis- (2, U, 5-tribromophenoxy) -propane, 1,3-bis- (2,3,4-tribromophenoxy) -propane, and 1,1-bis- (2,3,6- tribromophenoxy) propane.

The bis-tribromophenoxy compounds, the bromine substituents contained in the 2,4,6-position are because of their simple Manufacturing preferred.

In general, the bis-tribromophenoxy compounds are prepared by reacting a halogenated phenol with a halogenated one Alkane at elevated temperatures and in the presence of a basic substance such as alkali metal hydroxides, carbonates, Bicarbonates, oxides or hydrides. The preferred alkali metals are potassium and sodium. Should e.g. the handling of the reaction mass can be made easier, solvents such as ketones (e.g. acetone, methyl ethyl ketone and methyl isobutyl ketone), alcohols (e.g. methanol, ethanol, isopropyl alcohol, butyl alcohol and glycols), or aqueous solvents (e.g. water, a mixture of water and alcohol, or a mixture of water and ketone) are used will. The desired end products, i.e. the bis-tribromophenoxy compounds, can be extracted from the reaction mass with various known methods can be obtained. If the end product has to be obtained by crystallization, can various aromatic solvents such as benzene, toluene,

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- χΤ-

Xylene, dichlorobenzene and the like can be used.

The bis-tribromophenoxy compounds are made according to the following Reactions produced:

OII + X (alkylene) X

0 - (alkylene) - 0
+ Salt of the base

In this reaction, X is halogen, preferably bromine. It is carried out at temperatures between the freezing point of the initial reaction mass and its boiling point. The temperatures are preferably between about 10 and 200 ^° C., better still between about 50 and 175 ^° C. The reaction can be carried out under reduced pressure (0.1 to 0.8 bar), but normal pressure is preferred.

The procedures described can be carried out using conventional, readily available chemical apparatus. For example, a conventional, glass-lined container that comes with Heat transfer device, reflux condenser and mechanical Agitator can be used well for carrying out any of the embodiments of the invention, those for the preparation of the bisphenoxy examples shown here to be discribed.

909884/0555

-if-

The flame-retardant polystyrene preparations according to the invention contain a poly (brominated phenylene oxide) condensation product, obtained from brominated phenol; this condensation product has a repeating one Structural unit of the formula ι a

where a is an integer from about 0 to 4, b is an integer from about 0 to 2, and c is an integer from about 1 to 5, a plus b plus c is equal to 5, Q is a monovalent bond between a carbon atom in the aromatic ring of the repeating structural unit and an oxygen atom bonded to an aromatic ring. These Monovalent bond can be at any point on the aromatic rings in the preparation that contains a carbon Possessed bromine bond; it is formed by displacing bromine. For example, it can be in the para position to the oxygen-carbon bond to be available. A repeating structural unit with this para bond can be represented by the formula II are represented, in which χ 1,2,3 or M- (preferably

(Br).

II

0 -

se means 2 or 3); this repeating unit forms linear chains. In other cases where c means 1, the monovalent bond in the ortho position can be present (hereinafter referred to as III). If c means 2, then

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the bond can be in the ortho and in the para position (hereinafter referred to as IV); and it can do both ortho positions and the para position to the carbon-oxygen bond be present when c is 3 (hereinafter referred to as V). The flame retardant condensation product contains at least one of the repeating structural units labeled II, III, IV and V. At least 80% by weight of this product consists of polymer chains that contain one or more of these units.

The poly (brominated phenylene oxide) product has a molecular weight of at least about 750. The molecular weight of this product can be compared to that described in ASTM Test D 2503-67 Vapor phase osmometric methods are determined. Preferably, however, the molecular weight is determined by the known method determined by gel permeation chromatography; unless nothing otherwise stated, the references to the molecular weight used here relate to average molecular weights, those with the gel permeation method and Polystyrene reference standards have been determined.

For the gel permeation method used to determine molecular weight of the poly-Cbrominated phenylene oxide) preparations according to the invention Four stainless steel columns (from Waters Associates, Inc.) were used that came with "Styragel" are filled, connected in series. These pillars each 122 cm long and 9.5 mm in diameter have pore

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$ 09884/0555

sizes from 1.5 μm to 5 μm, or 800 nm, 25 nm, and 25 nm. Tetrahydrofuran is used as the solvent; 33.5 mg of the poly (brominated phenylene oxide) sample are added to 15.0 ml Tetrahydrofuran is mixed and the mixture is added to the chromatograph. It becomes a tetrahydrofuran flow rate of 1 ml / min used. The chromatograph is calibrated with commercially available polystyrene standards, and the Molecular weight values found are given in relation to polystyrene.

Preferably, the average Molekulargwicht the invention poly (brominated phenylene oxide) preparation less than about 100 000 and preferably less than about 10 000. In the preferred embodiment, the average molecular weight is less than about ¹ ^ 500th

One or more polymer units that contain at least four Containing aromatic rings make up at least about 80% by weight of the poly (brominated phenylene oxide) formulation described herein the end.

The poly (brominated phenylene oxide) condensation product is obtained from a brominated phenol which is selected from the group Tribromophenol, tetrabromophenol and pentabromophenol is chosen. The brominated phenol is preferably selected from the group Tribromophenol and tetrabromophenol selected; it is best

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Tribromophenol.

Contains the poly (brominated phenylene oxide) condensation product about 17 to 31% by weight of carbon, about 0 to 1.0% by weight of elemental hydrogen, about 3 to 8% by weight of elemental oxygen and at least about 60 weight percent elemental bromine. This product preferably contains about 62 to 66% by weight elemental bromine.

Preferably, the poly (brominated phenylene oxide) product used in the formulation of the present invention, when melted into 3.175 mm thick test specimens, has a notched Izod impact strength of less than about 0.21 J / cm (ASTM D 256), an elongation of less than about 2.0% and a tensile strength of less than about 140 N / cm ² (ASTM D 638).

The poly (brominated phenylene oxide) product can be made by any of the known methods. Generally, the brominated phenol will be contacted with an effective amount of an activator; then it is allowed to condense at a temperature of up to about 300 ^{° C. for a period of up to 18 hours.} Suitable activators include heat, light, organic and inorganic peroxides such as benzoyl peroxide, hydrogen peroxide, dimethanesulfonyl peroxide, lauroyl peroxide, caprylyl peroxide, succinic acid peroxide, acetyl peroxide, p-tert.-butylbenzoyl peroxide, tert.-butylperoxyisopropyl carbonate peroxide, hydroxyheptyl peroxide,

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hexane peroxide, 2,5-dimethylhexane peroxide, di-tert-butyl diterephthalate peroxide, tert-butyl perbenzoate peroxide, and the like; Azo compounds such as azobisisobutyronitrile; Persulfates, such as Ammoniur: persulfate, potassium persulfate, and Sodium persulfate; Hypochlorites; Ferricyanide; Ferric chloride; Copper salts in which the copper is monovalent or divalent, e.g. copper-I-2, M-, 6-tribromophenate, copper-II-2,4,6-tribromophenate, Copper-I-chloride, copper-II-chloride, Copper-I-nitrate, copper-II-nitrate, copper-I-sulfate, copper-II-sulfate, Mixtures with one or more of the salts mentioned, etc .; Metal oxides, such as lead oxide, mercury oxide, Silver oxide, and the like; Halogen such as iodine, bromine, and chlorine; Lead tetraacetate, sodium bismuthate, etc. In general, can any activator known to promote free radical chain initiation can be used.

Optionally one can put together a metal salt of the brominated phenol use with the activators. Suitable salts that can be used include the lithium, Sodium, potassium, barium, zinc and tin salts of the brominated phenol. Other known phenates can also be used will.

The brominated phenol (or the metal salt derived from it) can be brought into contact with the activator in the solid state. Optionally, the polymerization of the bro-

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mated phenol (or its salt) in a suitable inert solvents are carried out. In general, any inert aqueous or organic solvent, in which phenol or its salt is known to be soluble, can be used to make the flame retardant condensation product to manufacture. Suitable solvents include water, dimethyl sulfoxide, acetone, hexane, methanol, ethanol, propanol, Butanol, benzene, toluene, tetrahydrofuran, etc. Also, aqueous salt solutions can be used, with the salt selected of the group barium chloride, calcium chloride, magnesium chloride, strontium chloride, potassium chloride, lithium chloride, sodium chloride and the like. Is selected. Mixtures of organic solvents and water can be used; so are aqueous acetone solutions, benzene and water, aqueous alkali solutions and organic compounds insoluble in water (such as octyl alcohol, toluene and heptane), carbon tetrachloride and water, amyl alcohol and water and the like are usable.

One of the many methods of making the condensation product involves dissolving a metal hydroxide in water; the activator and the brominated phenol are added to this solution; then the reaction mixture is at a held at a certain temperature.

-.Si

An emulsifying agent can be used in this process be to the condensation product in the aqueous medium

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9098SUQ58S

• 3k-

suspend; in this case about 0.1 to 5.0% of this agent (based on the weight of water in the hydroxide solution) be present in the reaction mixture.

In this process, an alkali or alkaline earth metal hydroxide be used. A metal hydroxide from the group consisting of sodium, potassium and lithium hydroxide is preferred used; Sodium hydroxide is preferred. About 0.5 to 5.0 moles of hydroxide are used per 1 liter of water. Preferably about 1 to 3 mol of hydroxide per 1 liter of water are used, preferably about 2 mol of hydroxide per 1 liter of water.

The brominated phenol is added to the reaction mixture in one concentration from about 0.5 to 5 mol per 1 l of the water with which the hydroxide solution is produced in this process, admitted. Preferably about 1 to 3 moles of phenol per

1 liter of water is used, the preferred concentration is around

2 mol of phenol per 1 liter of water.

In this process, although not essential, an organic solvent can be added to the reaction mixture will; any of the organic solvents listed above can be used for this purpose. Preferably be in such a case about 1 to 20% organic solvent (based on the volume of the water with which the hydroxide solution is used). To be favoured

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about 3 to 10% organic solvent in this process, most preferably about M to 8% organic solvent. The organic solvents include toluene, benzene, chloroform, chlorinated benzene and the like.

In this process, the activator is brought into contact with the reaction mixture after all other ingredients available. If the activator is solid, liquid or gaseous, then at least about 1 10 mol of it are used (based on the amount of water used to prepare the hydroxide solution in 1); preferably about 0.01 up to 0.1 mol of these activators are used.

The third component of the flame retardant according to the invention Plastic preparation is represented by certain compounds, which when taken together with the bisphenoxy compounds and the poly (brominated phenylene oxides) can promote interaction between them and thus the flame retardancy of the plastic preparation obtained raise. These promoters include the oxides and halides of groups IVA and VA of the periodic table the elements such as the oxides and halides of antimony, bismuth, arsenic, tin, lead and germanium; Antimony oxychloride, Antimony chloride, antimony oxide, tin oxide, tin chloride, arsenic III oxide, arsenic trichloride and the like. Can be used. Other well-known promoters are the organic and inorganic compounds of phosphorus,

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909884/0555

Nitrogen, boron and sulfur; for example triphenyl phosphate, ammonium phosphate, zinc borate, thiourea, urea, Tin IV sulfide and the like are suitable promoters. The oxides and halides of titanium, vanadium, chromium, manganese, iron, niobium, molybdenum, copper, zinc, magnesium (such as e.g. titanium dioxide, titanium chloride, vanadium pentoxide, chromium bromide, Manganese-II-oxide, molybdenum trioxide, ammonium molybdate) can also be used. The hydrates of the substances mentioned are also effective, e.g. tin (II) oxide hydrate and lead hydrate. The preferred promoters are the antimony, arsenic and bismuth oxides. However, it is any connection suitable, which in the event of decay, e.g. due to ignition, releases these oxides. So are some organic antimonates preferred. The promoters described in US Pat. No. 3,205,196 are also suitable.

Antimony oxide is the preferred one in the process of the invention Antimony compound, but many organic antimony compounds can also be used (e.g. the antimony salts organic acids and their pentavalent derivatives, see US Pat. No. 2,996,528). These include: antimony butyrate, antimony valerate, Antimony caproate, antimony heptylate, antimony caprylate, Antimony pelargonate, antimony caprate, antimony cinnamate, antimony anisate and their pentavalent dihalide derivatives. Also the esters of antimony acid and their in US Pat. No. 2,993,924

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pentavalent derivatives described (such as Tris (n-octyl) antimonite, tris (2-ethylhexyl) antimonite, Tribenzyl antimonite, tris (2-chloroethyl) antimonite, tris (chloropropyl) antimonite and tris (2-chlorobutyl) antimonite).

If these three components, ie the bisphenoxy compound, the poly (brominated phenylene oxide) and the promoter, are added to the polystyrene copolymers, then they make them flame-retardant. The term polystyrene used here means polymers that contain more than 60% styrene (phenylethylene, vinylbenzene, styrene, cinnamen) CH ₁ -CH = CH- or other unsaturated aromatic monomers consisting of variously substituted styrene derivatives. This term also includes rubber modified high impact polystyrenes (HIPS) and styrene copolymers such as styrene / acrylonitrile (sometimes referred to in the trade as "SA" or "SAN"). Of these, rubber modified high impact polystyrene is preferred.

The polystyrene used in the preparation according to the invention can be a "pure" material. Optionally, it can already contain additives, or these can be added at the same time or after the bisphenoxy compounds, poly (brominated Phenylene oxides) and promoters are added to the polystyrene.

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909834/0555

■ 2906QJ5

• a?

To produce the plastic preparations, the bisphenoxy compounds,. 'Poly- (brominated phenylene oxide' and promoters during "any ^; ', or during, the process of the StyroEril- · ^ dung mixing, if desired ,, can then Sispfrenoxy- compounds ¹ and / or poly (brominated "phenylene oxides and / or' prior to processing either by mechanical promoters' prior to installation in the polystyrene, the particles distributed in the polystyrene must be finely sandblasted. -, .- ■ - ..

In the context of the invention, the inventions "For · - .--; ■ -: Preparations can also be used with other substances""if" a special result is to be achieved with them. . These -ge-- hear UVA Haf tf Örderer - precipitant j ^ antioxidants anti-STATIKA _s antimicrobial ^agents.... FarbenV -FIaiTimiXemraer: ^ Me "s-ie -eg. on SeitW it56. To: ^ 8T ₅ . iiodern .PΪastixs- ^ Ency-cl op; e ^, dia>; listed are "in addition to: .4e: n" Ä £ jerr -breSieteieBepen-new Fla: mmteimem) Y ^ ä ^ ■ ■ ^: ·.

fen, dyes ^. WeichniacherV- Kois && r ^ ievujxgs.miiMXi: inHtrs-. . ; .. '". ^; violettstabilisätoreri * Fülimitte"! lind "Zoi & ätZTejL önd ^: dgl *.

suitable fuKirfittel are ζ.Β> SlasL ρ .Köhie ψ stoffe- fHolzmeitlj, KörTe- ^: - "and,

Metal oxide
siumöxid) _r Me-tfa: Hpülver tAliimiriium \ - Bronze ^ Bled ^

He steel and zinc) ^ "Polymers (crushed polymers and Elas: tomer ~ Kunsts ±« fgerais-che), silicon dioxide products Oiatome earth, novaculite, quartz, sand, trapezium, Tcollo-! dales. silicon oxide, 'SiJieiumdioxidaerogel, wet process : dioxid ^ -Sllikat-e i. Asbestos, -Kaolxnit., Mica-, "Nepheliiv syenitj TaIk ^ -Wollastonit, aluminum silicate and -Calcium-

as well as, inorganic compounds like. Bariujnfemt, : ^ HolybdändlsHlTid and "Slieiumkarbid, -

The substances mentioned, including ¹ ! the filling part, are -ausiuerlieher. in.. the Moderji Plastics Eneyelopedia- besehrieberu - ... - -. ^r '■.

The substances mentioned can be used in the inventive products in any amount which results in the obtained iron: the preparation according to the invention, which is essentially not adversely affected, can be used Amount ^ based on the total weight of the preparation) to as much% "amounts to ₃ that the preparation can still be referred to as plastic bnn. tw-ä 3. to Sö

The polystyrene preparation according to the invention "contains" a henge the bis ^ -trlbromophenoxyverbindungen-, ties poly-brominated Phenylene oxide) and -of the promoter, which-this preparation in effectively makes it flame retardant. In general, the

23Q603S ■■ -30 · ""

uses "amount of bis-tribromophenoxy compound plus poly-; Xbrominated phenylene oxide plus promoter -between about 2 and 35 wt.% TC based on the total weight of the preparation) ^ - The amount used is preferably between about 5 and 30 wt; "%;,; .- better * at about HO to 20 wt. %. Us can -be used any amount ^: -as long as it -chemical. and / odex? -physikalischen and / or ¹ mechanasehen features 4-Plaids ^ ffzufenrextungen-not adversely affected

- The- • yei ¹ häl ± Kis - = - def ¹ ^ ewitsh'tsteile ^ is-trrbromphenoxyve-rbxnduÄg to "Eoly-Chroirii-ertem PhenyienQxid") is about 1: 9 to ^ about 9: 1, preferred is one Ratio of the weight percentage of "Bi.s - ^: i52; bromophenoxyver ⁽ binding to poly-tiromized iheiiylene oxide) of about"; ~ 1 to about t: 2L

• In the aHgeiaein% ti ^ atiht> the used From © to * amount X related aiif.the used iienge-von "Bis-tribr © mphemoxyverbindungen plus - PQly- ^ bromi-ei'tem PhenyienöXiO ^ ertwa-1 ^J bls 1/8 Weight from., · .Preferred ^ we-d etW-a ^ / B bxn 1/2 .Weight portion ,.

Thus, for example, contains a -typical ^ iDevoRferred addition H% der

yverfeiiiöiingi ^ν 1ΐ% ^ .bs poly- (brominated -des

A de ^ -wesanglichen properties of the invention Pdlystyrolzübereltghg .is ^ the unusually strong Flammhem—

mung same. .

':: ■■. "■■" ■ "■. ■.-.-: ■■ -.- · ■■■.' ■ - / 3.0

.Zn.

The importance of the light stability of .Plastic preparations- ~ .. gen. receives attention in the professional world; cf., on this "'---" "-" The Measurement of Appearance, "Richard S. Hunter (Hunter Associates Laboratory, Inc., 9529 Lee Highway, Fairfax, Virginia) 197 3. This publication is hereby incorporated by reference taken.

The polystyrene preparations according to the invention are both. flame retardant as well as not discolored, i.e. they have a relative low E-value ("the higher the E-value, the stronger the Discoloration). '

Another essential property of the plastic preparation according to the invention is its relatively high deformation temperature. This quality is-important- if- the. Plastic preparations are used in the vicinity of Warrtre sources, when they are processed, for example, into wanderlust and radio equipment housings. This property is also essential for the removal of the plastic article from the "mold;" contain these items-polymers with fioher Verforraungstewperatur "Rönnen .then it out of shape b'ei relatively high temperatures" en-tf ERNT ₄ without her before. * mold removal must be abgelcüh-lt del * and without "doing more than a minimal deformation_occurs.

In general, compounds of the formula 1 result, even if they together with the listed promoters to the

Polystyrene, no plastic preparations with the necessary deformation temperatures. However, if the described poly- (brominated Phenylene oxides), then the plastic preparations obtained have the necessary deformation temperatures, as well as all of the desirable material and flame retardant properties described above.

Another advantage of the method according to the invention is that the fire retardant system, i.e. the bis-tribromophenoxy compound and the poly (brominated phenylene oxide) easily using those normally available Single-screw injection molding machines with which polystyrene, especially high-impact polystyrene, can be combined, since both the bis-tribromophenoxy compound and the poly (brominated phenylene oxide) are melt-miscible. With many other flame retardant systems, e.g. decabromobiphenyl oxide, it is essential to combine the flame retardant with the polystyrene especially high-impact polystyrene, using special, expensive, high-intensity mixing devices such as twin-screw extruders, connect to. This is due to the high melting points of some of these previous flame retardants such as Decabromobiphenyl oxide (^ 300 C) conditional. Will be such If the device is not used, irregular flame retardancy and material properties may result.

A second embodiment of the invention is shown

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90 ^ 884/0555

with a three-component, flame-retardant Additional preparation for the flame retardancy of polystyrene preparations. The additional mixture contains a bis-tril romphenoxyver> L: inäung of the formula I, a poly (brominated Phenylene oxide) and the promoter mentioned above. In general, the fire retardant additive contains about 5 to 80 weight percent bis-tribromophenoxy compound, about 5 up to 80% by weight poly (brominated phenylene oxide) and about 11 to 50% by weight promoter; preferably it contains about 16 to 65 Weight percent bis-tribromophenoxy compound, about 16 to 65 weight percent poly (brominated phenylene oxide), and about 1 to 3 weight percent promoter.

The flame retardant additive can be added to the polystyrene plastic preparation either during the manufacture of the polystyrene polymer itself or after the formation of the polystyrene polymer, however, during the formation of the plastic formulation be admitted. The installation of the additional preparation is achieved by simply adding the additive while mixing the preparation containing the styrene monomer (if the additional preparation is added during the step of polystyrene formation), or the polystyrene plastic containing preparation (if the additive is added after the polymerization process).

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908884/0555

The following examples are intended to explain the invention in more detail; Unless stated otherwise, all parts are based on weight, temperatures are in ⁰ C, weights in g and volumes in now.

Examples

High impact polystyrene plastic preparations were made with prepared using the procedure described below and subjected to the following tests to compare properties of the plastic preparations obtained to enable:

1. Flammability

a) Oxygen index, O.I .: ASTM Test No. D 2863-70

b) UL 9 4 ·: UL 9 4 procedure as described below

2. Notched Izod Impact Strength: ASTM Test No. D 256-70

3. Deformation Temperature (HDT): ASTM Test No. D 64-8-72
4 ·. Gardner impact strength.

The plastics subjected to these tests were made as follows: With the exception of the "base resin", the
or the special additives in the polystyrene polymer plastic material (Cosden 825 TV-PI, a product of Cosden Oil and Chemical Company) by adding with the aid of a Brabender Prep Center Mixer ("Measuring Head", Model R6, CW
Brabender Instruments, Inc., South Hackensack, NJ). The mixer was barrel-shaped with a pair

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90SS84 / 0555

Blades and a heat transfer device. The mixture obtained was ^{heated to about 205 °} C., at which temperature it had melted. Each recipe was drained from the mixer, "solidified on cooling, and then crushed into chunks." These bits came in a 1 oz. Newbury Injection Molder (Model KI-30 RS, manufactured by Newbury Industries, Inc., Newbury, Ohio) was injection molded. A cycle of 60 s and a stamp pressure of 1400 N / cm were used for this. The bits contained in the molder were melted by heat transfer, and the melted plastic was injected into a mold so that solid specimens were obtained (after cooling).

Portions of molded coupons of each formulation of Examples 1 to 5 made by the above procedure were subjected to two different flammability tests, namely UL 94 and ASTI Tr 2863-70. The UL 94 test is described in detail in the Underwriter's Laboratories Bulletin, UL 94, Standard for Safety, First Ed., Sept. 1972. ASTM No. D 2 86 3-70 describes a flammability test in which the flammability of a plastic sample is related to the oxygen present in the immediate vicinity. This correlation is expressed as the "Oxygen Index"("OI"). This is based on the volume of oxygen in the gaseous medium that is necessary to

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909804/0555

the plastic sample continues to burn evenly enable. This ASTM procedure is fully detailed in 19 71 Annual Book of ASTM Standards-Part 2 7 (published by the American Society for Testing and Materials, 1916 Race Street, Philadelphia, PA.).

It can be seen from Table I that the polystyrene / Sb _{2 O 3} / bisphenoxy compound / poly (dibromophenylene oxide) combination has excellent flame retardant properties, good deformation temperatures and acceptable impact resistance.

In Examples 6 to 8, molded test pieces that prepared essentially according to the method described above were subjected to a color determination test (Gardner Colorimeter Test) to determine the discoloration. A Gardner XL10-CDM colorimeter was used to measure the color development. The surface of each specimen was measured before and after exposure to UV light.

A pair of specimens from each molding was tested and the results recorded as the average of the two specimens. Example 8 is a comparative example in which the previous flame retardant decabromobiphenyl oxide was used. A special device is required for satisfactory processing of this known flame retardant. A comparison of the light stability in Table II shows ₅

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903004/0555

that the formulation of Example 8 is visually unacceptable and was already significantly changed after 2 5 hours of exposure.

The plastic preparations that make up the 4-component system made of polystyrene / promoter / bisphenoxy compound / poly-chromated Phenylene oxide) have properties that could not be achieved with the previously known processes, namely good flame retardancy, good deformation temperature and acceptable material properties.

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9 0 ¹ J -3 -S 4/0 5 5

ZS-

Table I.

29 06 O 3 S ⁵

example

additive

1,2-bis (2,4,6-tribromophenoxy) ethane

Poly (dibromophenylene oxide)

Sb ₂ O ₃

Flammability and material properties

Notched Izod Impact Strength (0.10 "notch)

1 2 base resin

0 0

J / cm " Thickness 1/8 " Impact strength 1, 16 UL 94, Deformation temperature
(tempered 1 h at
77 ⁰ C) ⁰ C
at 150 N / cm ² HB Oxygen index%
at 2 3 ⁰ C 89 ⁰ C Gardner
J 18 0 12, 4th

3.75 6

11.25 9 3 3

6 3

0.924 0.907 0.890 0.878 V-O V-O V-O V-O

69 ⁰ C 86 ⁰ C 83 ⁰ C 78 ⁰ C 24.0 23.5 23.5 24.0 13.0 5.65 5.65 6.78

Percentage by weight based on the entire preparation

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909884 / OSSS

Table II example

Base resin 3.75 Comparison
example additive 11.25 1,2-bis (2,4,6-tribromo-
phenoxy) eth ₀ (i) 3.0 0 Poly (dibromophenylene
oxide) 0 0 0 Sb ₂ O ₃ 0 2.4 Decabromobiphenyl oxide 0 12th Material properties
E color value (2)
Hours ^J

25th

100 200 300 500

1.9 8.2 32.3 4.4 11.0 34.8 5.7 12.7 36.1 6.2 13.8 36.0 9.2 15.8 47.2 12th 16.6 46.5 18th 18.9 49.1

Percentage by weight based on the entire preparation Exposure to UV light (Xenon Are)

909884/0555

Claims (9)

DR. BERG DIPL.-ING. STAPF DIPL.-ING. SCHWABE DR. DR. SANDMAIR PATENTANWÄLTE Postfach 8602 45 · 8000 Munich 86 Attorney's file: 29707 patent claims 1. Flame-retardant plastic preparation, thereby characterized as being a polystyrene polymer and a flame retardant amount of a flame retardant Contains additional system, which in turn includes: 1.1 a bisphenoxy compound of the formula ^3r \ 0- alkylene wherein alkylene is a straight chain hydrocarbon group with 1 to 6 carbon atoms means 1.2 a flame retardant promoter and 1.3 a poly (brominated phenylene oxide) condensation product, the one \ on a brominated phenol from the group tribromophenol, tetrabromophenol and Pentabromophenol and which is a repeating structural unit of the formula (H) _b (Q) _c - / 2 P (089) 988272 Telegrams: Bank accounts: Hypo-Bank Munich 4410122850 988273 BERGSTAPFPATENT Munich (BLZ 70020011) Swift Code: HYPO DE MM 988274 TELEX: Bayer. Vereinsbank Munich 453100 (bank code 70020270) 983310 0524560 BERG d _A "Postscheck Munich 65343-808 (bank code 70010080) $ 290603 owns, where a is an integer from about 1 to ¹ I-, b is an integer from about 0 to 2, and c is an integer from about 1 to 5, a plus b plus G equals 5, and Q is a monovalent bond between represents a carbon atom in the aromatic ring of the repeating unit and an oxygen atom attached to an aromatic ring, and the polymer units containing the repeating structural unit make up at least 80% by weight of the said condensation product from; this contains about 17 to 31 wt.% elemental carbon, about 0 to 1.0% by weight of elemental hydrogen, about 3 to 8% by weight of elemental oxygen and at least about 60% by weight elemental bromine, it has a molecular weight of at least about 7 50, and one or more polymer units, which contain at least 4 aromatic nuclei per unit make up at least about 80% by weight of the condensation product the end. 2. Preparation according to claim 1, characterized that about 2 to 35% of the flame retardant additive system (based on the weight of polystyrene, Bisphenoxy compound, promoter and poly (brominated Phenylene oxide)) contained in the plastic preparation are. , _ 90S864 / 055S 3. Preparation according to claim 2, characterized that in the flame retardant additive system about 1/9 to 9 parts by weight of the bisphenoxy compound are present per 1 portion of the poly (brominated phenylene oxide) condensation product. Ί. Preparation according to claim 3, characterized in that that the promoter from the group of oxides and halides of groups IVA and VA of the Periodic Table of the Elements is chosen. 5. Preparation according to claim 4, d a d u r c h g e indicates that the promoter is antimony trioxide. 6. Flame-retardant additional preparation for polystyrene plastic preparations, characterized that it consists essentially of 6.1 of a bisphenoxy preparation of the formula Alkylene wherein alkylene is a straight-chain hydrocarbon group having 1 to 6 carbon atoms, 6.2 a flame retardant promoter and - I ₄ . _ 6.3 consists of a poly (brominated phenylene oxide) condensation product that is obtained from a brominated Phenol from the group tribromophenol, tetrabromophenol and pentabromophenol is obtained and which one is repeating structural unit of the formula CBr) ₃ ^rH) b owns, where a is an integer from about 1 to 4, b is an integer from about 0 to 2, and c is an integer means from about 1 to 5, a plus b plus c equals 5, and Q is a monovalent bond between one Carbon atom in the aromatic ring of the repeating unit and one on an aromatic Ring-bound oxygen atom, and the polymer units that make up the repeating structural unit contain, make up at least 80% by weight of said condensation product; this contains about 17 to 31% by weight of elemental carbon, about 0 to 1.0% by weight of elemental hydrogen, about 3 to 8% by weight of elemental Oxygen and at least about 60 wt.% Elemental bromine, it has a molecular weight of at least about 750, and one or more polymer units - / 5 909884/0555 290803§ units that have at least 4 aromatic nuclei per unit make up at least about 80% by weight of the condensation product the end. 7. Preparation according to claim 6, characterized in that in the additional flame-retardant system about 1/9 to 9 parts by weight of the bisphenoxy compound per 1 part by weight of the poly (brominated phenylene oxide) condensation product. 8. Preparation according to claim 7, characterized in that the promoter from the Group of oxides and halides of groups IVA and VA of the Periodic Table of the Elements is selected. 9. Preparation according to claim 8, characterized that the promoter is antimony trioxide. - / 6 S09884 / OS55