DE1270797B - Decrease the flammability of plastics - Google Patents

Description

GERMAN PATENT OFFICE

German class: 39 b -22/01

EDITORIAL

Number: 1270 797

File number: P 12 70 797.0-43

1270 797 filing date; September 29, 1965

Opening day: June 20, 1968

Several attempts have been made to make combustible plastics flame-retardant equip. Thus, chlorinated hydrocarbons, together with salts of metals, became the V group of the periodic table and esters of halophenols with organic acids as fire retardant additives used. However, mixtures of this type tend to be at the elevated processing temperatures that are usually customary to thermal decomposition reactions which, depending on the duration of the temperature stress, the damage the mechanical and optical properties of the plastic.

Other flame retardants, such as nuclear chlorinated or brominated diaromatic or aromatic-aliphatic ones Ether or nuclear brominated anilines which, in combination with antimony trioxide, are especially mixed with polyolefins show emigration during storage with the formation of efflorescence on the products made with them self-extinguishing molding compounds.

Additions of compounds play a special role in flame-retardant plastic mixtures of metals of group V of the periodic table, in particular of antimony trioxide. These However, metal compounds are not effective on their own, but only in combination with halogen, with the antimony oxyhalide can then form as an extinguishing agent during a fire.

The subject of the invention is the use of compounds of the general formula

Si-R ₄

in an amount of 1 to 35 percent by weight, based on the plastic without additives, to reduce the flammability of plastics, where R is one, two or three

- O - II groups,

the remaining R are optionally substituted, aliphatic, cycloaliphatic or aromatic radicals, X is fluorine, chlorine and / or bromine atoms and η is 2 to 5.

The aliphatic radicals can be straight-chain or branched and e.g. ethyl, amyl, decyl, isopropyl, Isobutyl or the like. Cycloaliphatic radicals include, for example, cyclopentyl, cyclohexyl, cyclododecyl or like groups understood. Aromatic radicals are e.g. phenyl, naphthyl or like groups. The substituents are alkyl, aralkyl, aryl, endo-methylene, alkyl ether, Oxalkyl, aryl, oxy, silyl or the like groups reduce the flammability of Plastics

Applicant:

Dynamit Nobel Aktiengesellschaft, 5210 Troisdorf

Named as inventor:

Dr. Roshdy Ismail,

Dr. Hans-Joachim Kötzsch,

Dr. Gerhard Bier, 5210 Troisdorf

in question, it being possible for one to three substituents to occur as a rule. Suitable plastics are, for. B. Soft PVC, homopolymers or copolymers of olefins, polystyrene, copolymers of styrene with acrylonitrile and / or butadiene, polymethacrylates, alkyd resins, ethyl cellulose, acetyl cellulose, polyester resins, Epoxy resins, polybutadienes, polyisoprenes, polyphenylene oxides, corresponding plastic mixtures or the like

As flame-retardant additives according to the invention, for. B. the following connections are mentioned:

Cyclohexyl-tri- (pentachlorophenoxy) -silane, cyclohexen- (3) -yl-tri - (pentachlorophenoxy) -silane, Decyl-tri- (pentachlorophenoxy) -silane, y-chloropropyl-tri- (pentachlorophenoxy) -silane, Amyl-tri- (pentachlorophenoxy) -silane, phenyl-tri- (pentachlorophenoxy) -silane, toluyl-tri- (pentachlorophenoxy) -silane, Cyclohexyl-tri- (pentabromophenoxy) -silane, Cyclohexen- (3) -yl-tri- (pentabromophenoxy) -silane, Decyl-tri- (pentabromophenoxy) -silane, y-chloropropyl-tri- (pentabromophenoxy) -silane, amyl-tri- (pentabromophenoxy) -silane, Phenyl-tri- (pentabromophenoxy) -silane, toluyl-tri- (pentabromophenoxy) -silane, 1,4,5,6,7,7-hexachlorobicyclo- (2,2,1) -hepten- (5) -yl- (2) -tri- (pentachlorophenoxy) -silane, Dimethyl-di- (pentachlorophenoxy) -silane, diphenyl-di- (pentachlorophenoxy) -silane, dimethyl-di- (2,3,4,5-tetrachlorophenoxy) -silane, Diphenyl-di- (2,3,4,5-tetrachlorophenoxy) -silane, 1,2-di- (tris-pentachlorophenoxysilyl) -ethane, 1,2-di (tris-2,4,6-tribromophenoxysilyl) ethane,

809 560/503

Claims (1)

l, 2-di- (tris-tricMorphenoxysilyl) -ethane, l- (Tris-pentacMorphenoxysiIyl) -2- (methyl-bis- pentachlorophenoxysilyl) ethane, l, 2 ₅ 4-tri-j8- (tris-pentachlorophenoxysilyl) -ethyl- cyclohexane, Di- (tris-pentacMorphenoxysilyl) -5,8-endomethylene-perhydroindane,
Di- (tris-pentachlorophenoxysilyl) -benzene,
Di-jö- (tris-pentaclilorphenoxysilyl) -ethylbenzene. IO These substances can be prepared by process ₅ , which is not claimed here, for example by reacting organofunctional silicon compounds with the corresponding phenols, for example organo-halogen-sulfide compounds in a solution of hydrocarbons at elevated temperature in the presence of catalytic amounts of a tertiary amine that forms thermally unstable hydrochlorides . By varying the organo the flame retardants can the very different properties ao be matched transactions of different plastics, with regard to the compatibility gellability, even at relatively low temperatures. Optionally, the fire retardant additives according to the invention can also be used in combination with 1 to 20 percent by weight of plastic with oxides and / or sulfides of antimony and / or bismuth and other fire retardants, e.g. B. chlorinated paraffins can be used. The molding compositions can also contain other customary additives, such as plasticizers, heat and light stabilizers, lubricants and fillers, such as carbon black, zinc oxide or sulfide, titanium oxide, etc. The fire retardant additives of the present invention are among those required for most materials increased processing temperatures in contrast to the previously known flame retardants absolute stable. This surprisingly good heat resistance makes additional heat stabilization in general superfluous. However, if particularly high processing temperatures are used, e.g. for the thermoplastic processing of polyphenylene oxide-containing molding compounds, an additional Stabilization with common polyvinyl chloride stabilizers, such as barium, cadmium, tin or lead compounds, or with bisphenol A. The incorporation of the flame-retardant additives, if appropriate together with further additives, can be carried out by customary methods, for example in a kneader, on a roll or by pre-extrusion. It is advantageous to preheat the components to 120 ° C before combining. The molding compounds produced in this way were processed into rods measuring 100-20-1 mm on a piston injection molding machine. To test the self-extinguishing properties, these sprayed rods were placed vertically in a 4 cm high, non-luminous Bunsen flame in a draft-free room for 10 seconds. held. The after-burning time from the removal of the gas flame to the extinction of the test specimen was measured. example 1 80 parts of polyphenylene oxide with a reduced viscosity of 0.7, 20 parts of polystyrene, 10 parts of 1,2-di- (trispentachlorophenoxysilyl) -ethane, 4 parts of antimony trioxide, 1 part of titanium dioxide and 2 parts of bisphenol A were preheated to 120 ° C. and placed in a laboratory mixer mixed. The mixture was extruded and granulated. The granules became test specimens of the same size 100 - 20-1 mm processed. All of ten samples extinguished immediately in the fire test. Example 2 From 100 parts of polystyrene, 15 parts of cyclohexyltri- (phenabromophenoxy) -silane and 8 parts of antimony trioxide Sample injection molds were produced analogously to Example 1. All ten samples examined in the burn test went out immediately. Example 3 From 100 parts of high pressure polyethylene, 17 parts of 1,2 - di - (tris - 2,4,6 - tribromophenoxysilyl) - ethane and 12 parts of antimony trioxide were prepared analogously to Example 1 sample moldings. Of ten samples went out five after 2 seconds and five after 4 seconds. Example 4 From 100 parts of an ethylene-propylene copolymer, 20 parts of dimethyl-di (pentachlorophenoxy) -silane and IOTeiIen antimony trioxide were prepared analogously to sample moldings. Every ten samples went out after 3 seconds. Example 5 From 60 parts of polyvinyl chloride, produced by the emulsion process, 40 parts of dioctyl phthalate, 1 part of Ba-Cd laurate, 14 parts of decyl-tri- (pentachlorophenoxy) -silane and 6 parts of antimony trioxide were analogously to Example 1 test moldings produced. Out of ten samples, three extinguished after 2 seconds, three after 4 seconds and four after 8 seconds. Claim: Use of compounds of general formula Si-R ₄ In .ein an amount of 1 to 35 percent by weight based on the plastic without surcharges for Decrease the flammability of plastics, where R is one, two or three / X X _ji -O- -Groups, the remaining R are optionally substituted, aliphatic, cycloaliphatic or aromatic Radicals, X fluorine, chlorine and / or bromine atoms and η 2 to 5 mean.