CA1145083A - Fire-retardant polystyrenic compositions - Google Patents
Fire-retardant polystyrenic compositionsInfo
- Publication number
- CA1145083A CA1145083A CA000345834A CA345834A CA1145083A CA 1145083 A CA1145083 A CA 1145083A CA 000345834 A CA000345834 A CA 000345834A CA 345834 A CA345834 A CA 345834A CA 1145083 A CA1145083 A CA 1145083A
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- alkyl radical
- composition
- fire
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Disclosed is a self-extinguishing polystyrenic composition comprising a polystyrenic resin, a fire-re-tardant amount of a halogenated organic fire-retardant agent and a nitrogen-containing organic compound selected from the group consisting of amines, amides and ammonium compounds containing from 20 to 40 carbon atoms and their mixtures, said nitrogen-containing compound being used in an amount varying between 0.5 and 50% based on the weight of fire-retardant agent.
Disclosed is a self-extinguishing polystyrenic composition comprising a polystyrenic resin, a fire-re-tardant amount of a halogenated organic fire-retardant agent and a nitrogen-containing organic compound selected from the group consisting of amines, amides and ammonium compounds containing from 20 to 40 carbon atoms and their mixtures, said nitrogen-containing compound being used in an amount varying between 0.5 and 50% based on the weight of fire-retardant agent.
Description
~45~38~3 FIRE-RETARDANT POLYSTYRENIC COMPSOITIONS
BACKGROUND OF THE INVENTION
This invention relates to fire-retardant polystyrenic compositions.
For many uses, fire-retardant agents may be in-corporated into polystyrenic resins, such as polystyrene, styrene-acrylonitrile copolymers (known as SAN resins3, acrylonitrile-butadiene-styrene copolymers (known as ABS
resins), high impact polystyrenes and the like, to impart fire-resistance to such resins. Organic compounds containing bromine and/or chlorine are frequently employed as ~ire-retardant agents. However, large amounts of fire-retardant agents are often required to obtain polystyrenic compositions which fulfill specifications relating to flame propagation;
and these large amounts are detrimental for other properties of the polystyrenic compositions, such as tensile strength and thermal stability.
With a view toward decreasing the amount of fire-retardant agent which must be added to such resins, the synergistic action of some additives (or synergistic compounds) which, when used alone, do not ac~ as fire-retardant agents, has been contemplated. Organic peroxides have been suggested as synergistic compounds, but they have several drawbacks, more particularly with respect to toxicity and stability.
U.S. Patent No. 4,092,281 to the above-named inventor discloses certain nitrogen-containing synergistic compounds for use in fire-retardant polystyrenic compositions. The present invention represents an improvement thereover.
~52~
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide new and improved fire-retardant styrenic polymer compositions.
Another object of the present invention is to pro-vide new fire-retardant polystyrenic compositions comprising a polystyrenic resin, a halogenated organic fire-retardant agent and a new synergistic compound.
A further object of the present invention is to provide polystyrenic compositions which obviate the above-mentioned drawbacks.
Still another object of the invention resides in providing new synergistic compounds which are very active.
In accomplishing these objects, there has been provided according to one embodiment of the present invention, a polystyrenic composition comprising a polystyrenic polymer, a halogenated organic fire-retardant agent and a nitrogen-containing organic compound selected from the group consisting of amines, amides and ammonium compounds containing from 20 to 40 carbon atoms and other mixtures, said nitrogen-contain-ing organic compound being used in an amount varying between 0.5 and 50% based on the weight of fire-retardant agent.
Thus, in accordance with the present teachings, a self-extinguishing polystyrenic composition is provided which comprises a homogeneous combination of a polystyrenic resin, a fire-retardant amount of a halogenated organic fire-retardant agent and a nitrogen-containing organic compound containing from about 20 to 40 carbon atoms and being selected from a) a secondary or tertiary amine having the formula NtRl~ (R21 R3~, wherein Rl is ~ or an alkyl radical containing from 9 to 18 carbon atoms and R2 and R3, which may be the same or different, are each an alkyl radical containing from 9 to 18 ~5~
~2a-carbon atoms;
b~ an alkylene-bis-fatty acid amide containing at least 26 carbon atoms wherein the alkylene group contains 1 to 5 carbon atoms;
c~ an ammonium compound ~elected from ci~ an alkylpyridinium bromide of the formula ~ R4 - ~ )N ~ ~ Br( )~
wherein R4 is an alkyl radical containing at least 15 carbon atoms, or cii) an ammonium compound of the ~ormula rR6 N (+)~. R ~ X~~) wherein R5 and R7 are methyl radicals, and 1.) R6 iæ an alkyl radical ~ontaining at least 9 carbon atoms or a dialkyl-phenoxy-ethQxyethyl radical/ R8 is an alkyl radical containing at least 9 carbon atoms or a benzyl radical, and X is Cl or Br; or
BACKGROUND OF THE INVENTION
This invention relates to fire-retardant polystyrenic compositions.
For many uses, fire-retardant agents may be in-corporated into polystyrenic resins, such as polystyrene, styrene-acrylonitrile copolymers (known as SAN resins3, acrylonitrile-butadiene-styrene copolymers (known as ABS
resins), high impact polystyrenes and the like, to impart fire-resistance to such resins. Organic compounds containing bromine and/or chlorine are frequently employed as ~ire-retardant agents. However, large amounts of fire-retardant agents are often required to obtain polystyrenic compositions which fulfill specifications relating to flame propagation;
and these large amounts are detrimental for other properties of the polystyrenic compositions, such as tensile strength and thermal stability.
With a view toward decreasing the amount of fire-retardant agent which must be added to such resins, the synergistic action of some additives (or synergistic compounds) which, when used alone, do not ac~ as fire-retardant agents, has been contemplated. Organic peroxides have been suggested as synergistic compounds, but they have several drawbacks, more particularly with respect to toxicity and stability.
U.S. Patent No. 4,092,281 to the above-named inventor discloses certain nitrogen-containing synergistic compounds for use in fire-retardant polystyrenic compositions. The present invention represents an improvement thereover.
~52~
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide new and improved fire-retardant styrenic polymer compositions.
Another object of the present invention is to pro-vide new fire-retardant polystyrenic compositions comprising a polystyrenic resin, a halogenated organic fire-retardant agent and a new synergistic compound.
A further object of the present invention is to provide polystyrenic compositions which obviate the above-mentioned drawbacks.
Still another object of the invention resides in providing new synergistic compounds which are very active.
In accomplishing these objects, there has been provided according to one embodiment of the present invention, a polystyrenic composition comprising a polystyrenic polymer, a halogenated organic fire-retardant agent and a nitrogen-containing organic compound selected from the group consisting of amines, amides and ammonium compounds containing from 20 to 40 carbon atoms and other mixtures, said nitrogen-contain-ing organic compound being used in an amount varying between 0.5 and 50% based on the weight of fire-retardant agent.
Thus, in accordance with the present teachings, a self-extinguishing polystyrenic composition is provided which comprises a homogeneous combination of a polystyrenic resin, a fire-retardant amount of a halogenated organic fire-retardant agent and a nitrogen-containing organic compound containing from about 20 to 40 carbon atoms and being selected from a) a secondary or tertiary amine having the formula NtRl~ (R21 R3~, wherein Rl is ~ or an alkyl radical containing from 9 to 18 carbon atoms and R2 and R3, which may be the same or different, are each an alkyl radical containing from 9 to 18 ~5~
~2a-carbon atoms;
b~ an alkylene-bis-fatty acid amide containing at least 26 carbon atoms wherein the alkylene group contains 1 to 5 carbon atoms;
c~ an ammonium compound ~elected from ci~ an alkylpyridinium bromide of the formula ~ R4 - ~ )N ~ ~ Br( )~
wherein R4 is an alkyl radical containing at least 15 carbon atoms, or cii) an ammonium compound of the ~ormula rR6 N (+)~. R ~ X~~) wherein R5 and R7 are methyl radicals, and 1.) R6 iæ an alkyl radical ~ontaining at least 9 carbon atoms or a dialkyl-phenoxy-ethQxyethyl radical/ R8 is an alkyl radical containing at least 9 carbon atoms or a benzyl radical, and X is Cl or Br; or
2.) R6 is an alkyl radical containing at least 4 carbon atoms, R8 is H, and X is an alkyl~ulfate group wherein the alkyl contains at least 12 carbon atoms, or d) a mixture thereof said nitrogen-containing compound being present in an amount between a~out 0.5 and 50~ ba ed on the weight of the ~ire-retardant agent.
In another embodiment, the present invention provides a fire-retardant composition for u~e in combination with poly-styrenic resins, said compo~ition containing a halogenated or-ganic fire-retardant agent and a nitrogan-containing organic compound as hereinabove specified.
~S~8~
-2b-DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
POlystyrenic resins" include not only styrene homopolymers, such as crystal polystyrene, but also sty-rene-based cGpolymers containing a major amount of styrene, such as ABS resins, SAN resins and high-impact polystyrenes containing an elastomer, such as rubber, in an amount which may reach as much as about 15% by weight. The inventiOn applies also to expanded polystyrene, which may be produced either by molding expandable beads of polystyrene or by extruding mixtures of polystyrene and a blowing agent. It has been found that expanded polystyrene produced by extruding polystyrenic resins in the presence of a blowing agent together with a nitrogen-containing compound of the present invention have cells the average size of which is substantially lower when compared with similar expanded polystyrenes produced in the absence of such a nitrogen-containing compound. For instance, the size of the cells of an expanded polystyrene produced in the presence of an ammonium compound of the present invention varies between about 80 to 100 microns, whereas the size of the cells is about 200 microns when the ammonium compound is not used. As a result, the expanded polysiyrenes prepared from the compositions of the present invention have a lower density and improved self-extinguishing properties, and they are therefore particularly advantageous for many uses.
The flame-retardant agent is a halo~enated organic compound more particularly a brominated and/or chlorinated or~anic compound.
These halogenated compounds are generally used in an amount such that the halogen-content in the polystyrenic composition is at least about 0.2~. Contents higher than about 15% do not bring any advantage. More generally, the halogen-content in the final polystyrenic composition lies between about 0.5 and 10~ by weight. This amount depends mainly on the kind of halogenated fire-retardant agent: brominated compounds are generally more 2Q active than the corresponding chlorinated compounds and they may therefore be used in lower amounts. These agents and their use are well known in the art. Typical halogenated fire-retardant agents are acetylene tetrabromide, dibromotetrachloroethane, tetrachloro-ethane, pentachloroethane, hexachloro- or hexabromobenzene, tetrabromobutane, polyhalobiphenyls, polyhalobiphenylethers, perhalopentacyclododecanes, pentabromochlorocyclohexane, solid and liquid chlorinated paraffins and the 1~5~ 8~3 like and mixtures thereof.
The nitrogen-CQntainingorganic compounds of this in~ention are synergis~ic compounds for the halogenated organic compounds which are used as fire-retardant agents for polystyrenic resins.
These nitrogen-containing compounds are amines, amides or ammonium compounds eontaining from about 20 to about 40 carbon atoms and preferably from 26 to 40 carbon atoms. They are very acti~e synergistic compounds and they are generally used in an amount which may vary between `about 0.5% and about 50~, based on the weight of fire-retardant agent~ This amount depends on the type of fire retardant agent and on the type of nitrogen-containing compound. Generally, the synergistic compound may be used in an amount comprised between about 0.02 and 2% by weight of poly-styrenic resin.
The choice of the nitrogen-containing organic compound depends mainly on its price and its availability. Particularly advantageous nitrogen-containing compounds are:
a) secondary and tertiary amines having the general formula N~Rl) (R2) (R3), wherein Rl is H or an alkyl radical containing from 9 to 18 carbon atoms and R2 and R3, which may or may not be the same, are each an alkyl radical containing from 9 to 18 earbon atoms;
b) fatty acid amides eontaining more than 25 carbon atoms, more partieularly, alkylene-bis-amides, preferably lower alkylene-bis-amides and most preferably alkylene-bis-amides ~herein the alkylene ~roup eontains 1 to 5 earbon atoms, sueh as ethylene-bis-stearylamide and similar, e) ammonium compounds, such as ei) alkylpyridinium bromides of the formula [R4- ( ) N ~ ~ Br, wherein R4 is an alkyl radical eontaining at least 15 carbon atomsl or X
cii) ammonium compounds of the general foxmula r R5 R6 - I 8 X , wherein X is Cl, Br or R7 , L
alkylsulfate and the radicals R5 to R8 axe H oX
radicals con~ain,in.g from l to 18 carbon atoms, the total of the carbon,a,toms o the am~oni~m.compou~d being at least 20. By wa.~ of example, thexe may be mentioned the follo~ing preferred ammonium compounds wherein l.) R5 and R7 are methyl radicalsi R6 is an alkyl ra.dica.l containing at least 9 carbon atoms, such as lauryl or stearyl; R8 is the same as R6 or is a benzyl radi.cal~
and X is Cl or Br~
2.) R5 and R7 are methyl radicals; R6 is a dialkyl-phenoxyethoxyethyl radical, preferably,diisobutyl-.
phenoxy-ethoxyethyl; R8 is a benzyl radical L and X.
is Cl or Br~
In another embodiment, the present invention provides a fire-retardant composition for u~e in combination with poly-styrenic resins, said compo~ition containing a halogenated or-ganic fire-retardant agent and a nitrogan-containing organic compound as hereinabove specified.
~S~8~
-2b-DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
POlystyrenic resins" include not only styrene homopolymers, such as crystal polystyrene, but also sty-rene-based cGpolymers containing a major amount of styrene, such as ABS resins, SAN resins and high-impact polystyrenes containing an elastomer, such as rubber, in an amount which may reach as much as about 15% by weight. The inventiOn applies also to expanded polystyrene, which may be produced either by molding expandable beads of polystyrene or by extruding mixtures of polystyrene and a blowing agent. It has been found that expanded polystyrene produced by extruding polystyrenic resins in the presence of a blowing agent together with a nitrogen-containing compound of the present invention have cells the average size of which is substantially lower when compared with similar expanded polystyrenes produced in the absence of such a nitrogen-containing compound. For instance, the size of the cells of an expanded polystyrene produced in the presence of an ammonium compound of the present invention varies between about 80 to 100 microns, whereas the size of the cells is about 200 microns when the ammonium compound is not used. As a result, the expanded polysiyrenes prepared from the compositions of the present invention have a lower density and improved self-extinguishing properties, and they are therefore particularly advantageous for many uses.
The flame-retardant agent is a halo~enated organic compound more particularly a brominated and/or chlorinated or~anic compound.
These halogenated compounds are generally used in an amount such that the halogen-content in the polystyrenic composition is at least about 0.2~. Contents higher than about 15% do not bring any advantage. More generally, the halogen-content in the final polystyrenic composition lies between about 0.5 and 10~ by weight. This amount depends mainly on the kind of halogenated fire-retardant agent: brominated compounds are generally more 2Q active than the corresponding chlorinated compounds and they may therefore be used in lower amounts. These agents and their use are well known in the art. Typical halogenated fire-retardant agents are acetylene tetrabromide, dibromotetrachloroethane, tetrachloro-ethane, pentachloroethane, hexachloro- or hexabromobenzene, tetrabromobutane, polyhalobiphenyls, polyhalobiphenylethers, perhalopentacyclododecanes, pentabromochlorocyclohexane, solid and liquid chlorinated paraffins and the 1~5~ 8~3 like and mixtures thereof.
The nitrogen-CQntainingorganic compounds of this in~ention are synergis~ic compounds for the halogenated organic compounds which are used as fire-retardant agents for polystyrenic resins.
These nitrogen-containing compounds are amines, amides or ammonium compounds eontaining from about 20 to about 40 carbon atoms and preferably from 26 to 40 carbon atoms. They are very acti~e synergistic compounds and they are generally used in an amount which may vary between `about 0.5% and about 50~, based on the weight of fire-retardant agent~ This amount depends on the type of fire retardant agent and on the type of nitrogen-containing compound. Generally, the synergistic compound may be used in an amount comprised between about 0.02 and 2% by weight of poly-styrenic resin.
The choice of the nitrogen-containing organic compound depends mainly on its price and its availability. Particularly advantageous nitrogen-containing compounds are:
a) secondary and tertiary amines having the general formula N~Rl) (R2) (R3), wherein Rl is H or an alkyl radical containing from 9 to 18 carbon atoms and R2 and R3, which may or may not be the same, are each an alkyl radical containing from 9 to 18 earbon atoms;
b) fatty acid amides eontaining more than 25 carbon atoms, more partieularly, alkylene-bis-amides, preferably lower alkylene-bis-amides and most preferably alkylene-bis-amides ~herein the alkylene ~roup eontains 1 to 5 earbon atoms, sueh as ethylene-bis-stearylamide and similar, e) ammonium compounds, such as ei) alkylpyridinium bromides of the formula [R4- ( ) N ~ ~ Br, wherein R4 is an alkyl radical eontaining at least 15 carbon atomsl or X
cii) ammonium compounds of the general foxmula r R5 R6 - I 8 X , wherein X is Cl, Br or R7 , L
alkylsulfate and the radicals R5 to R8 axe H oX
radicals con~ain,in.g from l to 18 carbon atoms, the total of the carbon,a,toms o the am~oni~m.compou~d being at least 20. By wa.~ of example, thexe may be mentioned the follo~ing preferred ammonium compounds wherein l.) R5 and R7 are methyl radicalsi R6 is an alkyl ra.dica.l containing at least 9 carbon atoms, such as lauryl or stearyl; R8 is the same as R6 or is a benzyl radi.cal~
and X is Cl or Br~
2.) R5 and R7 are methyl radicals; R6 is a dialkyl-phenoxyethoxyethyl radical, preferably,diisobutyl-.
phenoxy-ethoxyethyl; R8 is a benzyl radical L and X.
is Cl or Br~
3.) R5 and R7 are methyl radicalsi R6 is an a.lkyl radica.l containing at least 4 carbon atoms, such as butyl or hexyl~ R8 is H; and X is an alkylsul~ate gxoup wherein the alkyl radical contains at lea.st 12 carbon.atoms;.
such as lauryl or stearyl.
The nitrogen-containing organic compounds of ths present invention may be incorporated into the resin by intimately mixing the polystyrenic resin, the fixe-retardant agent, the ni.trogen-containing compound and optionally other usual additi~es, such as dyes, lubricants and the like. The nitrogen-containing compound may also be added to the styrene monomer or monomer and/
or polymer mixture before polymeri~.ation~
X
5~
Some fire-retardant agentsl ~ore particularly the agents which possess a high thermal stability, are advantageously used in admixture with antimony oxide. It has been found that the amount of antimony oxide to be added may be decreased b~ about 50%
below that conventionally employed without detrimental effect on the fire-retardant properties or on the thermal stability of the final polystyrenic composition when a nitrogen-containing compound is incorporated as a synergistic compound into the composition.
The amount of antimony oxide, when used, does not generally exceed 7~ by weight of polystyrenic resin. This amount depends on the kind and amount of fire-retardant agent, and it may vary generally between about 2 and 5%. With other fire-retardant agents, more particularly with halogenated aliphatic compounds, the use of antimony oxide is not required.
The following examples are provided to illustrate the features of the present invention, without in any way limiting the invention.
The sel~-extinguishing properties of the polystyrenic compositions are determined with the use of specimens measuring ~ 12.70 x 1.27 x 0.32 cm, according to the following test:
Each specimen is hung, the larger dimension being vertical and the distance between the lower end of the specimen and the upper end of the burner being 0.95 cm. The burner is lighted and the flame has a height of 1.9 cm. Air is premixed with the gas in order to avoid any yellow tip at the top of the flame.
This flame is disposed under the lower end of the specimen for a period of 10 seconds. The burner is then remo~ed and the flaming combustion time is measured. Immediately after extinction, the flame is again disposed under the specimen for a period of 10 seconds. The burner is then removed,and the flaming combustion time is again measured. The data given in the examples are the average of 20 successive tests (10 specimens and 2 determinations fo~ each specimen). In the case of foamed polystyrene, the same procedure is. used, except the fla~e i.s disposed under the specimen.on.ly 1 time and for a period of 3 seconds.
Unless otherwise expressed, the weight percenta.ges are based on the weight of total composition.
Compsitions are prepared from.crystal polystyrene,0.75%
pentabromomonochlorocyclohexane, 0.05~ di-tert-butyl-hydroxy-toluene (BHT), 0.035% zinc stearate and 0.20% of the following synergistic compounds.
The self-extinguishing times are as follows:
Synergistic compound Flaming combustion time (in seconds) Stearyl-dimethyl-benzyl ammonium chloride 0.42 Distearyl dimethyl ammonium chloride 0.44 Dilauryl dimethyl ammonium bromide 0.23 Diisobutyl-phenoxy-ethoxy-ethyl-di-methylbenzyl ammonium chloride monohydrate 0~51 Cetylpyridinium bromide 2.07 Ethylene-bis-stearylamide 0.87 ~5 Distearylamine 0.54 ~rilaurylamine 0~80 Hexyl-dimethyl-ammonium stearyl-sulfate 0.44 A similar composition but without any synergistic compound has a flaming combustion time of 11.71 seconds.
Compositions are prepared from crystal polystyrene, 0.05%
BHT, 0.035% zinc stearate, and a fire-retardant agent (for the type and amount, see the following table?, dilauryl-dimethyl-ammonium chloride as the synergistic compound (for the amount,see the fo~lo~-ing table) .,, . .. . ... , v . . . ~
5~8~
Fire-retardant agent Amount of Amount of Flaming com-Sb O (%) synergistic bustion time 2 3 cmpd. (%) (in seconds~
Acetylene tetrabromide (0.75%) o 0.20 0.49 Dibromotetrachloro-ethane (0.75%3 0 0.20 1.24 Pentachloroethane ` (0.75%) 0 0.10 9.17 Tetrabromobutene (~.75~) 0 0.05 1.58 Example 2B
Compositions are prepared from high impact polystyrene (containing 6% rubber~, 0.05~ 8HT, 0.035% zinc stearate, and a fire-retardant agent (for the type and amount, see the following table), dilauryl-dimethyl-ammonium chloride as the synergistic compound (for the amount, see the following table), and antimony oxide Sb203 (for the amount, see the following table):
- Fire-retardant agent Amount of Amount of Flaming com-Sb O (~) synergistic bustion time 2 3 cmpd. (%) (in seconds) Hexabromobenzene tlO~) 3 0.05 1.24 Polybromo biphenyl-ether (10~) 3 2.00 0.97 Perchloropentacyclodo-decane (15%) 3 2.00 1.12 Perchloropentacyclodo-decane (10%) 3 2~00 3.17 Polystyrene is prepared by suspension polymerization of styrene in the presence of pentabromomonochlorocyclohexane ~1%) and distearyl-dimethyl-ammonium chloride (0.15%). The beads of polystyrene are washed with water and then kept under ~acuum at '~
75'~C for one ~ight.
The flaming combustion time o~ specimens produced from this polystyrene is 0,46 seconds~
~XAMPL~ 4 A composition is prepared from high~impact polystyrene (containing 5~ of rubber), 10% decabromobiphenyl, 3% Sb203 and 0.5% trilaurylamine.
The flaming combustion time is 1.10 seconds.
A similar composition but without the fatty amine has a flaming combustion time of 2.18 seconds.
Specimens of expanded polystyrene are prepared by injection molding expandable beads of polystyrene (containing pPntane as ~he blowing agent). Pentabromomonochlorocyclohexane (1.5%) and dilauryl-dimethyl ammonium chloride (0.2%) are added to these beads.
The flaming combustion time is 0.70 seconds (as compared with 3.21 seconds in the absence of the ammonium compound).
Specimens of expand~ed polystyrene are prepared by extruding polystyrene in the presence of a blowing mixture (containing equal weights of CF2C12 and CFC13?, 3% pentabromomonochloro-cyclohexane and 0.1% distearyl-dimethyl ammonium chloride.
The flaming combustion time is 1.10 seconds. The cells of ~5 the expanded polystyrene have an average size of 80 microns, and the density of the final product is 35 kg/m .
A similar product but prepared without the ammonium compound has the following properties:
flaming combustion time: 4.38 seconds cell size : 200 microns density : 39 kg/m .
8~
A composition is prepared from crystal polystyrene, 5%
chlorinated para~fin (average of 25 carbon atoms and chlorine-content = 70%), 0.1% BHT, 0.035% zinc stearate and 0.2% distearyl-dimethyl-ammonium chloride.
The flaming combustion time is 10.6 seconds.
A similar composition but without ammonium compound has a flaming combustion time higher than 60 seconds.
A composition is prepared from ABS rPsin (con~aining 7 butadiene and 17% acrylonitrile), 12% decabromodiphenyloxide, 5% Sb203 and 2% distearyl-dimethyl-ammonium chloride.
The flaming combustion time is 1.17 seconds.
A similar composition but without ammonium compound has a flaming combustion time of 3.48 seconds.
such as lauryl or stearyl.
The nitrogen-containing organic compounds of ths present invention may be incorporated into the resin by intimately mixing the polystyrenic resin, the fixe-retardant agent, the ni.trogen-containing compound and optionally other usual additi~es, such as dyes, lubricants and the like. The nitrogen-containing compound may also be added to the styrene monomer or monomer and/
or polymer mixture before polymeri~.ation~
X
5~
Some fire-retardant agentsl ~ore particularly the agents which possess a high thermal stability, are advantageously used in admixture with antimony oxide. It has been found that the amount of antimony oxide to be added may be decreased b~ about 50%
below that conventionally employed without detrimental effect on the fire-retardant properties or on the thermal stability of the final polystyrenic composition when a nitrogen-containing compound is incorporated as a synergistic compound into the composition.
The amount of antimony oxide, when used, does not generally exceed 7~ by weight of polystyrenic resin. This amount depends on the kind and amount of fire-retardant agent, and it may vary generally between about 2 and 5%. With other fire-retardant agents, more particularly with halogenated aliphatic compounds, the use of antimony oxide is not required.
The following examples are provided to illustrate the features of the present invention, without in any way limiting the invention.
The sel~-extinguishing properties of the polystyrenic compositions are determined with the use of specimens measuring ~ 12.70 x 1.27 x 0.32 cm, according to the following test:
Each specimen is hung, the larger dimension being vertical and the distance between the lower end of the specimen and the upper end of the burner being 0.95 cm. The burner is lighted and the flame has a height of 1.9 cm. Air is premixed with the gas in order to avoid any yellow tip at the top of the flame.
This flame is disposed under the lower end of the specimen for a period of 10 seconds. The burner is then remo~ed and the flaming combustion time is measured. Immediately after extinction, the flame is again disposed under the specimen for a period of 10 seconds. The burner is then removed,and the flaming combustion time is again measured. The data given in the examples are the average of 20 successive tests (10 specimens and 2 determinations fo~ each specimen). In the case of foamed polystyrene, the same procedure is. used, except the fla~e i.s disposed under the specimen.on.ly 1 time and for a period of 3 seconds.
Unless otherwise expressed, the weight percenta.ges are based on the weight of total composition.
Compsitions are prepared from.crystal polystyrene,0.75%
pentabromomonochlorocyclohexane, 0.05~ di-tert-butyl-hydroxy-toluene (BHT), 0.035% zinc stearate and 0.20% of the following synergistic compounds.
The self-extinguishing times are as follows:
Synergistic compound Flaming combustion time (in seconds) Stearyl-dimethyl-benzyl ammonium chloride 0.42 Distearyl dimethyl ammonium chloride 0.44 Dilauryl dimethyl ammonium bromide 0.23 Diisobutyl-phenoxy-ethoxy-ethyl-di-methylbenzyl ammonium chloride monohydrate 0~51 Cetylpyridinium bromide 2.07 Ethylene-bis-stearylamide 0.87 ~5 Distearylamine 0.54 ~rilaurylamine 0~80 Hexyl-dimethyl-ammonium stearyl-sulfate 0.44 A similar composition but without any synergistic compound has a flaming combustion time of 11.71 seconds.
Compositions are prepared from crystal polystyrene, 0.05%
BHT, 0.035% zinc stearate, and a fire-retardant agent (for the type and amount, see the following table?, dilauryl-dimethyl-ammonium chloride as the synergistic compound (for the amount,see the fo~lo~-ing table) .,, . .. . ... , v . . . ~
5~8~
Fire-retardant agent Amount of Amount of Flaming com-Sb O (%) synergistic bustion time 2 3 cmpd. (%) (in seconds~
Acetylene tetrabromide (0.75%) o 0.20 0.49 Dibromotetrachloro-ethane (0.75%3 0 0.20 1.24 Pentachloroethane ` (0.75%) 0 0.10 9.17 Tetrabromobutene (~.75~) 0 0.05 1.58 Example 2B
Compositions are prepared from high impact polystyrene (containing 6% rubber~, 0.05~ 8HT, 0.035% zinc stearate, and a fire-retardant agent (for the type and amount, see the following table), dilauryl-dimethyl-ammonium chloride as the synergistic compound (for the amount, see the following table), and antimony oxide Sb203 (for the amount, see the following table):
- Fire-retardant agent Amount of Amount of Flaming com-Sb O (~) synergistic bustion time 2 3 cmpd. (%) (in seconds) Hexabromobenzene tlO~) 3 0.05 1.24 Polybromo biphenyl-ether (10~) 3 2.00 0.97 Perchloropentacyclodo-decane (15%) 3 2.00 1.12 Perchloropentacyclodo-decane (10%) 3 2~00 3.17 Polystyrene is prepared by suspension polymerization of styrene in the presence of pentabromomonochlorocyclohexane ~1%) and distearyl-dimethyl-ammonium chloride (0.15%). The beads of polystyrene are washed with water and then kept under ~acuum at '~
75'~C for one ~ight.
The flaming combustion time o~ specimens produced from this polystyrene is 0,46 seconds~
~XAMPL~ 4 A composition is prepared from high~impact polystyrene (containing 5~ of rubber), 10% decabromobiphenyl, 3% Sb203 and 0.5% trilaurylamine.
The flaming combustion time is 1.10 seconds.
A similar composition but without the fatty amine has a flaming combustion time of 2.18 seconds.
Specimens of expanded polystyrene are prepared by injection molding expandable beads of polystyrene (containing pPntane as ~he blowing agent). Pentabromomonochlorocyclohexane (1.5%) and dilauryl-dimethyl ammonium chloride (0.2%) are added to these beads.
The flaming combustion time is 0.70 seconds (as compared with 3.21 seconds in the absence of the ammonium compound).
Specimens of expand~ed polystyrene are prepared by extruding polystyrene in the presence of a blowing mixture (containing equal weights of CF2C12 and CFC13?, 3% pentabromomonochloro-cyclohexane and 0.1% distearyl-dimethyl ammonium chloride.
The flaming combustion time is 1.10 seconds. The cells of ~5 the expanded polystyrene have an average size of 80 microns, and the density of the final product is 35 kg/m .
A similar product but prepared without the ammonium compound has the following properties:
flaming combustion time: 4.38 seconds cell size : 200 microns density : 39 kg/m .
8~
A composition is prepared from crystal polystyrene, 5%
chlorinated para~fin (average of 25 carbon atoms and chlorine-content = 70%), 0.1% BHT, 0.035% zinc stearate and 0.2% distearyl-dimethyl-ammonium chloride.
The flaming combustion time is 10.6 seconds.
A similar composition but without ammonium compound has a flaming combustion time higher than 60 seconds.
A composition is prepared from ABS rPsin (con~aining 7 butadiene and 17% acrylonitrile), 12% decabromodiphenyloxide, 5% Sb203 and 2% distearyl-dimethyl-ammonium chloride.
The flaming combustion time is 1.17 seconds.
A similar composition but without ammonium compound has a flaming combustion time of 3.48 seconds.
Claims (16)
1 A self-extinguishing polystyrenic composition comprising a homogeneous combination of a polystyrenic resin, a fire-retardant amount of a halogenated organic fire-retardant agent and a nitrogen-containing organic compound containing from about 20 to 40 carbon atoms and being selected from a) a secondary or tertiary amine having the formula N(R1) (R2) (R3), wherein R1 is H or an alkyl radical containing from 9 to 18 carbon atoms and R2 and R3, which may be the same or different, are each an alkyl radical containing from 9 to 18 carbon atoms;
b) an alkylene-bis-fatty acid amide containing at least 26 carbon atoms wherein the alkylene group contains 1 to 5 carbon atoms;
c) an ammonium compound selected from ci) an alkylpyridinium bromide of the formula Br(-), wherein R4 is an alkyl radical containing at least 15 carbon atoms, or cii) an ammonium compound of the formula (-) X
wherein R5 and R7 are methyl radicals, and
1.) R6 is an alkyl radical containing at least 9 carbon atoms or a dialkyl-phenoxy-ethoxyethyl radical, R8 is an alkyl radical containing at least 9 carbon atoms or a benzyl radical, and X is C1 or Br; or 2.) R6 is an alkyl radical containing at least 4 carbon atoms, R8 is H, and X is an alkylsulfate group wherein the alkyl radical contains at least 12 carbon atoms, or d) a mixture thereof, said nitrogen-containing compound being present in an amount between about 0.5 and 50% based on the weight of the fire-retardant agent.
2. The composition of Claim 1, wherein said nitro-gen-containing compound is used in an amount between about 0.01 and 5% by weight of the polystyrenic resin.
3. The composition of Claim 2, wherein the amount of nitrogen-containing compound is comprised between about 0.02 and 2% by weight of the polystyrenic resin.
4. The composition of Claim 1, further comprising antimony oxide in an amount which does not exceed about 7%
by weight of the polystyrenic resin.
by weight of the polystyrenic resin.
5. The composition of Claim 4, wherein the amount of antimony oxide comprises between about 2 and 5% by weight of the polystyrenic resin.
6. The composition of Claim 1, wherein the poly-styrenic resin comprises homopolystyrene or a styrene co-polymer containing a major amount of styrene.
7. The composition of Claim 6, wherein said styrene copolymer comprises an ABS copolymer, a SAN copolymer or a rubber-modified polystyrene.
8. The composition of Claim 1, wherein the poly-styrenic resin comprises an expanded resin.
9. The composition of Claim 1, wherein said fire-retardant agent is acetylene tetrabromide, dibromo-tetrachloroethane, tetrachloroethane, pentachloroethane, hexacloro-or hexabromobenzene, tetrabromobutane, polyhalobiphenyls, polyhalobiphenylethers, perhalopentacyclododecanes, penta-bromomonochlorocyclohexane, a chlorinated paraffin or a mixture thereof.
10. The composition of Claim 1, wherein said nitrogen-containing organic compound comprises a secondary or tertiary amine having the formula N(R1) (R2) (R3), wherein R1 is H or an alkyl radical containing from 9 to 18 carbon atoms and R2 and R3, which may or may not be the same, are each an alkyl radical containing from 9 to 18 carbon atoms.
11. The composition of Claim 1, wherein said nitrogen-containing organic compound comprises an alkylene-bis-fatty acid amide.
12. The composition of Claim 1, wherein said nitrogen-containing organic compound comprises an ammonium compound of the formula , wherein X is Cl, Br or alkyl- sulfate wherein 1.) R5 and R7 are methyl radicals, R6 is an alkyl radical containing at least 9 carbon atoms, R8 is the same as R6 or is a benzyl radical; and X is Cl or Br; or 2.) R5 and R7 are methyl radicals, R6 is a dialkyl-phenoxy-ethoxyethyl radical; R8 is a benzyl radical;
and X is Cl or Br; or 3.) R5 and R7 are methyl radicals, R6 is an alkyl radical containing at least 4 carbon atoms, R8 is H and X is an alkylsulfate group wherein the alkyl radical con-tains at least 12 carbon atoms.
and X is Cl or Br; or 3.) R5 and R7 are methyl radicals, R6 is an alkyl radical containing at least 4 carbon atoms, R8 is H and X is an alkylsulfate group wherein the alkyl radical con-tains at least 12 carbon atoms.
13. The composition of Claim 12, wherein R6 in compound 1.) is lauryl or stearyl.
14. The composition of Claim 12, wherein R6 in compound 3.) is butyl or hexyl and the alkyl radical of the alkylsulfate group is lauryl or stearyl.
15. The composition of Claim 1, wherein said nitrogen-containing compound comprises stearyl-dimethyl-benzyl ammonium chloride, distearyl dimethyl ammonium chloride, dilauryl dimethyl ammonium bromide, diisobutyl-phenoxy-ethoxy-ethyl-dimethylbenzyl ammonium chloride monohydrate, cetylpyridinium bromide, ethylene-bis-stearyl-amide, distearylamine, trilaurylamine, hexyl-dimethyl-ammonium stearyl-sulfate, or dilauryl-dimethyl-ammonium chloride.
16. A fire-retardant composition for use in com-bination with polystyrenic resins, comprising a homogeneous comination of a halogenated organic fire retardant agent and a nitrogen-containing organic compound containing from about 20 to 40 carbon atoms and being selected from a) a secondary or tertiary amine having the formula N(R1) (R2) (R3), wherein R1 is H or an alkyl radical containing from 9 to 18 carbon atoms and R2 and R3, which may be the same or different, are each an alkyl radical containing from 9 to 18 carbon atoms;
b) an alkylene-bis-fatty acid amide containing at least 26 carbon atoms wherein the alkylene group contains 1 to 5 carbon atoms c) an ammonium compound selected from ci) an alkylpyridinium bromide of the formula Br(-), wherein R4 is an alkyl radical containing at least 15 carbon atoms, or cii) an ammonium compound of the formula (-) X
wherein R5 and R7 are methyl radicals, and 1.) R6 is an alkyl radical containing at least 9 carbon atom. or a dialkyl-phenoxy-ethoxyethyl radical, R8 is an alkyl radical containing at least 9 carbon atoms or a benzyl radical, and X is Cl or Br; or 2.) R6 is an alkyl radical containing at least 4 carbon atoms, R8 is H, and X is an alkylsulfate group wherein the alkyl radical contains at least 12 carbon atoms, or d) a mixture thereof, said nitrogen-containing compound being present in an amount between about 0.5 and 50% based on the weight of the fire-retardant agent.
b) an alkylene-bis-fatty acid amide containing at least 26 carbon atoms wherein the alkylene group contains 1 to 5 carbon atoms c) an ammonium compound selected from ci) an alkylpyridinium bromide of the formula Br(-), wherein R4 is an alkyl radical containing at least 15 carbon atoms, or cii) an ammonium compound of the formula (-) X
wherein R5 and R7 are methyl radicals, and 1.) R6 is an alkyl radical containing at least 9 carbon atom. or a dialkyl-phenoxy-ethoxyethyl radical, R8 is an alkyl radical containing at least 9 carbon atoms or a benzyl radical, and X is Cl or Br; or 2.) R6 is an alkyl radical containing at least 4 carbon atoms, R8 is H, and X is an alkylsulfate group wherein the alkyl radical contains at least 12 carbon atoms, or d) a mixture thereof, said nitrogen-containing compound being present in an amount between about 0.5 and 50% based on the weight of the fire-retardant agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2225779A | 1979-03-20 | 1979-03-20 | |
| US22,257 | 1979-03-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1145083A true CA1145083A (en) | 1983-04-19 |
Family
ID=21808670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000345834A Expired CA1145083A (en) | 1979-03-20 | 1980-02-18 | Fire-retardant polystyrenic compositions |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS55125140A (en) |
| BE (1) | BE882241A (en) |
| CA (1) | CA1145083A (en) |
| CS (1) | CS226409B2 (en) |
| DE (1) | DE3009065A1 (en) |
| FR (1) | FR2451928B1 (en) |
| GB (1) | GB2048276B (en) |
| IT (1) | IT1140778B (en) |
| NL (1) | NL190163C (en) |
| NO (1) | NO162077C (en) |
| SE (1) | SE8002057L (en) |
| SU (1) | SU1097200A3 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3047443A1 (en) * | 1980-12-17 | 1982-07-22 | Bayer Ag, 5090 Leverkusen | MOLDED STABILIZERS AGAINST THERMOLYSIS WITH LOW MONOMER CONTENT |
| IT1395379B1 (en) * | 2009-09-07 | 2012-09-14 | Polimeri Europa Spa | PROCEDURE FOR THE PREPARATION OF EXPANDABLE VINYLAROMATIC POLYMERS WITH REDUCED THERMAL CONDUCTIVITY BY MEANS OF SUSPENSION POLYMERIZATION |
| RU2532519C1 (en) * | 2013-04-15 | 2014-11-10 | Открытое акционерное общество "Казанский химический научно-исследовательский институт" | Polymer-rubber waterproofing composition with reduced fire hazard and method of obtaining thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE817625A (en) * | 1974-07-12 | 1974-11-04 | FLAME-RESISTANT POLYSTYRENE COMPOSITIONS. | |
| CS210623B2 (en) * | 1974-07-12 | 1982-01-29 | Labofina Sa | Polymere heat resistant mixture |
-
1980
- 1980-02-11 GB GB8004433A patent/GB2048276B/en not_active Expired
- 1980-02-18 CA CA000345834A patent/CA1145083A/en not_active Expired
- 1980-02-28 SU SU802888301A patent/SU1097200A3/en active
- 1980-02-29 NL NLAANVRAGE8001248,A patent/NL190163C/en not_active IP Right Cessation
- 1980-03-10 DE DE19803009065 patent/DE3009065A1/en active Granted
- 1980-03-10 FR FR8005297A patent/FR2451928B1/en not_active Expired
- 1980-03-12 IT IT20521/80A patent/IT1140778B/en active
- 1980-03-14 BE BE0/199810A patent/BE882241A/en not_active IP Right Cessation
- 1980-03-17 SE SE8002057A patent/SE8002057L/en unknown
- 1980-03-18 NO NO800768A patent/NO162077C/en unknown
- 1980-03-18 JP JP3351880A patent/JPS55125140A/en active Granted
- 1980-03-19 CS CS801902A patent/CS226409B2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3009065C2 (en) | 1993-04-15 |
| FR2451928B1 (en) | 1986-08-01 |
| JPS55125140A (en) | 1980-09-26 |
| IT1140778B (en) | 1986-10-10 |
| NO800768L (en) | 1980-09-22 |
| NL8001248A (en) | 1980-09-23 |
| NO162077B (en) | 1989-07-24 |
| NO162077C (en) | 1989-11-01 |
| GB2048276B (en) | 1983-03-30 |
| SU1097200A3 (en) | 1984-06-07 |
| NL190163B (en) | 1993-06-16 |
| JPH0255454B2 (en) | 1990-11-27 |
| BE882241A (en) | 1980-07-01 |
| GB2048276A (en) | 1980-12-10 |
| SE8002057L (en) | 1980-09-21 |
| FR2451928A1 (en) | 1980-10-17 |
| IT8020521A0 (en) | 1980-03-12 |
| NL190163C (en) | 1993-11-16 |
| CS226409B2 (en) | 1984-03-19 |
| DE3009065A1 (en) | 1980-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3207731A (en) | Self-extinguishing alkenyl aromatic polymeric compositions containing polybromophenyl acrylates and dibromocyclopropyl styrenes | |
| US4092281A (en) | Fire retardant polystyrenic compositions | |
| US6908949B2 (en) | Foamable interpolymer resin particles containing limonene as a blowing aid | |
| US4476267A (en) | High impact polystyrene containing halophenoxyalkylsilane flame retardant | |
| US3271333A (en) | Self-extinguishing alkenyl aromatic polymers | |
| US3943195A (en) | Self-extinguishing thermoplastic molding material | |
| US3819547A (en) | Self-extinguishing polymer compositions containing hexabromo-2-butene | |
| CA1145083A (en) | Fire-retardant polystyrenic compositions | |
| EP0014764B1 (en) | Finely divided, expandable, self extinguishing styrene polymers | |
| US4230821A (en) | Fire-retardant polystyrenic compositions | |
| US4359538A (en) | Fire-retardant polystyrenic compositions | |
| US3284544A (en) | Self-extinguishing alkenyl aromatic resins containing organic polysulfide | |
| US2760947A (en) | Self-extinguishing alkenyl polymer compositions containing bromochloro compounds | |
| US4430467A (en) | Self-extinguishing propylene polymer | |
| US3296340A (en) | Self-extinguishing alkenyl aromatic resins containing sulfenamides | |
| US3971758A (en) | Plastic compositions containing acrylonitrile-butadiene-styrene polymer and a bis-phenoxy flame retardant | |
| CA1116800A (en) | Self-extinguishing polystyrenic compositions and process for their preparation | |
| CA1067240A (en) | Smoke-and flame-retardant styrene/acrylonitrile/methyl methacrylate interpolymeric molding compositions | |
| JPS63117057A (en) | Flame-retardant, heat-resistant aromatic vinyl resin composition | |
| EP0013051B1 (en) | Thermoplastic moulding material and article prepared thereof | |
| US4028285A (en) | Styrene polymer foams having reduced flammability containing allyl ether synergists | |
| US3892710A (en) | ABS plastic compositions containing halogenated aryl flame retardants | |
| US3883479A (en) | ABS plastic compositions containing bio-phenoxy flame retardants | |
| US4200696A (en) | Process for preparing expandible particles of styrene-based polymers | |
| US4057531A (en) | Fire retardant polystyrene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |