CA2025172A1 - Smoke suppressed flame retardant thermoplastic resin compositions - Google Patents
Smoke suppressed flame retardant thermoplastic resin compositionsInfo
- Publication number
- CA2025172A1 CA2025172A1 CA002025172A CA2025172A CA2025172A1 CA 2025172 A1 CA2025172 A1 CA 2025172A1 CA 002025172 A CA002025172 A CA 002025172A CA 2025172 A CA2025172 A CA 2025172A CA 2025172 A1 CA2025172 A1 CA 2025172A1
- Authority
- CA
- Canada
- Prior art keywords
- flame retardant
- composition
- chain
- retardant agent
- phosphate 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.)
- Abandoned
Links
Classifications
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
GL353.APP
ABSTRACT
Smoke suppressed flame retardant thermoplastic resin compositions comprise bicyclic phosphate compound(s), flame retardant(s) and polyvinyl halide, polyolefin or polystyrene resins. These compositions exhibit a reduced tendency to smoke under conditions of burning.
ABSTRACT
Smoke suppressed flame retardant thermoplastic resin compositions comprise bicyclic phosphate compound(s), flame retardant(s) and polyvinyl halide, polyolefin or polystyrene resins. These compositions exhibit a reduced tendency to smoke under conditions of burning.
Description
~?J~ r GL353.APP
CROSS-REFERENCE
This application is a continuation-in part of co-pending application Serial No. 289,973, fil2d December 22, 19~8.
BACKGROUND OF THE INVENTION
Field of the Invention. This invention relates to flame retardant thermoplastic resin compositions that exhibit a reduced tendency to generate smoke under burning conditions. More particularly, this invention relates to thermoplastic compositions such as polyvinyl chloride ("PVC"), polystyrene and polyolefins, comprising bicyclic phosphate compound(s); and flame retardant agent(s). The compositions produced in accordance with this invention exhibit a reduced tendency to smoke under burning conditions.
DescriPtion of the Prior Art. It is known in the art that the flammability of thermoplastics, such as polystyrene, polyolefins, and polyvinyl halides, can be reduced by incorporation of a flame retardant agent. Typical flame retardant agents include reactive or additive haloganated organic compounds, inorganic fillers, and special formulations ~ased on phosphorous and ammonium salts.
Although efficient in suppressing the rate of combustion in a resin system, most flame retardants tend to affect adversely one or more key properties of the resin. For example, many flame retardant additives are ineffective at producing low smoke ("smoke suppressed") formulations.
.. . .
.
-, ,~3J J ~ .~
GL353.APP
Recent public awareness about risk and hazard assessment during fire situatiens, and technical limitations of conventional flame retardant additives warrant a need for improved flame retardant thermoplastic compositions. In particular, a need exists for a thermoplastic composition that passes flammability standards with low smoke and combustion by-product formation, and does not detract from overall polymer performance.
Many prior art references describe the use of a variety of smoke additives in polystyrene and polyolefins. Modern Pla~tics EncvcloDedia, Vol. 63, No. lOA, McGraw-Hill, Inc., pp. 17~-180 (1986). However, the selection of a suitable smoke suppressant for thermoplastic resins is not predictable. Selection is particularly difficult when flame retardants are employed, exacerbated by the complex interaction between the polymer and the flame retardant agent.
Hechenbleikner, et al. describe in U.S. Patent No. 3,293,327 the production of bicyclic phosphites, phosphonates, thiophosphates, and selenophosphates. These compositions are said to be stabilizers for vinyl halide resins. They are alleged to be useful as heat stabilizers for vinyl chloride resin, and as antioxidants for fats and oils. The Hechenbleikner patent does not specify the use of bicyclic phosphates to achieve low smoke thermoplastic resin compositions, nor does it disclose that cyclic phosphates of the present invention could be used with flame retardant agents to produce smoke suppressed flame retardant thermoplastic compositions.
- . . .
, ~ , - ~
- . ~ , . . .
PI ~
GL353.APP
British Patent No. 999,793 describes a process for producing organic phosphates by subjecting organic phosphites to reaction with peracetic acid. This patent shows a method for producing the most preferred bicyclic phosphate of the present invention, 2,6,7-trioxa-1-phosphobicyclol2.2.2]-octane-4- methanol-l-oxide and teaches the use of acetal ring-containing phosphates as plasticizers or functional fluids. The British patent, however, does not disclose the present invention. It does not mention bicyclic phosphates as being useful for flame retardant thermoplastic resins, nor that the most preferred bicyclic phosphate of the present invention can be used with flame retardant additives to yield improved smoke suppressed thermoplastic compositions.
Hills, et al. describe in U.S. Patent No. 3,873,496 a flame retardant polyester composition which contains 5 to 25 percent of a hydroxymethyl bicyclic phosphate compound as a flame retardant additive. Hills did not observe the ability for bicyclic phos-phates to act as smoke suppressors for thermoplastic resin compositions which employ halogenated compounds as the primary flame retardant additive.
Halpern, et al. describe in U.5. Patent No. 4,341,694 a composition comprising 2,6,7-trioxa-1-phosphobicyclo~2.2.2~-octane-4-methanol-1-oxide and a nitrogen-containing co-additive, which are intumescent and are adaptable to flame retard polyolefins, polyvinylaromatic resins, polycarbonates, PVC and blends thereof. Halpern did not observe any smoXe suppression o the present invention.
, GL353.APP
Parr, et al. describe in U.S. Patent No. 4,801,625 a flame resist~nt composition having (1) an organic polymeric substance in intimate contact with ~2) a bicyclic phosphorous compound, and (3) a gas producing compound. Parr is silent on the use of bicyclic compounds to attain smoke suppressed flame retardation thermoplastic compositions.
Accordingly, a primary object of this invention is to provide smoke suppressed flame retardant thermoplastic compositions.
A related object is to provide flame retardant thermoplastic polyvinyl chloride compositions with a reduced tendency to smoke under burning conditions.
A further object is to provide polyvinyl chloride resin compositions incorporating bicyclic phosphate compound and flame retardants.
.
~ -5-:`
,, ~' ~ ~ , ' , ' :
~ 3 GL353.APP
SUMMARY OF THE INVENTION
The foregoing and other objects, advantages and features of the present invention may be achievable with smoke suppressed thermoplastic polyvinyl halide, polyolefin or polystyrene resin compositions incorporating an effective amount of an additive mixture comprising a flame retardant agent and a bicyclic phosphate compound of the following Formula (I):
O R
(I) O=P\ ~ CH
where X is OH, OR', or OC(O~R'; R is H or a saturated or unsaturated straight-chain or branched-chain C1-C17 alkyl; and R' is a saturated or unsaturated straight-chain or branched-chain Cl-C17 alkyl. Compositions in accordance with this invention exhibit a reduced tendency to smoke under burning conditions.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
This invention relates to smoke suppre6sed flame retardant thermoplastic polyvinyl halide, polyolefin and polystyrene compositions. In particular, the invention relates to thermoplastic polyvinyl chloride, polyolefin and polystyrene resin compositions which are flame retardant and which exhibit a reduced tendency to smoke when burning. Compositions in accordance with this invention incorporate an additive mixture comprising one or more bicyclic phosphate compounds and one or more flame retardant agents.
. ~ , .
- ': :~.' ' ' ' . , :
"':''~' " :' ~L353.APP
Preferred bicyclic phosphates in accordance with this invention are compounds of Formula (I) where X is OH or OC(O)R'.
The most preferred bicyclic compounds are 2,6,7-trioxa-phosphobicyclo[2.2.2]-octane-4-methanol-1-oxide (Compound BCP, that is, Formula [I] when R is H and X is OH), and 2,6,7-trioxa-1-phosphobicyclo[2.2.2]-octane-4-methanol, acetate, l-oxide (Compound BCP-A, that is, when R is H and X is OC(O)CH3).
The flame retardant agent employed in accordance with the present invention may be any common flame retardant age~t which can be used to reduce the flammability of thermopla6tic resins, such as halogenated compounds containing bromine and/or chlorine, or inorganic materials, such as metal hydrates, metal borates, antimony-containing compounds, or phosphorous-containing compounds.
Preferred halogen-containing compounds are di-(2-ethylhexyl)tetrabromophthalate, hexabromocyclododecane, tetrabromobisphenol h, tetrabromobisphenol A
bis-(dibromopropylether)~ dibromo(dibromoethyl)cyclohexane, tetrabromocyclooctane, bis-(dibromonorbornane dicarboximido)ethane, bis-(tetrabromophthalimido)ethane, Diels-Alder adduct of chlorinated cyclopentadiene and an unsaturated cycloaliphatic compound, bis-(tribromophenoxyethyl) -tetrabromobisphenol A ether, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, bis-(tribromophenoxy)ethane, bis-(pentabromophenoxy)ethane, chloropentabromocyclohexane, (tribromophenoxy)-(dibromononylphenoxy)ethane, pentabromoethylbenzene, :, - : . , ;, :
~ i f`J
GL353.APP
pentabromododecylbenzene, carbonate oligomers of tetrabromobisphenol A, poly(bromostyrene), and brominated polystyrene, poly(bromophenylene) ether, and mixtures thereof.
Particularly preferred is di-(2-ethylhexyl)tetrabromophthalate.
Substantially any suitable metal hydrates and oxides may be employed as flame retardant agents, including hydrates and oxides of aluminum, iron, inc, magnesium, tin, molybdenum and antimony.
Alumina trih ~ rate, magnesium hydroxide, and antimony trioxide are the preferred compounds in this class.
Suitable metal boron-containing flame retardant compounds include zinc, barium, calcium, magnesium, cadmium and mercury.
Zinc borate is the preferred compound in this class.
Substantially any suitable phosphorus-containing compound may be used as a flame retardant agent, including ammonium polyphosphate, arylphosphates, alkarylphosphates and alXylphosphates. Particularly preferred are phenyl isopropylphenyl phosphate and isodecyldiphenyl phosphate commercially available from FMC Corporation under the trademarks Kronit.ex lOO and Santicizer 148.
The foregoing flame retardant compounds are added to thermo-plastic resins at effective levels such that the resultant resin composition may be rendered flame retardant.
, ~. :
.
, GL353.APP
Thermoplastic resins which may be treated in accordance with the invention include thermoplastics such as polyvinyl halides, polystyrene, and homopolymers and copolymers of polypropylene, polyethylene, and polybutylene. Polyvinyl chloride is most preferred in accordance with this invention.
The scope of the present invention also includes the incorporation of other additives in the composition so far as to produce a particular end result. Such additives incll~de, without limitation, blowing agents, heat stabilizers, light stabilizers, plasticizers, pi~ments, preservatives, ultraviolet light stabi-lizers, fillers, antioxidants, antistatic agents and other materials well known to those skilled in the art, for example, as described in Modern Plastics EncYclopedia, Vol. 63, No. lOA, McGraw-Hill, Inc. (1986).
The bicyclic phosphates of the present invention may be used alone or as mixtures of any such compounds. When mixtures of bicyclic phosphates are employed, substantially any combinations of amounts and proportions of the individual compounds may be used. The use of Compound BCP and Compound BCP A is especially preferred in accordance with this invention.
The bicyclic phosphate may be employed at substantially any level because even very low levels are believed to assist in smoke ~uppression. Preferably it is present at a level of at least 2 percent and preferably about 3 percent up to about 20 percent by weight of the composition.
: : ' ~' ' . :
.
GL353.APP
The flame retardant agents of the present invention may be used alone or as mixtures of any such compounds. When mixtures of flame agents are employed, substantially any combinations of amounts and proportions of the individual compounds may be used.
The use of di-(2-ethylhexyl)- tetrabromophthalate, alumina trihydrate, magnesium hydroxide, zinc borate, antimony trioxide, and alkylaryl phosphates are especially preferred in accordance with this invention.
Desirably, flame retardants are employed at a level of about 2 to 50 percent by weight of the composition, preferably about 3 to 20 percent, depending on the specific flame retardant and thermoplastic resin employed. Operative and preferred ranges for various flame retardants in accordance with this invention are given in the Table I.
`' ' ~ .
, :
~ . , .,, ' , q 7 ~ ~
.
. GL353.APP
:
TABLE I
:: OPERATING RANGES
-` MATERIAL OPERATIVE RANGE PREFERRED RANGE
:. BrFr 2-50 3-20 ~" AAP 2-50 3-20 ;~~ MgOH 2-50 5-10 ;~ ZnBor 2-50 5-10 SbOx 1-15 5-10 BrFr - di-(2-ethylhexyl)tetrabromophthalides brominated flame retardant AAP - alkylarylphosphate (Kronitex 100 - FMC Corp.) ATH - alumina trihydrate . MgOH - magnesium hydroxide 2nBor - zinc borate - SbOx - antimony oxide Desirably, the bicyclic phosphate compound and flame ; retardant are provided as a mixture useful as an additive which may be added to polystyrene or polyolefin resin compositions.
. ~
The additive mixture utilizes bicyclic phosphate and flame retardant in a weight ratio lying in the range of about 1:25 to 20:1, most preferably, about 3:20 to 20:3.
The additive mixture is incorporated into the polymer composition at an effective level such thzt the resulting resin composition i8 rendered flame retardant. In general, the additive mixture is provided in the flame retardant at a level of about 2 - 50 percent by weight of the resin composition, preferably about 3 - 30 percent by weight.
.
-11~
;
:
. ~ . . ~. .
2~,~2P;~-r! ~
GL353.APP
Practice of the present invention is illustrated by the following examples, which are given to illustrate the invention and should not be construed as limiting its scope.
EXAMPLES
Preparation of Polwinylchloride Resin Svstems. A general purpos~ polyvinylchloride ("PVC") resin was u~ed in the study.
PVC resin, powdered additive~ and flame retardant were blended in a mixing bowl and warmed to 90C. Liguid plasticizer was ~dded, ~ and the admixture was compounded on a two-roll mill at 160C.
`; The compounded PVC material was compression molded at 180C.
Table II shows examples of the use of Compound BCP in flexible PVC formulations. The general formulation used is as follows:
. Material /~by weiqht . PVC Resin varied Compound BCP varied (see Table) Flame Retardant varied (see Table) Dioctylphthalate Plasticizer varied (see below~
Epoxidized Soya Plasticizer 5 Stabilizer 3 The amount of dioctyl phthalate ("DOP") plastici~er wa adjusted to give compositlonR with comparable physical properties (i.e., approximately 90 Shore A hardness) and flammability (approximately 30 OI) performance.
, '`
.
` -12-: : . . ~; .
. :
~ , . ` ' ~ ' ':- . ` ~ ` :
, ' 2 ~
GL353.APP
:.
:`
Flammabilit~ Test Procedures. The following flammability tests were used throughout the study:
- Test Method Description ASTM D-2863 Limiting Measurement of the minimum oxygen Oxygen Index necessary to ~ustain burning of a vertically supported sample for - thrse minutes. High values indicate improved re~istance to burning.
NBS Smoke Chamber Smoke density determinations ASTM -662 under smolderinq conditions. Low values indicate low smoke evolution.
~' A series of experimental and comparative studies were performed using the foregoing techniques. The data are given in Table II.
` , ..
:~ -13-. . .
!, ~ " : ' ' "~ , .
j, ' ' ' , ~ ' ,, r~
GL353 . APP
i TABLE II
` FLAMMABILITY AND PHYSICAL PROPERTY PERFORMANCE
FLEXIBLE POLYVINYLCHLORIDE COMPOSITIONS
~` E.YAMPLE AMOUNT OF FLAME RETARDANT NBS SMOKE OXYGEN HARDNESS
NUMBER BCP TYPE AMOUNT SMOLDERING INDEX SHORE A
wt % wt % ASTM ~662 ASTM ASTM
-. D-2863 CONTROL5.0 ----- 0.0 170 30 90 - 1 5.0 BrFr10.0 165 30 90 COMP 2 0.0 BrFr10.0 210 30 90 2 5.0 AAP 15.0 160 30 90 COMP 3 0.O AAP 15.0 200 30 90 3 5.0 ATH 15.0 145 30 90 COMP 4 0.0 ATH 15.0 160 30 gO
CROSS-REFERENCE
This application is a continuation-in part of co-pending application Serial No. 289,973, fil2d December 22, 19~8.
BACKGROUND OF THE INVENTION
Field of the Invention. This invention relates to flame retardant thermoplastic resin compositions that exhibit a reduced tendency to generate smoke under burning conditions. More particularly, this invention relates to thermoplastic compositions such as polyvinyl chloride ("PVC"), polystyrene and polyolefins, comprising bicyclic phosphate compound(s); and flame retardant agent(s). The compositions produced in accordance with this invention exhibit a reduced tendency to smoke under burning conditions.
DescriPtion of the Prior Art. It is known in the art that the flammability of thermoplastics, such as polystyrene, polyolefins, and polyvinyl halides, can be reduced by incorporation of a flame retardant agent. Typical flame retardant agents include reactive or additive haloganated organic compounds, inorganic fillers, and special formulations ~ased on phosphorous and ammonium salts.
Although efficient in suppressing the rate of combustion in a resin system, most flame retardants tend to affect adversely one or more key properties of the resin. For example, many flame retardant additives are ineffective at producing low smoke ("smoke suppressed") formulations.
.. . .
.
-, ,~3J J ~ .~
GL353.APP
Recent public awareness about risk and hazard assessment during fire situatiens, and technical limitations of conventional flame retardant additives warrant a need for improved flame retardant thermoplastic compositions. In particular, a need exists for a thermoplastic composition that passes flammability standards with low smoke and combustion by-product formation, and does not detract from overall polymer performance.
Many prior art references describe the use of a variety of smoke additives in polystyrene and polyolefins. Modern Pla~tics EncvcloDedia, Vol. 63, No. lOA, McGraw-Hill, Inc., pp. 17~-180 (1986). However, the selection of a suitable smoke suppressant for thermoplastic resins is not predictable. Selection is particularly difficult when flame retardants are employed, exacerbated by the complex interaction between the polymer and the flame retardant agent.
Hechenbleikner, et al. describe in U.S. Patent No. 3,293,327 the production of bicyclic phosphites, phosphonates, thiophosphates, and selenophosphates. These compositions are said to be stabilizers for vinyl halide resins. They are alleged to be useful as heat stabilizers for vinyl chloride resin, and as antioxidants for fats and oils. The Hechenbleikner patent does not specify the use of bicyclic phosphates to achieve low smoke thermoplastic resin compositions, nor does it disclose that cyclic phosphates of the present invention could be used with flame retardant agents to produce smoke suppressed flame retardant thermoplastic compositions.
- . . .
, ~ , - ~
- . ~ , . . .
PI ~
GL353.APP
British Patent No. 999,793 describes a process for producing organic phosphates by subjecting organic phosphites to reaction with peracetic acid. This patent shows a method for producing the most preferred bicyclic phosphate of the present invention, 2,6,7-trioxa-1-phosphobicyclol2.2.2]-octane-4- methanol-l-oxide and teaches the use of acetal ring-containing phosphates as plasticizers or functional fluids. The British patent, however, does not disclose the present invention. It does not mention bicyclic phosphates as being useful for flame retardant thermoplastic resins, nor that the most preferred bicyclic phosphate of the present invention can be used with flame retardant additives to yield improved smoke suppressed thermoplastic compositions.
Hills, et al. describe in U.S. Patent No. 3,873,496 a flame retardant polyester composition which contains 5 to 25 percent of a hydroxymethyl bicyclic phosphate compound as a flame retardant additive. Hills did not observe the ability for bicyclic phos-phates to act as smoke suppressors for thermoplastic resin compositions which employ halogenated compounds as the primary flame retardant additive.
Halpern, et al. describe in U.5. Patent No. 4,341,694 a composition comprising 2,6,7-trioxa-1-phosphobicyclo~2.2.2~-octane-4-methanol-1-oxide and a nitrogen-containing co-additive, which are intumescent and are adaptable to flame retard polyolefins, polyvinylaromatic resins, polycarbonates, PVC and blends thereof. Halpern did not observe any smoXe suppression o the present invention.
, GL353.APP
Parr, et al. describe in U.S. Patent No. 4,801,625 a flame resist~nt composition having (1) an organic polymeric substance in intimate contact with ~2) a bicyclic phosphorous compound, and (3) a gas producing compound. Parr is silent on the use of bicyclic compounds to attain smoke suppressed flame retardation thermoplastic compositions.
Accordingly, a primary object of this invention is to provide smoke suppressed flame retardant thermoplastic compositions.
A related object is to provide flame retardant thermoplastic polyvinyl chloride compositions with a reduced tendency to smoke under burning conditions.
A further object is to provide polyvinyl chloride resin compositions incorporating bicyclic phosphate compound and flame retardants.
.
~ -5-:`
,, ~' ~ ~ , ' , ' :
~ 3 GL353.APP
SUMMARY OF THE INVENTION
The foregoing and other objects, advantages and features of the present invention may be achievable with smoke suppressed thermoplastic polyvinyl halide, polyolefin or polystyrene resin compositions incorporating an effective amount of an additive mixture comprising a flame retardant agent and a bicyclic phosphate compound of the following Formula (I):
O R
(I) O=P\ ~ CH
where X is OH, OR', or OC(O~R'; R is H or a saturated or unsaturated straight-chain or branched-chain C1-C17 alkyl; and R' is a saturated or unsaturated straight-chain or branched-chain Cl-C17 alkyl. Compositions in accordance with this invention exhibit a reduced tendency to smoke under burning conditions.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
This invention relates to smoke suppre6sed flame retardant thermoplastic polyvinyl halide, polyolefin and polystyrene compositions. In particular, the invention relates to thermoplastic polyvinyl chloride, polyolefin and polystyrene resin compositions which are flame retardant and which exhibit a reduced tendency to smoke when burning. Compositions in accordance with this invention incorporate an additive mixture comprising one or more bicyclic phosphate compounds and one or more flame retardant agents.
. ~ , .
- ': :~.' ' ' ' . , :
"':''~' " :' ~L353.APP
Preferred bicyclic phosphates in accordance with this invention are compounds of Formula (I) where X is OH or OC(O)R'.
The most preferred bicyclic compounds are 2,6,7-trioxa-phosphobicyclo[2.2.2]-octane-4-methanol-1-oxide (Compound BCP, that is, Formula [I] when R is H and X is OH), and 2,6,7-trioxa-1-phosphobicyclo[2.2.2]-octane-4-methanol, acetate, l-oxide (Compound BCP-A, that is, when R is H and X is OC(O)CH3).
The flame retardant agent employed in accordance with the present invention may be any common flame retardant age~t which can be used to reduce the flammability of thermopla6tic resins, such as halogenated compounds containing bromine and/or chlorine, or inorganic materials, such as metal hydrates, metal borates, antimony-containing compounds, or phosphorous-containing compounds.
Preferred halogen-containing compounds are di-(2-ethylhexyl)tetrabromophthalate, hexabromocyclododecane, tetrabromobisphenol h, tetrabromobisphenol A
bis-(dibromopropylether)~ dibromo(dibromoethyl)cyclohexane, tetrabromocyclooctane, bis-(dibromonorbornane dicarboximido)ethane, bis-(tetrabromophthalimido)ethane, Diels-Alder adduct of chlorinated cyclopentadiene and an unsaturated cycloaliphatic compound, bis-(tribromophenoxyethyl) -tetrabromobisphenol A ether, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, bis-(tribromophenoxy)ethane, bis-(pentabromophenoxy)ethane, chloropentabromocyclohexane, (tribromophenoxy)-(dibromononylphenoxy)ethane, pentabromoethylbenzene, :, - : . , ;, :
~ i f`J
GL353.APP
pentabromododecylbenzene, carbonate oligomers of tetrabromobisphenol A, poly(bromostyrene), and brominated polystyrene, poly(bromophenylene) ether, and mixtures thereof.
Particularly preferred is di-(2-ethylhexyl)tetrabromophthalate.
Substantially any suitable metal hydrates and oxides may be employed as flame retardant agents, including hydrates and oxides of aluminum, iron, inc, magnesium, tin, molybdenum and antimony.
Alumina trih ~ rate, magnesium hydroxide, and antimony trioxide are the preferred compounds in this class.
Suitable metal boron-containing flame retardant compounds include zinc, barium, calcium, magnesium, cadmium and mercury.
Zinc borate is the preferred compound in this class.
Substantially any suitable phosphorus-containing compound may be used as a flame retardant agent, including ammonium polyphosphate, arylphosphates, alkarylphosphates and alXylphosphates. Particularly preferred are phenyl isopropylphenyl phosphate and isodecyldiphenyl phosphate commercially available from FMC Corporation under the trademarks Kronit.ex lOO and Santicizer 148.
The foregoing flame retardant compounds are added to thermo-plastic resins at effective levels such that the resultant resin composition may be rendered flame retardant.
, ~. :
.
, GL353.APP
Thermoplastic resins which may be treated in accordance with the invention include thermoplastics such as polyvinyl halides, polystyrene, and homopolymers and copolymers of polypropylene, polyethylene, and polybutylene. Polyvinyl chloride is most preferred in accordance with this invention.
The scope of the present invention also includes the incorporation of other additives in the composition so far as to produce a particular end result. Such additives incll~de, without limitation, blowing agents, heat stabilizers, light stabilizers, plasticizers, pi~ments, preservatives, ultraviolet light stabi-lizers, fillers, antioxidants, antistatic agents and other materials well known to those skilled in the art, for example, as described in Modern Plastics EncYclopedia, Vol. 63, No. lOA, McGraw-Hill, Inc. (1986).
The bicyclic phosphates of the present invention may be used alone or as mixtures of any such compounds. When mixtures of bicyclic phosphates are employed, substantially any combinations of amounts and proportions of the individual compounds may be used. The use of Compound BCP and Compound BCP A is especially preferred in accordance with this invention.
The bicyclic phosphate may be employed at substantially any level because even very low levels are believed to assist in smoke ~uppression. Preferably it is present at a level of at least 2 percent and preferably about 3 percent up to about 20 percent by weight of the composition.
: : ' ~' ' . :
.
GL353.APP
The flame retardant agents of the present invention may be used alone or as mixtures of any such compounds. When mixtures of flame agents are employed, substantially any combinations of amounts and proportions of the individual compounds may be used.
The use of di-(2-ethylhexyl)- tetrabromophthalate, alumina trihydrate, magnesium hydroxide, zinc borate, antimony trioxide, and alkylaryl phosphates are especially preferred in accordance with this invention.
Desirably, flame retardants are employed at a level of about 2 to 50 percent by weight of the composition, preferably about 3 to 20 percent, depending on the specific flame retardant and thermoplastic resin employed. Operative and preferred ranges for various flame retardants in accordance with this invention are given in the Table I.
`' ' ~ .
, :
~ . , .,, ' , q 7 ~ ~
.
. GL353.APP
:
TABLE I
:: OPERATING RANGES
-` MATERIAL OPERATIVE RANGE PREFERRED RANGE
:. BrFr 2-50 3-20 ~" AAP 2-50 3-20 ;~~ MgOH 2-50 5-10 ;~ ZnBor 2-50 5-10 SbOx 1-15 5-10 BrFr - di-(2-ethylhexyl)tetrabromophthalides brominated flame retardant AAP - alkylarylphosphate (Kronitex 100 - FMC Corp.) ATH - alumina trihydrate . MgOH - magnesium hydroxide 2nBor - zinc borate - SbOx - antimony oxide Desirably, the bicyclic phosphate compound and flame ; retardant are provided as a mixture useful as an additive which may be added to polystyrene or polyolefin resin compositions.
. ~
The additive mixture utilizes bicyclic phosphate and flame retardant in a weight ratio lying in the range of about 1:25 to 20:1, most preferably, about 3:20 to 20:3.
The additive mixture is incorporated into the polymer composition at an effective level such thzt the resulting resin composition i8 rendered flame retardant. In general, the additive mixture is provided in the flame retardant at a level of about 2 - 50 percent by weight of the resin composition, preferably about 3 - 30 percent by weight.
.
-11~
;
:
. ~ . . ~. .
2~,~2P;~-r! ~
GL353.APP
Practice of the present invention is illustrated by the following examples, which are given to illustrate the invention and should not be construed as limiting its scope.
EXAMPLES
Preparation of Polwinylchloride Resin Svstems. A general purpos~ polyvinylchloride ("PVC") resin was u~ed in the study.
PVC resin, powdered additive~ and flame retardant were blended in a mixing bowl and warmed to 90C. Liguid plasticizer was ~dded, ~ and the admixture was compounded on a two-roll mill at 160C.
`; The compounded PVC material was compression molded at 180C.
Table II shows examples of the use of Compound BCP in flexible PVC formulations. The general formulation used is as follows:
. Material /~by weiqht . PVC Resin varied Compound BCP varied (see Table) Flame Retardant varied (see Table) Dioctylphthalate Plasticizer varied (see below~
Epoxidized Soya Plasticizer 5 Stabilizer 3 The amount of dioctyl phthalate ("DOP") plastici~er wa adjusted to give compositlonR with comparable physical properties (i.e., approximately 90 Shore A hardness) and flammability (approximately 30 OI) performance.
, '`
.
` -12-: : . . ~; .
. :
~ , . ` ' ~ ' ':- . ` ~ ` :
, ' 2 ~
GL353.APP
:.
:`
Flammabilit~ Test Procedures. The following flammability tests were used throughout the study:
- Test Method Description ASTM D-2863 Limiting Measurement of the minimum oxygen Oxygen Index necessary to ~ustain burning of a vertically supported sample for - thrse minutes. High values indicate improved re~istance to burning.
NBS Smoke Chamber Smoke density determinations ASTM -662 under smolderinq conditions. Low values indicate low smoke evolution.
~' A series of experimental and comparative studies were performed using the foregoing techniques. The data are given in Table II.
` , ..
:~ -13-. . .
!, ~ " : ' ' "~ , .
j, ' ' ' , ~ ' ,, r~
GL353 . APP
i TABLE II
` FLAMMABILITY AND PHYSICAL PROPERTY PERFORMANCE
FLEXIBLE POLYVINYLCHLORIDE COMPOSITIONS
~` E.YAMPLE AMOUNT OF FLAME RETARDANT NBS SMOKE OXYGEN HARDNESS
NUMBER BCP TYPE AMOUNT SMOLDERING INDEX SHORE A
wt % wt % ASTM ~662 ASTM ASTM
-. D-2863 CONTROL5.0 ----- 0.0 170 30 90 - 1 5.0 BrFr10.0 165 30 90 COMP 2 0.0 BrFr10.0 210 30 90 2 5.0 AAP 15.0 160 30 90 COMP 3 0.O AAP 15.0 200 30 90 3 5.0 ATH 15.0 145 30 90 COMP 4 0.0 ATH 15.0 160 30 gO
4 5.0 MgOH15.0 140 30 90 - COMP 5 0.0 MgOHlS.O 165 30 90 5.0 ZnBor15.0 130 30 90 COMP 6 0.0 ZnBor15.0 155 30 90 .
BCP - Preferxed bicyclic phosphate BrFr - di-(2-ethylhexyl)tetrabromophthalates AAP - alkylarylphosphate (Kronitex 100 - FMC Corp.) ATH - alumina trihydrate MgOH - magnesium hydroxide ZnBor - zinc borate ;
. , , , ~ ~ , .
GL353 . APP
.
These data demonstrate the patentability of the subject invention as follows. The Control Example shows the effect of 5.0% BCP alone on the smoke performance of a 30 OI flexible PVC
composition. Comparative Examples 2-6 show the effect of various flame retardants on smoke performance when Compound BCP is not present.
Example 1 illustrates the invention when the flame retardant is a bromine-containing flame retardant. Example 2 illustrates the invention when the flame retardant is phosphate-containing flame retardant (an alkarylphosphate). Example 3-5 illustrate the invention when the flame retardant i5 an inorganic flame retardant.
In the case of each invention composition, compositions comprising a bicyclic phosphate (Compound BCP) and a flame retardant had lower smoke than the Control ~i.e., a system without any additional flame retardant a~ent) or the corresponding Comparative Examples 2-6 ~i.e., a system without bicyclic phosphate).
`............................... --15--~ ; ' ' .~' . ' : ' - .: ~ .
BCP - Preferxed bicyclic phosphate BrFr - di-(2-ethylhexyl)tetrabromophthalates AAP - alkylarylphosphate (Kronitex 100 - FMC Corp.) ATH - alumina trihydrate MgOH - magnesium hydroxide ZnBor - zinc borate ;
. , , , ~ ~ , .
GL353 . APP
.
These data demonstrate the patentability of the subject invention as follows. The Control Example shows the effect of 5.0% BCP alone on the smoke performance of a 30 OI flexible PVC
composition. Comparative Examples 2-6 show the effect of various flame retardants on smoke performance when Compound BCP is not present.
Example 1 illustrates the invention when the flame retardant is a bromine-containing flame retardant. Example 2 illustrates the invention when the flame retardant is phosphate-containing flame retardant (an alkarylphosphate). Example 3-5 illustrate the invention when the flame retardant i5 an inorganic flame retardant.
In the case of each invention composition, compositions comprising a bicyclic phosphate (Compound BCP) and a flame retardant had lower smoke than the Control ~i.e., a system without any additional flame retardant a~ent) or the corresponding Comparative Examples 2-6 ~i.e., a system without bicyclic phosphate).
`............................... --15--~ ; ' ' .~' . ' : ' - .: ~ .
Claims (13)
1. A smoke suppressed thermoplastic resin composition comprising a polyvinyl halide, polyolefin or polystyrene resin and an effective amount of a mixture comprising;
at least one flame retardant agent; and at least one bicyclic phosphate compound of the formula:
where X is OH, OR', or OC(O)R'; R is H or a saturated or unsaturated straight-chain or branched-chain C1-C17 alkyl; and R' is a saturated or unsaturated straight-chain or branched-chain C1-C17 alkyl.
at least one flame retardant agent; and at least one bicyclic phosphate compound of the formula:
where X is OH, OR', or OC(O)R'; R is H or a saturated or unsaturated straight-chain or branched-chain C1-C17 alkyl; and R' is a saturated or unsaturated straight-chain or branched-chain C1-C17 alkyl.
2. A composition, as claimed in claim 1, wherein the flame retardant agent is a member selected from the group consisting of halogenated compounds, metal hydrates, metal borates, antimony compounds, phosphorous compounds, and mixtures thereof.
3. A composition, as claimed in claim 1, wherein the flame retardant agent is a member selected from the group consisting of di-(2-ethylhexyl)tetrabromophthalate, alumina trihydrate, magnesium hydroxide, antimony trioxide, zinc borate and alkarylphosphates.
GL353.APP
GL353.APP
4. A composition, as claimed in claim 1, wherein the bicyclic phosphate compound is 2,6,7-trioxa-phosphobicyclo [2.2.2]-octane-4-methanol-1-oxide; or 2,6,7-trioxa-1-phosphobicyclo[2.2.2]-octane-4-methanol, acetate, 1-oxide.
5. A composition, as claimed in claim 1, wherein the resin is a member selected from the group consisting of polyvinyl chloride, polystyrene and polyethylene, polypropylene and polybutylene homo- and copolymers.
6. A composition, as claimed in claim 4, wherein the member is polyvinyl chloride.
7. A composition, as claimed in claim 1, wherein the weight ratio of bicyclic phosphate compound to flame retardant agent lies in the range of about 1:25 to 20:1.
8. A composition, as claimed in claim 1, wherein the mixture of bicyclic phosphate compound and flame retardant agent is provided in the resin composition at a level lying in the range of about 2 - 50 percent by weight of the overall composition.
GL353.APP
GL353.APP
9. A method for suppressing the tendency of polyvinyl halide, polyolefin or polystyrene resin compositions to smoke under conditions of burning comprising the step of incorporating therein an effective amount of a mixture comprising:
a flame retardant agent; and a bicyclic phosphate compound of the formula:
where X is OH, OR', or OC(O)R'; R is H or a saturated or unsaturated straight-chain or branched-chain C1-C17 alkyl; and R' is a saturated or unsaturated straight-chain or branched-chain C1-C17 alkyl.
a flame retardant agent; and a bicyclic phosphate compound of the formula:
where X is OH, OR', or OC(O)R'; R is H or a saturated or unsaturated straight-chain or branched-chain C1-C17 alkyl; and R' is a saturated or unsaturated straight-chain or branched-chain C1-C17 alkyl.
10. A method, as claimed in claim 9, wherein the flame retardant agent is a member selected from the group consisting of halogenated compounds, metal hydrates, metal borates, antimony compounds, phosphorous compounds, and mixtures thereof.
11. A method, as claimed in claim 9, wherein the flame retardant agent is a member selected from the group consisting of di-(2-ethylhexyl)tetrabromophthalate, alumina trihydrate, magnesium hydroxide, antimony trioxide, zinc borate and alkarylphosphates.
GL353.APP
GL353.APP
12. A method, as claimed in claim 9, wherein the bicyclic phosphate compound is 2,6,7-trioxa-phosphobicyclo [2.2.2]-octane-4-methanol-1-oxide; or 2,6,7-trioxa-1-phosphobicylo[2.2.2]-octane-4-methanol, acetate, 1-oxide.
13. A method, as claimed in claim 9, wherein the weight ratio of bicyclic phosphate compound to flame retardant agent lies in the range of about 1:25 to 20:1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40814289A | 1989-09-15 | 1989-09-15 | |
| US408,142 | 1989-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2025172A1 true CA2025172A1 (en) | 1991-03-16 |
Family
ID=23615027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002025172A Abandoned CA2025172A1 (en) | 1989-09-15 | 1990-09-12 | Smoke suppressed flame retardant thermoplastic resin compositions |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0500608A1 (en) |
| JP (1) | JPH05500983A (en) |
| KR (1) | KR927003711A (en) |
| AU (2) | AU6625390A (en) |
| CA (1) | CA2025172A1 (en) |
| IL (1) | IL95673A (en) |
| WO (1) | WO1991004294A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110894331A (en) * | 2019-12-19 | 2020-03-20 | 天津金发新材料有限公司 | Environment-friendly low-smoke flame-retardant HIPS material and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997041173A1 (en) * | 1996-04-26 | 1997-11-06 | Akzo Nobel N.V. | Flame retardant composition for polymers |
| US10851228B2 (en) | 2018-07-26 | 2020-12-01 | FSIT Services LLC | Flame-retardant composition |
| CN115340736B (en) * | 2022-05-20 | 2023-09-29 | 扬州实嘉电缆材料有限公司 | Nitrogen-phosphorus flame retardant modified polyvinyl chloride fireproof cable material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4341694A (en) * | 1981-07-06 | 1982-07-27 | Borg-Warner Corporation | Intumescent flame retardant compositions |
| US4801625A (en) * | 1987-08-27 | 1989-01-31 | Akzo America Inc. | Bicyclic phosphate ether, ester, and carbonate intumescent flame retardant compositions |
| EP0401366A4 (en) * | 1988-12-22 | 1991-06-05 | Great Lakes Chemical Corporation | Thermally stable and light stable flame retardant thermoplastic polyolefin and polystyren compositions |
-
1990
- 1990-09-12 WO PCT/US1990/005147 patent/WO1991004294A1/en not_active Application Discontinuation
- 1990-09-12 KR KR1019920700594A patent/KR927003711A/en not_active Application Discontinuation
- 1990-09-12 CA CA002025172A patent/CA2025172A1/en not_active Abandoned
- 1990-09-12 EP EP19900916156 patent/EP0500608A1/en not_active Withdrawn
- 1990-09-12 AU AU66253/90A patent/AU6625390A/en not_active Abandoned
- 1990-09-12 JP JP2514943A patent/JPH05500983A/en active Pending
- 1990-09-13 IL IL9567390A patent/IL95673A/en not_active IP Right Cessation
-
1994
- 1994-08-18 AU AU70355/94A patent/AU7035594A/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110894331A (en) * | 2019-12-19 | 2020-03-20 | 天津金发新材料有限公司 | Environment-friendly low-smoke flame-retardant HIPS material and preparation method thereof |
| CN110894331B (en) * | 2019-12-19 | 2022-04-08 | 天津金发新材料有限公司 | Environment-friendly low-smoke flame-retardant HIPS material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1991004294A1 (en) | 1991-04-04 |
| IL95673A0 (en) | 1991-06-30 |
| KR927003711A (en) | 1992-12-18 |
| AU6625390A (en) | 1991-04-18 |
| EP0500608A1 (en) | 1992-09-02 |
| JPH05500983A (en) | 1993-02-25 |
| IL95673A (en) | 1995-05-26 |
| AU7035594A (en) | 1994-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3945974A (en) | Smoke suppressants for halogen-containing plastic compositions | |
| US3869420A (en) | Smoke-retardant halogen-containing polymer systems | |
| EP0317849A2 (en) | Flame resistant polymer | |
| US4246359A (en) | Flame retardant for hydrocarbon diene rubbers | |
| US4439572A (en) | Zinc oxide-zinc salt smoke suppressant/flame retardants | |
| US4021406A (en) | Flame retardant compositions | |
| US4083789A (en) | Composition containing halogenated polyphosphates | |
| CA2025172A1 (en) | Smoke suppressed flame retardant thermoplastic resin compositions | |
| EP0401366A4 (en) | Thermally stable and light stable flame retardant thermoplastic polyolefin and polystyren compositions | |
| US3591507A (en) | Flame-resistant compositions comprising 1,2 bis(3,4-dibromocyclohexyl)-1,2-dibromoethane and antimony trioxide | |
| US5346938A (en) | Smoke suppressed flame retardant unsaturated polyester resin compositions | |
| US4699734A (en) | Flame-retardant polyolefin compositions containing exudation inhibitor and process for producing same | |
| AU640959B2 (en) | Smoke suppressed flame retardant unsaturated polyester resin compositions | |
| US3787356A (en) | Fire retardant compositions | |
| US3899463A (en) | Flame-retardant composition | |
| US4725638A (en) | Flame retardant polymer compositions | |
| US4211853A (en) | Flame retardant halohydrocarbon polymer composition | |
| EP0691374A1 (en) | Reinforced, flame-resistant thermoplastic composition | |
| JP2848906B2 (en) | Flame retardant of polyhalo aromatic ester used for polyolefin resin | |
| US3761443A (en) | Diels alder adduct flame retardants for polymers | |
| US4175071A (en) | Titanium dioxide as a U.V. screen in fire retardant vinyl polymers | |
| US4346187A (en) | Flame retardant polypropylene compositions containing trityl synergists | |
| US4606852A (en) | Flame retardant polymer compositions | |
| US3835119A (en) | Poly (phosphine oxide derivative) with ammonium polyphosphate as a flame retardant composition for polymers | |
| GB2300860A (en) | Flame retardant styrene polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |