CA1190684A - Compositions of alkylene-alkyl acrylate copolymers having improved flame retardant properties - Google Patents
Compositions of alkylene-alkyl acrylate copolymers having improved flame retardant propertiesInfo
- Publication number
- CA1190684A CA1190684A CA000371565A CA371565A CA1190684A CA 1190684 A CA1190684 A CA 1190684A CA 000371565 A CA000371565 A CA 000371565A CA 371565 A CA371565 A CA 371565A CA 1190684 A CA1190684 A CA 1190684A
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- Canada
- Prior art keywords
- composition
- flame retardant
- alkylene
- compositions
- alkyl acrylate
- 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.)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/105—Compounds containing metals of Groups 1 to 3 or Groups 11 to 13 of the Periodic system
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- 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
- C08K5/02—Halogenated hydrocarbons
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
Abstract
COMPOSITIONS OF ALKYLENE-ALKYL ACRYLATE
COPOLYMERS HAVING IMPROVED FLAME RETARDANT PROPERTIES
SUMMARY OF THE INVENTION
This invention relates to compositions, having improved flame retardant properties and reduced gas evolution on burning, which contain an alkylene-alkyl acrylate copolymer, a halogenat-ed flame retardant additive and an oxide, carbonate, hydroxide or sulfate of magnesium or calcium in an amount of more than 20 and up to about 30 percent by weight. The compositions of the present invention are particularly useful as jacketing material about industrial control cables and telephone wires and cables and as insulation about electrical conductors.
COPOLYMERS HAVING IMPROVED FLAME RETARDANT PROPERTIES
SUMMARY OF THE INVENTION
This invention relates to compositions, having improved flame retardant properties and reduced gas evolution on burning, which contain an alkylene-alkyl acrylate copolymer, a halogenat-ed flame retardant additive and an oxide, carbonate, hydroxide or sulfate of magnesium or calcium in an amount of more than 20 and up to about 30 percent by weight. The compositions of the present invention are particularly useful as jacketing material about industrial control cables and telephone wires and cables and as insulation about electrical conductors.
Description
Q~
BACXGROUND OF THE INVENTION
Compo~itions based on olefin polymers, such a~ co-polymers of an alkylene-alkyl acrylate, by reason of their advantageous physical and electrical properties, have been suggested for use in various commercial applicafions. For example, alkylene-alkyl acrylate copol~ners are corrosion resis-tant, tough an~ ahrasion resistant. Consequently, alkylen~-al~yl acrylate copolymers have been suggested for use in com-positions to be used as 3acketing material about industrial control cables and telephone wires and cables and as insulation about electrical conductors.
Although alkylene-alkyl acrylate copolymers have pro-perties which make them desirable for use in compositions which are to be used as jacketing material and as insulation, as described, alkylene-alkyl acrylate copolymers suffer the dis-advantage of being flammable. In order to render these co-polymers fl~me retardant and also, in order to reduce gas evolu-tion on burning, a halogenated flame retardant additive and an alkaline earth metal salt or base have been added thereto, as 20 described in U.S. Patent 4,243,579. Such compositions are commercially attractive systems which are flame retardant, and upon burning, do not produce dense smoke and do not evolve high levels of acidic ana corrosive gases.
Currently, in light of more stringent indus'cry stand-ards and more stringent gov~rnment regulations, there is an in~lediate need for compositions which are characterized by a higher degree of flame retardancy wîth no unacceptable degrada-tion of other desirable properties previously descri~ed.
3~ l4 DESCRIPTION OF THE INVENTION
The present invention provides compositions whi h meet the need of improved flame retardancy whLle maintaining accept-able standards with re5pect to other desi.xable propertie~.
Compositiorls o~ the present invention, useful for the applications described, comprise a normally solid alkylene~
alkyl acrylate copolymer, from about one to about 30 percent by weight and preferably about 5 to about 20 percent by weight of a halogenated flame retardant additive, and more 10 than 2 0 ana up to about 30 percent by weight of an oxide, carbonate, hydroxide or sulfate of magnesium or calcium. Percent by weight, unless otherwise stated, is based on the total weight of the composition.
The alkylene-alkyl acryl~te copolymers of the present invention are known proaucts produced by reacting an alkene with an alkyl acrylate and usually contain about 2 to about 50 percen~
by weight combined alkyl acrylate.
Suitable al~enes are ethylene, propylene, butene-l, isohutylene, pen~ene-1, 2-methylbutene-1, 3-methylbutene-i, hexene-l, heptene-l, octene-l ana the like.
The alkylene moie~y of the alkylene-alkyl acrylate copol~ners contain from 2 to 18 carbon atoms inclusive, preferably 2 to 3 carbon atoms inclusive.
- Suitable alkyl acrylate monomers which are copolymer-ized with the al~enes fall within the scope o~ the following formula: ~
CH2=C-C=O
OR
wherein Rl is hydroyen or methyl and ~2 is alkyl having one to 8 caxbon atorns :i.nclusi~Je Illustra-tive compounds encompassed by this formula arc: methyl acrylate~ ethyl acrylate, methyl ,.^., ~.
~ ~ D-12277-3 methacrylate, n-butyl acrylate, t-butyl acrylate, n-bu~yl methacrylate, 2-ethylhexyl acrylate and the likP.
Alkylene-alkyl acrylate copolymer~ generally ha~e a density ~ASTMD 1505) with a conditioning as in ASTMD 147-72 o~
about 0.92 to about 0.94 and a melt index (AS~MD-1237 at 44 psi tested pressure) of about 0.5 to about 500 decigrams per minute.
Por purposes of the present invention, the p~eferred copolymer is ethylene-ethyl acrylate, generally having about three to about 40 percent by weight combined ethyl acrylate, preferably having about 5 to about 20 percent by weight combined ethyl acrylate. Comhined alkyl acrylate is conveniently deter-mined by infrared analysis.
Halogenated flame retardant additives, useful for pur-poses of the present invention, are well known to those skilled in the art. These flame retardant additives are halogenated (brominated orchlorinated) organic compounds. The preferred halogenated organic compounds include chloxinated polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride copolymPrs, halogenated paraffin and paraffin waxes, chlorinated alicyclic hydrocarbons, and brominated aromatic compounds. The most preferred include decabromodiphenyl oxide and compounds of the following formulae:
n ~ Rn O O
Il 11 R ~ N ~ N
Il 11 0 0 r n --4~
wherei~ R is independently chlorine or bromine and n is an integer from 1 to 6,such as ethylene(bis-tetrabromophthalimide).
The calcium or magnesium oxides, carbonates, hydrox~
ide~, or sulfates of the present inventior4 are cor~ercially available in different forms and grades.
~ he calcium or rnagnesium oxides, carbonate5, hydrox-ides, or sulfates may be optionally coated with any compatible hydrophobic material7 The preferred coating materials are metal salts of fatty acids, organo silanes and organo titanates.
Exemplary metals of the metal component of the salts of the fatty acids fall in GrouFs~a, IIa or IIb of the Periodic Table ~andbook of Chemistry and Physic~ - 50th Edition). Acids used to form the metal salts are saturated or unsaturated monobasic or dibasic, branched or straight chain fatty acids of 8-20 carbon atoms. Such acids that may be inclu~ed within the prac-tice of this invention, but not limited thereto, are palmi-tic, stearic, lauric, oleic, sebacic, ricinoleic~ palmitoleic and the like. The preferrea acid is stearic acid while the preferred metal salts are calcium stearate and zinc stearate.
The organo silanes are preferably alkoxy silanes such as alkyl alkoxy silane, alkenyl alkoxy silane, alXynyl alkoxy silane, alkyl aryl alXoxy silane, alkenyl aryl alkoxy silane and alkynyl aryl alkoxy silane. Suitable alkoxy silanes include, for example, methyltriethoxy silane, methyl-tris-(2-m~thoxy-ethoxy) silane, dimethyldiethoxy silane, allyltrimethoxy silane and the li~e. Also suitable are the vinyl silanes such as vinyl-tris-(2-methoxyethoxy) silane, vinyl trimetho~y silane, vinyl triethoxy silane and the like. If desired, the organo 5i lane, per se, can be included in the composition as an additive.
Illustrative suitable organo titanates fall within the scQpe of the follo~ing fonnula:
~i(o~3)~
3~
whereinR3 is a hydrocarbon radical- Exemplary of organo titanates are tetrabutyl titanate, tetraisopropyl titanate and the like.
The alkaline earth metal compounds can be coated by admixing about 0.05 to about 5 parts by weight of hydrophobic material per 100 parts by weight of alkaline earth metal salt or base in a two-roll mill, Hensc~el mixer, Wariny blender and the like.
The compositions of the present invention can contai~
other additives, as is well known in the art, depending upon the ultimate use of the composition.
For exarnple, the compositions can contain peroxides, to cure the compositions to crosslinked products, generally on the order of about 0.05 to about 4.0 percent by weight;
antioxidan~s generally on the order of about 0.01 to about 3.0 percent by weight; carbon blacks as well as other additives co~nonly used in moldable compositions, curable compositions, compositions to be extruded into film rnaterial, compositions to be used as coatings and the like~
When the compositions of the present invention are to be used in wire and cable or molding applications, it is aavan-tageous that the compositions contain a filler. A preferred filler is talc, especially talc coated with a metal salt of a fatty acid, previously described. Another preferred filler is clay, especially clay which is calcined.
The compositions of the present invention are conven-iently prepared by blending or compounding the cornponents ~here-of in a suitable apparatus. The aLkylene-alkyl acrylate co-polymer and the other described components rnay be blendedtoye~er by an~ ol the techniques used in ~he art to blend and colnpound thermoplastics to hoMogeneous masses. Prior to or during the blendiny of the cornponents toyether, the calciurn or magnesi~n oxide, carbonate, hydroxide or sulfate may be coated by known Trademark ~6-*
, .
techniques. -As regards bl~nding, the components m~y be fluxed on a variety of apparatus includiny multi-roll mills, screw mill~, continUol~s mixers, extruders and Banbury mixers.
When all the solid components o~ the compositions ilre availahle in the form of a powder, or as small particles, the compositions are most conveniently prepared by firsk making a blend of the components, for instance, in a Banbury*rnixer or a continuous extruder, and then masticating this blend on a heated mill, for instance~ a two-roll mill, and the milling continued until an ultimate mixture of the components is obtained.
~ n those instances wherein the copolymer is not avail-able in powder form, the compositions may be prepared by intro-ducing the copolymer to a two-roll mill, masticating it until it forms a band around roll, after which a blend of the remaining components is added and the milling continued until an ultimate mixture is obtained. The rolls are preferably maintained at a temperature whi~h is within th~ range of 80C to 135C and whic~ is below the decomposition temperatures of the pero~ide compounds if such are usedO The composition, in the form of a sheet, is removed from the mill and then brought into a form, typically dice-like pieces, suitable for subsequent processing.
The compositions may then be extruded onto a wire or cahle, or other substrate. If the cornpositions of the present invention are chemically curableg they are extruded onto wire or cable, or other substrate and vulcanized at elevated tempera-tures of about ~180C and preferably at >200-230C using con-ventional vulcanizing procedures.
The following examples are illustrative of the present inventiOn and are not intended to limit the scope thereof in any manner.
* Tradernark EXAMPL~ 1 Composition, the formulation of which i~ set forth below, was prepared by mixing the cu~.~onents thereof in a Brabender Plastioorder mixer preheated ~o a temperature of 129C.
The compoRition was mixed to homogenietyat a temperature below 135~
Percent By ~7eight Æthylene-ethyl acxylate copolymex having a m~lt index of 1.2 a.nd combine~ ethyl acrylate content of 15-17 percent by weight~ 57.0 Calcium carbonate~ 25.7 Flame retardant. 15 1,2-dihydro-2,3,4-trimethylquinoline (antioxidant). o~7 Di-dC-cumYl_~eroxide 1.6 _ _ _ _ ._ _ _ _ _ _ _ _ Limiting oxygen index (ASTMD 2863-70) 26.8 Th~ flame retardant used contained 67 percent by weight bromine an~ has the formula:
O O
5~c~ ~c~
BR~ o ~ BR4 Ethylene(bis-tetrabromophthalimide) Limiting oxygen index is a stanaard test used to quantitatively measure the deyree o~ flammability. The value o~ 26.8 indicates ~hat the composition of Example 1 is suitable to be used as jacketing about industrial control cables and telephone wir~s and cables and as insulation about electrical conductors such as copper wires~
Xn order to further illustrate the advantageous properties of the compositions of the present invention, * Trademark ~ ~ D-12277-3 compositions were prepared as described in Example 1 and tested for percent ash, percent halogen retained in the ash and percent smoke e~olved.
Percent ash value, which is a measure of retained ash, is important for several reasons. Retained ash serves a5 heat and electrical insulation, alding in maintaining the integrity of the product, on burning in a fire incident. Also, retained ash aids in reducing dripping from the burning product.
A higher percent halogen content in the ash means that less halogen has been released to the atmosphere. A composition which releases less halogen, measured as halogen acid, is less toxic to humans and less corrosive to equipment.
Percent by weight halogen con.ent of ash-determined by the procedure described in Quantitative Organic Microanalysis, A. Steyermark, Academic Press, New York and London, 1961, pages Percent by weight smoke evolved-determined by the procedure described in Journal of Fire and Flammability, Volume 9, October 1978, pages 459-466.
Percen~ by weight ash-determined by the procedure described in Plastics Technology, March 1976, pages 46-49.
Tests noted herein were conducted using plaques pre-pared from samples of the compositions. Plaquçs having dimen-sions of 3 inches by 8 inches by 0O125 inch, were prepared in a press under the following conditions: Pressure - 5000 psi, Temperature - 180C, Time Cyclç 15 minutes.
~9_ 06~34 D--12277--3 ,1 1 ~
O V~ O ~D ~ D O
$
~1 . ~D It'~ O ~D O O ~--1 h7 Ct) a- u~
E~l .) V
m E~
z O~D O O ~o ~ ID CO ~ O .-~
~9 0 ~ ~D O O ~i ~ ~D. `I ~D
a , ,"
~r~ O U:~ O
~4 . . . . . . I
~D O 11~ ~ O O r~
,r~
r r ~ , a) r ~ ~
~r 0 0 ~ ~ ~~ r ~1 11 1 5 t ~ n ~ tt I :, ~: Q ~ 31 _ ~ >1 '~ V J ~V ~' ~ I r ~u J ~1 r, ).4 ~ n ~ a C
~J ~ ~ U q ~ r O ) ~V rl J~ ~c r l .) ~ N S~ C ~:
~) ~ ~ r ~ ~.~ ; I r 1 t~ ~ tr~
~V /V ~rl ~ ) r rl rl 3 .Vl ~ Q al U rl ~ rl ~ `J ~ ~1 : 3 3 o ~ o L ~ I
h - J ~ c ~1 ~ I R ~ ~
(p r U ~ ~ ~V I ~I-r r~ 1 r~ - r 1 p~ r rJI I
L~ ,~r, r-l r- V 5~ -- r,~ r O C ~ rd ~ IJ ~ rl ,-1 ) P
~10--- C~mrArable results are achieved on varying the amounts of the specified salts and bases o~ calcium and magnesium within the range of greater than 20 to about 30 percent by weight.
BACXGROUND OF THE INVENTION
Compo~itions based on olefin polymers, such a~ co-polymers of an alkylene-alkyl acrylate, by reason of their advantageous physical and electrical properties, have been suggested for use in various commercial applicafions. For example, alkylene-alkyl acrylate copol~ners are corrosion resis-tant, tough an~ ahrasion resistant. Consequently, alkylen~-al~yl acrylate copolymers have been suggested for use in com-positions to be used as 3acketing material about industrial control cables and telephone wires and cables and as insulation about electrical conductors.
Although alkylene-alkyl acrylate copolymers have pro-perties which make them desirable for use in compositions which are to be used as jacketing material and as insulation, as described, alkylene-alkyl acrylate copolymers suffer the dis-advantage of being flammable. In order to render these co-polymers fl~me retardant and also, in order to reduce gas evolu-tion on burning, a halogenated flame retardant additive and an alkaline earth metal salt or base have been added thereto, as 20 described in U.S. Patent 4,243,579. Such compositions are commercially attractive systems which are flame retardant, and upon burning, do not produce dense smoke and do not evolve high levels of acidic ana corrosive gases.
Currently, in light of more stringent indus'cry stand-ards and more stringent gov~rnment regulations, there is an in~lediate need for compositions which are characterized by a higher degree of flame retardancy wîth no unacceptable degrada-tion of other desirable properties previously descri~ed.
3~ l4 DESCRIPTION OF THE INVENTION
The present invention provides compositions whi h meet the need of improved flame retardancy whLle maintaining accept-able standards with re5pect to other desi.xable propertie~.
Compositiorls o~ the present invention, useful for the applications described, comprise a normally solid alkylene~
alkyl acrylate copolymer, from about one to about 30 percent by weight and preferably about 5 to about 20 percent by weight of a halogenated flame retardant additive, and more 10 than 2 0 ana up to about 30 percent by weight of an oxide, carbonate, hydroxide or sulfate of magnesium or calcium. Percent by weight, unless otherwise stated, is based on the total weight of the composition.
The alkylene-alkyl acryl~te copolymers of the present invention are known proaucts produced by reacting an alkene with an alkyl acrylate and usually contain about 2 to about 50 percen~
by weight combined alkyl acrylate.
Suitable al~enes are ethylene, propylene, butene-l, isohutylene, pen~ene-1, 2-methylbutene-1, 3-methylbutene-i, hexene-l, heptene-l, octene-l ana the like.
The alkylene moie~y of the alkylene-alkyl acrylate copol~ners contain from 2 to 18 carbon atoms inclusive, preferably 2 to 3 carbon atoms inclusive.
- Suitable alkyl acrylate monomers which are copolymer-ized with the al~enes fall within the scope o~ the following formula: ~
CH2=C-C=O
OR
wherein Rl is hydroyen or methyl and ~2 is alkyl having one to 8 caxbon atorns :i.nclusi~Je Illustra-tive compounds encompassed by this formula arc: methyl acrylate~ ethyl acrylate, methyl ,.^., ~.
~ ~ D-12277-3 methacrylate, n-butyl acrylate, t-butyl acrylate, n-bu~yl methacrylate, 2-ethylhexyl acrylate and the likP.
Alkylene-alkyl acrylate copolymer~ generally ha~e a density ~ASTMD 1505) with a conditioning as in ASTMD 147-72 o~
about 0.92 to about 0.94 and a melt index (AS~MD-1237 at 44 psi tested pressure) of about 0.5 to about 500 decigrams per minute.
Por purposes of the present invention, the p~eferred copolymer is ethylene-ethyl acrylate, generally having about three to about 40 percent by weight combined ethyl acrylate, preferably having about 5 to about 20 percent by weight combined ethyl acrylate. Comhined alkyl acrylate is conveniently deter-mined by infrared analysis.
Halogenated flame retardant additives, useful for pur-poses of the present invention, are well known to those skilled in the art. These flame retardant additives are halogenated (brominated orchlorinated) organic compounds. The preferred halogenated organic compounds include chloxinated polyethylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride copolymPrs, halogenated paraffin and paraffin waxes, chlorinated alicyclic hydrocarbons, and brominated aromatic compounds. The most preferred include decabromodiphenyl oxide and compounds of the following formulae:
n ~ Rn O O
Il 11 R ~ N ~ N
Il 11 0 0 r n --4~
wherei~ R is independently chlorine or bromine and n is an integer from 1 to 6,such as ethylene(bis-tetrabromophthalimide).
The calcium or magnesium oxides, carbonates, hydrox~
ide~, or sulfates of the present inventior4 are cor~ercially available in different forms and grades.
~ he calcium or rnagnesium oxides, carbonate5, hydrox-ides, or sulfates may be optionally coated with any compatible hydrophobic material7 The preferred coating materials are metal salts of fatty acids, organo silanes and organo titanates.
Exemplary metals of the metal component of the salts of the fatty acids fall in GrouFs~a, IIa or IIb of the Periodic Table ~andbook of Chemistry and Physic~ - 50th Edition). Acids used to form the metal salts are saturated or unsaturated monobasic or dibasic, branched or straight chain fatty acids of 8-20 carbon atoms. Such acids that may be inclu~ed within the prac-tice of this invention, but not limited thereto, are palmi-tic, stearic, lauric, oleic, sebacic, ricinoleic~ palmitoleic and the like. The preferrea acid is stearic acid while the preferred metal salts are calcium stearate and zinc stearate.
The organo silanes are preferably alkoxy silanes such as alkyl alkoxy silane, alkenyl alkoxy silane, alXynyl alkoxy silane, alkyl aryl alXoxy silane, alkenyl aryl alkoxy silane and alkynyl aryl alkoxy silane. Suitable alkoxy silanes include, for example, methyltriethoxy silane, methyl-tris-(2-m~thoxy-ethoxy) silane, dimethyldiethoxy silane, allyltrimethoxy silane and the li~e. Also suitable are the vinyl silanes such as vinyl-tris-(2-methoxyethoxy) silane, vinyl trimetho~y silane, vinyl triethoxy silane and the like. If desired, the organo 5i lane, per se, can be included in the composition as an additive.
Illustrative suitable organo titanates fall within the scQpe of the follo~ing fonnula:
~i(o~3)~
3~
whereinR3 is a hydrocarbon radical- Exemplary of organo titanates are tetrabutyl titanate, tetraisopropyl titanate and the like.
The alkaline earth metal compounds can be coated by admixing about 0.05 to about 5 parts by weight of hydrophobic material per 100 parts by weight of alkaline earth metal salt or base in a two-roll mill, Hensc~el mixer, Wariny blender and the like.
The compositions of the present invention can contai~
other additives, as is well known in the art, depending upon the ultimate use of the composition.
For exarnple, the compositions can contain peroxides, to cure the compositions to crosslinked products, generally on the order of about 0.05 to about 4.0 percent by weight;
antioxidan~s generally on the order of about 0.01 to about 3.0 percent by weight; carbon blacks as well as other additives co~nonly used in moldable compositions, curable compositions, compositions to be extruded into film rnaterial, compositions to be used as coatings and the like~
When the compositions of the present invention are to be used in wire and cable or molding applications, it is aavan-tageous that the compositions contain a filler. A preferred filler is talc, especially talc coated with a metal salt of a fatty acid, previously described. Another preferred filler is clay, especially clay which is calcined.
The compositions of the present invention are conven-iently prepared by blending or compounding the cornponents ~here-of in a suitable apparatus. The aLkylene-alkyl acrylate co-polymer and the other described components rnay be blendedtoye~er by an~ ol the techniques used in ~he art to blend and colnpound thermoplastics to hoMogeneous masses. Prior to or during the blendiny of the cornponents toyether, the calciurn or magnesi~n oxide, carbonate, hydroxide or sulfate may be coated by known Trademark ~6-*
, .
techniques. -As regards bl~nding, the components m~y be fluxed on a variety of apparatus includiny multi-roll mills, screw mill~, continUol~s mixers, extruders and Banbury mixers.
When all the solid components o~ the compositions ilre availahle in the form of a powder, or as small particles, the compositions are most conveniently prepared by firsk making a blend of the components, for instance, in a Banbury*rnixer or a continuous extruder, and then masticating this blend on a heated mill, for instance~ a two-roll mill, and the milling continued until an ultimate mixture of the components is obtained.
~ n those instances wherein the copolymer is not avail-able in powder form, the compositions may be prepared by intro-ducing the copolymer to a two-roll mill, masticating it until it forms a band around roll, after which a blend of the remaining components is added and the milling continued until an ultimate mixture is obtained. The rolls are preferably maintained at a temperature whi~h is within th~ range of 80C to 135C and whic~ is below the decomposition temperatures of the pero~ide compounds if such are usedO The composition, in the form of a sheet, is removed from the mill and then brought into a form, typically dice-like pieces, suitable for subsequent processing.
The compositions may then be extruded onto a wire or cahle, or other substrate. If the cornpositions of the present invention are chemically curableg they are extruded onto wire or cable, or other substrate and vulcanized at elevated tempera-tures of about ~180C and preferably at >200-230C using con-ventional vulcanizing procedures.
The following examples are illustrative of the present inventiOn and are not intended to limit the scope thereof in any manner.
* Tradernark EXAMPL~ 1 Composition, the formulation of which i~ set forth below, was prepared by mixing the cu~.~onents thereof in a Brabender Plastioorder mixer preheated ~o a temperature of 129C.
The compoRition was mixed to homogenietyat a temperature below 135~
Percent By ~7eight Æthylene-ethyl acxylate copolymex having a m~lt index of 1.2 a.nd combine~ ethyl acrylate content of 15-17 percent by weight~ 57.0 Calcium carbonate~ 25.7 Flame retardant. 15 1,2-dihydro-2,3,4-trimethylquinoline (antioxidant). o~7 Di-dC-cumYl_~eroxide 1.6 _ _ _ _ ._ _ _ _ _ _ _ _ Limiting oxygen index (ASTMD 2863-70) 26.8 Th~ flame retardant used contained 67 percent by weight bromine an~ has the formula:
O O
5~c~ ~c~
BR~ o ~ BR4 Ethylene(bis-tetrabromophthalimide) Limiting oxygen index is a stanaard test used to quantitatively measure the deyree o~ flammability. The value o~ 26.8 indicates ~hat the composition of Example 1 is suitable to be used as jacketing about industrial control cables and telephone wir~s and cables and as insulation about electrical conductors such as copper wires~
Xn order to further illustrate the advantageous properties of the compositions of the present invention, * Trademark ~ ~ D-12277-3 compositions were prepared as described in Example 1 and tested for percent ash, percent halogen retained in the ash and percent smoke e~olved.
Percent ash value, which is a measure of retained ash, is important for several reasons. Retained ash serves a5 heat and electrical insulation, alding in maintaining the integrity of the product, on burning in a fire incident. Also, retained ash aids in reducing dripping from the burning product.
A higher percent halogen content in the ash means that less halogen has been released to the atmosphere. A composition which releases less halogen, measured as halogen acid, is less toxic to humans and less corrosive to equipment.
Percent by weight halogen con.ent of ash-determined by the procedure described in Quantitative Organic Microanalysis, A. Steyermark, Academic Press, New York and London, 1961, pages Percent by weight smoke evolved-determined by the procedure described in Journal of Fire and Flammability, Volume 9, October 1978, pages 459-466.
Percen~ by weight ash-determined by the procedure described in Plastics Technology, March 1976, pages 46-49.
Tests noted herein were conducted using plaques pre-pared from samples of the compositions. Plaquçs having dimen-sions of 3 inches by 8 inches by 0O125 inch, were prepared in a press under the following conditions: Pressure - 5000 psi, Temperature - 180C, Time Cyclç 15 minutes.
~9_ 06~34 D--12277--3 ,1 1 ~
O V~ O ~D ~ D O
$
~1 . ~D It'~ O ~D O O ~--1 h7 Ct) a- u~
E~l .) V
m E~
z O~D O O ~o ~ ID CO ~ O .-~
~9 0 ~ ~D O O ~i ~ ~D. `I ~D
a , ,"
~r~ O U:~ O
~4 . . . . . . I
~D O 11~ ~ O O r~
,r~
r r ~ , a) r ~ ~
~r 0 0 ~ ~ ~~ r ~1 11 1 5 t ~ n ~ tt I :, ~: Q ~ 31 _ ~ >1 '~ V J ~V ~' ~ I r ~u J ~1 r, ).4 ~ n ~ a C
~J ~ ~ U q ~ r O ) ~V rl J~ ~c r l .) ~ N S~ C ~:
~) ~ ~ r ~ ~.~ ; I r 1 t~ ~ tr~
~V /V ~rl ~ ) r rl rl 3 .Vl ~ Q al U rl ~ rl ~ `J ~ ~1 : 3 3 o ~ o L ~ I
h - J ~ c ~1 ~ I R ~ ~
(p r U ~ ~ ~V I ~I-r r~ 1 r~ - r 1 p~ r rJI I
L~ ,~r, r-l r- V 5~ -- r,~ r O C ~ rd ~ IJ ~ rl ,-1 ) P
~10--- C~mrArable results are achieved on varying the amounts of the specified salts and bases o~ calcium and magnesium within the range of greater than 20 to about 30 percent by weight.
Claims (20)
1. A flame retardant alkylene-alkyl acrylate copolymer composition comprising an alkylene-alkyl acrylate copolymer, from about 1 to 30 weight percent of a halogenated flame retardant ad-ditive, and more than 20, up to about 30 weight percent of at least one of calcium or magnesium oxide, carbonate, hydroxide or sulfate; said weight percents based on the total weight of the composition.
2. A composition as defined in claim 1 wherein the alkylene-alkyl acrylate copolymer is ethylene-ethyl acrylate copolymer.
3. A composition as defined in claim 1 which contains magnesium or calcium carbonate.
4. A composition as defined in claim 1 which contains magnesium or calcium oxide.
5. A composition as defined in claim 1 which contains magnesium or calcium hydroxide.
6. A composition as defined in claim 1 which contains magnesium or calcium sulfate.
7. A composition as defined in claim 1 which contains an antioxidant.
8. A composition as defined in claim 1 which contains a peroxide.
9. A composition as defined in claim 8 wherein the peroxide is di-.alpha.-cumyl peroxide.
10. A composition as defined in claim 1 wherein the flame retardant additive is ethylene(bis-tetrabromophthalimide).
11. A composition as defined in claim 1 wherein the halogenated flame retardant additive is present in an amount of about 5 to about 20 percent by weight.
12. An electrical conductor insulated with the com-position or crosslinked composition of claim 1.
13. A wire or cable jacketed with the composition or crosslinked composition of claim 1.
14. The crosslinked product of the composition defined in claim 1.
150 A composition as defined in claim 1 wherein said composition contains an additional filler.
16. A composition as defined in claim 15 wherein the additional filler is talc.
17. A composition as defined in claim 15 wherein the additional filler is clay.
18. A composition as defined in claim 15 wherein the additional filler is carbon black.
19. A composition as defined in claim 1 which contains an antioxidant, additional filler, and an organo silane.
20. A composition as defined in claim 1 which contains an antioxidant, additional filler and an organo titanate.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12750980A | 1980-03-05 | 1980-03-05 | |
US127,509 | 1980-03-05 | ||
US232,480 | 1981-02-11 | ||
US06/232,480 US4394471A (en) | 1978-09-21 | 1981-02-11 | Compositions of alkylene-alkyl acrylate copolymers having improved flame retardant properties |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1190684A true CA1190684A (en) | 1985-07-16 |
Family
ID=26825700
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000371565A Expired CA1190684A (en) | 1980-03-05 | 1981-02-24 | Compositions of alkylene-alkyl acrylate copolymers having improved flame retardant properties |
Country Status (15)
Country | Link |
---|---|
US (1) | US4394471A (en) |
EP (1) | EP0035279B1 (en) |
KR (1) | KR850001210B1 (en) |
AR (1) | AR223919A1 (en) |
AT (1) | ATE11297T1 (en) |
AU (1) | AU543362B2 (en) |
BR (1) | BR8101227A (en) |
CA (1) | CA1190684A (en) |
DE (1) | DE3168227D1 (en) |
DK (1) | DK98381A (en) |
ES (1) | ES8205000A1 (en) |
FI (1) | FI810646L (en) |
IN (1) | IN154993B (en) |
NO (1) | NO810722L (en) |
PL (1) | PL229993A1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59226413A (en) * | 1983-06-06 | 1984-12-19 | 住友電気工業株式会社 | Optical composite cable |
GB8300535D0 (en) * | 1983-01-10 | 1983-02-09 | Bicc Plc | High voltage electrical apparatus |
EP0207750A3 (en) * | 1985-07-04 | 1988-07-27 | Imperial Chemical Industries Plc | Fillers |
JPH0354233A (en) * | 1989-04-19 | 1991-03-08 | Furukawa Electric Co Ltd:The | Complex flame retardant and flame-retardant resin composition containing same |
FR2659083B1 (en) * | 1990-03-02 | 1993-05-07 | Atochem | FLAME RETARDANT THERMOPLASTIC RESIN COMPOSITION HAVING IMPROVED HEAT RESISTANCE. |
US5298544A (en) * | 1993-08-05 | 1994-03-29 | General Electric Company | Non-halogen flame retardant thermoplastic composition |
US5728323A (en) * | 1995-11-06 | 1998-03-17 | Unitex Chemical Corporation | Process for preparing dialkyl tetrahalophthalates |
US6337419B1 (en) | 1997-07-17 | 2002-01-08 | Unitex Chemical Corporation | Plasticized polyvinyl chloride compound |
KR20010001126A (en) * | 1999-06-02 | 2001-01-05 | 남창우 | Thermoplastic resin composition having low fume property and low toxicity |
US9085678B2 (en) | 2010-01-08 | 2015-07-21 | King Abdulaziz City For Science And Technology | Clean flame retardant compositions with carbon nano tube for enhancing mechanical properties for insulation of wire and cable |
US8871019B2 (en) | 2011-11-01 | 2014-10-28 | King Abdulaziz City Science And Technology | Composition for construction materials manufacturing and the method of its production |
Family Cites Families (26)
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DE1032540B (en) * | 1957-04-15 | 1958-06-19 | Roehm & Haas Gmbh | Process for the production of acrylate-based plastics with reduced flammability |
US3350372A (en) * | 1960-08-22 | 1967-10-31 | Gulf Oil Corp | Ethylene/acrylate ester copolymers |
US3326833A (en) * | 1964-03-06 | 1967-06-20 | Dow Chemical Co | Composition comprising a chlorinated olefin rubber and an ethylene copolymer |
US3382209A (en) * | 1966-05-23 | 1968-05-07 | American Cyanamid Co | Flame-retardant systems |
US3943087A (en) * | 1968-05-11 | 1976-03-09 | Kabel-Und Metallwerke Gutehoffnungshuette Ag | Fireproof self extinguishing composition |
US3873567A (en) * | 1968-09-05 | 1975-03-25 | Universal Oil Prod Co | N-substituted polybromoaromatic ortho-dicarboximides |
US4012343A (en) * | 1970-07-08 | 1977-03-15 | The Dow Chemical Company | Crosslinked olefin polymer having improved flame retardance |
DE2105187A1 (en) * | 1971-02-04 | 1972-08-10 | Veba Chemie Ag | Flame-resistant enamels |
US3816367A (en) * | 1971-06-12 | 1974-06-11 | M & T Chemicals Inc | Flame retardant compositions |
US3832326A (en) * | 1972-06-01 | 1974-08-27 | Nat Distillers Chem Corp | Flame retardant compositions |
US3772232A (en) * | 1971-06-30 | 1973-11-13 | Monsanto Chemicals | Flame-retardant polymers |
US3865782A (en) * | 1972-06-06 | 1975-02-11 | Michigan Chem Corp | Polyacrylate plastic compositions containing flame retardants |
US3897346A (en) * | 1972-06-16 | 1975-07-29 | Gaf Corp | Flame retardant agent for synthetic plastics |
JPS5436702B2 (en) * | 1972-10-18 | 1979-11-10 | ||
JPS5529824B2 (en) * | 1973-09-24 | 1980-08-06 | ||
GB1474777A (en) * | 1973-10-29 | 1977-05-25 | Tokuyama Soda Kk | Process for producing flame retardant shaped articles of thermoplastic synthetic resins |
NL7512126A (en) * | 1974-10-18 | 1976-04-21 | Mitsubishi Petrochemical Co | PROCEDURE FOR PREPARING A SELF-AGING RESIN COMPOSITION AND PRODUCTS MANUFACTURED FROM THIS. |
US3996142A (en) * | 1974-12-11 | 1976-12-07 | Nl Industries, Inc. | Smoke and fire retardants for halogen-containing plastic compositions comprising the reaction product of magnesium oxide and a zinc salt of an acid |
ES444945A1 (en) * | 1975-03-03 | 1977-08-16 | Gen Electric | Flame-resistant composition, and electrical product thereof |
US4094853A (en) * | 1975-05-15 | 1978-06-13 | Kenrich Petrochemicals, Inc. | Alkoxy titanate salts useful as coupling agents |
GB1510237A (en) * | 1975-10-18 | 1978-05-10 | Takahashi H | Inorganic filler and resin compositions filled therewith |
US4162245A (en) * | 1978-01-09 | 1979-07-24 | Dow Corning Corporation | Method of preparing an improved organic resin composition and an improved organic resin thereby |
US4353997A (en) * | 1978-03-31 | 1982-10-12 | Union Carbide Corporation | Compositions based on water-curable, silane modified copolymers of alkylene-alkyl acrylates |
US4291136A (en) * | 1978-03-31 | 1981-09-22 | Union Carbide Corporation | Water-curable silane modified alkylene alkylacrylate copolymer and a process for its production |
US4192792A (en) * | 1978-07-20 | 1980-03-11 | Kenrich Petrochemicals, Inc. | Atactic polypropylene |
US4243579A (en) * | 1978-09-21 | 1981-01-06 | Union Carbide Corporation | Flame retardant alkylene-alkyl acrylate copolymer composition |
-
1980
- 1980-03-02 AU AU67970/81A patent/AU543362B2/en not_active Ceased
-
1981
- 1981-02-11 US US06/232,480 patent/US4394471A/en not_active Expired - Lifetime
- 1981-02-24 CA CA000371565A patent/CA1190684A/en not_active Expired
- 1981-02-27 BR BR8101227A patent/BR8101227A/en unknown
- 1981-03-02 FI FI810646A patent/FI810646L/en not_active Application Discontinuation
- 1981-03-03 NO NO810722A patent/NO810722L/en unknown
- 1981-03-04 PL PL22999381A patent/PL229993A1/xx unknown
- 1981-03-04 AR AR284516A patent/AR223919A1/en active
- 1981-03-04 DK DK98381A patent/DK98381A/en not_active Application Discontinuation
- 1981-03-04 DE DE8181101552T patent/DE3168227D1/en not_active Expired
- 1981-03-04 ES ES500069A patent/ES8205000A1/en not_active Expired
- 1981-03-04 AT AT81101552T patent/ATE11297T1/en not_active IP Right Cessation
- 1981-03-04 IN IN233/CAL/81A patent/IN154993B/en unknown
- 1981-03-04 EP EP81101552A patent/EP0035279B1/en not_active Expired
- 1981-03-04 KR KR1019810000699A patent/KR850001210B1/en active
Also Published As
Publication number | Publication date |
---|---|
PL229993A1 (en) | 1981-11-13 |
ATE11297T1 (en) | 1985-02-15 |
NO810722L (en) | 1981-09-07 |
AR223919A1 (en) | 1981-09-30 |
AU543362B2 (en) | 1985-04-18 |
FI810646L (en) | 1981-09-06 |
EP0035279A3 (en) | 1982-02-03 |
AU6797081A (en) | 1981-09-10 |
KR850001210B1 (en) | 1985-08-20 |
DK98381A (en) | 1981-09-06 |
BR8101227A (en) | 1981-09-08 |
US4394471A (en) | 1983-07-19 |
ES500069A0 (en) | 1982-06-01 |
EP0035279B1 (en) | 1985-01-16 |
DE3168227D1 (en) | 1985-02-28 |
IN154993B (en) | 1984-12-22 |
EP0035279A2 (en) | 1981-09-09 |
KR830005301A (en) | 1983-08-13 |
ES8205000A1 (en) | 1982-06-01 |
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