CA2069075A1 - Low toxicity fire retardant thermoplastic material - Google Patents
Low toxicity fire retardant thermoplastic materialInfo
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- CA2069075A1 CA2069075A1 CA 2069075 CA2069075A CA2069075A1 CA 2069075 A1 CA2069075 A1 CA 2069075A1 CA 2069075 CA2069075 CA 2069075 CA 2069075 A CA2069075 A CA 2069075A CA 2069075 A1 CA2069075 A1 CA 2069075A1
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Abstract
ABSTRACT of the DISCLOSURE
A fire-retardant thermoplastic compound that can be used as compounded or further enhanced through chemical cross linkage. The compounding thereof and the composition are disclosed. The compound is manufactured from a composition of a copolymer or terpolymer with a carboxylic acid comonomer and optionally a low modulus polymer and a synthetic hydrocarbon elastomer with or without a graft of ethylenically unsaturated carboxylic acid or anhydride. A fire retardant additive comprising a group I, group II or group III metal oxide hydrate with the proviso that at least 1% by weight of the composition is in the form of an organopolysiloxane. The compound may be used for sheet or wire extrusion and action for injection or compression molding.
A fire-retardant thermoplastic compound that can be used as compounded or further enhanced through chemical cross linkage. The compounding thereof and the composition are disclosed. The compound is manufactured from a composition of a copolymer or terpolymer with a carboxylic acid comonomer and optionally a low modulus polymer and a synthetic hydrocarbon elastomer with or without a graft of ethylenically unsaturated carboxylic acid or anhydride. A fire retardant additive comprising a group I, group II or group III metal oxide hydrate with the proviso that at least 1% by weight of the composition is in the form of an organopolysiloxane. The compound may be used for sheet or wire extrusion and action for injection or compression molding.
Description
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LOW TOXICITY FIRE R~TARDAN~ THERNOP~A~TIC MATERIA~
FIELD OF THE INVENTION
This invention relates to very low toxicity, fire retardant thermoplastic compositions which may be processable into various products in which fire safety is a consideration.
BACKGROUND OF THE INVENTION
Although flame retardant polymer compositions have been in use for several decades, they have generally relied upon the presence of halogens, mainly chlorine or bromine containing chemicals, to yield flame retardancy.
Examples include polychloroprene ("neoprene"), chlorosulphonated polyethylene ("Hypalon"), thermoplastic PVC compounds, or compounds of polyethylene with halogenated flame retardant additives. Matex-ials under development over the last ten years, and even more intensively in the last five years in Europe and the United States have focused on halogen free, flame retardant (HFFR) compounds, since halogens give off very toxic and corrosive combustion products in fires.
Thermoset HFFR's have been developed based on polyethylene and its copolymer.s, but these materials have inherently high processing costs due to the need for cross-linking. Thermoplastic HFFR's, usually classified as thermoplastic polyolefins or TPO's since they are typically based on polymers and copolymers of ethylene and propylene, are the focus of much industrial materials research at present for construction and transportation because of their greater ease of use (fabrication into end use products) and the recyclability of trim or scrap.
Development of a cost ef~ective and acceptable performance HFFR/TPO is a challenging project. The essence of the technical challenge is as ~ollows:
Conventional materials, namely PVC compounds, have shown a good balance of properties in mechanical strength and flexibility, chemical, aging resistance and low cost.
Unfortunately, burning PVC's release a great deal o~
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black smoke and their combustion fumes contain HCl gas, which is highly corrosive, particularly in combination with the water used to fight fires. This hydrochloric acid is capable of destroying e~cpensive computer equipment and even such rugged electrical fixtures as fuse boxes which may not be directly destroyed by the flame or heat of a fire.
~ alogen free systems of modest cost are restricted ko polyolefins in terms of raw material. Polyole~ins do not have inherently good flame resistance. Choice of halogen free flame retardant additives is limited to certain hydrated halogen free flame retardant additive minerals such as alumina trihydrate ~ATH) or magnesium hydroxide, which are relatively inexpensive.
These flame retardant additives function by releasing their water of hydration, preferably at temperatures above those required for processing but below those of combustion of the flame retardant composition. At relatively high concentrations, such additives also impair combustion by conducting heat relatively e~ficiently from burning surfaces. To maximize these flame-retardant effects, it is preferable that the flame retardant additives be present at maximum levels.
However, these particular halogen free flame retardant materials are relatively inefficient and must be added in large amounts (>50% by weight). Because such flame retardant materials are non reinforcing in the final product, HFFR/TPO compounds using this conventional technology normally have poor strength and flexibility, poor processing characteristics (eg. ease of mixing and extrusion) and only fair flame retardancy.
Approaches tried to avoid these difficulties include the use of coupling agents (to compensate for the non-reinforcing nature of ATH~, and intumescent additives~al~o called char formers).
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Silicone flame retardants for plastic compositions have been extensively investigated in United States patent 4,387,176. A composition which lends fire-retardancy to a thermoplastics includes a silicone with a group IIA metal organic salt and a silicone resin which is soluble in the silicone to impart flame-retardancy to the thermoplastic. The silicone is of the general organopolysiloxane group, such as polydimethylsiloxane.
The silicone resin is generally represented by the formula MQ where M is the monofunctional group of the average formula R3Sioo5 and the tetrafunctional Q units of the average formula SiO2 with the average ratio of approximately 0.3:4 of M units per Q unit. The patent teaches that this fire-retardant composition is useful with a variety of thermoplastics including specifically polypropylene, polyethylene~ polycarbonate, polystyrene, acrylonitryl-butadiene-styrene terpolymer, polyphenylene oxide-polystyrene blends, acrylic polymer, polyurethane and polyamides. It is required that the group IIA metal organic salts be included to ensure solubility of the silicone resin in the polysiloxane base. Representative salts include magnesium stearate, calcium stearate, barium stearate, strontium stearate. It has been found, however, that compositions of this type are not readily processable particularly when high loadings of fire-retardant additives are included.
More particularly, Frye, discloses a flame retardant including three principal ingredients:
1. polysiloxanes which are organopolysiloxane polymers;
2. Group IIA metal carboxylic acid salts; for example, magnesium stearate, calcium stearate, barium stearate and strontium stearate; and 3. silicone resins such as the General Electric silicone sold under the trademark SR545.
Halides may be used to improve the fire retardancy properties of this combination of components. The major . ~ , .
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components may be used with various thermoplastics, suchas poly~thylenes, polypropylenes, and polybutylenes as well as copolymers and polycarbonates. Heat activated cross-linkers, such as peroxides, may be used to initiate cross linking in the composition in an attempt to improve physical characteristics of the material. Based on a review of the examples of this patent, generally Frye requires the use of halogens to achieve a suitable flame retardancy to meet commonly acceptable indexes for flame retardancy.
SUMMARY OF THE INVENTION
According to an aspect of the invention, a ~ire-retardant composition comprises:
~a) 5% to 60% by weight of an olefinic copolymer or terpolymer wherein 3% to 20% by weight of the copolymer or terpolymer is a carboxylic acid comonomer;
~b) 1% to 15% by weight of an organopolysiloxane;
and (c) 20% to ~5% by weight of a flame-retardant additive comprising a group I or group II or group III metal oxide hydrate.
According to another aspect of the invention, the processability of the above composition is greatly improved by including a dialdehyde in the composition.
According to another as~ect of the invention, the formability of the composition is greatly improved by the inclusion of polymers, such as low modulus ethylene copolymers, polyethylene, polypropylene, ethylenepropylene synthetic rubbers and ethylenepropylene elastomers with a reactive monomer graft.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the invention are shown in the drawings, wherein:
Figures :L and 2 show weight and percent weight loss of two compositions during heating.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
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s compositions of this invention provide a series of very low toxicity, ~ire-retardant compounds that comply with the requirements of a Class A
composition when tested in accordance with the procedures of ASTM E-84. The preferred compositions include a copolymer or terpolymer wherein 3% to 20% by weight of the copolymer or terpolymer is a carboxylic acid comonomer. These compounds are intended for use in the construction, building and wire insulation industries.
lo ~ire-retardant plastics are commonly availa~leO
However to achieve their ratings, it has been essential to use halogenated polymers or additives as flame retardant agents. As already noted, those materials are becoming unacceptable in respect to the toxicity and corrosivity of the decomposition products when subjected to heat and/or fire.
The flame retardant compositions of this invention release combustion products of low optical density and low levels of toxicity. These materials can be manufactured without using harmful halogenated additives.
The flame retardant propertiPs of these compositions are advantageous in the construction, building and wire insulation industries in meeting the requirements of burn tests in accordance with ASTM E-84 in addition to UL 94 V-O and UL wire and cable vertical flame tests.
These compositions perform particularly well in characteristics of Flame Spread Index [FSI3 and Smoke Density [SD~ These characteristics are now commonly specified in government regulations and included in specifications of other agencies i.e. Underwriters Laboratories, and State, Provincial and Municipal Building codes.
The composition, according to this invention, when cross-linXed by irradiation or chemical methods has quite surprisingly enhanced physical properties particularly with respect to the elongation parameter. Although the reasons are not readily understood, it appears that , .
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irradiation of the composition increases elongation properties of the composition rather than the commonly understood decraase in elongation. The composition o~
this invention is readily modified to permit processing into various articles of manufacture which include building materials, such as wallboards, ceiling panels, pipe wrap, wire cladding and insulation and the like.
Such processability may be improved and enhanced by various additives readily incorporated in the composition to enable injection molding of the composition as well as compression molding and blow molding.
The fire-retardant composition of this invention comprises:
5% to 60~ by weight of an olefinic copolymer or terpolymer wherein 3% to 20% by weight of the copolymer or terpolymer is a carboxylic acid comonomer.
According to a preferred embodiment of the invention, the copolymer or terpolymer is selected from the group consisting of a copolymer of ethylene and ethylene acrylic acid and a copolymer of ethylene and methacrylic acid. In each of these copolymers, there is 3~ to 20~ by weight of the copolymer of carboxylic acid comonomer. Although the reactivity of the copolymer, terpolymer with a carboxylic acid comonomer with other components of the composition i5 not fully understood, it is theorized that the carboxylic acid comonomer is reactive with the other components o~ the composition to improve processability, formability and fire retardancy.
In addition to the copolymer, terpolymer, another component of the composition is 1% to 15% by weight o~ an organopolysiloxane. The organopolysiloxane is a compound selected from the group represented by the formulae:
R3sios/ R2Sio~ Rlsiol5, RIR2sioo5~ Sio, (Rl)2sio, RSiol5 and SiO2, wherein each R represents independently a saturated or unsaturated monovalent hydrocarbon radical, R~ represents 2~9~7~
a radical such as R or a radical selected from the group consisting of a hydrogen atom, hydrGxyl, alkoxyl, aryl, vinyl, or allyl radicals; and wherein said organopolysiloxane has a viscosity of approximately 600 to 300,000,000 centipoise at 25OC.
Organopolysiloxane acts as a plasticizer (or internal lubricant), a low level linking agent and a coupling agent between the hydrophobic polymer and the hydrophilic flame retardant additive material. As a result of this unexpected effect of the organopolysiloxane, it is now possible to incorporate larger amou~ts of the hydrophilic flame retardant additive than in previous flame retardant compositions.
Surprisingly, compositions, in which an organopolysiloxane is thus utilized, retain plasticity and processability even at relatively low temperatures.
The fire retardancy of some of the compositions of this invention may be improved by including active silicone resin in the organopolysiloxane. The reactive resin is represented by the formula:
MQ
wherein said reactive silicone resin is comprised of monofunctional M units of the averagP formula R3Sioos and tetrafunctivnal Q units of the average formula sio2, and having an average ratio of approximately 0.3 to 4.0 M
units per Q unit.
From a solubility standpoint for the organosiloxane, processing conditions may require the use of group II
metal organic salts. Appropriate amounts of the group II
metal organic salt, such as metal stearates, are added to the composition as required to solubilize the reactive silicone resin in the polysiloxane base.
It is believed that the reactivity o~ the polysiloxane with the carboxyl moieties of the copolymer, terpolymer aids in the incorporation of the hydrophilic flame-retardant additives in the polymer composition.
Hence it is now possible to incorporate larger amounts of -:. ' ~ ~ ' ': , .
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the flame-retardant additives than in previous flame-retardant compositions while ret:aining processability and subsequent formability into desired commercial products.
One organopolysiloxane useful in the compositions of this invention is Dow Corning 200 Fluid. It is a dimethylsiloxane polymer. This silicone polymer is essentially non-reactive except for a small amount of silanol (approximately 200 to 800 parts per million) left over after processing. Dow Corning 200 Fluid can be made reactive, if desired, through the addition of a secondary hydroxyl functional silicone resin, such as Dow Corning 1248 Fluid.
Another useful organopolysiloxane is General Electric's SFR 100, which is essentially a silicone fluid similar to the Dow corning 200 Fluid with the difference that is has been modified through the addition of group II metal organic compound(s) and a reactive silicone resin (specifically polytrimethyl-silylsilicate) represented by the formula MQ, where said reactive silicone resin is comprised of monofunctional M units of the average formula ~3sio05 and tetrafunctional Q units of the average formula SiO2 and having an average ratio of approximately 0.3 to 4.0 M units per Q unit having a ratio of approximately 0.3 to 4.0 M units per Q unit.
The hydrophilic fire-retardant additives, according to this invention, are generally defined by group I and group II metal oxide hydrates. There are a variety of such hydrates available, although the preferred hydrates are selected from the group consisting of alumina trihydrate, magnesium hydroxide and hydrotalcite (sodium aluminum hydroxy carbonate). Another hydrate, which is useful in some compositions, is hydracarb, which is a form of hydrated calcium carbonate. A preferred concentration of the metal oxide hydrates is in the range of 20 to 40% by weight.
The organopolysiloxane may have a viscosity in the range of 0.6 centipoise to 300X106 centipoise, although in 7 ~
g most situations the preferred viscosity range is lOx103 centipoise to 900X103. For the compositions which are used in a variety of commercial products, such as coverings for wire cable, the viscosity is normally in the range of 30x103 centipoise to 600x~03 centipoise. The preferred organopolysiloxane is polydimethylsiloxane.
Other significant additives for use in the composition of this invention, which further enhance the fire retardancy thereof, is the use of red amorphous phosphorous. It has been found that the amount of red phosphorous used can range from approximately 1~ to 10%, pre~erably in the range of 1% to 4% and most preferred in the range of 1 to 2%.
In addition to the fire-retardant additive, other suitable fillers may be included, such as talc, calcium carbonate, mica, clay, zinc borate, wallastonite and mixtures thereof. A preferred amount of zinc borate is in the range of 5% to 30% by weight in the composition.
Zinc borate is particularly effective when used in combination with red amorphous phosphorous.
It has been found that the addition of dialdshydes surprisingly improves the processability and workability of the compositions. Preferred dialdehydes are selected from the group consisting of glyoxal and glutaraldehyde.
The dialdehydes are used in the range of 0.1% to 4%
by weight of the composition, although the preferred range is from 0.5% to 3% by weight of the selected dialdehyde in the composition.
Although the function of the dialdehyde in the composition is not fully understood, it is believed that the additional carboxyl groups of the dialdehyde react to combine with the organopolysiloxane and the carboxyl groups of the co- and terpolymers. A dialdehyde (such as glyoxal) is believed to cross-link the polymeric units by polycondensation reactive processing. In the field of ~ire retardant thermoplastics, free radical polymerization had heretofore been the method or choice.
20~9075 The use of polycondensation is a novel approach which gives unexpectedly good fire rel:ardancy and processability. This approach causes cross-linking which increases with the amount of dialdehyde used.
To further enhance this reactivity, it has also been found that the addition of monorner grafts, such as maleic anhydride, further enhance the composition. Furthermore, maleic anhydride may be used with other additives to be described. Such further uses include grafting of the maleic anhydride onto polyolefins. Also, maleic anhydride may be used as an alloying agent which facilitates the combination of polyolefins with copolymers thersof.
Formability of the composition, particularly in sheet form, becomes important in forming a variety of building products, such as ceiling tiles and the like.
To enhance the formability, the inclusion of up to 30% by weight of a pol~mer selected from the group consisting of low modulus ethylene copolymers, polyethylene, polypropylene, ethylenepropylene synthetic rubbers and ethylenepropylene elastomers with a reactive monomer graft are particularly useful. The low modulus ethylene copolymers may be selected from the group consisting of ethylenevinylacetate, ethylene-methylacrylate, ethyleneethylacrylate and ethylene-butylacrylate. As previously noted, the properties of the ethylenepropylene elastomer may be improved with a monomer graph, particularly maleic hydride.
Further enhancements of the processability of this composition may be achieved by the use of either short-chain carboxylic acids, such as fumeric acid, citric acid, formic acid, tartaric acid, lactic acid and short-chain (Cl- C6) amino acids. Of this group, tartaric acid is preferred. Also longer chain (C8 - C22)fatty acids are used, particularly stearic acid. One or more of these acids may be compounded into the mix or tumble blended after pelletiæing. The use of either or both o~ these .
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acids siynificantly reduces the pressures for extrusion thereof and hence increases processability. Preferred concentration for the tartaric acid in the composition is 0.1% to 5% by weight thereof. With stearic acid, the prefarred concentration is in the range of 0.1% to 3% by weight thereof. The acids can be incorporated directly in the blend, or as already mentioned tumble blended after pelletizing of the fire retardant composition so as to be part o~ the composition during extrusion.
Although the composition of this invention is intended to be halogen-free, in certain situations where use of halogens is not of particular concern, the fire retardancy of the composition can be enhanced by the addition of organic halides, such as decabromo-diphenyloxide. Normally when halogens are incorporated into a composition, an antimony oxide synergist is included with the composition up to approximately 10% by weight to improve flame retardancy hy combininy the halogens, thus preventing their loss to the atmosphere during combustion.
According to a preferred embodiment of the invention, a representative composition providing for fire retardancy and processability and formability is the following:
(a) 5% to 60% by weight of (i) a copolymer of ethylene and acrylic acid containing from 3% to 9.0% of the acrylic acid comonomer and (ii) with 2% to 10% by weight of the mixture comprised of the organopoly-siloxane coupling agent;
(b) 5% to 20% by weight of the composition of at least one polymeric material selected from ethylene copolymers, polyethylene and/or from a group of synthetic hydrocarbon elastomers;
(c) 50% to ~5% by weight of the composition of 35 a filler comprising 40% to 100% by weight of at least one of aluminum trihydrate and magnesium hydroxide and 0% to ~ .
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60% by weight of at le~st one of hydracarb, zinc borate, mica and clay.
These compositions may be extruded into sheet material having a Flame Spread Index [FSI] of less than 50 and a Smoke Density [SD] of less than 50.
Preferably the compositions of the present invention also contain 5% to 20% of a polymeric material selected from combinations of synthetic hydrocarbons elastomers and low modulus polymers and mixtures thereof. In embodiments of the composition the elastomer is defined as a substance that is capable of being extended to twice its length at 68C and on release of the applied stress returns with force to approximately its original length.
Compatibility with polyethylene is a desirable feature in order to improve product toughness. The use of high ethylene elastomers is essential to provide the melt flow properties required.
It has been found that the combined use of copolymer of ethylene acrylic acid with the oryanic polysiloxane provides a slight improvement in fire retardancy, particularly when only 1% to 5% by weight of the composition is the desired organopolysiloxane.
As already noted, the preferred elastomers are ethylenepropylene copolymer or an ethylenepro-pylenediene terpolymer or a terpolymer e.g. ethylenepropylenediene.
In combination the polymeric material may be a low modulus polymer. This category includes such polymers as polyethylene, ethylenevinylacetate, ethyleneethyl-acrylate, and ethylenemethylacrylate copolymers as well as branched polymers of the above having maleic anhydride or other suitable carboxylic group grafted thereon.
The carboxylic acid copolymer, such as EAA, plus other polymeric materials comprises 15% to 30% by weight of the composition~ However for most methods o~
fabrication, the carboxylic acid copolymer, such as FAA, plus other polymeric material should be at least 25% o~
the composition.
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The composition of the present invention also contains 50% to 85%, especially 55% to 75% and more particularly 55% to 65% by weight of the composition of fire-retardant additive. Of this filler 40 to 100 parts by weight is alumina trihydrate [ATH] viz, Al2033H20, and/or magnesium hydroxide and/c)r sodium aluminum hydroxy carbonate and hydrotalcite. According to an aspect o~
the invention all of the filler may be ATH or magnesium hydroxide. The remainder of the filler, i.e. up to 60%
parts by weight is hydracarb, zinc borate, mica and/or clay incorporating color pigments, lubricants and stabilizers not to exceed 10 parts of the 0 to 60 parts designated.
In order to facilitate processing of the compositions of this invention, it is preferred that the flame-retardant, additive material has a relatively broad particle size distribution. This requires selection of a mechanically ground flame-retardant, additive material or a precipitated product. According to one embodiment of the invention, the flame-retardant, additive material will have a coarse and fine fraction with a distribution of about o.5 to 60.0 mm and a median of about 2.5 mm.
The flame-retardant, additive material should have a coarse fraction of about 60% by weight. High proportions of fine particles may cause processing difficulties at high flame-retardant, additive material levels but may improve flame resistancy due to greater surface area.
The compositions of this invention should all be compounded prior to fabrication. The equipment recommended must be of the high intensity design. The mixer must also incorporate adequate auxiliary equipment including scales and finishing equipment with proper drying facilities. The compounder [mixer] should be computer controlled for optimum mixing cycle.
Recommended mixers are: Banbury, Moriyama, FCM ~Farrel Continuous Mixer], Pomini Continuous Mixer and other high intensity mixers, i.e. Berstorff, Werner Fleiderer etc.
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The compounding equipment should be operated at temperatures below the decomposition temperature of the filler, it being understood that if the material contains more than one flame-retardant, additive material, the temperature is lower than the lowest decomposition temperature of such flame-retardant, additive material.
It is anticipated that the compositions will contain at least one antioxidant and at least one ultraviolet (W) absorber. It will be appreciated by those skilled in the art that the amount and type of additive may effect changes in and the rate of change of properties over a period of time i.e. especially physical properties of products derived therefrom. One property of particular importance is the color of the composition.
Apart from matters like cigarette smoke and pollution the aesthetic qualities of the product must remain as installed.
In another embodiment of the present invention all components are equivalent except for the elastomer indicated. An elastomer may be substituted consisting of an ethylene propylene elastomer to which reactive monomer such as maleic anhydride has been grafted. As is appreciated, the polyolefin back-bone, provides outstanding environmental resistance, aging properties, thermostability, chemical resistance as well as ease of processing. The reactive group on the polyolefin back-bone results in improved adhesion properties to various substrate materials. It can be utilized directly as one of the polymeric materials as all or part of 5 - 20% by weight of the composition.
Optionally, a free radical acceptor (acrylic monomer or dimer) or a chemical cross linking agent (i.e., peroxide) enhances irradiatable cross linkage or chemical cross linkage respectively. Physical properties i.e.
tensile strength, tensile modulus, impact resistance and flexibility will show definite improvement.
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Free radical linking bet-ween carhon atoms of the formed composition, either through irradiation or chemical bonding, as noted u~ually increases many physical properties. However, it is generally understood cross-linking in the polymeric composition reduces elongation of the formed composition. This is due to the cross-linking bonds normally reducing the elastomeric properties in the composition. However, quite surprisingly with this composition, cross-linking increases elongation properties of the formed composition when subjected to tensile forces. Irradiation then provides increased tensile strength as well as increased elongation. The reasons for such reversal in properties of the composition are not readily understood. However, as demonstrated in the examples, such properties are readily repeatable with the composition of this invention.
The preferred technique for inducing cross-linking in the formed composition is the use of irradiation.
Normally irradiation takes place by the use of an electron beam having an ionization energy which releases radiation to encourage free radical cross-linking in the composition. The irradiation energy is measured in megarads where desired exposure is in the range of 2 to 15 megarads depending upon the rate of processing and the thickness of material to be treated. As is understood, gamma radiation from Colbat 60 has higher penetration rates than the normal form of electron beam radiation, so that lower dosages may be used in the range of one megarad and higher. The choice of tha irradiation is to some extent dependent upon the processing method and the type of article manufacture to be treated.
With glyoxal (tha preferred dialdehyde), use of 0.1%
to 4% by weight of the total product provides the preferred results. Concentrations of up to 10% by weight may be used where processability of the other components is a problem. Too high a concentration of dialdehyde, ' ~: , , ' ., ' ' .:
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however, yields a thermoset rather than a thermoplastic.
Thermosets have very reduced flow characteristics (compared to thermoplastics) and are extremely difficult, if not impossible, to process, so they normally would not be acceptable for formation into sheet, tiles, wire coverings and the like.
The use of glyoxal and an organopolysiloxane enables concentrations of flame retardant additives as high as 85% by weight to be practically processable using conventional extrusion and molding techniques.
Other members of the homologous series of dialdehydes will also aid processability such as glutaraldehyde.
Maleic anhydride is useful with polyolefins, such as PE, PP, EVA, etc. and with ethylene propylene synthetic rubbers in this composition. Maleic anhydride increases the flame retardancy as it produces a more viscous intumescent foam or char during combustion. This more viscous foam does not drip from the burning material and serves to shield material that would otherwise be exposed to combustion during burning.
Maleic anhydride is believed to aid in the formation a viscous intumescent foam during combustion by cross-linking the polymeric units as a result of its carboxylic functionality. This is believed to be a process analogous to the cross-linking that takes place with olefinic copolymers or terpolymers used in this invention, wherein 3% to 20% by weight of said copolymers or terpolymers are carboxylic acid comonomers.
Processing of the compositions of this invention can occur at relatively low temperatures. The haloyen free flame retardant materials such as alumina trihydrate lose their water of hydration at 420~F. The presence of this water of hydration is essential for effective fire retardancy. Formerly, processing had to take place at 350 to 410F, because old flame-retardant materials were .
'':': ~ ' ' ' ' , 206907~j so difficult to work with. This involved the risk of ruining the flame retardant materials' efficacy.
With glyoxal and an organopolysiloxane, much lower processing temperatures of 250 to 310F are possible, and with much higher flame retardant material concentrations. Also, the material is more fluid at the same concentration of flame retardant material than previous preparations. As a result, industrial production can run faster, with more production per person hour. The lower processing temperatures make for faster cooling and therefore slightly lower processing costs. With inclusion of tartaric acid, we have found that the processing temperature can be further expanded to range from 230F to 380F.
Several major developments are in progress in the area of understanding of fire dynamics and the scientific study of performance of materials in a fire. Work on fire dynamics centers around the building of mathematical, computer driven models of "compartment fires" (models of single room fires) and the extension of these fire models to multistory buildings. The objective is to be able to determine how the choice of materials and design of a building affect the fire death toll for a hypothetical fire in a real building.
From a materials viewpoint, the main impact of the fire science work is characterized by the following parameters:
Ignitability;
flame spread rate;
heat release rate;
smoke toxicity (mainly inhalation toxicity to humans);
smoke density (obscuration of visibility); and smoke corrosivity (corrosive effects on electronic equipment).
Conventional PVC compounds are inherently good in the first three items but perform poorly in smoke ' : :
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density. Their smoke toxicity :is the subject of debate, it may not be worse than that of other conventional plastics in this regard. On the issue of corrosivity, AT~T has publicly presented data on the serious building-wide damage to telephone switch:ing equipment experiencedwith burning PvC insulated wire.
The compositions, according to this invention, preform extremely well in the ignitability, flame spread rate, heat release rate, smoke toxicity, smoke corrosivity, and smoke density parameters.
In additionl success at maintaining good manufacturing processability for the compositions of this invention is maintained, which has been impossible with prior approaches. Surprisingly, the compositions of this invention are easily processed into end use products such as wire and cable extrusions, and sheet extrusions for a variety of construction products.
Further, addition of small amounts of zirconates, titanates, zinc, and tin salts enhances physical properties of the final product. These materials in combination with dialdehydes raise the viscosity of the burning material and thus improve flame retardancy by contributing to the intumescent char that forms at burning surfaces rather than dripping off ~nd leaving more new material exposed for combustion.
In all the compositions of this invention, reactive processing builds in a sufficient degree of cross-linking among polymeric units, and between polymeric units and particles of flame-retardant additives is such that the composition is easily processable (extrudable and moldable) at relatively low temperatures and relatively high flame retardant additive levels.
Performance and flame retardancy of these compositions could be enhanced by any of the conventionally known halogen-containing fire retardant additives such as decabromodiphenyloxide. Addition o~ an antimony oxide syneryist to the halides in appropriate ~9~
amounts to combine with and prevent them from being lost to the atmosphere considerably improves the flame retardancy of compositions containing the halides.
The fire retardant composition, according ta this invention, therefore has among others the following five distinct features:
(1) processability over a broad range o~ component concentrations in the composition;
(2) processability at considerably lower processing temperatures compared to prior art compositions;
(3) significant increase in the formability properties of the composition when extruded in sheet form due primarily to the presence of the low modulus copolymers and/or elastomers;
LOW TOXICITY FIRE R~TARDAN~ THERNOP~A~TIC MATERIA~
FIELD OF THE INVENTION
This invention relates to very low toxicity, fire retardant thermoplastic compositions which may be processable into various products in which fire safety is a consideration.
BACKGROUND OF THE INVENTION
Although flame retardant polymer compositions have been in use for several decades, they have generally relied upon the presence of halogens, mainly chlorine or bromine containing chemicals, to yield flame retardancy.
Examples include polychloroprene ("neoprene"), chlorosulphonated polyethylene ("Hypalon"), thermoplastic PVC compounds, or compounds of polyethylene with halogenated flame retardant additives. Matex-ials under development over the last ten years, and even more intensively in the last five years in Europe and the United States have focused on halogen free, flame retardant (HFFR) compounds, since halogens give off very toxic and corrosive combustion products in fires.
Thermoset HFFR's have been developed based on polyethylene and its copolymer.s, but these materials have inherently high processing costs due to the need for cross-linking. Thermoplastic HFFR's, usually classified as thermoplastic polyolefins or TPO's since they are typically based on polymers and copolymers of ethylene and propylene, are the focus of much industrial materials research at present for construction and transportation because of their greater ease of use (fabrication into end use products) and the recyclability of trim or scrap.
Development of a cost ef~ective and acceptable performance HFFR/TPO is a challenging project. The essence of the technical challenge is as ~ollows:
Conventional materials, namely PVC compounds, have shown a good balance of properties in mechanical strength and flexibility, chemical, aging resistance and low cost.
Unfortunately, burning PVC's release a great deal o~
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black smoke and their combustion fumes contain HCl gas, which is highly corrosive, particularly in combination with the water used to fight fires. This hydrochloric acid is capable of destroying e~cpensive computer equipment and even such rugged electrical fixtures as fuse boxes which may not be directly destroyed by the flame or heat of a fire.
~ alogen free systems of modest cost are restricted ko polyolefins in terms of raw material. Polyole~ins do not have inherently good flame resistance. Choice of halogen free flame retardant additives is limited to certain hydrated halogen free flame retardant additive minerals such as alumina trihydrate ~ATH) or magnesium hydroxide, which are relatively inexpensive.
These flame retardant additives function by releasing their water of hydration, preferably at temperatures above those required for processing but below those of combustion of the flame retardant composition. At relatively high concentrations, such additives also impair combustion by conducting heat relatively e~ficiently from burning surfaces. To maximize these flame-retardant effects, it is preferable that the flame retardant additives be present at maximum levels.
However, these particular halogen free flame retardant materials are relatively inefficient and must be added in large amounts (>50% by weight). Because such flame retardant materials are non reinforcing in the final product, HFFR/TPO compounds using this conventional technology normally have poor strength and flexibility, poor processing characteristics (eg. ease of mixing and extrusion) and only fair flame retardancy.
Approaches tried to avoid these difficulties include the use of coupling agents (to compensate for the non-reinforcing nature of ATH~, and intumescent additives~al~o called char formers).
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Silicone flame retardants for plastic compositions have been extensively investigated in United States patent 4,387,176. A composition which lends fire-retardancy to a thermoplastics includes a silicone with a group IIA metal organic salt and a silicone resin which is soluble in the silicone to impart flame-retardancy to the thermoplastic. The silicone is of the general organopolysiloxane group, such as polydimethylsiloxane.
The silicone resin is generally represented by the formula MQ where M is the monofunctional group of the average formula R3Sioo5 and the tetrafunctional Q units of the average formula SiO2 with the average ratio of approximately 0.3:4 of M units per Q unit. The patent teaches that this fire-retardant composition is useful with a variety of thermoplastics including specifically polypropylene, polyethylene~ polycarbonate, polystyrene, acrylonitryl-butadiene-styrene terpolymer, polyphenylene oxide-polystyrene blends, acrylic polymer, polyurethane and polyamides. It is required that the group IIA metal organic salts be included to ensure solubility of the silicone resin in the polysiloxane base. Representative salts include magnesium stearate, calcium stearate, barium stearate, strontium stearate. It has been found, however, that compositions of this type are not readily processable particularly when high loadings of fire-retardant additives are included.
More particularly, Frye, discloses a flame retardant including three principal ingredients:
1. polysiloxanes which are organopolysiloxane polymers;
2. Group IIA metal carboxylic acid salts; for example, magnesium stearate, calcium stearate, barium stearate and strontium stearate; and 3. silicone resins such as the General Electric silicone sold under the trademark SR545.
Halides may be used to improve the fire retardancy properties of this combination of components. The major . ~ , .
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components may be used with various thermoplastics, suchas poly~thylenes, polypropylenes, and polybutylenes as well as copolymers and polycarbonates. Heat activated cross-linkers, such as peroxides, may be used to initiate cross linking in the composition in an attempt to improve physical characteristics of the material. Based on a review of the examples of this patent, generally Frye requires the use of halogens to achieve a suitable flame retardancy to meet commonly acceptable indexes for flame retardancy.
SUMMARY OF THE INVENTION
According to an aspect of the invention, a ~ire-retardant composition comprises:
~a) 5% to 60% by weight of an olefinic copolymer or terpolymer wherein 3% to 20% by weight of the copolymer or terpolymer is a carboxylic acid comonomer;
~b) 1% to 15% by weight of an organopolysiloxane;
and (c) 20% to ~5% by weight of a flame-retardant additive comprising a group I or group II or group III metal oxide hydrate.
According to another aspect of the invention, the processability of the above composition is greatly improved by including a dialdehyde in the composition.
According to another as~ect of the invention, the formability of the composition is greatly improved by the inclusion of polymers, such as low modulus ethylene copolymers, polyethylene, polypropylene, ethylenepropylene synthetic rubbers and ethylenepropylene elastomers with a reactive monomer graft.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the invention are shown in the drawings, wherein:
Figures :L and 2 show weight and percent weight loss of two compositions during heating.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
7 ~
s compositions of this invention provide a series of very low toxicity, ~ire-retardant compounds that comply with the requirements of a Class A
composition when tested in accordance with the procedures of ASTM E-84. The preferred compositions include a copolymer or terpolymer wherein 3% to 20% by weight of the copolymer or terpolymer is a carboxylic acid comonomer. These compounds are intended for use in the construction, building and wire insulation industries.
lo ~ire-retardant plastics are commonly availa~leO
However to achieve their ratings, it has been essential to use halogenated polymers or additives as flame retardant agents. As already noted, those materials are becoming unacceptable in respect to the toxicity and corrosivity of the decomposition products when subjected to heat and/or fire.
The flame retardant compositions of this invention release combustion products of low optical density and low levels of toxicity. These materials can be manufactured without using harmful halogenated additives.
The flame retardant propertiPs of these compositions are advantageous in the construction, building and wire insulation industries in meeting the requirements of burn tests in accordance with ASTM E-84 in addition to UL 94 V-O and UL wire and cable vertical flame tests.
These compositions perform particularly well in characteristics of Flame Spread Index [FSI3 and Smoke Density [SD~ These characteristics are now commonly specified in government regulations and included in specifications of other agencies i.e. Underwriters Laboratories, and State, Provincial and Municipal Building codes.
The composition, according to this invention, when cross-linXed by irradiation or chemical methods has quite surprisingly enhanced physical properties particularly with respect to the elongation parameter. Although the reasons are not readily understood, it appears that , .
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irradiation of the composition increases elongation properties of the composition rather than the commonly understood decraase in elongation. The composition o~
this invention is readily modified to permit processing into various articles of manufacture which include building materials, such as wallboards, ceiling panels, pipe wrap, wire cladding and insulation and the like.
Such processability may be improved and enhanced by various additives readily incorporated in the composition to enable injection molding of the composition as well as compression molding and blow molding.
The fire-retardant composition of this invention comprises:
5% to 60~ by weight of an olefinic copolymer or terpolymer wherein 3% to 20% by weight of the copolymer or terpolymer is a carboxylic acid comonomer.
According to a preferred embodiment of the invention, the copolymer or terpolymer is selected from the group consisting of a copolymer of ethylene and ethylene acrylic acid and a copolymer of ethylene and methacrylic acid. In each of these copolymers, there is 3~ to 20~ by weight of the copolymer of carboxylic acid comonomer. Although the reactivity of the copolymer, terpolymer with a carboxylic acid comonomer with other components of the composition i5 not fully understood, it is theorized that the carboxylic acid comonomer is reactive with the other components o~ the composition to improve processability, formability and fire retardancy.
In addition to the copolymer, terpolymer, another component of the composition is 1% to 15% by weight o~ an organopolysiloxane. The organopolysiloxane is a compound selected from the group represented by the formulae:
R3sios/ R2Sio~ Rlsiol5, RIR2sioo5~ Sio, (Rl)2sio, RSiol5 and SiO2, wherein each R represents independently a saturated or unsaturated monovalent hydrocarbon radical, R~ represents 2~9~7~
a radical such as R or a radical selected from the group consisting of a hydrogen atom, hydrGxyl, alkoxyl, aryl, vinyl, or allyl radicals; and wherein said organopolysiloxane has a viscosity of approximately 600 to 300,000,000 centipoise at 25OC.
Organopolysiloxane acts as a plasticizer (or internal lubricant), a low level linking agent and a coupling agent between the hydrophobic polymer and the hydrophilic flame retardant additive material. As a result of this unexpected effect of the organopolysiloxane, it is now possible to incorporate larger amou~ts of the hydrophilic flame retardant additive than in previous flame retardant compositions.
Surprisingly, compositions, in which an organopolysiloxane is thus utilized, retain plasticity and processability even at relatively low temperatures.
The fire retardancy of some of the compositions of this invention may be improved by including active silicone resin in the organopolysiloxane. The reactive resin is represented by the formula:
MQ
wherein said reactive silicone resin is comprised of monofunctional M units of the averagP formula R3Sioos and tetrafunctivnal Q units of the average formula sio2, and having an average ratio of approximately 0.3 to 4.0 M
units per Q unit.
From a solubility standpoint for the organosiloxane, processing conditions may require the use of group II
metal organic salts. Appropriate amounts of the group II
metal organic salt, such as metal stearates, are added to the composition as required to solubilize the reactive silicone resin in the polysiloxane base.
It is believed that the reactivity o~ the polysiloxane with the carboxyl moieties of the copolymer, terpolymer aids in the incorporation of the hydrophilic flame-retardant additives in the polymer composition.
Hence it is now possible to incorporate larger amounts of -:. ' ~ ~ ' ': , .
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the flame-retardant additives than in previous flame-retardant compositions while ret:aining processability and subsequent formability into desired commercial products.
One organopolysiloxane useful in the compositions of this invention is Dow Corning 200 Fluid. It is a dimethylsiloxane polymer. This silicone polymer is essentially non-reactive except for a small amount of silanol (approximately 200 to 800 parts per million) left over after processing. Dow Corning 200 Fluid can be made reactive, if desired, through the addition of a secondary hydroxyl functional silicone resin, such as Dow Corning 1248 Fluid.
Another useful organopolysiloxane is General Electric's SFR 100, which is essentially a silicone fluid similar to the Dow corning 200 Fluid with the difference that is has been modified through the addition of group II metal organic compound(s) and a reactive silicone resin (specifically polytrimethyl-silylsilicate) represented by the formula MQ, where said reactive silicone resin is comprised of monofunctional M units of the average formula ~3sio05 and tetrafunctional Q units of the average formula SiO2 and having an average ratio of approximately 0.3 to 4.0 M units per Q unit having a ratio of approximately 0.3 to 4.0 M units per Q unit.
The hydrophilic fire-retardant additives, according to this invention, are generally defined by group I and group II metal oxide hydrates. There are a variety of such hydrates available, although the preferred hydrates are selected from the group consisting of alumina trihydrate, magnesium hydroxide and hydrotalcite (sodium aluminum hydroxy carbonate). Another hydrate, which is useful in some compositions, is hydracarb, which is a form of hydrated calcium carbonate. A preferred concentration of the metal oxide hydrates is in the range of 20 to 40% by weight.
The organopolysiloxane may have a viscosity in the range of 0.6 centipoise to 300X106 centipoise, although in 7 ~
g most situations the preferred viscosity range is lOx103 centipoise to 900X103. For the compositions which are used in a variety of commercial products, such as coverings for wire cable, the viscosity is normally in the range of 30x103 centipoise to 600x~03 centipoise. The preferred organopolysiloxane is polydimethylsiloxane.
Other significant additives for use in the composition of this invention, which further enhance the fire retardancy thereof, is the use of red amorphous phosphorous. It has been found that the amount of red phosphorous used can range from approximately 1~ to 10%, pre~erably in the range of 1% to 4% and most preferred in the range of 1 to 2%.
In addition to the fire-retardant additive, other suitable fillers may be included, such as talc, calcium carbonate, mica, clay, zinc borate, wallastonite and mixtures thereof. A preferred amount of zinc borate is in the range of 5% to 30% by weight in the composition.
Zinc borate is particularly effective when used in combination with red amorphous phosphorous.
It has been found that the addition of dialdshydes surprisingly improves the processability and workability of the compositions. Preferred dialdehydes are selected from the group consisting of glyoxal and glutaraldehyde.
The dialdehydes are used in the range of 0.1% to 4%
by weight of the composition, although the preferred range is from 0.5% to 3% by weight of the selected dialdehyde in the composition.
Although the function of the dialdehyde in the composition is not fully understood, it is believed that the additional carboxyl groups of the dialdehyde react to combine with the organopolysiloxane and the carboxyl groups of the co- and terpolymers. A dialdehyde (such as glyoxal) is believed to cross-link the polymeric units by polycondensation reactive processing. In the field of ~ire retardant thermoplastics, free radical polymerization had heretofore been the method or choice.
20~9075 The use of polycondensation is a novel approach which gives unexpectedly good fire rel:ardancy and processability. This approach causes cross-linking which increases with the amount of dialdehyde used.
To further enhance this reactivity, it has also been found that the addition of monorner grafts, such as maleic anhydride, further enhance the composition. Furthermore, maleic anhydride may be used with other additives to be described. Such further uses include grafting of the maleic anhydride onto polyolefins. Also, maleic anhydride may be used as an alloying agent which facilitates the combination of polyolefins with copolymers thersof.
Formability of the composition, particularly in sheet form, becomes important in forming a variety of building products, such as ceiling tiles and the like.
To enhance the formability, the inclusion of up to 30% by weight of a pol~mer selected from the group consisting of low modulus ethylene copolymers, polyethylene, polypropylene, ethylenepropylene synthetic rubbers and ethylenepropylene elastomers with a reactive monomer graft are particularly useful. The low modulus ethylene copolymers may be selected from the group consisting of ethylenevinylacetate, ethylene-methylacrylate, ethyleneethylacrylate and ethylene-butylacrylate. As previously noted, the properties of the ethylenepropylene elastomer may be improved with a monomer graph, particularly maleic hydride.
Further enhancements of the processability of this composition may be achieved by the use of either short-chain carboxylic acids, such as fumeric acid, citric acid, formic acid, tartaric acid, lactic acid and short-chain (Cl- C6) amino acids. Of this group, tartaric acid is preferred. Also longer chain (C8 - C22)fatty acids are used, particularly stearic acid. One or more of these acids may be compounded into the mix or tumble blended after pelletiæing. The use of either or both o~ these .
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acids siynificantly reduces the pressures for extrusion thereof and hence increases processability. Preferred concentration for the tartaric acid in the composition is 0.1% to 5% by weight thereof. With stearic acid, the prefarred concentration is in the range of 0.1% to 3% by weight thereof. The acids can be incorporated directly in the blend, or as already mentioned tumble blended after pelletizing of the fire retardant composition so as to be part o~ the composition during extrusion.
Although the composition of this invention is intended to be halogen-free, in certain situations where use of halogens is not of particular concern, the fire retardancy of the composition can be enhanced by the addition of organic halides, such as decabromo-diphenyloxide. Normally when halogens are incorporated into a composition, an antimony oxide synergist is included with the composition up to approximately 10% by weight to improve flame retardancy hy combininy the halogens, thus preventing their loss to the atmosphere during combustion.
According to a preferred embodiment of the invention, a representative composition providing for fire retardancy and processability and formability is the following:
(a) 5% to 60% by weight of (i) a copolymer of ethylene and acrylic acid containing from 3% to 9.0% of the acrylic acid comonomer and (ii) with 2% to 10% by weight of the mixture comprised of the organopoly-siloxane coupling agent;
(b) 5% to 20% by weight of the composition of at least one polymeric material selected from ethylene copolymers, polyethylene and/or from a group of synthetic hydrocarbon elastomers;
(c) 50% to ~5% by weight of the composition of 35 a filler comprising 40% to 100% by weight of at least one of aluminum trihydrate and magnesium hydroxide and 0% to ~ .
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60% by weight of at le~st one of hydracarb, zinc borate, mica and clay.
These compositions may be extruded into sheet material having a Flame Spread Index [FSI] of less than 50 and a Smoke Density [SD] of less than 50.
Preferably the compositions of the present invention also contain 5% to 20% of a polymeric material selected from combinations of synthetic hydrocarbons elastomers and low modulus polymers and mixtures thereof. In embodiments of the composition the elastomer is defined as a substance that is capable of being extended to twice its length at 68C and on release of the applied stress returns with force to approximately its original length.
Compatibility with polyethylene is a desirable feature in order to improve product toughness. The use of high ethylene elastomers is essential to provide the melt flow properties required.
It has been found that the combined use of copolymer of ethylene acrylic acid with the oryanic polysiloxane provides a slight improvement in fire retardancy, particularly when only 1% to 5% by weight of the composition is the desired organopolysiloxane.
As already noted, the preferred elastomers are ethylenepropylene copolymer or an ethylenepro-pylenediene terpolymer or a terpolymer e.g. ethylenepropylenediene.
In combination the polymeric material may be a low modulus polymer. This category includes such polymers as polyethylene, ethylenevinylacetate, ethyleneethyl-acrylate, and ethylenemethylacrylate copolymers as well as branched polymers of the above having maleic anhydride or other suitable carboxylic group grafted thereon.
The carboxylic acid copolymer, such as EAA, plus other polymeric materials comprises 15% to 30% by weight of the composition~ However for most methods o~
fabrication, the carboxylic acid copolymer, such as FAA, plus other polymeric material should be at least 25% o~
the composition.
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The composition of the present invention also contains 50% to 85%, especially 55% to 75% and more particularly 55% to 65% by weight of the composition of fire-retardant additive. Of this filler 40 to 100 parts by weight is alumina trihydrate [ATH] viz, Al2033H20, and/or magnesium hydroxide and/c)r sodium aluminum hydroxy carbonate and hydrotalcite. According to an aspect o~
the invention all of the filler may be ATH or magnesium hydroxide. The remainder of the filler, i.e. up to 60%
parts by weight is hydracarb, zinc borate, mica and/or clay incorporating color pigments, lubricants and stabilizers not to exceed 10 parts of the 0 to 60 parts designated.
In order to facilitate processing of the compositions of this invention, it is preferred that the flame-retardant, additive material has a relatively broad particle size distribution. This requires selection of a mechanically ground flame-retardant, additive material or a precipitated product. According to one embodiment of the invention, the flame-retardant, additive material will have a coarse and fine fraction with a distribution of about o.5 to 60.0 mm and a median of about 2.5 mm.
The flame-retardant, additive material should have a coarse fraction of about 60% by weight. High proportions of fine particles may cause processing difficulties at high flame-retardant, additive material levels but may improve flame resistancy due to greater surface area.
The compositions of this invention should all be compounded prior to fabrication. The equipment recommended must be of the high intensity design. The mixer must also incorporate adequate auxiliary equipment including scales and finishing equipment with proper drying facilities. The compounder [mixer] should be computer controlled for optimum mixing cycle.
Recommended mixers are: Banbury, Moriyama, FCM ~Farrel Continuous Mixer], Pomini Continuous Mixer and other high intensity mixers, i.e. Berstorff, Werner Fleiderer etc.
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The compounding equipment should be operated at temperatures below the decomposition temperature of the filler, it being understood that if the material contains more than one flame-retardant, additive material, the temperature is lower than the lowest decomposition temperature of such flame-retardant, additive material.
It is anticipated that the compositions will contain at least one antioxidant and at least one ultraviolet (W) absorber. It will be appreciated by those skilled in the art that the amount and type of additive may effect changes in and the rate of change of properties over a period of time i.e. especially physical properties of products derived therefrom. One property of particular importance is the color of the composition.
Apart from matters like cigarette smoke and pollution the aesthetic qualities of the product must remain as installed.
In another embodiment of the present invention all components are equivalent except for the elastomer indicated. An elastomer may be substituted consisting of an ethylene propylene elastomer to which reactive monomer such as maleic anhydride has been grafted. As is appreciated, the polyolefin back-bone, provides outstanding environmental resistance, aging properties, thermostability, chemical resistance as well as ease of processing. The reactive group on the polyolefin back-bone results in improved adhesion properties to various substrate materials. It can be utilized directly as one of the polymeric materials as all or part of 5 - 20% by weight of the composition.
Optionally, a free radical acceptor (acrylic monomer or dimer) or a chemical cross linking agent (i.e., peroxide) enhances irradiatable cross linkage or chemical cross linkage respectively. Physical properties i.e.
tensile strength, tensile modulus, impact resistance and flexibility will show definite improvement.
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Free radical linking bet-ween carhon atoms of the formed composition, either through irradiation or chemical bonding, as noted u~ually increases many physical properties. However, it is generally understood cross-linking in the polymeric composition reduces elongation of the formed composition. This is due to the cross-linking bonds normally reducing the elastomeric properties in the composition. However, quite surprisingly with this composition, cross-linking increases elongation properties of the formed composition when subjected to tensile forces. Irradiation then provides increased tensile strength as well as increased elongation. The reasons for such reversal in properties of the composition are not readily understood. However, as demonstrated in the examples, such properties are readily repeatable with the composition of this invention.
The preferred technique for inducing cross-linking in the formed composition is the use of irradiation.
Normally irradiation takes place by the use of an electron beam having an ionization energy which releases radiation to encourage free radical cross-linking in the composition. The irradiation energy is measured in megarads where desired exposure is in the range of 2 to 15 megarads depending upon the rate of processing and the thickness of material to be treated. As is understood, gamma radiation from Colbat 60 has higher penetration rates than the normal form of electron beam radiation, so that lower dosages may be used in the range of one megarad and higher. The choice of tha irradiation is to some extent dependent upon the processing method and the type of article manufacture to be treated.
With glyoxal (tha preferred dialdehyde), use of 0.1%
to 4% by weight of the total product provides the preferred results. Concentrations of up to 10% by weight may be used where processability of the other components is a problem. Too high a concentration of dialdehyde, ' ~: , , ' ., ' ' .:
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however, yields a thermoset rather than a thermoplastic.
Thermosets have very reduced flow characteristics (compared to thermoplastics) and are extremely difficult, if not impossible, to process, so they normally would not be acceptable for formation into sheet, tiles, wire coverings and the like.
The use of glyoxal and an organopolysiloxane enables concentrations of flame retardant additives as high as 85% by weight to be practically processable using conventional extrusion and molding techniques.
Other members of the homologous series of dialdehydes will also aid processability such as glutaraldehyde.
Maleic anhydride is useful with polyolefins, such as PE, PP, EVA, etc. and with ethylene propylene synthetic rubbers in this composition. Maleic anhydride increases the flame retardancy as it produces a more viscous intumescent foam or char during combustion. This more viscous foam does not drip from the burning material and serves to shield material that would otherwise be exposed to combustion during burning.
Maleic anhydride is believed to aid in the formation a viscous intumescent foam during combustion by cross-linking the polymeric units as a result of its carboxylic functionality. This is believed to be a process analogous to the cross-linking that takes place with olefinic copolymers or terpolymers used in this invention, wherein 3% to 20% by weight of said copolymers or terpolymers are carboxylic acid comonomers.
Processing of the compositions of this invention can occur at relatively low temperatures. The haloyen free flame retardant materials such as alumina trihydrate lose their water of hydration at 420~F. The presence of this water of hydration is essential for effective fire retardancy. Formerly, processing had to take place at 350 to 410F, because old flame-retardant materials were .
'':': ~ ' ' ' ' , 206907~j so difficult to work with. This involved the risk of ruining the flame retardant materials' efficacy.
With glyoxal and an organopolysiloxane, much lower processing temperatures of 250 to 310F are possible, and with much higher flame retardant material concentrations. Also, the material is more fluid at the same concentration of flame retardant material than previous preparations. As a result, industrial production can run faster, with more production per person hour. The lower processing temperatures make for faster cooling and therefore slightly lower processing costs. With inclusion of tartaric acid, we have found that the processing temperature can be further expanded to range from 230F to 380F.
Several major developments are in progress in the area of understanding of fire dynamics and the scientific study of performance of materials in a fire. Work on fire dynamics centers around the building of mathematical, computer driven models of "compartment fires" (models of single room fires) and the extension of these fire models to multistory buildings. The objective is to be able to determine how the choice of materials and design of a building affect the fire death toll for a hypothetical fire in a real building.
From a materials viewpoint, the main impact of the fire science work is characterized by the following parameters:
Ignitability;
flame spread rate;
heat release rate;
smoke toxicity (mainly inhalation toxicity to humans);
smoke density (obscuration of visibility); and smoke corrosivity (corrosive effects on electronic equipment).
Conventional PVC compounds are inherently good in the first three items but perform poorly in smoke ' : :
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density. Their smoke toxicity :is the subject of debate, it may not be worse than that of other conventional plastics in this regard. On the issue of corrosivity, AT~T has publicly presented data on the serious building-wide damage to telephone switch:ing equipment experiencedwith burning PvC insulated wire.
The compositions, according to this invention, preform extremely well in the ignitability, flame spread rate, heat release rate, smoke toxicity, smoke corrosivity, and smoke density parameters.
In additionl success at maintaining good manufacturing processability for the compositions of this invention is maintained, which has been impossible with prior approaches. Surprisingly, the compositions of this invention are easily processed into end use products such as wire and cable extrusions, and sheet extrusions for a variety of construction products.
Further, addition of small amounts of zirconates, titanates, zinc, and tin salts enhances physical properties of the final product. These materials in combination with dialdehydes raise the viscosity of the burning material and thus improve flame retardancy by contributing to the intumescent char that forms at burning surfaces rather than dripping off ~nd leaving more new material exposed for combustion.
In all the compositions of this invention, reactive processing builds in a sufficient degree of cross-linking among polymeric units, and between polymeric units and particles of flame-retardant additives is such that the composition is easily processable (extrudable and moldable) at relatively low temperatures and relatively high flame retardant additive levels.
Performance and flame retardancy of these compositions could be enhanced by any of the conventionally known halogen-containing fire retardant additives such as decabromodiphenyloxide. Addition o~ an antimony oxide syneryist to the halides in appropriate ~9~
amounts to combine with and prevent them from being lost to the atmosphere considerably improves the flame retardancy of compositions containing the halides.
The fire retardant composition, according ta this invention, therefore has among others the following five distinct features:
(1) processability over a broad range o~ component concentrations in the composition;
(2) processability at considerably lower processing temperatures compared to prior art compositions;
(3) significant increase in the formability properties of the composition when extruded in sheet form due primarily to the presence of the low modulus copolymers and/or elastomers;
(4) enhanced fire retardancy properties primarily due to the incorporation o~ very high amounts of fire-retardant additives facilitated primarily by the use of the polysiloxanes which ..
react with the carboxylic acid comonomers of the co- and terpolymers, and optionally the inclusion of a dialdehyde and/or tartaric acid;
and (5) enhanced slump stress cnaracteristics which ease lamination.
Preferred embodiments of the invention are demonstrated in the following Examples which are understood to be enabling with respect to pre~erred embodiments of the invention, but are not to be interpreted as restrictive to the scope of the appended set of claims.
EXAMPLE I
A number of samples of compositions of the invention were prepared in a laboratory Type BR Banbury mixer and compression molded into test specimens 25 to 35 mils thick. Their flame retardant properties were then compared with a commercially available competitive .
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material as the standard. A simulated ASTM E-84 test was used together with a much more severe vertical flame test.
The T.V.I. Vertical Flame Test is defined as follows:
Specimen: - 1" x 8" ex~ruded or pressed - 25 to 35 mils thick Flame Application: 30 seconds After burn: seconds Criteria: - Pass - self extinguishing - Fail - destructive burn or heavy drip .
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The low modulus polymer is CIL's 1830, an 18% vinyl acid copolymer.
The elastomer of all runs except sample 3 is ~psyn DE 208 supplied by Copolymer Corp.
The elastomer in sample 3 is Exxon's Exxolor VA 1801 consisting of an ethylene propylene elastomer to which a reactive monomer, such as maleic anhydride, has been grafted.
The silicon coupler is General Electric's SFR-100.
This material has proven effective on test with or without the addition of a metallic stearate.
Flame Evaluation:
Mortile Vertical Test_ Dupont 1 2 3 4 5 6 7 Std % % % % % % % %
AFTERBURN
Secs. 200 120 1.5 ~ 153 220 2.5 Criteria Fail Pass Pass Pass Pass Pass Pass Pass Sample No No Destroyed Ignition Ignition The samples produced in accordance with this invention exhibit superior flame resistance. The use of low modulus polymers and elastomers provides improved tensile and flexular strength making the finished product suitable for vacuum forming.
. . . :
'': ' ~ ..:' 23 2`~ 9~7~
EXAMPLE II
SAMPLE STD. 1 2 3 4 5 No. ~ % % % % %
5 LLPDE 26.0 Carboxylic acid - 22.0 22.0 2~.0 22.0 23.5 Copolymer . .
Low modulus - 5.05.0 5.0 5.0 5.0 Polymer lo Elastomer 100.0 4.5 - 4.5 4.5 Grafter elastomer - - 4.5 - - 7.5 Polydimethyl - 5.0 5.0 5.0 5.0 5.0 Siloxane Filler ATH 61.0 61.5 61.5 50.0 50.0 51.0 15 Zinc borate - - - - - 5.0 Mica - - - 11.5 Hydracarb - - - 11.5 Additives* 3.0 2.0 2.0 2.0 2.0 3.0 * Colors, antioxidants, lubricants, etc.
The elastomer used in Samples 3 and 4 is ethylenepropylene, terpolymer. The grafted elastomer is an ethylenepropylene terpolymer with a maleic anhydride graft.
The acrylic acid ethylene copolymers used are market ed under the trade name Primacor by Dow Chemical.
The reactive polydimethyl siloxane copolymer is SFR-100 supplied by the General Electric Co.
Flame Evaluations Mortile Vertical Flame Test 30 SAMPLE STD. 1 2 3 4 5 NO.
Afterburn (secs) ~00 145 _ 153 220 Test criteria Fail Pass Pass Pass Pass Pass Sample No No Destroyed Ignition Ignition All samples in this invention exhibit superior flame retardancy. The use of low modulus polymers and . . , .
24 ~9~7~
elastomers provide improved tensile and flexular strength making the finished products suitable for vacuum forming.
EXAMPLE III
Laboratory compounds were mixed in a Type BR Banbury and compression molded into test specimens 25 to 35 mils thick. Their flame retardant properties were then compar ed using a ~imulated vertical flame test against a commer cially available UL approved ceiling tile material that meets ASTM E-84.
Test Descriptlon:
Specimen - 1 x 8 x 0.025 to 0.035 inches Flame application - 30 seconds Criteria - pass - self extinguishing Fail - destructive burn and heavy drip.
Table 1 Sample STD 1 2 3 RESIN % % ~ %
Polyethylene (grafted) 26.0 - - _ Acrylic acid copolymer - 15.015.0 15.0 20 Low modulus polymer - 8.05.0 5.0 Elastomer 10.0 7.0 5.05.0 Polydimethylsiloxane - 5.0 5.0 5.0 FILLER
ATH 61.0 53.0 58.050.0 Zinc borate - 8.0 8.08.0 Calcium carbonate - - - 8.0 Additives* 3.0 4.0 4.04.0 Flame test results FAI~ PASS PASS PASS
Destructive --self extinguish Burn ~ drip --no drip--* Color, antioxidants, lubricants, etc.
The elastomer used in formulations 1 to 3 is an ethylene, propylene tsrpolymer to which a reactive monome r, such as maleic anhydride has been grafted. This elastomer was supplied by Exxon Chemical co~pany.
The low modulus polymer was an ethylenevinyl acetate copolymer obtained from Exxon Chemical Company.
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The acryli~ acid ethylene copolymers are obtained from Dow Chemical USA and are marketed under the trade name PRIMACOR.
The reactive polydimethylsiloxane copolymer is supplied by Genaral Electric Company under the trade name : SFR~100.
EXAMPLE IV
Biological, Physical and Chemical Data of Sample 8 of Example I.
AL Test #197, Sample #A-0028 Case # 010489-1 LC50~ 87.3 grams 95% Confidence interval~ 74.6 - 102.3 grams LC50 sample dimensions/descriptionb chips Furnace temperature at 1% weight lossb 299C
Furnace temperature range at most rapid weight lossb 420 - 600C
Furnace temperature at apparent spon-taneous flame (mean of 7 samples) 4S4C
Percent residue (mean of 6 samples) 50.6%
Maximal CO in exposure chamberb 0.08% 800 ppm Furnace temperature at maximal cob 570C
Maximal C02 in exposure chamberb 2.11%
Furnace temperature at maximal CO2b 570C
Minimal 2 in exposure chamberb 19.8%
Furnace temperature at minimal o2b 570C
Number of times exposure chamber exceeded 45OCb None Duration exposure chamber exceeded 45OCb 0 sac 30 Eye damage (corneal opacity)C None Eye damage (severity) None (1) Number of test runs on sample material 7 a - calculated according to the method of C. Weil, 1952.
b - from single experiment using 87.3 gram test sample.
2~69~7~
c - from single experiment with animals using 78.1 gram test sample; sample weight equal or closest to the LCso value.
The results of this test demonstrate characteristics which are approximately ten times better than polyethylene pellets and better than most other known ole fins from the standpoint of bio:Logical, physical and chemical data in the fire retardancy field.
~XAMPLE V
Vertical Burning Test - UL 94 (specimens were tested "as is", i.e. no conditioning).
Sample 9 of Example I (#0202-6, 125 to 130 mil) Three specimens 5 inches x 1/2 inch were cut from a sample. They were tested using the Vertical Burning Test for 94-Vo classification.
The burner was adjusted to produce a five inch flame with a one and a half inch inner blue cone (using natural gas~. The test flame was applied to one of the lower cor ners of the specimen at an angle of 20 from the vertical, so that the tip of the inner cone touches the specimen.
The flame was applied for 5 seconds and then removed for 5 seconds. This was repeated until the specimen was subjected to the test flame five times total.
Observa ons After Fifth Removal of Test Flame Duration of flaming and glowing, sec. 23 32 25 Affected length, in. 2.78" 2.50" 1.94"
30 Dripping None None None Deformation curled slightly at exposed end EXAMPLE_VI
Vertical Bur lng Test - UL 94 Sample 9 of Example I (#0202-6, 78 mils) Thickness was measured with a micrometer : ' " ~ ' ,` ' Ten specimens 4 9/16 inches x 1/2 inch were tested.
Five specimens were tested for 5U classification, since the burner was already adjusted for this test. It was found that two out of five specimens passed the criteria.
~ natural gas flame was used.
Duration of flaming and glowing, sec. 29 43 76 7a 102 10 Affected length, inchas 2.81 3.50 3.25 Burnt Burnt to to clump clump (4") (4") 15 Dripping None None None None None Deformation B e c a m e e l o n g a t e d EXAMPLE VII
Vertical B rn Test - UL 94 Sample 9 of Example I (#0202-6, 78 mil) Five specimens, 4 9/16 inches x one-half inch were tested for 94U-o, 94U-1 or 94U-2 classification.
The specimens were held vertically 9.5 mm above the orifice of the burner. The burner was adjusted to produce a three-quarter inch ~19 mm) flame. The air supply was increased until the yellow tip of the flame disappeared. The specimens were exposed to the test flame for 10 seconds. The burner was removed and any flaming was noted. When the specimens stopped burning, the burner was placed under the specimens for another 10 seconds.
Duration of flaming after 1st 55 40 70 26 l9 ten sec. exp. (in secs) Duration of flaming after 2nd 25 0 70 3 40 ten sec. exp. (in secs) Duration of glowing after 2nd None None None None None application ~ .
~9~7~
Dripping None None None None None Length of Affected Area - ~ 1 3~ 3h ~~ 1%
inches Burnt to clump No No No No No EXAMPLE VIII
Figures 1 and 2 show weigh~ and percent weight loss of two compositions during heating. The composition tested and results shown in Figure 1 is a polyethylene composition of the invention of Sample 2 of Example 1 not containing a dialdehyde. The composition tested and results shown in Figure 2 is Sample 9 of Example 1 with dialdehyde added.
The composition of Figure 2 lost the bulk of its mass at a substantially higher temperature, 472.59C than the composition of Figure 1, which lost the bulk of its mass at 437.22C.
Loss of mass at substantially higher temperatures indicates better flame retardancy or resistance. The results of Figures 1 and 2 indicate a marked improvement in flame retardancy characteristics with addition of a -dialdehyde to the compositions of the invention.
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EXAMPLE IX
Cable Physical Test Data Sample A* Sample B**
Tensile Elongation Elonga1ion/ Elongation/
5 Unmodified Sample Ultimate Ultimate Tensile Psi Tensile Psi .030 inch wall 80%/2100 Psi 105%/1896 Psi .008 inch wall 90%/221)0 Psi 110%/1817 Psi Tensile Elongation After B irradiation .030 inch wall 133~/2614 Psi 173%/2430 Psi Tensile Elongation After 7 Days Age Testing at .030 inch wall 20%/1589 Psi 20%/1532 Psi UW-1 Test .030 inch wall Pass Pass Insulation Resistance 10,000 Meg n 5,000 Meg n ShrinXage Test .030 inch wall None None * Sample A is Sample 10 of Example 1 ** Sample B is Sample 11 of Example 1 During the testing of the various flame retardant compositions o~ this invention, it is noted that the compositions fail to drip when exposed to flame. This is a significant development and is thought to be due to the degree of cross-linking in the composition. At the stage of processing, there appears to be a condensation-type polymerization taking place in the reactivity of the various components with the carboxyl groups. During exposure, however, to a flame, it is believed that, due to additional cross-linking, a solid charred substance is formed which is inclined not to drip and thereby not exposing fre~h polymer. This is a significant development, particularly when it is considered that the .. , , : , .
2~075 composition is particularly useful in the formation o~
ceiling tile. Ceiling tiles of this invention, when exposed to a flame, are less likely to drop from the ceiling and hence contain the fire for a longer period.
EXMAPLE X
Irradiation cross-linking has been investigated with respect to samples of the composition identified as follows:
SAMPLE A B C D E
Carboxylic Acid 24.0 24.0 24.0 24.0 24.0 Copolymer Low Modules Polymer 9.5 9.5 10.0 10.0 10.0 Grafter 20 Elastomer 9.5 9.5 10.0 10.0 10.0 Polydimethyl Siloxane 5.8 5.8 6.0 6.0 6.0 Filler ATH 60.0 60.0 63.0 63.0 63.0 Zinc Borate 6.5 6.5 7.0 7.0 7.0 Red Phosphorous 4.7 4.7 - - -* Additives *4.0 *4.0 *4.0 *4.0 *4.0 *Pigments, antioxidents, lubricants, etc.
*A. includes Carbon Black Pigment (2.6%) *B. includes Tio2 pigment (2.6~) *C. includes Tio2 pigment (2.6%) *D. includes Magnesium Oxide (2.6%) *E. contains ~ractional Melt Low Modules Polymer.
P~OCESSING NOTE: Materials excluding carboxylic acid copolymer were master-batched and then 25% carboxylic acid copolymer and 76% o~ the master-batch by weight were '' ~ . ' .,' : ~
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3~ 9 ~ 7 ~
mixed and compounded. Plaques were pressed and tested according to ASTM D-412.
Radiation induced cross-linking is preferably produced by high voltage linear accelerators which generate beams of high energy electonsO These beams may have energies in the range of 2 to 3 million electron volts (MEV~ and are high current beams capable of irradiating large volumes of materials in a short time.
Beam energies in excess of three MEV's are normally required to irradiate thicknesses of the composition in excess of 0.1 inches. For example, in wire and cable applications, the cable may be passed through the beam at a fairly high speed in a manner which ensures uniform dosage over the entire circumference of the cable and at a high enough dose rate to effect cross linkage. This may be accomplished by having a cable make multiple passes through the beam while rotating the cable so that all sides are illuminated by electron beam. It is appreciated that similar procedures may be used in treating sheet material which has previously been extruded and the like.
As a measure of the dosages in exposing the material to the beam of high energy electrons, in this Example, the dosage is in the range of 12 to 15 megarad. The cross-linking occurs when high energy electrons ionize the linear polymeric material so that adjacent chains may form chemical bonds to each other. Quite surprisingly as demonstrated by the ~ollowing data, such cross-linking does not decrease elongation but increases elonyation before failure at maximum tensile stress.
To test each of the above samples A through E, each sample is stretched linearly while recording the elongation of the sample during stretching and the pressure appl:ied in stretching the sample before breakage. Samples are tested be~ore they have been irradiated and after irradiation to determine the impact .
' . -2~6~75 o~ irradiation on elongation and tensile strength. Theresults are set out as follows:
SAMPLE PHYSICALSBEFORE AFTER ~ INCREAS
MEASURED RAD RAD
A) Elongation %118 155 31.36 Tensile PSI1425 1660 16.49 B) Elongation %130 182 40.00 Tensile PSI1525 1937 27.02 C) Elongation %150 200 33.30 Tensile PSI1635 2100 28.44 D) Elongation %164 190 15.85 Tensile PSI1650 2200 33.33 E) Elongation % 87 165 89.66 Tensile PSI1750 2500 42.86 :
EXAMPLE_XI
The use of red amorphous phosphorous has been investigatad to determine its impact on fire retardancy properties. From the following test results, it becomes apparent that less not necessarily more of the red amorphous phosphorous enhances the fire retardancy properties of the composition.
Four samples of this invention were prepared as followsO Each sample had a base formulation comprising:
40% EVA, EAA, EPD blend resins 55% by weight fillers - ATH zinc borate :., . , ~:
: . .
2 ~ 7 ~
5% polydimethylsilicone 1% glyoxol 1% processing aids - stearic acid.
~he above base formulation was modified as follows to prepare samples A, B, C and D.
A - base formulation B - base formulation plus 1.5% by weight red phosphorous C - base formulation plus 3.5% by weight red phosphorous D - base formulation plus 7.5% by weight red phosphorous All samples were extruded to a 0.75 inch thick sheet which was one-half inch wide and six inches long.
A flame was applied to each specimen and ignitiontextinguishing times were recorded. The procedure is that of other Examples where the sample was held in a vertical orientation and the flame applied at an angle to the bottom of each sample.
Sample A B C D
Sec. to ignition 35 sec 15 sec 20 sec 25 sec Sec. to extinguish 35 sec 0 sec 5 sec 2 sec It is apparent that red amorphous phosphorous surprisingly reduced the time to ignition of each of the samples, but in turn reduced the amount of time to self-extinguish. It is also of note that a lesser concentration of red amorphous phosphorous, as in sample B, resulted in a self-extinguishing time of zero seconds, whereas larger concentrations in sample C took longex to self-extinguish and then in sample D with high overloading, two seconds to self-extinguish. It i therefore believed that this data predicts in the range of 1% to 3~ o~ the red amorphous phosphorous is efective in reducing extinguishing times and it is not necessary .
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to use higher concentrations in the range of 7~ or greater.
EXAMPLE XII
The impact on the carboxylic acid comonomer for enhancing flame retardancy has been investigated. The carboxylic acid comonomer used :in the following formulations is ethylene acrylic acid. This was compared to a linear, low density polyethylene where aluminum trihydrate and the dimethylsiloxane polymer, SF~100 was used. The samples had the following compositions prepare d in accordance with the previous Examples.
SAMPLE ~
COMPONENTS (1) (2) t3) (4) 15 LLDPE 40.0%40.0% - -EAA 1430 - - 40.0%40.0%
SFR 100 - 5.0% - 5.0%
ATH 60.0%55.0% 60.0%55.0%
Two strips of each sample were prepared having the dimensions of the samples of Example XI. Flame was applied to each of the duplicates of the four samples.
Once ignition occurred, the flame was removed. The time to ignition was recorded. After removal of the flame time to self-extinguish or consumed by flame was recorded. The results are as follows:
SAMPLE Ignition Extinguish Consumed (1) a 25 sec -- 9 minfailed b 20 sec -- 8 minfailed (2) a 15 sec -- 3.5 min failed b 20 sec -- 4.0 min failed (3) a 20 sec 10 sec - Pass b 20 sec 0 -- Pass 40 (4) a 30 sec 0 -- Pass b 35 sec 0 -- Pass . 1 `, ~ ,`
.
`:
2 ~ 5 From the above results, it is apparent that samples 1 and 2 were total failures. Sample 1 did not contain the carboxylic acid comonomer. Sample 2 similarly did not contain the carboxylic acid comonomer, but did contain SFR100. Obviously SFR100 by itself without the metallic stearate and used with the polyolefin does not provide desirable fire retardancy properties. If anything, the rate of burn was increased since th~ sample was consumed within three to four minutes. However, lo samples 3 and 4, both of which contain the carboxylic acid comonomer with no linear monomer polyolefin, self-extinguished and readily passed the test. There is a slight improvement in ~he fire retarding when the of the carboxylic acid comonomer is used in combination with SFR100 as observed by increased time to ignition and both samples extinguishing in zero seconds, that is a non-detectable time period.
As an adjunct to this test, we have also demonstrated that the amount of SFR100 in the formulation does not increase flame retardancy with higher concentrations. With sample 4, 3% by weight SFR100 was compared to sample 4 with 8% SFR100. The flame test d~monstrated that sample 4 containing 3% SFR100 had a significantly better LOI, (limited oxygen index - a value indicating minimum oxygen needed for combustion) than the sample with 8% SFR100. This further example and the above examples demonstrata that fire retardancy is not due alone to the presence of SFR100 or other forms of dimethylsiloxane polymers.
It is thought that SFR functions primarily as a coupling, cross-linking, anti-drip and processing component and not essentially as a flame retardant.
Although preferred embodiments of the invention have been described herein in detail, it will be understood by those skilled in the art that variations may be made thereto without departing from the spirit of the invention or the scope of the appended claims.
react with the carboxylic acid comonomers of the co- and terpolymers, and optionally the inclusion of a dialdehyde and/or tartaric acid;
and (5) enhanced slump stress cnaracteristics which ease lamination.
Preferred embodiments of the invention are demonstrated in the following Examples which are understood to be enabling with respect to pre~erred embodiments of the invention, but are not to be interpreted as restrictive to the scope of the appended set of claims.
EXAMPLE I
A number of samples of compositions of the invention were prepared in a laboratory Type BR Banbury mixer and compression molded into test specimens 25 to 35 mils thick. Their flame retardant properties were then compared with a commercially available competitive .
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material as the standard. A simulated ASTM E-84 test was used together with a much more severe vertical flame test.
The T.V.I. Vertical Flame Test is defined as follows:
Specimen: - 1" x 8" ex~ruded or pressed - 25 to 35 mils thick Flame Application: 30 seconds After burn: seconds Criteria: - Pass - self extinguishing - Fail - destructive burn or heavy drip .
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The low modulus polymer is CIL's 1830, an 18% vinyl acid copolymer.
The elastomer of all runs except sample 3 is ~psyn DE 208 supplied by Copolymer Corp.
The elastomer in sample 3 is Exxon's Exxolor VA 1801 consisting of an ethylene propylene elastomer to which a reactive monomer, such as maleic anhydride, has been grafted.
The silicon coupler is General Electric's SFR-100.
This material has proven effective on test with or without the addition of a metallic stearate.
Flame Evaluation:
Mortile Vertical Test_ Dupont 1 2 3 4 5 6 7 Std % % % % % % % %
AFTERBURN
Secs. 200 120 1.5 ~ 153 220 2.5 Criteria Fail Pass Pass Pass Pass Pass Pass Pass Sample No No Destroyed Ignition Ignition The samples produced in accordance with this invention exhibit superior flame resistance. The use of low modulus polymers and elastomers provides improved tensile and flexular strength making the finished product suitable for vacuum forming.
. . . :
'': ' ~ ..:' 23 2`~ 9~7~
EXAMPLE II
SAMPLE STD. 1 2 3 4 5 No. ~ % % % % %
5 LLPDE 26.0 Carboxylic acid - 22.0 22.0 2~.0 22.0 23.5 Copolymer . .
Low modulus - 5.05.0 5.0 5.0 5.0 Polymer lo Elastomer 100.0 4.5 - 4.5 4.5 Grafter elastomer - - 4.5 - - 7.5 Polydimethyl - 5.0 5.0 5.0 5.0 5.0 Siloxane Filler ATH 61.0 61.5 61.5 50.0 50.0 51.0 15 Zinc borate - - - - - 5.0 Mica - - - 11.5 Hydracarb - - - 11.5 Additives* 3.0 2.0 2.0 2.0 2.0 3.0 * Colors, antioxidants, lubricants, etc.
The elastomer used in Samples 3 and 4 is ethylenepropylene, terpolymer. The grafted elastomer is an ethylenepropylene terpolymer with a maleic anhydride graft.
The acrylic acid ethylene copolymers used are market ed under the trade name Primacor by Dow Chemical.
The reactive polydimethyl siloxane copolymer is SFR-100 supplied by the General Electric Co.
Flame Evaluations Mortile Vertical Flame Test 30 SAMPLE STD. 1 2 3 4 5 NO.
Afterburn (secs) ~00 145 _ 153 220 Test criteria Fail Pass Pass Pass Pass Pass Sample No No Destroyed Ignition Ignition All samples in this invention exhibit superior flame retardancy. The use of low modulus polymers and . . , .
24 ~9~7~
elastomers provide improved tensile and flexular strength making the finished products suitable for vacuum forming.
EXAMPLE III
Laboratory compounds were mixed in a Type BR Banbury and compression molded into test specimens 25 to 35 mils thick. Their flame retardant properties were then compar ed using a ~imulated vertical flame test against a commer cially available UL approved ceiling tile material that meets ASTM E-84.
Test Descriptlon:
Specimen - 1 x 8 x 0.025 to 0.035 inches Flame application - 30 seconds Criteria - pass - self extinguishing Fail - destructive burn and heavy drip.
Table 1 Sample STD 1 2 3 RESIN % % ~ %
Polyethylene (grafted) 26.0 - - _ Acrylic acid copolymer - 15.015.0 15.0 20 Low modulus polymer - 8.05.0 5.0 Elastomer 10.0 7.0 5.05.0 Polydimethylsiloxane - 5.0 5.0 5.0 FILLER
ATH 61.0 53.0 58.050.0 Zinc borate - 8.0 8.08.0 Calcium carbonate - - - 8.0 Additives* 3.0 4.0 4.04.0 Flame test results FAI~ PASS PASS PASS
Destructive --self extinguish Burn ~ drip --no drip--* Color, antioxidants, lubricants, etc.
The elastomer used in formulations 1 to 3 is an ethylene, propylene tsrpolymer to which a reactive monome r, such as maleic anhydride has been grafted. This elastomer was supplied by Exxon Chemical co~pany.
The low modulus polymer was an ethylenevinyl acetate copolymer obtained from Exxon Chemical Company.
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The acryli~ acid ethylene copolymers are obtained from Dow Chemical USA and are marketed under the trade name PRIMACOR.
The reactive polydimethylsiloxane copolymer is supplied by Genaral Electric Company under the trade name : SFR~100.
EXAMPLE IV
Biological, Physical and Chemical Data of Sample 8 of Example I.
AL Test #197, Sample #A-0028 Case # 010489-1 LC50~ 87.3 grams 95% Confidence interval~ 74.6 - 102.3 grams LC50 sample dimensions/descriptionb chips Furnace temperature at 1% weight lossb 299C
Furnace temperature range at most rapid weight lossb 420 - 600C
Furnace temperature at apparent spon-taneous flame (mean of 7 samples) 4S4C
Percent residue (mean of 6 samples) 50.6%
Maximal CO in exposure chamberb 0.08% 800 ppm Furnace temperature at maximal cob 570C
Maximal C02 in exposure chamberb 2.11%
Furnace temperature at maximal CO2b 570C
Minimal 2 in exposure chamberb 19.8%
Furnace temperature at minimal o2b 570C
Number of times exposure chamber exceeded 45OCb None Duration exposure chamber exceeded 45OCb 0 sac 30 Eye damage (corneal opacity)C None Eye damage (severity) None (1) Number of test runs on sample material 7 a - calculated according to the method of C. Weil, 1952.
b - from single experiment using 87.3 gram test sample.
2~69~7~
c - from single experiment with animals using 78.1 gram test sample; sample weight equal or closest to the LCso value.
The results of this test demonstrate characteristics which are approximately ten times better than polyethylene pellets and better than most other known ole fins from the standpoint of bio:Logical, physical and chemical data in the fire retardancy field.
~XAMPLE V
Vertical Burning Test - UL 94 (specimens were tested "as is", i.e. no conditioning).
Sample 9 of Example I (#0202-6, 125 to 130 mil) Three specimens 5 inches x 1/2 inch were cut from a sample. They were tested using the Vertical Burning Test for 94-Vo classification.
The burner was adjusted to produce a five inch flame with a one and a half inch inner blue cone (using natural gas~. The test flame was applied to one of the lower cor ners of the specimen at an angle of 20 from the vertical, so that the tip of the inner cone touches the specimen.
The flame was applied for 5 seconds and then removed for 5 seconds. This was repeated until the specimen was subjected to the test flame five times total.
Observa ons After Fifth Removal of Test Flame Duration of flaming and glowing, sec. 23 32 25 Affected length, in. 2.78" 2.50" 1.94"
30 Dripping None None None Deformation curled slightly at exposed end EXAMPLE_VI
Vertical Bur lng Test - UL 94 Sample 9 of Example I (#0202-6, 78 mils) Thickness was measured with a micrometer : ' " ~ ' ,` ' Ten specimens 4 9/16 inches x 1/2 inch were tested.
Five specimens were tested for 5U classification, since the burner was already adjusted for this test. It was found that two out of five specimens passed the criteria.
~ natural gas flame was used.
Duration of flaming and glowing, sec. 29 43 76 7a 102 10 Affected length, inchas 2.81 3.50 3.25 Burnt Burnt to to clump clump (4") (4") 15 Dripping None None None None None Deformation B e c a m e e l o n g a t e d EXAMPLE VII
Vertical B rn Test - UL 94 Sample 9 of Example I (#0202-6, 78 mil) Five specimens, 4 9/16 inches x one-half inch were tested for 94U-o, 94U-1 or 94U-2 classification.
The specimens were held vertically 9.5 mm above the orifice of the burner. The burner was adjusted to produce a three-quarter inch ~19 mm) flame. The air supply was increased until the yellow tip of the flame disappeared. The specimens were exposed to the test flame for 10 seconds. The burner was removed and any flaming was noted. When the specimens stopped burning, the burner was placed under the specimens for another 10 seconds.
Duration of flaming after 1st 55 40 70 26 l9 ten sec. exp. (in secs) Duration of flaming after 2nd 25 0 70 3 40 ten sec. exp. (in secs) Duration of glowing after 2nd None None None None None application ~ .
~9~7~
Dripping None None None None None Length of Affected Area - ~ 1 3~ 3h ~~ 1%
inches Burnt to clump No No No No No EXAMPLE VIII
Figures 1 and 2 show weigh~ and percent weight loss of two compositions during heating. The composition tested and results shown in Figure 1 is a polyethylene composition of the invention of Sample 2 of Example 1 not containing a dialdehyde. The composition tested and results shown in Figure 2 is Sample 9 of Example 1 with dialdehyde added.
The composition of Figure 2 lost the bulk of its mass at a substantially higher temperature, 472.59C than the composition of Figure 1, which lost the bulk of its mass at 437.22C.
Loss of mass at substantially higher temperatures indicates better flame retardancy or resistance. The results of Figures 1 and 2 indicate a marked improvement in flame retardancy characteristics with addition of a -dialdehyde to the compositions of the invention.
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EXAMPLE IX
Cable Physical Test Data Sample A* Sample B**
Tensile Elongation Elonga1ion/ Elongation/
5 Unmodified Sample Ultimate Ultimate Tensile Psi Tensile Psi .030 inch wall 80%/2100 Psi 105%/1896 Psi .008 inch wall 90%/221)0 Psi 110%/1817 Psi Tensile Elongation After B irradiation .030 inch wall 133~/2614 Psi 173%/2430 Psi Tensile Elongation After 7 Days Age Testing at .030 inch wall 20%/1589 Psi 20%/1532 Psi UW-1 Test .030 inch wall Pass Pass Insulation Resistance 10,000 Meg n 5,000 Meg n ShrinXage Test .030 inch wall None None * Sample A is Sample 10 of Example 1 ** Sample B is Sample 11 of Example 1 During the testing of the various flame retardant compositions o~ this invention, it is noted that the compositions fail to drip when exposed to flame. This is a significant development and is thought to be due to the degree of cross-linking in the composition. At the stage of processing, there appears to be a condensation-type polymerization taking place in the reactivity of the various components with the carboxyl groups. During exposure, however, to a flame, it is believed that, due to additional cross-linking, a solid charred substance is formed which is inclined not to drip and thereby not exposing fre~h polymer. This is a significant development, particularly when it is considered that the .. , , : , .
2~075 composition is particularly useful in the formation o~
ceiling tile. Ceiling tiles of this invention, when exposed to a flame, are less likely to drop from the ceiling and hence contain the fire for a longer period.
EXMAPLE X
Irradiation cross-linking has been investigated with respect to samples of the composition identified as follows:
SAMPLE A B C D E
Carboxylic Acid 24.0 24.0 24.0 24.0 24.0 Copolymer Low Modules Polymer 9.5 9.5 10.0 10.0 10.0 Grafter 20 Elastomer 9.5 9.5 10.0 10.0 10.0 Polydimethyl Siloxane 5.8 5.8 6.0 6.0 6.0 Filler ATH 60.0 60.0 63.0 63.0 63.0 Zinc Borate 6.5 6.5 7.0 7.0 7.0 Red Phosphorous 4.7 4.7 - - -* Additives *4.0 *4.0 *4.0 *4.0 *4.0 *Pigments, antioxidents, lubricants, etc.
*A. includes Carbon Black Pigment (2.6%) *B. includes Tio2 pigment (2.6~) *C. includes Tio2 pigment (2.6%) *D. includes Magnesium Oxide (2.6%) *E. contains ~ractional Melt Low Modules Polymer.
P~OCESSING NOTE: Materials excluding carboxylic acid copolymer were master-batched and then 25% carboxylic acid copolymer and 76% o~ the master-batch by weight were '' ~ . ' .,' : ~
~ . ~ , i . . ,. ', ':' ' '~
3~ 9 ~ 7 ~
mixed and compounded. Plaques were pressed and tested according to ASTM D-412.
Radiation induced cross-linking is preferably produced by high voltage linear accelerators which generate beams of high energy electonsO These beams may have energies in the range of 2 to 3 million electron volts (MEV~ and are high current beams capable of irradiating large volumes of materials in a short time.
Beam energies in excess of three MEV's are normally required to irradiate thicknesses of the composition in excess of 0.1 inches. For example, in wire and cable applications, the cable may be passed through the beam at a fairly high speed in a manner which ensures uniform dosage over the entire circumference of the cable and at a high enough dose rate to effect cross linkage. This may be accomplished by having a cable make multiple passes through the beam while rotating the cable so that all sides are illuminated by electron beam. It is appreciated that similar procedures may be used in treating sheet material which has previously been extruded and the like.
As a measure of the dosages in exposing the material to the beam of high energy electrons, in this Example, the dosage is in the range of 12 to 15 megarad. The cross-linking occurs when high energy electrons ionize the linear polymeric material so that adjacent chains may form chemical bonds to each other. Quite surprisingly as demonstrated by the ~ollowing data, such cross-linking does not decrease elongation but increases elonyation before failure at maximum tensile stress.
To test each of the above samples A through E, each sample is stretched linearly while recording the elongation of the sample during stretching and the pressure appl:ied in stretching the sample before breakage. Samples are tested be~ore they have been irradiated and after irradiation to determine the impact .
' . -2~6~75 o~ irradiation on elongation and tensile strength. Theresults are set out as follows:
SAMPLE PHYSICALSBEFORE AFTER ~ INCREAS
MEASURED RAD RAD
A) Elongation %118 155 31.36 Tensile PSI1425 1660 16.49 B) Elongation %130 182 40.00 Tensile PSI1525 1937 27.02 C) Elongation %150 200 33.30 Tensile PSI1635 2100 28.44 D) Elongation %164 190 15.85 Tensile PSI1650 2200 33.33 E) Elongation % 87 165 89.66 Tensile PSI1750 2500 42.86 :
EXAMPLE_XI
The use of red amorphous phosphorous has been investigatad to determine its impact on fire retardancy properties. From the following test results, it becomes apparent that less not necessarily more of the red amorphous phosphorous enhances the fire retardancy properties of the composition.
Four samples of this invention were prepared as followsO Each sample had a base formulation comprising:
40% EVA, EAA, EPD blend resins 55% by weight fillers - ATH zinc borate :., . , ~:
: . .
2 ~ 7 ~
5% polydimethylsilicone 1% glyoxol 1% processing aids - stearic acid.
~he above base formulation was modified as follows to prepare samples A, B, C and D.
A - base formulation B - base formulation plus 1.5% by weight red phosphorous C - base formulation plus 3.5% by weight red phosphorous D - base formulation plus 7.5% by weight red phosphorous All samples were extruded to a 0.75 inch thick sheet which was one-half inch wide and six inches long.
A flame was applied to each specimen and ignitiontextinguishing times were recorded. The procedure is that of other Examples where the sample was held in a vertical orientation and the flame applied at an angle to the bottom of each sample.
Sample A B C D
Sec. to ignition 35 sec 15 sec 20 sec 25 sec Sec. to extinguish 35 sec 0 sec 5 sec 2 sec It is apparent that red amorphous phosphorous surprisingly reduced the time to ignition of each of the samples, but in turn reduced the amount of time to self-extinguish. It is also of note that a lesser concentration of red amorphous phosphorous, as in sample B, resulted in a self-extinguishing time of zero seconds, whereas larger concentrations in sample C took longex to self-extinguish and then in sample D with high overloading, two seconds to self-extinguish. It i therefore believed that this data predicts in the range of 1% to 3~ o~ the red amorphous phosphorous is efective in reducing extinguishing times and it is not necessary .
, , 2~
to use higher concentrations in the range of 7~ or greater.
EXAMPLE XII
The impact on the carboxylic acid comonomer for enhancing flame retardancy has been investigated. The carboxylic acid comonomer used :in the following formulations is ethylene acrylic acid. This was compared to a linear, low density polyethylene where aluminum trihydrate and the dimethylsiloxane polymer, SF~100 was used. The samples had the following compositions prepare d in accordance with the previous Examples.
SAMPLE ~
COMPONENTS (1) (2) t3) (4) 15 LLDPE 40.0%40.0% - -EAA 1430 - - 40.0%40.0%
SFR 100 - 5.0% - 5.0%
ATH 60.0%55.0% 60.0%55.0%
Two strips of each sample were prepared having the dimensions of the samples of Example XI. Flame was applied to each of the duplicates of the four samples.
Once ignition occurred, the flame was removed. The time to ignition was recorded. After removal of the flame time to self-extinguish or consumed by flame was recorded. The results are as follows:
SAMPLE Ignition Extinguish Consumed (1) a 25 sec -- 9 minfailed b 20 sec -- 8 minfailed (2) a 15 sec -- 3.5 min failed b 20 sec -- 4.0 min failed (3) a 20 sec 10 sec - Pass b 20 sec 0 -- Pass 40 (4) a 30 sec 0 -- Pass b 35 sec 0 -- Pass . 1 `, ~ ,`
.
`:
2 ~ 5 From the above results, it is apparent that samples 1 and 2 were total failures. Sample 1 did not contain the carboxylic acid comonomer. Sample 2 similarly did not contain the carboxylic acid comonomer, but did contain SFR100. Obviously SFR100 by itself without the metallic stearate and used with the polyolefin does not provide desirable fire retardancy properties. If anything, the rate of burn was increased since th~ sample was consumed within three to four minutes. However, lo samples 3 and 4, both of which contain the carboxylic acid comonomer with no linear monomer polyolefin, self-extinguished and readily passed the test. There is a slight improvement in ~he fire retarding when the of the carboxylic acid comonomer is used in combination with SFR100 as observed by increased time to ignition and both samples extinguishing in zero seconds, that is a non-detectable time period.
As an adjunct to this test, we have also demonstrated that the amount of SFR100 in the formulation does not increase flame retardancy with higher concentrations. With sample 4, 3% by weight SFR100 was compared to sample 4 with 8% SFR100. The flame test d~monstrated that sample 4 containing 3% SFR100 had a significantly better LOI, (limited oxygen index - a value indicating minimum oxygen needed for combustion) than the sample with 8% SFR100. This further example and the above examples demonstrata that fire retardancy is not due alone to the presence of SFR100 or other forms of dimethylsiloxane polymers.
It is thought that SFR functions primarily as a coupling, cross-linking, anti-drip and processing component and not essentially as a flame retardant.
Although preferred embodiments of the invention have been described herein in detail, it will be understood by those skilled in the art that variations may be made thereto without departing from the spirit of the invention or the scope of the appended claims.
Claims (33)
1. A fire retardant composition comprising:
(a) 5% to 60% by weight of an olefinic copolymer or terpolymer wherein 3% to 20% by weight of said copolymer or terpolymer is a carboxylic acid comonomer;
(b) 1% to 15% by weight of an organopolysiloxane;
and (c) 20% to 85% by weight of a flame retardant additive comprising group I, group II, or group III metal oxide hydrate.
(a) 5% to 60% by weight of an olefinic copolymer or terpolymer wherein 3% to 20% by weight of said copolymer or terpolymer is a carboxylic acid comonomer;
(b) 1% to 15% by weight of an organopolysiloxane;
and (c) 20% to 85% by weight of a flame retardant additive comprising group I, group II, or group III metal oxide hydrate.
2. A fire retardant composition of claim 1, wherein said copolymer or terpolymer is selected from the group consisting of a copolymer of ethylene and ethylene acrylic acid and a copolymer of ethylene and methacrylic acid, in each of said copolymers, there being 3% to 20%
by weight of said copolymer of said carboxylic acid comonomer.
by weight of said copolymer of said carboxylic acid comonomer.
3. A fire retardant composition of claim 1, wherein said organopolysiloxane has a viscosity in the range of 0.6 centipoise to 300x106 centipoise.
4. A fire retardant composition of claim 3, wherein said viscosity is in the range of 10x103 centipoise to 900x103 centipoise.
5. A fire retardant composition of claim 4, wherein said viscosity is in the range of 30x103 centipoise to 600x103 centipoise.
6. A fire retardant composition of claim 3, wherein said polysiloxane is a compound selected from the group represented by the formulae:
R3SiO0.5, R2SiO, R1SiO1.5, R1R2SiO0.5, RR1SiO, (R1)2SiO, RSiO1.5 and SiO2 wherein each R represents independently a saturated or unsaturated monovalent hydrocarbon radical, R1 represents a radical such as R or a radical selected from the group consisting of a hydrogen atom, hydroxyl alkoxyl, aryl, vinyl, or allyl radicals and wherein said organopolysiloxane has a viscosity of approximately 600 to 300,000,000 centipoise at 25°C.
R3SiO0.5, R2SiO, R1SiO1.5, R1R2SiO0.5, RR1SiO, (R1)2SiO, RSiO1.5 and SiO2 wherein each R represents independently a saturated or unsaturated monovalent hydrocarbon radical, R1 represents a radical such as R or a radical selected from the group consisting of a hydrogen atom, hydroxyl alkoxyl, aryl, vinyl, or allyl radicals and wherein said organopolysiloxane has a viscosity of approximately 600 to 300,000,000 centipoise at 25°C.
7. A fire retardant composition of claim 6 further comprising a reactive silicone resin represented by the formula:
MQ
where said reactive silicone resin is comprised of monofunctional M units of the average formula R3SiO0.5 and tetrafunctional Q units of the average formula SiO2, and having an average ratio of, approximately, 0.3 to 4.0 M
units per Q unit; and optionally a group II metal organic salt to enhance solubility of said reactive silicone resin in said organopolysiloxane.
MQ
where said reactive silicone resin is comprised of monofunctional M units of the average formula R3SiO0.5 and tetrafunctional Q units of the average formula SiO2, and having an average ratio of, approximately, 0.3 to 4.0 M
units per Q unit; and optionally a group II metal organic salt to enhance solubility of said reactive silicone resin in said organopolysiloxane.
8. A fire retardant composition of claim 5, wherein said organopolysiloxane is polydimethylsiloxane.
9. A fire retardant composition of claim 1, wherein said flame retardant additive is selected from the group consisting of alumina trihydrate, magnesium hydroxide and hydrotalcite (sodium aluminum hydroxy carbonate).
10. A fire retardant composition of claim 9 furthar comprising a filler to complete said composition, said filler being selected from the group consisting of talc, calcium carbonate, mica, clay, hydracarb, zinc borate, wallastonite and mixtures thereof.
11. A fire retardant composition of claim 1 further comprising up to 30% by weight of a polymer selected from the group consisting of:
i) low modulus ethylene copolymer ii) polyethylene iii) polypropylene iv) ethylene propylene synthetic rubbers, and v) ethylene propylene elastomer with a reactive monomer graft.
i) low modulus ethylene copolymer ii) polyethylene iii) polypropylene iv) ethylene propylene synthetic rubbers, and v) ethylene propylene elastomer with a reactive monomer graft.
12. A fire retardant composition of claim 11, wherein said low modulus ethylene copolymer is selected from the group consisting of ethylenevinylacetate, ethylenemethylacrylate, ethyleneethylacrylate and ethylenebutylacrylate and maleic anhydride grafts thereof.
13. A fire retardant composition of claim 11, wherein said reactive monomer graft in said ethylene propylene elastomer is maleic anhydride.
14. A fire retardant composition of claim 1 wherein 1%
to 15% by weight red amorphous phosphorous is incorporated in said composition.
to 15% by weight red amorphous phosphorous is incorporated in said composition.
15. A fire retardant composition of claim 1 wherein 20%
to 40% by weight of metal oxide hydrate selected from the group consisting of alumina trihydrate, magnesium hydroxide and mxitures thereof.
to 40% by weight of metal oxide hydrate selected from the group consisting of alumina trihydrate, magnesium hydroxide and mxitures thereof.
16. A fire retardant composition of claim 15 wherein 5%
to 30% by weight of zinc borate is incorporated in said composition.
to 30% by weight of zinc borate is incorporated in said composition.
17. A fire retardant composition of claim 1 wherein 1%
to 5% by weight of said organopolysiloxane is used with said copolymer of ethyleneacrylic acid.
to 5% by weight of said organopolysiloxane is used with said copolymer of ethyleneacrylic acid.
18. A fire retardant composition of claim l further comprising trace amounts of zirconates, titanates, zinc and tin salts.
19. A fire retardant composition of claim 1 further comprising up to 20% by weight of an organic halide fire retardant additive.
20. A fire retardant composition of claim 19, wherein said organic halide is decabromodiphenyloxide.
21. A fire retardant composition of claim 20 further comprising up to 10% by weight of antimony oxide.
22. A fire retardant composition having an olefinic base material for use in fabricating insulation for wire and cable, wherein compositional components are cross-linked in a hydrophobic/hydrophilic relationship by means of a condensation-type reaction between carboxyl groups contained within said olefinic base material and hydroxyl groups contained within a flame retardant additive, with silanol groups contained in an organopolysiloxane, said composition comprising:
a) approximately from 3% to 60% by weight of olefinic copolymer or terpolymer which includes a substance containing carboxyl groups;
b) approximately from 1% to 15% by weight of an organopolysiloxane; and c) approximately from 20% to 85% by weight of a flame retardant additive comprising group I, group II, or group III metal oxide hydrates
a) approximately from 3% to 60% by weight of olefinic copolymer or terpolymer which includes a substance containing carboxyl groups;
b) approximately from 1% to 15% by weight of an organopolysiloxane; and c) approximately from 20% to 85% by weight of a flame retardant additive comprising group I, group II, or group III metal oxide hydrates
23. A fire retardant composition of claim 22, wherein said copolymer or terpolymer is selected from the group consisting of a copolymer of ethylene and ethylene acrylic acid, a terpolymer of ethylene propylene and maleic anhydride, and a copolymer of ethylene and methacrylic acid, in each of which there being 3% to 20%
by weight a carboxylic acid comonomer providing said carboxyl groups.
by weight a carboxylic acid comonomer providing said carboxyl groups.
24. A polycondensation-type method of fabricating a fire retardant insulative composition, comprising the steps of:
a) linking carboxyl groups contained in a hydrophobic olefinic base material with silanol groups contained in a silicone material; and b) linking silanol groups of said silicone material additionally with hydroxyl groups contained in a hydrophilic fire retardant material, whereby said silicone material is linked to both said hydrophilic and hydrophobic materials.
a) linking carboxyl groups contained in a hydrophobic olefinic base material with silanol groups contained in a silicone material; and b) linking silanol groups of said silicone material additionally with hydroxyl groups contained in a hydrophilic fire retardant material, whereby said silicone material is linked to both said hydrophilic and hydrophobic materials.
25. The method of claim 24 further comprising the steps of:
c) blending said olefinic base material with an elastomer to which a monomer containing carboxyl groups has been grafted; and d) linking said carboxyl groups of said elastomer with silanol groups of said silicone material.
c) blending said olefinic base material with an elastomer to which a monomer containing carboxyl groups has been grafted; and d) linking said carboxyl groups of said elastomer with silanol groups of said silicone material.
26. A fire retardant composition formed by a polycondensation-type process, comprising:
a hydrophobic olefinic base material containing carboxyl groups;
a hydrophilic fire retardant filler material containing hydroxy groups; and a silicone material containing silanol groups linked to both said hydrophobic olefinic base material carboxyl groups and said hydrophilic fire retardant filler material hydroxyl groups.
a hydrophobic olefinic base material containing carboxyl groups;
a hydrophilic fire retardant filler material containing hydroxy groups; and a silicone material containing silanol groups linked to both said hydrophobic olefinic base material carboxyl groups and said hydrophilic fire retardant filler material hydroxyl groups.
27. The fire retardant composition of claim 26, further comprising an elastomer to which a material containing carboxyl groups has been grafted, said carboxyl groups of the elastomer being linked to silanol groups of said silicone material.
28. The fire retardant composition of claim 26, wherein said silicone material contains a silicone resin and siloxane fluid.
29. The fire retardant composition of claim 27, wherein said silicone material contains a silicone resin and siloxane fluid.
30. A fire retardant composition of claim 1 wherein processability of said composition into articles of manufacture is improved by addition of one of more components selected from the groups consisting of tartaric acid, stearic acid and mixtures thereof.
31. A fire retardant composition of claim 30 wherein 0.1% to 5% by weight of tartaric acid is used in said compositon.
32. A fire retardant composition of claim 30 wherein 0.1% to 3% by weight of stearic acid is used in said composition.
33. A fire retardant composition according to any one of claims 1 to 23 and 26 to 32 wherein said composition is irradiated to increase elongation and simultaneously tensile strength.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US702,893 | 1991-05-20 | ||
| US07/702,893 US5218027A (en) | 1988-03-18 | 1991-05-20 | Low toxicity fire retardant thermoplastic material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2069075A1 true CA2069075A1 (en) | 1992-11-21 |
Family
ID=24823038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2069075 Abandoned CA2069075A1 (en) | 1991-05-20 | 1992-05-20 | Low toxicity fire retardant thermoplastic material |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2069075A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115612363A (en) * | 2022-12-15 | 2023-01-17 | 潍坊亚贝涂料有限公司 | Wood surface water-based paint and preparation method thereof |
-
1992
- 1992-05-20 CA CA 2069075 patent/CA2069075A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115612363A (en) * | 2022-12-15 | 2023-01-17 | 潍坊亚贝涂料有限公司 | Wood surface water-based paint and preparation method thereof |
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