CA1240100A - Self-extinguishing compositions based on ethylene vinylacetate copolymers suitable for the preparation of foamed materials - Google Patents
Self-extinguishing compositions based on ethylene vinylacetate copolymers suitable for the preparation of foamed materialsInfo
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- CA1240100A CA1240100A CA000467848A CA467848A CA1240100A CA 1240100 A CA1240100 A CA 1240100A CA 000467848 A CA000467848 A CA 000467848A CA 467848 A CA467848 A CA 467848A CA 1240100 A CA1240100 A CA 1240100A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
Abstract
ABSTRACT OF THE DISCLOSURE
Compositions endowed with self-extinction properties and suitable for the preparation of foamed materials are disclosed, comprising:
(a) ethylene/vinylacetate copolymer having vinyl-acetate content less than 50% by weight of copolymer;
(b) at least one bromodiphenylether containing at least three bromine atoms in its molecule in an amount from about 5% to about 10% by weight of copolymer;
(c) a metal oxide selected from the group comprising antimony trioxide, bismuth oxide and tungsten oxide in an amount from about 2% to about 4% by weight of copolymer; and (d) at least one compound in an amount from about 0.1% to about 1% by weight of copolymer selected from the compounds represented by formula I
I
wherein R1, R2, R3, R4, which may be the same or different are independently selected from hydrogen, aliphatic hydrocarbon radicals with 1-6 carbon atoms, chlorine, bromine, phenyl or cyclohexyl radicals, nitro groups and -CN groups;
R5, R6, which may be the same or different are independently selected from hydrogen, chlorine, bromine, aliphatic hydrocarbon radicals containing 1-3 carbon atoms, alkoxy radicals containing 1-4 carbon atoms, and -?-OR7 groups, where R7 is an aliphatic hydrocarbon radical containing 1-3 carbon atoms.
Compositions endowed with self-extinction properties and suitable for the preparation of foamed materials are disclosed, comprising:
(a) ethylene/vinylacetate copolymer having vinyl-acetate content less than 50% by weight of copolymer;
(b) at least one bromodiphenylether containing at least three bromine atoms in its molecule in an amount from about 5% to about 10% by weight of copolymer;
(c) a metal oxide selected from the group comprising antimony trioxide, bismuth oxide and tungsten oxide in an amount from about 2% to about 4% by weight of copolymer; and (d) at least one compound in an amount from about 0.1% to about 1% by weight of copolymer selected from the compounds represented by formula I
I
wherein R1, R2, R3, R4, which may be the same or different are independently selected from hydrogen, aliphatic hydrocarbon radicals with 1-6 carbon atoms, chlorine, bromine, phenyl or cyclohexyl radicals, nitro groups and -CN groups;
R5, R6, which may be the same or different are independently selected from hydrogen, chlorine, bromine, aliphatic hydrocarbon radicals containing 1-3 carbon atoms, alkoxy radicals containing 1-4 carbon atoms, and -?-OR7 groups, where R7 is an aliphatic hydrocarbon radical containing 1-3 carbon atoms.
Description
The present invention relates to compositions based on ethylene/vinylacetate ~EVA) copolymers, provided with self-extinguishinq properties and suitable for the production of foamed materials.
The use of foamed thermoplastic materials in the building and furnishings fields involves more and more serious safety prob]ems as far as the flame reaction is concerned.
In particular, the foamed materials of polyolefins 10 havinq low riqidity (less than approx. 1,400 Kq/cm2), especially ethylene-vinylacetate copolymers, obtained by means of an ~trusion-foaming process with physical foaminq agents, respond differently a~ combustion temperature than do foamed materials having low density of ethylene homopolymers.
Despite addition of antiflame halogenated agents or synergic combinations thereof with Sb203 which typically provide olefins with generally satisfactory flame response characterics it has not yet been possible to achieve self-extinguishing properties in the EVA copolymers used in the production of low-density foamed materials which have the softness required in the building field (sheaths for hot and cold water piping insulation, as well as sheets and slabs for insulation) and also in the furniture industry.
Therefore the antiflame systems for polyolefins, comprising, for example, bromodiphenylethers in combination with antimony oxide (exemplified) in British patent No.
874006, fail to impart desirable flame extinguisninq properties to EVA copolymers.
The same applies to the antiflame systems based on haloqenated products and organic peroxides, used for styrol resins examplified in British patent No. 877864 and U.S.A.
patents ~o. 3058~26 and No. 3124557 as well as methods described in Bel~ium patent No. 867873 and in 35 Japanese Application No. 76/134.762, accordinq to which it is possible to obtain foamed polyolefinic products provided with self-extinguishing characteristics performing reticulation of polymers with peroxides and foaminq thereafter with chemical agents.
In the latter cases it is possible to obtain products provided with very hiqh density (exceedin~ lO0 Kg/m3), non-soft and of hiqher cost than those prepared according to physical processes of extrusion-foamin~.
Furthermore the decomposition residues of the chemical foaming agents in this case negatively affect the aginq resistance of the foamed materials themselves, particularly when such materials are in contact with metals (copper etc.~.
It has been now surprisin~ly found by the Applicant that it is possible to endow ethylene/vinylacetate copolymers with self-extinguishinq properties and at the same time to obtain products suitable for the preparation of soft foamed materials with low density by usin~ an antiflame system comprising one or more bromodiphenylethers containing at least 3 bromine atoms in their molecule, in combination with at least one metal oxide as hereinafter specified, and moreover at least one compound (activator) having the general formula:
R6 1l lZ R5 where:
The use of foamed thermoplastic materials in the building and furnishings fields involves more and more serious safety prob]ems as far as the flame reaction is concerned.
In particular, the foamed materials of polyolefins 10 havinq low riqidity (less than approx. 1,400 Kq/cm2), especially ethylene-vinylacetate copolymers, obtained by means of an ~trusion-foaming process with physical foaminq agents, respond differently a~ combustion temperature than do foamed materials having low density of ethylene homopolymers.
Despite addition of antiflame halogenated agents or synergic combinations thereof with Sb203 which typically provide olefins with generally satisfactory flame response characterics it has not yet been possible to achieve self-extinguishing properties in the EVA copolymers used in the production of low-density foamed materials which have the softness required in the building field (sheaths for hot and cold water piping insulation, as well as sheets and slabs for insulation) and also in the furniture industry.
Therefore the antiflame systems for polyolefins, comprising, for example, bromodiphenylethers in combination with antimony oxide (exemplified) in British patent No.
874006, fail to impart desirable flame extinguisninq properties to EVA copolymers.
The same applies to the antiflame systems based on haloqenated products and organic peroxides, used for styrol resins examplified in British patent No. 877864 and U.S.A.
patents ~o. 3058~26 and No. 3124557 as well as methods described in Bel~ium patent No. 867873 and in 35 Japanese Application No. 76/134.762, accordinq to which it is possible to obtain foamed polyolefinic products provided with self-extinguishing characteristics performing reticulation of polymers with peroxides and foaminq thereafter with chemical agents.
In the latter cases it is possible to obtain products provided with very hiqh density (exceedin~ lO0 Kg/m3), non-soft and of hiqher cost than those prepared according to physical processes of extrusion-foamin~.
Furthermore the decomposition residues of the chemical foaming agents in this case negatively affect the aginq resistance of the foamed materials themselves, particularly when such materials are in contact with metals (copper etc.~.
It has been now surprisin~ly found by the Applicant that it is possible to endow ethylene/vinylacetate copolymers with self-extinguishinq properties and at the same time to obtain products suitable for the preparation of soft foamed materials with low density by usin~ an antiflame system comprising one or more bromodiphenylethers containing at least 3 bromine atoms in their molecule, in combination with at least one metal oxide as hereinafter specified, and moreover at least one compound (activator) having the general formula:
R6 1l lZ R5 where:
- 2 -Rl, R2, R3, R4, which may be the same or different are independently selected from hydro~en, aliphatic hydrocarbon radicals with 1-6 carbon atoms, chlorine, bromine, phenyl or cyclohexyl radicals, nitro groups and -CN
groups;
RS, R6, which may be the same or different are independently selected from hydrogen, chlorine~ bromine, aliphatic hydrocarbon radicals containin~ 1-3 carbon atoms, alkoxy radicals containinq l-q carbon atoms, and -C-OR7 groups, where R7 is an aliphatic hydrocarbon radical containin~ 1-3 carbon atoms.
U.S.A. patents No. 3~4152~ and No. 3420786 have reported the use of representative diphenyl compounds included in formula (I) in combination with bromide orqanic compounds, to provide styrene polymers with antiflame characteristics. In this case the antiflame effect is associated with the ability of the diphenyl compounds to modify the polymer structure at the combustion temperature in such a way as to decrease its viscosity. The modified polymer tends to drip at such temperature conditions, with subsequent detachment of the flame from the polymeric material which thus stops burning.
In contrast, it has been found that use of said diphenyl compounds with ethylene/vinylacetate copolymers enables the composition to respond quite differently and desirably at the combustion temperature of the copolymer and generally at a temperature exceeding 200C. At such temperatures, it has been observed that copolymer viscosity is increased and therefore, no dripping of the copolymer occurs. It is believed that this property results from modification of the EVA copolymer struct~re by the diphenyl derivatives.
It is surprising therefore that it may be possible to obtain such antiflame effects in the EVA copolymer by the use of the said diphenyl derivatives~
Thus, in accordance with the present invention there is provided self-extinguishing polymeric compositions comprisin~:
(a) ethylene/vinylacetate copolymer havin~
vinylacetate content less than 50% by weight of copolymer, tb) at least one bromodiphenylether containing at least three bromine atoms in its molecule in an amount from about 5% to about 10% by weiqtlt of copolymer, (c) a metal oxide selected from the qroup comprising antimony trioxide, bismuth oxide and tun~sten oxide in an amount from about 2% to about 4~ by weight of copolymer~ and (d) at least one compound in an amount from about 0.1% to about 1% by weight of copolymer selected from the compounds represented by formula I.
The preferred metal oxide is antimony trioxide.
The ethylene/vinylacetate copolymer preferably contains from 8 to 10% by weiqht of copolymerized vinylacetate.
Bromodiphenylether is preferably present in amounts ranging between 6% and 8% by wei~ht of copolymer, while the compound of fGrmula (I) is preferably present in amounts ranging between 0.~% and 0.8% by weight of copolymer.
Examples of utilizable bromodiphenylethers are tribromodiphenylether, tetrabromodiphenylether, pentabromodiphenylether, hexabromodiphenylether, tribromochlorodiphenylether, tribromodichlorodiphenylether, tetrahromodichlorodi~henylether, octabromodiphenylether, decabromodiphenylether.
Examples of utilizable compounds of formula (I) (or activators) are 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-di-p-tolylbutane; 2,3-dimethyl-2,3-di-p-bromophenyl-butane; 2,3-dimethyl-2,3-di-p-chlorophenylbutane;
35 2,3-dimethyl-2,3-di-p-ethoxyphenylbutane; 2,2,3,3-tetra-phenylbutane; 1,2-dibromo-1,2~dimethyl-1,2-diphenylethane;
1,2-dibromo-1,2-diphenylethane; 1,2-dinitro-1,2-diphenyl-ethane, 1,2-dinitro-1,2-di-p-to]ylethane; 2,3-dicyano-2,3-diphenylbutane; 1~2-dichloro-1,2-diphenyle~hane and mixtures of said compounds. 2,3-dimethyl-2,3-diphenylbutane is qenerally preferred.
The utilized EYA copolymer preferably has rigidity values ranginq between 70 and 700 Kg/cm , with Melt Flow Index (MFI) values ranging between 0.3 and 4.5 and preferably between 1.3 and 1.8/10 min. and density between 0.92 and 0.95 and preferably of 0.928 q/cm3.
Said EVA copolymers can also be used accordinq to the present invention, in mixture up to 20% by weight, but preferably 5-10~ by weight, of polyethylene at low, medium and hiqh density, polypropylene, ethylene-Propylene copolymers and ethylene-vinylchloride copolymers.
Anti-oxidizing agents, U.V. and metal stabilizers, lubricants, pigments, nucleants, inert fillers can also be present in such copolymers or mixtures in amounts up to 3 by weight.
The ~elf-extinquishing compositions according to the present invention are preferably granulated before the extrusion-foaming process.
The EVA resin in granulated form is augmented with the antiflame agents and the activators, the synergic agents and all the other additives, such as for example nucleants, lubricants, anti-oxidizing agents, various stabilizers, pigments, antis~atic aqents etc., and successively submitted to mixing in a mixer equipped with heating means (Banbury).
The homogenized mixture undergoes calenderinq and the strip of the desired thickness is finally granulated.
In order to obtain good homoqenization of the compositions according to the invention, in particular when antiflame agents such as concentrated "masterbatches" are ~ 3~
used, it is preferable ~o perform cold mixing (for example in a Henschel type mixer) and then to carry out mixture granulation by extrusion.
The self-ex~inguishing com~ositions thus obtained are particularly suitable for the production of closed-celled soft self-extinguishing foamed materials having low density and endowed with good dimensional stability by means of a conventional process of extrusion-foaminq with physical foa~inq agents.
The physical foaming aqents appropriate for the extrusion-foaming process are qenerally constituted by fluorocarbons, in particular dichlorotetrafluoroethane or fluorotrichloromethane, difluoridichloromethane, difluorochloromethane and their mixtures.
The followin~ examples are reported in order to better illustrate the invention and have no limiting value.
For a preliminary evaluation of the flame reaction of the ethylene/vinylacetate (EV~) copolymer compositions with self-extinguishing properties according to the invention and to the examples reported, standard test pieces were prepared starting from the relevant granulated compositions, by injection molding and were then subjected to the tests reported in the UL 94 specification (Underwriters Laboratories Inc~,).
The test pieces obtained from compositions according to the invention proved to have specified extinction times as provided for the class V 0.
The foamed materials obtained by the extrustion-foaming process were on the contrary subjected to the flame reaction test outlined in the German specification DIN 4102, Class B.2. The test method under the specification DIN
53438 was used for this evaluation.
EXAMPLE 1 (reference composition) -100 parts by wei~ht of base resin consisting of ethylene/vinylacetate copolymer (trade ~m~ Baylon V 10 H
~.~.L~ r3~
460, produced by Bayer AG, vinylacetate content: 8.%, effective density: 0.92B g/cm3, Melt Flow Index according to DIN 53735: 1~5) were uniformly mixed (in a mixer) with 1.5 parts by weight of zinc stearate, with 0.8 parts by weight of talc and 0.1 parts of phenol anti-oxidizing aqent containing sulphur (trade-~m~ Irganox ;035 of Ciba-Geiqy) and were then auqmented with 7.2 parts by weiqht of decabromodiphenylether and 2.4 parts of Sb2O3.
The mixture was qranulated in a sinqle-screw extruder (L/~=25, screw diameter = 60 mm, at temperatures of 130-160C~.
Standard test pieces according to the UL (94-V.) specification were prepared from the granulated mixture by injection molding. The results relating to the extinction times obtained in the flame reaction tests according to the above mentioned specifications and reported in table 1, proved that the test pieces burnt completely indicating that the composition was not endowed with the necessary self-extinguishing properties.
The flame reaction of a foamed material obtained from the reference composition ~y a conventional extrusion-foaming process was also determined.
For this purpose the reference composition granulate was placed in a do~ble-screw extruder LMP - RC 27 25 (L/D = 16.6; D = 90 mm), equipped with an extrusion die having internal diameter outlet section of 10.5 mm and external diameter of 13.5 mm. The injection of 30 parts by weight of physical foaming aqent consisting of dichlorotetrafluoroethane took place at approximately one third of the screw length. The temperature of the outflowing molten material was approx. 95C.
The foamed tubular material had the following characteristics:
internal diameter = 40 mm, external diameter = 55 mm, density = 38 Kg/m3.
Test pieces having standard dimensions were obtained from the foamed tubular material and subjected to the flame tests accordinq to the German specification DIN
53438 for the class B 2.
Table 1 reports the values of the combustion times from which it appears that the test pieces did not meet the specifications required for Class B 2 and therefore the reference composition did no~ possess the necessary characteristics of self-extinction.
The compositio~ described in the reference example 1 was mixed with 0.6 parts by weiqht of 2,3-dimethyl-2,3-diphenylbutane (trade ~me-Interox CC DFB produced by Peroxyd~Chemie G.m.b.H.), then granulation was carried o~t.
Table 1 reports the extinction times of the relevant test pieces obtained according to the specification UL 94 and the combustion times of the foamed test pieces determined according to the specification DIN 53438.
The results of the flame reaction showed that the composition according to the invention was endowed with the necessary properties of self-extinction and the foamed material met the specifications required for class B 2.
100 parts by weight of resin base consisting of ethylene-vinylacetate copolymer (trade.~e Elvax 760 produced by Du Pont & de Nemours; vinylacetate content:
9.3%; effective density: 0.93 g/cm3; Melt Flow Index according to DIN 53735: 2.0)were additioned with 10 parts by weight of polyethylene homopolymer at low density (Baylon 23 L 430, produced by Bayer AG; effective density: 0.923 g/cm ; Melt Flow Index according to DIN 53735: 3.8), ~hen mixing was performed adding 1.5 parts by weight of zinc stearate, 0.8 parts of talc and 0.1 parts of phenol anti-oxidizing agen~ (Irganox 1035) and finally 13.2 parts by weight of an anti-flame Masterbatch were added (80%
J~ J9~
concentration of EVA resin base having 19% content by weiqht of Sb2O3; 56 b.w~ of decabromodiphenylether and 5% b.w.
of 2,3-dimethyl-2,3-diphenylbutane), obtaining a mixture having the followina composition, expressed in parts by weight:
ethylene/vinylacetate copolymer l00 polyethylene 10 Irqanox 1035 0.1 decabromodiphenylether 7.4 lG Sb23 2.5 2,3-dimethyl-2,3-diphenylbutane 0.65 zinc stearate 1.5 ~ he standard test pieces to be subjected to the flame reaction accordina to the specification UL 94 were prepared by injec~ion molding from the granulated mixture and the foamed test pieces (sheaths) to be subjected to the flame reaction according to the specification DIN 53438 were also prepared by the extrusion-foaming process.
The results of the extinction and combustion times reported in table 1 show that the composition according to the invention was endowed with the self-extinguishing properties required.
-The composition described in the reference example 7 was mixed in turn with the specific amounts of activators reported in table 1.
The relevant extinction and combustion times of the compositions accordina to the invention showed that all the compositions containing the claimed activators possessed the required characteristics of self-extinction.
c~
~BIE 1 % ~ r~a ~us~
E~ ~rIV~R __ wei.ghTIMES (U194) Tl~ (DIN53438) forrrD~la of E~n ~ seconds secorx:l~ cl~ss ' ~1 ~ . _ 1. ~ _ burns bur~s (re.f ) carpletely eCa~ly~
___ ICH 3 C ~ 3 2 ~ C I \~> 0.6 2 6 B 2
groups;
RS, R6, which may be the same or different are independently selected from hydrogen, chlorine~ bromine, aliphatic hydrocarbon radicals containin~ 1-3 carbon atoms, alkoxy radicals containinq l-q carbon atoms, and -C-OR7 groups, where R7 is an aliphatic hydrocarbon radical containin~ 1-3 carbon atoms.
U.S.A. patents No. 3~4152~ and No. 3420786 have reported the use of representative diphenyl compounds included in formula (I) in combination with bromide orqanic compounds, to provide styrene polymers with antiflame characteristics. In this case the antiflame effect is associated with the ability of the diphenyl compounds to modify the polymer structure at the combustion temperature in such a way as to decrease its viscosity. The modified polymer tends to drip at such temperature conditions, with subsequent detachment of the flame from the polymeric material which thus stops burning.
In contrast, it has been found that use of said diphenyl compounds with ethylene/vinylacetate copolymers enables the composition to respond quite differently and desirably at the combustion temperature of the copolymer and generally at a temperature exceeding 200C. At such temperatures, it has been observed that copolymer viscosity is increased and therefore, no dripping of the copolymer occurs. It is believed that this property results from modification of the EVA copolymer struct~re by the diphenyl derivatives.
It is surprising therefore that it may be possible to obtain such antiflame effects in the EVA copolymer by the use of the said diphenyl derivatives~
Thus, in accordance with the present invention there is provided self-extinguishing polymeric compositions comprisin~:
(a) ethylene/vinylacetate copolymer havin~
vinylacetate content less than 50% by weight of copolymer, tb) at least one bromodiphenylether containing at least three bromine atoms in its molecule in an amount from about 5% to about 10% by weiqtlt of copolymer, (c) a metal oxide selected from the qroup comprising antimony trioxide, bismuth oxide and tun~sten oxide in an amount from about 2% to about 4~ by weight of copolymer~ and (d) at least one compound in an amount from about 0.1% to about 1% by weight of copolymer selected from the compounds represented by formula I.
The preferred metal oxide is antimony trioxide.
The ethylene/vinylacetate copolymer preferably contains from 8 to 10% by weiqht of copolymerized vinylacetate.
Bromodiphenylether is preferably present in amounts ranging between 6% and 8% by wei~ht of copolymer, while the compound of fGrmula (I) is preferably present in amounts ranging between 0.~% and 0.8% by weight of copolymer.
Examples of utilizable bromodiphenylethers are tribromodiphenylether, tetrabromodiphenylether, pentabromodiphenylether, hexabromodiphenylether, tribromochlorodiphenylether, tribromodichlorodiphenylether, tetrahromodichlorodi~henylether, octabromodiphenylether, decabromodiphenylether.
Examples of utilizable compounds of formula (I) (or activators) are 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-di-p-tolylbutane; 2,3-dimethyl-2,3-di-p-bromophenyl-butane; 2,3-dimethyl-2,3-di-p-chlorophenylbutane;
35 2,3-dimethyl-2,3-di-p-ethoxyphenylbutane; 2,2,3,3-tetra-phenylbutane; 1,2-dibromo-1,2~dimethyl-1,2-diphenylethane;
1,2-dibromo-1,2-diphenylethane; 1,2-dinitro-1,2-diphenyl-ethane, 1,2-dinitro-1,2-di-p-to]ylethane; 2,3-dicyano-2,3-diphenylbutane; 1~2-dichloro-1,2-diphenyle~hane and mixtures of said compounds. 2,3-dimethyl-2,3-diphenylbutane is qenerally preferred.
The utilized EYA copolymer preferably has rigidity values ranginq between 70 and 700 Kg/cm , with Melt Flow Index (MFI) values ranging between 0.3 and 4.5 and preferably between 1.3 and 1.8/10 min. and density between 0.92 and 0.95 and preferably of 0.928 q/cm3.
Said EVA copolymers can also be used accordinq to the present invention, in mixture up to 20% by weight, but preferably 5-10~ by weight, of polyethylene at low, medium and hiqh density, polypropylene, ethylene-Propylene copolymers and ethylene-vinylchloride copolymers.
Anti-oxidizing agents, U.V. and metal stabilizers, lubricants, pigments, nucleants, inert fillers can also be present in such copolymers or mixtures in amounts up to 3 by weight.
The ~elf-extinquishing compositions according to the present invention are preferably granulated before the extrusion-foaming process.
The EVA resin in granulated form is augmented with the antiflame agents and the activators, the synergic agents and all the other additives, such as for example nucleants, lubricants, anti-oxidizing agents, various stabilizers, pigments, antis~atic aqents etc., and successively submitted to mixing in a mixer equipped with heating means (Banbury).
The homogenized mixture undergoes calenderinq and the strip of the desired thickness is finally granulated.
In order to obtain good homoqenization of the compositions according to the invention, in particular when antiflame agents such as concentrated "masterbatches" are ~ 3~
used, it is preferable ~o perform cold mixing (for example in a Henschel type mixer) and then to carry out mixture granulation by extrusion.
The self-ex~inguishing com~ositions thus obtained are particularly suitable for the production of closed-celled soft self-extinguishing foamed materials having low density and endowed with good dimensional stability by means of a conventional process of extrusion-foaminq with physical foa~inq agents.
The physical foaming aqents appropriate for the extrusion-foaming process are qenerally constituted by fluorocarbons, in particular dichlorotetrafluoroethane or fluorotrichloromethane, difluoridichloromethane, difluorochloromethane and their mixtures.
The followin~ examples are reported in order to better illustrate the invention and have no limiting value.
For a preliminary evaluation of the flame reaction of the ethylene/vinylacetate (EV~) copolymer compositions with self-extinguishing properties according to the invention and to the examples reported, standard test pieces were prepared starting from the relevant granulated compositions, by injection molding and were then subjected to the tests reported in the UL 94 specification (Underwriters Laboratories Inc~,).
The test pieces obtained from compositions according to the invention proved to have specified extinction times as provided for the class V 0.
The foamed materials obtained by the extrustion-foaming process were on the contrary subjected to the flame reaction test outlined in the German specification DIN 4102, Class B.2. The test method under the specification DIN
53438 was used for this evaluation.
EXAMPLE 1 (reference composition) -100 parts by wei~ht of base resin consisting of ethylene/vinylacetate copolymer (trade ~m~ Baylon V 10 H
~.~.L~ r3~
460, produced by Bayer AG, vinylacetate content: 8.%, effective density: 0.92B g/cm3, Melt Flow Index according to DIN 53735: 1~5) were uniformly mixed (in a mixer) with 1.5 parts by weight of zinc stearate, with 0.8 parts by weight of talc and 0.1 parts of phenol anti-oxidizing aqent containing sulphur (trade-~m~ Irganox ;035 of Ciba-Geiqy) and were then auqmented with 7.2 parts by weiqht of decabromodiphenylether and 2.4 parts of Sb2O3.
The mixture was qranulated in a sinqle-screw extruder (L/~=25, screw diameter = 60 mm, at temperatures of 130-160C~.
Standard test pieces according to the UL (94-V.) specification were prepared from the granulated mixture by injection molding. The results relating to the extinction times obtained in the flame reaction tests according to the above mentioned specifications and reported in table 1, proved that the test pieces burnt completely indicating that the composition was not endowed with the necessary self-extinguishing properties.
The flame reaction of a foamed material obtained from the reference composition ~y a conventional extrusion-foaming process was also determined.
For this purpose the reference composition granulate was placed in a do~ble-screw extruder LMP - RC 27 25 (L/D = 16.6; D = 90 mm), equipped with an extrusion die having internal diameter outlet section of 10.5 mm and external diameter of 13.5 mm. The injection of 30 parts by weight of physical foaming aqent consisting of dichlorotetrafluoroethane took place at approximately one third of the screw length. The temperature of the outflowing molten material was approx. 95C.
The foamed tubular material had the following characteristics:
internal diameter = 40 mm, external diameter = 55 mm, density = 38 Kg/m3.
Test pieces having standard dimensions were obtained from the foamed tubular material and subjected to the flame tests accordinq to the German specification DIN
53438 for the class B 2.
Table 1 reports the values of the combustion times from which it appears that the test pieces did not meet the specifications required for Class B 2 and therefore the reference composition did no~ possess the necessary characteristics of self-extinction.
The compositio~ described in the reference example 1 was mixed with 0.6 parts by weiqht of 2,3-dimethyl-2,3-diphenylbutane (trade ~me-Interox CC DFB produced by Peroxyd~Chemie G.m.b.H.), then granulation was carried o~t.
Table 1 reports the extinction times of the relevant test pieces obtained according to the specification UL 94 and the combustion times of the foamed test pieces determined according to the specification DIN 53438.
The results of the flame reaction showed that the composition according to the invention was endowed with the necessary properties of self-extinction and the foamed material met the specifications required for class B 2.
100 parts by weight of resin base consisting of ethylene-vinylacetate copolymer (trade.~e Elvax 760 produced by Du Pont & de Nemours; vinylacetate content:
9.3%; effective density: 0.93 g/cm3; Melt Flow Index according to DIN 53735: 2.0)were additioned with 10 parts by weight of polyethylene homopolymer at low density (Baylon 23 L 430, produced by Bayer AG; effective density: 0.923 g/cm ; Melt Flow Index according to DIN 53735: 3.8), ~hen mixing was performed adding 1.5 parts by weight of zinc stearate, 0.8 parts of talc and 0.1 parts of phenol anti-oxidizing agen~ (Irganox 1035) and finally 13.2 parts by weight of an anti-flame Masterbatch were added (80%
J~ J9~
concentration of EVA resin base having 19% content by weiqht of Sb2O3; 56 b.w~ of decabromodiphenylether and 5% b.w.
of 2,3-dimethyl-2,3-diphenylbutane), obtaining a mixture having the followina composition, expressed in parts by weight:
ethylene/vinylacetate copolymer l00 polyethylene 10 Irqanox 1035 0.1 decabromodiphenylether 7.4 lG Sb23 2.5 2,3-dimethyl-2,3-diphenylbutane 0.65 zinc stearate 1.5 ~ he standard test pieces to be subjected to the flame reaction accordina to the specification UL 94 were prepared by injec~ion molding from the granulated mixture and the foamed test pieces (sheaths) to be subjected to the flame reaction according to the specification DIN 53438 were also prepared by the extrusion-foaming process.
The results of the extinction and combustion times reported in table 1 show that the composition according to the invention was endowed with the self-extinguishing properties required.
-The composition described in the reference example 7 was mixed in turn with the specific amounts of activators reported in table 1.
The relevant extinction and combustion times of the compositions accordina to the invention showed that all the compositions containing the claimed activators possessed the required characteristics of self-extinction.
c~
~BIE 1 % ~ r~a ~us~
E~ ~rIV~R __ wei.ghTIMES (U194) Tl~ (DIN53438) forrrD~la of E~n ~ seconds secorx:l~ cl~ss ' ~1 ~ . _ 1. ~ _ burns bur~s (re.f ) carpletely eCa~ly~
___ ICH 3 C ~ 3 2 ~ C I \~> 0.6 2 6 B 2
3 3 _ 3 as above 0.6 3 7 B 2 _ _ . . ~. _
4 ~ 3 1~ 0 .6 5 8 B 2 B{~>C--C~3 r O .4 4 6 B 2 3 _ CH 3 C~
6 ICH2 CjH2 O .7 3 5 B 2 CN CH
;~ ¢ ~1~
c~
q~sIE 1 (contin~
_ _ 96 by JE~qcN jc~--EX _ weig~ qI~ (UL94) ~5 (I ~IN53438 . formula of E~IP r secor~ ' clas ~ I r I r 8 ~O> i <~> O .5 4 4 B 2 _ H H ~ ~ ~ I
9 C~c c ~> 0.6 4 5 B 2 o3 ~lo3 _ ~ _ _ . ~ __ ., .
.
t ~
6 ICH2 CjH2 O .7 3 5 B 2 CN CH
;~ ¢ ~1~
c~
q~sIE 1 (contin~
_ _ 96 by JE~qcN jc~--EX _ weig~ qI~ (UL94) ~5 (I ~IN53438 . formula of E~IP r secor~ ' clas ~ I r I r 8 ~O> i <~> O .5 4 4 B 2 _ H H ~ ~ ~ I
9 C~c c ~> 0.6 4 5 B 2 o3 ~lo3 _ ~ _ _ . ~ __ ., .
.
t ~
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Compositions endowed with self-extinction properties and suitable for the preparation of foamed materials, comprising:
(a) ethylene/vinylacetate copolymer having vinyl-acetate content less than 50% by weight of copolymer;
(b) at least one bromodiphenylether containing at least three bromine atoms in its molecule in an amount from about 5% to about 10% by weight of copolymer;
(c) a metal oxide selected from the group comprising antimony trioxide, bismuth oxide and tungsten oxide in an amount from about 2% to about 4% by weight of copolymer; and (d) at least one compound in an amount from about 0.1% to about 1% by weight of copolymer selected from the compounds represented by formula I
I
wherein R1, R2, R3, R4, which may be the same or different are independently selected from hydrogen, aliphatic hydrocarbon radicals with 1-6 carbon atoms, chlorine, bromine, phenyl or cyclohexyl radicals, nitro groups and -CN groups;
R5, R6, which may be the same or different are independently selected from hydrogen, chlorine, bromine, aliphatic hydrocarbon radicals containing 1-3 carbon atoms, alkoxy radicals containing 1-4 carbon atoms, and groups, where R7 is an aliphatic hydrocarbon radical containing 1-3 carbon atoms.
(a) ethylene/vinylacetate copolymer having vinyl-acetate content less than 50% by weight of copolymer;
(b) at least one bromodiphenylether containing at least three bromine atoms in its molecule in an amount from about 5% to about 10% by weight of copolymer;
(c) a metal oxide selected from the group comprising antimony trioxide, bismuth oxide and tungsten oxide in an amount from about 2% to about 4% by weight of copolymer; and (d) at least one compound in an amount from about 0.1% to about 1% by weight of copolymer selected from the compounds represented by formula I
I
wherein R1, R2, R3, R4, which may be the same or different are independently selected from hydrogen, aliphatic hydrocarbon radicals with 1-6 carbon atoms, chlorine, bromine, phenyl or cyclohexyl radicals, nitro groups and -CN groups;
R5, R6, which may be the same or different are independently selected from hydrogen, chlorine, bromine, aliphatic hydrocarbon radicals containing 1-3 carbon atoms, alkoxy radicals containing 1-4 carbon atoms, and groups, where R7 is an aliphatic hydrocarbon radical containing 1-3 carbon atoms.
2. Compositions according to claim 1, wherein the ethylene/vinylacetate copolymer contains 8-10% by weight of copolymerized vinylacetate.
3. Compositions according to claim 1, wherein bromodiphenylether is present in amounts ranging from about 6% to about 8% by weight of copolymer.
4. Compositions according to claim 2, wherein bromodiphenylether is present in amounts ranging from about 6% to about 8% by weight of copolymer.
5. Compositions according to claim 1, wherein the compound (d) is present in amounts ranging from about 0.4%
to about 0.8% by weight of copolymer.
to about 0.8% by weight of copolymer.
6. Compositions according to claim 2, wherein the compound (d) is present in amounts ranging from about 0.4%
to about 0.8% by weight of copolymer.
to about 0.8% by weight of copolymer.
7. Compositions according to claim 3, wherein the compound (d) is present in amounts ranging from about 0.4%
to about 0.8% by weight of copolymer.
to about 0.8% by weight of copolymer.
8. Compositions according to any one of claims 1, 2 or 3, wherein the compound (d) is 2,3-dimethyl-2,3-diphenyl butane.
9. Compositions according to any one of claims 4, 5 or 6, wherein the compound (d) is 2,3-dimethyl-2,3-diphenyl butane.
10. Compositions according to claim 7, wherein the compound (d) is 2,3-dimethyl-2,3-diphenylbutane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT8323705A IT1207989B (en) | 1983-11-14 | 1983-11-14 | SELF-EXTINGUISHING COMPOSITIONS BASED ON ETHYLENE / VINYLACETATE COPOLYMERS SUITABLE FOR THE PREPARATION OF EXPANDED DIMATERIALS. |
| IT23705A/83 | 1983-11-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1240100A true CA1240100A (en) | 1988-08-02 |
Family
ID=11209293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000467848A Expired CA1240100A (en) | 1983-11-14 | 1984-11-14 | Self-extinguishing compositions based on ethylene vinylacetate copolymers suitable for the preparation of foamed materials |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4666947A (en) |
| EP (1) | EP0144015B1 (en) |
| JP (1) | JPS60118726A (en) |
| CA (1) | CA1240100A (en) |
| DE (1) | DE3474031D1 (en) |
| IT (1) | IT1207989B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61151251A (en) * | 1984-12-24 | 1986-07-09 | Tokuyama Soda Co Ltd | Flame-retardant polyolefin composition |
| US4804698A (en) * | 1988-04-04 | 1989-02-14 | Ethyl Corporation | Flame retardant polypropylene based formulations |
| WO1989011501A1 (en) * | 1988-05-24 | 1989-11-30 | Reef Industries, Inc. | Flame retardant, antistatic thermoplastic |
| US5039729A (en) * | 1990-03-05 | 1991-08-13 | Ethyl Corporation | Novel mixtures of brominated diphenyl ethanes |
| US5136107A (en) * | 1990-06-04 | 1992-08-04 | Ethyl Corporation | Process for halogenating aromatic compounds |
| US5401890A (en) * | 1990-07-30 | 1995-03-28 | Albemarle Corporation | Process and apparatus for heat treating halogenated compounds |
| US5124496A (en) * | 1990-11-01 | 1992-06-23 | Ethyl Corporation | Process for decabromodiphenylalkane predominant product |
| US5055235A (en) * | 1990-12-12 | 1991-10-08 | Ethyl Corporation | Bromination process |
| US5324874A (en) * | 1992-05-26 | 1994-06-28 | Ethyl Corporation | Process for a decarbromodiphenylethane predominate product having enhanced whiteness |
| US5319013A (en) * | 1992-11-10 | 1994-06-07 | E. I. Du Pont De Nemours And Company | Fiber and film of improved flame resistance containing mixed oxides of tungsten |
| US5439965A (en) * | 1993-09-16 | 1995-08-08 | Quantum Chemical Corporation | Abrasion resistant crosslinkable insulation compositions |
| US6518468B1 (en) | 1994-09-16 | 2003-02-11 | Albemarle Corporation | Bromination process |
| US20020052426A1 (en) * | 2000-11-02 | 2002-05-02 | Tarantino Lawrence J. | E.V.A. furniture |
| US6743825B1 (en) * | 2001-08-03 | 2004-06-01 | Albemarle Corporation | Poly(bromoaryl)alkane additives and methods for their preparation and use |
| CN100448821C (en) | 2001-12-21 | 2009-01-07 | 帕布服务公司 | Method and apparatus for producing decabromodiphenyl alkanes |
| US6872756B2 (en) * | 2002-04-01 | 2005-03-29 | Sealed Air Corporation (Us) | Foam comprising ethylene/vinyl acetate copolymer |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA913827A (en) * | 1972-10-31 | Bakelite Xylonite Limited | Flame retardant polymer compositions | |
| DE1123823B (en) * | 1959-12-18 | 1962-02-15 | Huels Chemische Werke Ag | Flame-retardant molding compounds based on polyolefins |
| NL127714C (en) * | 1965-04-01 | |||
| DE1244395B (en) * | 1965-08-25 | 1967-07-13 | Basf Ag | Molding compounds for the production of self-extinguishing moldings |
| US3668155A (en) * | 1968-06-27 | 1972-06-06 | Dow Chemical Co | Self-extinguishing ethylene copolymer foams comprising a ternary mixture of an antimony compound, a halogen-containing compound and a bromine compound |
| CA919856A (en) * | 1969-10-13 | 1973-01-30 | Phillips Petroleum Company | Flame retarded compositions and additive systems for same |
| IT944979B (en) * | 1971-08-03 | 1973-04-20 | Dow Chemical Co | COMPOSITION CONTAINING A FIREPROOF COMPOUND FOR THE PROTECTIVE AND INSULATING COATING OF ELECTRIC CABLES |
| CA1011020A (en) * | 1973-02-08 | 1977-05-24 | Bruno L. Gaeckel | Flame resistant polyethylene composition |
| JPS5139739A (en) * | 1974-10-02 | 1976-04-02 | Toray Industries | NANNENSEINETSU KASOSEIJUSHISOSEIBUTSU |
| JPS51146565A (en) * | 1975-06-11 | 1976-12-16 | Furukawa Electric Co Ltd | Method of producing flame resisting polyethylene foam |
| JPS6032281B2 (en) * | 1977-07-27 | 1985-07-27 | 住友電気工業株式会社 | Crosslinked polyolefin insulated wire |
| US4323655A (en) * | 1980-05-07 | 1982-04-06 | Atlantic Richfield Company | Rubber-modified fire-retardant anhydride copolymers |
| IT1133878B (en) * | 1980-10-14 | 1986-07-24 | Vamp Srl | SELF-EXTINGUISHING POLYOLEFINIC COMPOSITIONS |
| JPS5876577A (en) * | 1981-10-26 | 1983-05-09 | 日石三菱株式会社 | Carpet backing composition |
| US4430467A (en) * | 1982-01-07 | 1984-02-07 | Saytech, Inc. | Self-extinguishing propylene polymer |
-
1983
- 1983-11-14 IT IT8323705A patent/IT1207989B/en active
-
1984
- 1984-11-12 DE DE8484113648T patent/DE3474031D1/en not_active Expired
- 1984-11-12 EP EP84113648A patent/EP0144015B1/en not_active Expired
- 1984-11-13 US US06/670,881 patent/US4666947A/en not_active Expired - Fee Related
- 1984-11-14 CA CA000467848A patent/CA1240100A/en not_active Expired
- 1984-11-14 JP JP59238714A patent/JPS60118726A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| EP0144015B1 (en) | 1988-09-14 |
| JPH0556376B2 (en) | 1993-08-19 |
| DE3474031D1 (en) | 1988-10-20 |
| IT8323705A0 (en) | 1983-11-14 |
| EP0144015A1 (en) | 1985-06-12 |
| JPS60118726A (en) | 1985-06-26 |
| US4666947A (en) | 1987-05-19 |
| IT1207989B (en) | 1989-06-01 |
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