CA2277081A1 - Flame resistant nylon elastomers - Google Patents
Flame resistant nylon elastomers Download PDFInfo
- Publication number
- CA2277081A1 CA2277081A1 CA002277081A CA2277081A CA2277081A1 CA 2277081 A1 CA2277081 A1 CA 2277081A1 CA 002277081 A CA002277081 A CA 002277081A CA 2277081 A CA2277081 A CA 2277081A CA 2277081 A1 CA2277081 A1 CA 2277081A1
- Authority
- CA
- Canada
- Prior art keywords
- composition
- flame
- nylon
- nylon elastomer
- retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A flame retardant nylon elastomer composition comprising a nylon elastomer and an effective amount of the following ingredients in mixture thereof: (1) a flame-retardant comprising a halogenated aromatic compound; (2) antimony oxide; and (3) a particulate inorganic compound. The nylon elastomers are characterized with a UL 94 V-0 rating, and an increased limiting oxygen index.
Description
WO 98!29492 PCT/US98I01122 I Flame Resistant Nylon Elastomers 2 Polyamide materials are used in the form of fibers, and they have also 3 become important as specialty thermoplastics for use in engineering applications.
' 4 The fiber forming polyamides are often referred to as nylons. Aliphatic polyamides such as nylon-6,6 is a linear polymer and thus thermoplastic, and 6 crystalline, and of high melting point. Aliphatic nylons tend to have good 7 mechanical properties, including good abrasion resistance, in addition to having 8 some measure of flexibility in spite of their high crystallinity and high melting 9 points.
With regards to the preparation of nylons with enhanced flexibility, I 1 thermoplastic polyamides of the elastomeric type have been more recently 12 prepared, which may be considered as polyamide analogues of the somewhat 13 older and more fully established polyester rubbers. The commercial polymers 14 consist of polyether blocks separated by polyamide blocks. The polyether blocks may be based upon polyethylene glycol, polypropylene glycol, or 16 polytetramethylene ether glycol. The polyamides are usually based upon nylon-17 11 but may be based upon nylons 6 of nylon-6,6 or even a copolymer such as 18 nylon-6/nylon-11. A wide range of block polyamides have been offered by I9 ATOCHEM under the trade name PEBAX~. Such resins vary in the type of polyether, the nature of the polyamide block and the ratio of polyether to 21 polyamide blocks. The polymers range in hardness from Shore A 60 to Shore 22 D72 which is broader than for the thermoplastic polyester and thermoplastic 23 polyurethane rubbers. Melting range is also dependent on the particular 24 composition, and varies between 140 - 215 °C.
With regard to nylons in general, and as with many other plastics a 26 materials, there have been substantial efforts to improve resistance to burning;
27 i.e., one of the long-standing problems with nylons is that they are flammable.
' 28 Halogen compounds synergised by zinc oxide or zinc borate have been used to 29 improve flame resistance, including compounds containing red phosphorous.
The 1 halongens and phosphorous formulations tend to darken the nylon's color and this 2 has led to halogen- and phosphorous-free grades of light color.
3 A recent review of issued U.S. Patents illustrates how the search for 4 improved flame resistant polyamides has progressed to the point where even today, specific formulations are still being explored to improve flame resistance 6 characteristics. For example, in U.S. Patent No. 5,543,452, there is disclosed a 7 flame-resistant polyamide resin comprising a blend of a polyamide or a blend of a 8 polyamide with another polymer and a flame retardant comprising a brominated 9 styrene or styrene derivative polymer having acid anhydride groups and a flame retardant comprising a brominated polystyrene.
11 In U.S. Patent No. 5,476,887 there is disclosed a flame retardant 12 polyamide composition consisting of a copolymer of polyamide-6,6 and at least 13 one other monomer selected from the group consisting of a dicarboxylic acid of 14 7-14 carbon atoms, m-benzenedicarboxylic acid, o-benzenedicarboxylic acid, and I 5 p-benzenedicarboxylic acid said copolymer having a melting point below 250 °C
16 and 10-20% by weight of melamine based on the weight of the composition.
17 In U.S. Patent 5,466,741 there is disclosed a polyamide-based 18 composition, suited for molding into a variety of shaped articles, containing an 19 effective amount of red phosphorous and a corrossion/migration-reducing amount of at least one zinc compound selected from amongst zinc oxide, zinc sulfide and 21 an oxygen-containing zinc salt, e.g., zinc borate.
22 In U.S. Patent No. 5,438,084 there is disclosed a flame retardant 23 polyamide composition containing 100 parts by weight of an aliphatic polyamide-24 containing resin, 2-50 parts by weight of magnesium hydroxide, 1 to 15 parts by weight of red phosphorous and 0. I to 5 parts by weight of an epoxy resin.
26 In U.S. Patent No. 5,378,750 there is disclosed a flame-resistant molding 27 composition consisting of thermoplastic, partially crystalline polyamide and 28 40-60% by weight, based upon weight of a molding composition, of magnesium 29 hydroxide and optionally one or more reinforcing materials, an elastomer, and processing additives.
1 U.S. Patent No. 5,412,014 discloses a fire retardant resin composition, 2 which rely upon a free-flowing silicone polymer powder, said powder having an 3 average particle size of 1 to 1000 microns and being prepared by mixing a 4 polydiorganosiloxane with a silica filler along with a phosphorous-based fire retardant compound, wherein the mixing occurs via single screw extrusion. The 6 resultant resin composition is said to provide a significant improvement in fire 7 retardancy but does not exhibit the severe deterioration of impact resistance 8 incurred when the resin is modified with only phosphorous-based fire retardant.
9 In U.S. Patent No. 5,391,594, the free-flowing silicon powder composition is described as a flame retardant in a variety of thermoplastic resins, including 11 nylons.
12 Accordingly, what the above review of recent technology reveals is that 13 there has been and remains a continuous effort to refine the various flame 14 retardant formulations to improve the resistance of nylons to burning.
Furthermore, with respect to the nylon elastomers noted above, until now, it has 16 remained unknown how one could modify such resins in order to produce a nylon 17 elastomer that would have improved resistance to burning, and meet or exceed 18 what is known as a "V-0" rating. A "V-0" rating is a rating developed by 19 Underwriters Laboratories, known as the UL94 test, in which 0.64 cm thick samples are held in vertical position and lit by a Bunsen burner at the bottom end 21 thereof. The material is then rated according to performance. A "V-0"
rating is 22 one in which no test specimens burn longer than 10 seconds after removal from 23 the flame, where no test specimens exhibit flaming drip that ignites dry surgical 24 cotton placed 30.5 cm below the test specimen, and one in which no afterglow persists for longer than 30 seconds.
26 Accordingly, it is an object of this invention to develop a new flame 27 retardant system to impart flame retardancy to nylon elastomer materials, such 28 as PEBAX~, that would additionally allow for the nylon elastomer to be 29 characterized with a UL 94 V-0 rating.
w0 98/29492 PCTlUS98101122 1 It is also an object of this invention, to provide in a nylon elastomer 2 material, a combination of flame retardant additives/components, characterized in 3 that the flame retardant components act in a synergistic manner to provide a flame 4 resistant nylon elastomer resin, of improved limiting oxygen index, which does not drip, and in which additives/components do not have a significant effect on 6 the nylon's elastomeric properties.
7 A flame resistant elastomeric polyamide resin composition comprising a 8 elastomeric polyamide and a flame retardant comprising a halogenated aromatic 9 compound, antimony oxide, and a powdered inorganic resin modifier. Expressed in method form, the present invention comprises dispersing in a nylon elastomer a 11 flame retardant comprising a halogentated aromatic compound, antimony oxide 12 and a particulate inorganic compound, wherein for each part by weight of nylon 13 elastomer to be modified, the dispersion contains about 0.5 parts of halogenated 14 aromatic compund, 0.3 parts antimony oxide, 0.1 part of particulate inorganic compound, and the remainder, anti-oxidant.
16 The present invention, in a preferred embodiment, comprises about 50 17 (wt.) of an elastomeric nylon, about 25 % {wt.) of a brominated aromatic 18 compound, about 15-20% of antimony oxide, and about 5% of a powdered 19 inorganic filler or an inorganic polymer resin. Stated another way, for each part of nylon elastomer to be modified, the elastomeric nylon preferably contains 21 about 0.5 parts of brominated aromatic compound, 0.3 parts of antimony oxide, 22 and 0.1 parts of a particulate inorganic compound, and optionally, a small amount 23 of antioxidant.
24 The elastomeric polyamides which have been rendered flame-retardant preferably include those resins sold by ATOCHEM Inc. under the tradename 26 PEBAX~. Accordingly, such nylon elastomers range in hardness from Shore A
27 60 to Shore D 72. It can therfore be appreciated that when durometer hardness 28 values increases (which represent an increase in polyamide over polyether 29 segment concentration) the overall amount of flame retardant system as disclosed herein can be reduced. For example, at durometer hardness values of Shore D
72, 1 the overall amount of flame retardant in the system can be reduced to a total of 2 about 40 % (wt).
3 The preferred aromatic brominated flame retardants which have been 4 found suitable include SAYTEX~ 102E, which is available from Albemarle Corporation. SAYTEX~102E is described as a high purity grade of deca-6 bromodiphenyl oxide, of molecular formula C,ZOBr,° containing a high level of 7 aromatic bromine.
8 Also preferred as an aromatic bromine flame retardant is SAYTEX BT-9 93 W~, which is again available from Albemarle. SAYTEX BT-93 W~ is described as an aromatic bromine with an imide structure, of molecular formula 11 of C,8H404NZBrg.
12 The preferred antimony oxide is antimony trioxide TMS, which is 13 available from Anzon Inc. Antimony trioxide TMS contains 99% antimony oxide 14 as Sb203 along with other elemental inorganic ingredients.
The preferred particulate inorganic compounds include Dow Corning Si 16 powder resin modifiers which are 100 percent active, free-flowing, silicone 17 powders. They are available in several grades with varying types of organic 18 reactivities (none, epoxy, methacrylate and amine). Particularly preferred and as 19 disclosed herein, Dow Corning 4-7081 was employed, which is a resin modifier designed for methacrylate type materials.
21 Finally, in accordance with the present invention, it is preferred to 22 incorporate in the flame retardant composition a small amount of an antioxidant.
23 Preferred antioxidants include IRGANOX~ 1010, which is available from Ciba-24 Geigy, which is sold as a high performance solid antioxidant. In addition, IRGAFOS~ 168 can be employed, which is also available from Ciba-Geigy 26 Corporation.
27 As noted above, when the above basic and preferred formulations are 28 herein employed, a flame-retardant elastomeric nylon composition is obtained, 29 that is specifically characterized as having a UL 94 V-0 rating. In addition, the limiting oxygen index (LOI) is seen to improve. For example, the LOI of WO 98!29492 PCT/iJS98l01122 1 ummodified PEBAX 3533 was measured to be less than 0.1 S. When such 2 PEBAX is combined at 50 %(wt.) with 25% SAYTEX BT-93W~ and 15-18 3 {wt.} of antimony oxide, along with about 5.0 % (wt.) of powdered silicon and 4 1-2% of an antioxidant, the LOI was measured on a 0.32 cm thick sample to be 0.27-0.28.
Examples 7 The following table describes the various formulations illustrative of the 8 present invention:
' 4 The fiber forming polyamides are often referred to as nylons. Aliphatic polyamides such as nylon-6,6 is a linear polymer and thus thermoplastic, and 6 crystalline, and of high melting point. Aliphatic nylons tend to have good 7 mechanical properties, including good abrasion resistance, in addition to having 8 some measure of flexibility in spite of their high crystallinity and high melting 9 points.
With regards to the preparation of nylons with enhanced flexibility, I 1 thermoplastic polyamides of the elastomeric type have been more recently 12 prepared, which may be considered as polyamide analogues of the somewhat 13 older and more fully established polyester rubbers. The commercial polymers 14 consist of polyether blocks separated by polyamide blocks. The polyether blocks may be based upon polyethylene glycol, polypropylene glycol, or 16 polytetramethylene ether glycol. The polyamides are usually based upon nylon-17 11 but may be based upon nylons 6 of nylon-6,6 or even a copolymer such as 18 nylon-6/nylon-11. A wide range of block polyamides have been offered by I9 ATOCHEM under the trade name PEBAX~. Such resins vary in the type of polyether, the nature of the polyamide block and the ratio of polyether to 21 polyamide blocks. The polymers range in hardness from Shore A 60 to Shore 22 D72 which is broader than for the thermoplastic polyester and thermoplastic 23 polyurethane rubbers. Melting range is also dependent on the particular 24 composition, and varies between 140 - 215 °C.
With regard to nylons in general, and as with many other plastics a 26 materials, there have been substantial efforts to improve resistance to burning;
27 i.e., one of the long-standing problems with nylons is that they are flammable.
' 28 Halogen compounds synergised by zinc oxide or zinc borate have been used to 29 improve flame resistance, including compounds containing red phosphorous.
The 1 halongens and phosphorous formulations tend to darken the nylon's color and this 2 has led to halogen- and phosphorous-free grades of light color.
3 A recent review of issued U.S. Patents illustrates how the search for 4 improved flame resistant polyamides has progressed to the point where even today, specific formulations are still being explored to improve flame resistance 6 characteristics. For example, in U.S. Patent No. 5,543,452, there is disclosed a 7 flame-resistant polyamide resin comprising a blend of a polyamide or a blend of a 8 polyamide with another polymer and a flame retardant comprising a brominated 9 styrene or styrene derivative polymer having acid anhydride groups and a flame retardant comprising a brominated polystyrene.
11 In U.S. Patent No. 5,476,887 there is disclosed a flame retardant 12 polyamide composition consisting of a copolymer of polyamide-6,6 and at least 13 one other monomer selected from the group consisting of a dicarboxylic acid of 14 7-14 carbon atoms, m-benzenedicarboxylic acid, o-benzenedicarboxylic acid, and I 5 p-benzenedicarboxylic acid said copolymer having a melting point below 250 °C
16 and 10-20% by weight of melamine based on the weight of the composition.
17 In U.S. Patent 5,466,741 there is disclosed a polyamide-based 18 composition, suited for molding into a variety of shaped articles, containing an 19 effective amount of red phosphorous and a corrossion/migration-reducing amount of at least one zinc compound selected from amongst zinc oxide, zinc sulfide and 21 an oxygen-containing zinc salt, e.g., zinc borate.
22 In U.S. Patent No. 5,438,084 there is disclosed a flame retardant 23 polyamide composition containing 100 parts by weight of an aliphatic polyamide-24 containing resin, 2-50 parts by weight of magnesium hydroxide, 1 to 15 parts by weight of red phosphorous and 0. I to 5 parts by weight of an epoxy resin.
26 In U.S. Patent No. 5,378,750 there is disclosed a flame-resistant molding 27 composition consisting of thermoplastic, partially crystalline polyamide and 28 40-60% by weight, based upon weight of a molding composition, of magnesium 29 hydroxide and optionally one or more reinforcing materials, an elastomer, and processing additives.
1 U.S. Patent No. 5,412,014 discloses a fire retardant resin composition, 2 which rely upon a free-flowing silicone polymer powder, said powder having an 3 average particle size of 1 to 1000 microns and being prepared by mixing a 4 polydiorganosiloxane with a silica filler along with a phosphorous-based fire retardant compound, wherein the mixing occurs via single screw extrusion. The 6 resultant resin composition is said to provide a significant improvement in fire 7 retardancy but does not exhibit the severe deterioration of impact resistance 8 incurred when the resin is modified with only phosphorous-based fire retardant.
9 In U.S. Patent No. 5,391,594, the free-flowing silicon powder composition is described as a flame retardant in a variety of thermoplastic resins, including 11 nylons.
12 Accordingly, what the above review of recent technology reveals is that 13 there has been and remains a continuous effort to refine the various flame 14 retardant formulations to improve the resistance of nylons to burning.
Furthermore, with respect to the nylon elastomers noted above, until now, it has 16 remained unknown how one could modify such resins in order to produce a nylon 17 elastomer that would have improved resistance to burning, and meet or exceed 18 what is known as a "V-0" rating. A "V-0" rating is a rating developed by 19 Underwriters Laboratories, known as the UL94 test, in which 0.64 cm thick samples are held in vertical position and lit by a Bunsen burner at the bottom end 21 thereof. The material is then rated according to performance. A "V-0"
rating is 22 one in which no test specimens burn longer than 10 seconds after removal from 23 the flame, where no test specimens exhibit flaming drip that ignites dry surgical 24 cotton placed 30.5 cm below the test specimen, and one in which no afterglow persists for longer than 30 seconds.
26 Accordingly, it is an object of this invention to develop a new flame 27 retardant system to impart flame retardancy to nylon elastomer materials, such 28 as PEBAX~, that would additionally allow for the nylon elastomer to be 29 characterized with a UL 94 V-0 rating.
w0 98/29492 PCTlUS98101122 1 It is also an object of this invention, to provide in a nylon elastomer 2 material, a combination of flame retardant additives/components, characterized in 3 that the flame retardant components act in a synergistic manner to provide a flame 4 resistant nylon elastomer resin, of improved limiting oxygen index, which does not drip, and in which additives/components do not have a significant effect on 6 the nylon's elastomeric properties.
7 A flame resistant elastomeric polyamide resin composition comprising a 8 elastomeric polyamide and a flame retardant comprising a halogenated aromatic 9 compound, antimony oxide, and a powdered inorganic resin modifier. Expressed in method form, the present invention comprises dispersing in a nylon elastomer a 11 flame retardant comprising a halogentated aromatic compound, antimony oxide 12 and a particulate inorganic compound, wherein for each part by weight of nylon 13 elastomer to be modified, the dispersion contains about 0.5 parts of halogenated 14 aromatic compund, 0.3 parts antimony oxide, 0.1 part of particulate inorganic compound, and the remainder, anti-oxidant.
16 The present invention, in a preferred embodiment, comprises about 50 17 (wt.) of an elastomeric nylon, about 25 % {wt.) of a brominated aromatic 18 compound, about 15-20% of antimony oxide, and about 5% of a powdered 19 inorganic filler or an inorganic polymer resin. Stated another way, for each part of nylon elastomer to be modified, the elastomeric nylon preferably contains 21 about 0.5 parts of brominated aromatic compound, 0.3 parts of antimony oxide, 22 and 0.1 parts of a particulate inorganic compound, and optionally, a small amount 23 of antioxidant.
24 The elastomeric polyamides which have been rendered flame-retardant preferably include those resins sold by ATOCHEM Inc. under the tradename 26 PEBAX~. Accordingly, such nylon elastomers range in hardness from Shore A
27 60 to Shore D 72. It can therfore be appreciated that when durometer hardness 28 values increases (which represent an increase in polyamide over polyether 29 segment concentration) the overall amount of flame retardant system as disclosed herein can be reduced. For example, at durometer hardness values of Shore D
72, 1 the overall amount of flame retardant in the system can be reduced to a total of 2 about 40 % (wt).
3 The preferred aromatic brominated flame retardants which have been 4 found suitable include SAYTEX~ 102E, which is available from Albemarle Corporation. SAYTEX~102E is described as a high purity grade of deca-6 bromodiphenyl oxide, of molecular formula C,ZOBr,° containing a high level of 7 aromatic bromine.
8 Also preferred as an aromatic bromine flame retardant is SAYTEX BT-9 93 W~, which is again available from Albemarle. SAYTEX BT-93 W~ is described as an aromatic bromine with an imide structure, of molecular formula 11 of C,8H404NZBrg.
12 The preferred antimony oxide is antimony trioxide TMS, which is 13 available from Anzon Inc. Antimony trioxide TMS contains 99% antimony oxide 14 as Sb203 along with other elemental inorganic ingredients.
The preferred particulate inorganic compounds include Dow Corning Si 16 powder resin modifiers which are 100 percent active, free-flowing, silicone 17 powders. They are available in several grades with varying types of organic 18 reactivities (none, epoxy, methacrylate and amine). Particularly preferred and as 19 disclosed herein, Dow Corning 4-7081 was employed, which is a resin modifier designed for methacrylate type materials.
21 Finally, in accordance with the present invention, it is preferred to 22 incorporate in the flame retardant composition a small amount of an antioxidant.
23 Preferred antioxidants include IRGANOX~ 1010, which is available from Ciba-24 Geigy, which is sold as a high performance solid antioxidant. In addition, IRGAFOS~ 168 can be employed, which is also available from Ciba-Geigy 26 Corporation.
27 As noted above, when the above basic and preferred formulations are 28 herein employed, a flame-retardant elastomeric nylon composition is obtained, 29 that is specifically characterized as having a UL 94 V-0 rating. In addition, the limiting oxygen index (LOI) is seen to improve. For example, the LOI of WO 98!29492 PCT/iJS98l01122 1 ummodified PEBAX 3533 was measured to be less than 0.1 S. When such 2 PEBAX is combined at 50 %(wt.) with 25% SAYTEX BT-93W~ and 15-18 3 {wt.} of antimony oxide, along with about 5.0 % (wt.) of powdered silicon and 4 1-2% of an antioxidant, the LOI was measured on a 0.32 cm thick sample to be 0.27-0.28.
Examples 7 The following table describes the various formulations illustrative of the 8 present invention:
' ~ , N , , , , , , O i ~ s N i i ; N V1 Q' 00 N v1 n i O i i i N i ~ N
i ~ i i ~ N i ~1 ~ N i , , i ~''I i i i O i ' ' i O i i i N i N i i W a z m Q
U °°
~! ~ ~ ~ ' ' , (% N ~ O i i i i ~ i ~ N i s ml O fuel i n i n i t'~1 Ov V1 O , n i i n f'l ~ _. ; i ~n ~, ~ ~ , w, , ~ , N ~ "" O i i i ~ N ; i ; ' m ~ , "~ ~ "~ ~n O , , O i '~ ~ ~I i ; ; i Wr1 O ~ , , ~ , , , , ~ v , vp O M i i i i i ; ;
M W pp C ~ C O 'E ~ ~ ,~ O p ,n V ~ ~ ''~) 00 cxv a aj p ° '° as .v o ~ .n ~ + ~ ~ °° ov U o al '~ ~ ~ ~ H Y W ' U ~ ~ U c.T, ate'., 1 In connection with Table I, note the following: Pyronil 45 is a brominated 2 flame-retardant available from ATOMCHEM, containing about 45% bromine.
3 Pyrocheck LM is also a brominated flame retardant, as is DE-83R (Great Lakes 4 Inc.). Dechlorane 25 is a chlorinated flamed retardant.
The following results were obtained with regards to the above 6 formulations. Samples 1 A and 1 B both failed to obtain a V-0 rating due to 7 dripping and ignition of cotton on 0.64 cm samples. Sample 2A failed to obtain a 8 V-0 rating due to slight dripping. Sample 2B showed flame retardant blooming to 9 the surface making the surface chalky in appearance. Sample 2C obtained a V-rating along with a limiting oxygen index of 0.25-0.26. Samples 3A and 3B
11 similarly obtained a V-0 rating, with a limiting oxygen index in 3A of 0.26 and in 12 3B of 0.27. Finally, samples 4A and 4B both achieved a V-0 rating at 0.64 cm 13 thickness, and sample 4A had an oxygen index of 0.27 and 4B was measured at 14 0.28.
i ~ i i ~ N i ~1 ~ N i , , i ~''I i i i O i ' ' i O i i i N i N i i W a z m Q
U °°
~! ~ ~ ~ ' ' , (% N ~ O i i i i ~ i ~ N i s ml O fuel i n i n i t'~1 Ov V1 O , n i i n f'l ~ _. ; i ~n ~, ~ ~ , w, , ~ , N ~ "" O i i i ~ N ; i ; ' m ~ , "~ ~ "~ ~n O , , O i '~ ~ ~I i ; ; i Wr1 O ~ , , ~ , , , , ~ v , vp O M i i i i i ; ;
M W pp C ~ C O 'E ~ ~ ,~ O p ,n V ~ ~ ''~) 00 cxv a aj p ° '° as .v o ~ .n ~ + ~ ~ °° ov U o al '~ ~ ~ ~ H Y W ' U ~ ~ U c.T, ate'., 1 In connection with Table I, note the following: Pyronil 45 is a brominated 2 flame-retardant available from ATOMCHEM, containing about 45% bromine.
3 Pyrocheck LM is also a brominated flame retardant, as is DE-83R (Great Lakes 4 Inc.). Dechlorane 25 is a chlorinated flamed retardant.
The following results were obtained with regards to the above 6 formulations. Samples 1 A and 1 B both failed to obtain a V-0 rating due to 7 dripping and ignition of cotton on 0.64 cm samples. Sample 2A failed to obtain a 8 V-0 rating due to slight dripping. Sample 2B showed flame retardant blooming to 9 the surface making the surface chalky in appearance. Sample 2C obtained a V-rating along with a limiting oxygen index of 0.25-0.26. Samples 3A and 3B
11 similarly obtained a V-0 rating, with a limiting oxygen index in 3A of 0.26 and in 12 3B of 0.27. Finally, samples 4A and 4B both achieved a V-0 rating at 0.64 cm 13 thickness, and sample 4A had an oxygen index of 0.27 and 4B was measured at 14 0.28.
Claims (10)
1. A flame retardant nylon elastomer composition comprising a nylon elastomer and the following ingredients in mixture therof: (1) a flame-retardant comprising a halogenated aromatic compound; (2) antimony oxide; and (3) a particulate inorganic compound.
2. The composition of claim 1, wherein for each part by weight of nylon, there is about 0.5 parts of halogenated aromatic compound, 0.3 parts antimony oxide, and 0.1 parts of particulate inorganic compound.
3. The composition of claim 1, further containing an antioxidant.
4. The composition of claim 1 characterized by one or more of the following features:
(a) wherein the nylon elastomer is a nylon block copolymer comprising an aliphatic polyamide block and a polyether block;
(b) wherein the nylon elastomer has a hardness range of about Shore A60 to Shore D72; and (c) wherein the nylon elastomer comprises about 50% (wt.) of the flame retardant composition.
(a) wherein the nylon elastomer is a nylon block copolymer comprising an aliphatic polyamide block and a polyether block;
(b) wherein the nylon elastomer has a hardness range of about Shore A60 to Shore D72; and (c) wherein the nylon elastomer comprises about 50% (wt.) of the flame retardant composition.
5. The composition of claim 1, wherein the halogenated aromatic compound is a brominated compound containing aromatic functionality.
6. The composition of claim 1, wherein the particulate inorganic compound contains powdered silicon.
7. The composition of claim 1, characterized by one or more of the following features:
(1) said composition exhibits a UL94 V-O rating; and (b) the LOI of the flame-retarded nylon elastomer is increased over the nylon elastomer prior to mixing with said flame-retardant ingredients.
(1) said composition exhibits a UL94 V-O rating; and (b) the LOI of the flame-retarded nylon elastomer is increased over the nylon elastomer prior to mixing with said flame-retardant ingredients.
8. A flame retardant nylon elastomer composition comprising about 50%
(wt.) of a nylon elastomer and the following ingredients in mixture therof:
(1) about 25 % (wt.) of a flame-retardant comprising a brominated aromatic compound; (2) about 15-20% (wt.) of antimony oxide; and (3) about 5 % (wt.) of a particulate inorganic compound containing silicon.
(wt.) of a nylon elastomer and the following ingredients in mixture therof:
(1) about 25 % (wt.) of a flame-retardant comprising a brominated aromatic compound; (2) about 15-20% (wt.) of antimony oxide; and (3) about 5 % (wt.) of a particulate inorganic compound containing silicon.
9. A method for imparting fire retardancy to a nylon elastomer comprising the steps of dispersing in said nylon elastomer the following phosphorous-free ingredients: (1) a flame-retardant comprising a halogenated aromatic compound; (2) antimony oxide; and (3) a particulate inorganic compound.
10. The method of claim 9, wherein for each part by weight of nylon elastomer to be modified, the dispersion contains about 0.5 parts of halogenated aromatic compound, 0.1 part of particulate inorganic compound, and 0.3 parts of antimony oxide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US77855097A | 1997-01-03 | 1997-01-03 | |
| US08/778,550 | 1997-01-03 | ||
| PCT/US1998/001122 WO1998029492A1 (en) | 1997-01-03 | 1998-01-05 | Flame resistant nylon elastomers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2277081A1 true CA2277081A1 (en) | 1998-07-09 |
Family
ID=25113737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002277081A Abandoned CA2277081A1 (en) | 1997-01-03 | 1998-01-05 | Flame resistant nylon elastomers |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0950076A4 (en) |
| JP (1) | JP2001507746A (en) |
| CA (1) | CA2277081A1 (en) |
| WO (1) | WO1998029492A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2948676B1 (en) * | 2009-07-29 | 2011-08-26 | Addiplast | ELASTOMERIC THERMOPLASTIC COMPOSITION BASED ON IMPROVED FIRE RESISTANT AMINO POLYETHER BLOCK (PEBA), PROCESS FOR PRODUCING THE SAME |
| CN105919196A (en) * | 2016-06-17 | 2016-09-07 | 优纤科技（丹东）有限公司 | Flame-retardant chinlon blended fabric and making method thereof |
| CN115850957A (en) * | 2022-11-29 | 2023-03-28 | 沧州旭阳化工有限公司 | Halogen-free flame-retardant polyamide elastomer material and preparation method and application thereof |
| CN115850958A (en) * | 2022-11-29 | 2023-03-28 | 沧州旭阳化工有限公司 | Flame-retardant polyamide elastomer material and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3044987A (en) * | 1958-08-05 | 1962-07-17 | Du Pont | Segmented copolymers and process for preparing same |
| US4582866A (en) * | 1984-04-30 | 1986-04-15 | E. I. Du Pont De Nemours And Company | Flame retardant thermoplastic multi-block copolyester elastomers |
| US5256718A (en) * | 1990-02-14 | 1993-10-26 | Mitsui Petrochemical Industries, Ltd. | Flame retardant polyamide thermoplastic resin composition |
| JP3071550B2 (en) * | 1992-03-16 | 2000-07-31 | 協和化学工業株式会社 | Flame retardant polyamide resin composition and flame retardant |
| WO1995016737A1 (en) * | 1992-07-30 | 1995-06-22 | E.I. Du Pont De Nemours And Company | Flame resistant aromatic polyamide resin composition |
| JPH07126523A (en) * | 1993-11-02 | 1995-05-16 | Teijin Ltd | Resin composition |
-
1998
- 1998-01-05 JP JP53037198A patent/JP2001507746A/en active Pending
- 1998-01-05 WO PCT/US1998/001122 patent/WO1998029492A1/en not_active Application Discontinuation
- 1998-01-05 EP EP98903616A patent/EP0950076A4/en not_active Withdrawn
- 1998-01-05 CA CA002277081A patent/CA2277081A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998029492A1 (en) | 1998-07-09 |
| JP2001507746A (en) | 2001-06-12 |
| EP0950076A4 (en) | 2000-09-13 |
| EP0950076A1 (en) | 1999-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4552912A (en) | Flame retardent polyamide compositions | |
| JP4246281B2 (en) | Flame retardant polyamide composition | |
| US4948669A (en) | Flame retardant ethylene polymer blends | |
| CA1200632A (en) | Silicone flame retardants for plastics | |
| AU598630B2 (en) | Polyamide compositions | |
| JPH11152402A (en) | Flame-retardant polybutylene terephthalate composition and method for making polybutylene terephthalate composition flame-retardant | |
| JPH11513722A (en) | Flame retardant polyketone polymer blend | |
| CA1090031A (en) | Thermoplastic polyamide composition | |
| WO2013085789A1 (en) | Low antimony or antimony trioxide-free flame retarded thermoplastic composition | |
| US4548972A (en) | Flame retardant polyamide compositions | |
| CA2277081A1 (en) | Flame resistant nylon elastomers | |
| EP0278559B1 (en) | Polyamide compositions | |
| US4525513A (en) | Flame retardant polyamide composition | |
| KR930010924B1 (en) | Flame retardant thermoplastic containing phospham | |
| US5216063A (en) | Polyamide compositions | |
| WO1998003587A1 (en) | Flame retardant polyolefins for molding applications | |
| EP0122697A2 (en) | Flame retardant polyamide compositions | |
| CA2030664A1 (en) | Polyamide compositions | |
| EP0026956B1 (en) | Polyethylene terephthalate moulding composition having reduced flammability, and the mouldings made therefrom | |
| EP0194719B1 (en) | Self-extinguishing polycarbonate composition | |
| US3730939A (en) | Flame retardant polyamide compositions containing certain sulfanilamides | |
| CA1266146A (en) | Silicone flame retardants for nylon | |
| GB2240108A (en) | Polyamide compositions | |
| WO1995028439A1 (en) | Moulding compositions containing a polyamide | |
| JPS61221250A (en) | Flame-retardant polystyrene resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |