EP0950076A1 - Elastomeres de nylon ignifuges - Google Patents

Elastomeres de nylon ignifuges

Info

Publication number
EP0950076A1
EP0950076A1 EP98903616A EP98903616A EP0950076A1 EP 0950076 A1 EP0950076 A1 EP 0950076A1 EP 98903616 A EP98903616 A EP 98903616A EP 98903616 A EP98903616 A EP 98903616A EP 0950076 A1 EP0950076 A1 EP 0950076A1
Authority
EP
European Patent Office
Prior art keywords
composition
flame
nylon elastomer
nylon
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.)
Withdrawn
Application number
EP98903616A
Other languages
German (de)
English (en)
Other versions
EP0950076A4 (fr
Inventor
Lawrence A. Acquarulo
Charles J. O'neil
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP0950076A1 publication Critical patent/EP0950076A1/fr
Publication of EP0950076A4 publication Critical patent/EP0950076A4/fr
Withdrawn legal-status Critical Current

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

Definitions

  • Polyamide materials are used in the form of fibers, and they have also become important as specialty thermoplastics for use in engineering applications.
  • 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 crystalline, and of high melting point.
  • Aliphatic nylons tend to have good mechanical properties, including good abrasion resistance, in addition to having some measure of flexibility in spite of their high crystallinity and high melting points.
  • thermoplastic polyamides of the elastomeric type have been more recently prepared, which may be considered as polyamide analogues of the somewhat older and more fully established polyester rubbers.
  • the commercial polymers consist of polyether blocks separated by polyamide blocks.
  • the polyether blocks may be based upon polyethylene glycol, polypropylene glycol, or polytetramethylene ether glycol.
  • the polyamides are usually based upon nylon- 11 but may be based upon nylons 6 of nylon-6,6 or even a copolymer such as nylon-6/nylon-l 1.
  • a wide range of block polyamides have been offered by 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 polyamide blocks.
  • the polymers range in hardness from Shore A 60 to Shore D72 which is broader than for the thermoplastic polyester and thermoplastic polyurethane rubbers.
  • Patents illustrates how the search for improved flame resistant polyamides has progressed to the point where even today, specific formulations are still being explored to improve flame resistance characteristics.
  • U.S. Patent No. 5,543,452 there is disclosed a flame-resistant polyamide resin comprising a blend of a polyamide or a blend of a polyamide with another polymer and a flame retardant comprising a brominated styrene or styrene derivative polymer having acid anhydride groups and a flame retardant comprising a brominated polystyrene.
  • a flame retardant polyamide composition consisting of a copolymer of polyamide-6,6 and at least one other monomer selected from the group consisting of a dicarboxylic acid of 7-14 carbon atoms, m-benzenedicarboxylic acid, o-benzenedicarboxylic acid, and p-benzenedicarboxylic acid said copolymer having a melting point below 250 °C and 10-20% by weight of melamine based on the weight of the composition.
  • Patent 5,466,741 there is disclosed a polyamide-based composition, suited for molding into a variety of shaped articles, containing an 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 an oxygen-containing zinc salt, e.g., zinc borate.
  • U.S. Patent No. 5,438,084 there is disclosed a flame retardant polyamide composition containing 100 parts by weight of an aliphatic polyamide- containing resin, 2-50 parts by weight of magnesium hydroxide, 1 to 15 parts by weight of red phosphorous and 0.1 to 5 parts by weight of an epoxy resin.
  • U.S. Patent No. 5,412,014 discloses a fire retardant resin composition, which rely upon a free-flowing silicone polymer powder, said powder having an average particle size of 1 to 1000 microns and being prepared by mixing a polydiorganosiloxane with a silica filler along with a phosphorous-based fire retardant compound, wherein the mixing occurs via single screw extrusion.
  • the resultant resin composition is said to provide a significant improvement in fire retardancy but does not exhibit the severe deterioration of impact resistance incurred when the resin is modified with only phosphorous-based fire retardant.
  • 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 nylons. Accordingly, what the above review of recent technology reveals is that there has been and remains a continuous effort to refine the various flame retardant formulations to improve the resistance of nylons to burning.
  • V-0 is a rating developed by 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 thereof. The material is then rated according to performance.
  • a "V-0" rating is one in which no test specimens burn longer than 10 seconds after removal from the flame, where no test specimens exhibit flaming drip that ignites dry surgical cotton placed 30.5 cm below the test specimen, and one in which no afterglow persists for longer than 30 seconds. Accordingly, it is an object of this invention to develop a new flame retardant system to impart flame retardancy to nylon elastomer materials, such as PEBAX®, that would additionally allow for the nylon elastomer to be characterized with a UL 94 V-0 rating.
  • a flame resistant elastomeric polyamide resin composition comprising a elastomeric polyamide and a flame retardant comprising a halogenated aromatic compound, antimony oxide, and a powdered inorganic resin modifier.
  • the present invention comprises dispersing in a nylon elastomer a flame retardant comprising a halogentated aromatic compound, antimony oxide and a particulate inorganic compound, wherein for each part by weight of nylon elastomer to be modified, the dispersion contains about 0.5 parts of halogenated aromatic compund, 0.3 parts antimony oxide, 0.1 part of particulate inorganic compound, and the remainder, anti-oxidant.
  • the present invention in a preferred embodiment, comprises about 50 % (wt.) of an elastomeric nylon, about 25 % (wt.) of a brominated aromatic compound, about 15-20% of antimony oxide, and about 5% of a powdered inorganic filler or an inorganic polymer resin.
  • the elastomeric nylon preferably contains about 0.5 parts of brominated aromatic compound, 0.3 parts of antimony oxide, and 0.1 parts of a particulate inorganic compound, and optionally, a small amount of antioxidant.
  • the elastomeric polyamides which have been rendered flame-retardant preferably include those resins sold by ATOCHEM Inc.
  • PEBAX® nylon elastomers range in hardness from Shore A 60 to Shore D 72. It can therfore be appreciated that when durometer hardness values increases (which represent an increase in polyamide over polyether 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, the overall amount of flame retardant in the system can be reduced to a total of about 40 % (wt).
  • the preferred aromatic brominated flame retardants which have been found suitable include SAYTEX® 102E, which is available from Albemarle Corporation.
  • SAYTEX® 102E is described as a high purity grade of deca- bromodiphenyl oxide, of molecular formula C, 2 OBr 10 containing a high level of aromatic bromine.
  • SAYTEX BT- 93 W® is again available from Albemarle.
  • SAYTEX BT-93W® is described as an aromatic bromine with an imide structure, of molecular formula of C 18 H 4 O4N 2 Br 8 .
  • the preferred antimony oxide is antimony trioxide TMS, which is available from Anzon Inc. Antimony trioxide TMS contains 99% antimony oxide as Sb 2 O 3 along with other elemental inorganic ingredients.
  • the preferred particulate inorganic compounds include Dow Corning Si powder resin modifiers which are 100 percent active, free-flowing, silicone powders. They are available in several grades with varying types of organic reactivities (none, epoxy, methacrylate and amine). Particularly preferred and as disclosed herein, Dow Corning 4-7081 was employed, which is a resin modifier designed for methacrylate type materials. Finally, in accordance with the present invention, it is preferred to incorporate in the flame retardant composition a small amount of an antioxidant. Preferred antioxidants include IRGANOX® 1010, which is available from Ciba- Geigy, which is sold as a high performance solid antioxidant.
  • IRGAFOS® 168 can be employed, which is also available from Ciba-Geigy Corporation.
  • a flame-retardant elastomeric nylon composition is obtained, that is specifically characterized as having a UL 94 V-0 rating.
  • the limiting oxygen index (LOI) is seen to improve.
  • the LOI of ummodified PEBAX 3533 was measured to be less than 0.15.
  • Pyronil 45 is a brominated flame-retardant available from ATOMCHEM, containing about 45% bromine.
  • Pyrocheck LM is also a brominated flame retardant, as is DE-83R (Great Lakes Inc.).
  • Dechlorane 25 is a chlorinated flamed retardant.
  • Sample 2C obtained a V-0 rating along with a limiting oxygen index of 0.25-0.26.
  • Samples 3 A and 3B similarly obtained a V-0 rating, with a limiting oxygen index in 3 A of 0.26 and in 3B of 0.27.
  • samples 4A and 4B both achieved a V-0 rating at 0.64 cm thickness, and sample 4A had an oxygen index of 0.27 and 4B was measured at

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

Cette composition à base d'élastomère de nylon ignifuge comporte un élastomère de nylon et une quantité efficace d'un mélange des ingrédients suivants: (1), un agent ignifuge comprenant un composé aromatique halogéné, (2), un oxyde d'antimoine et (3), un composé inorganique particulaire. Ces élastomères de nylon se caractérisent par la valeur nominale UL 94 V-0 et un indice limite d'oxygène accru.
EP98903616A 1997-01-03 1998-01-05 Elastomeres de nylon ignifuges Withdrawn EP0950076A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US77855097A 1997-01-03 1997-01-03
US778550 1997-01-03
PCT/US1998/001122 WO1998029492A1 (fr) 1997-01-03 1998-01-05 Elastomeres de nylon ignifuges

Publications (2)

Publication Number Publication Date
EP0950076A1 true EP0950076A1 (fr) 1999-10-20
EP0950076A4 EP0950076A4 (fr) 2000-09-13

Family

ID=25113737

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98903616A Withdrawn EP0950076A4 (fr) 1997-01-03 1998-01-05 Elastomeres de nylon ignifuges

Country Status (4)

Country Link
EP (1) EP0950076A4 (fr)
JP (1) JP2001507746A (fr)
CA (1) CA2277081A1 (fr)
WO (1) WO1998029492A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105919196A (zh) * 2016-06-17 2016-09-07 优纤科技（丹东）有限公司 一种阻燃锦纶混纺织物及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2948676B1 (fr) * 2009-07-29 2011-08-26 Addiplast Composition thermoplastique elastomere a base de polyether bloc amides (peba) a resistance au feu amelioree, procede de fabrication de ladite composition
CN115850958A (zh) * 2022-11-29 2023-03-28 沧州旭阳化工有限公司 阻燃聚酰胺弹性体材料及其制备方法和应用
CN115850957A (zh) * 2022-11-29 2023-03-28 沧州旭阳化工有限公司 无卤阻燃聚酰胺弹性体材料及其制备方法和应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07126523A (ja) * 1993-11-02 1995-05-16 Teijin Ltd 樹脂組成物
WO1995016737A1 (fr) * 1992-07-30 1995-06-22 E.I. Du Pont De Nemours And Company Composition ignifuge de resine polyamide aromatique

Family Cites Families (4)

* Cited by examiner, † Cited by third party
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 (ja) * 1992-03-16 2000-07-31 協和化学工業株式会社 難燃性ポリアミド系樹脂組成物および難燃剤

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995016737A1 (fr) * 1992-07-30 1995-06-22 E.I. Du Pont De Nemours And Company Composition ignifuge de resine polyamide aromatique
JPH07126523A (ja) * 1993-11-02 1995-05-16 Teijin Ltd 樹脂組成物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1995, no. 08, 29 September 1995 (1995-09-29) & JP 07 126523 A (TEIJIN LTD), 16 May 1995 (1995-05-16) *
See also references of WO9829492A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105919196A (zh) * 2016-06-17 2016-09-07 优纤科技（丹东）有限公司 一种阻燃锦纶混纺织物及其制备方法

Also Published As

Publication number Publication date
JP2001507746A (ja) 2001-06-12
EP0950076A4 (fr) 2000-09-13
CA2277081A1 (fr) 1998-07-09
WO1998029492A1 (fr) 1998-07-09

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