WO1999047606A1 - Improved thermally stable flame retardant polyamides - Google Patents
Improved thermally stable flame retardant polyamides Download PDFInfo
- Publication number
- WO1999047606A1 WO1999047606A1 PCT/US1999/005901 US9905901W WO9947606A1 WO 1999047606 A1 WO1999047606 A1 WO 1999047606A1 US 9905901 W US9905901 W US 9905901W WO 9947606 A1 WO9947606 A1 WO 9947606A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- flame retardant
- polyamide
- flame
- composition
- thermally stable
- Prior art date
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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/003—Control or safety devices for sterilisation or pasteurisation systems
-
- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
Definitions
- the instant invention relates to improved flame-retardant polyamides.
- this invention relates to polyamides including flame retardants that exhibit both improved flame resistance and thermal stability.
- halogen containing flame-retardant typically a bromine or chlorine compound
- starts to degrade slowly when in the presence of an antimony compound synergist
- One of the degradation products is the acid of the halogen (HC1 or HBr).
- the oxides, hydroxides or salts of weak mineral acids (used as an additive) neutralize the halogen acid that is formed, and prevent acid attack of the polymer which would otherwise lead to volatiles and corrosion.
- polyamide molding compositions having both improved flame resistance and heat stability comprising, in weight percent,
- component (e) is present in an amount of 1 - 5 weight percent are preferred.
- the polyamide used in this invention may be 20-78% (all percentages are weight percent unless designated otherwise) of any polyamide that has a melting point of from about 280°C to about 340°.
- An example of a suitable polyamide is a copolyamide composed of 20-80 mole % of units derived from hexamethylene terephthalamide and 80-20 mole % of units derived from hexamethylene adipamide. This polyamide is referred to hereinafter as 6T/66 copolymer.
- polyamides include polyamides composed of 20-80 mole % of units derived from hexamethylene terephthalamide and 80-20 mole % of units derived from hexamethylene sebacamide, hexamethylene dodecamide, hexamethylene isophthalamide, 2-methylpentamethylene terephthalamide, or mixtures thereof.
- copolyamide used in the composition of the present invention. It may be produced easily by ordinary melt polymerization.
- One method to produce the copolymer of this invention is an autoclave one-step polymerization process taught in US Patent No. 5,378,800 which is incorporated by reference herein. That process includes feeding to a reactor an aqueous salt solution of an admixture of desired diacids and diamines, heating the solution under pressure, reducing the pressure, maintaining the reaction mixture at a pressure that is not greater than about atmospheric pressure, and discharging the polyamide from the reactor.
- An alternative process includes preparing a prepolymer and subjecting the prepolymer to solid-phase polymerization or melt-mixing in an extruder to increase the degree of polymerization.
- the prepolymer is prepared by heating at 150°C-320°C an aqueous solution containing 6T salt (a salt formed from hexamethylenediamine and terephthalic acid) and 66 salt (a salt formed from hexamethylenediamine and adipic acid).
- 6T salt a salt formed from hexamethylenediamine and terephthalic acid
- 66 salt a salt formed from hexamethylenediamine and adipic acid
- the composition of the present invention contains 10-60% of an inorganic filler or reinforcing agent that includes, for example, fibrous reinforcement such as glass fiber and carbon fiber, glass beads, talc, kaolin, wollastonite and mica.
- fibrous reinforcement such as glass fiber and carbon fiber
- glass beads Preferable among them is glass fiber.
- Glass fibers suitable for use in the present invention are those generally used as a reinforcing agent for thermoplastics resins and thermosetting resins.
- Preferred glass fiber is in the form of glass rovings, glass chopped strands, and glass yarn made of continuous glass filaments 3-20 micron meters in diameter.
- the resin composition of the present invention contains 10-35% of a flame retardant. It is a flame retardant based on brominated polystyrene and/or brominated poly-phenylene ether containing 50-70%) by weight bromine.
- the polystyrene has a weight-average molecular weight higher than 5000, preferably higher than 20,000, and more preferably higher than 28,000.
- the ether has a molecular weight of at least 6000.
- An alternate flame retardant is bis(hexachlorocyclopentaieno)cyclooctane, containing approximately 65 wt. % chlorine.
- a preferred flame retardant is brominated polystyrene or polydibromostyrene.
- the bromine-containing flame retardant is used in combination with 1-10% of an auxiliary flame retardant that is a specific antimony compound which is selected from the group consisting of antimony trioxide, antimony tetraoxide, antimony pentoxide and sodium antimonate. Sodium antimonate is preferred.
- Oxides or hydroxides such as zinc oxide, magnesium oxide, calcium oxide, and hydrotalcite are useful in this invention.
- salts of weak mineral acids such as calcium carbonate and zinc borate
- a heat stabilizer such as copper iodide.
- the copolyamide resin of the present invention may have incorporated in it a variety of additives such as an impact modifier, a viscosity modifier, pigment, dye, antioxidant, and heat resistance improver, in such amounts that they do not harm its characteristic properties.
- additives such as an impact modifier, a viscosity modifier, pigment, dye, antioxidant, and heat resistance improver, in such amounts that they do not harm its characteristic properties.
- the nylon used was 6T66 (45/55 molar %) with a melting point of about 315°C.
- Stage 1 Examples and Comparative Examples Samples of various compositions were extruded on a 20 mm twin screw extruder (Welding Engineers Inc., Blue Bell, Pennsylvania). The material was placed in a glass tube 0.5 inch OD (12 cm) and 24_inch (62 cm) in length and heated at 340°C for 30 minutes, with a small helium purge. The contents of the heated glass tubes were visually graded for the amount of volatiles which had left the polymer and condensed higher on the glass tube. Off-gases were collected and analyzed. See Table 1. Stage 2 Examples and Comparative Examples
- a polyamide molding composition which has both improved flame resistance and heat stability comprising, in weight percent,
- component (a) is a copolyamide of 20 - 80 mole of units derived from hexamethylene terephthalamide and 80 - 20 mole % of units derived from hexamethylene adipamide.
- composition of Claim 1 where in the inorganic filler (b) is selected from the group consisting of glass fiber, carbon fiber, glass beads, talc, kaolin, wollastonite and mica.
- composition of Claim 1 wherein the flame retardant (c) is selected from the group consisting of brominated polystyrene, polydibromostyrene, and bis(hexachlorocyclopentaieno)cyclooctane.
- composition of Claim 1 where in the antimony compound (d) is selected from the group consisting of antimony trioxide, antimony tetraoxide, antimony pentoxide, and sodium antimonate.
- composition of Claim 1 wherein the component (e) is selected from one or more of the group consisting of zinc oxide, magnesium oxide, calcium oxide, hydrotalcite, calcium carbonate, and zinc borate.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Nutrition Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002321551A CA2321551A1 (en) | 1998-03-18 | 1999-03-18 | Improved thermally stable flame retardant polyamides |
JP2000536793A JP2002506910A (en) | 1998-03-18 | 1999-03-18 | Polyamide with improved thermal stability and flame retardancy |
EP99912653A EP1068269A1 (en) | 1998-03-18 | 1999-03-18 | Improved thermally stable flame retardant polyamides |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US7850498P | 1998-03-18 | 1998-03-18 | |
US60/078,504 | 1998-03-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999047606A1 true WO1999047606A1 (en) | 1999-09-23 |
Family
ID=22144438
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/005901 WO1999047606A1 (en) | 1998-03-18 | 1999-03-18 | Improved thermally stable flame retardant polyamides |
Country Status (5)
Country | Link |
---|---|
US (1) | US6350802B2 (en) |
EP (1) | EP1068269A1 (en) |
JP (1) | JP2002506910A (en) |
CA (1) | CA2321551A1 (en) |
WO (1) | WO1999047606A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7816438B2 (en) | 2005-04-08 | 2010-10-19 | Mitsui Chemicals, Inc. | Flame-retardant polyamide composition |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004015010A1 (en) * | 2002-08-09 | 2004-02-19 | E. I. Du Pont De Nemours And Company | Polyamide molding compositions and electrical and electronic components molded therefrom having improved heat stability |
DE50309009D1 (en) * | 2002-09-21 | 2008-03-06 | Evonik Degussa Gmbh | Method for producing a three-dimensional object |
EP1431346A1 (en) * | 2002-12-16 | 2004-06-23 | DSM IP Assets B.V. | Process for preparing a flame retardant polyamide composition |
EP1498445A1 (en) * | 2003-07-18 | 2005-01-19 | DSM IP Assets B.V. | Heat stabilized moulding composition |
US8247475B2 (en) | 2005-12-29 | 2012-08-21 | Toda Kogyo Corporation | Hydrotalcite-based compound particles, resin stabilizer using the same, halogen-containing resin composition and anion scavenger using the same |
US20080153947A1 (en) * | 2006-12-21 | 2008-06-26 | Richard Benton Booth | Methods and systems for fabricating fire retardant materials |
US8871874B2 (en) | 2012-06-13 | 2014-10-28 | E I Du Pont De Nemours And Company | Thermoplastic melt-mixed composition with epoxy-amino acid compound heat stabilizer and processes for their preparation |
JP6416756B2 (en) | 2012-06-13 | 2018-10-31 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company | Thermoplastic melt blend composition containing amino acid heat stabilizer |
JP2015519463A (en) | 2012-06-13 | 2015-07-09 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company | Thermoplastic melt blend composition containing polyetherol thermal stabilizer |
US20140252265A1 (en) * | 2013-03-07 | 2014-09-11 | Basf Se | Heat conducting thermoplastic moulding compositions comprising a flame retardant |
US20140288220A1 (en) | 2013-03-25 | 2014-09-25 | E I Du Pont De Nemours And Company | Heat resistant polyamide compositions |
CN109337362B (en) * | 2018-09-10 | 2021-01-05 | 广东聚石化学股份有限公司 | Special PA66 material for halogen-free and phosphorus-free circuit breaker and preparation method thereof |
CN111205637B (en) * | 2018-11-21 | 2022-04-19 | 杭州本松新材料技术股份有限公司 | Heat stabilizer and composite material containing same |
CN112358723B (en) * | 2020-09-29 | 2023-04-14 | 天津金发新材料有限公司 | High-heat-resistance flame-retardant nylon 66 composite material |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63150349A (en) * | 1986-12-12 | 1988-06-23 | Mitsubishi Gas Chem Co Inc | Flame-retardant polyamide resin composition |
WO1995018178A1 (en) * | 1993-12-28 | 1995-07-06 | E.I. Du Pont De Nemours And Company | A flame retardant polyamide resin composition |
JPH07292242A (en) * | 1994-04-25 | 1995-11-07 | Asahi Chem Ind Co Ltd | Flame-retarding polyamide resin composition |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4504611A (en) * | 1983-08-01 | 1985-03-12 | Occidental Chemical Corporation | Flame retardant polyamide compositions |
JP2582878B2 (en) * | 1988-11-22 | 1997-02-19 | 東レ株式会社 | Flame retardant polyamide resin composition |
DE3924869A1 (en) * | 1989-07-27 | 1991-01-31 | Basf Ag | FLAME RETARDED THERMOPLASTIC MOLDS |
JPH03152162A (en) * | 1989-11-09 | 1991-06-28 | Calp Corp | Thermoplastic composite resin composition |
US5256718A (en) * | 1990-02-14 | 1993-10-26 | Mitsui Petrochemical Industries, Ltd. | Flame retardant polyamide thermoplastic resin composition |
JPH07228775A (en) * | 1994-02-17 | 1995-08-29 | Kuraray Co Ltd | Flame-retardant polyamide composition |
US5773500A (en) * | 1996-05-14 | 1998-06-30 | Amoco Corporation | Flame retardant high temperature polyphthalamides having improved thermal stability |
-
1999
- 1999-03-17 US US09/270,871 patent/US6350802B2/en not_active Expired - Lifetime
- 1999-03-18 WO PCT/US1999/005901 patent/WO1999047606A1/en not_active Application Discontinuation
- 1999-03-18 JP JP2000536793A patent/JP2002506910A/en active Pending
- 1999-03-18 CA CA002321551A patent/CA2321551A1/en not_active Abandoned
- 1999-03-18 EP EP99912653A patent/EP1068269A1/en not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63150349A (en) * | 1986-12-12 | 1988-06-23 | Mitsubishi Gas Chem Co Inc | Flame-retardant polyamide resin composition |
WO1995018178A1 (en) * | 1993-12-28 | 1995-07-06 | E.I. Du Pont De Nemours And Company | A flame retardant polyamide resin composition |
JPH07292242A (en) * | 1994-04-25 | 1995-11-07 | Asahi Chem Ind Co Ltd | Flame-retarding polyamide resin composition |
Non-Patent Citations (2)
Title |
---|
DATABASE WPI Section Ch Week 8831, Derwent World Patents Index; Class A23, AN 88-215563, XP002107640 * |
DATABASE WPI Section Ch Week 9602, Derwent World Patents Index; Class A18, AN 96-017408, XP002107641 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7816438B2 (en) | 2005-04-08 | 2010-10-19 | Mitsui Chemicals, Inc. | Flame-retardant polyamide composition |
Also Published As
Publication number | Publication date |
---|---|
JP2002506910A (en) | 2002-03-05 |
US20010056145A1 (en) | 2001-12-27 |
CA2321551A1 (en) | 1999-09-23 |
US6350802B2 (en) | 2002-02-26 |
EP1068269A1 (en) | 2001-01-17 |
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