WO1994021723A1 - Flame retardant polyamides - Google Patents
Flame retardant polyamides Download PDFInfo
- Publication number
- WO1994021723A1 WO1994021723A1 PCT/US1994/002844 US9402844W WO9421723A1 WO 1994021723 A1 WO1994021723 A1 WO 1994021723A1 US 9402844 W US9402844 W US 9402844W WO 9421723 A1 WO9421723 A1 WO 9421723A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- polyamide
- melamine
- phenol
- flame retardant
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Definitions
- This invention relates to flame retardant polyamide compositions and more particularly to such compositions containing a combination of melamine and phenol-aldehyde resins.
- melamine has been the use of melamine derivatives or its condensation products such as melamine cyanurate; but, although these have presented solutions to the melamine blooming issues, they have proved difficult to scale-up to typical commercial processes without some loss of flammability control.
- the volatility rate of melamine from polyamides containing it is comparable to melamine itself because of the incompatibility of melamine with polyamides.
- phenol-aldehyde resins such as phenol-formaldehyde resins sold under the name novolac, reduce and in some cases eliminate mold deposit and humid blooming of the melamine during compounding and molding of the polyamide compositions.
- Polyamide compositions containing a combination of melamine and a phenol-aldehyde resin according to the invention have the advantages of having a flame resistant rating of VO under EL-94 and retaining their physical and electrical properties.
- a flame retardant polyamide composition which comprises:
- (d) 0-50% by weight, preferably 0-30% by weight, of at least one of a reinforcing agent or filler.
- a reinforcing agent and/or filler are preferably used at a concentration of 10-30% by weight.
- Polyamides useful in the compositions of this invention are well known in the art and embrace those semi-crystalline and amorphous polymers having a molecular weight of at least 5000 and commonly referred to as nylons.
- Suitable polyamides include those described in U.S. Patent Nos.2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 3,312,966, 2,512,606, and 3,393,210.
- the polyamide can be produced by condensation of equimolar amounts of a saturated dicarboxylic acid containing from 4 to 12 carbon atoms with a diamine, in which the diamine contains from 4 to 14 carbon atoms. Excess diamine can be employed to provide an excess of amine end groups over carboxy end groups in the polyamide. Mixtures of polyamides can also be used, as can block polymers and copolymers.
- polyamides examples include copolymers of polyhexamethylene adipamide (66 nylon), polyhexamethylene azellamide (69 nylon), polyhexamethylene sebacamide (610 nylon), and polyhexamethylene dodecanoamide (612 nylon), the polyamide produced by ring opening of lactams, i.e. polycaprolactam, polylauric lactam, poly-11- amino-undecanoic acid, bis (paraaminocyclohexyl) methane dodecanoamide.
- lactams i.e. polycaprolactam
- polylauric lactam poly-11- amino-undecanoic acid
- bis (paraaminocyclohexyl) methane dodecanoamide bis (paraaminocyclohexyl) methane dodecanoamide.
- polyamides prepared by the copolymerization of two of the above polymers or terpolymerization of the above polymers or their components e.g., for example, an adipic, isophthalic acid hexamethylene diamine copolymer.
- modified PA6.6 particularly a 6.6-6 copolymer
- PA6, PA6.10, PA6.12, PAH, PA12, PA12.12, PA6/6.6 etc. may be used.
- Particularly preferred because of high physical properties is a 6.6 polymer.
- polystyrene resin Preferable are polyamides with a relative viscosity (RV) according to ASTM D789 of 20 to 70, preferably 30-60.
- RV relative viscosity
- Phenol-aldehyde resins are linear condensation resins which are obtained by condensing phenols such as phenol, cresol, bis-phenol A, resorcinol, or phenol-cresol and higher alkyl substitutions of them, and aldehydes such as formaldehyde or acetaldehyde. Such resins are sold commercially under the name novolac. A phenol-formaldehyde resin is preferred.
- Suitable phenol-containing compounds from which useful resins can be produced are n- and isoalkyl phenols which contain up to 8 carbon atoms in the alkyl groups, naphthols, hydroxy diphenyls, hydroxy diphenyl ethers, hydroquinone, pyrocatechol, bis-(hydroxy-phenyl) alkanes or cycloalkanes having up to 20 carbon atoms, bis (hydroxyphenyl) sulphides (or sulfones) and hydroxy benzoic acids.
- the phenol-aldehyde resins can be prepared by known methods such as described in Houben-Weyl, Methoden der organischen Chemie, Vol. 14/2, 4th edition pages 274 et seq.
- Cross-linked phenol-aldehyde resins can also be used if a resin of higher melt viscosity is desired.
- Cross-linking can be conducted in a known manner using an acid such as phosphoric acid or boric acid, PC1 3 , or polyfunctional epoxides or isocyanates or a formaldehyde donor.
- Preferred phenol-aldehyde resins have softening temperatures in the range of 40 to 200°C, preferably above 100°C; and molecular weights (Mw) in the range of 5,000-30,000, preferably 10,000-20,000.
- the flame retardant polyamide compositions can also contain conventional additives, fillers, and reinforcing agents such as lubricants, mold-release agents, stabilizers, dyes, pigments, color concentrates, flow agents, glass and organic fibers, chalk, clay, quartz, and hydrated mineral fillers such as magnesium hydroxide. Fillers and reinforcing agents, when used, are used at concentrations of 10-50% based on the weight of the composition, preferably 10-30% by weight.
- compositions of the invention are prepared by thoroughly mixing or dissolving melamine in the phenol-aldehyde resin, or the two can be added simultaneously or separately to the polyamide during a compounding step.
- the resulting extrudate is cooled, pelletized and dried before molding the resulting composition into shaped articles.
- test bars at each condition described in the UL94 test were tested in order to give a percentage of the total which fail by igniting the cotton.
- CTI Comparative Tracking Index
- TGA Isothermal Thermogravimetric Analysis
- the resulting strand was cooled in water and pelletized.
- the resulting granules were vacuum dried at 80°C to a moisture content of less than 0.2%.
- the dried granules were then molded into the required test pieces using a standard thermoplastic molding machine using a melt temperature of 270°C and mold temperature of 60-70°C.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP52121394A JP3406603B2 (en) | 1993-03-17 | 1994-03-16 | Flame retardant polyamide |
EP94911619A EP0689565A1 (en) | 1993-03-17 | 1994-03-16 | Flame retardant polyamides |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4308534.2 | 1993-03-17 | ||
DE19934308534 DE4308534A1 (en) | 1993-03-17 | 1993-03-17 | Flame retardant polyamides |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994021723A1 true WO1994021723A1 (en) | 1994-09-29 |
Family
ID=6483061
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1994/002844 WO1994021723A1 (en) | 1993-03-17 | 1994-03-16 | Flame retardant polyamides |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0689565A1 (en) |
JP (1) | JP3406603B2 (en) |
CA (1) | CA2158336A1 (en) |
DE (1) | DE4308534A1 (en) |
WO (1) | WO1994021723A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102337022A (en) * | 2011-05-31 | 2012-02-01 | 深圳市科聚新材料有限公司 | Nylon material special for breakers and preparation method thereof |
WO2019204370A1 (en) * | 2018-04-18 | 2019-10-24 | Invista North America S.A R.L. | Flame-retardant polyamide composition |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2794467B1 (en) * | 1999-06-04 | 2004-08-20 | Rhodia Eng Plastics Srl | FLAME RETARDANT POLYAMIDE COMPOSITION |
FR2908418B1 (en) * | 2006-11-10 | 2012-08-17 | Rhodia Recherches & Tech | FLAME RETARDANT POLYAMIDE COMPOSITION. |
FR2935144B1 (en) | 2008-08-25 | 2011-12-16 | Rhodia Operations | USE OF A NOVOLAQUE RESIN FOR INCREASING THE ACID RESISTANCE OF A POLYAMIDE COMPOSITION |
JP5504803B2 (en) * | 2009-09-30 | 2014-05-28 | 住友ベークライト株式会社 | Phenolic resin molding material |
CN109467925B (en) * | 2018-11-29 | 2021-03-23 | 上海金发科技发展有限公司 | Moisture-heat aging precipitation-resistant halogen-free flame-retardant nylon composite material |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3663495A (en) * | 1968-10-17 | 1972-05-16 | Bayer Ag | Self-extinguishing polyamide moulding compositions |
US3793289A (en) * | 1971-10-13 | 1974-02-19 | Allied Chem | Flame retardant nylon compositions |
US3931386A (en) * | 1971-11-06 | 1976-01-06 | Nippon Kynol Incorporated | Process for producing drawn or undrawn flame-resistant, anti-fusing cured phenolic continuous filaments |
US4244858A (en) * | 1978-03-10 | 1981-01-13 | Bayer Aktiengesellschaft | Flameproof polyamide moulding compositions |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2800467A1 (en) * | 1978-01-05 | 1979-07-12 | Bayer Ag | FLAME RESISTANT POLYAMIDE MOLDING COMPOUNDS |
DE4141861A1 (en) * | 1991-12-18 | 1993-06-24 | Du Pont Int | FLAME-RESISTANT POLYAMID |
-
1993
- 1993-03-17 DE DE19934308534 patent/DE4308534A1/en not_active Withdrawn
-
1994
- 1994-03-16 JP JP52121394A patent/JP3406603B2/en not_active Expired - Fee Related
- 1994-03-16 WO PCT/US1994/002844 patent/WO1994021723A1/en not_active Application Discontinuation
- 1994-03-16 CA CA 2158336 patent/CA2158336A1/en not_active Abandoned
- 1994-03-16 EP EP94911619A patent/EP0689565A1/en not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3663495A (en) * | 1968-10-17 | 1972-05-16 | Bayer Ag | Self-extinguishing polyamide moulding compositions |
US3793289A (en) * | 1971-10-13 | 1974-02-19 | Allied Chem | Flame retardant nylon compositions |
US3931386A (en) * | 1971-11-06 | 1976-01-06 | Nippon Kynol Incorporated | Process for producing drawn or undrawn flame-resistant, anti-fusing cured phenolic continuous filaments |
US4244858A (en) * | 1978-03-10 | 1981-01-13 | Bayer Aktiengesellschaft | Flameproof polyamide moulding compositions |
Non-Patent Citations (1)
Title |
---|
See also references of EP0689565A4 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102337022A (en) * | 2011-05-31 | 2012-02-01 | 深圳市科聚新材料有限公司 | Nylon material special for breakers and preparation method thereof |
WO2019204370A1 (en) * | 2018-04-18 | 2019-10-24 | Invista North America S.A R.L. | Flame-retardant polyamide composition |
CN111971335A (en) * | 2018-04-18 | 2020-11-20 | 英威达纺织(英国)有限公司 | Flame retardant polyamide composition |
CN111971335B (en) * | 2018-04-18 | 2023-03-24 | 英威达纺织(英国)有限公司 | Flame retardant polyamide composition |
TWI823926B (en) * | 2018-04-18 | 2023-12-01 | 美商英維斯塔責任有限公司 | Flame-retardant polyamide composition |
Also Published As
Publication number | Publication date |
---|---|
JP3406603B2 (en) | 2003-05-12 |
DE4308534A1 (en) | 1994-09-22 |
CA2158336A1 (en) | 1994-09-29 |
JPH08507826A (en) | 1996-08-20 |
EP0689565A4 (en) | 1995-09-25 |
EP0689565A1 (en) | 1996-01-03 |
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