EP1773931A1 - Compositions thermoplastiques ignifuges, leur procede de preparation - Google Patents

Compositions thermoplastiques ignifuges, leur procede de preparation

Info

Publication number
EP1773931A1
EP1773931A1 EP05779718A EP05779718A EP1773931A1 EP 1773931 A1 EP1773931 A1 EP 1773931A1 EP 05779718 A EP05779718 A EP 05779718A EP 05779718 A EP05779718 A EP 05779718A EP 1773931 A1 EP1773931 A1 EP 1773931A1
Authority
EP
European Patent Office
Prior art keywords
composition according
polyamide
compositions
melamine cyanurate
mixture
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Withdrawn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
EP05779718A
Other languages
German (de)
English (en)
French (fr)
Inventor
Christelle Recoquille
Philippe Blondel
Jean-Jacques Flat
Jean-Claude Marais
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.)
Arkema France SA
Original Assignee
Arkema France SA
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 Arkema France SA filed Critical Arkema France SA
Publication of EP1773931A1 publication Critical patent/EP1773931A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • C08K5/3492Triazines
    • C08K5/34928Salts
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the subject of the present invention is flame retardant thermoplastic compositions based on polyamide resins having good mechanical characteristics, good thermal and chemical resistance and good fire performance, as well as their method of preparation.
  • thermoplastic polyamide resins are widely used in many applications in the automotive, aerospace, electrical, etc. industries, but their development is sometimes retarded because of their ability to burn.
  • Halogenated derivatives such as decabromodiphenyl ether, decabromodiphenyl, optionally in combination with Sb 2 O 3 , have been added but the halogenated compounds are halogenated acid generators which are released during manufacture and / or during use and / or during combustion of the compositions in which they are incorporated, thereby causing the risk of corrosion of equipment and environmental nuisance.
  • the antimony oxide Sb 2 O 3 is also used in combination with magnesium hydroxide and optionally melamine cyanurate in EP 571241 in the name of the applicant, for the fireproofing of thermoplastic polyamide compositions.
  • Melamine cyanurate improves the resistance to combustion of polyamides but is not as effective at equal weight as certain compounds with high chlorine or bromine content.
  • thermoplastic compositions based on polyamide resin which contain aliphatic and / or cycloaliphatic units. and / or aromatic to improve the resistance to combustion.
  • the compositions described are based on polyamide resin such as PA-11, PA-12, PA-12, 12, coPA-6/12 and / or PEBA.
  • the preparation method described in EP 758002 can be implemented by prior preparation of a master batch of the constituents and subsequent redilution of the masterbatch in the final resin, the resin of the masterbatch may be identical or different from the final resin.
  • the Applicant has now found flame retardant thermoplastic compositions having improved properties.
  • the subject of the invention is therefore a flame retardant thermoplastic composition
  • a flame retardant thermoplastic composition comprising a mixture of polyamide resins PA-11 and PA-12, and melamine cyanurate.
  • the PA-12 / PA-11 ratio in the composition is in the range from 99/1 to 1/99, preferably from 95/5 to 50/50 or 90/10. at 60/40.
  • the PA-12 / PA-11 ratio is in the range of 85/15 to 50/50.
  • the melamine cyanurate represents 5 to 20%, and preferably 10 to 15% of the total weight of the composition.
  • thermoplastic composition further comprises fire-resistant additives chosen from one or more polyols containing at least four times the alcohol function, the oxide of antimony Sb 2 O 3 , the magnesium hydroxide Mg (OH) 2 , ammonium polyphosphate, phosphorus derivatives, or mineral nanofillers.
  • fire-resistant additives chosen from one or more polyols containing at least four times the alcohol function, the oxide of antimony Sb 2 O 3 , the magnesium hydroxide Mg (OH) 2 , ammonium polyphosphate, phosphorus derivatives, or mineral nanofillers.
  • the anti-fire additive is chosen from polyols containing at least four times the alcohol function, preferably monopentaerythritol.
  • the polyol represents from 1 to 5% of the total weight of the composition.
  • Another subject of the invention relates to the process for preparing a thermoplastic composition as defined above comprising the following steps: a) preparation of a masterbatch comprising a polyamide resin PA-1 or PA-12 or a mixture PA-11 and PA-12, and melamine cyanurate; then b) dilution of the masterbatch in a PA-11 or PA-12 resin or a mixture of PA-I and PA-12.
  • the polyamide of step a) of the preparation process is PAl 1 and the polyamide of step b) is PAl 2.
  • a polyol is added to step b) of the preparation process.
  • the invention also relates to industrial articles obtained by transformation of the compositions as defined above.
  • compositions make it possible to obtain materials which have good mechanical performance, good thermal and chemical resistance and good fire resistance.
  • the materials obtained with the compositions according to the invention exhibit both good resistance to combustion and good mechanical performance (as resistance or elongation at break), especially after aging.
  • the polyamide resins PA present in the thermoplastic compositions according to the invention are known thermoplastic resins consisting of polyamide 11 polymers (PA-11) and polyamide 12 polymers (PA-12).
  • the PA-12 / P Al ratio is generally in the range from 99/1 to 1/99, preferably from 95/5 to 50/50, or from 90/10 to 60/40.
  • the PA-12 / PA-11 ratio is in the range of 85/15 to 50/50.
  • melamine cyanurate is meant the compounds resulting from the action of melamine on cyanuric acid, and particularly the compound resulting from the equimolar reaction of melamine on cyanuric acid, the latter may be in the enol or ketone.
  • the melamine cyanurate incorporated in the masterbatch generally represents 30 to 60% of the total weight of the masterbatch. In the final compositions based on PA-I mixture and 12, it generally represents from 5 to 20% of the total weight of the composition, and preferably from 10 to 15% of the total weight of the composition.
  • compositions according to the invention it is possible to add additional anti-fire additives chosen from one or more polyols containing, for example, four times the alcohol function, the oxide of antimony Sb 2 O 3 , the magnesium hydroxide Mg (OH) 2 , ammonium polyphosphate, melamine pyrophosphate and more generally phosphorus derivatives such as phosphinates, phosphates such as TPP, RDP, etc.
  • additional anti-fire additives chosen from one or more polyols containing, for example, four times the alcohol function, the oxide of antimony Sb 2 O 3 , the magnesium hydroxide Mg (OH) 2 , ammonium polyphosphate, melamine pyrophosphate and more generally phosphorus derivatives such as phosphinates, phosphates such as TPP, RDP, etc.
  • inorganic nanofillers in the process.
  • thermoplastic composition By way of example of these nanofillers, mention may be made of montmorillonite, nanotalcs, etc. It is
  • polyol compounds preferably containing at least four times the alcohol function such as tetrols such as erythrol, monopentaerythritol (PER) and its polysubstituted derivatives, pentols such as xylitol, arabitol and hexols such as than mannitol, sorbitol and its higher counterparts.
  • tetrols such as erythrol, monopentaerythritol (PER) and its polysubstituted derivatives
  • pentols such as xylitol, arabitol and hexols such as than mannitol, sorbitol and its higher counterparts.
  • the preferred additive selected from one or more polyols containing at least four times the alcohol function is monopentaerytritol (PER).
  • the amount of polyol represents from 1 to 5% of the total weight of the final composition.
  • the antimony oxide Sb 2 O 3 is generally in the form of a fine powder whose granulometry is of the order of one micron.
  • compositions according to the invention may also contain thermoplastic elastomers (TPE) based on polyamide which are block copolymers, also called polyetheramides or polyesteramides, the rigid sequences of which consist of polyamide and the flexible blocks of polyether or polyester.
  • TPE thermoplastic elastomers
  • compositions may also contain their blends with other polymers such as polyurethanes, polyolefins.
  • PA resin (s) as defined above represent at least 50% of the total weight of the mixture.
  • PAs can be plasticized with additives commonly used for this type of modification. They can be loaded and / or contain various additives, for example additives for protecting the PA against thermo-oxidation, thermo-UV-degradation, processing additives such as lubricants, dyes or pigments, etc. .
  • Copolyamides can also be added to the thermoplastic composition.
  • copolyamides is meant copolymers resulting from the condensation of at least two alpha omega aminocarboxylic acids or two lactams or a lactam and an alpha omega aminocarboxylic acid. Mention may also be made of the copolyamides resulting from the condensation of at least one alpha omega aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.
  • copolyamides By way of examples of copolyamides, mention may be made of copolymers of caprolactam and lauryl lactam (PA 6/12), copolymers of caprolactam, adipic acid and hexamethylenediamine (PA 6 / 6-6), copolymers caprolactam, lauryl lactam, adipic acid and hexamethylenediamine (PA 6/12 / 6-6), copolymers of caprolactam, lauryl lactam, amino 11 undecanoic acid, azelaic acid and hexamethylenediamine (PA 6 / 6-9 / 11/12), copolymers of caprolactam, lauryl lactam, amino undecanoic acid, adipic acid and hexamethylenediamine (PA 6 / 6-6 / 11 / 12), copolymers of lauryl lactam, azelaic acid and hexamethylenediamine (PA 6-9 / 12).
  • the preparation of the compositions according to the invention is carried out by first preparing a masterbatch of resin PA-I or PA-12 or a mixture of both with cyanurate ⁇ p melamine by mixing in the resin PA in the molten state. ; the kneading temperature is in general between 150 and 300 ° C. and preferably between 180 and 250 ° C.
  • the masterbatch has the advantage of ensuring a good predispersion of the constituents which will be kneaded again during the subsequent dilution of the masterbatch in the final resin consisting of PA-I or PA-12 or a mixture of the two. .
  • This method makes it possible to obtain the compositions comprising the mixture of two different resins PA-I 1 and PA12.
  • the additional additives described above can be added to the masterbatch or preferably in the dilution medium with the final resin or resins.
  • the monopentaerythritol is added to the final dilution step.
  • compositions are obtained making it possible to obtain materials which have both good resistance to combustion and good mechanical performance (as resistance or elongation at break), especially after aging.
  • compositions according to the invention find applications in various fields by transformation into industrial articles intended in particular for the automobile, aeronautics, household appliances, audiovisual equipment and electrical equipment industries; they are well suited for the realization of cabling elements, for example electrical equipment.
  • thermoplastic compositions can also find applications in the field of plastic optical fiber cladding. They are particularly suitable for processing into molded, extruded, injected, film, sheet, fiber, composite materials such as coextruded objects, multilayer films, as well as powders for coating substrates.
  • the inherent viscosity of PA is measured at 25 ° C. in the meta-cresol for 0.5 g of polymer in 100 ml of meta-cresol.
  • the melting point of PA resins is measured according to ASTM D 3418 and their Shore D hardness is measured according to ASTM D 2240.
  • Torque properties ARi and ARf (initial and ultimate elongation) and RRi and RRf (ultimate and ultimate tensile strength) are measured according to ISO R 527 IB.
  • the aging is carried out by heating at 90 ° C for 14 days in a ventilated oven.
  • Flexural modulus (MEF) is measured according to ISO 178.
  • the fire resistance is evaluated by measuring the limiting oxygen index (IOL) on ISO bars Rl 78 (80x10x4 mm ⁇ 3>) obtained on a KRAUSS MAFFEI Bl 6OT press under the following conditions from the above samples,
  • Injection temperature 210-230 ° C
  • the resistance to dripping (UL 94) is evaluated according to standard NF 51 0272.
  • CM melamine cyanurate
  • the monopentaerythritol (PER) used is sold by the company CELANESE.
  • the fire resistance (IOL & UL 94) and the initial and final mechanical properties after aging of the compositions obtained on bars, dumbbells or plates are evaluated according to the operating conditions of the products. measurement standards implemented.
  • ** is the amount of PA in the dilution medium.

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)
  • Processes Of Treating Macromolecular Substances (AREA)
EP05779718A 2004-07-02 2005-07-01 Compositions thermoplastiques ignifuges, leur procede de preparation Withdrawn EP1773931A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0407362A FR2872515B1 (fr) 2004-07-02 2004-07-02 Compositions thermoplastiques ignifuges, leur procede de preparation
PCT/FR2005/001686 WO2006013259A1 (fr) 2004-07-02 2005-07-01 Compositions thermoplastiques ignifuges, leur procede de preparation

Publications (1)

Publication Number Publication Date
EP1773931A1 true EP1773931A1 (fr) 2007-04-18

Family

ID=34946542

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05779718A Withdrawn EP1773931A1 (fr) 2004-07-02 2005-07-01 Compositions thermoplastiques ignifuges, leur procede de preparation

Country Status (6)

Country Link
US (1) US20080085956A1 (zh)
EP (1) EP1773931A1 (zh)
JP (1) JP2008504425A (zh)
CN (1) CN101010370A (zh)
FR (1) FR2872515B1 (zh)
WO (1) WO2006013259A1 (zh)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110039470A1 (en) * 2009-07-30 2011-02-17 E.I. Du Pont De Nemours And Company Overmolded heat resistant polyamide composite structures and processes for their preparation
CN102618026B (zh) * 2012-04-25 2014-07-02 中国科学院宁波材料技术与工程研究所 一种高cti值的无卤阻燃尼龙母料及制备方法
CN103965646A (zh) * 2014-04-11 2014-08-06 苏州市依星橡塑有限公司 一种阻燃塑料板的制备工艺
FR3032445A1 (fr) * 2015-02-05 2016-08-12 Arkema France Composition de polyamide a combustibilitee retardee
CN108350269A (zh) * 2015-10-30 2018-07-31 东丽株式会社 由含有聚酰胺树脂的树脂组合物形成的成型品
CN110218442A (zh) * 2019-06-25 2019-09-10 金旸(厦门)新材料科技有限公司 一种高流动导热尼龙复合材料及其制备方法和应用
CN117916316A (zh) 2021-08-30 2024-04-19 巴斯夫欧洲公司 聚酰胺组合物和制品
CN114517012B (zh) * 2022-03-14 2023-06-06 金旸(厦门)新材料科技有限公司 一种高外观抗菌无卤阻燃聚酰胺复合材料及其制备方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1524055A (en) * 1974-11-12 1978-09-06 Toa Gosei Chem Ind Adhesive polyamide compositions for metals
JPS523655A (en) * 1975-06-26 1977-01-12 Toa Gosei Chem Ind Method of producing nylon film
JPS5817539B2 (ja) * 1978-09-18 1983-04-07 旭化成株式会社 メラミンシアヌレ−ト含有ポリアミド組成物の製造方法
FR2564475B1 (fr) * 1984-05-21 1986-11-28 Atochem Compositions a base de polyamides a combustibilite retardee
FR2695395B1 (fr) * 1992-05-22 1994-10-28 Atochem Elf Sa Compositions thermoplastiques ignifuges à base de polyamide.
US6239219B1 (en) * 1995-07-21 2001-05-29 Atofina Thermoplastic compositions with improved fire resistance
FR2736920B1 (fr) * 1995-07-21 1997-08-22 Atochem Elf Sa Compositions thermoplastiques a tenue au feu amelioree
US6204314B1 (en) * 1998-06-08 2001-03-20 Ec-Showa Denko K.K. Film retardant polyamide resin composition
FR2789996B1 (fr) * 1999-02-24 2001-04-13 Rhodia Eng Plastics Srl Composition polyamide ignifugee
FR2791993B1 (fr) * 1999-03-26 2001-06-08 Atochem Elf Sa Compositions thermoplastiques a base de polyamide
EP1431346A1 (en) * 2002-12-16 2004-06-23 DSM IP Assets B.V. Process for preparing a flame retardant polyamide composition
US7352984B2 (en) * 2003-11-28 2008-04-01 Canon Kabushiki Kaisha Electrophotographic endless belt, electrophotographic apparatus having electrophotographic endless belt, and process for producing electrophotographic endless belt

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006013259A1 *

Also Published As

Publication number Publication date
WO2006013259A1 (fr) 2006-02-09
FR2872515A1 (fr) 2006-01-06
CN101010370A (zh) 2007-08-01
JP2008504425A (ja) 2008-02-14
FR2872515B1 (fr) 2006-10-13
US20080085956A1 (en) 2008-04-10

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