WO1986006397A1 - Compositions thermoplastiques multiphases et articles obtenus - Google Patents

Compositions thermoplastiques multiphases et articles obtenus Download PDF

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Publication number
WO1986006397A1
WO1986006397A1 PCT/FR1986/000135 FR8600135W WO8606397A1 WO 1986006397 A1 WO1986006397 A1 WO 1986006397A1 FR 8600135 W FR8600135 W FR 8600135W WO 8606397 A1 WO8606397 A1 WO 8606397A1
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WO
WIPO (PCT)
Prior art keywords
weight
ethylene
acrylate
alkyl
maleic anhydride
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.)
Ceased
Application number
PCT/FR1986/000135
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English (en)
French (fr)
Inventor
Lionel Guerdoux
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.)
Orkem SA
Original Assignee
Chimique des Charbonnages 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 Chimique des Charbonnages SA filed Critical Chimique des Charbonnages SA
Priority to DE8686902430T priority Critical patent/DE3662105D1/de
Publication of WO1986006397A1 publication Critical patent/WO1986006397A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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

Definitions

  • the present invention relates to muitiphase thermoplastic compositions with improved impact properties and articles obtained from said compositions.
  • Matrix compositions of polyamides and ethylenic polymers are already known for their impact resistance.
  • document EP-A-096.264 describes a material with high impact resistance containing:
  • thermoplastic nylon having a relative viscosity of 2.5 to 5, and (B) from 5 to 60% by weight, relative to (A), of a non-crosslinked ternary copolymer consisting of:
  • document US-A-3,373,223 describes a polymer alloy essentially consisting of 25 to 90% by weight of polyolefin, 5 to 70% by weight of polyamide and 1 I 10% by weight of an ethylene / acid copolymer (meth )acrylic.
  • these compositions have improved impact resistance compared to the polyamide matrix used alone, this improvement remains insufficient for many applications requiring excellent impact resistance.
  • the object of the present invention therefore consists in obtaining muitiphase thermoplastic compositions having excellent impact resistance, in particular at low temperature.
  • a first object of the present invention relates to compositions comprising from 50 to 95% by weight of at least one polyamide resin and from 5 to 50% by weight of at least one ethylene polymer containing from 0.9 to 16% in moles of units derived from maleic anhydride and / or from at least one alkyl acrylate or methacrylate in which the alkyl group has from 1 to 6 carbon atoms, characterized in that said ethylene polymer is present in the form of a mixture of ethylene / (methyl) acrylate copolymer (A) and of ethylene / maleic anhydride / (methyl) acrylate terpolymer (B), the weight ratio (A) / (B) being between 1/3 and 3.
  • the copolymer (A) comprises from 3 to 20 mol% of units derived from alkyl acrylate or methacrylate and has a melt index (measured according to the standard
  • the terpolymer (B) comprises from 0.3 to 2 mol% of units derived from maleic anhydride and from 0.3 to 3 mol% of units derived from acrylate or alkyl methacrylate and has a melt index (measured according to standard ASTM D 1238-73) of between 1 and 50 dg / min. It has in fact been found that the compositions with a polyamide matrix and with polyolefinic compounds known hitherto have improved impact resistance but still insufficient for certain applications.
  • the Applicant has found that the use, as ethylene polymer, of a mixture of 25 to 75% of a copolymer as defined above and of 75 to 25% of a terpolymer as defined above makes it possible to improve surprisingly and notably, the impact resistance of the compositions known up to now, in particular at low temperature.
  • polyamide resin is understood to mean, in a known manner, a resin produced by condensation of equimolar amounts of a saturated dicarboxylic acid containing from 4 to 12 carbon atoms with a diamine, the diamine containing from 4 to 14 atoms of carbon. An excess of diamine can be used so as to obtain an excess of amino end groups relative to the carboxyl end groups in the polyamide.
  • polyamides include polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610) and polyhexamethylene dodecanoamide (nylon 612), polyamides produced by the cyclization of lactams, i.e.
  • polycaprolactam poly- (lauric lactam), poly- (11 amino-undecanoic acid), bis (para-aminocyclohexyl) methane dodecanamide.
  • polyamides prepared by condensation of at least two of the above polymers or of their constituents. These resins have a molecular weight of at least 5000 and preferably a melting point greater than or equal to 200oC.
  • Stabilizers, release agents, lubricants, crystallization accelerators, plasticizers, pigments, dyes or mineral fillers can also be incorporated into the compositions. According to a variant, it is thus possible to stiffen the compositions described above by adding to it a large proportion of mineral fillers, advantageously up to 50 parts by weight of at least one mineral filler per 100 parts by weight of the total of polyamide resin. , from copo lymer and terpolymer.
  • the pulverulent mineral filler or in the form of fibers or platelets can, for example, be chosen from glass fibers, glass beads, mica, talc, clays, aluminates and silicates, for example calcium, alumina, alumina hydrate, carbon black, carbon or boron fibers, asbestos, oxide, hydroxide, carbonate and sulphate of magnesium or calcium, iron oxides, antimony, zinc , titanium dioxide, barium sulfate, bentonite, diatomaceous earth, kaolin, silica such as quartz, feldspar.
  • glass fibers glass beads, mica, talc, clays, aluminates and silicates, for example calcium, alumina, alumina hydrate, carbon black, carbon or boron fibers, asbestos, oxide, hydroxide, carbonate and sulphate of magnesium or calcium, iron oxides, antimony, zinc , titanium dioxide, barium sulfate, bentonite, diatomaceous earth, kaolin, silica
  • composition which is the subject of the present invention is obtained in a known manner by any technique of mixing in the molten state such as, for example, extrusion, working on an internal mixer.
  • a second object of the present invention relates to articles obtained from at least one composition described above. These articles can be obtained by any conventional method used in the thermoplastics industry, in particular articles molded by injection, or obtained by extrusion (film, pipes, plates, fibers, ...)
  • the muitiphase thermoplastic compositions obtained in the context of the present invention have a significantly improved impact resistance which makes them particularly advantageous for any application requiring this quality, in particular in the sector of the automobile and electronic industries, domestic or industrial appliances, sport stuff.
  • EXAMPLE 1 (Comparative) We consider a first control composition consisting of 80 parts of polyamide 6 marketed by the company BASF under the trademark "Ultramid B3" and of 20 parts of an ethylene / ethyl acrylate copolymer with a melt index. equal to 10.5 dg / min., the proportion of which in moles of ethyl acrylate is equal to 7.3%.
  • the composition obtained is then injected on a NETSTAL machine at a temperature in the sheath of 280oC; the injection cycle time is 18 seconds and the injection pressure 80 bars.
  • the mold temperature is 20oC.
  • Impact resistance R c obtained are expressed in kJ / m 2 as a function of the temperature T expressed in oC, in the Table below.
  • Example 1 a control composition consisting of:
  • Example 1 The following are mixed according to the operating conditions of Example 1: - 80 parts of polyamide 6 used in Example 1
  • Example 2 - 20 parts of a polymer consisting of one half by the copolymer used in Example 1 and for the other half by the terpolymer used in Example 2.
  • the composition obtained has a Charpy impact resistance R c expressed in kJ / m 2 as a function of the temperature T in oC, in the Table below.
  • Example 4 (comparative)
  • a control composition is prepared according to the operating conditions of Example 1 consisting of: - 80 parts of polyamide 66 sold by the company BASF under the trade name "Ultramid A3"
  • the composition obtained has a Charpy impact resistance R c expressed in kJ / m 2 as a function of the temperature T in ° C, in the Table below.
  • Example 1 a control composition consisting of:
  • the composition obtained has a Charpy impact resistance R c expressed in kJ / m 2 as a function of the temperature T in oC, in the table below.
  • Example 2 - 20 parts of a polymer consisting of one half by the copolymer used in Example 1 and for the other half by the terpolymer used in Example 2.
  • the composition obtained has a Charpy impact resistance R c expressed in kJ / m 2 as a function of the temperature T in oC, in the table

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)
PCT/FR1986/000135 1985-04-23 1986-04-22 Compositions thermoplastiques multiphases et articles obtenus Ceased WO1986006397A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE8686902430T DE3662105D1 (en) 1985-04-23 1986-04-22 Multiphase thermoplastic compositions and articles obtained therefrom

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR85/06105 1985-04-23
FR8506105A FR2580656B1 (fr) 1985-04-23 1985-04-23 Compositions thermoplastiques multiphases et articles obtenus

Publications (1)

Publication Number Publication Date
WO1986006397A1 true WO1986006397A1 (fr) 1986-11-06

Family

ID=9318535

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FR1986/000135 Ceased WO1986006397A1 (fr) 1985-04-23 1986-04-22 Compositions thermoplastiques multiphases et articles obtenus

Country Status (12)

Country Link
US (1) US5070145A (https=)
EP (1) EP0218665B1 (https=)
JP (1) JPS62502690A (https=)
AR (1) AR240334A1 (https=)
AU (1) AU584205B2 (https=)
CA (1) CA1277058C (https=)
DE (1) DE3662105D1 (https=)
FR (1) FR2580656B1 (https=)
GR (1) GR860999B (https=)
IL (1) IL78532A (https=)
NZ (1) NZ215923A (https=)
WO (1) WO1986006397A1 (https=)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0275518A1 (de) * 1986-12-30 1988-07-27 BASF Aktiengesellschaft Thermoplastische Formmassen auf der Basis von Polyamiden und Ethylencopolymerisaten
US5047478A (en) * 1986-08-28 1991-09-10 Sumitomo Chemical Co., Ltd. Thermoplastic resin composition
AU699659B2 (en) * 1994-11-22 1998-12-10 Elf Atochem S.A. Flexible translucent polyamide-based composition, process for its conversion and articles obtained from this composition
WO2008122743A3 (fr) * 2007-03-07 2008-12-18 Arkema France Utilisation d'une composition a base de polyamide pour des tuyaux flexibles destines a vehiculer du petrole ou du gaz et tuyau flexible a base d'une telle composition

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JPS62149745A (ja) * 1985-12-25 1987-07-03 Sumitomo Chem Co Ltd ポリアリ−レンエステル樹脂組成物
JPH0674377B2 (ja) * 1985-12-26 1994-09-21 住友化学工業株式会社 樹脂組成物
CA1290878C (en) * 1986-02-15 1991-10-15 Kentaro Mashita Thermoplastic resin composition
DE3751001T2 (de) * 1986-10-01 1995-05-24 Mitsui Petrochemical Ind Amorphe Polyester-Zusammensetzungen und ihre Verwendungen.
US5112908A (en) * 1986-12-23 1992-05-12 E. I. Du Pont De Nemours And Company Tough polyamide compositions having high melt flow for complex moldings
US5274033A (en) * 1986-12-23 1993-12-28 E. I. Du Pont De Nemours And Company Tough high melt flow polyamides
CA1319457C (en) * 1986-12-23 1993-06-22 Bennett Noah Epstein Tough high melt flow polyamides
FR2617176A1 (fr) * 1987-06-25 1988-12-30 Charbonnages Ste Chimique Compositions de polymeres thermoplastiques
FR2625215B1 (fr) * 1987-12-23 1990-04-27 Charbonnages Ste Chimique Compositions thermoplastiques a base de polyester sature et articles moules les contenant
JPH0715059B2 (ja) * 1987-12-26 1995-02-22 ユニチカ株式会社 耐ピンホール性に優れたポリアミドフィルム
AU616730B2 (en) * 1988-02-29 1991-11-07 Kuraray Co., Ltd. Multilayered container
GB2225583A (en) * 1988-12-05 1990-06-06 Du Pont Canada Films of polyamide and grafted olefin copolymer
US5317059A (en) * 1990-07-09 1994-05-31 Ferro Corporation Impact-resistant polymer blends of olefin polymers, polyamides, and terpolymer compatibilizers
DE4026475A1 (de) * 1990-08-22 1992-02-27 Bayer Ag Ternaere mischungen
US5124377A (en) * 1991-04-30 1992-06-23 Miles Inc. Flame retardant polycarbonate composition having improved impact strength
FR2689514B1 (fr) * 1992-04-03 1994-05-20 Elf Atochem Sa Composition thermoplastique multiphase a base de resine polyamide contenant un polymere d'ethylene a fonction epoxyde.
FR2716886B1 (fr) * 1994-03-04 1996-04-26 Atochem Elf Sa Composition de résines thermoplastiques.
US6407164B1 (en) 1994-03-04 2002-06-18 Atofina Sa Multiphase thermoplastic compositions
US5589544A (en) * 1994-07-06 1996-12-31 Advanced Elastomer Systems, L.P. Soft thermoplastic elastomers having improved resistance to oil swell and compression set
DE69602048T2 (de) 1995-03-09 1999-11-11 Elf Atochem S.A., Puteaux Auf Polyamid basierende Schläuche zum Kraftstofftransport
ES2153548T3 (es) * 1995-10-05 2001-03-01 Atofina Procedimiento de tratamiento de suelos mediante fumigacion.
US5674579A (en) * 1995-11-20 1997-10-07 Elf Atochem S.A. Flexible translucent polyamide composition
US5624303A (en) * 1996-01-22 1997-04-29 Micron Technology, Inc. Polishing pad and a method for making a polishing pad with covalently bonded particles
FR2743746B1 (fr) 1996-01-23 1998-04-03 Atochem Elf Sa Nouveau film de relachement pour produit de compoundage de moulage de feuilles
EP0787771A1 (fr) * 1996-01-31 1997-08-06 Elf Atochem S.A. Compositions à base de polyamides et de polyolefines très souples en flexion
FR2747392B1 (fr) * 1996-04-16 1998-05-22 Atochem Elf Sa Pieces injectees en polyamide qui comprennent un modifiant choc ayant une repartition particuliere dans le polyamide
FR2747391B1 (fr) * 1996-04-16 1998-05-22 Atochem Elf Sa Pieces injectees en polyamide et resistant au choc
EP0807519A3 (fr) * 1996-05-14 1999-12-08 Elf Atochem S.A. Films multicouches soudables par haute fréquence
DE69730296T2 (de) * 1996-06-05 2005-09-08 Atofina Flexible thermoplastische harze mit verbesserter zugstärke
ES2296304T3 (es) * 1996-07-23 2008-04-16 Arkema France Composiciones a base de poliamida resistentes al choque.
WO1998030389A1 (fr) * 1997-01-06 1998-07-16 Elf Atochem S.A. Film antistatique pour l'emballage de matieres qui diffusent des produits volatils
US5938801A (en) * 1997-02-12 1999-08-17 Micron Technology, Inc. Polishing pad and a method for making a polishing pad with covalently bonded particles
ES2229457T3 (es) 1997-02-26 2005-04-16 Arkema Composiciones flexibles en base de poliamida y aptas para la extrusion soplado.
FR2791116B1 (fr) 1999-03-16 2001-04-27 Atochem Elf Sa Tube antistatique a base de polyamides pour transport d'essence
FR2794837B1 (fr) 1999-06-10 2001-08-10 Atofina Tube pour le transport d'essence
FR2797880B1 (fr) 1999-08-27 2005-03-11 Atofina Resines thermoplastiques modifiees par des copolymeres a base d'acrylates lourds
ATE404619T1 (de) * 2002-04-12 2008-08-15 Procter & Gamble Flüssigkeitsundurchlässige, wasserdampfdurchlässige schichten und folien mit thermoplastischen hydrophilen polymerzusammensetzungen und erhöhter festigkeit
US20060006144A1 (en) * 2004-07-09 2006-01-12 S & C Electric Co. Arc-extinguishing composition and articles manufactured therefrom
US20080237194A1 (en) 2004-07-09 2008-10-02 S & C Electric Co. Metal-hydrate containing arc-extinguishing compositions and methods
US20060094807A1 (en) * 2004-09-09 2006-05-04 Prejean George W Injectable moldable thermoplastic compositions
FR2907125B1 (fr) 2006-10-12 2012-09-21 Arkema France Composition resistant au choc a base de resine polyamide et d'un melange d'au moins un copolymere greffe a blocs polyamides et de polymere ethylenique basse densite
US8980415B2 (en) 2010-12-03 2015-03-17 Benoit Ambroise Antistatic films and methods to manufacture the same
JP6121995B2 (ja) 2011-06-21 2017-04-26 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 熱安定化ポリアミド充填アクリレートポリマーの製造方法
JP6110373B2 (ja) 2011-06-21 2017-04-05 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 熱安定化アクリレートエラストマー組成物およびその製造方法
FR2979521B1 (fr) 2011-09-01 2013-08-23 Arkema France Film photocatalytique pour la fumigation des sols
US9068066B2 (en) 2012-12-04 2015-06-30 E I Du Pont De Nemours And Company Heat resistant hydrocarbon elastomer compositions
US9051460B2 (en) 2012-12-04 2015-06-09 E.I. Du Pont De Nemours And Company Heat resistant hydrocarbon elastomer compositions
US9062193B2 (en) 2012-12-04 2015-06-23 E. I. Du Pont De Nemours And Company Heat aging resistant ethylene vinyl acetate copolymer composition and process for its production
FR3028148B1 (fr) * 2014-11-10 2017-05-19 Arkema France Film autoadhesif pour la fumigation des sols
CN108912672A (zh) * 2018-08-10 2018-11-30 江苏德威新材料股份有限公司 一种光纤电缆用尼龙紧包护套材料及其制备方法和应用

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5047478A (en) * 1986-08-28 1991-09-10 Sumitomo Chemical Co., Ltd. Thermoplastic resin composition
EP0275518A1 (de) * 1986-12-30 1988-07-27 BASF Aktiengesellschaft Thermoplastische Formmassen auf der Basis von Polyamiden und Ethylencopolymerisaten
US4847330A (en) * 1986-12-30 1989-07-11 Basf Aktiengesellschaft Thermoplastic molding materials based on nylons and ethylene copolymers
AU699659B2 (en) * 1994-11-22 1998-12-10 Elf Atochem S.A. Flexible translucent polyamide-based composition, process for its conversion and articles obtained from this composition
WO2008122743A3 (fr) * 2007-03-07 2008-12-18 Arkema France Utilisation d'une composition a base de polyamide pour des tuyaux flexibles destines a vehiculer du petrole ou du gaz et tuyau flexible a base d'une telle composition
RU2504709C2 (ru) * 2007-03-07 2014-01-20 Аркема Франс Гибкая труба, предназначенная для транспортировки нефти или газа
EP3181345A1 (fr) * 2007-03-07 2017-06-21 Arkema France Utilisation d'une composition a base de polyamide pour des tuyaux flexibles destines a vehiculer du petrole ou du gaz et tuyau flexible a base d'une telle composition

Also Published As

Publication number Publication date
AU584205B2 (en) 1989-05-18
IL78532A0 (en) 1986-08-31
CA1277058C (fr) 1990-11-27
FR2580656A1 (fr) 1986-10-24
NZ215923A (en) 1988-05-30
US5070145A (en) 1991-12-03
JPH0225941B2 (https=) 1990-06-06
AR240334A1 (es) 1990-03-30
JPS62502690A (ja) 1987-10-15
IL78532A (en) 1990-07-26
AU5777486A (en) 1986-11-18
FR2580656B1 (fr) 1987-09-11
EP0218665A1 (fr) 1987-04-22
EP0218665B1 (fr) 1989-02-15
GR860999B (en) 1986-08-13
DE3662105D1 (en) 1989-03-23

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