EP0605583A1 - Poly(meta-xylylene adipamide) tenace a module de flexion eleve - Google Patents

Poly(meta-xylylene adipamide) tenace a module de flexion eleve

Info

Publication number
EP0605583A1
EP0605583A1 EP92920629A EP92920629A EP0605583A1 EP 0605583 A1 EP0605583 A1 EP 0605583A1 EP 92920629 A EP92920629 A EP 92920629A EP 92920629 A EP92920629 A EP 92920629A EP 0605583 A1 EP0605583 A1 EP 0605583A1
Authority
EP
European Patent Office
Prior art keywords
terpolymer
composition
poly
ethylene
acrylate
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
EP92920629A
Other languages
German (de)
English (en)
Inventor
Clifford Cheng-Shiou Chang
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0605583A1 publication Critical patent/EP0605583A1/fr
Ceased legal-status Critical Current

Links

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
    • 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
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • This invention relates to an improved poiyamide composition that is very tough, has low moisture sensitivity, and retains good flexural modulus.
  • Polyamides are well known industrial polymers, finding numerous applications in such diversified fields as textile fibers, molding resins, films, and composites.
  • the commercially most important poiyamide is poly(hexamethylene adipamide), also known as nylon 66; and the next most important commercial poiyamide is poly( ⁇ -caprolactam), also known as nylon 6.
  • Another, much more recently commercialized poiyamide is poIy(m-xylylene adipamide), (sometimes referred to herein as poly-MXD6), which is sold by Mitsubishi Gas Chemical Company, Inc. of Japan under the tradename "RENY". While both nylon 66 and nylon 6 can be made very tough by the addition of certain rubbery materials, as described in U.S.
  • Patent 4,174,358 to Epstein they are somewhat moisture-sensitive and have only a modest flex modulus.
  • Poly(m-xylylene adipamide) has a flex modulus that under dry conditions is about 50% higher than that of nylon 66. It also is significantly less sensitive to moisture than nylon 66.
  • poly-MXD6 has some drawbacks, such as having a very low elongation at break (less than 3%) and being very brittle (notched Izod value of 20-25 J/m). Because of those, poly-MXD6 has achieved only a limited industrial acceptance in the United States.
  • Additives such as, for example, EPDM rubber grafted with maleic anhydride (EPDMG) or ethylene/butyl acrylate/glycidyl methacrylate (E/BA/GMA) terpolymer, increase the toughness of poly-MXD6 when present in amounts of 25 % by weight or less, but the improvement is far from dramatic, and the poly-MXD6 thus toughened still fails in a brittle fashion after impact.
  • EPDM rubber grafted with maleic anhydride EPDMG
  • E/BA/GMA ethylene/butyl acrylate/glycidyl methacrylate
  • EPDMG can in some cases improve the notched Izod value of the
  • Solid phasing is a procedure for increasing the molecular weight of a poiyamide by passing an inert gas, such as nitrogen, through a bed of resin pellets, which is maintained at a temperature between the glass transition temperature and the melt temperature of the poiyamide.
  • an inert gas such as nitrogen
  • Proper solid phasing improves the toughness of rubber/poIy-MXD6 blends by increasing the melt viscosity of poly-MXD6, thus improving rubber dispersion as a result of a better viscosity match between the rubber and the poiyamide.
  • a toughened poly(m-xyIylene adipamide) composition having a flexural modulus of at least 2 MPa, when measured according to ASTM D-790 and a notched impact strength of at least 500 J/m, said composition consisting of a blend of about 50-90% of poly(m-xylylene adipamide) with complementary amounts of 5-25% of EPDM rubber grafted with about 0.2-5% of maleic anhydride or maleic anhydride precursor and about 5-25% of an E/X/Y terpolymer in which E stands for ethylene; X stands for an alkyl acrylate or methacrylate; and Y stands for glycidyl acrylate or glycidyl methacrylate, and the respective monomer percentages are about 40-90%, 10-40%, and 0.5- 20%, their sum always being 100%; all the percentages being by weight.
  • Such blends exhibit a greatly improved notched Izod impact strength, as compared with uncompounded poIy-MXD6 and a higher flex modulus than either nylon 66 or nylon 6 toughened to the same degree.
  • Poly-MXD6 is, as earlier indicated, a commercial product manufactured by Mitsubishi Gas Chemical company, Inc. This material may be available in different grades, although the particular grade used in the experiments reported in the examples, below, was designated "RENY" 6001. Quantitative analyses established that this polymer had an amine end group concentration of about 40 equivalents per 10 6 g and a carboxyl group concentration of about 80 equivalents per 10 6 g. The relative viscosity of this poiyamide was found to be about 19.
  • EPDM rubber grafted with maleic anhydride or maleic anhydride precursor can be made accordinging to the process described in U.S. Patent 3,884,882 to Caywood.
  • the term "maleic anhydride precursor” includes other unsaturated compounds capable of being grafted onto EPDM rubber and of being converted under the grafting conditions, at least in part, to maleic anhydride or of forming after grafting a succinic anhydride unit. Typical such precursors include, la., maleic acid, fumaric acid, and lower akyl monoesters of maleic and fumaric acids such as, for example, monoethyl maleate, monomethyl maleate, monoethyl fumarate, and monomethyl fumarate.
  • EPDM rubbers are well known to the art as terpolymers or tetrapolymers of ethylene with one or two ethylenically unsaturated monomers and with a diene having only one terminal double bond.
  • E/X/Y terpolymers suitable in the present invention also are well known. They can be made by copolymerization of ethylene with the other two monomers under pressure in the presence of a free radical initiator, at elevated temperatures, preferably about 100-270° C, especially 130-230° C, and at elevated pressures, preferably at least 70 MPa, and especially 140-350 MPa. This is most advanatgeously done in a continuous process, adjusting the monomer ratios according to the final comonomer composition in the terpolymer while taking into account the different respective polymerization activities of the comonomers.
  • unsaturated comonomers are well known, for example from U.S. Patents 4,351,931 to Armitage; 3,658,741 to Knutson et al.; and 3,115,485 to Bartl et al.
  • the preferred comonomer weight ratio in the E/X/Y terpolymer is about 55-83:15-35:2-10, especially 57-77:20-35:3-8.
  • E/X/Y terpolymers include ethylene/n-butyl acrylate/glycidyl methacrylate, ethylene/isobutyl acrylate/glycidyl methacrylate, elhylene/methyl methacrylate/glycidyl methacrylate, and ethylene/methyl
  • the preferred weight ratio of grafted EPDM rubber to E/X/Y terpolymer is 1:4 to 4:1, especially 1:1 to 2:1.
  • the preferred weight ratio of poly-MXD6 to the sum of grafted EPDM rubber and E/X/Y terpolymer is
  • Blending of poly-MXD6 with the other two components of the improved compositions of the present invention can be accomplished in a conventional manner in standard equipment, preferably under high shear and at an elevated temperature at which all three polymers are in the melt.
  • standard equipment preferably under high shear and at an elevated temperature at which all three polymers are in the melt.
  • Typical such equipment includes single-screw and twin-screw extruders, rubber mills, and Banbury mixers.
  • composition of the present invention may be further blended with small amounts of additional components which would not detract from the operability of the invention, such as, for example, additional plastic or elastomeric resins, antioxidants, stabilizers, pigments, plasticizers, and melt processing aids, as is generally known and practiced in the art of compounding polymers.
  • additional plastic or elastomeric resins such as, for example, additional plastic or elastomeric resins, antioxidants, stabilizers, pigments, plasticizers, and melt processing aids, as is generally known and practiced in the art of compounding polymers.
  • Example 4 Mitsubishi Gas Chemical Company, Inc., unless otherwise indicated.
  • Example 5 it first was solid phased in a stream of nitrogen at 190°C for 24 hours.
  • Example 7 it was first solid phased in a stream of nitrogen at 180°C for 3 hours.
  • EPDMG rubber was a graft of 1.5-2.0% of maleic anhydride on a backbone of an ethylene/propylene/1,4-hexadiene 70:24:6 terpolymer made according to the teachings of U.S. Patent 3,884,882
  • the E/X/Y terpolymer was a 66.7:28:5.3 ethylene/n-butyl acrylate/glycidyl methacrylate (E/BA/GMA) terpolymer.
  • Example 7 shows that solid phasing poly-MXD6 in a stream of nitrogen at 180° C for 3 hours did improve the toughness of the rubber/poly-MXD6 blends but the mode of impact failure still was brittle.
  • Examples 6 and 8 show the exceptional improvement of notched Izod impact strength obtained with a combination of grafted EPDM rubber and an E/X/Y terpolymer according to the present invention.
  • Example 9 shows that a 20:80 blend of E/BA/GMA

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

Un mélange de 50 à 90 % de poly(m-xylylène adipamide) avec 5 à 25 % de caoutchouc EPDM greffé avec de l'anhydride maléique, et de 5 à 25 % d'un terpolymère d'éthylène/acrylate ou méthacrylate d'alkyle/acrylate ou méthacrylate de glucidyle présente une résistance élevée à l'impact Izod par entaille, un module de flexion élevé, une faible sensibilité à l'humidité, ainsi qu'un bon allongement à la rupture.
EP92920629A 1991-09-26 1992-09-24 Poly(meta-xylylene adipamide) tenace a module de flexion eleve Ceased EP0605583A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US765883 1985-08-14
US76588391A 1991-09-26 1991-09-26
PCT/US1992/007907 WO1993006176A1 (fr) 1991-09-26 1992-09-24 Poly(meta-xylylene adipamide) tenace a module de flexion eleve

Publications (1)

Publication Number Publication Date
EP0605583A1 true EP0605583A1 (fr) 1994-07-13

Family

ID=25074781

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92920629A Ceased EP0605583A1 (fr) 1991-09-26 1992-09-24 Poly(meta-xylylene adipamide) tenace a module de flexion eleve

Country Status (4)

Country Link
EP (1) EP0605583A1 (fr)
JP (1) JPH06511031A (fr)
CA (1) CA2119856A1 (fr)
WO (1) WO1993006176A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2723745A1 (fr) * 1994-08-16 1996-02-23 Solvay Compositions de polyamide presentant une rheologie amelioree
US7479315B2 (en) 2002-12-10 2009-01-20 Toyo Boseki Kabushiki Kaisha Material for fuel-system part and fuel-system part comprising the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9306176A1 *

Also Published As

Publication number Publication date
CA2119856A1 (fr) 1993-04-01
JPH06511031A (ja) 1994-12-08
WO1993006176A1 (fr) 1993-04-01

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