WO1998003565A1 - Modificateurs acides multifonctionnels pour systemes polymeres contenant de l'acide - Google Patents

Modificateurs acides multifonctionnels pour systemes polymeres contenant de l'acide Download PDF

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Publication number
WO1998003565A1
WO1998003565A1 PCT/US1997/011724 US9711724W WO9803565A1 WO 1998003565 A1 WO1998003565 A1 WO 1998003565A1 US 9711724 W US9711724 W US 9711724W WO 9803565 A1 WO9803565 A1 WO 9803565A1
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WIPO (PCT)
Prior art keywords
acid
weight
composition
parts
component
Prior art date
Application number
PCT/US1997/011724
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English (en)
Inventor
Jeffrey A. Gates
Original Assignee
Henkel Corporation
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 Henkel Corporation filed Critical Henkel Corporation
Publication of WO1998003565A1 publication Critical patent/WO1998003565A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids

Definitions

  • the present invention generally relates to polycarboxylic acids used as modifiers for acid-containing polymers. More particularly, by introducing polycarboxylic acids into acid-containing polymers and ionomeric resins, the rheological properties of the resins can be modified.
  • Ionomeric resins are polymers containing interchain ionic bonding.
  • Ionomeric resins are ionic copolymers of an olefin, such as ethylene, and a metal salt of an unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, or maleic acid.
  • an additional softening comonomer such as an acrylic ester can also be included to form a terpolymer.
  • the pendent ionic groups in the ionomeric resins interact to form ion-rich aggregates contained in a non-polar matrix.
  • the ionic copolymers generally comprise one or more ⁇ -olefins and from about 9 to about 30 weight percent of ⁇ , ⁇ -ethylenically unsaturated mono- or dicarboxylic acid, the basic copolymer neutralized with metal ions to
  • Suitable olefins for use in preparing the ionomeric resins include ethylene, propylene, butene-1 , hexane-1 , and the like.
  • Unsaturated carboxylic acids include acrylic, methacrylic, ethacrylic, ⁇ -chloroacrylic, crotonic, maleic, fumaric, itaconic acids, and the like.
  • metal ions such as sodium, zinc, magnesium, lithium, potassium, calcium, etc.
  • metal ions such as sodium, zinc, magnesium, lithium, potassium, calcium, etc.
  • polycarboxylic acids can be used as additives to modify the physical properties of ionomeric resins.
  • the present invention is thus directed to a novel polymeric composition containing a blend
  • the present invention also provides a process for modifying the Theological properties of ionomeric polymer resins involving blending the
  • ionomers with from about 1 to about 20 pph, per 100 parts of ionomeric polymer resin, of a polycarboxylic acid.
  • a preferred class of ionomers are copolymers of alpha-olefins containing, for example, about 2 to about 10, preferably 2 to 6 carbon atoms with from about 0.2 to 50 mol% and, preferably about 3 to 30 mol% of an unsaturated monocarboxylic acid having from about 3 to about 8 carbon atoms, in which up to 70% of the carboxyl groups are neutralized with cations having a valence of 1 to 3.
  • the neutralizing cations are metals from Groups IA, IIA, IIA, and the transitions elements of the Periodic Table, e.g., transition elements such as zinc, alkaline earth metals such as calcium and magnesium, and alkali metals such as sodium and potassium.
  • the ionomer may have a molecular weight within a wide range as indicated, for example, by a number average
  • Suitable alpha-olefins which may be used in the preparation of the contemplated ionomers are ethylene, propylene, butene-1 , pentene-1 , hexene- 1, heptene-1, 3-methylbutene-1 , and 4-methylbutene-1.
  • the preferred alpha- olefin is ethylene.
  • the alpha, beta-ethylenically unsaturated carboxylic acids which can be copolymerized with the alpha-olefin preferably have 3 to 8 carbon atoms.
  • examples of such acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid monoesters of dicarboxylic acids, such as methyl hydrogen maleate, methyl hydrogen fumarate, and ethyl hydrogen fumarate, and maleic anhydride, which is considered to be an acid in the present invention.
  • the olefin content of the ionic copoiymer should be at least 50 mol percent, more than one olefin can be employed to provide the hydrocarbon segments of the copoiymer.
  • alpha, beta- ethylenically unsaturated carboxylic acid may also be employed.
  • any third copolymerizable monomer can be employed in combination with the olefin and the carboxylic acid comonomer.
  • Preferred termonomers are vinyl
  • esters and acrylates e.g., vinyl alkanoates and alkyl acrylates and methacrylates having up to eight carbon atoms, such as vinyl acetate, vinyl propionate, methyl methacrylate, ethyl acrylate and isobutyl acrylate.
  • suitable commercial ionomers are those sold by DuPont Company under the trademark SURLYN ® .
  • a particularly preferred ionomer for use in the present invention is the reaction product of ethylene and methacrylic acid.
  • the reaction product thus formed preferably has a degree of neutralization of up to 100% of the ionomer,
  • the neutralization can be performed using ions selected from the group consisting of sodium, zinc, lithium, aluminum and potassium.
  • the polycarboxylic acids which may be employed in the present invention are, in general, those organic acids containing two or more carboxyl (COOH) groups.
  • Dibasic acids ranging from succinic acid, i.e., 4 carbon diacids, to dimer acid, i.e., 36 carbon diacids, as well as 54 carbon trimer acids or those of higher functionality may also be used.
  • a particularly preferred group of polycarboxylic acids are those selected from the group consisting of adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, and mixtures thereof, including their salts.
  • polycarboxylic acids can be combined with ionomeric polymer resins in order to modify their rheological and physical properties. For example, by blending a multifunctional acid with an ionomer, one can modify the ionomer's tensile strength, flex modulus and peel strength.
  • a polymeric composition in accordance with the present invention contains a blend of 100 parts by weight of an ionomer resin and from about 1 to about 20 parts by weight, and preferably from about 2 to about 10 parts by weight of a polycarboxylic acid per 100 parts of ionomer resin.
  • the ionomer resin is preferably the reaction product of ethylene and methacrylic acid, with the resultant ionomer having a degree of neutralization of up to 100%, and most preferably up to about 70%.
  • the polycarboxylic acid is preferably chosen from adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and dimer acid, their salts, and mixtures thereof.
  • novel polymeric composition of the invention formed by blending the ionomeric resin with the polycarboxylic acid, as stated above, can have a degree of neutralization of up to about 100% based on the novel polymeric composition as a whole, and preferably up to about 50%.
  • Auxiliaries may also be added to the polymeric composition such as, for example, dyes, optical brighteners, additional plasticizers and the like, in order to further alter the physical properties of the composition.
  • the polymeric composition of the present invention can be produced from either solution, from a melt phase or by dry blending.
  • the ionomeric resins and the polycarboxylic acids are blended in a Banbury type mixer, two-roll mill or extruded.
  • the polymeric composition is blended using a twin-screw extruder. The blended polymeric composition can then be formed into slabs or pellets and stored in such a state until molding.
  • the present invention utilizes compounding/blending techniques, which are significantly less costly than changing the polymer's chemical structure, to achieve the same variation in physical properties.
  • Polymeric compositions in accordance with the present invention were prepared by twin-screw extrusion and injection molded in order to evaluate their physical properties.
  • the polymeric compositions were formed by blending
  • SURLYN ® 9910 which is a high acid (about 15% by weight) polymer, highly neutralized with zinc, with various polycarboxylic acids, in varying amounts. Their composition and physical properties are listed in Table
  • Polymeric compositions in accordance with the present invention were prepared by twin-screw extrusion and injection molded in order to evaluate their physical properties.
  • the polymeric compositions were formed by blending 100 parts of NUCREL ® 960, which is a high acid (about 15% by weight) polymer, with various polycarboxylic acids, in varying amounts. Their composition and physical properties are listed in Table 2 below.
  • Example 3 Polymeric compositions in accordance with the present invention were prepared by twin-screw extrusion and injection molded in order to evaluate their physical properties.
  • the polymeric composition were formed by blending
  • the polymeric composition were formed by blending 100 parts of SURLYN ® 8920, which is a high acid (about 15% by weight) polymer, highly neutralized with sodium, with azelaic acid. Their composition and physical properties are listed in Table 4 below.
  • Example 5 Polymeric compositions in accordance with the present invention were prepared on a Brabender Plasticorder and compression molded in order to evaluate their physical properties. The polymeric compositions were formed
  • composition and melt index are listed in Table 6 below.
  • compositions and physical properties are listed in Table 7 below.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une composition polymère comprenant: (a) 100 parties en poids d'une résine ionomère; et (b) environ 1 à 20 parties en poids d'un acide polycarboxylique ou d'un sel de celui-ci.
PCT/US1997/011724 1996-07-19 1997-07-14 Modificateurs acides multifonctionnels pour systemes polymeres contenant de l'acide WO1998003565A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US68452896A 1996-07-19 1996-07-19
US08/684,528 1996-07-19

Publications (1)

Publication Number Publication Date
WO1998003565A1 true WO1998003565A1 (fr) 1998-01-29

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PCT/US1997/011724 WO1998003565A1 (fr) 1996-07-19 1997-07-14 Modificateurs acides multifonctionnels pour systemes polymeres contenant de l'acide

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WO (1) WO1998003565A1 (fr)
ZA (1) ZA975954B (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998036003A1 (fr) * 1997-02-18 1998-08-20 E.I. Du Pont De Nemours And Company Ionomeres modifies presentant des proprietes et des possibilites de mise en oeuvre ameliorees
WO2000023519A1 (fr) * 1998-10-21 2000-04-27 E.I. Du Pont De Nemours And Company Compositions elastomeres thermoplastiques tres elastiques
US6653382B1 (en) 1999-10-21 2003-11-25 E. I. Du Pont De Nemours And Company Highly-neutralized ethylene copolymers and their use in golf balls
WO2004043155A2 (fr) * 2002-11-12 2004-05-27 E.I. Du Pont De Nemours And Company Films ionomeriques non poreux permeables au gaz et a l'humidite
US6777472B1 (en) 1998-10-21 2004-08-17 E. I. Du Pont De Nemours And Company Highly-neutralized ethylene copolymers
US6815480B2 (en) 1998-10-21 2004-11-09 E. I. Du Pont De Nemours And Company Highly-resilient thermoplastic elastomer compositions
US6953820B2 (en) 1999-10-21 2005-10-11 E. I. Du Pont De Nemours And Company Highly-neutralized ethylene copolymers and their use in golf balls
US7335424B2 (en) 2001-03-29 2008-02-26 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
US7405008B2 (en) 2001-03-29 2008-07-29 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
CN102549061A (zh) * 2009-10-09 2012-07-04 三井-杜邦聚合化学株式会社 离子交联聚合物组合物、以及成型体及其制造方法
JP2012187134A (ja) * 2011-03-08 2012-10-04 Du Pont Mitsui Polychem Co Ltd ゴルフボール材料用アイオノマー組成物及びゴルフボール

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3620878A (en) * 1968-07-26 1971-11-16 Grace W R & Co Bonding with ethylene copolymer adhesive and adhesion promoting agent
US4136069A (en) * 1975-07-18 1979-01-23 Eastman Kodak Company Hot melt sizing compositions and fibrous articles sized therewith
US4500664A (en) * 1981-11-16 1985-02-19 The Dow Chemical Company Stabilized carboxyl-containing ethylene interpolymers
US4602058A (en) * 1984-07-02 1986-07-22 The Dow Chemical Company Compatibility and stability of blends of polyamide and ethylene copolymers
US4611017A (en) * 1983-08-31 1986-09-09 The Dow Chemical Company Stabilized carboxyl-containing ethylene interpolymers
US5296522A (en) * 1991-05-15 1994-03-22 Basf Aktiengesellschaft Electrical medium and high voltage cable with a cable sheath having high resistance to the formation and the growth of water trees

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3620878A (en) * 1968-07-26 1971-11-16 Grace W R & Co Bonding with ethylene copolymer adhesive and adhesion promoting agent
US4136069A (en) * 1975-07-18 1979-01-23 Eastman Kodak Company Hot melt sizing compositions and fibrous articles sized therewith
US4500664A (en) * 1981-11-16 1985-02-19 The Dow Chemical Company Stabilized carboxyl-containing ethylene interpolymers
US4611017A (en) * 1983-08-31 1986-09-09 The Dow Chemical Company Stabilized carboxyl-containing ethylene interpolymers
US4602058A (en) * 1984-07-02 1986-07-22 The Dow Chemical Company Compatibility and stability of blends of polyamide and ethylene copolymers
US5296522A (en) * 1991-05-15 1994-03-22 Basf Aktiengesellschaft Electrical medium and high voltage cable with a cable sheath having high resistance to the formation and the growth of water trees

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5973046A (en) * 1997-02-18 1999-10-26 E. I. Du Pont De Nemours And Company Modified-ionomers having improved properties and processability
WO1998036003A1 (fr) * 1997-02-18 1998-08-20 E.I. Du Pont De Nemours And Company Ionomeres modifies presentant des proprietes et des possibilites de mise en oeuvre ameliorees
WO2000023519A1 (fr) * 1998-10-21 2000-04-27 E.I. Du Pont De Nemours And Company Compositions elastomeres thermoplastiques tres elastiques
US6777472B1 (en) 1998-10-21 2004-08-17 E. I. Du Pont De Nemours And Company Highly-neutralized ethylene copolymers
US6815480B2 (en) 1998-10-21 2004-11-09 E. I. Du Pont De Nemours And Company Highly-resilient thermoplastic elastomer compositions
US6653382B1 (en) 1999-10-21 2003-11-25 E. I. Du Pont De Nemours And Company Highly-neutralized ethylene copolymers and their use in golf balls
US6953820B2 (en) 1999-10-21 2005-10-11 E. I. Du Pont De Nemours And Company Highly-neutralized ethylene copolymers and their use in golf balls
US7335424B2 (en) 2001-03-29 2008-02-26 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
US7405008B2 (en) 2001-03-29 2008-07-29 Exxonmobil Chemical Patents Inc. Ionomer laminates and articles formed from ionomer laminates
WO2004043155A2 (fr) * 2002-11-12 2004-05-27 E.I. Du Pont De Nemours And Company Films ionomeriques non poreux permeables au gaz et a l'humidite
WO2004043155A3 (fr) * 2002-11-12 2004-07-01 Du Pont Films ionomeriques non poreux permeables au gaz et a l'humidite
CN102549061A (zh) * 2009-10-09 2012-07-04 三井-杜邦聚合化学株式会社 离子交联聚合物组合物、以及成型体及其制造方法
EP2487201A1 (fr) * 2009-10-09 2012-08-15 Du Pont-Mitsui Polychemicals Co., Ltd. Composition d'ionomère, corps moulé et procédés de fabrication associés
US20120208940A1 (en) * 2009-10-09 2012-08-16 Du Pont-Mitsui Polychemicals Co., Ltd. Ionomer composition, formed body, and method of producing the same
EP2487201A4 (fr) * 2009-10-09 2013-04-17 Mitsui Du Pont Polychemical Composition d'ionomère, corps moulé et procédés de fabrication associés
JP2012187134A (ja) * 2011-03-08 2012-10-04 Du Pont Mitsui Polychem Co Ltd ゴルフボール材料用アイオノマー組成物及びゴルフボール

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