WO2005021606A1 - Procede de fabrication de polyolefines nucleophiles et leur utilisation - Google Patents

Procede de fabrication de polyolefines nucleophiles et leur utilisation Download PDF

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Publication number
WO2005021606A1
WO2005021606A1 PCT/US2004/027135 US2004027135W WO2005021606A1 WO 2005021606 A1 WO2005021606 A1 WO 2005021606A1 US 2004027135 W US2004027135 W US 2004027135W WO 2005021606 A1 WO2005021606 A1 WO 2005021606A1
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WIPO (PCT)
Prior art keywords
amino
polyolefin
alcohol
nucleophilic
maleated
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PCT/US2004/027135
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English (en)
Inventor
Scott M. Hacker
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Honeywell International Inc.
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Publication of WO2005021606A1 publication Critical patent/WO2005021606A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • 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
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines

Definitions

  • the present invention relates to functionalized polyolefin wax, to nucleophilic polyolefins, and to methods of producing such waxes and polyolefins. More specifically, the invention relates to methods for the efficient production of polyolefins derived from maleated polyolefins and having one or more nucleophilic moieties thereon, to the nuclephilic polyolefins derived from such methods, and to the uses of such nucleophilic polyolefins.
  • U.S. Patent 4,632,962 - Gallucci is directed to graft modified polyolefins having functional hydroxyl groups, primarily for use as a compatibilizer for blends of polyolefins and polycarbonates, polyesters, polyamides and similar polymers.
  • This patent discloses specific examples based on the use of low-density polyethylene grafted with maleic anhydride and the reaction of same with limited amounts of mono-substituted amino-alcohol. Applicants have come to appreciate that there is a substantial opportunity to provide methods for the production of graft modified polyolefins having advantages and benefits that are not suggested or disclosed by U.S. Patent 4,632,962 - Gallucci, as described in detail below.
  • Anucleophilic polyolefin® refers generally to a polyolefin comprising at least one moiety capable of acting as a nucleophile to form a bond, preferably via covalent bonding, with an acidic or electrophilic moiety on another molecule.
  • nucleophilic olefins examples include nucleophilic polyolefins having a nucleophilic, pendant hydroxyl group, such preferred nucleophilic olefins being formed by reacting a maleated polyolefin with an amino-alcohol (a molecule comprising an amine moiety and at least one hydroxyl moiety) as shown in the Description in Scheme 1.
  • amino-alcohol a molecule comprising an amine moiety and at least one hydroxyl moiety
  • the present methods facilitate the production of certain nucleophilic derivatives of maleated polyolefins by reacting a maleated polyolefin with an amino-alcohol under conditions effective to produce a nucleophilic polyolefin having at least one pendant, nucleophilic hydroxyl group, with little or no undesired cross-linking between polyolefins.
  • a starting graft modified polyolefin for example a maleated polyolefin, having a relative high density of grafted moieties is capable of providing nucleophilic polyolefin products with substantial advantages.
  • a maleated polyolefin having an SAP value of at least about 20, and even more preferably at least about 25 it is preferred to utilize a maleated polyolefin having an SAP value of at least about 20, and even more preferably at least about 25.
  • applicants have discovered that the use of amino-alcohol having at least two hydroxyl groups per molecule to produce the nucleophilic polyolefin with substantial advantages relative to those made by many of the prior techniques.
  • Applicants have recognized that the use of molecules comprising two or more reactive amine and/or alcohol groups (for example, diamines, diols, triols, and amine-alcohols) for reaction with polyolefins in conventional methods to produce nucleophilic polyolefins tends to be problematic in that the diamines/diols/triols/amine-alcohols tend to react not only with the desired polyolefins to form nucleophilic polyolefins, but also with additional polyolefin molecules to form an undesired amount of cross-linking there between.
  • amines for example, diamines, diols, triols, and amine-alcohols
  • maleated polyolefins particularly those having the preferred SAP values
  • amino-alcohols according to the present invention with little or no undesired cross-linking.
  • the nucleophilic polyolefins produced according to the present invention tend to dissolve in hot xylenes (indicating a sufficiently low amount of cross-linking), and do not merely swell or gel in xylenes (as rubbery, relatively highly cross linked polymers tend to do).
  • the methods of the present invention allow for the efficient production of nucleophilic polyolefins that are not excessively rubbery and are suitable for a variety of uses, including as compatibilizers. Applicants have also discovered unexpectedly that the present methods allow for the production of nucleophilic polyolefins with low cross-linking even in the presence of very little, or preferably in the absence of, reaction solvent.
  • the present invention comprises methods of producing a nucleophilic polyolefin derived from a maleated polyolefin and an amino-alcohol comprising reacting a maleated polyolefin having an SAP of at least about 25, and in some embodiments with an SAP of at least about 40, with an amino-alcohol, preferably in a melt reaction, to produce a nucleophilic polyolefin having at least one pendant hydroxyl group.
  • nucleophilic polyolefins produced according to the present invention can be used advantageously for compatibilizing polymers, particularly polyolefins with various other polymers comprising one or more acidic and/or electrophilic moieties.
  • Applicants have recognized that a wide variety of known maleated polyolefins, while used conventionally to compatibilize mixtures of polyolefins with polymers comprising nucleophilic moieties (for example, polyamides), tend to be unsuitable for use in compatibilizing polyolefins with other polymers comprising one or more acidic and/or electrophilic moieties.
  • the anhydride group of a maleated polyolefin receives and reacts with a nucleophilic moiety on the polar polymer to form a covalent bond there between and to form a block-copolymer in situ which acts as the compatibilizer.
  • a compatibilizer that has nucleophilic moieties thereon.
  • the nucleophilic polyolefins produced according to present methods are of particular interest in such uses. Accordingly, the present invention provides a compatibilizer composition comprising a nucleophilic polyolefin produced according to the present invention.
  • the present invention also provides methods for compatibilizing a mixture comprising a polyolefin and a polar polymer having at least one electrophilic or acidic moiety comprising adding a nucleophilic polyolefin produced according to the present invention to a mixture comprising a polyolefin and a polar polymer having at least one electrophilic or acidic moiety.
  • the present invention provides glass fiber sizing agents comprising a nucleophilic polyolefin produced according to the present methods. A properly sized glass fiber is used in polypropylene composites to enhance its properties.
  • the present invention provides glass fiber sizing agents comprising a nucleophilic polyolefin produced according to the present methods, and methods of sizing a glass fiber using the glass fiber sizing agents of the present invention.
  • nucleophilic polyolefins produced according to the present methods are used to bond cement, mineral fillers (for example, talc, calcium carbonate, mica, wollastonite) and metals to additional non- polar substrates without additional expensive coupling agents.
  • mineral fillers for example, talc, calcium carbonate, mica, wollastonite
  • the present nucleophilic polyolefins are suitable for use in a variety of adhesive compositions (for adhering any of a variety of substrates), including polyurethanes.
  • the present invention provides adhesive compositions comprising a nucleophilic polyolefin of the present invention.
  • the present invention provides methods of producing a nucleophilic polyolefin comprising reacting a maleated polyolefin with an amino-alcohol, preferably in a melt reaction.
  • the general reaction scheme for reacting a maleated polyolefin (A) with an amino-alcohol (B) to form a nucleophilic polyolefin (C) having a pendant, nucleophilic hydroxyl moiety according to the present invention is shown in Scheme 1 , below.
  • P is a polyolefin backbone and X is a substituted or unsubstituted, aliphatic (cyclic or non-cyclic) or aromatic moiety, each of which moiety may (or may not) contain one or more heteroatom within the moiety backbone.
  • X is a substituted or unsubstituted, aliphatic (cyclic or non-cyclic) or aromatic moiety, each of which moiety may (or may not) contain one or more heteroatom within the moiety backbone.
  • various particular process and unit parameters can be adapted for use with the present reaction step, and a wide range of known methods and steps for combining and reacting a maleated polyolefin with an amino-alcohol in a reaction mixture can be used according to the present invention.
  • the reaction is advantageously conducted in a melt, for example, via melt grafting (as is known in the art), and the like.
  • the temperature of the reaction be above the melt temperature of the maleated polyolefin for at least a portion of the reaction.
  • the reaction temperature will thus be dependant, at least in part, on the particular polyolefin used, examples of suitable reaction temperatures include from greater than about 110°C to about 200°C, and the like.
  • the maleated polyolefin and amino-alcohol reagents are preferably and advantageously reacted in the absence of a solvent, or substantially in the absence of a solvent.
  • a reaction is considered to be conducted Asubstantially in the absence of a solvent® if it meets either, or preferably both, of the following criteria: (a) the reaction is conducted in the absence of solvent for greater than 50%, preferably greater than 75%, and more preferably greater than 90% of the reaction time; or (b) the amount of solvent present in the reaction at any given time during reaction is equal to, or less than, the total weight of maleated polyolefin and amino-alcohol reagents in the reaction, and preferably less than 2, more preferably less than 3, and even more preferably less than 1/10, the total weight of maleated polyolefin and amino-alcoho! reagents in the reaction.
  • maleated polyolefins Any of a wide variety of maleated polyolefins is suitable for use in the methods of the present invention.
  • suitable maleated polyolefins include maleated derivatives of: polyethylenes (including low density, high density, and linear low density polyethylenes), polypropylenes, polystyrenes and the like, co- and terpolymers including ethylene-butylene, EPDM (ethylene, propylene, diene monomer), EVA (ethylene-vinyl acetate), ethylene-butyl acrylate-carbon monoxide, and the like, and combinations of two or more thereof.
  • the term Apolyethylene® refers to and includes homopolymers of polyethylene and all forms of polyethylene copolymers and terpolymers, including ethylene-propylene copolymers, provided that at least about the majority of the polymer is formed of polyethylene moieties on a mole percent basis.
  • Apolypropylene® refers to and includes homopolymers of polypropylene and all forms of polypropylene copolymers and terpolymers, including propylene-ethylene copolymers, provided that at least about the majority of the polymer is formed of polypropylene moieties on a mole percent basis.
  • Certain preferred polyolefins include maleated derivatives of: polyethylenes, polypropylenes, polystyrenes, polypropylene-polyethylene, polyethylene- polypropylene, ethylene-butylene, EPDM, and the like. Certain more preferred maleated polyolefins include maleated polyethylenes, and maleated polypropylenes.
  • maleated polyethylenes are available commercially and/or are obtainable using known procedures. For example, maleated polyethylenes are available from Honeywell under the trade names A-C 575 and A-C 573, and from DuPont as products listed as part of their Fusabond E series.
  • Maleated polypropylenes are available from Honeywell under the trade names A-C 597 and A-C 950, from DuPont as products listed under the Fusabond P trade named series, and from Eastman under the trade names E-43, G-3015, and G-3003. Any of a variety of known procedures for producing maleated polyolefins from precursor compounds can be adapted for use to make starting materials suitable for use herein. For example, U.S. Patent Application No. 10/140,429 filed on May 6, 2002, incorporated herein by reference, discloses certain preferred methods for producing maleated polypropylenes suitable for use herein.
  • the graft-modified polyolefin, including the preferred maleated polyolefin, of the present invention can have a large variety and range of physical and chemical characteristics. In many preferred embodiments, however, it is preferred to utilize as a starting material of the present invention a graft modified polyolefin, including the preferred maleated polyolefin, having an SAP value of at least about 25, more preferably at least about 40, and even more preferably at least about 50. Any of a wide number of amino-alcohols is suitable for use in the present methods. Furthermore, is contemplated that the amino-alcohol of the present invention may comprise a combination of two or more amino-alcohols.
  • the amino alcohol of the present invention comprises at least about 25 mole percent, and in certain embodiments at least about 50 mole percent, of amino alcohol having at least two hydroxyl groups per molecule. In such embodiments, the balance of the amino-alcohol will be mono-hydroxy amino alcohols. In certain preferred embodiments, the amino alcohol of the present invention consists essentially of amino alcohol having at least two hydroxyl groups per molecule.
  • suitable amino-alcohols include: aliphatic and cycloaliphatic mono-alcohols, such as, ethanolamine, 2-(2-aminoethylamino)ethanol (AEAE), 2-(2- aminoethoxy)ethanol, 3-amino-1-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 1-amino-2-butanol, 2-amino-1-butanol, 1-amino-2-propanol, 2- amino-1-propanol, 2-amino-3-methyl-1-butanol, 2-amino-cyclohexanol, 4-amino- cyclohexanol, leucinol, and the like; aliphatic aminodiols, such as, 2-amino-2-ethyl- 1 ,3-propanediol, 2-amino-1 ,3-propanediol
  • amino-alcohols examples include aliphatic and cycloaliphatic mono-alcohols, such as, ethanolamine, 2-(2-aminoethylamino)ethanol (AEAE), and the like.
  • AEAE 2-(2-aminoethylamino)ethanol
  • the amounts of maleated polyolefin and amino-alcohol for use in any particular application will depend on a number of factors, including the particular polyolefin and amino-acid reagents used. Preferably, the amounts are selected according to the factors highlighted herein to produce a nucleophilic polyolefin according to the present invention with little or no cross-linking.
  • the amount of amino-alcohol used, relative to the amount of maleated polyolefin, may vary, at least in part, depending on the number of alcohol moieties on the amino-alcohol and on the characteristics of the graft modified polyolefin. For example, applicants have recognized generally that the greater the number of alcohol moieties on the amino-alcohol reagent the more molar equivalents of it are required to react efficiently therewith according to the present invention.
  • the molecular weight of the graft modified polyolefin, and in particular the maleated polyolefin, used in the process, in conjunction with the saponifioation number (SAP) of the polyolefin affect the relative amounts of reagents that are preferred for effective use in accordance with the methods of the present invention.
  • SAP saponifioation number
  • the present methods comprise reacting a maleated polyolefin, preferably a maleated polyolefin with an SAP of at least about 25, with an amino-(mono)alcohol in an amount of from about 0.8 to about 1.3 equivalents of amino-alcohol to maleated polyolefin in the reaction, more preferably from about 0.9 to about 1.2 equivalents, and even more preferably from about 1 to about 1.1 equivalents.
  • the present methods comprise reacting a maleated polyolefin, preferably a maleated polyolefin with an SAP of at least about 25, with an amino-diol in an amount of from about 1.3 to about 2.2 equivalents of amino-alcohol to maleated polyolefin, more preferably from about 1.4 to about 2.1 equivalents, and even more preferably from about 1.5 to about 2 equivalents.
  • Certain embodiments of the present methods comprise reacting a maleated polyolefin, preferably a maleated polyolefin with an SAP of at least about 25, with an amino-triol in an amount of that is greater than about 2 equivalents to about 3.5 equivalents of amino-alcohol to maleated polyolefin, more preferably from greater than about 2 equivalents to about 3.3 equivalents, and even more preferably from greater than about 2 equivalents to about 3.1 equivalents.
  • those of skill in the art will be readily able to select appropriate amounts of maleated polyolefin and amino-alcohol for use in the present methods without undue experimentation.
  • the present methods may be conducted on a continuous basis, on a batch basis, or on a combination of both. In light of the teachings set forth herein, those of skill in the art will be able to adapt the present invention to any of these modes of operation without undue experimentation.
  • Example 1 A-C 575 (750 gm) was melted and heated to 170°C. One equivalent (25.8 gm) of 2-(2-aminoethylamino)-ethanol (AEAE) was added all at once. There was initially some foaming which caused the polymer melt to rise. Water formed simultaneously in the condenser, suggesting rapid reaction to form the imide, with the liberated water acting as a foaming agent. The melt has thickened which contributes to the foaming problem. IR after 5 minutes reaction showed a new peak that was assigned to the imide - no starting anhydride peaks are seen.
  • AEAE 2-(2-aminoethylamino)-ethanol
  • Example 2 A-C 575® (400 gm) was melted and heated to 170°C to fully dehydrate the sample and then cooled to 115°C. 2-(2-Aminoethylamino)-ethanol (AEAE, 1.1 equivalent (28.3 gm)) was added all at once. There was initially some foaming which caused the polymer melt to rise. Water formed simultaneously in the condenser, suggesting rapid reaction to form the imide, with the liberated water acting as a foaming agent. The melt has thickened and become somewhat clumpy. IR after 5 minutes reaction showed a new peak that was assigned to the imide. The temperature was raised to 170°C over ⁇ 60 minutes to facilitate reaction of any acid- ester with free amine to form the imide.
  • AEAE 2-(2-Aminoethylamino)-ethanol
  • the temperature was held at 170°C for 30 minutes. A vacuum was applied to remove any unreacted AEAE. There was noticeable discoloration so the vacuum was replaced with nitrogen after five minutes.
  • the well-behaved melt (non-rubbery or gelatinous) was discharged and cooled under nitrogen. The product was light brown with an Acid Number of 1.2, a SAP of 3.1 and a viscosity of 8,320 cps @ 140°C.
  • Example 4 Example 3 is repeated using 400 gm of maleated polyethylene and 16 gm of the amino-diol ( ⁇ 1.5 equivalents.). The melt thickens appreciably but does not clump or climb the stir shaft. After six hours the thick, somewhat elastic melt is discharged. The material dissolves in hot xylene and has a viscosity of 7,800 cps @ 190°C.
  • Example 5 A-C 575® (400 gm) is melted at 180°C. Two equivalents (32 gm) of the amino-diol are added all at once. The melt is stirred for 5 hours at temperature. The brown and viscous melt is discharged. The material dissolves in hot xylene and has a viscosity of 2,330 cps @ 190°C.
  • Example 6 Maleated polyethylene with a SAP of -26 (400 gm) is melted and brought to a temperature of 190°C whereupon 22.1 gm ( ⁇ 2 equivalents) of tris(hydroxymethyl)aminomethane (amino-triol) is added. The melt thickens but remains well behaved. The temperature held for 2 A hours before it is gradually raised to 200°C where it is held for 1 hour. The well-behaved melt is discharged. The orange product has a viscosity of 2,755 cps@ 190°C.
  • Comparative Example 2 The maleated polyethylene (2000 gm, SAP ⁇ 26) was heated to 180°C to melt. 2-Amino-2-ethyl-1 ,3-propanediol (58 gm, ⁇ 1.1 eq.) was added all at once. A thick, rubbery "ball” of wax forms around the agitator. The stirring rate is decreased to prevent the mass from climbing the agitator shaft. After approximately five hours, the thick rubbery mass is discharged.
  • 2-Amino-2-ethyl-1 ,3-propanediol 58 gm, ⁇ 1.1 eq.
  • Comparative Example 3 A-C 575 (400 gm) is melted at 190°C. Amino-triol (32.5 gm, ⁇ 2 eq.) is added all at once. The melt thickens and is held at temperature (190°C) for five hours. The rubbery mass is discharged.

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Abstract

L'invention concerne des procédés de fabrication de polyoléfines nucléophiles, qui consistent à faire réagir une polyoléfine greffe modifiée telle qu'une polyoléfine maléate, avec une amine et/ou un composé fonctionnel d'alcool, tel qu'une amino-alcool, dans des conditions efficaces pour produire une polyoléfine nucléophile possédant au moins un groupe hydroxyle nucléophile latéral, avec peu ou aucune réticulation indésirable entre polyoléfines. Dans un aspect, on utilise une polyoléfine maléate possédant une densité relativement élevée de groupes fonctionnels greffés. Dans un autre aspect, on utilise de préférence des alcools aminés possédant au moins deux groupes hydroxyles par molécule.
PCT/US2004/027135 2003-08-21 2004-08-20 Procede de fabrication de polyolefines nucleophiles et leur utilisation WO2005021606A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007025272A2 (fr) * 2005-08-26 2007-03-01 Honeywell International Inc. Premelanges biocides

Citations (8)

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US3269946A (en) * 1961-08-30 1966-08-30 Lubrizol Corp Stable water-in-oil emulsions
US3948909A (en) * 1974-06-26 1976-04-06 Toa Nenryo Kogyo Kabushiki Kaisha Ashless detergent dispersant for hydrocarbon oils
GB1441600A (en) * 1971-07-01 1976-07-07 Lubrizol Corp Dispersant compositions
US4102798A (en) * 1974-03-27 1978-07-25 Exxon Research & Engineering Co. Oxazoline additives useful in oleaginous compositions
US4632962A (en) * 1984-12-24 1986-12-30 General Electric Company Hydroxyl group graft modified polyolefins
US4654401A (en) * 1984-12-24 1987-03-31 General Electric Company Hydroxyl group graft modified polyolefins
US5128056A (en) * 1988-08-01 1992-07-07 Exxon Chemical Patents Inc. Ethylene alpha-olefin copolymer substituted amino phenol mannich base lubricant dispersant additives
US5871554A (en) * 1989-12-13 1999-02-16 Exxon Chemical Patents Inc. Polyolefin-substituted amines grafted with poly(aromatic-n-monomers) for olegaginous compositions

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3269946A (en) * 1961-08-30 1966-08-30 Lubrizol Corp Stable water-in-oil emulsions
GB1441600A (en) * 1971-07-01 1976-07-07 Lubrizol Corp Dispersant compositions
US4102798A (en) * 1974-03-27 1978-07-25 Exxon Research & Engineering Co. Oxazoline additives useful in oleaginous compositions
US3948909A (en) * 1974-06-26 1976-04-06 Toa Nenryo Kogyo Kabushiki Kaisha Ashless detergent dispersant for hydrocarbon oils
US4632962A (en) * 1984-12-24 1986-12-30 General Electric Company Hydroxyl group graft modified polyolefins
US4654401A (en) * 1984-12-24 1987-03-31 General Electric Company Hydroxyl group graft modified polyolefins
US5128056A (en) * 1988-08-01 1992-07-07 Exxon Chemical Patents Inc. Ethylene alpha-olefin copolymer substituted amino phenol mannich base lubricant dispersant additives
US5871554A (en) * 1989-12-13 1999-02-16 Exxon Chemical Patents Inc. Polyolefin-substituted amines grafted with poly(aromatic-n-monomers) for olegaginous compositions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007025272A2 (fr) * 2005-08-26 2007-03-01 Honeywell International Inc. Premelanges biocides
WO2007025272A3 (fr) * 2005-08-26 2007-08-30 Honeywell Int Inc Premelanges biocides
CN102246761A (zh) * 2005-08-26 2011-11-23 霍尼韦尔国际公司 生物杀灭剂预混合物

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