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EP0677070A1 - Antioxydants a ancrage aminoplaste - Google Patents

Antioxydants a ancrage aminoplaste

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Publication number
EP0677070A1
EP0677070A1 EP94904898A EP94904898A EP0677070A1 EP 0677070 A1 EP0677070 A1 EP 0677070A1 EP 94904898 A EP94904898 A EP 94904898A EP 94904898 A EP94904898 A EP 94904898A EP 0677070 A1 EP0677070 A1 EP 0677070A1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
group
aminoplast
point
linear
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.)
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Application number
EP94904898A
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German (de)
English (en)
Inventor
Jeno G. Szita
Vazken A. Alexanian
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Cytec Technology Corp
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Cytec Technology Corp
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Publication of EP0677070A1 publication Critical patent/EP0677070A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • This invention relates to the preparation and use of novel aminoplast anchored phenolic antioxidants.
  • U.S. Patent No. 4,284,790 describes an antioxidant system produced by alkylation of N,N',N"- trimethylmelamine with a meta-halomethyl substituted antioxidant.
  • the anchored antioxidant described therein does not contain any alkoxymethyl groups, but contains N-methyl groups.
  • U.S. Patent No. 4,721 ,792 describes a limited number of stabilizer species utilizing acetylenecarbamide (glycoluril) as an anchor group.
  • This invention provides novel aminoplast anchored, hindered phenolic antioxidants represented by the formula:
  • R 1 is selected from the group consisting of tertiary alkyl of 1 to 20 carbon atoms and tertiary aralkyl of 9 to 20 carbon atoms; and wherein R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of hydrogen, alkyl of 1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, and a methylene bridge attached to A, with the proviso that one of R 2 , R 3 ,
  • R 4 , or R 5 is a methylene bridge attached to A; and wherein A is an m functional aminoplast anchor molecule to which n phenol rings are attached through n methylene bridges; and wherein m is at least 1 ; and wherein n is at least 0.01; and with the proviso that
  • the aminoplast anchor molecule is selected from the group consisting of:
  • R 7 and R 8 are independently selected from the group consisting of hydrogen, alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; and wherein R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms; and
  • R 10 is selected from the group consisting of alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; and wherein R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms;
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms; and provided the (c) is not N-alkyl substituted;
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms; (h) oligomeric aminoplast anchor molecules derived from self- or cross- condensation of any of (a) through (g) and mixtures thereof; and (i) mixtures of any of (a) through (h);
  • the aminoplast anchor molecule when A is attached through a methylene bridge at a point meta- to the point of attachment of the hydroxy group, the aminoplast anchor molecule is selected from the group consisting of (a), (b), (c), (d), (e), (f), (g), (h) and (i); and (3) when A is attached through a methylene bridge at a point para- to the point of attachment of the hydroxy group, the aminoplast anchor molecule is selected from the group consisting of (b), (c), (d), (e), (f), (g), (h), and mixtures of any of (b) through (h).
  • These anchored antioxidants are useful as stabilizers for polymers such as polyethylene, polypropylene, and the like to extend their useful life. The anchored antioxidants have reduced volatility and increased compatibility compared with their unanchored precursors.
  • This invention is also an oxidation-stable composition containing the novel aminoplast-anchored antioxidants of the invention.
  • aminoplast-anchor molecules of this invention are aminoplast crosslinkers commonly used in coatings, moldings, and adhesives.
  • aminoplast is defined herein as a class of resins prepared by the reaction of an amino group-containing compound and an aldehyde.
  • aminoplast as used in the context of this invention comprises monofunctional or polyfunctional amino resins, and may be monomeric or oligomeric.
  • aminoplasts in the preparation of aminoplasts from amino group-containing compounds and aldehydes and subsequent alkylation, dimeric and oligomeric products resulting from self-condensation reaction are often obtained. These oligomeric self-condensation products are included in the "aminoplast” definition given above.
  • aminoplast anchors are described herein as being m functional, it is meant that there are m reactive groups on the aminoplast-anchor molecule, each of which can potentially react with an antioxidant stabilizer group to form the aminoplast-anchored antioxidants of this invention.
  • the aminoplast anchors of this invention include the groups represented by the formulae (1 )-(17):
  • R 7 and R 8 are independently hydrogen, alkyl or aryl groups of 1 to 20 carbon atoms;
  • R 10 is an aliphatic or cycloaliphatic alkyl group of 1 to 20 carbon atoms, such as methyl, ethyl, butyl, cyclohexyl and the like; or
  • R 10 is an aromatic group of 1 to 20 carbon atoms, such as phenyl, tolyl, naphthyl, and the like; or
  • R 10 is an aralkyl group of 1 to 20 carbon atoms, such as benzyl, cumyl, and the like;
  • R is an alkylene or an arylene of 1 to 20 carbon atoms
  • R is hydrogen or alkyl, and m is at least 1 ;
  • the aminoplasts may have, as substituents, a hydrogen, an alkyl or an aryl group of 1 to about 20 carbon atoms, or a stabilizer reactive group such as -CH 2 OH and -CH 2 OR 9 wherein R 9 is an alkyl group of 1 to about 20 carbon atoms or an aminoplast group-containing oligomeric group provided that the total number of stabilizer reactive groups per each aminoplast anchor is at least 1 , and preferably more than 1 , and further provided that melamine-type aminoplasts are not N-alkyl substituted.
  • the preferred aminoplast anchors of this invention are substantially fully etherified, substantially fully methylolated, substantially monomeric aminoplast crossiinkers commonly used in the coatings industry. They are characterized by having at least 2, and preferably more than 2 stabilizer reactive groups per anchor molecule.
  • the most preferred aminoplast anchors of the invention are selected from a group consisting of substantially fully etherified, substantially fully methylolated, substantially monomeric glycoluril, melamine, benzoguanamine, cyclohexanecarboguanamine. urea, and mixtures thereof.
  • substantially monomeric amine-aldehyde aminoplast anchors described above
  • the non-etherified or partially etherified, substantially fully methylolated or partially methylolated monomeric and oligomeric aminoplasts are also usable in the composition of this invention.
  • Aminoplast anchors which contain very few alkoxymethyl groups generally have low solubilities due to the high N-H levels, and therefore are less preferred.
  • glycoluril anchors of this invention are N-substituted glycolurils represented by the formula:
  • R R wherein at least two of the R groups are selected from the group consisting of methoxym ethyl, ethoxymethyl, propoxym ethyl, butoxymethyl, pentoxymethyl, hexoxymethyl, heptoxy methyl, octoxymethyl, nonoxymethyl, decoxymethyl and mixtures thereof, and the remaining R groups are selected from hydrogen, alkyl, hydroxymethyl, and glycoluril group-containing oligomeric moieties.
  • R is an alkyl group of 1 to about 20 carbon atoms.
  • the glycoluril anchor may contain monomeric as well as oligomeric components.
  • the monomeric tetraalkoxyglycolurils themselves are not considered to be resinous materials since they are, as individual entities, non-polymeric compounds. They are considered, however, to be potential resin-forming compounds when subjected to heat, and particularly when subjected to heat under acidic conditions.
  • the substantially monomeric glycoluril aminoplasts of this invention may produce, during the course of the reaction, varying amounts of oligomeric components such as dimers, trimers, and tetramers.
  • glycoluril anchor of this invention is POWDERLINK® 1174 powder aminoplast resin, a product of Cytec Industries Inc., West Paterson, N.J., and it has the following properties: CH -OCH - CH ,0CH - I 2 i I 2 i
  • glycoluril anchor usable in this invention is CYMEL®
  • urea usable in this invention is BEETLE® 80 butylated urea-formaldehyde resin, a product of Cytec Industries Inc., West Paterson, New Jersey, having the following properties:
  • the melamine-based aminoplast anchors are well known in the art and have been used extensively as effective crossiinkers in coatings.
  • alkoxymethylmelamine functionality can be a maximum of six in a stabilizingly effective range of 1 to 6 stabilizer- reactive alkoxymethyl groups per each meiamine molecule.
  • the melamine- based aminoplast anchors of this invention are exclusive of N-alkyl substituted melamines.
  • alkoxymethyl melamines can contain dimers, trimers, tetramers, and higher oligomers, each given combination of monomers and oligomers being preferred for a given application.
  • the lower viscosity monomer-rich compositions are preferred for solvent-based high solids coatings.
  • substantially fully etherified, substantially fully methylated, substantially monomeric melamines usable in this invention is CYMEL® 303 meiamine crosslinking agent, a product of Cytec Industries Inc., West Paterson, New Jersey, and has the following properties:
  • Non-Volatiles (% by weight) * 98 Color, Maximum (Gardner 1963) 1 Viscosity (Gardner-Holt, at 25°C) X-Z 2 Free Formaldehyde, maximum (Weight 0.5
  • CYMEL® 300 crosslinker also a product of Cytec Industries Inc, West Paterson, New Jersey, which is the solid version of CYMEL® 303, with an average degree of polymerization of 1.35.
  • CYMEL® 1168 aminoplast resin a product of Cytec Industries Inc., West Paterson, New Jersey.
  • the alkyl group in CYMEL® 1168 consists essentially of a mixture of methyl and isobutyl groups. It has the following properties:
  • R is methyl or isobutyl
  • CYMEL® 370 crosslinking agent a product of Cytec Industries Inc., West Paterson, New Jersey. It has the following properties:
  • the partially or fully methylolated or etherified alkyl and aryl guanamine aminoplasts are usable as anchors in this invention, with the selection depending on the particular application or the properties desired in the product.
  • Benzoguanamine, cyclohexylcarboguanamine and acetoguanamine aminoplasts are especially preferred as crossiinkers in this invention.
  • the benzoguanamine crossiinkers are represented by the formula:
  • R is an alkyl group of 1 to about 20 carbon atoms, or a mixture thereof.
  • An example of a benzoguanamine-based crosslinking agent is CYMEL® 1123 resin as described above, wherein R is a mixture of methyl and ethyl groups.
  • the acetoguanamine-based crossiinkers are represented by the formula:
  • R is an alkyl group of 1 to about 20 carbon atoms, or a mixture thereof.
  • the cyclohexylcarboguanamine-based crossiinkers are represented by the formula:
  • R is an alkyl group of 1 to about 20 carbon atoms, or a mixture thereof.
  • the hindered phenol-type antioxidants suitable for use as starting material in the preparation of the aminoplast anchored antioxidants of the invention are represented by the formula:
  • R 1 is selected from the group consisting of tertiary alkyl of 1 to 20 carbon atoms and tertiary aralkyl of 9 to 20 carbon atoms; and R 2 , R 3 , R 4 , and R ⁇ are each independently selected from the group consisting of hydrogen, alkyl of 1 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms.
  • the preferred hindered phenols are represented by the formulae:
  • R is an alkyl of 1 to 20 carbon atoms
  • hindered phenol-type aminoplast anchored antioxidants are represented by the formula:
  • A is an m functional aminoplast anchor molecule to which n phenol rings are attached through n methylene bridges, said bridges replacing R 3 , R 4 , or R 5 groups on said phenol rings, which aminoplast anchor molecule is selected from the group consisting of:
  • R 7 and R 8 are independently selected from the group consisting of hydrogen, alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; and wherein R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms;
  • R 10 is selected from the group consisting of alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; and wherein R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms;
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms; and provided that (c) is not N-alkyl substituted;
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms; wherein R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms;
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms; (h) oligomeric aminoplast anchor molecules derived from self- or cross- condensation of any of (a) through (g) and mixtures thereof; and (i) mixtures of any of (a) through (h); wherein m is at least 1; and wherein n is at least 0.01; and wherein R 1 is selected from the group consisting of tertiary alkyl of 1 to 20 carbon atoms and tertiary aralkyl of 9 to 20 carbon atoms; and wherein R 2 , R 3 , R 4 , and R 5 are each independently selected from the group consisting of hydrogen, alkyl of 1 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms.
  • the aminoplast anchored antioxidants of the invention are prepared by contacting a hindered phenol with an alkoxymethylated or hydroxymethylated amino resin such as those referred to herein as aminoplasts.
  • the contacting is carried out in the presence of an acid catalyst to accelerate the formation of the anchored antioxidants.
  • the acid catalyst is typically a sulfonic acid, however any acid known to catalyze the reactions of aminoplasts may be used.
  • the hindered phenol-type aminoplast anchored antioxidants wherein the methylene bridges are attached at a point para- to the point to attachment of the hydroxy group may be represented by the formula:
  • R 27 and R 28 are the same or different and are independently selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl, 1 -butyl, 2-butyl, 1-pentyl, 2-pentyl, 3-pentyl, and neopentyl groups; and wherein A is an m functional aminoplast anchor molecule-to which n phenol rings are attached through n methylene bridges, which aminoplast anchor molecule is selected from the group consisting of:
  • R 7 and R 8 are independently selected from the group consisting of hydrogen, alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; and wherein R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms;
  • R 10 is selected from the group consisting of alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; and wherein R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms;
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms; and provided that (c) is not N-alkyl substituted;
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms; wherein R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms;
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms
  • the preferred para- bridged hindered phenol-type antioxidants are those represented by the formula: wherein A is an m functional aminoplast anchor molecule to which n phenol rings are attached through n methylene bridges at a point of attachment para- to the point of attachment of the hydroxy group, which aminoplast anchor molecule is selected from the group consisting of:
  • R 9 is selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl, 1 -butyl, 2-butyl, and mixtures thereof;
  • R 9 is selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl, 1 -butyl, 2-butyl, and mixtures thereof; and provided that (b) is not N-alkyl substituted; wherein R 9 is selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, and mixtures thereof;
  • oligomeric aminoplast anchor molecules derived from self- or cross- condensation of (a), (b), (c), or mixtures thereof;
  • the preferred aminoplast anchor molecules are selected from the group consisting of:
  • oligomeric aminoplast anchor molecules derived from self- or cross- condensation of (a), (b), (c), or mixtures thereof;
  • A is a glycoluril anchor, and wherein m is 2 to 14, and wherein n is in the range of 1 to about 14, and wherein the ratio of the hindered phenol to glycoluril is from about 1 :1 to about
  • glycoluril is a mixture of monomeric, dimeric, trimeric, tetrameric, and higher oligomeric units.
  • the hindered phenol-type aminoplast anchored antioxidants wherein the methylene bridges are attached at a point meta- to the point of attachment of the hydroxy group and ortho- to R 29 may be represented by the formula:
  • A is an m functional aminoplast anchor molecule to which n phenol rings are attached through n methylene bridges at a point of attachment meta- to the point of attachment of the hydroxy group, which aminoplast is selected from the group consisting of:
  • R 7 and R 8 are independently selected from the group consisting of hydrogen, alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; and wherein R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms;
  • R 9 is selected from the group consisting of alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; and wherein R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms;
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms; and provided that (c) is not N-alkyl substituted; wherein R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms;
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms; (h) oligomeric aminoplast anchor molecules derived from self- or cross- condensation of any of (a) through (g) and mixtures thereof; and (i) mixtures of any of (a) through (h); wherein m is at least 1 ; and wherein n is at least 0.5; and wherein R 27 is selected from the group consisting of methyl, ethyl, 1 -propyl, 2- propyl, 1 -butyl, 2-butyl, 1-pentyl, 2-pentyl, 3-pentyl, and neopentyl groups; and wherein R 29 is an alkyl of 1 to 20 carbon atoms.
  • the preferred hindered phenol-type antioxidants bridged meta- to the hydroxy group are represented by the formula:
  • A is an m functional aminoplast anchor molecule to which n phenol rings are attached through n methylene bridges at a point of attachment meta- to the point of attachment of the hydroxy group, which aminoplast anchor molecule is selected from the group consisting of:
  • R 9 is selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl, 1 -butyl, 2-butyl, and mixtures thereof;
  • R 9 is selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl, 1 -butyl, 2-butyl, and mixtures thereof; and provided that (b) is not N-alkyl substituted;
  • R 9 is selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl, 1 -butyl, 2-butyl, and mixtures thereof;
  • oligomeric aminoplast anchor molecules derived from self- or cross- condensation of (a), (b), (c), or mixtures thereof;
  • the preferred aminoplast anchor molecules are selected from the group consisting of:
  • oligomeric aminoplast anchor molecules derived from self- or cross- condensation of (a), (b), (c), or mixtures thereof;
  • A is a glycoluril anchor; and wherein m is 2 to 14; and wherein n is in the range of 1 to about 14; and wherein the ratio of the hindered phenol to glycoluril is from about 1 :1 to about
  • glycoluril is a mixture of monomeric, dimeric, trimeric, tetrameric, and higher oligomeric units.
  • the hindered phenol-type aminoplast anchored antioxidant wherein the methylene bridges are attached at a point ortho- to the point of attachment of the hydroxy group may be represented by the formula: wherein A is an m functional aminoplast anchor molecule to which n phenol rings are attached through n methylene bridges at a point of attachment ortho- to the point of attachment of the hydroxy group, which aminoplast is selected from the group consisting of:
  • R 7 and R 8 are independently selected from the group consisting of hydrogen, alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; and wherein R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms;
  • R 9 is selected from the group consisting of alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; and wherein R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms; wherein R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms; and provided that (c) is not N-alkyl substituted;
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms
  • R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms; wherein R 9 is a linear or branched alkyl group of 1 to 20 carbon atoms;
  • A is an m functional aminoplast anchor molecule to which n phenol rings are attached through n methylene bridges at a point of attachment ortho- to the point of attachment of the hydroxy group, which aminoplast anchor molecule is selected from the group consisting of: wherein R 9 is selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl, 1 -butyl, 2-butyl, and mixtures thereof;
  • R 9 is selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl, 1 -butyl, 2-butyl, and mixtures thereof; and provided that (b) is not N-alkyl substituted;
  • R 9 is selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl, 1 -butyl, 2-butyl, and mixtures thereof;
  • oligomeric aminoplast anchor molecules derived from self- or cross- condensation of (a), (b), (c), or mixtures thereof;
  • A is a glycoluril anchor; and wherein m is in the range of from 2 to 14; and wherein n is in the range of from about 1 to 14; and wherein the ratio of hindered phenol to glycoluril is 3.7:1; and wherein the glycoluril anchor is a mixture of monomeric, dimeric, trimeric, tetrameric, and higher oligomeric units having an average methoxymethyl to glycoluril ratio of 0.1:1.
  • the anchored antioxidants of the invention are used as additives to stabilize thermoset or thermoplastic polymers against the degrading action of oxygen, heat, and light. They may be chemically bound to the polymer (reactive antioxidants) or they may be used as an additive to the polymer (non-reactive antioxidant).
  • the aminoplast-anchored antioxidants of the invention may participate in the crosslinking process as crosslinking agents if they possess at least two alkoxymethyl groups. If the antioxidant has only one alkoxymethyl group present, it may still react non-crosslinkingly with an alkoxym ethyl-reactive group present in a curable composition and thereby become part of the cured or crosslinked polymer.
  • aminoplast-anchored antioxidants of the invention function as "reactive" antioxidants.
  • the antioxidant In situations wherein the antioxidant contains little or no alkoxymethyl groups, the antioxidant cannot participate in the reaction which could bind the antioxidant to the polymer. In this case, it is merely an additive to the polymeric material and functions as a "non-reactive" antioxidant. Oxidation-Stable Compositions
  • This invention is also an oxidation-stable composition
  • aminoplast-anchored antioxidants (ii) usable in the oxidation stable compositions are the novel aminoplast-anchored antioxidants of the invention described hereinabove in the section entitled "AMINOPLAST ANCHORED ANTIOXIDANTS.”
  • the polymeric materials usable in the oxidation-stable composition are the polymers generally referred to as thermoset or thermoplastic polymers.
  • thermoset systems include amino resins, urethanes, epoxies, phenolplasts, and any reactive, curable system capable of forming a polymeric crosslinked material upon curing.
  • the anchored antioxidant (ii) is typically added to the curable composition prior to curing the thermoset systems to ensure uniform distribution of the additive in the crosslinked polymer.
  • thermoplastic systems include polyolefins such as polyethylene, polypropylene, polystyrene, polyacrylates, polyvinyl chloride, polyvinyl acetate or condensation polymers such as polycarbonates, polyesters, polyamides, polysulfones and the like.
  • the thermoplastic polymeric material (i) may be a mixture of at least two polymers or it may be a polymer derived from the copolymerization of at least two monomers.
  • the polypropylene resins may be any of the commercially produced polypropylenes, inducing impact-improved polypropylene polymers, polypropylene blends, and ethylene-containing polypropylene copolymers. They may be produced by polymerization of propylene or propylene-ethylene mixtures by contacting the monomers with Ziegler-Natta coordination catalysts, specifically those in which the transition metal is titanium, according to well known and widely practiced methods.
  • the anchored antioxidant (ii) is typically blended with solid polymeric material with or without other stabilizers, and the admixture thereafter is melted to obtain uniform oxidation-stable compositions.
  • the optional stabilizers include UV absorbers, hindered amine light stabilizers, phosphites, sulfides and the like.
  • the concentration of the anchored antioxidant in the oxidation-stable compositions is in the range of from about 0.01 weight percent to about 5 weight percent, with 0.1 to 1.2 weight percent range being preferred.
  • the product was purified by dissolving in acetone and pouring the acetone solution into heptane.
  • the product was the para- bridged adduct of 2,6-di- tertiarybutyl phenol with POWDERLINK® 1 174 resin.
  • Example 2 The procedure of Example 1 was repeated using 2-tertiary-butyl-4-methyl phenol instead of the 2,6-di-tertiary-butyl phenol.
  • the product was the ortho- bridged adduct having a hindered phenol to glycoluril ratio of 3.7:1 and methoxymethyl to glycoluril ratio of 0.1 :1.
  • the Number Average Molecular Weight (Mn) of the product was about 2,300.
  • polypropylene films were prepared as follows: PROFAX® 6501 Polypropylene Resin was milled at 165-175°C and then it was compression molded into an 18-20 mil (0.46-0.51 mm) film at 210°C to give the Control Film.
  • a set of three additional films were prepared as follows: The procedure in (A) was repeated with a 0.2 weight percent of the anchored antioxidant of Example 1 being added to the polypropylene in the milling step to give Stabilized Film (1 ).
  • Formulations A, B, and C were tested by exposing three films of each formulation to air at 140°C in a Forced Air Oven until degradation occurred.
  • Formulation A with no antioxidant additive, served as the control.
  • the test results are summarized in Table 1. It is concluded from the results in Table 1 that films containing the anchored antioxidants of the invention (Formulations B and C) are effective antioxidants for polypropylene, with the antioxidant having the higher hindered phenol content being the more active.
  • PROFAX 6501 Polypropylene Film Containing: Days to Failure 1
  • meta-bridged hindered phenol stabilizers One possible method of producing meta-bridged hindered phenol stabilizers would be to use an ortho-, para-blocked hindered phenol, such as 2,6 d.-tertiary-butyl-4-methyl phenol, as the hindered phenolic starting material in the above-described examples. It is well known to those skilled in the art that phenolic electrophilic substitution is favored on the aromatic ring at those positions ortho and para to the hydroxy group. By blocking the favored ortho and para positions, it should be possible to produce the meta-bridged hindered phenol stabilizers of this invention. It is expected that the meta-bridged stabilizers would be at least as effective as the ortho- and para- bridged stabilizers as anchored antioxidants.
  • an ortho-, para-blocked hindered phenol such as 2,6 d.-tertiary-butyl-4-methyl phenol

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne de nouveau antioxydants phénoliques empêchés à ancrage aminoplaste qui sont utiles comme stabilisateurs pour des revêtements et des polymères tels que du polyéthylène, du polypropylène et autre afin d'accroître leur vie utile. Les antioxydants à ancrage aminoplaste sont moins volatiles et plus compatibles que leurs précurseurs non ancrés, on peut les préparer par exemple, en faisant réagir des phénols empêchés avec des aminoplastes alcoxyméthylés par exemple.
EP94904898A 1992-12-29 1993-12-28 Antioxydants a ancrage aminoplaste Withdrawn EP0677070A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US99831592A 1992-12-29 1992-12-29
US998315 1992-12-29
PCT/US1993/012622 WO1994014864A1 (fr) 1992-12-29 1993-12-28 Antioxydants a ancrage aminoplaste

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EP0677070A1 true EP0677070A1 (fr) 1995-10-18

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EP94904898A Withdrawn EP0677070A1 (fr) 1992-12-29 1993-12-28 Antioxydants a ancrage aminoplaste

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EP (1) EP0677070A1 (fr)
JP (1) JPH08505887A (fr)
KR (1) KR960700284A (fr)
WO (1) WO1994014864A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA9810599B (en) * 1998-06-22 1999-07-30 Cytec Tech Corp Triazine UV absorber comprising amino resins.

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Publication number Priority date Publication date Assignee Title
US3308206A (en) * 1963-10-31 1967-03-07 American Cyanamid Co Cationic-dyeable amine-aldehyde modified polypropylene
DE3481911D1 (de) * 1984-11-13 1990-05-17 Mobil Oil Corp Mannich-basen als oelzusaetze.
CA2019320A1 (fr) * 1989-07-27 1991-01-27 Jerry J. Weers Antioxydants pour hydrocarbures liquides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9414864A1 *

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Publication number Publication date
JPH08505887A (ja) 1996-06-25
KR960700284A (ko) 1996-01-19
WO1994014864A1 (fr) 1994-07-07

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