WO2013009372A1 - Composés amines secondaires à teneur en phosphore - Google Patents

Composés amines secondaires à teneur en phosphore Download PDF

Info

Publication number
WO2013009372A1
WO2013009372A1 PCT/US2012/032177 US2012032177W WO2013009372A1 WO 2013009372 A1 WO2013009372 A1 WO 2013009372A1 US 2012032177 W US2012032177 W US 2012032177W WO 2013009372 A1 WO2013009372 A1 WO 2013009372A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
phosphorus
secondary amine
containing secondary
reaction product
Prior art date
Application number
PCT/US2012/032177
Other languages
English (en)
Inventor
Haibo Zhao
Cheng-Kuang Li
Jr. Ernest L. Rister
Nicholas KOB
Mark L. Posey
Original Assignee
Huntsman Petrochemical Llc
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 Huntsman Petrochemical Llc filed Critical Huntsman Petrochemical Llc
Publication of WO2013009372A1 publication Critical patent/WO2013009372A1/fr

Links

Classifications

    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
    • C08G18/509—Polyethers having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/544—Polycondensates of aldehydes with nitrogen compounds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • 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
    • C08G2150/00—Compositions for coatings
    • C08G2150/60—Compositions for foaming; Foamed or intumescent coatings

Definitions

  • the present invention relates generally to phosphorus-containing secondary amine compounds and polymers and coating compositions comprising the same.
  • Amine compounds are widely used for curing polyurea and polyurethane-polyurea hybrid polymer systems.
  • polyurea curing the amine functionality reacts with an isocyanate functionality to yield urea linkages.
  • a fast-reacting amine functionality such as a primary amine
  • a slow-reacting hydroxyl functionality will react with isocyanate functionality to produce a polyurethane portion, typically with the help of a catalyst.
  • the two reactions give rise to a mixture, or hybrid, of polyurea and polyurethane.
  • Catalysts typically used in polyurethane-urea nonfoaming systems include metal based compounds and a few tertiary amines which promote only a gelling reaction between hydroxyl functionality and isocyanate functionality.
  • Phosphorus-containing polyols can provide improved flame retardancy.
  • a conventional phosphorus-containing polyol is defined as a polyol containing at least one phosphorus-containing group. It is typically a polymeric or oligomeric polyol. This polyol may be selected from, for example, polyester polyols.
  • the main disadvantage of the use of phosphorus-containing polyols, however, is the lack of hydrolytic stability of these chemicals. Hydrolysis of phosphorus- containing polyols can result in loss of properties in polyurethanes. Therefore, there is a need for hydrolytically stable phosphorus-containing fire retardants.
  • Embodiments described herein generally relate to a phosphorus- containing secondary amine compound comprising the reaction product of a polyamine compound, a carbonyl compound, and a phosphorus-containing compound.
  • a phosphorus-containing primary amine may be formed by reducing the phosphorus-containing secondary amine compound and an acrylonitrile.
  • a polymer comprising the reaction product of an isocyanate compound, the phosphorus-containing secondary amine compound, and, optionally, a polyol compound and one or more additives, wherein the polymer comprises a urea moiety, a urethane moiety, or combinations thereof.
  • a coating composition comprising the reaction product of an isocyanate compound, the phosphorus-containing secondary amine compound, and, optionally, a polyol compound and one or more additives, wherein the coating composition comprises a urea moiety, a urethane moiety, or combinations thereof.
  • a polyurethane composition comprising the reaction product of an isocyanate compound, the phosphorus- containing secondary amine compound, and, optionally, a polyol compound, wherein the polyurethane composition comprises a urea moiety, a urethane moiety, or combinations thereof.
  • a polyurethane foam is provided comprising the reaction product of an isocyanate compound, the phosphorus-containing secondary amine compound, and, optionally, a polyol compound, wherein the polyurethane foam comprises a urea moiety, a urethane moiety, or combinations thereof.
  • a polyurethane elastomer comprising the reaction product of an isocyanate compound, the phosphorus- containing secondary amine compound, and, optionally, a polyol compound, wherein the polyurethane elastomer comprises a urea moiety, a urethane moiety, or combinations thereof.
  • an epoxy composition comprising the reaction product of an epoxy resin compound, the phosphorus-containing secondary amine compound, and, optionally one or more additives, wherein the epoxy composition comprises an epoxy.
  • an epoxy composition comprising the reaction product of an epoxy resin compound, a phosphorus-containing primary amine compound, and, optionally one or more additives.
  • the phosphorus-containing primary amine compound is formed by reacting a polyamine compound, a carbonyl compound, and a phosphorus-containing compound to form a phosphorus-containing secondary amine compound, reacting the phosphorus-containing secondary amine compound with acrylonitrile to form a reaction product, and reducing the reaction product.
  • the epoxy composition comprises an epoxy.
  • the phosphorus-containing secondary amine described in this invention is further reacted with acrylonitrile then reduced to impart a primary amine functionality.
  • a polymer comprising the reaction product of an isocyanate compound, a phosphorus-containing secondary amine compound, and, optionally, a polyol compound, wherein the phosphorus-containing secondary amine compound is the reaction product of a polyamine compound, a carbonyl compound, and a phosphorus-containing compound, and wherein the polymer comprises a urea moiety, a urethane moiety, or combinations thereof.
  • a coating composition comprising the reaction product of an isocyanate compound, a phosphorus- containing secondary amine compound, and, optionally, a polyol compound, wherein the phosphorus-containing secondary amine compound is the reaction product of a polyamine compound, a carbonyl compound, and a phosphorus- containing compound, and wherein the coating composition comprises a urea moiety, a urethane moiety, or combinations thereof.
  • a foam composition comprising the reaction product of an isocyanate compound, a phosphorus-containing secondary amine compound, and, optionally, a polyol compound, wherein the phosphorus-containing secondary amine compound is the reaction product of a polyamine compound, a carbonyl compound, and a phosphorus-containing compound, and wherein the foam composition comprises a urea moiety, a urethane moiety, or combinations thereof.
  • a polymer comprising the reaction product of an epoxy resin with the phosphorus-containing secondary amine described in this invention which is further reacted with acrylonitrile then reduced to impart a primary amine functionality. This results in incorporation of the phosphorus containing amine into the polymer matrix.
  • an olefin polymerizable compound is formed by reacting the phosphorus-containing secondary amine compound with an acrylate, wherein the olefin polymerizable compound has an amide linkage and a free olefinic group.
  • the present invention relates generally to phosphorus-containing secondary amine compounds such as the aminophosphonate (“AP") compounds discussed below.
  • AP compounds have been found surprisingly useful as reactive components for polyurea and poiyurethane-polyurea systems, and other related amine reactions.
  • the secondary amine phosphates unexpectedly impart the right reaction speed along with improved hydrolytic stability and fire retardancy.
  • the addition of phosphorus functionality in proximity of the secondary amine results in a secondary amine that has moderate reactivity in polymerization reactions.
  • the addition of phosphorus offers flame retardation benefits as well as hydrolytic stability.
  • the phosphorus-containing secondary amines of this invention do not contain ester linkages that anchor the phosphorus to the polymer matrix as do conventional phosphate ester polyols. Therefore, the phosphorus attachment to the polymer using the phosphorus- containing secondary amines of the present invention is hydrolytically stable.
  • AP compounds may be made by combined reaction of a carbonyl compound, an amine compound such as a polyamine compound, and a phosphorus containing compound. Accordingly, in certain embodiments, suitable aminophosphonate compounds may generally be produced according to Equation 1 :
  • the AP compound comprises a moiety comprising the following general structure (A) below:
  • R 2 OR 1 — NR 4 C— P 0 R 3 OR 1 wherein R 1 , R 2 , R 3 , and R 4 are each independently hydrogen or an organic group, such as an alkyl or aryl group.
  • R 1 , R 2 , R 3 , and R 4 are each independently hydrogen or an organic group, such as an alkyl or aryl group.
  • the phosphorus-containing secondary amine compounds of the present invention may have any number of these moieties substituted on a hydrocarbon backbone.
  • Higher functionality polyamines may form poly-AP compounds, up to thermodynamic limits. That is, in these particular compounds, the compounds comprise a plurality of moieties such as those depicted in structure (A) above.
  • the secondary amine functionals produced by such reactions have been found to be useful in various amine-mediated polymerization reactions.
  • Amines, R a (NR b x ) y can be reacted with isocyanates, R c NCO, to form polyureas, [R a N(R b )CON(R b )] n , wherein R a is an organic subsiituent such as a hydrocarbon chain, R b is hydrogen or an organic group, for example a hydrocarbon group, and R c is hydrogen or an organic group, for example a hydrocarbon group.
  • a mono-AP compound such as the reaction product depicted in Equation 1 above, is used as an amine source for a polyurea or a polyurethane / urea polymer
  • R 1 may be an alkyl, alkenyl, alkynyi, or aryl group of about 1 -10 carbon atoms.
  • R 2 and R 3 can each be hydrogen or an alkyl, alkenyl, alkynyi, or aryl group having about 1-10 carbon atoms.
  • R(AP) X R may be an alkyl, cycloalkyl, polyether, or aryl group, or a combination thereof.
  • the phosphorus-containing secondary amine compounds described above may be reacted with an isocyanate compound, a polyol compound, and optionally, one or more additives to form a polymer, a polyurethane composition, a polyurethane foam (such as spray foams), or a polyurethane elastomer comprising urea moieties and/or urethane moieties.
  • additives may be incorporated into the reaction mixture (a polymer system, including but not limited to polyurethanes, polyureas, and epoxies) to impart specific desired properties. These additives include but are not limited to: colorants, UV stabilizers, plasticizers, surfactants, and anti-static agents.
  • Examples are trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, triphenyl phosphite, triisodecyl phosphite, tris(t-butyl dimethylsilyl) phosphite, tris(1 ,1 ,1 ,3,3,3-hexafluoro-2-propyl) phosphite, tris(2,2,2-trifluoroethyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(2-chloroethyl) phosphite, tris(nonylphenyl) phosphite, tris(tridecyl) phosphite, tris(trimethylsilyl) phosphit
  • Carbonyls that may be used in the present invention include, without limitation, ketones or aldehydes such as formaldehyde, paraformaldehyde, paraldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, hexaldehyde, nonanal, octanal, undecanal, dodecyl aldehyde, acrolein, methacrolein, furfural, benzaldehyde, substituted benzaldehyde, naphthaldehyde, substituted naphthaldehyde, phthaldialdehyde, tolualdehyde, crotonaldehyde, anisaldehyde, valeraldehyde, isovaleraldehyde, 4- (dimethylamino) benzaldehyde, 2-bromoacrolein, glutaraldehyde
  • Linear aliphatic amines that may be used in the present invention include, without limitation, ⁇ , ⁇ '-diisopropylethylenediamine, N,N'-di-sec-butyl- 1 ,2-diaminopropane, N,N'-di(3,3-dimethyl-2-butyl)-1 ,4,diamine-2-methylpentane, N,N'-di-sec-butyl-1 ,6-diaminohexane, N,N'-di(3-pentyl)-2,5-dimethyl-2,5- hexanediamine, N,N'-diisopropyl-1 ,7-diaminoheptane, N,N'-di-sec-butyl-1 ,8- diaminooctane, N,N'-di(2-pentyl)-1 , 10-diaminodecane, and N,N'--di
  • Linear aliphatic primary diamines that may be used in the present invention include, without limitation, ⁇ , ⁇ '-didodecylethylenediamine, N,N'-didecyl-1 ,3-diaminopropane, N,N'-dinonyl-1 ,5-diaminopentane, N,N'-diheptyl-1 ,5-diamino-2-methylpentane, N,N'-di-n-butyl-1 ,6-diaminohexane, N,N'-di-n-propyl-2,5-dimethyl-2,5- hexanediamine, N,N'-di-n-propyl-1 ,7-diaminoheptane, N,N'-di-n-butyl-1 ,8- diaminooctane, N,N'-dipentyl-1 ,10-diaminodecane,
  • Cyclic amines that are suitable for use in the present invention include, without limitation, N,N'-d(1-cyclopropylethyl)-1 ,5-diaminopentane, N,N'-di(4- hexyl)-1 ,2-diaminocyclohexane, N,N'-dicyclohexyl-1 ,3-dimethyl-3-pentyl-1 ,3- cyclohexanebis(methylamine), N,N'-di(3-methyl-2-cyclohexenyl)-1 ,2- diaminopropane, N,N'-di(2,5-dimethylcyclopentyl)-1 ,4-diaminobutane, ⁇ , ⁇ '- di(isophoryl)-1 ,5-diaminopentane, N,N'-di(methyl)-2,5-dimethyl-2,5- hexanediamine, N,
  • Aromatic amines that may be used in the present invention include, without limitation, 1 ,2-phenylenediamine (phenylenediamine is also called benzenediamine), 1 ,3-phenylenediamine, 1 ,4-phenylenediamine, 4-ethyl-1 ,2- phenylenediamine, 2-isopropyl-1 ,3-phenylenediamine, 4-t-butyl-1 ,3- phenylenediamine, 2-pentyl-1 ,4-phenylenediamine, 4,5-dihexyl-1 ,2- phenylenediamine, 4-methyl-5-heptyl-1 ,3-phenylenediamine, 4,6-di-propyl- ,3- phenylenediamine, 2,5-dioctyl-1 ,4-phenylenediamine, 2,3-diethyl-1 ,4- phenylenediamine, 4,5,6-trihe
  • Polyether amines that are suitable for use in the present invention include, without limitation, polyether amines such as polyethylene oxide amine, polypropylene oxide amine, and poly-THF amine.
  • Mixed polyether amines such as poly-(EO)(PO) amine, [-(EO)i-(PO) r ] k (NH 2 )i, and mixed polyether amines with any mixture of EO, PO, and THF, may also be used.
  • such amines are produced by Huntsman under the tradename JEFFAMINE.
  • the amine of 1 ,3-propanediol (PDO) oligomer, as well as mixed polymer amines with any mixture of EO, PO, THF, and PDO may also be used.
  • Secondary amines may be used in polyurethane-polyurea hybrid reactions as chain extenders.
  • a secondary amine reacts with an isocyanate to form urea linkages, while a tertiary amine catalyzes reaction of the isocyanate with an alcohol to form a polyurethane. If x equivalents of a secondary amine and y equivalents of an alcohol are mixed with x+y equivalents of an isocyanate, with a catalytic amount of a tertiary amine, a polyurethane-polyurea blend results.
  • AP compounds as secondary amines adds phosphorus structures to the resulting polymers, improving fire resistance without compromising hydrolytic stability.
  • the phosphorus-containing secondary amine compounds described above may be reacted with an isocyanate compound, a polyol compound, and optionally, one or more additives to form a phosphorus- containing polymer, a polyurethane composition, a polyurethane foam (such as spray foams), or a polyurethane elastomer comprising urea moieties and/or urethane moieties.
  • Various additives may be incorporated into the reaction mixture (a polymer system, including but not limited to polyurethanes, polyureas, and epoxies) to impart specific desired properties. These additives include but are not limited to: colorants, UV stabilizers, plasticizers, surfactants, and antistatic agents.
  • the resulting phosphorus-containing species now contains a primary amine which can be used in epoxy polymers.
  • This new phosphorus-containing primary amine compound offers the same flame retardant and hydrolytic stability benefits of the other phosphorus-containing secondary amines of the invention.
  • An epoxy composition may be formed by reacting an epoxy resin compound, the phosphorus-containing primary amine compound, and, optionally one or more additives.
  • additives may be incorporated into the epoxy reaction mixture to impart specific desired properties. These additives include but are not limited to: colorants, UV stabilizers, plasticizers, surfactants, and anti-static agents.
  • a trialkylphosphite may be reacted with a carbonyl and a diamine or triamine, as shown in Equations 3 and 4:
  • the carbonyl may be an aldehyde or ketone, such as any of the compounds listed above.
  • R1 may be an organic group, such as an alkyl or aryl group, which may contain a halogen.
  • R2 and R3 may be hydrogen or an organic group, such as an alkyl or aryl group, which may contain a halogen.
  • R may be an organic group, such as an alkyl, cycloalkyl, polyether, or aryl group. Any of the carbonyl compounds, phosphites, and amines listed above may be used to perform the reactions of Equations 3 and 4.
  • reaction products I, II, and III may react with isocyanate compounds to form linkages that incorporate the phosphonate groups into either polyurea or polyurethane/ureas including but not limited to coatings and foams.
  • Equation 5 shows how reaction product I may react with an isocyanate compound:
  • Equation 5 The products of the reaction shown by Equation 5 have advantageous properties, such as flame retardancy and hydrolytic stability of the flame retardant phosphorus-containing moiety.
  • the phosphorus-containing amines of this invention can react with epoxy resins to form epoxy polymers resulting in the same flame retardant and hydrolytic stability advantages.
  • the secondary phosphorus-containing amine molecules of this invention can also be modified to impart a polymerizable olefinic group into the molecule such that it can be co-polymerized with other polymeric olefinic monomers such as, but not limited to acrylics, and maleic anhydride.
  • the phosphorus-containing secondary amine compound may be reacted with an acrylate, such as, but not limited to methylmethacrylate or acrylic acid.
  • Equation 6 shows an example of use of a methylmethacrylate to modify the secondary phosphorus-containing amine molecules of this invention (making an amide linkage) and impart a polymerizable olefinic group such that the new resulting molecule can be co-polymerized via olefin polymerization into, for example, but not limited to polystyrene or polyacrylates.
  • the polymer formed by modifying the secondary phosphorus-containing amine molecule may have other olefin polymerizable groups such as, but not limited to, acrylates, itaconics, maleic anhydride, and styrene.
  • IPDA isophorone diamine
  • Desmophen ® N3400 an HDI based isocyanate at 21 % NCO from Bayer Corp., was also used in cure speed/pot life characterization testing. When reacted with the Desmophen, the products of equation 4 above had a gel time of 1 minute and tack free time of 10 minutes. By comparison, the gel time for Polyclear 136, in combination with Desmophen, was too short to be measured with the same mixing and processing conditions.
  • Amine 1 JEFFAMINE T-3000 amine (Glyceryl poly(oxypropylene) triamine)
  • Amine 2 JEFFAMINE T-403 amine (Trimethylolpropane polyoxypropylene triamine)
  • Amine 3 (N,N'-diisopropyl)-3-aminomethyl-3,5,5-trimethylcyclohexylamine
  • Amine 4 3- ⁇ 3-[(2-cyanoethylamino)methyl]-3,5,5-trimethyl-cyclohexylamino propionitrile
  • Amine 5 bis-(4-N-sec-butylaminocyclohexyl)-methane Flame resistance was tested by subjecting a .5" x 5" strip of each resin to a Bunsen burner flame for 10 seconds, approximately according to the UL94 flame resistance standard,
  • Samples 1 , 2, and 4 were tested for flame resistance as described above. Sample 1 continued to burn and exhibited dripping, even after igniting flame was removed. Sample 2 charred on its surface, but did not allow flame to propagate, and did not drip. Sample 4 burned and dripped at a slower rate than sample 1.
  • Table 1 thus indicate a flame resistance benefit of using phosphorus containing amines of this invention versus other conventional amines used in polyurea systems.
  • the polyurea formulation from sample 2 containing the phosphorus- containing secondary amine of Example 1 also had a slower gel time when compared to the other formulations containing conventional amine systems. Moreover, the polyurea formulation from sample 2 had a slower gel time than the polyurea formulation of sample 4 made from a conventional non-phosphorus- containing secondary amine. The gel time is related to the speed of reaction of the amine with the isocyanate. Slower formulation systems are desired in many applications.
  • Table 2 shows results of a comparison similar to that shown in Table 1 , but using the diaminophosphonate of Example 2 above.
  • the prepolymer used for the samples in Table 2 is a blend of 48.5% by weight IPDI and 51.5% by weight JEFFAMlNE SD-2001 amine with an isocyanate content of about 16% by weight.
  • Sample 7 had higher gel times and tack free times than Samples 5, 6 and 8, indicative of a slower reaction between the isocyanate and the secondary aminophosphate. Moreover, the polyurea formulation of sample 7 even had a higher gel time and tack free time than the polyurea formulation of sample 8 made from a conventional non-phosphorus-containing secondary amine.
  • the polyurea products described above are typically used as coating agents. Because the secondary aminophosphonates described herein are less reactive overall than primary amines, a liquid reaction mixture of isocyanate and secondary aminophosphonate reacts slowly enough to allow time for application of the reaction mixture to a substrate before hardening. For example, a mixture of an isocyanate and a secondary aminophosphonate may be spin coated, ribbon coated, or spray coated onto a substrate to a desired thickness and allowed to cure and set. The coating thus formed is electrically, thermally, and vibrationally insulating, and shows improved flame resistance over polyureas made using some other amines. Substrates which may be coated with such mixtures include metals, cellulosic substrates, polymers, polyurethane or polyurea foams, wood, glasses, and the like.
  • EDA ethylenediamine
  • other amines such as JEFFAMINE® D2000 and JEFFAMINE® D230, produced by Huntsman Corp.
  • the resin blend was prepared as follows:
  • Terol® 925 is an aromatic polyester polyol available from Oxid Chemical, Inc.
  • JEFFOL®R 425-X is a mannich base polyol available from Huntsman Corp.
  • CARPOL GSP 280 is a sucrose glycerin EO/PO polyol available from E.R. Carpenter.
  • SILSTAB 2 00 is a silicone surfactant available from Siltech Corp.
  • TCPP is trichloropropylphosphate fire retardant available from Supresta as
  • RB-79 is an aromatic bromine containing fire retardant available from Albermarle Corp.
  • JEFFCAT®ZF-10 is a tertiary amine catalyst available from Huntsman Corp.
  • JEFFCAT®ZR-70 is a tertiary amine catalyst available from Huntsman Corp.
  • JEFFCAT®ZR-50 is a tertiary amine catalyst available from Huntsman Corp.
  • JEFFCAT®Z-1 10 is a tertiary amine catalyst available from Huntsman Corp. 245fa is 1 ,1 ,1 ,trifloroethane available from Honeywell Corp. Table 3
  • the resin blend was prepared as follows:
  • JEFFOL G31 -35 is a flexible glycerin based PO/EO capped polyol OH # 35 available from Huntsman.
  • JEFFOL SD-441 is a sucrose/DEG base polyol OH# 441 available from Huntsman.
  • SURFONIG N-95 is a 9.5 mole ethoxylate of Nonylphenol available from Huntsman.
  • TCPP is trichloropropylphosphate fire retardant available from Supresta as Fyrol® PCF.
  • Silstab 2760 is a silicone surfactant available from Siltech.
  • JEFFCAT®ZF-20 is a tertiary amine catalyst available from Huntsman.
  • JEFFCAT®Z-130 is a tertiary amine catalyst available from Huntsman.
  • JEFFCAT®Z-1 10 is a tertiary amine catalyst available from Huntsman.
  • TCPP (parts by weight) 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0
  • the resin blend was prepared as follows:
  • JEFFOL®SG-522 is a sucrose/glycerin PO polyol available from Huntsman Corp.
  • JEFFOL®G30-240 is a glycerin PO polyol available from Huntsman Corp.
  • JEFFOL®G30-650 is a glycerin PO polyol available from Huntsman Corp.
  • Surfonic®T-15 is a 15 mole ethoxylate of tallow amine available from Huntsman Corp.
  • JEFFCAT®ZR-50 is a low odor amine catalyst available from Huntsman Corp.
  • TEGOSTAB B 8404 is a silicone surfactant available from Evonik.
  • 245fa is a1 ,1 ,1 , trichloroethane available from Honeywell Corp.
  • TCPP is trichloropropylphosphate fire retardant available from Supresta as

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des composés amines secondaires à teneur en phosphate, qui sont utilisés dans des polymères, des polyuréthanes, des compositions de revêtement et des compositions époxy. L'invention concerne un composé amine secondaire à teneur en phosphore comprenant le produit de réaction d'un composé polyamine, d'un composé carbonyle et d'un composé à teneur en phosphore. Une amine primaire à teneur en phosphore peut être formée par réduction du composé amine secondaire à teneur en phosphore et d'un acrylonitrile. L'invention concerne un polymère comprenant le produit de réaction d'un composé isocyanate, du composé amine secondaire à teneur en phosphore, et, éventuellement, d'un composé polyol et d'un ou plusieurs additifs, le polymère comprenant une fraction urée, une fraction uréthane ou des combinaisons de celles-ci.
PCT/US2012/032177 2011-07-11 2012-04-04 Composés amines secondaires à teneur en phosphore WO2013009372A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161506511P 2011-07-11 2011-07-11
US61/506,511 2011-07-11

Publications (1)

Publication Number Publication Date
WO2013009372A1 true WO2013009372A1 (fr) 2013-01-17

Family

ID=47506381

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/032177 WO2013009372A1 (fr) 2011-07-11 2012-04-04 Composés amines secondaires à teneur en phosphore

Country Status (1)

Country Link
WO (1) WO2013009372A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015065816A1 (fr) * 2013-10-30 2015-05-07 Anocoil Corporation Précurseurs et revêtement de plaque d'impression lithographique
CN107840936A (zh) * 2017-11-19 2018-03-27 哈尔滨师范大学 一种抗静电生物基非离子表面活性剂及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5147925A (en) * 1990-02-14 1992-09-15 Imperial Chemical Industries Plc Production of polyurethane polymers, the polymers so produced, and compositions containing them
US5914310A (en) * 1994-08-19 1999-06-22 Rhodia Inc. Amphoteric surfactants having multiple hydrophobic and hydrophilic groups
US20020158237A1 (en) * 1996-09-30 2002-10-31 Blount David H. Production of amino-aldehyde-phosphate resins and copolymers
US20030195293A1 (en) * 2002-04-05 2003-10-16 Lubnin Alexander V. Breathable polyurethanes, blends, and articles
WO2010071946A1 (fr) * 2008-12-24 2010-07-01 Orica Explosives Technology Pty Ltd ÉMULSIONS EXPLOSIVES ÉPAISSIES PAR UN COMPOSÉ CARBONYLE α,β-INSATURÉ AYANT RÉAGI AVEC UNE AMINE

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5147925A (en) * 1990-02-14 1992-09-15 Imperial Chemical Industries Plc Production of polyurethane polymers, the polymers so produced, and compositions containing them
US5914310A (en) * 1994-08-19 1999-06-22 Rhodia Inc. Amphoteric surfactants having multiple hydrophobic and hydrophilic groups
US20020158237A1 (en) * 1996-09-30 2002-10-31 Blount David H. Production of amino-aldehyde-phosphate resins and copolymers
US20030195293A1 (en) * 2002-04-05 2003-10-16 Lubnin Alexander V. Breathable polyurethanes, blends, and articles
WO2010071946A1 (fr) * 2008-12-24 2010-07-01 Orica Explosives Technology Pty Ltd ÉMULSIONS EXPLOSIVES ÉPAISSIES PAR UN COMPOSÉ CARBONYLE α,β-INSATURÉ AYANT RÉAGI AVEC UNE AMINE

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015065816A1 (fr) * 2013-10-30 2015-05-07 Anocoil Corporation Précurseurs et revêtement de plaque d'impression lithographique
US20160252813A1 (en) * 2013-10-30 2016-09-01 Anocoil Corporation Lithographic Printing Plate Precursors and Coating
US10012904B2 (en) 2013-10-30 2018-07-03 Mark'Andy Inc. Lithographic printing plate precursors and coating
CN107840936A (zh) * 2017-11-19 2018-03-27 哈尔滨师范大学 一种抗静电生物基非离子表面活性剂及其制备方法

Similar Documents

Publication Publication Date Title
US7629433B2 (en) Compounds containing aldimine
JP5254719B2 (ja) 自己触媒性ポリオール
KR101455878B1 (ko) 연질 폴리우레탄 발포체의 제조 방법
JP5567242B2 (ja) 自己触媒特性をもったポリオールおよびこれから製造されたポリウレタン製品
US20090176944A1 (en) Aldimines Comprising Reactive Groups Containing Active Hydrogen, and Use Thereof
MXPA04006152A (es) Polioles modificados con amina terciaria y productos de poliuretano hechos de los mismos.
US20040242832A1 (en) Autocatalytic polyols with gelling characteristics and polyurethane products made therefrom
US20060052570A1 (en) Amine-epoxy autocatalytic polymers and polyurethane products made therefrom
US20120022177A1 (en) Non-fugitive catalysts containing imine linkages and tertiary amines, and polyurethane products made therefrom
JP2007516340A (ja) 第三級アミンでキャップされたポリエーテルポリオール
CN117384371A (zh) 硬质泡沫
US20210189053A1 (en) Stable modified polymer polyol dispersions
US20190092897A1 (en) Novel compositions for polyurethane applications
CN113004488B (zh) 稳定的改性聚合物多元醇分散体
US10640475B2 (en) Compositions and methods to produce alkoxylated triazine-arlhydroxy-aldehyde condensates
WO2013009372A1 (fr) Composés amines secondaires à teneur en phosphore
CA1047700A (fr) Mousse de polyurethanne obtenue a partir de polyols modifies par un polymere
EP3827040A1 (fr) Nouvelles compositions et procédés pour produire des condensats de triazine-arylhydroxy-aldéhyde alcoxylés
JPH0148276B2 (fr)
JPS62500666A (ja) ポリ尿素および／またはポリ尿素−ポリウレタンポリマ−の製造方法
JPH0249028A (ja) ポリウレタン物質の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12811823

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12811823

Country of ref document: EP

Kind code of ref document: A1