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WO2008112636A1 - Allongeurs de chaîne - Google Patents

Allongeurs de chaîne Download PDF

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Publication number
WO2008112636A1
WO2008112636A1 PCT/US2008/056415 US2008056415W WO2008112636A1 WO 2008112636 A1 WO2008112636 A1 WO 2008112636A1 US 2008056415 W US2008056415 W US 2008056415W WO 2008112636 A1 WO2008112636 A1 WO 2008112636A1
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Prior art keywords
diamine
butyl
aliphatic
composition
methyl
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Inventor
John Y. Lee
Paul L. Wiggins
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Albemarle Corp
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Albemarle Corp
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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
    • 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
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/325—Polyamines containing secondary or tertiary 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines

Definitions

  • This invention relates to the use of cycloaliphatic secondary diamines to form polyurethanes, polyureas, and polyurea-urethanes.
  • This invention in part provides chain extenders which are mixtures of an aliphatic secondary ⁇ , ⁇ -diamine having at least one internal secondary amino group and one or more other components.
  • This invention also provides in part chain extenders which are mixtures of N,N'-dicyclohexyl-l,6-hexanediamine and one or more other components. These mixtures, when included in formulations for polyurethanes, polyureas, and polyurea-urethanes, produce such polymers at desired cure rates and having desirable physical properties.
  • One embodiment of this invention provides a chain extender composition.
  • the composition comprises either (i) N,N'-dicyclohexyl-l,6-hexanediamine or (ii) an aliphatic secondary ⁇ , ⁇ -diamine having a secondary amino straight chain.
  • said composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine, (b) an aliphatic secondary diamine and an aliphatic primary diamine, (c) an aliphatic diimine, (d) an aromatic primary diamine, and (e) a combination of any two or more of (a) through (d).
  • said composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine, (d) an aromatic primary diamine, (f) an aliphatic secondary ⁇ , ⁇ -diamine having at least one internal secondary amino group, and (g) a combination of any two or more of (a), (d), and (f).
  • Another embodiment of this invention is a process for producing a polymer which is a polyurethane, polyurea, or polyurea-urethane.
  • the process comprises mixing together (A) at least one aliphatic polyisocyanate, (B) at least one polyol and/or at least one polyetheramine, and (C) a chain extender comprised of either (i) N,N'-dicyclohexyl-l,6- hexanediamine or (ii) an aliphatic secondary ⁇ , ⁇ -diamine having at least one internal secondary amino group.
  • said composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine, (b) an aliphatic secondary diamine and an aliphatic primary diamine, (c) an aliphatic diimine, (d) an aromatic primary diamine, and (e) a combination of any two or more of (a) through (d).
  • said composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine, (d) an aromatic primary diamine, (f) an aliphatic secondary ⁇ , ⁇ -diamine having at least one internal secondary amino group, and (g) a combination of any two or more of (a), (d), and (f).
  • Still another embodiment of this invention is a polymer which is a polyurethane, polyurea, or polyurea-urethane, which polymer is formed from ingredients comprising (A) at least one aliphatic polyisocyanate, (B) at least one polyol and/or at least one polyetheramine, and (C) a chain extender comprised of either (i) N,N'-dicyclohexyl-l,6- hexanediamine or (ii) an aliphatic secondary ⁇ , ⁇ -diamine having at least one internal secondary amino group.
  • said composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine, (b) an aliphatic secondary diamine and an aliphatic primary diamine, (c) an aliphatic diimine, (d) an aromatic primary diamine, and (e) a combination of any two or more of (a) through (d).
  • said composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine, (d) an aromatic primary diamine, (f) an aliphatic secondary ⁇ , ⁇ -diamine having at least one internal secondary amino group, and (g) a combination of any two or more of
  • Chain extender compositions of this invention comprise either N,N'-dicyclohexyl- 1,6-hexanediamine or an aliphatic secondary ⁇ , ⁇ -diamine having at least one internal secondary amino group.
  • the chain extender composition comprises N 5 N'- dicyclohexyl-l,6-hexanediamine, one or more other components selected from (a) an aliphatic secondary diamine; (b) an aliphatic secondary diamine and an aliphatic primary diamine; (c) an aliphatic diimine; and (d) an aromatic primary diamine are present in the chain extender composition.
  • Preferred components for use with N,N'-dicyclohexyl-l,6- hexanediamine are aliphatic secondary diamines.
  • the components can be present in the chain extender composition in a variety of proportions; the preferred ratios vary with the type of component(s) (a)-(d).
  • the chain extender composition comprises an aliphatic secondary ⁇ , ⁇ - diamine having at least one internal secondary amino group, one or more other components selected from (a) an aliphatic secondary diamine; (d) an aromatic primary diamine; and (f) an aliphatic secondary ⁇ , ⁇ -diamine having at least one internal secondary amino group.
  • Preferred components for use with an aliphatic secondary ⁇ , ⁇ -diamine having at least one internal secondary amino group include aliphatic secondary diamines.
  • the components can be present in the chain extender composition in a variety of proportions; the preferred ratios vary with the type of component(s) (a), (d), and (f).
  • Component (i) is N,N'-dicyclohexyl-l,6-hexanediamine, which is sometimes also called N,N'-dicyclohexylhexane-l,6-diamine, N,N'-dicyclohexyl-l,6-diaminohexane, or
  • Component (ii) is an aliphatic secondary ⁇ , ⁇ -diamine having at least one internal secondary amino group.
  • These diamines are secondary diamines which are in the form of a straight chain, with a secondary amino group bound to each of the two terminal carbon atoms.
  • the straight chain is a secondary amino straight chain, where "secondary amino straight chain” means a straight chain in which at least one of the -CH 2 - moieties in a hydrocarbyl straight chain is instead an — NH- moiety.
  • an aliphatic secondary ⁇ , ⁇ -diamine with at least one internal secondary amino group has about six to about thirty carbon atoms; more preferably, the aliphatic secondary ⁇ , ⁇ -diamine with at least one internal secondary amino group has about eight to about twenty-five carbon atoms.
  • the terminal secondary amino groups of the aliphatic secondary ⁇ , ⁇ -diamine are amino hydrocarbyl groups which can be cyclic, branched, or straight chain.
  • the amino hydrocarbyl groups are straight chain or, more preferably, branched chain alkyl groups having from three to about twelve carbon atoms.
  • suitable amino hydrocarbyl groups for the secondary amino groups include ethyl, propyl, isopropyl, n- butyl, sec-butyl, t-butyl, 3,3-dimethyl-2-butyl, pentyl, cyclopentyl, 4-methyl-2-pentyl, 2,4- dimethyl-3-pentyl, hexyl, methylcyclohexyl, heptyl, octyl, cyclooctyl, nonyl, decyl, dodecyl, and the like.
  • Suitable aliphatic secondary ⁇ , ⁇ -diamines having at least one internal secondary amino group include, but are not limited to, N,N'-di(l-propyl)-diethylenetriamine, N 5 N'- diisopropyl-diethylenetriamine, N,N'-di(sec-butyl)-diethylenetriamine, N,N'-di(3,3- dimethyl-2-butyl)-diethylenetriamine, N,N'-di(2-pentyl)-diethylenetriamine, N,N'-di(4- methyl-2-pentyl)-diethylenetriamine, N,N'-di(6-undecyl)-norspermidine, N,N'-di(2,4- dimethyl-3-pentyl)-spermidine, N,N'-diisopropyl-dihexylenetriamine, N,N'-diisopropyl- triethylenet
  • Preferred aliphatic secondary ⁇ , ⁇ -diamines having at least one internal secondary amino group include N,N'-diisopropyl-diethylenetriamine and N,N'-di(sec-butyl)-diethylenetriamine.
  • the chain extender composition comprises (i), N,N'-dicyclohexyl-l,6- hexanediamine
  • the composition is also comprised of a component selected from the group consisting of (a) an aliphatic secondary diamine; (b) an aliphatic secondary diamine and an aliphatic primary diamine; (c) an aliphatic diimine; (d) an aromatic primary diamine; and (e) a combination of any two or more of (a) through (d).
  • the chain extender composition comprises (ii), an aliphatic secondary ⁇ , ⁇ - diamine having at least one internal secondary amino group
  • the composition is also comprised of a component selected from the group consisting of (a), (d), and (f).
  • a component selected from the group consisting of (a), (d), and (f) selected from the group consisting of (a), (d), and (f).
  • Aliphatic secondary diamines are component (a).
  • the aliphatic secondary diamines are hydrocarbyl secondary diamines where the hydrocarbyl portion of the diamine is aliphatic, where "hydrocarbyl portion” refers to the moiety to which the amino groups are bound.
  • the hydrocarbyl portion of the aliphatic diamine can be cyclic, branched, or, preferably, straight chain.
  • the amino hydrocarbyl groups of the aliphatic secondary diamine can be cyclic, branched, or straight chain.
  • the amino hydrocarbyl groups are straight chain or, more preferably, branched chain alkyl groups having from three to about twelve carbon atoms.
  • Suitable amino hydrocarbyl groups include ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, cyclopentyl, hexyl, methylcyclohexyl, heptyl, octyl, cyclooctyl, nonyl, decyl, dodecyl, and the like.
  • the aliphatic secondary diamine has about eight to about forty carbon atoms; more preferably, the aliphatic secondary diamine has about ten to about thirty carbon atoms.
  • Aliphatic secondary diamines have cyclic or straight chain hydrocarbyl portions and have about twelve to about twenty- five carbon atoms.
  • Aliphatic secondary diamines that can be used in this invention include, but are not limited to, N,N'-diisopropylethylenediamine, N,N'-di-sec-butyl-l,2-diaminopropane, N 5 N'- di(2-butenyl)-l,3-diaminopropane, N,N'-di(l-cyclopropylethyl)-l,5-diaminopentane,
  • Preferred aliphatic secondary diamines for use with component (i) include N,N'-di(sec- butyl)-4,4'-di(cyclohexylamino)methane, N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diamino- hexane, N,N'-di(4-methyl-2-pentyl)-l,6-diaminohexane, and N,N'-diisopropyl-l,6- diaminohexane.
  • Preferred aliphatic secondary diamines for use with component (ii) include at least N,N'-di(sec-butyl)-4,4'-di(cyclohexylamino)methane and N,N'-di-(3,3- dimethyl-2 -butyl)- 1 ,6-diaminohexane.
  • Relative proportions of N,N'-dicyclohexyl-l,6-hexanediamine or an aliphatic secondary ⁇ , ⁇ -diamine having at least one internal secondary amino group to aliphatic secondary diamine in the chain extender composition are preferably about 0.1 :1 to about 1 :0.1 on an equivalent basis; more preferably, the relative proportions on an equivalent basis are about 0.5:1 to about 1 :0.5.
  • An aliphatic secondary diamine and an aliphatic primary diamine are component (b).
  • the aliphatic secondary diamine and the aliphatic primary diamine can be in any suitable proportion relative to each other, and their combined total amount can be in any relative proportion to the N,N'-dicyclohexyl-l,6-hexanediamine.
  • Preferred proportions of aliphatic secondary diamine to aliphatic primary diamine are in the range of about 0.1 :1 to about 1 :0.1 on an equivalent basis.
  • the proportions of the combined total amount of aliphatic secondary diamine and aliphatic primary diamine relative to the N 5 N'- dicyclohexyl-l,6-hexanediamine is preferably in the range of about 0.5:1 to about 1 :0.5 on an equivalent basis.
  • Aliphatic primary diamines for component (b) are hydrocarbyl primary diamines where the hydrocarbyl portion of the diamine is aliphatic.
  • the hydrocarbyl portion of the aliphatic diamine can be cyclic, branched, or straight chain.
  • the aliphatic primary diamine has about four to about thirty carbon atoms; more preferably, the aliphatic primary diamine has about six to about twenty carbon atoms.
  • Particularly preferred aliphatic diamines have cyclic or straight chain hydrocarbyl portions and have about four to about ten carbon atoms.
  • Suitable aliphatic primary diamines include, but are not limited to, ethylenediamine, 1 ,2-diaminopropane, 1,3-diaminopropane, 1 ,4-diaminobutane, 1,5- diaminopentane, l,5-diamino-2-methylpentane, 1 ,6-diaminohexane, 2,5-dimethyl-2,5- hexanediamine, 1 ,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4- diaminocyclohexane, 2,4-diethyl-6-methyl-l ,3-cyclohexanediamine, 4,6-diethyl-2-methyl- 1 ,3-cyclohexanediamine, 1 ,3-cyclohexanebis(methylamine), 1 ,4-cyclohexanebis- (methylamine), iso
  • a preferred chain extender composition in this invention is one in which the aliphatic secondary diamine is N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane.
  • Aliphatic diimines are also called diketimines
  • component (c) are component (c).
  • Proportions of N,N'-dicyclohexyl-l,6-hexanediamine to aliphatic diimine in the chain extender composition are generally about 0.1 :1 to about 1 :0.1 on an equivalent basis; preferably, the relative proportions on an equivalent basis are about 0.75:1 to about 1 :0.75.
  • the relative proportions of N,N'-dicyclohexyl-l,6-hexanediamine to aliphatic diimine in the chain extender composition are preferably about 0.25:1 to about 5:1; more preferably, the relative proportions on a weight basis are about 0.5:1 to about 3:1.
  • the hydrocarbyl portion of the aliphatic diimine can be cyclic, branched, or straight chain hydrocarbyl group, where "hydrocarbyl portion" refers to the moiety to which the imino groups are bound.
  • the aliphatic diimine has about six to about forty carbon atoms; more preferably, the aliphatic diimine has about ten to about thirty carbon atoms.
  • the hydrocarbylidene groups of the imino groups of the aliphatic diimine generally have from one to about twenty carbon atoms; the hydrocarbylidene groups may be straight chain, branched, or cyclic.
  • the imino hydrocarbylidene groups are straight chain or branched chain alkylidene groups having from three to about six carbon atoms.
  • suitable imino hydrocarbylidene groups include ethylidene, propylidene, isopropylidene, 1-cyclopropylethylidene, n-butylidene, sec-butylidene, cyclobutylidene, 2-ethylbutylidene, 3,3-dimethyl-2-butylidene, 3-pentylidene, 3-penten-2- ylidene, cyclopentylidene, 2,5-dimethylcyclopentylidene, 2-cyclopentenylidene, hexylidene, methylcyclohexylidene, menthylidene, ionylidene, phorylidene, isophorylidene, heptylidene, 2,6,-dimethyl-3-
  • Aliphatic diimines that can be used in this invention include, but are not limited to, N,N'-diisopropylidene-ethylenediamine, N,N'-di-sec-butylidene- 1 ,2-diaminopropane,
  • Aromatic primary diamines are component (d) of the chain extenders of this invention.
  • the relative proportions of N,N'-dicyclohexyl-l,6-hexanediamine or aliphatic secondary ⁇ , ⁇ -diamine having at least one internal secondary amino group to aromatic primary diamine in the chain extender composition are generally about 0.1 :1 to about 1 :0.1 on an equivalent basis; preferably, the relative proportions on an equivalent basis are about 0.75:1 to about 1 :0.75.
  • the relative proportions of N,N'-dicyclohexyl- 1,6-hexanediamine or aliphatic secondary ⁇ , ⁇ -diamine having at least one internal secondary amino group to aromatic primary diamine in the chain extender composition are preferably about 0.25:1 to about 5:1; more preferably, the relative proportions on a weight basis are about 0.5:1 to about 3:1.
  • aromatic primary diamine that can be used in this invention is an aromatic primary diamine in which at least one position ortho to each amino group has a hydrogen atom as a substituent, and which aromatic primary diamine is either in the form of one phenyl ring having two amino groups on the ring or in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring.
  • the phenyl rings may have, but need not have, one or more hydrocarbyl groups on the phenyl ring(s). Hydrocarbyl groups, when present on the phenyl rings, may be the same or different.
  • the amino groups When both amino groups are on one phenyl ring, the amino groups may be in any position relative to each other on the ring; preferably, the amino groups are meta or para relative to each other.
  • the amino groups When the amino groups are on two phenyl rings connected by an alkylene bridge, they may be in any position on the rings; preferably, each amino group is meta or para relative to the alkylene bridge.
  • the alkylene bridge of the two-ring diamine has from one to about six carbon atoms; preferably, the alkylene bridge has from one to about three carbon atoms. More preferably, the alkylene bridge has one or two carbon atoms; highly preferred is an alkylene bridge having one carbon atom.
  • hydrocarbyl groups when present on the phenyl ring(s), are as described above for the aromatic diimines.
  • the hydrocarbyl groups can have from one to about twenty carbon atoms; preferably, the hydrocarbyl groups have from one to about six carbon atoms.
  • Suitable aromatic primary diamines of this type having both amino groups on one phenyl ring include, but are not limited to, 1 ,2-benzenediamine, 1,3-benzenediamine, 1,4- benzenediamine, 4-ethyl-l,2-benzenediamine, 2-isopropyl-l,3-benzenediamine, 4-tert- butyl- 1 ,3-benzenediamine, 2-pentyl- 1 ,4-benzenediamine, 4,5-dihexyl-l ,2- benzenediamine, 4-methyl-5-heptyl- 1 ,3-benzenediamine, 4,6-di-n-propyl- 1 ,3- benzenediamine, 2,5-dioctyl-l,4-benzenediamine, 2,3-diethyl-l,4-benzenediamine, and 4,5,6-trihexyl-l,3-benzenediamine.
  • Examples of suitable aromatic primary diamines of this type in which one amino group is on each of two phenyl rings include 2,2'-methylenebis(benzeneamine), 2,3'- methylenebis-(benzeneamine), 2,4'-methylenebis(benzeneamine), 3,3'-methylenebis- (benzeneamine), 3 ,4'-methylenebis(benzeneamine), 4,4'-methylenebis-(benzeneamine), 4,4'-(l ,2-ethanediyl)bis-(benzeneamine), 3,4'-(l ,3-propanediyl)bis-(benzeneamine), 2,2'- methylenebis(5-tert-butyl-benzeneamine), 3,3'-methylenebis(2-methylbenzeneamine), 3,3'-methylenebis(5-pentylbenzeneamine), 3,3'-methylenebis(6-isopropylbenzeneamine), 4,4'-methylenebis(2-methylbenzen
  • aromatic primary diamine that can be used in this invention, which is a preferred type of aromatic primary diamine, is an aromatic primary diamine in which each position ortho (immediately adjacent) to an amino group bears a hydrocarbyl group, and which aromatic primary diamine either is in the form of one phenyl ring having two amino groups on the ring, which amino groups are meta or para relative to each other, or is in the form of two phenyl rings connected by an alkylene bridge and having one amino group on each ring.
  • the hydrocarbyl groups on the phenyl rings (adjacent to the amino groups) generally have up to about twenty carbon atoms, and the hydrocarbyl groups may be the same or different.
  • the alkylene bridge of the two-ring primary diamine has from one to about six carbon atoms; preferably, the bridge has from one to about three carbon atoms. More preferably, the alkylene bridge has one or two carbon atoms; especially preferred as the alkylene bridge is a methylene group.
  • Particularly preferred hydrocarbyl groups on the phenyl ring(s) are methyl, ethyl, isopropyl, butyl, and mixtures of two or more of these groups.
  • butyl groups include n-butyl, sec-butyl, and t-butyl groups.
  • More preferred aromatic primary diamines with two amino groups on one phenyl ring have the amino groups meta relative to each other.
  • Highly preferred hydrocarbyl groups are methyl, ethyl, isopropyl, butyl, and mixtures thereof, where the preference for butyl groups includes n-butyl, sec-butyl, and t-butyl groups.
  • aromatic primary diamines in which the hydrocarbyl group between the two meta amino groups is a methyl group, while the two remaining hydrocarbyl groups are ethyl groups, and those in which the hydrocarbyl group between the two meta amino groups is an ethyl group, while one of the two remaining hydrocarbyl groups is a methyl group and the other is an ethyl group, and mixtures thereof.
  • More preferred aromatic primary diamines are also those in which one amino group is on each of two phenyl rings, where the two phenyl rings are connected via an alkylene bridge, and have both amino groups para relative to the alkylene bridge.
  • An especially preferred aromatic primary diamine of this type is a compound where each hydrocarbyl group ortho to an amino group is an ethyl group and the alkylene bridge is a methylene group.
  • a preferred aromatic primary diamine is one in which each position ortho to an amino group bears a hydrocarbyl group, and which aromatic primary diamine is in the form of one phenyl ring having two amino groups on the ring, which amino groups are meta or para relative to each other, and in which the aromatic primary diamine has amino groups are meta relative to each other, and/or the ortho hydrocarbyl groups are methyl, ethyl, isopropyl, butyl, or mixtures thereof.
  • aromatic primary diamines examples include 3,6-di-n-butyl-l,2- benzenediamine, 2,4,6-triethyl-l,3-benzenediamine, 2,4-diethyl-6-methyl-l,3-benzene- diamine, 4,6-diethyl-2-methyl- 1 ,3-benzenediamine, 2,4-diisopropyl-6-methyl- 1 ,3- benzenediamine, 2-methyl-4,6-di-sec-butyl- 1 ,3-benzenediamine, 2-ethyl-4-isopropyl-6- methyl-l,3-benzenediamine, 2,3,5-tri-n-propyl-l,4-benzenediamine, 2,3-diethyl-5-sec- butyl- 1 ,4-benzenediamine, 3 ,4-dimethyl-5 ,6-diheptyl- 1 ,2-benzenediamine, 2,4,5 ,6-t
  • aromatic primary diamines particularly preferred are 4,4'-methylenebis(2,6-diethylbenzeneamine), 4,4'-methylenebis-(2,6-diisopropyl- benzeneamine), and a mixture of 2,4-diethyl-6-methyl-l,3-benzene-diamine and 4,6- diethyl-2-methyl-l,3-benzenediamine (DETDA, Ethacure ® 100).
  • aromatic primary diamine which represents another particularly preferred aromatic primary diamine in this invention, can be called 4,4'-methylenbis(2,6-diethylbenzeneamine), 4,4'-methylenbis(2,6- diethylaniline), or 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane.
  • Aliphatic secondary ⁇ , ⁇ -diamines having at least one internal secondary amino group are component (f). Suitable aliphatic secondary diamines for component (f) are as described above for component (ii). Preferred aliphatic secondary ⁇ , ⁇ -diamines having at least one internal secondary amino group for component (f) include N,N'-di(3,3-dimethyl-
  • Component (g) is a combination of any two or more of (a), (d), and (f).
  • Preferred combinations for (g) include combinations of at least one component (a) and at least one component (d); more preferably, such combinations include only one component (a) and one component (d).
  • Preferred diamines for component (g) are the same as those described above for components (a), (d), and (f).
  • a preferred combination for (g) is N 5 N'- di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane and a mixture of 2,4-diethyl-6-methyl-l,3- benzene-diamine and 4,6-diethyl-2-methyl-l,3-benzenediamine (DETDA, Ethacure ® 100).
  • Relative proportions of an aliphatic secondary ⁇ , ⁇ -diamine having at least one internal secondary amino group to component (g) in the chain extender composition are preferably about 0.1 :1 to about 1 :0.1 on an equivalent basis; more preferably, the relative proportions on an equivalent basis are about 0.1 :1 to about 1 :0.5.
  • a polymer which is a polyurethane, polyurea, or polyurea-urethane is made by mixing together at least one polyisocyanate, at least one polyol and/or at least one polyetheramine, and a chain extender composition of the invention.
  • other components may also be included when making the polyurethane, polyurea, or polyurethane -urea, such as one or more flame retardants, thermal stabilizers, and/or surfactants.
  • the polyol or polyetheramine, chain extender composition, and when used, optional ingredients are blended together to form a first mixture, followed by blending this first mixture with the isocyanate to form a second mixture; this second mixture is allowed to cure.
  • the isocyanate and the polyol or polyetheramine are blended together to form a prepolymer, which prepolymer is then mixed together with the chain extender composition to form the desired polymer.
  • the isocyanate is mixed with polyol or polyetheramine to form a quasiprepolymer; polyol or polyetheramine is mixed with the chain extender composition to form a mixture; and then the mixture is mixed with the quasiprepolymer to form the desired polymer.
  • the chain extender composition is reacted with an aliphatic polyisocyanate and at least one polyol and/or at least one polyetheramine or with a prepolymer or a quasiprepolymer of the isocyanate and the polyol or polyetheramine.
  • use of quasiprepolymers is preferred way of producing polyureas.
  • the aliphatic polyisocyanates are organic polyisocyanates having at least two isocyanate groups. Generally, the isocyanates have a free -NCO content of at least about 0.1% by weight.
  • Aliphatic polyisocyanates that can be used in the practice of this invention include isophorone diisocyanate (IPDI), cyclohexylene diisocyanate, 4,4'- methylenedicyclohexyl diisocyanate (H 12MD I); mixed aralkyl diisocyanates including tetramethylxylyl diisocyanates; and polymethylene isocyanates including 1,4- tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HMDI), 1 ,7-heptamethylene diisocyanate, 2,2,4-and 2,4,4- trimethylhexamethylene diisocyanate, 1,10-decamethylene diisocyanate
  • aromatic polyisocyanates can be used in the processes of this invention.
  • Aromatic polyisocyanates that can be used with an aliphatic secondary ⁇ , ⁇ -diamine having a secondary amino straight chain are organic polyisocyanates having at least two isocyanate groups. Generally, the isocyanates have a free -NCO content of at least about 0.1% by weight.
  • Aromatic polyisocyanates that can be used in the practice of this invention include phenylene diisocyanate, toluene diisocyanate (TDI), xylene diisocyanate, 1,5 -naphthalene diisocyanate, chlorophenylene 2,4-diisocyanate, bitoluene diisocyanate, dianisidine diisocyanate, tolidine diisocyanate, alkylated benzene diisocyanates, methylene -interrupted aromatic diisocyanates such as methylenediphenyl diisocyanates, especially 4,4'-methylenediphenyl diisocyanate (MDI), alkylated analogs of methylene-interrupted aromatic diisocyanates (such as 3,3'-dimethyl- 4,4'-diphenylmethane diisocyanate), and polymeric methylenediphenyl diisocyanates.
  • TDI toluene diiso
  • a preferred aromatic polyisocyanate is 4,4'-methylenediphenyl diisocyanate (MDI).
  • MDI 4,4'-methylenediphenyl diisocyanate
  • isocyanates that can be used are also taught in, for example, U.S. 4,595,742.
  • Isocyanate-reactive polyols and polyetheramines (sometimes referred to as amine- terminated polyols) that are typically used in making polyurethanes, polyureas, and polyurea-urethanes range in molecular weight from about 60 to over 6,000.
  • the polyols can be dihydric, trihydridic, or polyhydric polyols, but are usually dihydric.
  • polystyrene foams examples include poly(ethyleneoxy) glycols, dipropylene glycol, poly(propyleneoxy) glycols, dibutylene glycol, poly(butyleneoxy) glycols, and the polymeric glycol from caprolactone, commonly known as polycaprolactone.
  • the polyetheramines used to make polyurethanes, polyureas, and polyurea-urethanes are amine-capped polyols which are the reaction product of a polyol and then an amine with alkylene oxides as well as amine-capped hydroxyl-containing polyesters.
  • Polyetheramines typically have a molecular weight of about 200 to about 6000.
  • Jeffamines ® available from Huntsman Chemical Company and include Jeffamine ® T-5000, a polypropylene oxide triamine of about 5000 molecular weight, XTJ-509, a polypropylene oxide triamine of about 3000 molecular weight, XTJ-510, a polypropylene oxide diamine of about 4000 molecular weight, and Jeffamine ® D-2000, a polypropylene oxide diamine of about 2000 molecular weight.
  • Jeffamine ® T-5000 and Jeffamine ® D-2000 are preferred polyetheramines in the practice of this invention.
  • Proportions of polyol and/or polyetheramine to the chain extender composition are typically about 75:25 to about 50:50, and preferably are about 70:30 to about 55:45. More preferably, the proportions of polyol and/or polyetheramine to the chain extender composition are about 65:35 to about 60:40. Normally and preferably, the polyisocyanate and the polyol and/or polyetheramine are brought together in approximately equal volumes.
  • the chain extenders are N,N'-dicyclohexyl- 1,6-hexanediamine and N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane or N 5 N'- dicyclohexyl-l,6-hexanediamine and a mixture of 2,4-diethyl-6-methyl-l,3-benzene- diamine and 4,6-diethyl-2-methyl-l,3-benzenediamine (Ethacure ® 100, Albemarle Corporation).
  • the chain extenders are N 5 N'- diisopropyl-diethylenetriamine and N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane or N,N'-diisopropyl-diethylenetriamine and N,N'-di(3,3-dimethyl-2-butyl)- diethy lenetriamine .
  • the polymers formed by the invention are polyurethanes, polyureas, and polyurea- urethanes (sometimes called polyurea-polyurethanes). Because of their differing gel times
  • polyurethanes, polyureas, and polyurea-urethanes made with the chain extender compositions of the invention have more desirable gel times, and, at a minimum, the physical properties of the polymers are not adversely affected by the use of the chain extender compositions of the invention.
  • a stiffer polymer is obtained when made from chain extender compositions in which N,N'-dicyclohexyl-l,6-hexanediamine is used, in comparison to polymers made with the individual chain extenders.
  • Preferred polymers formed by this invention are formed when N,N'-dicyclohexyl- 1,6-hexanediamine and N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane or N 5 N'- dicyclohexyl-l,6-hexanediamine and a mixture of 2,4-diethyl-6-methyl-l,3- benzenediamine and 4, 6-diethyl-2 -methyl- 1,3-benzenediamine (Ethacure ® 100) are used as chain extenders in the formation of the polymers.
  • polymers formed by this invention are formed when N,N'-diisopropyl-diethylenetriamine and N,N'-di-(3,3- dimethyl-2 -butyl)- 1,6-diaminohexane or N,N'-diisopropyl-diethylenetriamine and N 5 N'- di(3,3-dimethyl-2-butyl)-diethylenetriamine are used as chain extenders in the formation of the polymers.
  • a pneumatic dispensing gun (DP-400-85-1, Mixpac Systems AG, Switzerland) was used in conjunction with a static mixer.
  • the static mixer was either a plastic spiral bell mixer with 30 elements and an inner diameter of 0.37 inches (-0.94 cm; EA 370-30, Ellsworth Adhesives) or a plastic bell mixer with 48 elements and an inner diameter of 0.25 inches (-0.64 cm; Statomix ® MS 06-48).
  • Polyurea formulations containing isophorone diisocyanate (IPDI), Jeffamine ® D- 2000 (a polyetheramine, Huntsman Chemical), N,N'-dicyclohexyl- 1,6-diaminohexane, and another aliphatic secondary diamine are prepared.
  • the isocyanate is mixed together with a portion of the Jeffamine ® D-2000 to form a quasiprepolymer.
  • the remainder of the Jeffamine ® D-2000 is blended with the N,N'-dicyclohexyl- 1,6-diaminohexane and the other aliphatic secondary diamine to form a mixture.
  • This mixture is then added to one compartment of the pneumatic mixing gun; the quasiprepolymer is added to the other compartment.
  • the mixture and quasiprepolymer are mixed (reacted) by pushing them through a static mixer onto a steel plate and curing at room temperature.
  • Four formulations were prepared, each containing a different aliphatic secondary diamine with the N,N'-dicyclohexyl-l,6-diaminohexane.
  • the other aliphatic secondary diamines were N,N'-di(sec-butyl)-4,4'-di(cyclohexylamino)methane, N,N'-di-(3,3-dimethyl-2-butyl)-l,6- diaminohexane, N,N'-(4-methyl-2-pentyl)-l,6-diaminohexane, and N,N'-diisopropyl-l,6- diaminohexane.
  • Another formulation is prepared; in this formulation, aliphatic primary diamines, a mixture of 2,4-diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2- methyl-l,3-benzenediamine (Ethacure ® 100, Albemarle Corporation), is mixed with the N,N'-dicyclohexyl-l,6-diaminohexane.
  • aliphatic primary diamines a mixture of 2,4-diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2- methyl-l,3-benzenediamine
  • Ethacure 100 is a mixture of 2,4- diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2-methyl-l,3-benzenediamine.
  • the isocyanate was mixed together with a portion of the Jeffamine ® polyetheramines to form a quasiprepolymer.
  • the remainder of the Jeffamine polyetheramines was blended with the chain extender(s) to form a mixture.
  • This mixture was then added to one compartment of the pneumatic mixing gun; the quasiprepolymer was added to the other compartment.
  • the mixture and quasiprepolymer were mixed (reacted) by pushing them through a static mixer onto a steel plate and cured at room
  • the invention may comprise, consist, or consist essentially of the materials and/or procedures recited herein.
  • the term "about" modifying the quantity of an ingredient in the compositions of the invention or employed in the methods of the invention refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or carry out the methods; and the like.
  • the term about also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term "about”, the claims include equivalents to the quantities.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des compositions d'allongeur de chaîne. Ces compositions comprennent soit (i) une N,N'-dicyclohexyl-1,6-hexanediamine ou(ii) une α,ω-diamine secondaire aliphatique ayant une chaîne droite aminée secondaire. Lorsque ladite composition comprend (i), ladite composition est également composée d'un composant choisi dans le groupe constitué par (a) une diamine secondaire aliphatique, (b) une diamine secondaire aliphatique et une diamine primaire aliphatique, (c) une diimine aliphatique, (d) une diamine primaire aromatique, et (e) une combinaison de deux ou plus de (a) à (d). Lorsque ladite composition comprend (ii), ladite composition est également composée d'un composant choisi dans le groupe constitué par (a) une diamine secondaire aliphatique, (d) une diamine primaire aromatique, (f) une a,w-diamine secondaire aliphatique ayant au moins un groupe amino secondaire interne, et (g) une combinaison de deux ou plus de (a), (d) et (f). L'invention concerne également des procédés de production de poly(uréthanes), de poly(urées) et de poly(urée-uréthanes).
PCT/US2008/056415 2007-03-13 2008-03-10 Allongeurs de chaîne Ceased WO2008112636A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010101560A1 (fr) * 2009-03-02 2010-09-10 Albemarle Corporation Bis[(alkylamino)alkyl]amines
WO2014144539A3 (fr) * 2013-03-15 2014-12-11 The Board Of Trustees Of The University Of Illinois Liaisons urée dynamiques pour polymères réversibles et autoréparants

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3609121A (en) * 1967-06-08 1971-09-28 Ciba Ltd Curable epoxy resin compositions containing novel disecondary diamines
US3658937A (en) * 1969-08-11 1972-04-25 Montedison Spa Process for preparing dye-receptive polyolefinic fibers
US4806616A (en) * 1987-12-09 1989-02-21 Uop Inc. N-N'-dialkylphenylenediamines as curing agents in polyurethane and polyurea manufacture by reaction injection molding
WO2002102869A1 (fr) * 2001-06-15 2002-12-27 Huntsman Petrochemical Corporation Extendeurs de chaine aminee synergique dans des elastomeres en spray a base de polyuree
WO2006104528A1 (fr) * 2005-03-28 2006-10-05 Albemarle Corporation Diimines et diamines secondaires

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3609121A (en) * 1967-06-08 1971-09-28 Ciba Ltd Curable epoxy resin compositions containing novel disecondary diamines
US3658937A (en) * 1969-08-11 1972-04-25 Montedison Spa Process for preparing dye-receptive polyolefinic fibers
US4806616A (en) * 1987-12-09 1989-02-21 Uop Inc. N-N'-dialkylphenylenediamines as curing agents in polyurethane and polyurea manufacture by reaction injection molding
WO2002102869A1 (fr) * 2001-06-15 2002-12-27 Huntsman Petrochemical Corporation Extendeurs de chaine aminee synergique dans des elastomeres en spray a base de polyuree
WO2006104528A1 (fr) * 2005-03-28 2006-10-05 Albemarle Corporation Diimines et diamines secondaires

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010101560A1 (fr) * 2009-03-02 2010-09-10 Albemarle Corporation Bis[(alkylamino)alkyl]amines
WO2014144539A3 (fr) * 2013-03-15 2014-12-11 The Board Of Trustees Of The University Of Illinois Liaisons urée dynamiques pour polymères réversibles et autoréparants

Also Published As

Publication number Publication date
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