WO2008086437A1 - Formulations for reaction injection molding and for spray systems - Google Patents

Formulations for reaction injection molding and for spray systems Download PDF

Info

Publication number
WO2008086437A1
WO2008086437A1 PCT/US2008/050659 US2008050659W WO2008086437A1 WO 2008086437 A1 WO2008086437 A1 WO 2008086437A1 US 2008050659 W US2008050659 W US 2008050659W WO 2008086437 A1 WO2008086437 A1 WO 2008086437A1
Authority
WO
WIPO (PCT)
Prior art keywords
benzenediamine
mixture
methyl
diethyl
diaminohexane
Prior art date
Application number
PCT/US2008/050659
Other languages
French (fr)
Inventor
William R. Brown
Paul L. Wiggins
John Y. Lee
Original Assignee
Albemarle Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Albemarle Corporation filed Critical Albemarle Corporation
Priority to BRPI0809262-1A2A priority Critical patent/BRPI0809262A2/en
Priority to AU2008204847A priority patent/AU2008204847A1/en
Priority to CN2008800012980A priority patent/CN101568566B/en
Priority to EP08705821A priority patent/EP2102265A1/en
Priority to EA200970678A priority patent/EA200970678A1/en
Priority to US12/444,870 priority patent/US8143365B2/en
Priority to JP2009545665A priority patent/JP2010515811A/en
Priority to CA002670041A priority patent/CA2670041A1/en
Publication of WO2008086437A1 publication Critical patent/WO2008086437A1/en

Links

Classifications

    • 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
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • 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
    • C08G18/3234—Polyamines cycloaliphatic
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C09D175/04—Polyurethanes
    • 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
    • C08G2120/00—Compositions for reaction injection moulding processes
    • 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
    • C08G2150/50—Compositions for coatings applied by spraying at least two streams of reaction components

Definitions

  • This invention relates to formulations to make polyureas and polyurea-urethanes via reaction injection molding or via spray systems.
  • Polyurethane, polyurea, and polyurethane-urea polymers are used in spray coatings and in reaction injection molding.
  • Spray coatings find application in concrete coatings, building coatings, secondary containment coatings, parking deck coatings, moisture seal coatings, blast abatement coatings, roof coatings, bridge coatings, tunnel liners, pipe liners, manhole liners, truck bed liners, and the like.
  • Reaction injection molding finds application in making body parts for automobiles, recreational vehicles, and farm equipment.
  • This invention provides spray coatings and articles made by reaction injection molding, and processes for spray coating and for reaction injection molding using mixtures of chain extenders. It has been discovered that the use of certain mixtures of chain extenders provide polyureas and polyurea-urethanes having desirable physical properties. Thus, a feature of this invention is that, by appropriate selection of chain extenders, the reactivity and physical properties of the coating can be tailored depending on the particular characteristics desired.
  • An embodiment of this invention is a spray coating which is formed from ingredients comprising at least (A) an aromatic polyisocyanate; and (B) a mixture formed from components comprised of
  • Another embodiment of this invention is a process for forming a spray coating, which process comprises bringing together at least (A) an aromatic polyisocyanate; and
  • Still another embodiment of this invention is an article formed by reaction injection molding, which article is formed from ingredients comprising at least (A) an aromatic polyisocyanate; and (B) a mixture formed from components comprised of
  • Yet another embodiment of this invention is a process for preparing a reaction injection molding product.
  • the process comprises I) bringing together at least (A) an aromatic polyisocyanate and (B) a mixture formed from components comprised of (i), (ii), and (iii) to form a molding mixture; II) injecting the molding mixture formed in I) into a mold to form a molded product; and III) opening the mold and removing the product formed in II).
  • the mixture (B), (i), (ii), and (iii) as used in forming the mixture are as follows:
  • the coatings and articles are polymers which are polyureas or polyurea-urethanes (sometimes called polyurea-polyurethanes).
  • the processes of this invention produce polymers which are polyureas or polyurea-urethanes.
  • a polyurethane-urea a polyisocyanate, usually and preferably a diisocyanate, is reacted with a diol.
  • a polyisocyanate (usually and preferably a diisocyanate) is reacted with a polyetheramine.
  • the aromatic polyisocyanates (A) in the coatings, articles, and processes of the present invention are organic polyisocyanates having at least two isocyanate groups.
  • the isocyanates have a free -NCO content of at least about 0.1% by weight.
  • the isocyanates have a free -NCO content of at about 10% to about 35% 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 and 2,4-methylenediphenyl diisocyanate (MDI), alkylated analogs of methylene-interrupted aromatic diisocyanates (such as 3,3'- dimethyl-4,4'-diphenylmethane diisocyanate), and polymeric methylenediphenyl diisocyanates.
  • aromatic polyisocyanates can be used in the practice of this invention.
  • Preferred aromatic polyisocyanates include 2,4- methylenediphenyl diisocyanate (MDI), 4,4-methylenediphenyl diisocyanate, and mixtures thereof. Examples of isocyanates that can be used are also taught in, for example, U.S. 4,595,742.
  • Isocyanate-reactive polyols that are typically used in making polyurea-urethanes and polyetheramines (sometimes referred to as amine-terminated polyols) that are typically used in making 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.
  • suitable polyols include poly(ethyleneoxy) glycols, dipropylene glycol, poly(propyleneoxy) glycols, dibutylene glycol, poly(butyleneoxy) glycols, and the polymeric glycol from caprolactone, commonly known as polycaprolactone.
  • polyetheramines used to make polyureas 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. Mixtures of two or more polyetheramines can be used in the practice of this invention.
  • Polyetheramines typically have a molecular weight of about 200 to about 6000.
  • XTJ-509 a polypropylene oxide triamine of about 3000 molecular weight
  • XTJ-510 a polypropylene oxide triamine of about 3000 molecular weight
  • Chain extenders employed in this invention are made up of an aromatic primary diamine and an aliphatic secondary diamine which has about twelve to about forty carbon atoms and in which the amino hydrocarbyl groups are secondary or tertiary hydrocarbyl groups.
  • the components can be present in the chain extender in a variety of proportions; the preferred ratios vary with the desired reactivity for forming a coating or article.
  • Aromatic primary diamines are component (ii) of the chain extenders used in this invention.
  • 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), may be the same or different.
  • suitable hydrocarbyl groups on the aromatic ring include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, cyclopentyl, hexyl, methylcyclohexyl, heptyl, octyl, cyclooctyl, nonyl, decyl, dodecyl, phenyl, benzyl, and the like.
  • Preferred hydrocarbyl groups on the phenyl ring(s) (ortho to an imino group) of the aromatic diimines are straight-chain or branched-chain alkyl groups having from one to about six carbon atoms; particularly preferred hydrocarbyl groups are methyl, ethyl, isopropyl, butyl, and mixtures of two or more of these groups.
  • the preference for butyl groups includes n-butyl, sec -butyl, and t-butyl groups.
  • 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- 1,2-benzenediamine, 2-isopropyl- 1,3-benzenediamine, 4-tert- butyl- 1 ,3-benzenediamine, 2-pentyl- 1 ,4-benzenediamine, 4,5-dihexyl- 1 ,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- 1 ,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-methylbenzeneamine), 4,4''-m
  • 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.
  • 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.
  • Particularly preferred are 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.
  • Examples of more preferred aromatic primary diamines include 3,6-di-n-butyl-l,2- benzenediamine, 2,4,6-triethyl- 1 ,3-benzenediamine, 2,4-diethyl-6-methyl- 1 ,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- 1,3-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-tetra-
  • 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-benzenediamine and 4,6-
  • Component (iii) is an aliphatic secondary diamine having amino hydrocarbyl groups which are secondary or tertiary hydrocarbyl groups.
  • the amino hydrocarbyl groups of the aliphatic secondary diamine can be cyclic or branched.
  • the amino hydrocarbyl groups are branched chain alkyl groups having from three to about twelve carbon atoms.
  • Suitable amino hydrocarbyl groups include isopropyl, sec-butyl, t-butyl, 3,3-dimethyl-2-butyl, 3-pentyl, cyclopentyl, 4-hexyl, cyclohexyl, methylcyclohexyl, cyclooctyl, 5-nonyl, and the like.
  • 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 a straight chain.
  • Cyclic and straight chain are preferred as the hydrocarbyl portion of the aliphatic secondary diamine.
  • the hydrocarbyl portion of the diamine is cyclic, the cyclic moiety can be fused rings, bicyclic rings, or a tricyclic system (which tricyclic system can contain fused rings and/or bicyclic rings).
  • the amino groups may be attached directly to the ring, or one or both amino groups may be bound to a group that is a substituent of the ring; it is preferred that at least one of the amino groups is bound to the ring.
  • the aliphatic secondary diamine typically has about twelve to about forty carbon atoms; preferably, the aliphatic secondary diamine has about fifteen to about twenty- five carbon atoms.
  • the relative proportions of aromatic primary diamine to aliphatic secondary diamine in the chain extender composition are preferably about 9:1 to about 1:9 on an equivalent basis; more preferably, the relative proportions on an equivalent basis are about 3:1 to about 2:3.
  • the relative proportions of aromatic primary diamine to aliphatic secondary diamine in the chain extender composition are preferably about 6:1 to about 1:6; more preferably, the relative proportions on a weight basis are about 2:1 to about 1:3.
  • Aliphatic secondary diamines that can be used in this invention include, but are not limited to, N,N'-di(l-cyclopropylethyl)-l,5-diaminopentane, N,N'-di(3,3-dimethyl-2- butyl)- 1 ,5-diamino-2-methylpentane, N,N'-di- sec-butyl- 1 ,6-diaminohexane, N,N'- dicyclohexyl- 1 ,6-diaminohexane, N,N'-di(3-pentyl)-2,5-dimethyl-2,5-hexanediamine, N,N'-di-(2,4-dimethyl-3-pentyl)-l,3-cyclohexanebis(methylamine), N,N'-diisopropyl-l,7- diaminoheptane, N,N'
  • Preferred aliphatic secondary diamines include N,N'-di-(3,3-dimethyl-2-butyl)-l,6- diaminohexane, N,N'-dicyclohexyl-l,6-diaminohexane, and N,N'-di-(3,3-dimethyl-2- butyl)-TCD diamine.
  • Relative proportions of aromatic primary diamine to aliphatic secondary diamine are can be about 5:1 to about 1:5 on an equivalent basis.
  • the relative proportions of aromatic primary diamine to aliphatic secondary diamine on an equivalent basis are about 3:1 to about 1:3.
  • the relative proportions of the polyol and/or polyetheramine to the chain extender are usually in the range of about 1:1 to about 1:4, and preferably are in the range of about 1:1.5 to about 1:3.
  • ingredients that may optionally be used include, but are not limited to, flame retardants or flame suppressant agents, catalysts, solvents, diluents, moisture scavenging agents, accelerators, antioxidants, coupling agents, stabilizers, lubricants, surfactants, emulsifiers, viscosity control agents, plasticizers, biocides, antistatic agents, fillers, fibrous reinforcing agents such as chopped glass fibers, pigments, dyes, blowing agents, foaming agents, thixotropic agents, cell regulators, and polymeric and resin additives.
  • the optional ingredients also include internal and/or external mold release agents.
  • the "A side” reactant comprises the polyisocyanate
  • the "B side” reactant comprises the polyol and/or polyetheramine in admixture with the diamine chain extender together with any optional ingredients.
  • the polyisocyanate is mixed with polyol and/or polyetheramine to form a quasiprepolymer.
  • the quasiprepolymer is at least part of the side A reactant; the B side reactant still comprises polyol and/or polyetheramine in admixture with the diamine chain extender.
  • use of quasiprepolymers is preferred way of producing polyureas.
  • Coatings of the present invention are prepared by using a high-pressure impingement spray apparatus designed to mix and spray a two-component liquid chemical system.
  • the liquid system is made up of a polyisocyanate (A side) with a polyol and/or polyetheramine and chain extender (B side), which A side and B side components are mixed in the apparatus under high pressure and sprayed onto a substrate so as to form a polyurea or polyurea-urethane coating on the substrate.
  • Coating thicknesses as low as about 0.03 inches (0.08 cm) can be obtained.
  • coatings of this invention have thicknesses in the range of about 0.05 inches to about 0.125 inches (0.32 cm), although coatings deviating from these thicknesses are within the scope of the invention. Coatings with desirable gel times can be obtained without adversely affecting the coating's properties, such as sandability, durability, cure temperature, appearance of the coating, and application parameters such as sprayability.
  • the reactants may be sprayed to produce coatings on a variety of substances, including glass or synthetic fibers, woven or non- woven substrates, wood, concrete, stone, and metal, including metal foil and steel. If desired, the substrate may be heated prior to and/or during the application of the reactants.
  • the polyisocyanate (A side) and polyol and/or polyetheramine and chain extender (B side) generally are placed in separate containers and then are sprayed by a variable or fixed spray nozzle together onto a substrate.
  • the A side reactant and the B side reactant are sprayed at substantially equal volumes (e.g., a 1:1 volume ratio).
  • Other volume ratios, such as substantially 2:1 (A side to B side) are possible and within the scope of this invention.
  • Desired gel times vary with the particular substrate and application of the coating being formed, but gel times of about 2 seconds to about 50 seconds are typical. Preferred gel times again can vary, but are often in the range of about 6 seconds to about 15 seconds. As mentioned above, changing the components of the chain extender and/or their relative proportions can alter the gel time for the coating.
  • reaction injection molding Articles of the present invention are prepared by reaction injection molding.
  • a polyisocyanate (A side reactant) and a polyol and/or polyetheramine together with a chain extender (B side reactant) are brought together, injected into a mold, and exposed to conditions such that a solidified article is prepared. Thereafter the solidified article is removed from the mold.
  • the reaction injection molding process comprises bringing together the A side and B side reactants, usually prior to injection. The bringing together can occur in a mixing head from which the mixture is injected into the mold. It is recommended and preferred that the reactants are fed so that they are brought together in a desired weight ratio.
  • the reactants react rapidly after mixing to form polyurea or polyurethane/polyurea polymers; in reaction injection molding, it is intended that the polymers form primarily in the mold to form a molded article.
  • the reactants are usually stored in separate vessels prior to molding.
  • Desired gel times vary with the particular application of the article being formed, but gel times of about 1 second to about 20 seconds are typical. Preferred gel times again can vary, but are often in the range of about 2 seconds to about 6 seconds. As mentioned above, changing the components of the chain extender and/or their relative proportions can alter the gel time for forming the article.
  • the B side reactant was made by mixing together two polyetheramines,
  • the A side reactant was a quasiprepolymer of 2,4-methylenediphenyl diisocyanate
  • the B side reactant was loaded into a tank of the spray machine and a pad of nitrogen (55 psi) was placed in the tank.
  • the A side reactant was loaded into another tank of the spray machine and a pad of nitrogen (55 psi, 3.79x10 5 Pa) was placed in the tank.
  • the hoses were purged of air with nitrogen, and 4-5 liters of material was flushed through the hoses to remove any remnants of previous systems that were used.
  • the reactants in the tanks were heated to 5O 0 C and the mixing/spray pressure was set at 2100 psi (1.45xlO 7 Pa).
  • the gel time was measured by spraying an amount of the liquid reaction mixture onto a vertical panel, while measuring the time from spray impingement until the coating no longer ran.
  • Panel molds were made by using a metal panel with a polished surface that had been fitted with four 0.125-inch (3.18 mm) thick bars to create dams on four sides.
  • the molds were pretreated with a silicone material (Chesterton 983, a mold release agent) to facilitate coating removal.
  • Sample panels were produced by spraying, in multiple passes, the mixture of reactants onto panel molds while the panel molds were in horizontal positions. The coatings were allowed to cure at room temperature in the panel mold until they could be removed without distorting the resultant panels ( ⁇ 1-2 hr.). After 24 hours, test parts were stamped from the panels according to dimensions for each applicable ASTM test. The test parts were aged at 75 0 F (+/-5 0 F) (-24 0 C +/-2.8 0 C) for two weeks before testing.
  • Results are summarized in Table 1. Each sample shown is an average of three runs, with four samples used for each run. Sample 1 was too fast to spray. Results outside two standard deviations were not used to determine the values shown in Table 1.
  • Results are summarized in Table 2. Each sample shown is an average of three runs, with four samples used for each run.
  • reactants and components referred to by chemical name or formula anywhere in this document, whether referred to in the singular or plural, are identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type (e.g., another reactant, a solvent, or etc.). It matters not what preliminary chemical changes, transformations and/or reactions, if any, take place in the resulting mixture or solution or reaction medium as such changes, transformations and/or reactions are the natural result of bringing the specified reactants and/or components together under the conditions called for pursuant to this disclosure.
  • the reactants and components are identified as ingredients to be brought together in connection with performing a desired chemical operation or reaction or in forming a mixture to be used in conducting a desired operation or reaction.
  • an embodiment may refer to substances, components and/or ingredients in the present tense ("is comprised of”, “comprises”, “is”, etc.), the reference is to the substance, component or ingredient as it existed at the time just before it was first contacted, blended or mixed with one or more other substances, components and/or ingredients in accordance with the present disclosure.

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)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

This invention provides articles made by reaction injection molding and spray coatings, and processes for forming such articles and coatings. The coatings and articles are polyureas or polyurea-urethanes. The ingredients used to form the coatings and articles comprise at least (A) an aromatic polyisocyanate and (B) a mixture formed from components comprised of (i) at least one polyol and/or at least one polyetheramine, (ii) an aromatic primary diamine, and (iii) an aliphatic secondary diamine which has about twelve to about forty carbon atoms and in which the having amino hydrocarbyl groups are secondary or tertiary hydrocarbyl groups.

Description

FORMULATIONS FOR REACTION INJECTION MOLDING AND FOR SPRAY SYSTEMS
TECHNICAL FIELD [0001] This invention relates to formulations to make polyureas and polyurea-urethanes via reaction injection molding or via spray systems.
BACKGROUND
[0002] In the preparation of polyurea and polyurethane-urea polymers, there are many polyfunctional compounds which are indicated to be useful as chain extenders, including diols and aromatic diamines. None of these compounds has a reactivity such as to make it universally ideal, and many fail to provide satisfactory properties in the products made by their use. Thus, there is still a need to find compounds capable of serving as chain extenders or curing agents. U.S. Pat. No. 4,806,616 teaches the use of certain N,N'- dialkylphenylenediamines as chain extenders in preparing polyurethanes and polyureas. In this connection, also see for example U.S. 4,528,363, which teaches the use of secondary aliphatic diamines as part of a resin binder, and U.S. 6,218,480 Bl, which discloses use of aromatic diamines as hardeners for polyurethane-ureas. [0003] Polyurethane, polyurea, and polyurethane-urea polymers are used in spray coatings and in reaction injection molding. Spray coatings find application in concrete coatings, building coatings, secondary containment coatings, parking deck coatings, moisture seal coatings, blast abatement coatings, roof coatings, bridge coatings, tunnel liners, pipe liners, manhole liners, truck bed liners, and the like. Reaction injection molding finds application in making body parts for automobiles, recreational vehicles, and farm equipment. In this connection, there is a need for a spray system incorporating a mixture of chain extenders which provides coatings that have acceptable physical properties via formulations having appropriate gel times. Similarly, there is a need for a reaction injection molding process incorporating a mixture of chain extenders which provides a reaction injection mixture that has an appropriate gel time, has suitable properties at demolding, and has acceptable physical properties. SUMMARY OF THE INVENTION
[0004] This invention provides spray coatings and articles made by reaction injection molding, and processes for spray coating and for reaction injection molding using mixtures of chain extenders. It has been discovered that the use of certain mixtures of chain extenders provide polyureas and polyurea-urethanes having desirable physical properties. Thus, a feature of this invention is that, by appropriate selection of chain extenders, the reactivity and physical properties of the coating can be tailored depending on the particular characteristics desired.
[0005] An embodiment of this invention is a spray coating which is formed from ingredients comprising at least (A) an aromatic polyisocyanate; and (B) a mixture formed from components comprised of
(i) at least one polyol and/or at least one polyetheramine,
(ii) an aromatic primary diamine, and
(iii) an aliphatic secondary diamine which has about twelve to about forty carbon atoms and in which the having amino hydrocarbyl groups are secondary or tertiary hydrocarbyl groups.
[0006] Another embodiment of this invention is a process for forming a spray coating, which process comprises bringing together at least (A) an aromatic polyisocyanate; and
(B) a mixture formed from components comprised of (i) at least one polyol and/or at least one polyetheramine,
(ii) an aromatic primary diamine, and
(iii) an aliphatic secondary diamine which has about twelve to about forty carbon atoms and in which the having amino hydrocarbyl groups are secondary or tertiary hydrocarbyl groups. [0007] Still another embodiment of this invention is an article formed by reaction injection molding, which article is formed from ingredients comprising at least (A) an aromatic polyisocyanate; and (B) a mixture formed from components comprised of
(i) at least one polyol and/or at least one polyetheramine,
(ii) an aromatic primary diamine, and (iii) an aliphatic secondary diamine which has about twelve to about forty carbon atoms and in which the having amino hydrocarbyl groups are secondary or tertiary hydrocarbyl groups.
[0008] Yet another embodiment of this invention is a process for preparing a reaction injection molding product. The process comprises I) bringing together at least (A) an aromatic polyisocyanate and (B) a mixture formed from components comprised of (i), (ii), and (iii) to form a molding mixture; II) injecting the molding mixture formed in I) into a mold to form a molded product; and III) opening the mold and removing the product formed in II). In the mixture (B), (i), (ii), and (iii) as used in forming the mixture are as follows:
(i) at least one polyol and/or at least one polyetheramine, (ii) an aromatic primary diamine, and
(iii) an aliphatic secondary diamine which has about twelve to about forty carbon atoms and in which the having amino hydrocarbyl groups are secondary or tertiary hydrocarbyl groups.
[0009] These and other embodiments and features of this invention will be still further apparent from the ensuing description and appended claims.
FURTHER DETAILED DESCRIPTION OF THE INVENTION
[0010] In this invention, the coatings and articles are polymers which are polyureas or polyurea-urethanes (sometimes called polyurea-polyurethanes). Similarly, the processes of this invention produce polymers which are polyureas or polyurea-urethanes. [0011] To form a polyurethane-urea, a polyisocyanate, usually and preferably a diisocyanate, is reacted with a diol. To form a polyurea, a polyisocyanate (usually and preferably a diisocyanate) is reacted with a polyetheramine.
I. Ingredients
A. Aromatic polyisocyanate [0012] The aromatic polyisocyanates (A) in the coatings, articles, and processes of the present invention 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. Preferably, the isocyanates have a free -NCO content of at about 10% to about 35% 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 and 2,4-methylenediphenyl diisocyanate (MDI), alkylated analogs of methylene-interrupted aromatic diisocyanates (such as 3,3'- dimethyl-4,4'-diphenylmethane diisocyanate), and polymeric methylenediphenyl diisocyanates. Mixtures of two or more aromatic polyisocyanates can be used in the practice of this invention. Preferred aromatic polyisocyanates include 2,4- methylenediphenyl diisocyanate (MDI), 4,4-methylenediphenyl diisocyanate, and mixtures thereof. Examples of isocyanates that can be used are also taught in, for example, U.S. 4,595,742.
B. Polyols and polyetheramines
[0013] Isocyanate-reactive polyols that are typically used in making polyurea-urethanes and polyetheramines (sometimes referred to as amine-terminated polyols) that are typically used in making 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. Examples of suitable polyols include poly(ethyleneoxy) glycols, dipropylene glycol, poly(propyleneoxy) glycols, dibutylene glycol, poly(butyleneoxy) glycols, and the polymeric glycol from caprolactone, commonly known as polycaprolactone. Mixtures of two or more polyols can be used in the practice of this invention. The polyetheramines used to make polyureas 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. Mixtures of two or more polyetheramines can be used in the practice of this invention. Polyetheramines typically have a molecular weight of about 200 to about 6000. Several commercially available polyetheramines
® known as 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. C. Chain extenders
Components (ii) and (iii) are referred to collectively as chain extenders throughout this document. Chain extenders employed in this invention are made up of an aromatic primary diamine and an aliphatic secondary diamine which has about twelve to about forty carbon atoms and in which the amino hydrocarbyl groups are secondary or tertiary hydrocarbyl groups. The components can be present in the chain extender in a variety of proportions; the preferred ratios vary with the desired reactivity for forming a coating or article.
1. Component (ii)
[0014] Aromatic primary diamines are component (ii) of the chain extenders used in this invention.
[0015] One type of 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. 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. 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), may be the same or different. Examples of suitable hydrocarbyl groups on the aromatic ring include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, cyclopentyl, hexyl, methylcyclohexyl, heptyl, octyl, cyclooctyl, nonyl, decyl, dodecyl, phenyl, benzyl, and the like. Preferred hydrocarbyl groups on the phenyl ring(s) (ortho to an imino group) of the aromatic diimines are straight-chain or branched-chain alkyl groups having from one to about six carbon atoms; particularly preferred hydrocarbyl groups are methyl, ethyl, isopropyl, butyl, and mixtures of two or more of these groups. Here, the preference for butyl groups includes n-butyl, sec -butyl, and t-butyl groups. When one or more hydrocarbyl groups are present on the phenyl ring(s), the hydrocarbyl groups can have from one to about twenty carbon atoms; preferably, the hydrocarbyl groups have from one to about six carbon atoms.
[0016] 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- 1,2-benzenediamine, 2-isopropyl- 1,3-benzenediamine, 4-tert- butyl- 1 ,3-benzenediamine, 2-pentyl- 1 ,4-benzenediamine, 4,5-dihexyl- 1 ,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- 1 ,3-benzenediamine.
[0017] 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-methylbenzeneamine), 4,4'- methylenebis(3-sec-butylbenzeneamine), 4,4'-(l,2-ethanediyl)bis(2-methylbenzeneamine), 3,3'-methylenebis(2,4-dipentylbenzeneamine), 3,3'-methylenebis(5,6- diisopropylbenzeneamine), 4,4'-methylenebis(2,3-di-sec-butylbenzeneamine), 4,4'- methylenebis(3,5-di-tert-butylbenzeneamine), and the like. [0018] Another type of 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. Here, butyl groups include n-butyl, sec-butyl, and t-butyl groups. [0019] 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. Particularly preferred are 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. [0020] 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.
[0021] Examples of more preferred aromatic primary diamines include 3,6-di-n-butyl-l,2- benzenediamine, 2,4,6-triethyl- 1 ,3-benzenediamine, 2,4-diethyl-6-methyl- 1 ,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- 1,3-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-tetra- n-propyl- 1 ,3-benzenediamine, 2,3,5,6-tetraethyl- 1 ,4-benzenediamine, 2,2'-methylenebis(6- n-propylbenzeneamine), 2,2'-methylenebis(3,6-di-n-propylbenzeneamine), 3,3'- methylenebis(2,6-di-n-butylbenzeneamine), 4,4'-methylenebis(2,6-diethylbenzeneamine), 4,4'-methylenebis(2,6-diisopropylbenzeneamine), 4,4'-methylenebis(2-isopropyl-6- methylbenzeneamine), 4,4'-(l,2-ethanediyl)bis(2,6-diethylbenzeneamine), 4,4'-(l,2- ethanediyl)bis(2,6-diisopropylbenzeneamine), 2,2'-methylenebis(3,4,6-tripentylbenzene- amine), 3,3'-methylenebis(2,5,6-trihexylbenzeneamine), 4,4'-methylenebis(2,3,6- trimethylbenzeneamine), 4,4'-methylenebis(2,3,4,6-tetramethylbenzeneamine), and the like. Of these more preferred types of 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-benzenediamine and 4,6-
® diethyl-2-methyl-l,3-benzenediamine (DETDA, Ethacure 100).
[0022] Those of skill in the art will recognize that there are several ways to name the aromatic primary diamines used in this invention. For example, the structure
Figure imgf000009_0001
which represents a particularly preferred aromatic primary diamine in this invention, can be called 2,4-diethyl-6-methyl-l,3-benzenediamine, 2,4-diethyl-6-methyl-l,3- phenylenediamine, 3,5-diethyl-2,4-diaminotoluene, or 3,5-diethyl-toluene-2,4-diamine. Similarly, the structure
Figure imgf000009_0002
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. 2. Component (iii)
[0023] Component (iii) is an aliphatic secondary diamine having amino hydrocarbyl groups which are secondary or tertiary hydrocarbyl groups. The amino hydrocarbyl groups of the aliphatic secondary diamine can be cyclic or branched. Preferably, the amino hydrocarbyl groups are branched chain alkyl groups having from three to about twelve carbon atoms. Examples of suitable amino hydrocarbyl groups include isopropyl, sec-butyl, t-butyl, 3,3-dimethyl-2-butyl, 3-pentyl, cyclopentyl, 4-hexyl, cyclohexyl, methylcyclohexyl, cyclooctyl, 5-nonyl, and the like. [0024] 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 a straight chain. Cyclic and straight chain are preferred as the hydrocarbyl portion of the aliphatic secondary diamine. When the hydrocarbyl portion of the diamine is cyclic, the cyclic moiety can be fused rings, bicyclic rings, or a tricyclic system (which tricyclic system can contain fused rings and/or bicyclic rings). The amino groups may be attached directly to the ring, or one or both amino groups may be bound to a group that is a substituent of the ring; it is preferred that at least one of the amino groups is bound to the ring. The aliphatic secondary diamine typically has about twelve to about forty carbon atoms; preferably, the aliphatic secondary diamine has about fifteen to about twenty- five carbon atoms. The relative proportions of aromatic primary diamine to aliphatic secondary diamine in the chain extender composition are preferably about 9:1 to about 1:9 on an equivalent basis; more preferably, the relative proportions on an equivalent basis are about 3:1 to about 2:3. On a weight basis, the relative proportions of aromatic primary diamine to aliphatic secondary diamine in the chain extender composition are preferably about 6:1 to about 1:6; more preferably, the relative proportions on a weight basis are about 2:1 to about 1:3.
[0025] Aliphatic secondary diamines that can be used in this invention include, but are not limited to, N,N'-di(l-cyclopropylethyl)-l,5-diaminopentane, N,N'-di(3,3-dimethyl-2- butyl)- 1 ,5-diamino-2-methylpentane, N,N'-di- sec-butyl- 1 ,6-diaminohexane, N,N'- dicyclohexyl- 1 ,6-diaminohexane, N,N'-di(3-pentyl)-2,5-dimethyl-2,5-hexanediamine, N,N'-di-(2,4-dimethyl-3-pentyl)-l,3-cyclohexanebis(methylamine), N,N'-diisopropyl-l,7- diaminoheptane, N,N'-di-sec-butyl-l,8-diaminooctane, N,N'-di-(2-pentyl)-l,10- diaminodecane, N,N'-di-(3-hexyl)-l,12-diaminododecane, N,N'-di-(3-methyl-2- cyclohexenyl)- 1 ,2-diaminopropane, N,N'-di-(2,5-dimethylcyclopentyl)- 1 ,4-diamino- butane, N,N'-di(isophoryl)-l,5-diaminopentane, N,N'-di-(menthyl)-2,5-dimethyl-2,5- hexanediamine, and N,N'-di-(3,3-dimethyl-2-butyl)-3(4),8(9)-bis-(aminomethyl)- tricyclo[5.2.1.0(2,6)]decane (also called N,N'-di-(3,3-dimethyl-2-butyl)-TCD diamine). Preferred aliphatic secondary diamines include N,N'-di-(3,3-dimethyl-2-butyl)-l,6- diaminohexane, N,N'-dicyclohexyl-l,6-diaminohexane, and N,N'-di-(3,3-dimethyl-2- butyl)-TCD diamine.
[0026] Relative proportions of aromatic primary diamine to aliphatic secondary diamine are can be about 5:1 to about 1:5 on an equivalent basis. Preferably, the relative proportions of aromatic primary diamine to aliphatic secondary diamine on an equivalent basis are about 3:1 to about 1:3.
[0027] The relative proportions of the polyol and/or polyetheramine to the chain extender are usually in the range of about 1:1 to about 1:4, and preferably are in the range of about 1:1.5 to about 1:3.
D. Other ingredients
[0028] Other ingredients that may optionally be used include, but are not limited to, flame retardants or flame suppressant agents, catalysts, solvents, diluents, moisture scavenging agents, accelerators, antioxidants, coupling agents, stabilizers, lubricants, surfactants, emulsifiers, viscosity control agents, plasticizers, biocides, antistatic agents, fillers, fibrous reinforcing agents such as chopped glass fibers, pigments, dyes, blowing agents, foaming agents, thixotropic agents, cell regulators, and polymeric and resin additives. When the polyurea or polyurethane-urea polymer is formed via reaction injection molding, the optional ingredients also include internal and/or external mold release agents.
II. Processes of the invention
[0029] In the processes of the invention, the "A side" reactant comprises the polyisocyanate, and the "B side" reactant comprises the polyol and/or polyetheramine in admixture with the diamine chain extender together with any optional ingredients. In some processes of the invention, the polyisocyanate is mixed with polyol and/or polyetheramine to form a quasiprepolymer. When a quasiprepolymer is used, the quasiprepolymer is at least part of the side A reactant; the B side reactant still comprises polyol and/or polyetheramine in admixture with the diamine chain extender. In the practice of this invention, use of quasiprepolymers is preferred way of producing polyureas.
A. Spray coating [0030] Coatings of the present invention are prepared by using a high-pressure impingement spray apparatus designed to mix and spray a two-component liquid chemical system. The liquid system is made up of a polyisocyanate (A side) with a polyol and/or polyetheramine and chain extender (B side), which A side and B side components are mixed in the apparatus under high pressure and sprayed onto a substrate so as to form a polyurea or polyurea-urethane coating on the substrate. Coating thicknesses as low as about 0.03 inches (0.08 cm) can be obtained. Generally, coatings of this invention have thicknesses in the range of about 0.05 inches to about 0.125 inches (0.32 cm), although coatings deviating from these thicknesses are within the scope of the invention. Coatings with desirable gel times can be obtained without adversely affecting the coating's properties, such as sandability, durability, cure temperature, appearance of the coating, and application parameters such as sprayability. The reactants may be sprayed to produce coatings on a variety of substances, including glass or synthetic fibers, woven or non- woven substrates, wood, concrete, stone, and metal, including metal foil and steel. If desired, the substrate may be heated prior to and/or during the application of the reactants. [0031] In spray coating, the polyisocyanate (A side) and polyol and/or polyetheramine and chain extender (B side) generally are placed in separate containers and then are sprayed by a variable or fixed spray nozzle together onto a substrate. Normally and preferably, the A side reactant and the B side reactant are sprayed at substantially equal volumes (e.g., a 1:1 volume ratio). Other volume ratios, such as substantially 2:1 (A side to B side), are possible and within the scope of this invention.
[0032] It cannot be stressed strongly enough that one must not gain the impression that inconsequential variations in one or both streams cannot occur. Interruptions which do not materially affect the conduct of the process are not excluded from the scope of this invention. To safeguard against hypertechnical legalistic word interpretation, it has been deemed prudent to employ terms such as "substantially equal" and "substantially 2:1" in describing this invention. But whatever the terms used, the process should be conducted as one of ordinary skill in the art would carry out the processes after a thorough, unbiased reading of this entire disclosure and in keeping with the spirit of the invention gained from such a reading.
[0033] Desired gel times vary with the particular substrate and application of the coating being formed, but gel times of about 2 seconds to about 50 seconds are typical. Preferred gel times again can vary, but are often in the range of about 6 seconds to about 15 seconds. As mentioned above, changing the components of the chain extender and/or their relative proportions can alter the gel time for the coating.
B. Reaction injection molding [0034] Articles of the present invention are prepared by reaction injection molding. In reaction injection molding, a polyisocyanate (A side reactant) and a polyol and/or polyetheramine together with a chain extender (B side reactant) are brought together, injected into a mold, and exposed to conditions such that a solidified article is prepared. Thereafter the solidified article is removed from the mold. [0035] More specifically, the reaction injection molding process comprises bringing together the A side and B side reactants, usually prior to injection. The bringing together can occur in a mixing head from which the mixture is injected into the mold. It is recommended and preferred that the reactants are fed so that they are brought together in a desired weight ratio. The reactants react rapidly after mixing to form polyurea or polyurethane/polyurea polymers; in reaction injection molding, it is intended that the polymers form primarily in the mold to form a molded article. The reactants are usually stored in separate vessels prior to molding.
[0036] Desired gel times vary with the particular application of the article being formed, but gel times of about 1 second to about 20 seconds are typical. Preferred gel times again can vary, but are often in the range of about 2 seconds to about 6 seconds. As mentioned above, changing the components of the chain extender and/or their relative proportions can alter the gel time for forming the article.
[0037] The following examples are presented for purposes of illustration, and are not intended to impose limitations on the scope of this invention. [0038] In the following Examples, the reactants were sprayed with a two-part proportioning spray machine (Graco, Inc., model # E-XP2), fitted with 2.5 gallon (9.5 L) feed tanks, 60 feet (18 m) of 0.25-inch (6.35 mm) inner diameter high pressure hoses and an internal mechanical multi-feed mixing spray gun (Graco, Inc., Fusion MP). A direct impingement mixing module (Graco, Inc., model # XF1818) was used, and the spray nozzle was a metal alloy (Graco, Inc., CeramTip # 424). This apparatus is designed to deliver a 1 : 1 volume ratio of the A and B sides.
EXAMPLE 1 (COMPARATIVE)
[0039] The B side reactant was made by mixing together two polyetheramines,
® ®
Jeffamine D-2000 and Jeffamine T-5000 (Huntsman Polyurethanes), a mixture of 2,4- diethyl-6-methyl- 1 ,3-benzenediamine and 4,6-diethyl-2-methyl- 1 ,3-benzenediamine
® (Ethacure 100, Albemarle Corporation), and N,N'-di-(sec-butyl)-4,4'-methylenebis-
® (benzeneamine) (Unilink 4200, Dorf Ketal Ltd.). Proportions in the B side were varied in each run; see Table 1. Each ingredient was weighed to the nearest 0.1 gram into a lined 5-gallon (-22 L) can fitted with a bung lid. A 12 kilogram batch was made. After all of the ingredients had been placed in the 5-gallon can, the can was sealed and placed on a horizontal drum roller and rolled for four hours at ambient temperature until the mixture inside was uniform.
[0040] The A side reactant was a quasiprepolymer of 2,4-methylenediphenyl diisocyanate
® ®
(MDI) and Jeffamine D-2000, which quasiprepolymer is sold as Rubinate 9480
(Huntsman Polyurethanes).
[0041] The B side reactant was loaded into a tank of the spray machine and a pad of nitrogen (55 psi) was placed in the tank. The A side reactant was loaded into another tank of the spray machine and a pad of nitrogen (55 psi, 3.79x105 Pa) was placed in the tank.
The hoses were purged of air with nitrogen, and 4-5 liters of material was flushed through the hoses to remove any remnants of previous systems that were used. The reactants in the tanks were heated to 5O0C and the mixing/spray pressure was set at 2100 psi (1.45xlO7 Pa).
[0042] The gel time was measured by spraying an amount of the liquid reaction mixture onto a vertical panel, while measuring the time from spray impingement until the coating no longer ran.
[0043] Panel molds were made by using a metal panel with a polished surface that had been fitted with four 0.125-inch (3.18 mm) thick bars to create dams on four sides. The molds were pretreated with a silicone material (Chesterton 983, a mold release agent) to facilitate coating removal. Sample panels were produced by spraying, in multiple passes, the mixture of reactants onto panel molds while the panel molds were in horizontal positions. The coatings were allowed to cure at room temperature in the panel mold until they could be removed without distorting the resultant panels (~ 1-2 hr.). After 24 hours, test parts were stamped from the panels according to dimensions for each applicable ASTM test. The test parts were aged at 750F (+/-50F) (-240C +/-2.80C) for two weeks before testing.
[0044] Results are summarized in Table 1. Each sample shown is an average of three runs, with four samples used for each run. Sample 1 was too fast to spray. Results outside two standard deviations were not used to determine the values shown in Table 1.
TABLE 1
Figure imgf000015_0001
Figure imgf000016_0001
EXAMPLE 2 [0045] The procedures of Example 1 were repeated, except that the chain extender (in the
® B side) was Ethacure 100 and N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane.
Results are summarized in Table 2. Each sample shown is an average of three runs, with four samples used for each run.
TABLE 2
Figure imgf000016_0002
Figure imgf000017_0001
[0046] It is to be understood that the reactants and components referred to by chemical name or formula anywhere in this document, whether referred to in the singular or plural, are identified as they exist prior to coming into contact with another substance referred to by chemical name or chemical type (e.g., another reactant, a solvent, or etc.). It matters not what preliminary chemical changes, transformations and/or reactions, if any, take place in the resulting mixture or solution or reaction medium as such changes, transformations and/or reactions are the natural result of bringing the specified reactants and/or components together under the conditions called for pursuant to this disclosure. Thus the reactants and components are identified as ingredients to be brought together in connection with performing a desired chemical operation or reaction or in forming a mixture to be used in conducting a desired operation or reaction. Also, even though an embodiment may refer to substances, components and/or ingredients in the present tense ("is comprised of", "comprises", "is", etc.), the reference is to the substance, component or ingredient as it existed at the time just before it was first contacted, blended or mixed with one or more other substances, components and/or ingredients in accordance with the present disclosure.
[0047] Except as may be expressly otherwise indicated, the article "a" or "an" if and as used herein is not intended to limit, and should not be construed as limiting, the description or a claim to a single element to which the article refers. Rather, the article "a" or "an" if and as used herein is intended to cover one or more such elements, unless the text expressly indicates otherwise.
[0048] Also, even though the claims may refer to substances in the present tense (e.g., "comprises", "is", etc.), the reference is to the substance as it exists at the time just before it is first contacted, blended or mixed with one or more other substances in accordance with the present disclosure.
[0049] Each and every patent or other publication or published document referred to in any portion of this specification is incorporated in toto into this disclosure by reference, as if fully set forth herein.
[0050] This invention is susceptible to considerable variation within the spirit and scope of the appended claims.

Claims

1. A spray coating which is formed from ingredients comprising at least (A) an aromatic polyisocyanate; and (B) a mixture formed from components comprised of (i) at least one polyol and/or at least one polyetheramine, (ii) an aromatic primary diamine, and
(iii) an aliphatic secondary diamine which has about twelve to about forty carbon atoms and in which the having amino hydrocarbyl groups are secondary or tertiary hydrocarbyl groups.
2. A coating as in Claim 1 wherein
(ii) is an aromatic primary diamine 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/or the hydrocarbyl portion of the aliphatic secondary diamine is a straight chain.
3. A coating as in Claim 1 wherein
(ii) is a mixture of 2,4-diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2- methyl- 1 ,3-benzenediamine, and/or
(iii) is N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane or N,N'-dicyclohexyl- 1,6-diaminohexane.
4. A coating as in Claim 3 wherein (ii) is a mixture of 2,4-diethyl-6-methyl- 1,3-benzenediamine and 4,6-diethyl-2-methyl-l,3-benzenediamine, and wherein (iii) is N,N'-di-(3,3-dimethyl-2-butyl)- 1 ,6-diaminohexane or N,N'-dicyclohexyl- 1 ,6- diaminohexane.
5. A coating as in any of Claims 1-4 wherein said polyisocyanate is 4,4- methylenediphenyl diisocyanate, 2,4-methylenediphenyl diisocyanate, or a mixture thereof.
6. A process for forming a spray coating, which process comprises bringing together at least (A) at least one aromatic polyisocyanate; and
(B) a mixture formed from components comprised of
(i) at least one polyol and/or at least one polyetheramine, (ii) an aromatic primary diamine, and (iii) an aliphatic secondary diamine which has about twelve to about forty carbon atoms and in which the having amino hydrocarbyl groups are secondary or tertiary hydrocarbyl groups; and spraying said mixture onto a surface.
7. A process as in Claim 6 wherein
(ii) is an aromatic primary diamine 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/or the hydrocarbyl portion of the aliphatic secondary diamine is a straight chain.
8. A process as in Claim 6 wherein
(ii) is a mixture of 2,4-diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2- methyl- 1 ,3-benzenediamine, and/or
(iii) is N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane or N,N'-dicyclohexyl- 1,6-diaminohexane.
9. A process as in Claim 8 wherein (ii) is a mixture of 2,4-diethyl-6-methyl- 1,3-benzenediamine and 4,6-diethyl-2-methyl-l,3-benzenediamine, and wherein (iii) is N,N'-di-(3,3-dimethyl-2-butyl)- 1 ,6-diaminohexane or N,N'-dicyclohexyl- 1 ,6- diaminohexane.
10. A process as in any of Claims 6-9 wherein said polyisocyanate is 4,4- methylenediphenyl diisocyanate, 2,4-methylenediphenyl diisocyanate, or a mixture thereof.
11. A process as in any of Claims 6-10 wherein at least a portion of (i) is a quasiprepolymer.
12. An article formed by reaction injection molding, which article is formed from ingredients comprising at least (A) an aromatic polyisocyanate and (B) a mixture formed from components comprised of (i) at least one polyol and/or at least one polyetheramine, (ii) an aromatic primary diamine, and (iii) an aliphatic secondary diamine which has about twelve to about forty carbon atoms and in which the having amino hydrocarbyl groups are secondary or tertiary hydrocarbyl groups.
13. An article as in Claim 12 wherein
(ii) is an aromatic primary diamine 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/or the hydrocarbyl portion of the aliphatic secondary diamine is a straight chain.
14. An article as in Claim 12 wherein
(ii) is a mixture of 2,4-diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2- methyl- 1 ,3-benzenediamine, and/or (iii) is N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane or N,N'-dicyclohexyl-
1 ,6-diaminohexane.
15. An article as in Claim 14 wherein (ii) is a mixture of 2,4-diethyl-6-methyl- 1,3-benzenediamine and 4,6-diethyl-2-methyl-l,3-benzenediamine, and wherein (iii) is N,N'-di-(3,3-dimethyl-2-butyl)- 1 ,6-diaminohexane or N,N'-dicyclohexyl- 1 ,6- diaminohexane .
16. An article as in any of Claims 12-15 wherein said polyisocyanate is 4,4- methylenediphenyl diisocyanate, 2,4-methylenediphenyl diisocyanate, or a mixture thereof.
17. A process for preparing a reaction injection molding product, which process comprises
I) bringing together at least (A) an aromatic polyisocyanate and (B) a mixture formed from components comprised of
(i) at least one polyol and/or at least one polyetheramine, (ii) an aromatic primary diamine, and (iii) an aliphatic secondary diamine which has about twelve to about forty carbon atoms and in which the having amino hydrocarbyl groups are secondary or tertiary hydrocarbyl groups, forming a molding mixture;
II) injecting said molding mixture formed in I) into a mold to form a molded product; and
III) opening the mold and removing the product formed in II).
18. A process as in Claim 17 wherein
(ii) is an aromatic primary diamine 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/or the hydrocarbyl portion of the aliphatic secondary diamine is a straight chain.
19. A process as in Claim 17 wherein
(ii) is a mixture of 2,4-diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2- methyl- 1 ,3-benzenediamine, and/or
(iii) is N,N'-di-(3,3-dimethyl-2-butyl)-l,6-diaminohexane or N,N'-dicyclohexyl-
1 ,6-diaminohexane.
20. A process as in Claim 19 wherein (iii) is N,N'-di-(3,3-dimethyl-2-butyl)-
1,6-diaminohexane or N,N'-dicyclohexyl-l,6-diaminohexane, and wherein (ii) is a mixture of 2,4-diethyl-6-methyl-l,3-benzenediamine and 4,6-diethyl-2-methyl-l,3- benzenediamine .
21. A process as in any of Claims 17-20 wherein (i) is at least one polyetheramine.
22. A process as in any of Claims 17-21 wherein said polyisocyanate is 4,4- methylenediphenyl diisocyanate, 2,4-methylenediphenyl diisocyanate, or a mixture thereof.
23. A process as in any of Claims 17-22 wherein at least a portion of (i) is a quasiprepolymer.
PCT/US2008/050659 2007-01-10 2008-01-09 Formulations for reaction injection molding and for spray systems WO2008086437A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
BRPI0809262-1A2A BRPI0809262A2 (en) 2007-01-10 2008-01-09 ASPERSION COATING; PROCESS FOR FORMATION OF AN ASPERSION COATING; ARTICLE FORMED THROUGH REACTION INJECTION MOLDING; AND PROCESS FOR PREPARING A REACTION INJECTION MOLDING PRODUCT.
AU2008204847A AU2008204847A1 (en) 2007-01-10 2008-01-09 Formulations for reaction injection molding and for spray systems
CN2008800012980A CN101568566B (en) 2007-01-10 2008-01-09 Formulations for reaction injection molding and for spray systems
EP08705821A EP2102265A1 (en) 2007-01-10 2008-01-09 Formulations for reaction injection molding and for spray systems
EA200970678A EA200970678A1 (en) 2007-01-10 2008-01-09 COMPOSITIONS FOR REACTIVE-CASTING FORMING AND SPRAYING SYSTEMS
US12/444,870 US8143365B2 (en) 2007-01-10 2008-01-09 Formulations for reaction injection molding and for spray systems
JP2009545665A JP2010515811A (en) 2007-01-10 2008-01-09 Compositions for reaction injection molding and spray systems
CA002670041A CA2670041A1 (en) 2007-01-10 2008-01-09 Formulations for reaction injection molding and for spray systems

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US88429307P 2007-01-10 2007-01-10
US60/884,293 2007-01-10

Publications (1)

Publication Number Publication Date
WO2008086437A1 true WO2008086437A1 (en) 2008-07-17

Family

ID=38221955

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2008/050659 WO2008086437A1 (en) 2007-01-10 2008-01-09 Formulations for reaction injection molding and for spray systems

Country Status (10)

Country Link
US (1) US8143365B2 (en)
EP (1) EP2102265A1 (en)
JP (1) JP2010515811A (en)
KR (1) KR20090098961A (en)
CN (1) CN101568566B (en)
AU (1) AU2008204847A1 (en)
BR (1) BRPI0809262A2 (en)
CA (1) CA2670041A1 (en)
EA (1) EA200970678A1 (en)
WO (1) WO2008086437A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2466501A (en) * 2008-12-23 2010-06-30 Isothane Ltd Method for preparing a composite material
GB2560224A (en) * 2016-12-22 2018-09-05 Hardshell Uk Ltd Reinforced polymer coating

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5427296B2 (en) * 2010-08-06 2014-02-26 川崎重工業株式会社 Gas pressure regulator
WO2015189045A1 (en) * 2014-06-11 2015-12-17 Basf Se Polyurethane compound for producing an integrated insulation component
NL2018902B1 (en) * 2017-05-11 2018-11-15 Cleopatra B V Method for manufacturing a self-supporting product
DE102019113433A1 (en) * 2019-05-21 2020-11-26 Dr. Ing. H.C. F. Porsche Aktiengesellschaft Component with a coating and method for coating
US11358169B2 (en) * 2019-08-26 2022-06-14 Raymond Micucci, JR. Automated system for applying coating to a surface

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
EP0420426A2 (en) * 1989-09-29 1991-04-03 Texaco Chemical Company Sprayable and pourable polyurea elastomer
US5616677A (en) * 1994-06-24 1997-04-01 Huntsman Petrochemical Corporation Preparation of sprayable aliphatic polyurea elastomers having improved properties
EP0802209A1 (en) * 1996-04-16 1997-10-22 Huntsman Petrochemical Corporation Polyurea spray railcar lining system
WO2002102869A1 (en) * 2001-06-15 2002-12-27 Huntsman Petrochemical Corporation Synergistic amine chain-extenders in polyurea spray elastomers
WO2004092632A2 (en) * 2003-04-04 2004-10-28 Fmc Technologies, Inc. Process and coating for sealing freezer enclosures

Family Cites Families (90)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2380420A (en) 1940-12-16 1945-07-31 William S Emerson Production of secondary and tertiary amines from nitrogen compounds
US2497292A (en) 1946-05-07 1950-02-14 Du Pont Preparation of n-isobutyl hexamethylenediamines
US2582128A (en) 1950-02-11 1952-01-08 Rohm & Haas Aldimines
US2953579A (en) 1958-05-07 1960-09-20 Shell Oil Co Epoxy aldimines
US2965605A (en) 1958-06-23 1960-12-20 Shell Oil Co Nu, nu'-dialkyl aromatic diamines
US3209030A (en) 1962-07-09 1965-09-28 Universal Oil Prod Co Reductive alkylation of amines
NL127232C (en) 1963-03-12 1900-01-01
US3275567A (en) 1963-06-27 1966-09-27 Engelhard Ind Inc Method of preparing a sulfided platinum on carbon catalyst
US3350450A (en) 1963-08-12 1967-10-31 Uniroyal Inc Process of preparing aromatic amines by the catalytic hydrogenation of aromatic nitro compounds
GB1070759A (en) 1964-02-13 1967-06-01 Goodyear Tire & Rubber Polyurethanes and method of making
FR1456497A (en) 1964-05-25 1966-10-28 Monsanto Co Catalytic condensation of carbonyl compounds with amines
CH481963A (en) 1967-06-08 1969-11-30 Ciba Geigy New curable mixtures of diepoxy compounds, disecondary amines and polyamines containing at least 3 amine hydrogen atoms
US3538161A (en) 1967-10-20 1970-11-03 Uniroyal Inc Reductive alkylation of aromatic amino compounds utilizing platinum metal selendies and tellurides as catalysts
US3625710A (en) 1969-06-25 1971-12-07 Procter & Gamble Aldimines as chocolate-like flavors
NL7011639A (en) 1969-08-11 1971-02-15
US3943158A (en) 1970-07-01 1976-03-09 Bayer Aktiengesellschaft Urea diisocyanate compositions
US3761425A (en) 1971-02-19 1973-09-25 Hoechst Ag Process for preparing sulfided platinum on carbon catalysts
US3952056A (en) 1972-02-07 1976-04-20 Ciba-Geigy Corporation Plant growth regulating agent
US3937730A (en) 1972-06-06 1976-02-10 Ciba-Geigy Corporation Plant growth regulating agent
US3994975A (en) 1974-10-07 1976-11-30 Petrolite Corporation Cyclohexylamines
US4161492A (en) 1975-01-24 1979-07-17 Bayer Aktiengesellschaft Cycloaliphatic amines and process for preparing same
DE2503261C2 (en) 1975-01-28 1976-12-30 Ruhrchemie Ag PROCESS FOR SULFIDATION OF PLATINUM-ON-CARBON CATALYSTS
DE2525295C3 (en) 1975-06-06 1980-02-14 Bayer Ag, 5090 Leverkusen Process for the production of azomethines
US4140718A (en) 1976-10-14 1979-02-20 Uop Inc. Preparation of N,N'-dialkylphenylenediamines
US4317916A (en) 1979-04-16 1982-03-02 Ciba-Geigy Corporation Process for producing N-substituted-N-acetyl-2,6-dialkyl-anilines
JPS6033423B2 (en) 1980-08-13 1985-08-02 宇部興産株式会社 Process for producing N-alkylalkylene diamine
DE3126435A1 (en) 1981-07-04 1983-01-20 Basf Ag, 6700 Ludwigshafen METHOD FOR THE PRODUCTION OF CELL-MADE POLYURETHANE-POLYURANE MOLDED BODIES, IF ANY, AND ALKYL-SUBSTITUTED PHENYLENE DIAMONIES THEREFOR
US4900868A (en) 1982-01-18 1990-02-13 Monsanto Company Process for producing N,N'-disubstituted paraphenylene diamine mixtures by sequential reductive alkylation
DE3232736A1 (en) 1982-09-03 1984-03-08 Bayer Ag, 5090 Leverkusen AROMATIC URETDION DI-UREA DIAMINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN POLYURETHANE SYNTHESIS
JPS59155470A (en) 1983-02-23 1984-09-04 Kansai Paint Co Ltd Resin composition for thermosetting paint
US4521624A (en) 1984-04-16 1985-06-04 Ethyl Corporation Process for making cyclic amines
US4714512A (en) 1985-03-25 1987-12-22 Uop Inc. Polyurethane coatings and adhesives
DE3528262A1 (en) 1985-08-07 1987-02-12 Hoechst Ag METHOD FOR PRODUCING AROMATIC DIALKYLAMINE
US4631298A (en) 1985-12-16 1986-12-23 Ethyl Corporation Mixed diamine chain extender
US4663201A (en) 1986-04-25 1987-05-05 Uop Inc. Polyurea coatings for objects of metal glass wood or plastic
MX170643B (en) 1986-08-01 1993-04-12 Ici America Inc POLYUREAS PREPARED FROM A MIXTURE OF POLYAMINS AND A POLYISOCYANATE
DE3710432A1 (en) 1987-03-28 1988-10-06 Basf Ag ELASTOMERS CONTAINING POLYAMIDE AND POLYROCURATE TIES, AND METHOD FOR THE PRODUCTION OF ELASTIC, COMPACT OR CELL-MOLDED MOLDED BODIES THEREOF
JPH06102710B2 (en) * 1987-04-07 1994-12-14 ザ ダウ ケミカル カンパニー Flexible polyurea or polyurea-polyurethane foam made from high equivalent weight amine terminated compounds and process for making same
EP0288067A1 (en) 1987-04-24 1988-10-26 Asahi Glass Company Ltd. Process for producing polyurethane elastomer and compositon as starting material therefor
EP0309980A1 (en) 1987-10-02 1989-04-05 The B.F. Goodrich Company Alkylated polyalkylene polyamines and process for selective alkylation
DE3739480A1 (en) 1987-11-21 1989-06-01 Huels Chemische Werke Ag METHOD FOR PRODUCING BLOCKED UREA GROUP-CONTAINING POLYISOCYANATES AND THE PRODUCTS MANAGED THEREFROM
US5001267A (en) 1987-12-21 1991-03-19 Texaco Chemical Company Secondary alkyl amine derivatives of ethylenediamine
US5008453A (en) 1989-04-14 1991-04-16 Ethyl Corporation Aromatic diimines
US5041668A (en) 1989-04-14 1991-08-20 Ethyl Corporation Secondary diamines
US5002806A (en) 1990-01-11 1991-03-26 Ashland Oil, Inc. Curative for structural urethane adhesive
US5059672A (en) 1990-06-25 1991-10-22 Thare Coat, Inc. Elastomeric reaction products of aromatic isocyanate, aliphatic isocyanate and aromatic diamine components
US5087661A (en) 1990-07-20 1992-02-11 Mitsui Toatsu Chemicals, Inc. Moisture curable polyurethane composition comprising polyaldimine
US5145825A (en) 1991-04-08 1992-09-08 Engelhard Corporation Oxidation catalyst resistant to sulfation
US5198524A (en) 1991-04-22 1993-03-30 W.R. Grace & Co.-Conn. Moisture-curing acrylate/epoxy hybrid adhesives
MY109091A (en) 1992-12-29 1996-11-30 Syngenta Participations Ag Process for the preparation of 2-alkyl-6-methyl-n-(1''''''''- methoxy-2''''''''-propyl)-aniline and a process for the preparation of their chloracetanilides.
TW322432B (en) 1993-06-14 1997-12-11 Degussa
US5312886A (en) 1993-09-20 1994-05-17 Uop Bis(N-alkylaminocyclohexyl)methanes as curing agents for polyurethanes and polyureas
DE4406949A1 (en) 1994-03-03 1995-09-07 Bayer Ag Process for the preparation of aliphatic imines
DE4413618A1 (en) 1994-04-19 1995-10-26 Hoechst Ag Process for the preparation of glycoloylanilides
US5470890A (en) 1994-06-17 1995-11-28 Uop Bis-(N-alkylaminocyclohexyl)methanes as curing agents in polyurethane and polyurea flexible foam manufacture
WO1996002584A1 (en) * 1994-07-14 1996-02-01 The Gates Rubber Company High temperature polyurethane/urea elastomers
US5646235A (en) 1995-03-27 1997-07-08 Huntsman Petrochemical Corporation Reductive alkylation of polyamines
JPH09100260A (en) 1995-04-13 1997-04-15 Nippon Kayaku Co Ltd Production of 4,4'-di(n-alkylaniline) compound
US5591807A (en) 1995-05-23 1997-01-07 The Sherwin-Williams Company Polyimine/polyisocyanate coating composition containing polymeric anhydride
AU6287596A (en) 1995-06-28 1997-01-30 Minnesota Mining And Manufacturing Company Ketimine curing agents and rapidly curing magnetic recording media and films prepared with ketimines
DE19546750A1 (en) 1995-12-14 1997-06-19 Huels Chemische Werke Ag Uretdione group-containing poly-addition products
DE19637375A1 (en) 1996-09-13 1998-03-19 Huels Chemische Werke Ag Polyisocyanates containing uretdione groups, a process for their preparation and their use
DE19637377A1 (en) 1996-09-13 1998-03-19 Huels Chemische Werke Ag Polyaddition compounds containing uretdione groups, a process for their preparation and their use
US6013755A (en) 1997-03-11 2000-01-11 Huntsman Petrochemical Corporation Method of preparing an aliphatic polyurea spray elastomer system
US6399736B1 (en) 1997-03-11 2002-06-04 Huntsman Petrochemical Corporation Method of preparing spray elastomer systems
US6218480B1 (en) 1997-06-16 2001-04-17 Mmr Technologies, Inc. Water-compatible urethane-containing amine hardener
US6103799A (en) 1998-01-20 2000-08-15 Air Products And Chemicals, Inc. Surface tension reduction with N,N'-dialkylalkylenediamines
US5874619A (en) 1998-04-07 1999-02-23 Albemarle Corporation Reducing the coloration of aromatic diamines
DE19816547A1 (en) 1998-04-15 1999-10-21 Degussa Polyisocyanates containing urea and uretdione groups
AUPP991799A0 (en) 1999-04-23 1999-05-20 Cardiac Crc Nominees Pty Limited Siloxane-containing polyurethane-urea compositions
EP1067116A1 (en) 1999-07-09 2001-01-10 The Procter & Gamble Company Process for the production of imines
WO2001036379A1 (en) 1999-11-11 2001-05-25 Idemitsu Petrochemical Co., Ltd. Transition metal compound, olefin polymerization catalyst, and method of polymerizing olefin
DE10002089A1 (en) 2000-01-19 2001-07-26 Basf Ag Weather-stable, radiation-curable polyurethanes
US6403752B1 (en) 2000-07-17 2002-06-11 Uop Llc Secondary aliphatic diamines as curing agents for polyurethanes and polyureas prepared using high-pressure impingement mixing
US20030004265A1 (en) 2001-05-16 2003-01-02 Gupta Laxmi C. Polyurea coating composition
US6803445B2 (en) 2001-08-08 2004-10-12 The Yokohama Rubber Co., Ltd. Moisture curable polyurethane and/or epoxy resin composition and storage stabilizer contained therein
AUPR732601A0 (en) 2001-08-28 2001-09-20 Polychip Pharmaceuticals Pty Ltd Methods for the synthesis of amines such as ephedrine and inter mediates
US6831187B2 (en) 2001-12-18 2004-12-14 Univation Technologies, Llc Multimetallic catalyst compositions for the polymerization of olefins
US6429338B1 (en) 2002-01-17 2002-08-06 Air Products And Chemicals, Inc. Hydrogenation of single ring aromatic diamines
US20040015016A1 (en) 2002-07-22 2004-01-22 Huntsman Petrochemical Corporation Preparation of secondary amines
WO2004073634A2 (en) 2003-02-20 2004-09-02 Encysive Pharmaceuticals Inc. Phenylenediamine urotensin-ii receptor antagonists and ccr-9 antagonists
US6939939B2 (en) 2003-02-24 2005-09-06 Younger Mfg. Polyurea/urethane optical material and method for making it
US7045632B2 (en) 2003-03-04 2006-05-16 Chevron Phillips Chemical Company, Lp Composition and method for a hexadentate ligand and bimetallic complex for polymerization of olefins
GB0323213D0 (en) 2003-10-03 2003-11-05 Univ Warwick Metallo-supramolecular arrays as anti-cancer and anti-viral agent
US20060068198A1 (en) 2004-09-02 2006-03-30 Bratys Dan M Composite films and process for making the same
US8076518B2 (en) 2005-03-28 2011-12-13 Albemarle Corporation Chain extenders
CA2602352C (en) 2005-03-28 2011-04-26 Albemarle Corporation Diimines and secondary diamines
US7964695B2 (en) 2005-03-28 2011-06-21 Albemarle Corporation Chain extenders
US20070066786A1 (en) 2005-09-22 2007-03-22 The Hanson Group, Llc Methods of preparing and using polyurea elastomers
US20070100112A1 (en) 2005-10-27 2007-05-03 Bayer Materialscience Llc Polyurethane-urea elastomers

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
EP0420426A2 (en) * 1989-09-29 1991-04-03 Texaco Chemical Company Sprayable and pourable polyurea elastomer
US5616677A (en) * 1994-06-24 1997-04-01 Huntsman Petrochemical Corporation Preparation of sprayable aliphatic polyurea elastomers having improved properties
EP0802209A1 (en) * 1996-04-16 1997-10-22 Huntsman Petrochemical Corporation Polyurea spray railcar lining system
WO2002102869A1 (en) * 2001-06-15 2002-12-27 Huntsman Petrochemical Corporation Synergistic amine chain-extenders in polyurea spray elastomers
WO2004092632A2 (en) * 2003-04-04 2004-10-28 Fmc Technologies, Inc. Process and coating for sealing freezer enclosures

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2466501A (en) * 2008-12-23 2010-06-30 Isothane Ltd Method for preparing a composite material
GB2466501B (en) * 2008-12-23 2012-11-28 Isothane Ltd Method for preparing a composite material
GB2560224A (en) * 2016-12-22 2018-09-05 Hardshell Uk Ltd Reinforced polymer coating
GB2560224B (en) * 2016-12-22 2022-03-30 Hardshell Uk Ltd Reinforced polymer coating

Also Published As

Publication number Publication date
US8143365B2 (en) 2012-03-27
KR20090098961A (en) 2009-09-18
US20100160592A1 (en) 2010-06-24
EP2102265A1 (en) 2009-09-23
JP2010515811A (en) 2010-05-13
EA200970678A1 (en) 2009-12-30
CA2670041A1 (en) 2008-07-17
BRPI0809262A2 (en) 2014-10-07
CN101568566B (en) 2012-07-11
AU2008204847A1 (en) 2008-07-17
CN101568566A (en) 2009-10-28

Similar Documents

Publication Publication Date Title
AU563124B2 (en) A process for preparing polyurea and/or polyurea-polyurethanepolymers
US8143365B2 (en) Formulations for reaction injection molding and for spray systems
CA2673071C (en) Triamine/aspartate curative and coatings comprising the same
US6013755A (en) Method of preparing an aliphatic polyurea spray elastomer system
AU674250B2 (en) Bis(N-alkylaminocyclohexyl)methanes as curing agents for polyurethanes and polyureas
JPH03185020A (en) Atomizable and flowable polyurea elastomer
AU2007300409B2 (en) Diamine chain extender compositions
JP3204783B2 (en) Polyurea elastomers prepared using polyoxyalkylene tetrafunctional or polyfunctional amines as chain extenders
JPH04175326A (en) Quickly drying polyurea elastomer
AU2007300253B2 (en) Chain extenders
US8759470B2 (en) Mixed polycycloaliphatic amines (MPCA) and MPCA alkylates
US5262448A (en) Process for the preparation of polyurea elastomers containing urethane groups
JPH04270274A (en) Piperazine derivative as chain extender comprising polyurea elastomer and preparation thereof
CA2026032C (en) Isocyanate reactive mixture and the use thereof in the manufacture of flexible polyurethane foams
EP0494546A1 (en) Foamed polyurea elastomer
JPH03273016A (en) Resin composition for reaction injection molding
JPH02300227A (en) Production of polyurea elastomer molding
WO2008039715A1 (en) Chain extenders
JPH04270275A (en) Alkyl-substituted piperazine and its use as chain extender in polyurea elastomer system
JPH07686B2 (en) Reaction injection molding resin composition
JPH0241310A (en) Production of polyurea-based elastomer

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200880001298.0

Country of ref document: CN

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

Ref document number: 08705821

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2008204847

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 2511/DELNP/2009

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 1020097009782

Country of ref document: KR

ENP Entry into the national phase

Ref document number: 2008204847

Country of ref document: AU

Date of ref document: 20080109

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2008705821

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2670041

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2009545665

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 200970678

Country of ref document: EA

WWE Wipo information: entry into national phase

Ref document number: 12444870

Country of ref document: US

ENP Entry into the national phase

Ref document number: PI0809262

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20090429