WO2002102871A1 - Mousse de pulverisation en polyuree souple exempte de tensioactif - Google Patents

Mousse de pulverisation en polyuree souple exempte de tensioactif Download PDF

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Publication number
WO2002102871A1
WO2002102871A1 PCT/US2002/018868 US0218868W WO02102871A1 WO 2002102871 A1 WO2002102871 A1 WO 2002102871A1 US 0218868 W US0218868 W US 0218868W WO 02102871 A1 WO02102871 A1 WO 02102871A1
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WO
WIPO (PCT)
Prior art keywords
carbon atoms
polyurea
group
chain
branched
Prior art date
Application number
PCT/US2002/018868
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English (en)
Inventor
Jerry L. Reddinger
Kenneth M. Hillman
Original Assignee
Huntsman Petrochemical 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 Huntsman Petrochemical Corporation filed Critical Huntsman Petrochemical Corporation
Publication of WO2002102871A1 publication Critical patent/WO2002102871A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/325—Polyamines containing secondary or tertiary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G2150/00—Compositions for coatings
    • C08G2150/60—Compositions for foaming; Foamed or intumescent coatings

Definitions

  • This invention relates to the formulation and manufacture of surfactant-free, flexible polyurea spray foams.
  • foams are derived from typically encountered polyurea coating formulations, but also employ water as the blowing agent in conjunction with standard urethane foam catalysts.
  • polyurea spray foams are potentially useful in application areas that require impact/damage protection(e.g. rail auto-hauler linings) from spray-applied coatings.
  • Polyureas are materials which are classified by those skilled in the art as having the general chemical structure:
  • n an organic di-isocyanate (hereinafter simply referred to as "isocyanate”) having at least two isocyanate groups and an organic di-amine having at least two different nitrogen atoms, each of which nitrogen atoms have an active hydrogen bonded to them.
  • the R groups are derived from the isocyanate component and the R' groups are derived from the amine component.
  • the value of n is often difficult to define in instances where crosslinldng occurs, and the above structure is thus at least useful for representing the general nature of the polyurea linkage.
  • Polyureas may be prepared in accordance with the invention having values of n in the range of about 10 on the lower end to the maximum number permitted by diffusion and other reaction kinetic factors, which maximum number is on the order of many tens of thousands.
  • foam stabilizers These stabilizers help generate uniform cell structure and protect the foam from preemptive collapse prior to cure.
  • foam density is often limited as the surfactant has an inherent threshold beyond which the stabilizer cannot support the weight of the foam and preserve cell structure.
  • the second approach involves initial spraying of a flexible foam layer followed by application of a polyurea elastomer top-coat.
  • One drawback to this method is its two-step nature. Also, inter-layer adhesion problems may arise between the foam and top-coat layers that may not be initially detected.
  • This invention relates to the formulation and manufacture of surfactant-free, flexible polyurea spray foams.
  • foams are derived from typically encountered polyurea coating formulations, but also employ water as the blowing agent in conjunction with standard urethane foam catalysts.
  • An added benefit of this chemistry is that these foams do not require foam-stabilizing surfactants, and thus, are free from foam density limitations that can be encountered with standard surfactant- stabilized foam technology.
  • these foams are self-skinning in nature and obviate the need of a secondary top-coat.
  • these spray foams can be coated with a secondary polyurea elastomer system to produce a smooth finish exhibiting similar surface properties as a standard polyurea spray elastomer coating.
  • These polyurea spray foams are potentially useful in application areas that require impact/damage protection(e.g. rail auto-hauler linings) from spray-applied coatings.
  • This invention relates to flexible polyurea spray foams based upon plural component coating technology.
  • the resulting polyurea materials are derived from an isocyanate component (A) and amine resin component (B).
  • the (A) component, or isocyanate component can consist of any number of suitable aromatic or aliphatic-based prepolymers or quasi-prepolymers. These are standard isocyanate compositions known to those skilled in the art. Preferred examples include MDI-based quasi prepolymers such as those available commercially
  • Liquefied MDI such as MONDUR® ML may be used as all or
  • the isocyanates employed in component (A) are generally known to one skilled in the art. Thus, for instance, they can include aliphatic isocyanates of the type described in U.S. Pat. No. 4,748,192. Accordingly, they are typically aliphatic diisocyanates and, more particularly, are the trimerized or the biuretic form of an aliphatic diisocyanate, such as hexamethylene diisocyanate, or the bifunctional monomer of the tetraalkyl xylene diisocyanate, such as the tetramethyl xylene diisocyanate. Cyclohexane diisocyanate is also to be considered a preferred aliphatic isocyanate.
  • aliphatic polyisocyanates include aliphatic diisocyanates, for example, alkylene diisocyanates with 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dodecane diisocyanate and 1,4-tetramethylene diisocyanate.
  • cycloaliphatic diisocyanates such as 1,3 and 1,4- cyclohexane diisocyanate as well as any desired mixture of these isomers, 1- isocyanato-3 ,3 ,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate); 4,4'-,2,2'- and 2,4'-dicyclohexylmethane diisocyanate as well as the corresponding isomer mixtures, and the like.
  • aromatic polyisocyanates may be used to form the foamed polyurea elastomer of the present invention.
  • Typical aromatic polyisocyanates include p-phenylene diisocyanate, polymethylene polyphenylisocyanate, 2,6-toluene diisocyanate, dianisidine diisocyanate, bitolylene diisocyanate, naphthalene- 1,4-diisocyanate, bis(4- isocy anatophenyl)methane, bis(3 -methyl-3 -iso-cyanatophenyl)methane, bis(3 -methyl- 4-isocyanatophenyl)methane, and 4,4'-diphenylpropane diisocyanate.
  • aromatic polyisocyanates used in the practice of the invention are methylene-bridged polyphenyl polyisocyanate mixtures which have a functionality of from about 2 to about 4. These latter isocyanate compounds are generally produced by the phosgenation of corresponding methylene bridged polyphenyl polyamines, which are conventionally produced by the reaction of formaldehyde and primary aromatic amines, such as aniline, in the presence of hydrochloric acid and/or other acidic catalysts.
  • Known processes for preparing polyamines and corresponding methylene- bridged polyphenyl polyisocyanates therefrom are described in the literature and in many patents, for example, U.S. Pat. Nos.
  • methylene-bridged polyphenyl polyisocyanate mixtures contain about 20 to about 100 weight percent methylene diphenyldiisocyanate isomers, with the remainder being polymethylene polyphenyl diisocyanates having higher functionalities and higher molecular weights.
  • polyphenyl polyisocyanate mixtures containing about 20 to about 100 weight percent diphenyldiisocyanate isomers, of which about 20 to about 95 weight percent thereof is the 4,4'-isomer with the remainder being polymethylene polyphenyl polyisocyanates of higher molecular weight and functionality that have an average functionality of from about 2.1 to about 3.5.
  • isocyanate mixtures are known, commercially available materials and can be prepared by the process described in U.S. Pat. No. 3,362,979.
  • a preferred aromatic polyisocyanate is methylene bis(4-phenylisocyanate) or "MDI". Pure MDI, quasi-prepolymers of MDI, modified pure MDI, etc.
  • liquid products based on MDI or methylene bis(4- phenylisocyanate) are used herein.
  • U.S. Pat. No. 3,394,164 incorporated herein by reference thereto, describes a liquid MDI product. More generally, uretonimine modified pure MDI is included also. This product is made by heating pure distilled MDI in the presence of a catalyst. The liquid product is a mixture of pure MDI and modified MDI.
  • isocyanate also includes quasi-prepolymers of isocyanates or polyisocyanates with active hydrogen containing materials.
  • the active hydrogen containing materials of component (A) can include, but are not limited to, a polyol or polyols, a high molecular weight polyoxyalkyleneamine or combinations thereof.
  • the (B) component, or amine resin component typically consists of a blend comprised of mid- to high-molecular weight polyether amines, low-molecular weight amine chain extenders, tertiary amine catalyst(s), blowing agent, and optionally, pigment and other additives known to those skilled in the art.
  • a single high molecular weight amine- terminated polyol may be used.
  • mixtures of high molecular weight amine terminated polyols such as mixtures of di- and tri-functional materials and/or different molecular weight or different chemical composition materials, may be used.
  • high-molecular weight, amine-terminated polyethers or simply polyether amines may be included in component (B) and may be used alone or in combination with the aforestated polyols.
  • the term "high molecular weight” is intended to include polyether amines having a molecular weight of at least about 200.
  • Huntsman Chemical Company they include without limitation JEFF AMINE® D-230,
  • suitable polyether amines include those commercially available from Huntsman Petrochemical
  • chain extenders utilized can include both aromatic and aliphatic molecules commonly employed in the current polyurea technology. It is also quite useful to use blends of chain extenders to tailor the gel, rise, and tack-free times of the resulting polyurea elastomers. Most preferably these chain extenders include the products
  • ETHACURE ® 100 from Albemarle Corp and UNILLNK ®
  • the chain extenders useful in this invention also include, l-methyl-3,5-diethyl-2,4-diaminobenzene, l-methyl-3,5-diethyl-2,6- diaminobenzene (both of these materials are also called diethyltoluene diamine or "DETDA” and are commercially available as ETHACURE® 100 from the Albemarle Corporation, Baton Rouge, La.), 4,4'-bis(sec-butylamino)diphenylmethane (commercially available as UNILINK® 4200, a product of UOP Corporation), and
  • aromatic diamine chain extenders are 1-methyl- 3,5-diethyl-2,4-diaminobenzene or a mixture of this compound with 4,4'-bis(sec- butylamino)diphenylmethane or l-methyl-3,5-diethyl-2,6-diaminobenzene. It is within the scope of this invention to include some aliphatic chain extender materials as described in U.S. Pat. Nos. 4,246,363, 4,269,945, and 5,470,890. Other chain extenders include 4,4'-bis(sec-butylamino), di(methylthio)-toluene
  • N,N'-bis(t-butyl)ethylenediamine each of which can be used alone or, preferably, in combination with l-methyl-3,5-diethyl-2,4-diaminobenzene or 1- methyl-3,5-diethyl-2,6-diaminobenzene.
  • the aforementioned combination includes from about 1 to about 99 parts of 4,4'-bis(sec-butylamino)diphenylmethane, di(methylthio)-toluene diamine, or N,N'-bis(t-butyl)ethylenediamine to about 99 to about 1 parts of DETDA.
  • the tertiary amine catalysts employed in this invention are those commonly used in polyurea and polyurethane foam chemistries.
  • JEFFCAT ® ZF-20 includes a blend of tertiary amines available commercially as JEFFCAT ® ZF-20 and
  • the (A) component and (B) component of the present polyurea elastomer system are combined or mixed under high pressure; most preferably, they are impingement-mixed directly in the high-pressure equipment, which is, for example, a
  • GUSMER ® H-V proportioner (or a GUSMER ® UR-H-2000) fitted with a GUSMER ®
  • Model GX-7 spray gun where open-mold work or coating is desired.
  • the ratios of these components are adjusted such that they are processed at a 1 : 1 volume ratio at an index between 0.9 and 1.20.
  • These systems can be processes within a pressure range
  • conditions including pressures between 1500-2500psi and temperature of 140-170°F.
  • the useful pressure range at which a surfactant-free polyurea may be prepared according to the invention is any pressure between 1000-3500 psi. However, one of ordinary skill recognizes that temperatures and pressures outside these ranges are also useful; thus the present invention is not necessarily limited to being practiced wi in these parameters.
  • Spray gun 400 spray gun.
  • the equipment was set so as to process each example at an isocyanate to resin blend volume ratio of 1.00.
  • Spray processing pressure was maintained at 1500 psi to 2500 psi on both the isocyanate and resin blend components.
  • the (A) component of a spray polyurea elastomer comprised a mixture 60
  • JEFFCAT® ZF-20 1.25 parts JEFFCAT® TD33A, and 10.0 parts titanium dioxide.
  • the (A) and (B) components were mixed in the high-pressure, high-temperature, impingement-mix spray equipment, at an (A):(B) weight ratio of 1.09 and a volumetric ratio of 1.00.
  • the resulting polyurea elastomer was sprayed onto a flat metal substrate coated with a sodium oleate based external mold release agent.
  • a good foam resulted with an instant cream time ( ⁇ 2.0 sec), a 3-6 second rise time, and a 12-16 second tack-free time.
  • the system was easily sprayable and exhibited an insignificant amount of shrinkage.
  • Example 2 The (A) component of a spray polyurea elastomer comprised a quasi-

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

Abstract

L'invention concerne des compositions et des méthodes pouvant fournir des revêtements à base de polyurée mousse élastomériques, tels que des calandrages intérieurs de camions. Les compositions et méthodes de l'invention conviennent pour la confection de revêtements à base de polyurée exempts d'un constituant tensioactif, lequel, dans les méthodes de la technique antérieure, est associé à des problèmes d'adhérence de la couche de finition et est difficile à enlever d'un équipement utilisé pour produire les revêtements.
PCT/US2002/018868 2001-06-15 2002-06-11 Mousse de pulverisation en polyuree souple exempte de tensioactif WO2002102871A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US29844601P 2001-06-15 2001-06-15
US60/298,446 2001-06-15

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WO2002102871A1 true WO2002102871A1 (fr) 2002-12-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9278889B2 (en) 2010-05-12 2016-03-08 3M Innovative Properties Company Method of reinforcing irregular structures

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5100997A (en) * 1990-05-29 1992-03-31 Olin Corporation Preparation of elastomers using high molecular weight polyols or polyamines, said polyols prepared using a double metal cyanide complex catalyst

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5100997A (en) * 1990-05-29 1992-03-31 Olin Corporation Preparation of elastomers using high molecular weight polyols or polyamines, said polyols prepared using a double metal cyanide complex catalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9278889B2 (en) 2010-05-12 2016-03-08 3M Innovative Properties Company Method of reinforcing irregular structures

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