Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
• • 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
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/20—Heterocyclic amines; Salts thereof
  • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
  • C08G18/2036—Heterocyclic amines; Salts thereof containing one heterocyclic ring having at least three nitrogen atoms in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4804—Two or more polyethers of different physical or chemical nature
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2110/00—Foam properties
  • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2115/00—Oligomerisation
  • C08G2115/02—Oligomerisation to isocyanurate groups

Definitions

• Urethane foam is used in architectural building panels, siding, shingles, marine floatation, ⁇ prayed-on roof materials, and as insulation for the tops of buildings both to prevent leaking and to provide insulation.
• the subject invention provides a composition which produces a rigid foam when combined with diphenyl ethane diisocyanate.
• the subject invention provides a water blown foam having a commercially valuable density of from, for example, about 0.3 lb/ft 3 to about 5 lb/ t 3 or more.
• the subject invention offers a low cost, environmentally safe alternative to conventional urethane foams.
• the subject invention provides a urethane foam which does not require chlorofluorocarbons to manufacture. Two embodiments of this invention are disclosed.
• the first embodiment is a composition useful for producing a foam which comprises: (a) an oxyalkylated polyol having a hydroxyl number of from about 28 to about 800, (b) a rigid polyether polyol, a polyester polyol or an oxyalkylated bisphenol A, (c) an organic surfactant, (d) an amine catalyst, (e) a polyisocyanate catalyst, and (f) a quaternary ammonium salt or a triazine.
• the second embodiment is a composition useful for producing a foam which comprises: (a) an oxyalkylated polyol having a hydroxyl number of from about 28 to about 800, (b) a rigid polyether polyol, a polyester polyol or oxyalkylated bisphenol A, (c) a polyalkyleneoxidemethylsiloxane copolymer, (d) an amine catalyst, (e) a polyisocyanurate catalyst, and (f) a quaternary ammonium salt or a triazine.
• compositions of the subject invention produce a foam when mixed with polymeric MDI or other suitable isocyanates known to those skilled in the art such as, for example, hexamethylene diisocyanate, phenylene diisocyanate, toluene diisocyanate, and 4,4'-diphenyl methane diisocyanate, and 2,4- and 2,6-toluene diisocyanates individually or together as their commercially available mixtures.
• suitable mixtures of diisocyanates are those known commercially as "crude MDI", also known as PAPI, which contain about 60% of 4,4'-diphenylmethane diisocyanate along with other iso eric and analogous higher polyisocyanates.
• prepolymers of these polyisocyanates comprising a partially pre-reacted mixture of polyisocyanates and polyether or polyester polyol.
• compositions of the subject invention are mixed in a ratio of about 1:1 with polymeric MDI, and may be present in substoichiometric amounts.
• MDI is diphenylmethane diisocyanate which is known in the art to produce modifiers and polyol.
• 1:1 MDI is present in substoichiometric amounts.
• a mixture of MDI and a composition of the subject invention may be obtained using standard equipment known to persons skilled in the art.
• composition useful for producing a foam which comprises: (a) an oxyalkylated polyol having a hydroxyl number of from about 28 to about 800, (b) a rigid polyether polyol, preferably with a functionality greater than 3.0 and most preferably with a functionality greater than
• a polyester polyol or an oxyalkylated bisphenol A
• an organic surfactant (c) an amine catalyst, (e) a polyisocyanate catalyst, and (f) a quaternary ammonium salt or a triazine.
• the oxyalklylated polyol has a functionality of from about 2 to about 4 and is most preferably oxyalkylated glycerine.
• composition is to be mixed with water, and the components are preferably present in amounts effective to produce a foam when mixed with diphenylmethane diisocyanate or other suitable isocyanate.
• the compounds are present in the amounts stated below:
• the oxyalkylated polyol having a hydroxyl number of from about 28 to about 800 is present in the range of from about 1% to about 80% by weight of the composition.
• the oxyalkylated polyol is a viscosity modifier.
• the most preferred compound of this type is LHT-240 which is produced by Union Carbide.
• a rigid polyether polyol, a polyester polyol or an oxyalklated bisphenol A must be present. If a rigid polyether polyol is used, the rigid polyether polyol the range of from about 20% to about 70% by weight of the composition. Preferably, the rigid polyether polyol has a functionality greater than 3.0 and most preferably greater than 3.8. 35OX is the preferred compound and is produced by Arco Chemical. This compound is a rigid polyol, and is useful for producing the cross-linking required to manufacture rigid foams.
• polyester polyol is present in the range of from about 5% to about 80% by weight of the composition.
• polyester polyols based on terephthalate such as polyethylene terephthalate and dimethyl terephthalate. Sources of these terephthal tes include bottle scrap and fiber scrap. Dimethyl terephthalate is most preferable TERATE-203 manufactured by Cape Industries and CHARDONAL-570 manufactured by Oxid Chemicals, Inc.
• Polyester polyols may also include those produced by reacting a dicarboxylic acid with an excess of a diol for example, adipic acid with ethylene glycol or butanediol, or by reacting a lactone with an excess of a diol such as caprolactone and propylene glycol.
• Polyester polyols generally have hydroxyl numbers ranging from about 100 to about 700, preferably from about 100 to about 400, and have an average functionality of from about 1 to 8, and more preferably from about 2 to 3.
• the oxyalkylated bisphenol A is present in the range of from about 50% to 95% by weight of the composition.
• the use of oxylalkylated bisphenol A renders the final foam stable at temperatures greater than 350*F.
• an oxyalkylated bisphenol A produces foam suitable for use at high temperatures.
• the organic surfactant is present in the range of from about 0.5% to about 4.0% by weight of the composition.
• Organic surfactants are well known to those skilled in the art and are readily deter inable. Both silicone and non-silicone organic surfactants may be utilized. However, non-silicone organic surfactants are preferred.
• the most preferred compound is LK-443 which is manufactured by Air Products. A surfactant is utilized for stabilizing and forming cell structure.
• the amine catalyst is present in the range of from about 0.1% to about 10.0% by weight of the composition.
• N,N- dimethylcyclohexyla ine is the preferred amine catalyst.
• N,N- dimethylcyclohexylamine is available as polycat-8, referred to in the trade as PC-8, which is produced by Air Products.
• the amine catalyst initiates the reaction between the above- identified composition and the isocyanate.
• Tertiary and delayed action amines, such as triethylene diamine and triethanol amine may also be employed.
• the polyisocyanate catalyst employed may be any known in the art. It is preferred, however, that the isocyanate catalyst is lead, present in the form of 24% lead naphthanate which is present in the range of from about 0.1% to about 5.0% by weight of the composition. Other heavy metal catalysts, tin catalysts, and potassium catalysts may also be employed.
• Water is present in the range of from about 0.4% to about 80% by weight of the composition.
• the quaternary ammonium salt and/or triazine is the key component to provide a stable low density, water blown foam. It is preferred that the quaternary ammonium salt is TMR, however, other compounds such as Polycat 41, Polycat 43, or Dabco HB may be used.
• TMR which is a quaternary ammonium salt of a carboxylic acid
• TMR is manufactured by Air Products.
• TMR is a trimerization catalyst and is available as TMR 1, TMR 2, TMR 3, and TMR 4. The lower the number which follows TMR, the slower the reaction time.
• the most preferred embodiment is sprayable foam which comprises about 47.50% by weight of LHT-240; about 47.25% by weight of 350X; about 1.00% by weight of LK-443; about 0.25% by weight of PC-8; about 0.20% by weight of 24% lead naphthanate; about 2.80% by weight of water; and about 1.00% by weight of TMR.
• the first embodiment may also contain one or more fire retardants.
• Various fire retardants (this term is to include smoke suppressers, intumescent compositions and coatings, anti- dripping agents, etc.) may be added including, but not limited to, ammonium phosphate, such as ammonium polyphosphate and monoammonium phosphate, melamine, tetrakis (2-chloroethyl) ethylene phosphonate, pentabromodiphenyl oxide, tris (1,3- dichloropropyl) phosphate, tris(beta-chloroethyl) phosphate, molybdenum trioxide , ammonium molybdatate , pentabromodiphenyloxide , tricresyl phosphate, 2,3- d i b romop rop anol , hexabromocyc lododecane , dibro oethyldibromocycl
• a second composition useful for producing foam comprises: (a) an oxyalkylated polyol, preferably having a hydroxyl number of from about 28 to about 800, (b) a rigid polyether polyol, preferably with a functionality greater than 3.0, and most preferably with a functionality greater than 3.8 and a hydroxyl number of from about 250 to about 800, a polyester polyol or an oxyalkylated bisphenol A, (c) a polyalkyleneoxide ethylsiloxane copolymer, (d) an amine catalyst, (e) a polyisocyanurate catalyst, and (f) a quaternary ammonium salt or a triazine.
• an oxyalkylated polyol preferably having a hydroxyl number of from about 28 to about 800
• a rigid polyether polyol preferably with a functionality greater than 3.0, and most preferably with a functionality greater than 3.8 and a hydroxyl number of from about 250 to about 800,
• the oxyalkylated polyol has a functionality of from about 2 to about 4, and is most preferably oxyalkylated glycerine.
• the above composition is to be mixed with water, and the components are preferably present in amounts effective to produce a foam when mixed with diphenylmethane diisocyanate or other suitable isocyanate.
• the oxyalkylated polyol having a hydroxyl number of from about 28 to about 800 is present in the range of from about 1% to about 80% by weight of the composition.
• the composition requires a polyether polyol, a polyester polyol or an oxyalkylated bisphenol A.
• a rigid polyether polyol is used, the rigid polyether polyol is present in the range of from about 20% to about 70% by weight of the composition.
• the rigid polyether polyol has a functionality of greater than 3.0 and most preferably greater than 3.8; typically, the hydroxyl number is from about 250 to about 800. Most preferably, this compound is 74-532 which is manufactured by Olin Corporation.
• the polyester polyol is present in the range of from about 5% to about 80% by weight of the composition.
• polyester polyols based on terephthalate such as polyethylene terephthalate and dimethyl terephthalate. Sources of these terephthalates include bottle scrap and fiber scrap. Dimethyl terephthalate is most preferable TERATE-203 manufactured by Cape Industries and CHARDONAL-570 manufactured by Oxid Chemicals, Inc. Polyester polyols may also include those produced by reacting a dicarboxylic acid with an excess of a diol for example, adipic acid with ethylene glycol or butanediol, or by reacting a lactone with an excess of a diol such as caprolactone and propylene glycol.
• Polyester polyols generally have hydroxyl numbers ranging from about 100 to about 700, preferably from about 100 to about 400, and have an average functionality of from about 1 to 8, and more preferably from about 2 to 3.
• the oxyalkylated bisphenol A is present in the range of from about 50% to 95% by weight of the composition.
• the use of oxylalkylated bisphenol A renders the final foam stable at temperatures greater than 350"F. Accordingly, the use of an oxyalkylated bisphenol A produces foam suitable for use at high temperatures.
• the polyalkylenoxidemethylsiloxane copolymer is present in the range of from about 0.5% to about 4.0% by weight of the composition.
• the most preferred compound is L-5420 which produced by Union Carbide. L-5420 functions to improve mixing and to form fine cell structure.
• the amine catalyst is present in the range of from about 0.1% to about 10.0% by weight of the composition.
• Water is present in the range of from about 0.4% to about 80% by weight of the composition.
• the polyisocyanurate catalyst is present in the range of from about 0.5% to about 1.5% by weight of the composition. Most preferably, the catalyst is Curithane 52 which is manufactured by Air Products. It is a final curative and functions to increase adhesion and thermal stability.
• the quaternary ammonium salt is TMR, which is present in the range of from about 0.1% to about 3.0% by weight of the composition.
• TMR may be present as TMR 1, TMR 2, TMR 3, or TMR 4.
• the second embodiment may also contain one or more fire retardants.
• Various fire retardants (this term is to include smoke suppressers, intumescent compositions and coatings, anti- dripping agents, etc.) may be added including, but not limitation to, ammonium phosphate, such as ammonium polyphosphate an monoammonium phosphate, melamine, tetrakis (2-chloroethyl ethylene phosphonate, pentabromodiphenyl oxide, tris (1,3 dichloropropyl) phosphate, tris(beta-chloroethyl) phosphate molybdenum trioxide , ammonium molybdatate pentabromodiphenyloxide , tricresyl phosphate, 2,3 d ib rom op rop an ol , hexabromocycl ododecane dibromoethyldibro ocyclohexame, tris
• the subject invention also provides foams comprising eithe of the two above-identified compositions and diphenylmethan diisocyanate or other suitable isocyanate.
• the first compositio is preferably a sprayable composition which is useful in th roofing and insulation industries.
• the second composition i preferably a pourable composition which is useful in producin blocks of foam for siding, shingles, insulation and marin floatation, among other things.
• the subject invention also provides a process for producin a foam which comprises mixing the above-identified composition with diphenylmethane diisocyanate or other suitable isocyanate.
• the subject invention provides a low density foam, preferably, by using substoichiometric amounts of isocyanate.
• An index of 100 indicates a 1:1 stoichiometric ratio.
• the urethane foams of the prior art have isocyanate indices of greater than 100. The higher the index, the greater the excess of the first component, i.e. isocyanate.
• a B side was prepared which did not contain a quaternary ammonium salt or a triazine, i.e. the above-identified B side without TMR-3.
• This control B side although not known in the prior art, represents a typical water blown foam.
• Foams were made at each of the above indices and were allowed to cure for 24 hours at 72"F, in an atmosphere of 50% relative humidity. Two sets of foam were tested, one using the preferred sprayable foam composition of the subject invention, the second using the same composition without TMR-3.
• Samples were cut into 2 inch square cubes and subjected to temperatures of 20°F. A second set of samples were subjected to temperatures of 250*F.

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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)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
• Insulated Conductors (AREA)

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• 1991
  • 1991-04-19 CA CA002119882A patent/CA2119882A1/fr not_active Abandoned
  • 1991-04-19 HU HU9400541A patent/HUT68199A/hu active IP Right Revival
  • 1991-04-19 EP EP19910909352 patent/EP0615526A4/fr not_active Withdrawn
  • 1991-04-19 BR BR9107331A patent/BR9107331A/pt not_active IP Right Cessation
  • 1991-04-19 WO PCT/US1991/002799 patent/WO1992016574A1/fr not_active Application Discontinuation
  • 1991-04-19 AU AU78589/91A patent/AU7858991A/en not_active Abandoned
  • 1991-04-22 MY MYPI91000689A patent/MY106388A/en unknown

Patent Citations (4)

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