EP3307799A1 - Meerschaum - Google Patents

Meerschaum

Info

Publication number
EP3307799A1
EP3307799A1 EP16808419.2A EP16808419A EP3307799A1 EP 3307799 A1 EP3307799 A1 EP 3307799A1 EP 16808419 A EP16808419 A EP 16808419A EP 3307799 A1 EP3307799 A1 EP 3307799A1
Authority
EP
European Patent Office
Prior art keywords
polyol
approximately
blowing agent
group
phthalic anhydride
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP16808419.2A
Other languages
English (en)
French (fr)
Other versions
EP3307799A4 (de
Inventor
Anthony J. Taylor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ICP Adhesives and Sealants Inc
Original Assignee
ICP Adhesives and Sealants Inc
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
Priority claimed from US14/737,879 external-priority patent/US9481790B2/en
Application filed by ICP Adhesives and Sealants Inc filed Critical ICP Adhesives and Sealants Inc
Publication of EP3307799A1 publication Critical patent/EP3307799A1/de
Publication of EP3307799A4 publication Critical patent/EP3307799A4/de
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • 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
    • 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
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/487—Polyethers containing cyclic groups
    • C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0019—Use of organic additives halogenated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0038—Use of organic additives containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/022—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/10—Water or water-releasing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences

Definitions

  • the invention described herein pertains generally to a composition and a method involving the use of polyurethane or polyisocyanurate foam blown by a blowing agent having a boiling point at atmospheric pressure of between ⁇ 5°C to -50 °C, which passes all United States Coast Guard Title 33, Part 183 specifications wherein the buoyant force of the froth polyurethane or polyisocyanurate foam is not reduced more than 5% after exposure to being immersed in a fully saturated gasoline vapor atmosphere at an elevated temperature, as well as being tested at room temperature in reference fuel B, in reference oil No. 2, and in a 5% solution of Na 3 P0 4 for defined periods of time.
  • a frothable foam which a polyurethane or polyisocyanurate foam is blown by at least one HFC blowing agent having a boiling point at atmospheric pressure of between ⁇ 5°C to ⁇ 50°C, including miscible blends thereof, which passes all United States Coast Guard Title 33, Part 183 specifications wherein the buoyant force of the foam is not reduced more than 5% after exposure to each of the following conditions, namely:
  • the polyurethane or polyisocyanurate foam comprises:
  • a polyol blend which comprises:
  • At least one phthalic anhydride based aromatic polyester polyol present in a minor amount in the polyol blend, the at least one phthalic anhydride based aromatic polyester polyol comprising at least 35% of the polyol blend;
  • At least one other additive comprising at least one plasticizer and at least one flame retardant
  • the at least one phthalic anhydride based aromatic polyester polyol is
  • R 2 and R 5 are independently -[CH 2 CH 2 0] x -,
  • each R is independently an alkylene group of from 2 to 4 carbon atoms; and x, m, and n are independently from 1 -200.
  • the at least one phthalic anhydride based aromatic polyester polyol preferably is
  • an hydroxyl number in mg KOH/g is between 230-250 inclusive;
  • a viscosity value at 25 °C is between 2,000 - 4,500 cP inclusive;
  • an equivalent average weight is approximately 234;
  • an average molecular weight is approximately 468.
  • the at least one polyether polyol preferably is
  • an hydroxyl number in mg KOH/g is approximately 600;
  • a viscosity value at 25 °C is approximately 380 cP
  • an average molecular weight is approximately 280.
  • the at least one other additive preferably is selected from the group comprising
  • the at least one catalyst preferably is at least two catalysts
  • the water is added in an amount of approximately 1 % by weight and preferably the at least one HFC blowing agent has a boiling point at atmospheric pressure of between ⁇ 10°C to ⁇ 40°C.
  • the at least one HFC blowing agent is typically 1 ,1 ,1 ,3,3-pentafluoropropane, optionally combined with a second blowing agent.
  • a process to achieve the above is also described involving the synthesizing a polyurethane or polyisocyanurate foam blown by at least one HFC blowing agent having a boiling point at atmospheric pressure of between ⁇ 5°C to -50 °C, which passes all United States Coast Guard Title 33, Part 183 specifications.
  • a frothable foam which a polyurethane or polyisocyanurate foam is blown by at least one HFO blowing agent having a boiling point at atmospheric pressure of between ⁇ 5°C to -50 °C, including miscible blends thereof, which passes all United States Coast Guard Title 33, Part 183 specifications wherein the buoyant force of the foam is not reduced more than 5% after exposure to each of the following conditions, namely:
  • the polyurethane or polyisocyanurate foam comprises:
  • a polyol blend which comprises:
  • At least one phthalic anhydride based aromatic polyester polyol present in a minor amount in the polyol blend, the at least one phthalic anhydride based aromatic polyester polyol comprising at least 35% of the polyol blend;
  • At least one other additive comprising at least one plasticizer and at least one flame retardant
  • the at least one phthalic anhydride based aromatic polyester polyol is
  • R 2 and R 5 are independently -[CH 2 CH 2 0] x -,
  • each R is independently an alkylene group of from 2 to 4 carbon atoms; and x, m, and n are independently from 1 -200.
  • the at least one phthalic anhydride based aromatic polyester polyol preferably is
  • an hydroxyl number in mg KOH/g is between 230-250 inclusive;
  • a viscosity value at 25 °C is between 2,000 - 4,500 cP inclusive;
  • an equivalent average weight is approximately 234;
  • an average molecular weight is approximately 468.
  • the at least one polyether polyol preferably is
  • an hydroxyl number in mg KOH/g is approximately 600;
  • a viscosity value at 25 °C is approximately 380 cP
  • an average molecular weight is approximately 280.
  • the at least one other additive is preferably selected from the group comprising
  • the at least two catalysts comprise
  • the at least one HFO blowing agent preferably has a boiling point at atmospheric pressure of between ⁇ 10°C to ⁇ 40°C and is 1 ,1 ,1 ,4,4,4 hexafluoro-2-butene, optionally combined with a second blowing agent.
  • a process to achieve the above is also described involving the synthesizing a polyurethane or polyisocyanurate foam blown by at least one HFO blowing agent having a boiling point at atmospheric pressure of between ⁇ 5°C to -50 °C, which passes all United States Coast Guard Title 33, Part 183 specifications.
  • the invention relates to improved polyurethane and polyisocyanurate foams, which employ at least an effective amount of a low pressure, higher boiling point blowing agent(s) including miscible blends thereof.
  • Polyurethanes are produced by the polyaddition reaction of a polyisocyanate with a polyalcohol (polyol) in the presence of a catalyst and other additives.
  • the reaction product is a polymer containing the urethane linkage, -RNHCOOR'-.
  • Isocyanates will react with any molecule that contains an active hydrogen.
  • isocyanates react with water to form a urea linkage and carbon dioxide gas.
  • polyurethanes are produced by reacting a liquid isocyanate with a liquid blend of polyols, catalyst, and other additives.
  • the isocyanate is commonly referred to in North America as the "A-side” or just the “iso".
  • the blend of polyols and other additives is commonly referred to as the "B-side” or as the "poly”. In Europe the definitions for the contents of the "A” and “B” compositions are reversed.
  • MDI diphenylmethane diisocyanate
  • TDI toluene diisocyanate
  • HDI hexamethylene diisocyanate
  • polymeric isocyanate is polymeric diphenylmethane diisocyanate, which is a blend of molecules with two-, three-, and four- or more isocyanate groups, with an average functionality of 2.7.
  • Isocyanates can be further modified by partially reacting them with a polyol to form a prepolymer.
  • Any organic polyisocyanate can be employed in the polyurethane or polyisocyanurate foam synthesis inclusive of aliphatic and aromatic polyisocyanates.
  • Suitable organic polyisocyanates include aliphatic, cycloaliphatic, arylaliphatic, aromatic, and heterocyclic isocyanates which are well known in the field of polyurethane chemistry.
  • polyisocyanates correspond to the formula:
  • R is a polyvalent organic radical which is either aliphatic, arylalkyl, aromatic or mixtures thereof, and z is an integer which corresponds to the valence of R and is at least two.
  • organic polyisocyanates contemplated herein includes, for example, the aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, crude toluene diisocyanate, methylene diphenyl diisocyanate, crude methylene diphenyl diisocyanate and the like; the aromatic triisocyanates such as 4,4',4"-triphenylmethane triisocyanate, 2,4,6-toluene triisocyanates; the aromatic tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2'5,5'-tetraisocyan
  • organic polyisocyanates include polymethylene polyphenylisocyanate, hydrogenated methylene diphenylisocyanate, m-phenylene diisocyanate, naphthylene-1 ,5-diisocyanate, 1 -methoxyphenylene-2,4-diisocyanate, 4,4'- biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate;
  • Typical aliphatic polyisocyanates are alkylene diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, isophorene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyan
  • polyol which includes mixtures of polyols, can be any polyol which reacts in a known fashion with an isocyanate in preparing a polyurethane or polyisocyanurate foam.
  • polyol means a moiety which contains more than one hydroxyl group. Molecules that contain two hydroxyl groups are called diols, those with three hydroxyl groups are called triols, et cetera. Polyols are polymers in their own right.
  • polystyrene resins are formed by base- catalyzed addition of propylene oxide (“PO”), ethylene oxide (“EO”) onto a hydroxyl or amine containing initiator, or by polyesterification of a di-acid, such as adipic acid, with glycols, such as ethylene glycol (“EG”) or dipropylene glycol (“DPG”).
  • PO propylene oxide
  • EO ethylene oxide
  • DPG dipropylene glycol
  • Polyols extended with PO or EO are polyether polyols.
  • Polyols formed by polyesterification are polyester polyols. The choice of initiator, extender, and molecular weight of the polyol greatly affect its physical state, and the physical properties of the polyurethane polymer.
  • polyols Important characteristics of polyols are their molecular backbone, initiator, molecular weight, % primary hydroxyl groups, functionality, and viscosity.
  • Useful polyols comprise one or more of a sucrose containing polyol; phenol, a phenol formaldehyde containing polyol; a glucose containing polyol; a sorbitol containing polyol; a methylglucoside containing polyol; an aromatic polyester polyol; polyols derived from natural products (e.g.
  • soy beans glycerol
  • ethylene glycol diethylene glycol
  • propylene glycol graft copolymers of polyether polyols with a vinyl polymer
  • a copolymer of a polyether polyol with a polyurea one or more of (a) condensed with one or more of (b) as illustrated by (a) glycerine, ethylene glycol, diethylene glycol, trimethylolpropane, ethylene diamine, pentaerythritol, soy oil, lecithin, tall oil, palm oil, castor oil; and (b) ethylene oxide, propylene oxide, a mixture of ethylene oxide and propylene oxide; or combinations thereof.
  • the Poly-G 37-600 polyether polyol will mean and have the following characteristics.
  • one of the preferred phthalic anhydride based polyester polyols is and has the following physical characteristics.
  • the terephthalic anhydride based polyester polyol will mean and having the following characteristics.
  • Ft 1 is selected from the group consisting of an alkylene group of from 2 to 10 carbon atoms, -CH 2 -R 3 -CH 2 - and -(R 4 0) m -R 4 - ;
  • R 2 and R 5 are independently -[CH 2 CH 2 0] x -,
  • each R 4 is independently an alkylene group of from 2 to 4 carbon atoms; and x, m, and n are independently from 1 -200.
  • polyol premix which includes mixtures of polyol premixes, means a polyol premix which includes a catalyst.
  • catalysts are primary amines, secondary amines or most typical tertiary amines.
  • Useful tertiary amine catalysts non- exclusively include dicyclohexylmethylamine; ethyldiisopropylamine; dimethylcyclohexylamine;
  • dimethylisopropylamine dimethylisopropylamine; methylisopropylbenzylamine; methylcyclopentylbenzylamine; isopropyl-sec-butyl- trifluoroethylamine; diethyl-(a-phenylethyl)amine, tri-n-propylamine, or combinations thereof.
  • Useful secondary amine catalysts non-exclusively include dicyclohexylamine; t-butylisopropylamine; di-t-butylamine; cyclohexyl-t-butylamine; di-sec-butylamine, dicyclopentylamine; di-( a-trifluoromethylethyl)amine; di-a- phenylethyl)amine; or combinations thereof.
  • Useful primary amine catalysts non-exclusively include:
  • triphenylmethylamine and 1 ,1 -diethyl-n-propylamine are useful amines.
  • Other useful amines include morpholines, imidazoles, ether containing compounds, and the like. These include dimorpholinodiethylether; N-ethylmorpholine; N- methylmorpholine; bis(dimethylaminoethyl)ether; imidazole; n-methylimidazole; 1 ,2-dimethylimidazol;
  • the polyol premix composition may contain an optional silicone surfactant.
  • the silicone surfactant is used to form a foam from the mixture, as well as to control surface tension that impacts the size of the bubbles of the foam so that a foam of a desired open or closed cell structure is obtained.
  • the polyol premix composition may optionally contain a non-silicone surfactant, such as a non-silicone, non-ionic surfactant.
  • a non-silicone surfactant such as a non-silicone, non-ionic surfactant.
  • non-silicone surfactant such as a non-silicone, non-ionic surfactant.
  • a non-silicone surfactant such as a non-silicone, non-ionic surfactant.
  • non-silicone surfactant such as a non-silicone, non-ionic surfactant.
  • LK-443 is commercially available from Air Products Corporation.
  • a non-limiting exemplary definition for the term "polyisocyanurate” or "PIR”, which includes mixtures of polyisocyanurates, means the reaction the reaction product of MDI and a polyol, which typically takes place at higher temperatures compared to the reaction temperature for the manufacture of PUR.
  • PUR polyisocyanurate
  • MDI will first react with itself, producing a stiff, ring molecule, which is a reactive intermediate (a tri-isocyanate isocyanurate compound).
  • This isocyanurate polymer has a relatively strong molecular structure, because of the combination of strong chemical bonds, the ring structure of isocyanurate and high cross link density, each contributing to the greater stiffness than found in comparable polyurethanes.
  • the greater bond strength also means these are more difficult to break, and as a result a PIR foam is chemically and thermally more stable: breakdown of isocyanurate bonds is reported to start above 200 °C, compared with urethane at 100 to 1 ⁇ 0°C.
  • PIR typically has an MDI/polyol ratio, also called its index (based on isocyanate/polyol stoichiometry to produce urethane alone), of between 200 and 500.
  • index based on isocyanate/polyol stoichiometry to produce urethane alone
  • PUR indices are normally around 100.
  • chemical and/or thermal stability may be desirable.
  • PIR manufacturers offer multiple products with identical densities but different indices in an attempt to achieve optimal end use performance.
  • blowing agent which includes miscible mixtures and azeotropes of blowing agents, means a propellant or solvent which are useful and provide efficacy to various applications in the form of insulation performance, pressure performance, or solubility, without deleterious effect due to molar gas volume, flammability migration, or GWP reduction, yet which have a vapor pressure within defined limits as defined herein.
  • blowing agents include HFC-245fa (Honeywell Intl.), namely 1 ,1 ,1 ,3,3 pentafluoropentane or FEA-1 100 (DuPont), namely 1 ,1 ,1 ,4,4,4 hexafluoro-2-butene.
  • GWP global warming potential
  • blowing agent aerosol, or solvent compositions.
  • GWP is measured relative to that of carbon dioxide and over a 100 year time horizon, as defined in "The Scientific Assessment of Ozone Depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project.”
  • the present compositions also preferably have an Ozone Depletion Potential (“ODP") of not greater than 0.05, more preferably not greater than 0.02 and even more preferably about zero.
  • ODP Ozone Depletion Potential
  • ODP Ozone Depletion Potential
  • co-blowing agent which includes mixtures or miscible blends and/or azeotropes of blowing agents, means a one or more co-blowing agents, co- propellants, or co-solvents which are useful and provide efficacy to various applications in the form of insulation performance, pressure performance, or solubility, without deleterious effect due to molar gas volume, flammability mitigation, or GWP reduction.
  • co-agents include but are not limited to: one or more additional components of hydrofluorocarbons, Ci to C 6 hydrocarbons, Ci to C 8 alcohols, ethers, diethers, aldehydes, ketones, hydrofluoroethers, Ci to C 4 chlorocarbons, methyl formate, water, carbon dioxide, C 3 to C 4 hydrofluoroolefins, and C 3 to C 4 hydrochlorofluoroolefins.
  • Examples of these non- exclusively include one or more of difluoromethane, trans-1 ,2-dichloroethylene, difluoroethane, 1 ,1 ,1 ,2,2- pentafluoroethane, 1 ,1 ,2,2-tetrafluoroethane, 1 ,1 ,1 ,2-tetrafluoroethane, 1 ,1 ,1 -trifluoroethane, 1 ,1 - difluoroethane, fluoroethane, hexafluoropropane isomers, including HFC-236fa, pentafluoropropane isomers of HFC-245fa, heptafluoropropane isomers, including HFC-227ea, hexafluorobutane isomers, and pentafluorobutane isomers including HFC-365mfc, tetrafluoropropane isomers, and trifluoroprop
  • HFO-1234 examples include 1 ,1 ,1 ,2- tetrafluoropropene (HFO-1234yf), and cis- and trans-1 ,2,3,3-tetrafluoropropene (HFO-1234ye), HFC-1233zd, and HFC-1225ye.
  • Preferred co-blowing agents non-exclusively include: hydrocarbons, methyl formate, halogen containing compounds, especially fluorine containing compounds and chlorine containing compounds such as halocarbons, fluorocarbons, chlorocarbons, fluorochlorocarbons, halogenated hydrocarbons such as hydrofluorocarbons, hydrochlorocarbons, hydrofluorochlorocarbons,
  • hydrofluoroolefins hydrochlorofluoroolefins, C0 2 , C0 2 generating materials such as water, and organic acids that produce C0 2 such as formic acid.
  • examples non-exclusively include low-boiling, aliphatic hydrocarbons such as ethane, propane(s), i.e. normal pentane, isopropane, isopentane and cyclopentane; butanes(s), i.e.
  • dichlorodifluoromethane CFC-12
  • HFC-236fa 1 ,1 ,1 ,3,3,3-hexafluoropropane
  • HFC-236ea difluoromethane
  • HFC-32 difluoroethane
  • HFC-152a difluoroethane
  • trifluoropropenes pentafluoropropenes, chlorotrifluoropropenes, tetrafluoropropenes including 1 ,1 ,1 ,2-tetrafluoropropene (HFO-1234yf), 1 ,1 ,1 ,2,3-pentafluoropropene (HFO-1225ye), and 1 -chloro-3,3,3-trifluoropropene (HCFC- 1233zd).
  • an effective amount means a quantity sufficient to improve the result of the foaming operation when compared to a control without the added low pressure blowing agent.
  • higher boiling point blowing agent means a blowing agent having a boiling point at atmospheric pressure of between ⁇ 5°C to -50 °C, more preferably ⁇ 10 ⁇ €to ⁇ 40°C.
  • lower pressure blowing agent means a blowing agent having a vapor pressure of between ⁇ 5 psig to -30 psig at approximately room temperature, -75 °F (equivalents -34.5 kPa to -206.9 kPa at approximately room temperature, -24 °C).
  • the polymerization reaction is catalyzed by tertiary amines, such as dimethylcyclohexylamine, and organometallic compounds, such as dibutyltin dilaurate or bismuth octanoate.
  • catalysts can be chosen based on whether they favor the urethane (gel) reaction, such as 1 ,4-diazabicyclo[2.2.2]octane (also called DABCO or TEDA), or the urea (blow) reaction, such as bis-(2-dimethylaminoethyl)ether, or specifically drive the isocyanate trimerization reaction, such as potassium octoate.
  • PIR and PUR polymers are not large.
  • the proportion of MDI is higher than for PUR and instead of a polyether polyol, a polyester derived polyol is used in the reaction.
  • Catalysts and additives used in PIR formulations also differ from those used in PUR.
  • the foam of the invention dispenses from relatively inexpensive pressurized, but considered low- pressure (130-225 psi) cylinders rather than high pressure dispensing equipment (> 1 ,000 psi as typically used in impingement mixing) of the prior art.
  • low- pressure (130-225 psi) cylinders rather than high pressure dispensing equipment (> 1 ,000 psi as typically used in impingement mixing) of the prior art.
  • the use of cylinder dispensed polyurethane foam does not have upfront capital costs for equipment as would be necessary with high pressure dispensed polyurethane foam, which is in the order of $30,000 to $100,000 for the special handling equipment required, including proportioning units and spray guns.
  • a typical polyurethane foam was made in by combining two polyether polyols, e.g., poly-G 37-600 and Voranol ® 360 in addition one aromatic polyester polyol (Terol ® 352) in the ratios illustrated in Table I. Plasticizer, flame retardant, surfactants, catalysts & water were also added in the ratios illustrated in Table I to form the "B"-side cylinder. Diphenylmethane diisocyanate was used to form the "A"-side cylinder. The propellant HFC-245fa was employed for both the "A" and "B” cylinders in the quantities illustrated in Table II.
  • a new formulation polyurethane foam was made by combining one polyether polyol (poly-G 37-600) with one aromatic polyester polyol (Stepanpol ® PS-3524) in the ratio illustrated in Table I.
  • the total amounts of polyols of Example #1 and Example #2 were adjusted to be equal.
  • Plasticizer, flame retardant, surfactants, catalysts & water were also added in the ratios illustrated in Table I to form the "B"-side cylinder.
  • Diphenylmethane diisocyanate was used to form the "A"-side cylinder.
  • the propellant HFC-245fa was employed for both the "A" and "B” cylinders in the quantities illustrated in Table II.
  • a new formulation polyurethane foam was made by combining one polyether polyol (poly-G 37-600) with one aromatic polyester polyol (Stepanpol ® PS-3524) in the ratio illustrated in Table I.
  • the total amounts of polyols of Example #1 , #2 and #3 were adjusted to be equal.
  • Plasticizer, flame retardant, surfactants, catalysts & water were also added in the ratios illustrated in Table I to form the "B"-side cylinder.
  • Diphenylmethane diisocyanate was used to form the "A"-side cylinder.
  • the propellant FEA-1 100 was employed for both the "A" and “B” cylinders in the quantities illustrated in Table II noting that the catalyst package was different due to the internal olefin propellant used in the formulation, which also requires essentially the absence of water due at least in part to the reactivity of the internal olefinic bond of the propellant or synonymously blowing agent.
  • Example #1 and Example #2 were made using the hydrofluorocarbon (“HFC”) high boiling point propellant 1 ,1 ,1 ,3,3-pentafluoropropane (HFC-245fa) while Example #3 was made using the hydrofluoroolefin (“HFO”) internal olefin propellant 1 ,1 ,1 ,4,4,4 hexafluoro-2-butene (FEA-1 100) as illustrated in Table II.
  • HFC hydrofluorocarbon
  • HFC-245fa hydrofluoroolefin
  • FEA-1 100 internal olefin propellant 1 ,1 ,1 ,4,4,4 hexafluoro-2-butene
  • Example #1 One important test for flotation purposes, is the ability of any synthesized foam to pass the U.S. Coast Guard Title 33, Part 183 test, which employs a series of ASTM standards, namely ASTM D471 & ASTM D2842.
  • ASTM D471 & ASTM D2842 The results of the testing for Example #1 , Example #2 and Example #3 are illustrated in Table IV and the adjacent P/F columns are a shorthand notation as to whether the composition passed or failed the identified testing protocol.
  • the flotation material must not reduce in buoyant force more than 5% after being immersed for 30 days at 23 °C plus or minus 2°C in a 5% solution of trisodium phosphate in water.

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP16808419.2A 2015-06-12 2016-06-10 Meerschaum Pending EP3307799A4 (de)

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US14/737,879 US9481790B2 (en) 2012-10-08 2015-06-12 Marine foam
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WO2019050970A1 (en) * 2017-09-05 2019-03-14 Huntsman Petrochemical Llc CATALYST SYSTEM FOR PREMIXES OF POLYOLS CONTAINING HYDROHALOOLEFIN EXPANSION AGENTS
US11161931B2 (en) * 2019-03-08 2021-11-02 Covestro Llc Polyol blends and their use in producing PUR-PIR foam-forming compositions
EP4229119A1 (de) * 2020-10-13 2023-08-23 Covestro Deutschland AG Zusammensetzung zur herstellung von polyisocyanuratschaum, polyisocyanuratschaum und wärmedämmendes material
EP4011945A1 (de) * 2020-12-14 2022-06-15 Covestro Deutschland AG Zusammensetzung zur herstellung von polyisocyanuratschaum, polyisocyanuratschaum und wärmeisolierendes material

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US5488072A (en) * 1995-02-06 1996-01-30 Basf Corporation Rigid closed cell polyisocyanate based foams for use as positive flotation materials in watercraft
US6534556B2 (en) * 2001-02-20 2003-03-18 Basf Corporation Sprayable autofrothing polyisocyanate foam and delivery system
CN101878253B (zh) * 2007-11-29 2013-05-29 纳幕尔杜邦公司 包含顺式-1,1,1,4,4,4-六氟-2-丁烯泡沫形成组合物的组合物以及所述组合物制备基于多异氰酸酯的泡沫的用途
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