EP3827040A1 - Nouvelles compositions et procédés pour produire des condensats de triazine-arylhydroxy-aldéhyde alcoxylés - Google Patents

Nouvelles compositions et procédés pour produire des condensats de triazine-arylhydroxy-aldéhyde alcoxylés

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Publication number
EP3827040A1
EP3827040A1 EP19840750.4A EP19840750A EP3827040A1 EP 3827040 A1 EP3827040 A1 EP 3827040A1 EP 19840750 A EP19840750 A EP 19840750A EP 3827040 A1 EP3827040 A1 EP 3827040A1
Authority
EP
European Patent Office
Prior art keywords
arylhydroxy
triazine
aldehyde
polymer
free
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
EP19840750.4A
Other languages
German (de)
English (en)
Other versions
EP3827040A4 (fr
Inventor
Ganapathy S. Viswanathan
Anthony Maiorana
Stephan Schroter
Pravin Kukkala
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.)
Bakelite UK Holding Ltd
Original Assignee
Hexion Research Belgium SA
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 US16/043,871 external-priority patent/US10604614B2/en
Application filed by Hexion Research Belgium SA filed Critical Hexion Research Belgium SA
Publication of EP3827040A1 publication Critical patent/EP3827040A1/fr
Publication of EP3827040A4 publication Critical patent/EP3827040A4/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/3851—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing 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
    • C08G18/08—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
    • C08G18/28—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
    • C08G18/3271—Hydroxyamines
    • C08G18/3293—Hydroxyamines containing heterocyclic 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
    • C08G18/487—Polyethers containing cyclic groups
    • C08G18/4879—Polyethers 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
    • C08G18/70—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
    • 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
    • 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
    • C09D175/08—Polyurethanes from polyethers
    • 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
    • C08G2110/0008—Foam properties flexible
    • 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
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3

Definitions

  • This invention relates to alkoxy!ated triazine-arylhydroxy-aidehyde condensate compositions and methods for making these compositions.
  • Polyurethanes are one of the most versatile class of polymeric materials.
  • Flexible polyurethane foams are used as cushioning for a variety of consumer and commercial products, including bedding, furniture, automotive interiors, carpet underlay and packaging.
  • Rigid polyurethane and polyisocyanurate (polyiso) foams create one of the world's most popular, energy-efficient and versatile insulations. Environmental health and safety, along with fire protection, are driving change within the insulation industry. The high thermal insulation of rigid polyurethane makes them the most suited and efficient technologies to address these needs. These global trends drives demand for continuous innovation across the polyurethane industry.
  • Polyurethane foams are produced by reacting an isocyanate with a polyol.
  • the polyol component is typically one or more polyols along with a surfactant, catalyst, fire retardant and a blowing agent to make a foam.
  • the most common polyols used in the industry are polyether polyols and polyester polyols. Each of these class of compounds have their own merits and demerits.
  • Polyether polyols provides hydrolytic stability, lower viscosity and flexibility.
  • Aromatic polyester are known to contribute to flame retardance and higher modulus. However, they are typically limited in functionality and inherently, higher in viscosity and hence formulations especially in rigid PU systems have to use a co- poiyoi such as polyether polyols with higher functionality.
  • sugar-based polyols that are one of the most commonly used co-polyol in these formulations do not offer any bum resistance.
  • Alkoxylated phenol-aldehyde resins have been found to be useful in the preparation of various polymeric products including polyurethane compositions and foamed products. These are typically called novoiac based polyether polyols. They are prepared by reacting novolacs with alkylene oxides. These types of polyols have the advantage of having a high aromatic content which is known in the industry to aid in improved reaction to fire and can have high functionality. However, formulators still need to use other polyols along with amine-based catalysts and fire retardants to achieve the desired thermal, fire and mechanical performance.
  • the Spray Polyurethane Foam (SPF) market is one of the fastest growing polyurethane segments due to the superior ability of SPF to provide high insulation, reduce noise and for the ability to retrofit existing buildings and infrastructure.
  • SPF formulations utilize small molecule organic and inorganic catalysts to provide quick reaction and phosphate or phosphate-chlorinated additives in order to function and meet building regulations for fire ratings.
  • Small molecule catalysts such as amines can be volatilized during spray polyurethane installation that poses health hazard.
  • Small molecule fire retardants that are invariably added to these formulations, are under regulatory scrutiny for concerns related to their effect on the environment.
  • an alkoxylated triazine-arylhydroxy-aldehyde condensate compound is prepared by a process comprising, consisting of, or consisting essentially of: reacting a triazine-aiylhydroxy-aldehyde condensate; and at least one an alkoxylation agent, optiona!iy in the presence of a catalyst, to form an aikoxylated triazine-arylhydroxy- aldehyde condensate compound.
  • the alkoxylation agent may be an aikylene oxide, alone or in combination with an aikylene carbonate. In a further embodiment, the alkoxylation agent may be an aikylene carbonate.
  • a condensation product including a reaction mixture comprising a triazine-arylhydroxy-aldehyde condensate, and an alkoxylation agent comprising an aikylene oxide and an optional aikylene carbonate, and an optional catalyst.
  • an aikoxylated triazine- aryihydroxy-aldehyde condensate compound is provided.
  • a process including reacting a triazine-arylhydroxy-aldehyde condensate and at least one aikylene oxide, alone or in combination with an aikylene carbonate, optionally in the presence of a catalyst and forming an aikoxylated triazine-arylhydroxy-aldehyde condensate composition.
  • the condensate composition is free of a catalyst, free of a fire retardant, free of Mannich polyols, or combinations thereof.
  • the condensate composition is free of amine catalysts.
  • a polymer including using a formulation comprising a poly isocyanate and an isocyanate-reactive compound comprising at least one aikoxylated triazine-arylhydroxy-aldehyde condensate.
  • An article may be prepared from the polymer.
  • the formulation is free of a catalyst, free of a fire retardant, free of Mannich polyols, or combinations thereof.
  • the formulation is free of amine catalysts,
  • a process including forming a reaction mixture comprising a poly isocyanate and an isocyanate-reactive compound comprising at least one aikoxylated triazine-arylhydroxy-aldehyde condensate, and curing the reaction mixture to form a polymer.
  • the reaction mixture is free of a catalyst, free of a fire retardant, free of Mannich polyols, or combinations thereof.
  • the formulation is free of amine catalysts.
  • the process may further include applying the polymer to a substrate. DETAILED DESCRIPTION OF THE INVENTION
  • Embodiments of the invention are directed to alkoxylated triazine- ary! hydroxy-aldehyde condensates, methods for making the alkoxylated triazine- aryihydroxy-aldehyde condensates, and the use of alkoxylated triazine-arylhydroxy- aldehyde condensates in the manufacture of polyurethane and polyisocyanurate resins.
  • An alkoxylated triazine-arylhydroxy-aldehyde condensate is formed by reacting a triazine-arylhydroxy-aldehyde condensate with an a!kylene oxide.
  • An alkoxylated triazine-arylhydroxy-aldehyde condensate is formed by reacting a triazine- arylhydroxy-aldehyde condensate with an alky!ene oxide and an alkylene carbonate.
  • An alkoxylated triazine-arylhydroxy-aldehyde condensate is formed by reacting a triazine-arylhydroxy-aldehyde condensate with an alkylene carbonate.
  • any suitable triazine-arylhydroxy-aldehyde condensate can be used in the reaction with the alkylene oxide, the alkylene carbonate, or both.
  • the triazine-arylhydroxy-aldehyde condensate is formed from a reaction mixture of a triazine monomer, an arylhydroxy monomer, and an aldehyde monomer.
  • the triazine-arylhydroxy-aldehyde condensate is a novolac.
  • An example of a triazine compound is melamine and an example of a triazine derivative is a melamine derivative.
  • Suitable compounds that can be used as the triazine monomer include compounds from the aminotriazine group such as, 4-methyi- l ,3,5-triazine-2-amine, 2- amino-4, 6-dimethyl- 1 ,3,5-triazine, melamine, hexamethoxymethylmelamine, hexamethy!olmelamine, guanamine, acetoguanamine, propioguanamine, butyroguanamine, benzoguanamine, vinylguanamine, 6-(hydroxyphenyl)-2,4-diamino- 1 ,3,5-triazine, and combinations thereof.
  • aminotriazine group such as, 4-methyi- l ,3,5-triazine-2-amine, 2- amino-4, 6-dimethyl- 1 ,3,5-triazine, melamine, hexamethoxymethylmelamine, hexamethy!olmelamine, guanamine, aceto
  • the arylhydroxy monomer can be any suitable aromatic monomer with one or more hydroxyl groups per molecule, such as a monohydroxy, dihydroxy or a trihydroxy benzene. They can be mononuclear or binuciear.
  • the arylhydroxy monomer is a phenol monomer compound. Phenol monomer compounds having at least one ortho or para position available for bonding are preferred compounds.
  • the phenol monomer compound can be an unsubstituted or substituted compound, for example, with an alkyl group, a phenyl group, a hydroxy benzene group, an aikoxy group, and combinations and subsets thereof.
  • the phenol monomer compound can also include compounds having up to about 15 carbon atoms such as up to about 8 carbon atoms.
  • ary!hydroxy monomers include, but are not limited to phenol, cresols, xyleno!s, resorcinol, catechol, hydroquinone, naphthols, dihydroxynaphthalenes, biphenols, bisphenois, phloroglucinol, pyrogaliol or their derivative ⁇ .
  • the aldehyde monomer includes compounds having one or more aldehyde functional groups (-CHO) and any compounds yielding aldehydes.
  • the aldehyde monomer can be represented by the formula R-CHO, and R can be an aliphatic or aromatic organic functional group.
  • the aldehyde monomer can be a dialdehyde such as glyoxal.
  • Suitable aldehydes include, but are not limited to compounds such as formaldehyde, paraformaldehyde, acetaldehyde, i-butyraldehyde (isobutyraldehyde), benzaidehyde, acrolein, crotonaldehyde, salicylaldehyde, 4-hydroxybenzaldehyde, furfural, pyrroie-2- carboxaldehyde, cinnamaldehyde, trioxymethylene, paraldehyde, terephtha!dialdehyde, glyoxal, g!utaraldehyde and combinations thereof.
  • the triazine-arylhydroxy-aldehyde condensate can be comprised of a variety of triazine, arylhydroxy, and aldehyde combinations.
  • the condensate is a melamine, phenol, and formaldehyde novolac. Further details about the triazine-arylhydroxy-aldehyde condensate and its preparation can be found in US Patent Nos. 6,239,248 and 9,249,251, which are both herein incorporated by reference.
  • the triazine-arylhydroxy-aldehyde condensate is reacted with at least one aikoxylation agent to form the alkoxylated triazine-arylhydroxy-aldehyde condensate.
  • the aikoxylation agent may be m!kylene oxide, alone or in combination with an alkylene carbonate. Alternatively, the aikoxylation agent may be alkylene carbonate.
  • Suitable alkylene oxides may comprise linear aliphatic alkylene oxides, branched aliphatic alkylene oxides, cyclic aliphatic a!kyene oxides, aromatic alkylene oxides, alkyl aromatic alkylene oxides, alkylene oxides with ethers (commonly known as glycidyl ethers), and alkylene oxides with esters (commonly known as glycidyl esters).
  • alkylene oxides can be one or more alkylene oxides selected from the group comprising ethylene oxide, propylene oxide, glycidol, styrene oxide, epichlorohydrin, butylene oxide, isobuty!eneoxide, cyclohexane oxide, 2,3- epoxyhexane, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl sulfide, glycidyl methyl sulfone, glycidyl methacrylate, glycidyl ailyl phthalate, and combinations thereof.
  • preferred a!kylene oxides include compounds selected from the group consisting of ethylene oxide, ! propylene oxide, butylene oxide, and combinations thereof
  • the alky!ene pxide can comprise from about 5 wt.% to about 90 wt.% of the triazine-arylhydroxy-aldehyde condensate and at least one alky!ene oxide reaction mixture.
  • the triazine-arylhydroxy-aldehyde condensate and alkoxy!ation agent may be present with a reactive site to alkoxylation agent ratio, such as alky!ene oxide and/or alkylene carbonate, from about 20: 1 to about 1 :20.
  • suitable alkylene carbonates may comprise linear aliphatic alkylene carbonates, branched aliphatic alkylene carbonates, aromatic alkylene carbonates, alkyl aromatic alkylene carbonates, alkyl hydroxide carbonates, vinyl carbonates, acrylic carbonates, and ester carbonates.
  • Examples of preferred alkylene carbonates may include one or more alkylene carbonate selected from the group comprising ethylene carbonate, propylene carbonate, butylene carbonate, glycerol carbonate, styrene carbonate, 1-ch!oro- propylene carbonate, isobutylene carbonate cyclohexene carbonate, ailyl carbonate, methacrylate carbonate, vinyl carbonate, ailyl phthalate carbonate, and combinations thereof
  • Examples of preferred alkylene carbonates include compounds selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, and combinations thereof
  • Suitable alkylene carbonate can be prepared from suitable mono-epoxide compounds such as ethylene oxide, propylene oxide, glycidol, styrene oxide, epichlorohydrin, butylene oxide, isobutyleneoxide, cyclohexane oxide, 2,3-epoxyhexane, ailyl glycidyl ether, methyl glycidyl ether, butyl glycidyl sulfide, glycidyl methyl sulfone, glycidyl methaciyiate, glycidyl aliyl phthalate.
  • suitable mono-epoxide compounds such as ethylene oxide, propylene oxide, glycidol, styrene oxide, epichlorohydrin, butylene oxide, isobutyleneoxide, cyclohexane oxide, 2,3-epoxyhexane, ailyl glycidyl ether,
  • the alkylene carbonate can comprise from about 5 wt.% to about 50 wt.% of the triazine-arylhydroxy-aldehyde condensate and at least one alkylene carbonate, and optionally, at least one alkylene oxide, reaction mixture.
  • the triazine- arylhydroxy-aldehyde condensate and at least one alkylene carbonate may be present with an reactive site to alkylene carbonate ratio from about 1 : 1 to about 1 :2.
  • the alkoxylation agent can be one or more compounds selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate and mixtures thereof [0029] lf both the alkylene oxide and the aiky!ene carbonate are present, the components can comprise frqrn about 2 wt.% to about 90 wt.% of the triazine-arylhydroxy- aidehyde condensate, at least one alkylene oxide, and at least one alkylene carbonate, reaction mixture.
  • the triazine-arylhydroxy-aldehyde condensate and the combined components of the at least one alkylene oxide and at least one alkylene carbonate may be present at reactive site to alkylene oxide and at least one alkylene carbonate ratio from about 20: 1 to about 1 :20.
  • the alkylene carbonate can comprise from about 5 wt.% to about 90 wt.% of the triazine-arylhydroxy-aldehyde condensate and an alkylene carbonate reaction mixture,
  • a reactive site is defined as any site that has a labile proton below a pKa of
  • phenolic hydroxyl such as a phenolic hydroxyl, primary hydroxyl, secondary hydroxyl, tertiary hydroxyl, aminic hydroxyls such as primary amines, secondaiy amines, primary aromatic amines, or secondary aromatic amines,
  • a primary amine would possess two reactive sites and a secondaiy amine would possess one reactive sites.
  • reaction conditions can include a reaction temperature in the range of from about 50°C to about 270°C. Any and all temperatures within the range of about 50°C to about 270°C are incorporated herein and disclosed herein; for example, the reaction temperature can be from about 100°C to about 200°C, from about 140°C to about 1 80°C, or from about 160°C to about : 175°C.
  • the reaction conditions can also include a reaction pressure in the range of from about 0.01 bar to about 100 bar. Any and all pressures within the range of from 0.01 bar to 100 bar are included herein and disclosed herein; for example, the reaction pressure can be from about 0.1 bar to about 50 bar, from about 0.5 bar to about 20 bar, or from about 1 bar to about 10 bar.
  • the components can be added together in any suitable manner.
  • the reaction can take place ih a batch system, a continuous system, a semi-batch system, or a semi-continuous system.
  • the alkylene oxide can be added slowly to molten triazine-arylhydroxy-aldehyde condensate and then reacted until the alkylene oxide has been consumed.
  • the alkylene oxide can be bulk charged to a molten triazine-arylhydroxy-aldehyde condensate under pressure and reacted to a specific lowering of pressure or until all the alkylene oxide has been consumed.
  • the process of the invention may be conducted in a suitable solvent.
  • suitable solvents are those that dissolve the reactants and the product and are themselves inert in the process. After the reaction, such solvents can be removed from the reaction mixture through a distillation process. Examples of solvents include, but are not limited to acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, and combinations thereof.
  • the aikoxylation of triazine-aryihydroxy-aldehyde condensate can be carried out in the presence of reactive diluents.
  • Example of reactive diluents that can be used include, but are not limited to ethylene glycol, glycerol, methanol, ethanol, propanol, butanol, and combinations thereof.
  • Alkylene oxide can be reacted with both the reactive diluent and the triazine-aiy!hydroxy-aldehyde condensate to yield liquid materials of various viscosities.
  • the reaction between the triazine-aryihydroxy-aldehyde condensate and the alkylene oxide can take place in the presence of a catalyst.
  • Suitable catalysts include metal hydroxides, metal carbonates, metal phosphates, tertiary amines, phosphines, transition metal bases, organic acids, inorganic acids, and combinations thereof.
  • Examples of catalysts that can be used include, but are not limited to sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, potassium phosphate, sodium phosphate, lithium phosphate, and combinations thereof.
  • organic acids include oxalic acid, formic acid, acetic acid, trifluoroacetic acid, methane sulfonic acid, salicylic acid, benzoic acid, adipic acid, or p-toluenesulfonic acid
  • inorganic acids include hydrochloric acid, sulfuric acid, phosphoric acid, and combinations thereof. The organic acids and inorganic acids can also be used to neutralize the reaction mixture.
  • the formulation used to form the condensate is free of a catalyst, free of a fire retardant, free of Mannich polyols, or combinations thereof. In one embodiment, the condensate is free of am ine catalysts.
  • An organic acid such as oxalic acid, formic acid, acetic acid, trifluoroacetic acid, methane sulfonic acid, salicylic acid, phosphoric acid, benzoic acid, adipic acid, or p- toluenesulfonic acid can be used to neutralize the reaction mixture.
  • the catalyst may comprise from about 0.05 wt.% to about 5 wt.% of the triazine-ary!hydroxy-aldehyde condensate and at least one alkyiene oxide reaction mixture.
  • the alkoxylated triazine-arylhydroxy-aldehyde condensate compound can be represented by Formula I below.
  • the Rr, functional group is represented by Formula ⁇ I or Formula HI.
  • the Rj functional group of Formula 1 can be a hydrogen atom or represented by Formula II or Formula IV.
  • Rs and Rg can each independently be a hydrogen atom, an alkyl group with
  • R 1 and R 2 are independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group, or an alkyl group with 1 to 4 carbon atoms containing a hydroxyl group.
  • Rio can be a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an alkyl group with 1 to 10 carbon atoms containing a hydroxyl group, a phenyl group, a vinyl group, a propenyl group, a hydroxyl-containing phenyl group, a pyrrole group, or a furany! group.
  • Rn and Rn are each independently a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a hydoxybenzene group, or an alkyl group with 1 to 10 carbon atoms with at least one carbon substituted with i) a hydroxyl group, ii) a hydroxybenzene group or iii) a phenyl group.
  • Ru and R 12 can jointly form a common aromatic ring with or without a hydroxyl group
  • R 13 and RH are each independently a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a vinyl group, a phenyl group, a hydroxyphenyl group, -NH(Formula IV), -N(Formuia IV) 2 , -NH(FormuIa IV), -N((Formula II)(Formula IV)), -N(Formula IV) 2 , or -NH 2 .
  • R 15 R 16 , and R 17 are each independently a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a vinyl group, a phenyl group, a hydroxyphenyl group, - NH(Formula IV), -N(Formula IV) 2 , -NMfFormula V), -N(Formula IV)(Formula V), - N(Formula V) 2 , or -Ni b.
  • each m is independently from 1 to 10
  • each n is independently from 0 to 10
  • each x is independently from 3 to 10
  • each x’ is independently from 3 to 10 when alkylene carbonates are used as the sole alkoxy lating agent.
  • Monomers depicted by m and n can be arranged in any order, combination, or sub combination.
  • each m is independently from 1 to 10
  • each n is independently from 0 to 10
  • each x is independently from 1 to 20
  • each x 1 is independently from 1 to 20 when alkylene oxides are the sole aikoxylation agent.
  • Monomers depicted by m and n can be arranged in any order, combination, or sub- combination.
  • each x is independently from 1 to 2
  • each x’ is independently from 1 to 2 when alkylene oxides are the sole aikoxylation agent.
  • each x is independently from 3 to 20, and each x' is independently from 3 to
  • each m is independently from 1 to 10
  • each n is independently from 0 to 10
  • each x is independently from 1 to 20
  • each x’ is independently from 1 to 20 when aikylene oxides and aikylene carbonates are both used as alkoxylation agents.
  • Monomers depicted by m and n can be arranged in any order, combination, or sub-combination.
  • each x is independently from 1 to 2
  • each x’ is independently from 1 to 2 when aikylene oxides and aikylene carbonates are both used as alkoxylation agents.
  • each x is independently from 3 to 20, and each x’ is independently from 3 to 20 when aikylene carbonates and aikylene oxides are used as alkoxylation agents.
  • the average of all x and x * is greater than 2 when the average of all x and x’ is greater than 2 when the alkoxylation agent is a combination of an aikylene oxide and an aikylene carbonate.
  • the alkoxylated triazine-ary!hydroxy-a!dehyde condensates generally have a nitrogen content of from about 0.5 wt,% (weight percent) to about 41 wt%, such as from about 1 wt.% to about 23 wt.%, for example, from about 5 wt.% to about 15 wt.%, in various other embodiments.
  • the alkoxylated triazine-arylhydroxy-aldehyde condensates generally have an aromatic content of from about 0.5 wt.% (weight percent) to about 69 wl%, such as from about 5 wt.% to about 40 wt.%, for example, from about l2wt.% to about 30 wt.%, in various other embodiments.
  • T he alkoxylated triazine-arylhydroxy-aldehyde condensates of this invention generally have a viscosity from about 0.01 Pascal second to 60 Pascal seconds at 25°C, such as from about 0.01 Pascal second to 30 Pascal seconds at 25°C. Any and all ranges within 0.01 to 60 Pascal seconds are included herein and disclosed herein, for example, the alkoxylated triazine-arylhydroxy-aldehyde condensates in solvents can have a viscosity in the range of from 0.1 to 30 Pascal seconds or from 10 to 20 Pascal seconds at 25°C.
  • the alkoxylated triazine-arylhydroxy-aldehyde condensates of this invention can additionally exhibit non-newtonian behavior such as shear thinning behavior, which can be influenced by the type of alkoxylating agent and the number of x and x’ introduced via the alkoxylating agent.
  • the manufacturing of the triazine-arylhydroxy-aldehyde condensate and forming the alkoxylated triazine-arylhydroxy-aldehyde condensate composition can be carried out in the same reactor or different reactors.
  • the manufacturing of triazine- arylhydroxy-aldehyde condensate and/or forming the alkoxylated triazine-ary!hydroxy- aldehyde condensate composition may be carried out in a continuous, semi-continuous, semi-continuous to batch, or batch type process and/or reactor.
  • alkoxylated triazine-arylhydroxy-aldehyde condensates of this invention can be used as polyisocyanate-reactive compounds to make polyurethanes and polyisocyanurate-based polymers.
  • a polymer may be prepared using a formulation, referred to herein as a reaction mixture, comprising a polyisocyanate and an isocyanate-reactive compound comprising at least one alkoxylated triazine-arylhydroxy-aldehyde condensate as described herein.
  • the polyisocyanate component may also be referred to as the“A Side” in a polyurethane reaction process.
  • the isocyanate-reactive compound component such as the alkoxylated triazine-arylhydroxy-aldehyde condensate described herein alone or in combination with another polyol, may also be referred to as the“B Side” in a polyurethane reaction process.
  • the formulation or reaction mixture is free of a catalyst, free of a fire retardant, free of Mannich polyols, or combinations thereof.
  • the formulation is free of amine catalysts.
  • the at least one polyisocyanate comprises from about 33 wt. to about 83 wt, such as from about 49 wt. to about 51 wt., of the reaction mixture, the isocyanate-reactive compound comprises from about 13 wt. to about 51 wt., such as from about 38 wt. to about 40 wt, of the reaction mixture, wherein the total amount of components equal 100 wt.% of the reaction mixture.
  • the reaction mixture may further include optional additive materials as described herein, and if present, may be present in an amount from about 4 wt. to about 16 wt.%, such as from about 1 1 wt. to about 13 wt.%, of the formulation or reaction mixture, wherein the total amount of components equal 100 wt.% of the reaction mixture.
  • a reaction mixture is formed with at least one polyisocyanate and at least one alkoxylated triazine-arylhydroxy-aldehyde condensate.
  • Suitable poiyisocyanates include diisocyanates, triisocyanates, and combinations thereof.
  • suitable poiyisocyanates include, but are not limited to, m-phenylene diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, hexamethylene-1, 6-di isocyanate, tetremethy!ene- 1 ,4-diisocyanate, cyclohexane-1 , 4- diisocyanate, hexahydrotoluene diisocyanate, naphthylene-l, 5-diisocyanate, methoxyphenyI-2,4-diisocyanate, diphenyl methane-4 ,4’-diisocyanate, diphenylmethane- 2, 4-diisocyanate, 4,4’-biphenyiene diisocyanate, 3,3’-dimethoxy
  • 4,4’-diisocyanate, 4,4’,4”-triphenyl methane triisocyanate a polymethylene polyphenylisocyanate, polymeric diphenylmethane diisocyanate (PMDI), isophorone diisocyanate, toluene-2, 4, 6-triisocyanate, 4, -dimethyldiphenylmeihane-2,25,5'- tetraisocyanate, isophorone diisocyanate, hexamethylene- 1 , 6-diisocyanate, polymethylene polyphenylisocyanate, and combinations thereof.
  • PMDI polymeric diphenylmethane diisocyanate
  • isophorone diisocyanate toluene-2, 4, 6-triisocyanate, 4, -dimethyldiphenylmeihane-2,25,5'- tetraisocyanate
  • isophorone diisocyanate hexamethylene- 1
  • Diphenylmethane-4,4’-diisocyanate, diphenylmethane-2, 4-diisocyanate and mixtures thereof are generically referred to as MDI and ail can be used.
  • Poly versions of the compounds are may also be used, such as polymeric diphenylmethane diisocyanate (PMDI).
  • PMDI polymeric diphenylmethane diisocyanate
  • Toluene-2, 4-di isocyanate, toluene-2, 6- diisocyanate and mixtures thereof are generically referred to as TDI and all can be used.
  • any of the foregoing poiyisocyanates can be modified to include urethane, urea, biuret, carbodiimide, allophonate, uretonimine, isocyanurate, amide, or like linkages.
  • modified isocyanates of these types include various urethane group and/or urea group-containing prepolymers and so-called‘liquid MDE products and the like.
  • the polyisocyanate can be a blocked isocyanate, where a standard polyisocyanate is prereacted with a blocking agent containing active hydrogen groups, which can then be deblocked at temperatures greater than 40°C (typically in the range of from 100°C to 190°C).
  • blocking agents include, but are not limited to g-capro lactam, phenol, methyl ketone oxime, 1 ,2,4-triazole, dimethyl malonate, and combinations thereof.
  • the isocyanate-reactive compound comprising at least one alkoxylated triazine-arylhydroxy-aldehyde condensate may further include one or more additional polyols.
  • Polyols which can be used in conjunction with the alkoxylated triazine- arylhydroxy-aldehyde condensate include polyether polyols. These may be prepared by polymerizing an alkylene oxide onto an initiator compound that has multiple active hydrogen atoms.
  • Suitable initiator compounds include, but are not limited to alkylene glycols, glycol ethers, glycerine, trimethylolpropane, sucrose, glucose, fructose, phenol formaldehyde condensates, ethylene diamine, hexamelhylene diamine, diethanolamine, monoethanolamine, piperazine, aminoethylpiperazine, diisopropanolamine, monoisopropanolamine, methanol amine, dimethanol amine, and toluene diamine.
  • An example of such a polyol is Poly-G 74-376, a sucrose initiated polyether polyol made with ethylene oxide and propylene oxide commercially available from Monument Chemical.
  • Polyester polyols can also be used as part of the isocyanate-reactive compound.
  • Polyester polyols include reaction products of polyols, usually diols, with polycarboxy!ic acids or their anhydrides, usually dicarboxylic acids or dicarboxyllc acid anhydrides.
  • the polycarboxyl ie acids or anhydrides can be aliphatic, cycloaliphatic, aromatic, and/or heterocyclic.
  • An example of such a polyol is Terol 250, an aromatic polyester polyol commercially available from Huntsman Corporation.
  • the isocyanate-reactive compounds may also include a Mannich polyol.
  • Mannich polyol most established in the formulations especially in the spray foam application is the reaction product of nonyl phenol, formaldehyde, and diethanolamine. Manufacturers of Mannich polyols provide formulation flexibility by varying the ratio of formaldehyde, ethanolamine, and a!koxylate to provide a specific functionality and equivalent weight.
  • the Mannich polyol used as one of the reference polyols in the examples herein is one that is also nonyl phenol initiated.
  • the isocyanate- reactive compound may be free of Mannich polyols.
  • An example of a Mannich polyol is Jeffol R-470X, commercially available from Huntsman Corporation.
  • the alkoxylated triazine-arylhydroxy-aldehyde condensate is present in the isocyanate-reactive compound in a range of from about 1 weight percent to about 50 weight percent. Any and all ranges between 1 and 50 weight percent are included herein and disclosed herein; for example, the alkoxylated triazine-arylhydroxy- a!deliyde condensate can be present in the isocyanate-reactive compound in a range of from 5 weight percent to 35 weight percent, from 15 weight percent to 25 weight percent, or from 9 weight percent to 21 weight percent.
  • the alkoxylated triazine-arylhydroxy-aldehyde condensate has been observed to have a sufficiently high reactivity that a catalyst is optional.
  • the reaction and/or reaction mixture of the alkoxylated triazine-arylhydroxy-aldehyde condensate and polyisocyanate compound may be free of a catalyst, such as free of an amine catalyst. Additionally, The reaction and/or reaction mixture of the alkoxylated triazine- arylhydroxy-aldehyde condensate and polyisocyanate compound may be free of a catalyst, free of a fire retardant, free of Mannich polyols, or combinations thereof,
  • the polyisocyanate and alkoxylated triazine- arylhydroxy-aldehyde condensate mixture further comprises a phosphorus-containing flame retardant, a diluent, a catalyst, or combinations thereof.
  • the polyisocyanate and alkoxylated triazine-arylhydroxy-aldehyde condensate mixture further comprises a cell opener, a surfactant, a blowing agent, and combinations thereof.
  • the alkoxylated triazine-arylhydroxyl-aldehyde condensate has been observed to have a sufficient reactivity that the addition of a catalyst is not needed for polymer forming reactions.
  • the polyisocyanate and alkoxylated triazine- arylhydroxy-aldehyde condensate mixture may be may be free of a catalyst, free of a fire retardant, free of Mannich polyols, or combinations thereof.
  • the condensate mixture may be free of an amine catalyst.
  • the poly isocyanate and alkoxylated triazine-arylhydroxy-aldehyde condensate mixture can also include a catalyst.
  • catalysts include, but are not limited to tertiary amines such as dimethylbenzylamine, 1 ,8- diaza(5,4,0)undecane-7, pentamethyldiethy!enetriamine, dimethy!cyclohexylamine, and triethylene diamine.
  • Potassium salts such as potassium acetate and potassium octoate can also be used as catalysts.
  • the alkoxylated triazine-arylhydroxyl- aldehyde condensate through its inherent high reactivity towards isocyanate (autocatalytic), minimizes the use of a catalyst or allows the formulation to be free of a catalyst as described herein.
  • the aikoxylated triazine-arylhydroxy-aldehyde condensate also contains a diluent. Suitable diluents include, but are not limited to polyglycols, ethcrified polyglycols, dibasic esters of acids, and combinations thereof.
  • diluents include, but are not limited to, ethylene glycol, glycerol, diethylene glycol, monomethyl ether of ethylene glycol, dimethyl ether of ethylene glycol, diethyl adipate, dimethyl adipate, diethyl succinate, dimethyl succinate, and combinations thereof.
  • additive materials include, but are not limited to, surfactants, blowing agents, cell openers, fillers, pigments and/or colorants, desiccants, reinforcing agents, biocides, preservatives, antioxidants, flame retardants, and combinations thereof.
  • the additive materials may be present in an amount from about 0 wt. to about 20 wt.%, such as from about 4 wt. to about 16 wt.%, for example, from about 1 1 wt. to about 13 wt.%, of the formulation or reaction mixture.
  • the flame retardant is can be a phosphorus- containing flame retardant.
  • phosphorus-containing flame retardants include, but are not limited to triethyl phosphate (TEP), triphenyi phosphate (TPP), trischloropropylphosphate (TCPP), dimethylpropanephosphate, resorcinol bis(diphenylphosphate) (RDP), bisphenol A diphenyl phosphate (BADP), and tricresyl phosphate (TCP), dimethyl methylphosphonate (DMMP), diphenyl cresyl phosphate and aluminium diethyl phosphinate.
  • TPP triethyl phosphate
  • TPP triphenyi phosphate
  • TCPP trischloropropylphosphate
  • RDP resorcinol bis(diphenylphosphate)
  • BADP bisphenol A diphenyl phosphate
  • TCP dimethyl methylphosphonate
  • DMMP diphenyl cres
  • the relative amounts of polyisocyanate and aikoxylated triazine- arylhydroxy-aldehyde condensate are selected to produce a polymer.
  • the ratio of these components is generally referred to as the‘isocyanate index’ which means 100 times the ratio of isocyanate groups :to isocyanate-reactive groups provided by the aikoxylated triazine-arylhydroxy-aldehyde condensate.
  • the isocyanate index is generally at least 50 and can be up to 1000 or more, for example from about 50 to about 900.
  • Rigid polymers such as structural polyurethanes and rigid foams are typically made using an isocyanate index of from 90 to 200.
  • the isocyanate index is generally from 70 to 125.
  • Polymers containing isocyanurate groups are often made at isocyanate indices of at least 150, up to 600 or more.
  • the polyisocyanate compound and the alkoxylated triaziue- arylhydroxy-aldehyde condensate are mixed and cured.
  • the curing step is achieved by subjecting the reaction mixture to conditions sufficient to cause the polyisocyanafe compound and alkoxylated triazine-arylhydroxy-aidehyde condensate to react to form the polymer.
  • An example would be mixing the the alkoxylated triazine- arylhydroxy- aldehyde condensate with pMDl for 10 seconds at ambient conditions in order to generate a reaction between the hydroxyl groups and the isocyanate. This reaction generates heat and depending on the length of alkoxylation can yield rigid or flexible foams.
  • polymers can be made in accordance with the invention through the proper selection of particular alkoxylated-triazine-aryihydroxy-aldehyde condensates, particular polyisocyanates, the presence of optional materials as described below, and reaction conditions.
  • the process of the invention can be used to produce polyurethane and/or polyisocyanurate polymers of various types, including rigid polyurethane foams, sealants and adhesives (including moisture-curable types), hot-melt powders, wood binders, cast elastomers, flexible or semi-flexible reaction injection molded pails, rigid structural composites, flexible polyurethane foams, binders, cushion and/or unitary backings for carpet and other textiles, semi-flexible foams, pipe insulation, automotive cavity sealing, automotive noise and/or vibration dampening, microceilular foams such as shoe soles, tire fillers and the like. These polymers can then be used to manufacture articles.
  • novel polymers produced herein may be applied to substrates as part of the polymer production process, such as point of use applications, or applied after complete polymer production for latefuse in application processes.
  • Suitable substrates may include inorganic material, such as silica or metal, or an organic material, such as wood or plastic, or a combination thereof.
  • suitable substrates include proppants and proppant substrates, wood, building materials, and structural surfaces, among others.
  • the triazine-arylhydroxy-aldehyde condensate compositions were prepared using methods described in US Patent No. 9,249,251, which is incorporated herein by reference to the extent not inconsistent with the invention.
  • % Water The percentage of water remaining in the product after alkoxylafion was determined by a standard Karl Fischer titration via a Karl Fischer titration apparatus which is similar to ASTM D6304.
  • Hydroxyl Value The value was obtained from utilizing the titration method as specified by American Oil Chemists’ Society (AOCS) CD 13-60 method,
  • 5% solubility in water The was determined by mixing 5 grams of the materials from examples 1 -6 with 95 grams of distilled dionized water for 30 minutes and checking the visual appearance of the system. If the system was clear and exhibited no sediment it would be considered soluble and if the system exhibited any haze, cloudiness, or sediment it was considered insoluble.
  • Viscosity at 30 °C The viscosity of the materials were determined from a parallel plate Rheometer operated in rotational mode with a scanning shear rate of 0. 1 to 100 1/s at 30 °C. The viscosity of the materials of extrapolated to the zero shear viscosity and was reported in mPa.s.
  • pH 5% in I PA/ Water: The pH was determined by dissolving the material in 50% isopropanoi (1PA) in water and utilizing a calibrated pH probe to read the pH of the overall system.
  • a triazine-arylhydroxy-aldehyde condensate Control sample was prepared according to the process US Patent No. 9,249,251. It is briefly described in part as follows. 546.0 gram of phenol (5.8 moles), 1.1 g benzoic acid, and 79.1 g of melamine (0.63 moles) were charged to a reaction vessel to form a reaction mixture. The reaction mixture was heated to 80 °C and 55.8 g of formaldehyde was added in the form of a 50% solution in water over 40 minutes. The reaction was atmospherically distilled to 123 °C after addition and maintained at 123 °C for 2 hours.
  • reaction mixture was then cooled to 80 °C and 37.2 g of aqueous formaldehyde in the form of a 50% solution in water was added over 30 minutes and then atmospherically distilled to 123 °C and maintained at 123 °C for 2 hours.
  • the reaction mixture was then further atmospherically distilled to 165 °C and then was gradually vacuumed distilled to 27 inches of mercury over 3 hours while maintaining 165 °C and then heated to 175 °C while maintaining 27 inches of mercury.
  • the reaction mixture was held for 1 hour at 175 °C and then steam sparged for 60 minutes while under vacuum distillation. A total of 426.6 g of distillate was removed and 212.9 g of arylhydroxy- aidehyde condensate was discharged from the reaction vessel and upon cooling exhibited a brittle and solid like materials properties.
  • Control example and 50% potassium hydroxide in methanol was charged to a 2 L pressure reactor equipped with mechanical agitator, reflux condense!, thermocouple, and thermocouple controlled heating mantle.
  • the reactor was flushed with nitrogen to remove air and heated to 90 °C followed by vacuum dehydration at 120 °C to remove trace water and methanol.
  • the mixture was then heated to a temperature of 150-160 °C.
  • 20% of 1015 grams of ethylene oxide was then charged to the flask to initiate the reaction followed by the addition of the remaining ethylene oxide to a pressure of 4.0 kg/cm 2 .
  • the reaction mixture was allowed to react at 165 °C at 4.0 kg/cm 2 then cooled to 70-75 °C and neutralized to a pH of 7-8, The yield was 87%
  • Control example and 50% potassium hydroxide in methanol was charged to a 2 L pressure reactor equipped with mechanical agitator, reflux condenser, thermocouple, and thermocouple controlled heating mantle.
  • the reactor was flushed with nitrogen to remove air and heated to 90 °C followed by vacuum dehydration at 120 °C to remove trace water and methanol.
  • the mixture was then heated to a temperature of 150-160 °C.
  • 20% of 1370 grams of ethylene oxide was then charged to the flask to initiate the reaction followed by the addition of the remaining ethylene oxide to a pressure of 4.0 kg/cm 2 .
  • the reaction mixture was allowed to react at 165 °C at 4.0 kg/cm 2 then cooled to 70-75 °C and neutralized to a pH of 7-8.
  • the yield was 92%.
  • Table 1 demonstrates the properties of the alkoxylated triazine-arylhydroxy- aldehyde condensates after alkoxylation and shows a control prior to aikoxyiation.
  • the properties specifically viscosity, hydroxyl value the % water, and the pH, are important for the application of alkoxylated triazine-arylhdroxy-aldehyde condensates in the preparation of polyurethane foams.
  • the solubility in water indicates if the resulting alkoxylated triazine- arylhydroxy-aldehyde condensates were hydrophilic or hydrophobic.
  • Example 3 condensate being soluble in water and thus hydrophilic or miscible with water
  • Example 1 and 2 condensates being insoluble and, thus, hydrophobic.
  • the alkoxyiation yields materials that are liquid at 30 °C and enables their use into liquid polyurethane applications such as mixing with other polyols with addition of heat or require special handling conditions.
  • the hydroxyl number for the control sample is extremely high at 739 mg KOH/g and would require a high amount of isocyanate to maintain a typical isocyanate index for polyurethane foams, whereas hydroxyl numbers in the range of 150-400 mg KOH/g are more suitable for most polyurethane foam applications.
  • Control example and 50% potassium hydroxide in methanol was charged to a 2 L pressure reactor equipped with mechanical agitator, reflux condenser, thermocouple, and thermocouple controlled heating mantle.
  • the reactor was flushed with nitrogen to remove air and heated to 90 °C followed by vacuum dehydration at 120 °C to remove trace water and methanol.
  • the mixture was then heated to a temperature of 150-160 °C.
  • 20% of 1092 grams of propylene oxide was then charged to the flask to initiate the reaction followed by the addition of the remaining propylene oxide to a pressure of 4.0 kg/cm 2 .
  • the reaction mixture was allowed to react at 165 °C at 4.0 kg/cm 2 then cooled to 70-75 °C and neutralized to a pH of 7-8.
  • the isolated yield was 48%
  • Control example and 50% potassium hydroxide in methanol was charged to a 2 L pressure reactor equipped with mechanical agitator, reflux condenser, thermocouple, and thermocouple controlled heating mantle.
  • the reactor was flushed with nitrogen to remove air and heated to 90 °C followed by vacuum dehydration at 120 °C to remove trace water and methanol.
  • the mixture was then heated to a temperature of 150-160 °C.
  • 20% of 1316 grams of propylene oxide was then charged to the flask to initiate the reaction followed by the addition of the remaining propylene oxide to a pressure of 4.0 kg/cm 2 .
  • the reaction mixture was allowed to react at 165 °C at 4.0 kg/cm 2 then cooled to 70-75 °C and neutralized to a pH of 7-8.
  • the isolated yield was 86%
  • Table 2 demonstrates the properties of the alkoxylated triazine-arylhydroxy- aldehyde condensates after aikoxylation with propylene oxide and compares the results against a control of triazine-arylhydroxy aldehyde condensate.
  • the properties are important for the application of alkoxylated triazine-arylhydroxy aldehyde condensates in the preparation of polyurethane foams, specifically viscosity, hydroxyl value the % water, and the pH, The solubility in water was used as an indication if the resulting alkoxylated triazine- arylhydroxy-aldehyde condensates were hydrophilic or hydrophobic and it can be seen that the alkoxylated triazine-aryihydroxy-aldehyde condensates prepared with propylene oxide are all hydrophobic and not soluble in water even with long propoxy!ation lengths as seen in Example 6.
  • Example 7 Viscosities of Alkoxylated Triazine-Arylhydroxy-Aldehyde
  • An ARES-G2 rheometer (TA Instruments) equipped with stainless steel parallel plates was operated under rotational mode to determine the viscosities of Examples 1-6 at 25°C, 30°C, 35°C, and 40°C.
  • the viscosity was determined from a“zero-shear” approximation in which the viscosity is measured as a function of shear rate (0.1 -100 1/s).
  • the zero shear viscosity was determined by extrapolation of the viscosity curve to zero shear, which takes into account non-Newtonian behavior at low shear rates such as shear thinning.
  • Tables 3a and 3b show the temperature dependence of viscosity for the different alkoxylated triazine-arylhydroxy-aldehyde condensates. Temperature has a significant influence on the viscosity of the products with a 5 °C change in temperature at times reducing the viscosity by 40% for Newtonian alkoxylated triazine-arylhydroxy- aldehyde condensates and 93% for the Non-Newtonian alkoxylated triazine-arylhydroxy- aldehyde condensates.
  • the data is important for polyurethane formulators as viscosity of each component in a polyurethane system can have significant impacts on the overall properties of the final system.
  • an alkoxylated triazine-ary!hydroxy- a!dehyde condensate can be used as a rheology modifier for polyurethane crosstinkers to further adjust the viscosities of polyurethane systems.
  • Example 8 Polyurethane '
  • Table 4 indicates that the onset of degradation for the polyurethanes prepared from Examples 1 1, 12, and 13 exhibit different thermal stabilities. The onset of degradation was determined by the weight loss at 5% (Td5%) and 10% (T di o%).
  • Example 13 exhibited the highest thermal stability with a T d 5 % of 262 °C and T d so% of 3 14 °C.
  • the polyurethanes from Example 13 exhibited about 6% higher thermal stability than example 12 and 18% higher thermal stability than example ⁇ 1 . This indicates that ethoxyiation length plays an important role in the thermal stability of the final polyurethane polymer.
  • Foams were prepared using a high-torque mixer (CRAFSTMAN 10-lnch Drill Press, Model No. 137.219000) at 3, 100 rpm speed. Polyol components and isocyanate components of the foam systems were mixed for 5 seconds. Afterwards, the mixture was transferred into an open cake box before the cream time and was allowed to rise. Foams were prepared by pouring the foaming mix into cake boxes of 9”x9”x5” dimensions. The foams were used to assess cream time, gel time, rise time, tack-free time, density, and visual appearance of cell structure.
  • Lupranate M20S is a polymeric methylene diphenyl diisocyanate (pMDI) available from BASF Corporation.
  • a polyurethane foam was prepared, according to the process herein, by reacting Lupranate M20S, a polymeric methylene diphenyl diisocyanate with an isocyanate index of 1 10, (A side) and a polyol component (B side) prepared from the corresponding components in Table 5.
  • the mix time was held constant and the cream time, gel time, rise time, and tack free time, were all measured after the mixture had been poured into a polyethylene lined cardboard box.
  • the resulting foam had a density of 29.52 kilogram per cubic meter and had a uniform and coarse cell structure.
  • a polyurethane foam was prepared, according to the process herein, by reacting Lupranate M20S, a polymeric methylene diphenyl diisocyanate with an isocyanate index of 1 10, (A side) and a polyol component (B side) prepared from the corresponding components in Table 5.
  • the mix time was held constant and the cream time, gel time, rise time, and tack free time, were all measured after the mixture had been poured into a polyethylene lined cardboard box.
  • the resulting foam had a density of 30.69 kilogram per cubic meter and had a uniform and fine cell structure.
  • a polyurethane foam was prepared, according to the process herein, by reacting Lupranate M20S, a polymeric methylene diphenyl diisocyanate with an isocyanate index of 1 10, (A side) and a polyol component (B side) prepared from the corresponding components in Table 5, The mix time was held constant and the cream time, gel time, rise time, and tack free time, were all measured after the mixture had been poured into a polyethylene lined cardboard box. The resulting foam had a density of 28.45 kilogram per cubic meter and had a uniform and slightly coarse cell structure.
  • a polyurethane foam was prepared, according to the process herein, by reacting Lupranate M20S, a polymeric methylene diphenyl diisocyanate with an isocyanate index of 1 10, (A side) and a polyol component (B side) prepared from the corresponding components in Table 5.
  • the mix time was held constant and the cream time, gel time, rise time, and tack free time, were all measured after the mixture had been poured into a polyethylene lined cardboard box.
  • the resulting foam had a density of 30,23 kilogram per cubic meter and had a uniform and fine cell structure.
  • a polyurethane foam was prepared, according to the process herein, by reacting Lupranate M20S, a polymeric methylene diphenyl diisocyanate with an isocyanate index of 1 10, (A side) and a polyol component (B side) prepared from the corresponding components in Table 5.
  • the mix time was held constant and the cream time, gel time, rise time, and tack free time, were all measured after the mixture had been poured into a polyethylene lined cardboard box.
  • the resulting foam had a density of 37.25 kilogram per cubic meter and had a very fine cell structure.
  • a polyurethane foam was prepared, according to the process herein, by reacting Lupranate M20S, a polymeric methylene diphenyl diisocyanate with an isocyanate index of 1 10, (A side) and a polyol component (B side) prepared from the corresponding components in Table 5.
  • the mix time was held constant and the cream time, gel time, rise time, and tack free time, were all measured after the mixture had been poured into a polyethylene lined cardboard box.
  • the resulting foam had a density of 28.90 kilogram per cubic meter and had a fine cell structure.
  • a polyurethane foam was prepared, according to the process herein, by reacting Lupranate M20S, a polymeric methylene diphenyl diisocyanate with an isocyanate index of 1 10, (A side) and a polyol component ⁇ B side) prepared from the corresponding components in Table 5.
  • Example 20 formulation is free of a catalyst. The mix time was held constant and the cream time, gel time, rise time, and tack free time, were all measured after the mixture had been poured into a polyethylene lined cardboard box. The resulting foam had a density of 42.36 kilogram per cubic meter.
  • Tero! 250 is an aromatic polyester polyol commercially available from Huntsman Corporation.
  • Jeffol R-470X is a Mannich polyol commercially available from Huntsman Corporation.
  • Poly-G 74-376 is a sucrose initiated polyether polyol made with ethylene oxide and propylene oxide commercially available from Monument Chemical.
  • Polycat 8 is a small molecule amine catalyst commercially available from Air Products and Chemicals, Inc.
  • Pelcat 9540-A is a potassium salt of octanoic acid catalyst commercially available from Ele Corporation.
  • Diluent DBE esters are a mixture of dibasic esters of the methyl and ethyl esters of adipic, succinic, and giutaric acids commercially available from Invista, Inc.
  • CO- 28B is a cell opener commercially available from Ventrex Chemical.
  • Dow Coming 193 is a silicone surfactant commercially available from Dow Coming.
  • Solistice LBA is a hydrofiuorinated olefin blowing agent commercially available from Honeywell Inc.
  • the alkoxylated tnazine-arylhydroxy-a!dehyde (ATAHA) condensate in Table 5 was prepared by the following procedure. 1000 grams of triazine-arylhydroxy- aidehyde condensate, 50 grams of glycerol, 6.6 grams of potassium hydroxide dissolved in 13.3 grams of methanol was charged to a 5 L pressure reactor equipped with mechanical agitator, reflux condenser, thermocouple, and thermocouple controlled heating mantle. The reactor was flushed with nitrogen to remove air and heated to 90 °C followed by vacuum dehydration at 120 °C to remove trace water and methanol. The mixture was then heated to a temperature of 140- 150 °C.
  • Table 5 displays the different formulation variants in using an alkoxylated- triazine-atylhydroxy-aldehyde condensate prepared from Example 1 with Example 36 representing a control formulation without alkoxylated triazine-arylhydroxy-aldehyde condensate.
  • the resulting polyurethane foam reactivity properties are shown in Table 6. Methods for measuring the reactivity in Table 6 were done in accordance with ASTM D7487- l 3el . Examples 1 5, 18, and 20 are free of a Mannich (base) polyol. Example 20 is free of catalysts.
  • Reactivity of a foam formulation is evaluated based on the time it takes to achieve the cream, gel, rise and tack-free states. Lesser the time it takes to achieve these states, faster is the reactivity of the formulation. From Table 6, Example 18 that contains the maximum concentration of alkoxylated triazine-aryihydroxy-a!dehyde condensate exhibited the highest reactivity of all the polyurethane foams produced and is significantly faster than Example 16, which is the control. Examples 14 and 18 are direct comparison of reactivity between Mannich polyol against alkoxylated triazine-arylhydroxy-aldehyde condensate.
  • alkoxylated triazine-arylhydroxy-aldehyde condensate is significantly more reactive than Mannich polyol ln addition
  • Examples 16, 19, 15 and 18 illustrate the effect of increasing the concentration of alkoxylated triazine-arylhydroxy- aldehyde condensate.
  • concentration of the alkoxylated triazine-arylhydroxy- aldehyde condensate increase from 0% to 10% to 15% to 30% respectively in these examples, the reactivity also increase consistently as shown by decrease in cream, gel, rise and tack-free times.
  • the data in Table 5 demonstrates the significantly higher reactivity of alkoxylated triazine-arylhydroxy-aldeyhde condensate compared to the reference polyols.
  • the table also shows that use of the novel polyol of the said invention can minimize or allow the formulation to be free of the use of Mannich (base) polyols or small molecule amine catalysts that can cause a myriad of health problems for humans including G!aucopsia and respiratory irritation
  • a formulator could likely develop a polyurethane composition that has no catalyst and no additional polyols, which could simplify complex formulations and minimize errors in producing B side formulations.
  • An example of this formulation could be alkoxylated triazine arylhydroxy-aldehyde condensate, a suitable surfactant, a suitable blowing agent, and a suitable fire retardant.
  • Table 7 shows the effect of polyol on the foam’s reaction to fire.
  • concentration of the alkoxylated triazine-arylhydroxy-aldehyde condensate increase from 0% to 10% to 15% to 30% respectively in Examples 16, 19, 15 and 18 respectively, the burn rate decrease consistently and at a maximum concentration of 30% in the absence of both- the sugar-based polyether and Mannich polyol, the foam displayed self-extinguishing property.
  • the higher mass retention of the remnants is also a direct consequence of improved flame resistance.
  • Example 16 the control sample had a mass retention of 45%;
  • Example 18 with 30% of alkoxylated triazine-arylhydroxy-aldehyde condensate had a mass retention of 87%.
  • alkoxylated triazine arylhydroxy-aldehyde condensates will have better miscibility with aromatic isocyanates and blowing agents such as pentanes and their associate isomers, hydroxyl fluorinated olefins, hydroxyl fluorinated hydrocarbons, and other ha!ogenated blowing agents when compared to common polyols such as sucrose polyether po!yls or other polyethers of sufficient hydrophilicity, Mannich polyols, aromatic polyester polyols, ethylene diamine polyethers polyols.
  • aromatic isocyanates and blowing agents such as pentanes and their associate isomers, hydroxyl fluorinated olefins, hydroxyl fluorinated hydrocarbons, and other ha!ogenated blowing agents when compared to common polyols such as sucrose polyether po!yls or other polyethers of sufficient hydrophilicity, Mannich polyols, aromatic polyester polyols, ethylene diamine polyether
  • alkoxylated triazine-arylhydroxy-aldehyde condensates when reacted with an isocyanate have demonstrated relatively high onsets of thermal degradation and due to the nitrogen content present in the polyol could yield a synergistic effect with phosphorous containing compounds, which could significantly improve the fire retardant properties of a typical polyurethane foam or associated article.

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  • 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)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

Les modes de réalisation de la présente invention concernent généralement des procédés et des compositions chimiques de condensats de triazine-arylhydroxy-aldéhyde. Dans un mode de réalisation, un condensat de triazine-arylhydroxy-aldéhyde est mis à réagir avec au moins un agent d'alkoxylation pour former des condensats de triazine-arylhydroxy-aldéhyde alcoxylés.
EP19840750.4A 2018-07-24 2019-07-19 Nouvelles compositions et procédés pour produire des condensats de triazine-arylhydroxy-aldéhyde alcoxylés Pending EP3827040A4 (fr)

Applications Claiming Priority (2)

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US16/043,871 US10604614B2 (en) 2017-09-22 2018-07-24 Compositions and methods to produce alkoxylated triazine-arylhydroxy-aldehyde condensates
PCT/US2019/042593 WO2020023308A1 (fr) 2018-07-24 2019-07-19 Nouvelles compositions et procédés pour produire des condensats de triazine-arylhydroxy-aldéhyde alcoxylés

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EP3827040A1 true EP3827040A1 (fr) 2021-06-02
EP3827040A4 EP3827040A4 (fr) 2022-04-20

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EP3833699A4 (fr) * 2018-07-24 2022-08-03 Bakelite UK Holding Ltd. Nouvelles compositions et procédés pour produire des condensats de triazine-arylhydroxy-aldéhyde alcoxylés

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DE2807744A1 (de) * 1978-02-23 1979-09-06 Basf Ag Verfahren zur herstellung modifizierter aminoplastharze
US4485195A (en) * 1983-10-25 1984-11-27 Texaco Inc. Alkoxylated Mannich condensates having fire retardancy properties and manufacture of rigid polyurethane foam therewith
US4487852A (en) * 1983-10-25 1984-12-11 Texaco Inc. Modified Mannich condensates and manufacture of rigid polyurethane foam with alkoxylation products thereof
US4489178A (en) * 1983-10-25 1984-12-18 Texaco Inc. Mannich condensates having fire retardancy properties and manufacture of rigid polyurethane foam therewith
US4939182A (en) * 1988-07-27 1990-07-03 The Dow Chemical Company Melamine-alkanolamine condensates and polyurethanes prepared therefrom
US6239248B1 (en) 1998-09-22 2001-05-29 Borden Chemical, Inc. Phenol-novolacs with improved optical properties
DE10136321C1 (de) * 2001-07-26 2002-12-12 Agrolinz Melamin Gmbh Linz Polymere aus Triazinderivaten
DE10313200A1 (de) * 2003-03-19 2004-10-07 Ami-Agrolinz Melamine International Gmbh Prepregs für Faserverbunde hoher Festigkeit und Elastizität
US9249251B2 (en) 2010-08-17 2016-02-02 Hexion Inc. Compositions and methods to produce triazine-arylhydroxy-aldehyde condensates with improved solubility
CN103709395B (zh) * 2013-12-16 2016-06-08 中国林业科学研究院林产化学工业研究所 生物质基结构阻燃型多元醇及其制备方法和应用
WO2017160362A1 (fr) * 2016-03-17 2017-09-21 Huntsman Petrochemical Llc Sels métalliques de triazines d'aminio-acide en tant que catalyseurs de polyuréthane et de polyisocyanurate
US10435503B2 (en) * 2017-09-22 2019-10-08 Hexion Inc. Compositions for polyurethane applications
WO2019060422A2 (fr) * 2017-09-22 2019-03-28 Hexion Inc. Nouvelles compositions et procédés pour produire des condensats de triazine-arylhydroxy-aldéhyde alcoxylés

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CN112638972B (zh) 2023-05-30
EP3827040A4 (fr) 2022-04-20
CN112638972A (zh) 2021-04-09
KR20210034061A (ko) 2021-03-29
WO2020023308A1 (fr) 2020-01-30

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