WO2019060426A1 - Nouvelles compositions pour applications de polyuréthane - Google Patents

Nouvelles compositions pour applications de polyuréthane Download PDF

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Publication number
WO2019060426A1
WO2019060426A1 PCT/US2018/051766 US2018051766W WO2019060426A1 WO 2019060426 A1 WO2019060426 A1 WO 2019060426A1 US 2018051766 W US2018051766 W US 2018051766W WO 2019060426 A1 WO2019060426 A1 WO 2019060426A1
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Prior art keywords
arylhydroxy
aldehyde condensate
triazine
polymer
percent
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PCT/US2018/051766
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English (en)
Inventor
Ganapathy S. Viswanathan
Anthony Maiorana
Stephan Schröter
Pravin Kukkala
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Hexion Inc.
Hexion Research Belgium S.A.
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Priority claimed from US15/713,577 external-priority patent/US10118905B1/en
Priority claimed from US15/713,583 external-priority patent/US10435503B2/en
Application filed by Hexion Inc., Hexion Research Belgium S.A. filed Critical Hexion Inc.
Priority to EP18857994.0A priority Critical patent/EP3684830A4/fr
Priority to CN201880061043.7A priority patent/CN111108136B/zh
Publication of WO2019060426A1 publication Critical patent/WO2019060426A1/fr

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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
    • C08G18/70—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
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • C07D251/64—Condensation products of melamine with aldehydes; Derivatives 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
    • C08G18/38—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
    • C08G18/28—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
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/546—Oxyalkylated polycondensates of aldehydes
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • 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
    • C08G2110/0025—Foam properties rigid

Definitions

  • This invention relates to processes for making polymers from polyisocyanates and isocyanate reactive materials.
  • this invention relates to alkoxylated triazine-arylhydroxy-aldehyde condensate compositions useful as isocyanate reactive materials.
  • Aromatic polyols are used as cross-linkers for isocyanates and isocyanurates that go into polyurethane and polyisocyanurate-based polymers.
  • the largest end use for aromatic polyols is in applications where insulation, flammability, and structural performance are most important.
  • halogenated flame retardants are inexpensive, they have been linlced to environmental concerns. Accordingly, there remains an opportunity to develop rigid polyurethane foam that has a minimum amount of halogenated flame retardants or eliminate the need to have an additional flame retardant that resists scorching, burning, and smoking, while simultaneously having acceptable physical properties.
  • Novolacs are known to the polyurethane industry as aromatic polyols that typically go into rigid polyurethane and polyisocyanurate foam applications.
  • the novolac polyol is said to promote intumescence (i.e., swelling) of the rigid polyurethane foam, promotes char, decreases scorch, and decreases flammability of the foam.
  • the novolac polyol is also thought to react with isocyanates more quickly than the isocyanates react with water thereby increasing production speed, reducing cost, and allowing the rigid polyurethane foam prepared from a novolac polyol to be used in a wide variety of applications, especially those that require fast foaming times.
  • the gel time is typically 10-
  • the current polyurethane formulations for applications such as rigid foam require multifunctional polyols as isocyanate reactive chemicals.
  • the common ones are carbohydrate-based polyols, which are not very effective when it comes to flame resistance.
  • a process comprising, consisting of, or consisting essentially of: forming a reaction mixture containing at least one polyisocyanate and an isocyanate-reactive compound comprising at least one alkoxylated triazine-arylhydroxy-aldehyde condensate composition wherein the alkoxylated triazine-arylhydroxy-aldehyde condensate composition is a reaction product of a triazine-arylhydroxy-aldehyde condensate and at least one alkylene carbonate.
  • Embodiments of the invention are directed to alkoxylated triazine- arylhydroxy-aldehyde condensates, methods for making the alkoxylated triazine- arylhydroxy-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 alkylene carbonate.
  • any suitable triazine-arylhydroxy-aldehyde condensate can be used in the reaction with the alkylene carbonate.
  • 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.
  • the triazine monomer can be a triazine compound or a triazine derivative.
  • 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 selected from the group of aminotriazine, 4-methyl-l,3,5-triazine-2-amine, 2- amino-4,6-dimethyl- 1 ,3 ,5-triazine, melamine, hexamethoxymethylmelamine, hexamethylolmelamine, guanamine, acetoguanamine, propioguanamine, butyroguanamine, benzoguanamine, vinylguanamine, 6-(hydroxyphenyl)-2,4-diamino- 1,3,5-triazine, and combinations thereof.
  • 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 binuclear.
  • 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 hydroxybenzene group, an alkoxy 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.
  • arylhydroxy monomers include, but are not limited to phenol, cresols, xylenols, resorcinol, catechol, hydroquinone, naphthols, biphenols, bisphenols, phloroglucinol, pyrogallol or their derivatvies.
  • 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 selected from the group of formaldehyde, paraformaldehyde, acetaldehyde, i-butyraldehyde (isobutyraldehyde), benzaldehyde, acrolein, crotonaldehyde, salicylaldehyde, 4- hydroxybenzaldehyde, furaldehyde, pyrrolaldehyde, cinnamaldehyde, trioxymethylene, paraldehyde, terephthaldialdehyde, glyoxal, glutaraldehyde 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 alkylene carbonate to form the alkoxylated triazine-arylhydroxy-aldehyde condensate.
  • the alkylene carbonate can be a variety of alkylene carbonates. Mixtures of alkylene carbonates can also be used.
  • the general structure of an alkylene carbonate is represented by Formula I, below: Formula I
  • Ri and R 2 are each 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.
  • the alkylene carbonate can also be a six-membered structure, as represented by Formula II, below:
  • R 3 , R 4 , and R 5 are each 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.
  • Ri and R 2 in the product structure generally correspond to the Ri and R 2 groups of Formula I.
  • R 3 , R 4 , and/or R 5 groups are substituted for the R.i and R 2 groups.
  • the alkylene carbonate can be selected from the group consisting of ethylene carbonate, propylene carbonate, and mixtures thereof.
  • reaction conditions can include a reaction temperature in the range of from 50°C to 270°C. Any and all temperatures within the range of 50°C to 270°C are incorporated herein and disclosed herein; for example, the reaction temperature can be from 100°C to 200°C, from 140°C to 180°C, or from 160°C to 175°C.
  • the reaction conditions can also include a reaction pressure in the range of from 0.01 bar to 100 bar.
  • reaction pressure can be from 0.1 bar to 50 bar, from 0.5 bar to 20 bar, or from 1 bar to 10 bar.
  • the components can be added together in any suitable manner.
  • the reaction can take place in a batch system, a continuous system, a semi-batch system, or a semi-continuous system.
  • the alkylene carbonate can be added slowly to molten triazine-arylhydroxy-aldehyde condensate and then reacted until C0 2 evolution has ceased.
  • the reaction between the triazine-arylhydroxy-aldehyde condensate and the alkylene carbonate can take place in the presence of a catalyst.
  • catalysts 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, and lithium phosphate.
  • an organic acid such as oxalic acid, formic acid, acetic acid, trifluoroacetic acid, methane sulfonic acid, salicylic acid, or p-toluenesulfonic acid can be used to neutralize the reaction mixture.
  • the alkoxylated triazine-arylhydroxy-aldehyde condensate compound can be represented by Formula III below.
  • R 6 functional group is represented by Formula IV or Formula V.
  • R functional group of Formula III can be a hydrogen atom or represented by Fonnula IV or Formula VI.
  • R 8 and R9 can each independently be a hydrogen atom, an alkyl group with
  • Ri 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 furanyl group.
  • Rii and R 12 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.
  • Rn and R12 can jointly form a common aromatic ring with or without a hydroxyl group.
  • R 13 and R14 are each independently a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a vinyl group, a phenyl group, a hydro xyphenyl group, -NH(Formula VI), -N(Formula VI) 2 , -NH(Formula VI), -N((Formula IV)(Formula VI)), -N(Formula VI) 2 , or -NH 2 .
  • Ri 5 , Ri6, and Rn 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(FormulaVI), -N(Formula VI) 2 , -NH(Formula VII), -N(Formula VI)(Formula VII), - N(Formula VII) 2 , or -NFI2.
  • each m is independently from 1 to 10
  • each n is independently from 0 to 10
  • each x is independently from 1 to 2
  • each ' is independently from 0 to 2.
  • Monomers depicted by m and n can be arranged in any order, combination, or sub-combination.
  • the alkoxylated triazine-arylhydroxy-aldehyde condensates generally have a nitrogen content of from 0.5 weight percent to 40 weight percent, and from 5 weight percent to 15 weight percent in various other embodiments.
  • alkoxylated triazine-arylhydroxy-aldehyde condensate is represented by Formula VIII, below:
  • Formula XIV Another example of the alkoxylated triazine-arylhydroxy-aldehyde condensate is represented by Formula XV, below:
  • the alkoxylated triazine-arylhydroxy-aldehyde condensates of this invention generally have a viscosity in a solvent in the range of from about 1 Pascal second to 1,700 Pascal seconds at 25°C. Any and all ranges within 1 to 1,700 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 10 to 1,500 Pascal seconds or from 100 to 1,000 Pascal seconds at 25 °C.
  • the alkoxylated triazine-arylhydroxy-aldehyde condensates of this invention can be used as polyisocyanate-reactive compounds to make polyurethanes and polyisocyanurate-based polymers.
  • a reaction mixture is formed with at least one alkoxylated triazine-arylhydroxy-aldehyde condensate and at least one polyisocyanate.
  • polyisocyanates that can be used include, but are not limited to m-phenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, hexamethylene-1,6- diisocyanate, tetremethylene- 1 ,4-diisocyanate, cyclohexane- 1 ,4-diisocyanate, hexahydrotoluene diisocyanate, naphthylene- 1,5 -diisocyanate, methoxyphenyl-2,4- diisocyanate, diphenylmethane-4,4'-diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-
  • the polyisocyanate is diphenylmethane- 4,4 '-diisocyanate, diphenylmethane-2,4-diisocyanate, hexamethylene-1 ,6-diisocyanate, isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate or mixtures thereof.
  • Diphenylmethane-4,4' -diisocyanate, diphenylmethane-2,4-diisocyanate and mixtures thereof are generically referred to as MDI and all can be used.
  • Toluene-2,4- diisocyanate, toluene-2,6-diisocyanate and mixtures thereof are generically referred to as TDI and all can be used.
  • any of the foregoing polyisocyanates 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 MDI' 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 ⁇ -caprolactam, phenol, methyl ketone oxime, 1,2,4-triazole, and dimethyl malonate.
  • Polyols which can be used in conjunction with the alkoxylated triazine- arylhydroxy-aldehyde condensate include polyether polyols.
  • Suitable initiator compounds include, but are not limited to alkylene glycols, glycol ethers, glycerine, trimethylolpropane, sucrose, glucose, fructose, ethylene diamine, hexamethylene diamine, diethanolamine, monoethanolamine, piperazine, aminoethylpiperazine, diisopropanolamine, monoisopropanolamine, methanol amine, dimethanol amine, and toluene diamine.
  • Polyester polyols can also be used as part of the isocyanate-reactive compound.
  • Polyester polyols include reaction products of polyols, usually diols, with polycarboxylic acids or their anhydrides, usually dicarboxylic acids or dicarboxylic acid anhydrides.
  • the polycarboxylic acids or anhydrides can be aliphatic, cycloaliphatic, aromatic, and/or heterocyclic.
  • Mannich base polyols which are synthesized from Mannich bases, can also be used as part of the isocyanate-reactive compound.
  • the alkoxylated triazine-arylhydroxy-aldehyde condensate is present in the isocyanate-reactive compound in a range of from about 5 weight percent to about 50 weight percent. Any and all ranges between 5 and 50 weight percent are included herein and disclosed herein; for example, the alkoxylated triazine- arylhydroxy-aldehyde 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 can also act as a catalyst. Therefore, no extra catalyst is necessary for the reaction of the alkoxylated triazine-arylhydroxy-aldehyde condensate and polyisocyanate compound.
  • the polyisocyanate and alkoxylated triazine-arylhydroxy-aldehyde condensate mixture can also include a catalyst.
  • catalysts include, but are not limited to tertiary amines such as dimethylbenzylamine, l,8-diaza(5,4,0)undecane-7, pentamethyldiethylenetriamine, dimethylcyclohexylamine, and triethylene diamine.
  • Potassium salts such as potassium acetate and potassium octoate can also be used as catalysts.
  • the alkoxylated triazine- arylhydroxyl-aldehyde condensate can also act as a catalyst.
  • the alkoxylated triazine-arylhydroxy-aldehyde condensate also contains a diluent.
  • diluents include, but are not limited to polyglycols such as ethylene glycol, glycerol, or diethylene glycol, etherified polyglycols such as monomethyl ether of ethylene glycol or dimethyl ether of ethylene glycol, and dibasic esters of acids such as diethyl adipate, dimethyl adipate, diethyl succinate, or dimethyl succinate. Mixtures of any of these diluents can also be used.
  • additional materials can be present during the reaction of the polyisocyanate compound with the alkoxylated triazine- arylhydroxy- aldehyde condensate.
  • these 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 the like.
  • the flame retardant is can be a phosphorus- containing flame retardant.
  • phosphorus-containing flame retardants include, but are not limited to triethyl phosphate (TEP), triphenyl phosphate (TPP), trischloropropylphosphate, dimethylpropanephosphate, resorcinol bis(diphenylphosphate) (RDP), bisphenol A diphenyl phosphate (BADP), and tricresyl phosphate (TCP), dimethyl methylphosphonate (DMMP), diphenyl cresyl phosphate and aluminium diethyl phosphinate.
  • TEP triethyl phosphate
  • TPP triphenyl phosphate
  • RDP resorcinol bis(diphenylphosphate)
  • BADP bisphenol A diphenyl phosphate
  • TCP tricresyl phosphate
  • DMMP dimethyl methylphosphonate
  • DMMP diphenyl cresyl
  • the relative amounts of polyisocyanate and alkoxylated 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 alkoxylated triazine-arylhydroxy-aldehyde condensate.
  • the isocyanate index is generally at least 50 and can be up to 1000 or more.
  • 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 triazine- arylhydroxy-aldehyde condensate are mixed and cured.
  • the curing step is achieved by subjecting the reaction mixture to conditions sufficient to cause the polyisocyanate compound and alkoxylated triazine-arylhydroxy-aldehyde condensate to react to form the polymer.
  • the polymer formed by the process of this invention can generally have a burn rate in the range of from 50 percent to 60 percent lower than a polyurethane composition that was not prepared with an alkoxylated triazine-arylhydroxy-aldehyde condensate.
  • the polymer can also have a weight retention after burning in the range of from 70 percent to 115 percent higher than a polyurethane composition that was not prepared with an alkoxylated triazine-arylhydroxy-aldehyde condensate.
  • the polymer can have a compressive strength at yield in the range of from 25 percent to 60 percent higher than a polyurethane composition that was not prepared with an alkoxylated triazine-arylhydroxy-aldehyde condensate.
  • polymers can be made in accordance with the invention through the proper selection of particular alkoxylated-triazine-arylhydroxy-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 polyurethane foams, sealants and adhesives (including moisture-curable types), hot-melt powders, wood binders, cast elastomers, flexible or semi-flexible reaction injection molded parts, rigid structural composites, flexible polyurethane foams, binders, cushion and/or unitary backings for caipet and other textiles, semi-flexible foams, pipe insulation, automotive cavity sealing, automotive noise and/or vibration dampening, microcellular foams such as shoe soles, tire fillers and the like. These polymers can then be used to manufacture articles.
  • polyurethane foams sealants and adhesives (including moisture-curable types)
  • hot-melt powders wood binders
  • cast elastomers flexible or semi-flexible reaction injection molded parts
  • rigid structural composites rigid structural composites
  • flexible polyurethane foams binders
  • cushion and/or unitary backings for cai
  • compositions were prepared using methods described in US Patent
  • Example 3 [0070] 103 grams of triazine-arylhydroxy-aldehyde condensate were charged to a
  • the alkoxylated triazine-arylhydroxy-aldehyde condensate from Example 3 was flaked and fed into a grinding mill and an amount of methylene diphenyl diisocyanate was also fed to achieve a desired isocyanate ratio of 1 : 1 based on the hydroxyl equivalent weight of the triazine-arylhydroxy-aldehyde condensate.
  • the composition was ground to a mesh size of 50-100% through 200 mesh.
  • the powdered composition was cured above the melting point or softening point of the resulting mixture to yield a cross-linked polyurethane.
  • Example 4 were dissolved in 20 grams of triethyl phosphate and 10 grams of ethylene glycol to yield a viscous solution with an approximate hydroxyl equivalent weight of 98. This mixture was further formulated with cyclopentane as a surfactant and emulsified. A polymeric isocyanate was added to achieve a specific isocyanate ratio of l .T and then mixed to create a polyurethane foam.
  • An ARES-G2 rheometer (TA Instruments) equipped with stainless steel parallel plates was operated under rotational mode to determine the viscosities of the formulation from Example 3 at 150°C, 140°C, and 130°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 averaging the viscosity in the Newtonian region, which is approximately 1-100 1/s.
  • Ten data points were measured for every magnitude change of shear rate such as 10 points between 0.1 and 1 1/s. The lower temperature was determined when the materials exhibited non-Newtonian behavior such as shear thinning.
  • an alkoxylated triazine-arylhydroxy- aldehyde condensate can be used as a rheology modifier for polyurethane crosslinking systems.
  • Test Polyurethane mixtures (Test Formulations #1 and #2) were prepared using the two formulations shown in Table 5, below.
  • the alkoxylated triazine-arylhydroxy-aldehyde condensate of the current invention was mixed into the reference carbohydrate-based aliphatic polyol (Reference Polyol #1) at a 80:20 ratio of Reference Polyol #1 to the ethoxylated condensate from Example 3 along with other components listed in the Table, at 100°C in a cup at 2200 RPM using Speed Mixer DAC 400 FV.
  • Reference Polyol #1 was blended with other components in the same manner as described above.
  • Test Formulation #2 Reference Polyol #1 was blended with a conventional aromatic-based polyol and the ethoxylated condensate of Example 3. [0082] These polyol mixtures were then mixed with Rubinate M, a polyisocyanate, to an isocyanate index of 110% to form a free-rise foam. The actual mixing technique and equipment used are described below in detail under 'Method to Prepare Foam Samples for Flame and Mechanical Tests'. The reactivity differences between the two formulations are measured as the mix time, cream time, gel time, rise time and tack-free time as shown in Table 5.
  • Foams were prepared using a high-torque mixer (CRAFSTMAN 10-Inch
  • Niax A-l a catalyst available from Momentive Performance Materials.
  • Example 13 Fire Resistance and Mechanical Properties
  • the second set of five specimens are conditioned in an air circulating oven for 168 ⁇ 2 h at 70 ⁇ 2 °C, and then cooled in a desiccator for at least 4 hours at room temperature prior to testing.
  • 6 specimens are cut prior to testing from foam aged at room conditions (ambient temperature and humidity) for a minimum of 7 days after preparation of the foam.
  • Table 6 shows properties of foams prepared using three different formulations.
  • One reference formulation used a carbohydrate-based aliphatic polyol.
  • the two test formulations (#3 and #4) are prepared from various amounts of the carbohydrate- based aliphatic polyol, a conventional aromatic-based polyol, and the ethoxylated triazine- arylhydroxy-aldehyde condensate of Example 3. These formulations were prepared as described in Example 12, above.
  • foams prepared from the alkoxylated triazine- arylhydroxy-aldehyde condensate provided slower burn rates, higher weight retentions, and good mechanical properties.
  • the compressive strength at yield and the compressive strength at maximum, load significantly increased with the introduction of the alkoxylated triazine-arylhydroxy-aldehyde condensate into the formulation.
  • the compressive strength is dependent on the foam density.
  • this increase in the compressive strength with introduction of alkoxylated triazine-arylhydroxy-aldehyde condensate into the formulation is much greater than the possible effect of an increase in the foam density.
  • polymers prepared with alkoxylated triazine-arylhydroxy- aldehyde condensates have cream times that are about 4 to 19 percent lower, gel times that are about 35 to 42 percent lower, rise times that are about 23 to 34 percent lower, and tack-free times that are about 32 to 43 percent lower than the reference formulation that was not prepared with an alkoxylated triazine-arylhydroxy-aldehyde condensate.
  • foams prepared from the alkoxylated triazine-arylhydroxy- aldehyde condensate have higher reactivites than the foam prepared from the reference formulation.

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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)
  • Polyurethanes Or Polyureas (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé comprenant les étapes consistant à, ou consistant essentiellement à : former un mélange réactionnel contenant au moins un polyisocyanate et un composé de réaction avec un isocyanate comprenant au moins une composition de condensat de triazine-arylhydroxy-aldéhyde alcoxylée, cette composition de condensat de triazine-arylhydroxy-aldéhyde alcoxylée étant un produit de réaction d'un condensat de triazine-arylhydroxy-aldéhyde et d'au moins un carbonate d'alkylène.
PCT/US2018/051766 2017-09-22 2018-09-19 Nouvelles compositions pour applications de polyuréthane WO2019060426A1 (fr)

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US15/713,583 2017-09-22
US15/713,577 US10118905B1 (en) 2017-09-22 2017-09-22 Compositions and methods to produce Alkoxylated triazine-arylhydroxy-aldehyde condensates
US15/713,583 US10435503B2 (en) 2017-09-22 2017-09-22 Compositions for polyurethane applications
US15/713,577 2017-09-22

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CN112673036A (zh) * 2018-07-24 2021-04-16 瀚森公司 用于生产烷氧基化的三嗪-芳基羟基-醛缩合物的新组合物和方法
WO2020023308A1 (fr) * 2018-07-24 2020-01-30 Hexion Inc. Nouvelles compositions et procédés pour produire des condensats de triazine-arylhydroxy-aldéhyde alcoxylés
CN111848919A (zh) * 2020-08-07 2020-10-30 宁波耀众模塑科技有限公司 一种聚氨酯发泡产品阻用阻燃剂

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WO2016064948A1 (fr) * 2014-10-21 2016-04-28 Momentive Performance Materials Inc. Mousses rigides de polyuréthane comprenant des additifs de résines phénoliques modifiées
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WO2019060422A2 (fr) 2019-03-28
EP3684830A4 (fr) 2021-08-11
CN111108136B (zh) 2023-03-21
EP3684760A4 (fr) 2021-11-10
CN111094257A (zh) 2020-05-01
WO2019060422A3 (fr) 2019-05-02
EP3684830A1 (fr) 2020-07-29
EP3684760A2 (fr) 2020-07-29

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