WO2021067553A1 - Guanamines et bis-guanamines utiles dans des polyols et des mousses - Google Patents

Guanamines et bis-guanamines utiles dans des polyols et des mousses Download PDF

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WO2021067553A1
WO2021067553A1 PCT/US2020/053731 US2020053731W WO2021067553A1 WO 2021067553 A1 WO2021067553 A1 WO 2021067553A1 US 2020053731 W US2020053731 W US 2020053731W WO 2021067553 A1 WO2021067553 A1 WO 2021067553A1
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polyol
guanamine
nitrile
alkoxylated
bis
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PCT/US2020/053731
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English (en)
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Richard BEATTY
Ning Luo
Kevin WIACEK
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INVISTA North America S.à r.l.
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Publication of WO2021067553A1 publication Critical patent/WO2021067553A1/fr

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    • 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
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    • 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
    • C07D251/14—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 hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/16—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 hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
    • C07D251/18—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 hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines
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    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
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    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
    • C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
    • C08G18/4638—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/4661—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
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    • 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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5054—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/5063—Polyethers 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
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/508—Amines heterocyclic containing only nitrogen as a heteroatom having three nitrogen atoms in the ring
    • C08G59/5086—Triazines; Melamines; Guanamines
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    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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    • C08J2203/00—Foams characterized by the expanding agent
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms

Definitions

  • the present disclosure relates to the use of guanamines and bis-guanamines in the production of polyol formulations and foams.
  • PUR Polyurethane
  • PIR polyisocyanurate foams
  • PURs can be manufactured into flexible foams, high- resilience foams, rigid foams, insulation panels, microcellular foam seals, durable tires, automotive suspension bushings, electrical potting compounds, high performance adhesives, coatings, surface sealants, synthetic fibers, carpet underlay, etc.
  • PUR and PIR polymers are formed by reacting isocyanates with polyols.
  • Toluene diisocyanate (TDI) and methylene diphenyl diisocyanate (MDI) are the two major types of di-isocyanates used in rigid polyurethane foams.
  • Aromatic Polyester Polyols (herein referred to as APPs) have been in the PUR/PIR industry for the past five decades and play a role in various PUR/PIR rigid foam applications, including PUR spray foam systems.
  • Industrial uses of APPs include manufacture of PUR and/or PIR polymer products.
  • the PUR and PIR polymers are polyfunctional and can be used as adhesives, binders (e.g., for wood fibers), coatings, and foams.
  • the known benefits include low-cost, rigid cellular structure and excellent properties that are desired for many end-use applications.
  • polyester polyols that are used in polyurethane applications as well.
  • Such polyester polyols may be prepared using non-aromatic diacids and diols.
  • the non-aromatic diacids may be obtained from cyclohexane or cyclohexene oxidation processes and other industrial-scale processes.
  • Japanese Patent No. Japanese Patent No.
  • JPS6324254A relates to a composition containing an aromatic primary amine color developing agent and a cyclohexane or benzene ring compound with hydroxyalkyl groups such as 2-hydroxyethyl group and 4- hydroxybutyl group, etc., each alkyl group such as methyl, ethyl and propyl group, etc.
  • An example includes a 1,2-cyclohexanediamine (DCH) structure with both -Nth groups ethoxylated with ethylene oxide into -N[C 2 H 4 OH] 2 .
  • DCH 1,2-cyclohexanediamine
  • polystyrene resin 357-360, pp 1441-1445; 2-methyl- 1,5-diaminopentane, industrially known as MPMD and commercially available under the tradename Dytek ® A amine from INVISTA Specialty Materials, which has two primary amino groups, was employed as initiator to prepare polyols.
  • This class of polyols were made via reacting two primary amine groups with an alkylene oxide monomer by oxirane ringopening reaction.
  • Propylene oxide (PO), phenylethylene oxide (PEO) and cyclohexene oxide were chosen as the alkylene oxide monomers.
  • United States Patent No. 2,381,121A relates to condensation products of triazines and substituted triazines with alkylene oxides.
  • United States Patent No. 3,399,151A relates to polyurethane foam prepared from an oxyalkylated polyamino - 1,3,5-triazine - organic polyisocyanate reaction product.
  • United States Patent No. 9,944,745B2 relates to a polyester (polyol) having flame-retardant properties, wherein melamine is synthesized onto the polyester backbone.
  • Industrial applications of aliphatic polyester polyols include elastomers, coatings, adhesives, sealants, foams, and composites.
  • a polyol comprising at least one guanamine moiety in a polyester polyol backbone wherein at least one amide bond linkage is formed between the guanamine moiety and an ester moiety in the polyester polyol.
  • polyol comprising an alkoxylated guanamine or bis-guanamine.
  • a polyol composition comprising (i) a polyol having at least one guanamine moiety in a polyester polyol backbone, wherein at least one amide bond linkage is formed between the guanamine moiety and an ester moiety in the polyester polyol; and (ii) a polyol comprising an alkoxylated guanamine or bis-guanamine.
  • Also disclosed herein is a method of making a polyol or polyol composition as described above, comprising (a) providing the at least one nitrile compound and dicyandiamide to a reaction zone; (b) condensing the nitrile compound with the dicyandiamide to form a guanamine; (c) recovering the guanamine; (d) providing the guanamine to an alkoxylation reaction zone in the presence of an alkoxylation reagent, and optionally in the presence of the at least one polyalcohol compound, and optionally in the presence of the at least one alkali metal catalyst, and optionally in the presence of the at least one aprotic solvent; (e) maintaining the alkoxylation reaction zone at conditions sufficient to produce an alkoxylated polyol; and (f) recovering the alkoxylated polyol, wherein the recovered alkoxylated polyol is characterized by the Hydroxyl number of 100-800 mg KOH/g sample and functionality of 2-8.
  • FIGURE 1 is a graphical representation of the measured R- value data according to the embodiments of Example 40.
  • FIGURE 2 is a graphical representation of the aged R-value data according to the embodiments of Example 40 DETAILED DESCRIPTION
  • All average molecular weights of polymers are weight- average molecular weights, unless otherwise specified.
  • OH # hydroxyl value
  • HN hydroxyl number
  • the term “functionality”, or “hydroxyl functionality” of a polyol indicates the number of - OH groups per molecule, on average.
  • the functionality of an isocyanate refers to the number of -NCO groups per molecule, on average.
  • the functionality of a B-side foam ingredient is the number of isocyanate reactive sites on a molecule.
  • the functionality is calculated as (total moles of -OH groups)/(total moles of polyol).
  • the term “foam” is used to refer to a cellular structure produced by an expansion process, known as “foaming", and also having a comparatively low weight per unit volume (or density) and with low thermal conductivity.
  • the cellular structure is made up of well-defined cell boundaries, wherein a low-density component (such as gas) is dispersed and confined within the cells distributed across a continuous phase (liquid or solid).
  • a low-density component such as gas
  • Cellular foams can be light-weight or heavy, porous or dense, semi-rigid or rigid, or flexible moldable, spongy materials depending on the end-use application.
  • a foam structure obtained from aqueous soap solutions may be an unstable cellular structure where the liquid surface tension dominates the stability of such foams.
  • Rigid foams are usually the solidified form of a continuous liquid matrix full of gas-filled cells or bubbles dispersed within the matrix.
  • Rigid foams are often used as insulators for noise abatement, shock absorption and/or as heat insulators in construction, in cooling and heating technology (e.g., household appliances), for producing composite materials (e.g., sandwich elements for roofing and siding), and for wood simulation material, model-making material, and packaging.
  • Flexible moldable foams are useful in automotive, bedding, furniture, electronics, packaging and other industries where load-bearing capability and softness for comfort and/or protection are important.
  • Psig pounds per square inch gauge
  • One pound per square inch equals 6.895 kilopascals (kPa).
  • One atmosphere is equivalent to 101.325 kPa or about 14.7 pounds per square inch absolute (Psia) or about zero Psig.
  • alkoxylation refers to a well-known chemical reaction that involves the addition of an epoxide to another compound via its oxirane ring-opening mechanism. Depending on the epoxide used in the process, alkoxylation may be called ethoxylation, propoxylation, butoxylation, etc.
  • epoxide is a cyclic ether with a three-atom ring called an oxirane ring.
  • epoxides are ethylene oxide [EO; epoxide of ethylene], propylene oxide [PO; epoxide of propylene], 1,2-epoxyheptane [epoxide of 1,2-heptane], epoxycyclohexane [epoxide of cyclohexene], phenylethylene oxide [PEO; epoxide of styrene], and such.
  • Alkoxylation or oxirane ring opening reactions are also possible with bi-functional epoxide- alcohols, such as glycidols.
  • a guanamine is an organic compound with the chemical formula R- (C3N3)-(NH2)2 with the single unit structure of
  • Guanamines are closely related to melamine except one amino substituent in the melamine structure is replaced by an organic “R” group.
  • the “R” group can be an alkyl, acyclic or aryl group.
  • Guanamines are high-melting point solid materials. Examples of some industrial guanamines are when “R” is methyl, nonyl and phenyl groups, known as, acetoguanamine, caprinoguanamine and benzoguanamine, respectively.
  • guanamines can be obtained from pure, refined or crude mono-nitrile streams or co-products available from the nitrile, cyanide, pigment and dyes industrial processes.
  • the guanamine comprises a mono-guanamine formed from condensation of a mononitrile with cyanoguanidine or dicyandiamide, and wherein the mono-nitrile is selected from the group consisting of an aliphatic nitrile, a cyclic nitrile, an aromatic nitrile, an alicyclic multiplering nitrile, an aromatic fused multiple-ring nitrile, a partially hydrogenated aromatic nitrile, and mixtures thereof.
  • Non-limiting examples of some suitable nitriles that are available in the commercial dinitriles process, for example, C6 d initriles manufacture from butadiene hydrocyanation, may include 2-pentenenitrile (2PN), 3-pentenenitrile (3PN), 2-methyl-3- butenenitrile (2M3BN), 2-methyl-2-butenenitrile (2M2BN), and mixtures thereof.
  • the “R” group could be a linear or branched C 2 , C 3 , C 4 , C 5 , cyclic, phenyl and such.
  • a dinitrile may undergo half-substitution of one of the nitrile groups in forming a mono-guanamine of industrial importance.
  • fatty acids derived mono-guanamines wherein a particular fatty acid may be converted to a fatty nitrile which is subsequently reacted with dicyandiamide to produce its corresponding fatty mono-guanamine.
  • Fatty acids for this purpose may include short-chain ( ⁇ C 5 ’s), medium-chain (C 6-12 ’s), long-chain (C 13-21 ’s), very long-chain (>C22’s) fatty acids and mixtures thereof.
  • the fatty acids may be saturated or unsaturated fatty acids.
  • Such fatty acids could be derived from triglycerides or obtained from various sources such as conventional, bio-based, recycled oils, vegetable oils, most seed oils, soybean oil, flaxseed oil, sunflower oil, etc.
  • saturated fatty acids are Butyric acid (C4), Caprylic acid (Cs), Capric acid (C10), Why acid (C12), Myristic acid (C14), Palmitic acid (Ci6), Stearic acid (Cis), and such.
  • unsaturated fatty acids are Myristoleic acid, Palmitoleic acid, Sapienic acid, Oleic acid, Elaidic acid, Vaccenic acid, Linoleic acid, and others.
  • bis-guanamine or “bisguanamine” and its plural form, as used herein, is a class of chemical compounds with two interlinked units of nitrogen-containing heterocycles that are derived from s-triazine.
  • a general molecular structure of bis-guanamine is
  • Bis-guanamines can be obtained from pure, refined or crude dinitriles feedstock.
  • the bis-guanamine is formed by condensation of a dinitrile of the formula NC-R 1 - CN, with dicyandiamide, wherein R 1 is an alkyl, alicyclic or aryl group.
  • Suitable dinitriles include adiponitrile, 2-methylpentanedinitrile or 2-methylglutaronitrile, 2-ethylsuccinonitrile, phthalonitrile, isophthalonitrile, terephthalonitrile, isomers and mixtures thereof.
  • Non-limiting examples of bis-guanamines that may be obtained from six-carbon aliphatic dinitriles may include adipoguanamine [C 10 H 16 N 10 ; CAS No. 4341-27-9], 2-methyl- glutaroguanamine or iso-adipoguanamine [C 10 H 16 N 10 ; CAS No. 18006-65-0] and 2-ethyl- succinoguanamine [C 10 H 16 N 10 ; CAS No. 72987-36-1].
  • Some representative examples of bis- guanamines that can be obtained from the starting dinitriles are shown below:
  • the above bis-guanamines are also known as adipo-bisguanamine, iso-adipo- bisguanamine and 2-ethyl-succino-bisguanamine.
  • a dinitrile may be reacted with dicyandiamide (DiCY) to yield its corresponding bis-guanamine or a mixture of bis-guanamines when a dinitriles mixture is used.
  • DICY dicyandiamide
  • a general reaction scheme (I) is shown below:
  • the group “R 1 ” may be an alkyl, alicyclic or aryl group.
  • alkyl “R 1 ” groups may include aliphatic, linear or branched alkyl groups.
  • aliphatic C 6 dinitriles may include adiponitrile, 2-methylpentanedinitrile or 2- methylglutaronitrile, 2-ethylsuccinonitrile, isomers and mixtures thereof.
  • Other examples may include aliphatic C 4 or C 5 or C 7 or C 8 dinitriles.
  • Non-limiting examples of alicyclic “R 1 ” groups may include alicyclic, single-ring or multiple fused ring groups.
  • aryl “R 1 ” groups may include aromatic, single-ring or multiple fused ring groups.
  • these may include phthalonitrile, isophthalonitrile, terephthalonitrile, isomers and mixtures thereof.
  • fatty acids derived bis-guanamines wherein a particular fatty acid may first be dimerized into a fatty dimer acid, which is then converted to its corresponding fatty dinitrile. The fatty dinitrile is subsequently reacted with dicyandiamide according to Scheme (I) above to produce its corresponding fatty bis-guanamine.
  • Fatty acids for this purpose may include all those described above.
  • Dimer acids are dicarboxylic acids prepared by dimerizing unsaturated fatty acids obtained from tall oil.
  • the CAS number of the material is [61788-89-4].
  • Some examples of commercially available dimer acids are C36 dimer acid, a dimer of stearic acid, rapeseed fatty acid dimers and like.
  • guanamines and bis-guanamines may be incorporated in polyester polyol formulations via formation of amide linkages.
  • the resultant product is a polyol comprising at least one guanamine moiety in a polyester polyol backbone wherein at least one amide bond linkage is formed between the guanamine moiety and an ester moiety in the polyester polyol.
  • the polyol starting material comprises an aromatic polyester polyol or an aliphatic polyester polyol.
  • the amide bond linkage incorporates at least 2% of the guanamine moiety into the polyester polyol backbone, and the final polyol is characterized by a Hydroxyl number of 100-800 mg KOH/g sample and a functionality of 2-8.
  • a commercial INVISTA manufactured polyol such as Terate ® HT polyol may be mixed with a pre-determined amount of guanamine [e.g., benzoguanamine when “R” is phenyl] in a reaction vessel and reacted at 140-235 °C for about 2-4 hours to obtain a monoguanamine incorporated polyol, as schematically shown in Scheme (II) below.
  • guanamine e.g., benzoguanamine when “R” is phenyl
  • the above guanamines and bis-guanamines may be alkoxylated by an alkylene oxide, such as ethoxylated by EO or propoxylated by PO, and incorporated in the polyol backbone to yield high functionality polyols.
  • the polyols may be polyester polyols, either an aliphatic or aromatic polyester polyols, or a polyether polyols, with or without aromaticity.
  • alkoxylation can be achieved reaction with an alkylene carbonate, such as ethylene carbonate, propylene carbonate and cyclocarbonates.
  • alkoxylated guanamine and bis-guanamine polyols may bring improved reactivity, catalytic properties, load-bearing capability and flame retardancy when such high functionality polyols are used in the foam products.
  • alkoxylated guanamine and bis-guanamine polyols can be incorporated neat, as blends or in the polyol during foam production.
  • the reaction product on the right side of general scheme (I), bis-guanamine or a mixture of bis-guanamines may further undergo alkoxylation reaction with an epoxide to yield bis- guanamine polyol or a mixture of bis-guanamine polyols.
  • a general reaction scheme (III) is shown below:
  • the epoxide is a cyclic ether with a three-atom ring.
  • the group “R 2 ” may be a proton, or a C 1 to C 6 hydrocarbyl group, such as methyl, ethyl, propyl, and butyl groups.
  • the group “R 2 ” may also be cyclic, non-aromatic or aromatic, for example, epoxycyclohexane [epoxide of cyclohexene], and phenylethylene oxide.
  • X > 0 is an integer, for example, 1, 2, 3, 4,...
  • reaction product on the right side of Scheme (la), adipoguanamine may be alkoxylated as per general scheme (III), say, propoxylated with PO, to yield high-functionality adipoguanamine polyol.
  • iso-adipoguanamine [276.3 MW] may be produced by reacting a branched C 6 dinitrile, e.g., MGN, and DiCY, as shown in the reaction scheme (lb) below:
  • 2-ethylsuccinoguanamine [276.3 MW] may be produced by reacting a branched C 6 dinitrile, e.g., 2-ethylsuccinonitrile (ESN), and DiCY according to general scheme (I).
  • ESN 2-ethylsuccinonitrile
  • bis-guanamine (2-ethylsuccinoguanamine) may be alkoxylated, for example, propoxylated with PO, to yield high-functionality 2-ethylsuccinoguanamine polyol as per general scheme (III).
  • Product (A) and Product (B) represent the alkoxylated bis-guanamine and alkoxylated guanamine, respectively.
  • Product (A) can be obtained by propoxylating iso-adipoguanamine, i.e., the product in Scheme (lb).
  • PO is used as the alkylene oxide monomer.
  • the person skilled in the field will appreciate there are corresponding analogs of Product (A) and Product (B) possible when alkoxylated with EO, PEO, cyclohexene oxide, or other commercially available alkylene oxide monomers.
  • alkoxylated guanamines may be used to make polyurethane foams, the properties of alkoxylated bis-guanamines remain unpredictable when considering the differences in the functionality and molecular conformation between guanamines and bis-guanamines.
  • an amino group attached to a triazine ring has much less reactivity compared to that of a regular amino group, for example, the primary amine group in 2-methyl- pentamethylenediamine (INVISTA Dytek ® A amine).
  • Alkali bases e.g.: aqueous KOH, can be used as a catalyst that necessitates the post-reaction purification for the removal of alkali metal ions from the reaction product.
  • High melt points and poor solubility of amino-triazines also make the alkoxylation reaction even more challenging.
  • bis-guanamine derived from 2-methyl-pentanedinitrile is a high melt point (> 200 °C) solid.
  • High alkoxylation temperatures may help with the high melt point reagents but tend to generate undesirable high pressures in the reactor which makes it difficult to control the reaction rate. Poor solubility further requires the use of large amounts of aprotic solvent(s) to solubilize the high melt solids, and the solvent(s) use requires subsequent solvent stripping/removal from the final product.
  • the present disclosure recognizes and addresses the above problems experienced during the preparation of alkoxylated products from guanamines and bis-guanamines.
  • This present disclosure offers new formulations which may include alkoxylation products of guanamines and bis-guanamines obtained from the mixtures of nitriles, dinitriles, diamines and in the presence or absence of glycols, and optionally aprotic solvents.
  • the present disclosure improves the flame retardancy properties of the foam product when these alkoxylated guanamine and bis-guanamine polyol intermediates are incorporated either neat, as blends or in the polyol formulations during PUR/PIR foam preparations.
  • alkoxylated guanamine and alkoxylated bis-guanamine compositions that are suitable for making polyurethane materials including polyurethane foams.
  • An aprotic solvent such as DMSO or DMF may be used in such preparations but is not preferred as the solvent must be removed from the resultant polyols for further uses.
  • Alkali metal catalysts may be used but also are not preferred as the alkali metal ions are required to be removed from the resultant polyols for further uses.
  • Another object of this disclosure is to prepare alkoxylated guanamine and alkoxylated bis- guanamine in conjunction with polyols including both poly ether and polyester polyols.
  • the present disclosure provides a polyol composition comprising: a polyol having at least one guanamine moiety in a polyester polyol backbone, wherein at least one amide bond linkage is formed between the guanamine moiety and an ester moiety in the polyester polyol; and a further polyol comprising an alkoxylated guanamine or bis- guanamine.
  • the further polyol may be a polyester polyol, either an aliphatic or aromatic polyester polyol, or a poly ether polyol, with or without aromaticity.
  • Still another object of this disclosure is to provide the alkoxylated guanamine and alkoxylated bis-guanamine compositions suitable for making polyurethane foams.
  • a method of making a polyol or polyol composition comprising: providing the at least one nitrile compound and dicyandiamide to a reaction zone; condensing the nitrile compound with the dicyandiamide to form a guanamine; recovering the guanamine; providing the guanamine to an alkoxylation reaction zone in the presence of an alkoxylation reagent, and optionally in the presence of at least one polyalcohol compound, and optionally in the presence of the at least one alkali metal catalyst, and optionally in the presence of the at least one aprotic solvent; maintaining the alkoxylation reaction zone at conditions sufficient to produce an alkoxylated polyol; and recovering the alkoxylated polyol, wherein, the recovered alkoxylated polyol is characterized by a Hydroxyl number of 100- 800 mg KOH/g sample and functionality of 2-8.
  • Ethylene oxide (EO), propylene oxide (PO), phenylethylene oxide (PEO), Glycidol, 1,2-Butylene oxide, cyclohexene oxide may be used as alkoxylating compound.
  • the nitrile compound may include, and not limited to, aliphatic nitrile, cyclic nitrile, aromatic nitrile, alicyclic multiple-ring nitrile, aromatic fused multiple-ring nitrile, partially hydrogenated aromatic nitrile, and mixtures thereof.
  • the nitrile compound may include mono-nitrile, dinitrile, and mixtures thereof.
  • the nitrile compound may include C 1 -C 10 aliphatic mono-nitrile, C 1 -C 10 aliphatic dinitrile, cyclic nitrile, aromatic nitrile, and mixtures thereof.
  • the C 1 -C 10 aliphatic mono-nitrile may include acetonitrile, acrylonitrile, methacrylonitrile, propionitrile, butyronitrile, pentanenitrile, hexanenitrile, heptanenitrile, octanenitrile, nonanenitrile, decanenitrile, 2-pentenenitrile (2-PN), 3- pentenenitrile (3-PN), 4-pentenenitrile (4-PN), 2-methyl-2-butenenitrile (2M2BN), 2-methyl-3- butenenitrile (2M3BN), and mixtures thereof.
  • the C 1 -C 10 aliphatic dinitrile may include ethanedinitrile, propanedinitrile, butanedinitrile, pentanedinitrile, hexanedinitrile (also known as adiponitrile or ADN), heptanedinitrile, octanedinitrile, nonanedinitrile, decanedinitrile, 2- methylglutaronitrile (MGN), 2-ethylsuccinonitrile (ESN), dinitriles obtained from bio-based diacids, such as dimer acid dinitrile, and mixtures thereof.
  • ADN adiponitrile
  • MGN 2-methylglutaronitrile
  • ESN 2-ethylsuccinonitrile
  • the cyclic nitrile may include cyclopropylnitrile, cyclobutylnitrile, cyclopentylnitrile, cyclohexylnitrile, and mixtures thereof.
  • the aromatic nitrile may include benzonitrile, iso-phthalonitrile, dicyanobenzene, their isomers and mixtures thereof.
  • pure or refined mono-nitrile feeds may be used.
  • crude mono-nitrile streams may be used, such as crude 2-PN, crude 3-PN, crude 4-PN, crude 2M3BN, and combinations thereof.
  • Such crude mono-nitrile streams may be industrially available from nitriles and dinitriles manufacturing processes, for example, adiponitrile manufacture.
  • the products may contain a mixture of their corresponding guanamines, which may be alkoxylated to obtain a mixture of guanamine derivatives of commercial value.
  • pure or refined dinitrile feeds may be used.
  • crude dinitrile streams may be used, such as crude ADN, crude MGN, crude ESN, and combinations thereof.
  • Such crude dinitrile streams may be industrially available from nitriles and dinitriles manufacturing processes, for example, adiponitrile manufacture.
  • the products may contain a mixture of their corresponding bis-guanamines, which may be alkoxylated to obtain a mixture of bis-guanamine derivatives of commercial value.
  • Suitable glycols may include widely used glycols such as ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), glycerin, glycerol, polyethylene glycols (PEG) and polypropylene glycols (PPG) of varied molecular weights.
  • EG ethylene glycol
  • DEG diethylene glycol
  • TEG triethylene glycol
  • PEG polyethylene glycol
  • PPG polypropylene glycols
  • Organic solvents such as aprotic solvents may be used to prepare mixtures of guanamines/bis-guanamines that may be further alkoxylated into their corresponding alkoxylated guanamine/bis-guanamine containing polyols.
  • aprotic solvents may include DMF, THF, DMSO, acetone, acetonitrile.
  • the term “aprotic solvent” is referred to a solvent that has no O-H or N-H bonds.
  • guanamine and bis-guanamine showed appreciable solubilities in glycerin and PEG600 versus those measured in EG, DEG and TEG.
  • Benzoguanamine was highly soluble in the tested mixtures of glycerin/PEG600 (50/50 w/w), glycerin/Dytek ® A amine (50/50 w/w) as well as PEG600/Dytek ® A amine (50/50 w/w).
  • about 5-10% (w/w) of iso-adipoguanamine was soluble in each of these tested mixtures.
  • Table 2 summarizes the measured solubilities of benzoguanamine and iso-adipoguanamine in some commercially available polyols, namely, Terate ® HT4020 polyol, TerrinTM 168G polyol, and PPG-425.
  • the Terate ® and TerrinTM family of polyols are commercial products of INVISTA Specialty Materials.
  • PPG-425 is a polypropylene glycol [Mol. Wt. 425] commercial product of Dow Chemical.
  • Table 2 Measured Solubility of Guanamine and bis-Guanamine in polyols at 150°C.
  • the schematic reaction scheme (V) below represents the first reaction of solubilized benzoguanamine with the polyester polyol to give an amide linkage along with the remaining unreacted benzoguanamine in the polyol mixture.
  • This resulting mixture from the first reaction is then subsequently alkoxylated to yield a new polyester polyol composition having a higher functionality than the commercial polyols where no benzoguanamine derivatives are present.
  • Such high-functionality polyester polyols find commercial uses in the foam preparation.
  • a scheme similar to the Scheme (V) can be represented when benzoguanamine is replaced with the bis-guanamine, such as adipoguanamine or iso- adipoguanamine, in the first step of Scheme (V).
  • the alkoxylated product is a new polyester polyol composition having a higher functionality than the commercial polyols where no bis-guanamine derivatives are present in the mixture.
  • Such high-functionality polyester polyols find commercial uses in the foam preparation.
  • Some industrial uses for the disclosed alkoxylated guanamine/bis-guanamine containing polyols may include in-situ polyol blends [of Scheme (V)] and/or physically blending them with the commercially available APPs as well as aliphatic polyester polyols to improve fire performance of the foam products prepared from these polyols.
  • alkoxylated guanamine/bis-guanamine containing polyols may include adding them to a polyurethane flexible foam to improve reactivity (i.e ., due to catalytic N) and compression force deflection (CFD) or load-bearing capability, which may be the result of the high-functionality of the disclosed alkoxylated guanamine/bis-guanamine containing polyol component.
  • Use of the disclosed polyols may allow either the elimination or a significant reduction of the amine catalyst additives commonly used in the flexible molded foam industry.
  • Flexible molded foams are useful in the automotive, furniture, bedding, electronics, packaging, and other industries.
  • Some industrial uses for the disclosed alkoxylated guanamine/bis-guanamine containing polyols may include reacting them with a hydroxyl-reactive material such as an acid chloride to produce dendrimers of commercial importance.
  • a hydroxyl-reactive material such as an acid chloride
  • dendrimers refers to synthetic polymers with a branching, tree-like structure.
  • Polyurethane rigid foam can be made by reacting polyisocyanates with the disclosed alkoxylated guanamine/bis-guanamine containing polyols from these examples with good appearance, improved reactivity profile, and improved physical properties such as improved compressive strength and flame resistance.
  • the suitability of the disclosed alkoxylated guanamine/bis-guanamine containing polyols in preparing rigid PUR foams are tested using the cup foam method.
  • the disclosed polyol is mixed with other additive package including catalysts, blowing agents, foam stabilizers, surfactants, coagents such as co-blowing agents, and a homogenized polyol blend is prepared.
  • This polyol blend, and polymeric MDI are separately weighed and mixed together with rapid stirring.
  • the developed PUR foam is tested for performance properties of commercial importance.
  • the acid number (AN), Acid # or acid value (AV) determination is performed according to the ASTM D-4662 method.
  • the acid number unit of measurement is mg KOH/g of sample.
  • the hydroxyl number (HN), OH # or hydroxyl value (HV) determination is performed according to the ASTM D-4274 method.
  • the hydroxyl number unit of measurement is mg KOH/g of sample.
  • the sample viscosity at 25°C is determined according to the ASTM D-4878 method. The viscosity is measured in the units of centipoise (cps).
  • Foam properties are measured according to various standard test methods as set forth below:
  • K-factor is measured according to ASTM C518-04 Standard Test Method for Steady State Thermal Transmission Properties by Means of the Heat Flow Meter Apparatus.
  • Foam density is measured according to ASTM D 1622-93 Standard Test Method for Apparent Density of Rigid Cellular Plastics.
  • Compressive strength is measured according to ASTM D 1621-94 Standard Test Method for Compressive Properties of Rigid Cellular Plastics.
  • NCO Index is the ratio of amount of isocyanate used to theoretical amount of isocyanate needed to react all available OH groups in a formulation.
  • K-Factor is a measure of heat in British-thermal-units (BTUs) that passes through a 1-inch thick, 1-ft 2 of foam surface area in 1 hour, for each degree Fahrenheit (or °F) temperature interval.
  • BTUs British-thermal-units
  • R-Value is the inverse of the K-factor and is a measure of thermal resistance for a particular material such as rigid foam.
  • the units of measurement for R-Value are Kelvin.m 2 /Watt.
  • Foams are generated primarily via hand-mix preparations. Foam performance is monitored using procedures set forth in standard methods, namely, ASTM D-1622 for density measurements, ASTM C-518 for initial and aged K-factor data, ASTM D-2126 for dimensional stability, and ASTM D-1621 for compressive strength.
  • the polyols are characterized for acidity, hydroxyl values, and viscosities at 25 °C.
  • the total acid number (Acid #) and hydroxyl values (OH #) are determined by using the standard titration methods. Dynamic viscosity measurements are done at 25 °C on a Brookfield viscometer.
  • the term, “crude dinitriles” means not refined or not purified dinitriles mixture stream available from chemical processes.
  • the term, “crude MGN” means not refined or not purified MGN stream obtained from a chemical manufacturing facility, such as an adiponitrile (ADN) production facility.
  • the crude MGN stream may contain other dinitriles in measurable quantities, for example, about 5 wt% ADN and 10 wt% ESN, or about 10 wt% ADN and no ESN, or about 50% ESN and ⁇ lwt% ADN. There may be other dinitriles and components present in low levels as well.
  • MW means molecular weight of a material in grams/mole.
  • IM-45 apparatus is an in-house bench scale test device. A foam specimen is placed at a fixed 45 degree angle and a Bunsen burner is mounted at the lower end of the specimen. The burner flame contacts the surface of the foam specimen for 2 seconds in order to characterize smoke generation. During the bum test, one can observe the smoke generation, flame growth, and the resultant post-test char formation. The smoke generated in the test travels by air flow through the tunnel and is measured by a photometer, or smoke detector, positioned at the higher end of the tunnel. The signal from the detector is simultaneously collected by a computer and the data is further processed. The test results are average values from six test runs for each foam formulation.
  • Teerate ® HT 1100 Polyol refers to an aromatic polyester polyol that is manufactured by INVISTA and commercially available under the brand name INVISTA Terate ® HT 1100 polyol.
  • Teerate ® HT 4020 Polyol refers to an aromatic polyester polyol that is manufactured by INVISTA and commercially available under the brand name INVISTA Terate ® HT 4020 polyol.
  • Teerate ® HT 5349 Polyol refers to an aromatic polyester polyol that is manufactured by INVISTA and commercially available under the brand name INVISTA Terate ® HT 5349 polyol.
  • Teerate ® HT 5350 Polyol refers to an aromatic polyester polyol that is manufactured by INVISTA and commercially available under the brand name INVISTA Terate ® HT 5350 polyol.
  • Teerate ® HT 5500 Polyol refers to an aromatic polyester polyol that is manufactured by INVISTA and commercially available under the brand name INVISTA Terate ® HT 5500 polyol.
  • TCPP tris(2-chloro-l-methylethyl) phosphate.
  • the 95% (min.) concentration TCPP is available from Sigma-Aldrich, ICL Supresta, Albemarle, Shekoy, Cellchem and other commercial suppliers.
  • Total Catalyst may include commercially available catalysts Polycat® 46, Dabco® K-15, Polycat® 5 and such. These are a class of catalysts for PUR or PIR formation that are known industrially.
  • Surfactants - The surfactants for use may include organic, silicone-based surfactants and combinations thereof.
  • the surfactant can serve to regulate the cell structure of the foam by helping to control the cell size in the foam and reduce the surface tension during foaming via reaction of the APP and, optionally, other components, with an organic polyisocyanate.
  • Surfactants such as silicone-polyoxyalkylene block copolymers, nonionic polyoxyalkylene glycols and their derivatives, and ionic organic salts of these surfactants can be used.
  • surfactants such as polydimethylsiloxane-polyoxyalkylene block copolymers under the trade names DabcoTM DC- 193 and DabcoTM DC-5315 (Air Products and Chemicals, Allentown, Pa.), or Tegostab B8871 (EVON IC).
  • Organic surfactants are those non-ionic structures including fatty alcohol, amine oxides, amides, alkanol amides, ethoxylated fatty alcohol such as polyalkoxylated sorbitan, and a combination thereof, can be used.
  • the amount of surfactant in the composition can be about 0 wt % to 5 wt %, based on the total weight of the mixture.
  • the blowing agent can be made from any of the three classes of blowing agents and systems used to make polyurethane and polyisocyanurate foams which are well known in the art: a hydrocarbon/water co-blown system; the HFC or HFC/water co-blown system; the HFO and/or HFO/water co-blown and/or HFO/water/hydrocarbon system; and a water blown system (also referred to in the art as a carbon dioxide blown system since CO2 is derived from the water-isocyanate reaction).
  • blowing agents for making polyisocyanurate foams include low boiling point hydrocarbons, for example, n-pentane, isopentane, and cyclopentane, and their alternative blowing agents such as Methylal and Methyl formate.
  • the typical floro-containing or chloro-containing blowing agents are those commercially available under varied trade names and their equivalents.
  • Some examples of these type of blowing agents are HFC-245fa (from Honeywell), HCFO-1233zd (from either Arkema and Honeywell), HFO-1336mzz-Z (from Chemours), and Solkane 365/227 (from Solvay).
  • the blowing agent can include two or more blowing agents (e.g., blowing agent, coblowing agent, and the like).
  • the blowing agent can be pentane and the co-blowing agent can be water, where pentane can be about 60 to 99 % by weight of the blowing agents and water can be about 1 to 40 % by weight of the blowing agents.
  • a suitably sized, jacketed batch vessel with N 2 purge and stirring capability and adequate head space is used for the reaction.
  • About 1 mole of crude MGN (108 MW) is initially charged to the vessel and reacted by slow addition of about 2 moles of dicyandiamide (84 MW).
  • An inert organic solvent, 2-methoxyethanol is used as diluent for controlling the temperature exotherm.
  • the resulting 1 mole of bis-guanamine (276 MW) product in diluent solvent is recovered from the reaction vessel.
  • the prepared bis-guanamine polyol has about 600 mg KOH/g hydroxyl number [OH #] and functionality of 8.
  • the bis-guanamines in Table 4 can be prepared from their corresponding dinitriles as described here.
  • 115.5 g of dinitrile, 252 g of dicyandiamide, 2 L of 2-methoxy ethanol and 5 wt% of KOH are combined and purged with nitrogen for 15 minutes.
  • the reaction mixture is refluxed for 5 hours. Once the reaction has cooled down, the precipitate is collected and washed with hot water and methanol, and dried.
  • the product yield is 68-85 % depending on the bis-guanamine produced and their individual solubilities in the reaction medium.
  • bis-guanamines obtained from the branched dinitrile isomers [MGN, ESN] have high solubility in the reaction medium. While in the case of adipo-guanamine produced from ADN has low solubility and precipitation is observed during the course of the reaction.
  • Example 13 Propoxylation of iso-adipoguanamine in DMSO
  • a slurry mixture of 850 ml (915 g) of DMSO, 580.7 grams (2.0 moles) of iso- adipoguanamine solids and 15 grams of 85% (wt.) aqueous potassium hydroxide is prepared in a 5-liter autoclave. Water is removed via heating and vaporization overhead. A small portion of the total 1800 grams (31 moles) of propylene oxide is charged to the mixture and alkoxylation reaction temperature is maintained at about 100 °C. It is found that iso-adipoguanamine continues to solubilize in the reaction medium as the reaction proceeds.
  • the temperature is maintained at about 100 °C for about 30 minutes.
  • the product mixture is cooled down and neutralized with phosphoric acid, and further undergoes purification steps for the removal of DMSO solvent and the potassium ions.
  • the purified polyol has hydroxyl number of 337-359 mg KOH/g and nominal functionality of 8.
  • Example 14 Propoxylation of iso-adipoguanamine with Dytek ® A amine in DMSO
  • a slurry mixture of 850 ml (915 g) of DMSO, 580.7 grams (2.0 moles) of iso- adipoguanamine solids and 116 grams of Dytek ® A amine is prepared in a 5-liter autoclave.
  • a small portion of the total 2270 grams (39 moles) of propylene oxide is charged to the mixture and alkoxylation reaction temperature is gradually increased and maintained at about 100 °C. It is found that iso-adipoguanamine continues to solubilize in the reaction medium as the reaction proceeds.
  • the temperature is maintained at about 100 °C for about 30 minutes.
  • the product mixture is cooled down and washed with water to remove DMSO followed by drying under vacuum.
  • the final polyol has hydroxyl number of 385 mg KOH/g and nominal functionality of 6.7.
  • Example 15 Propoxylation of iso-adipoguanamine in Glycerin with KOH as catalyst
  • a mixture of 61.4 grams (0.22 moles) of iso-adipoguanamine, 553 grams of glycerin and 15 grams of aqueous KOH solution is prepared in a 5-liter autoclave to form a homogeneous solution. Water is removed by heating and overhead vaporization. A small portion of the total 3583 grams (62 moles) of propylene oxide is charged and the mixture temperature is raised gradually to 100 °C. After addition of all of propylene oxide, the mixture temperature is maintained at about 100 °C for 30 minutes. The product mixture is cooled down and washed with water and purified to remove DMSO and potassium ions. The final polyol has hydroxyl number of 263 mg KOH/g and nominal functionality of 3.2.
  • Example 16 Propoxylation of iso-adipoguanamine in PEG600 with KOH as catalyst
  • a mixture of 66.7 grams (0.23 moles) of iso-adipoguanamine, 600 grams of PEG600 and 15 grams of aqueous KOH solution is prepared in a 5-liter autoclave to form a homogeneous solution. Water is removed by heating the mixture and overhead vaporization. A small portion of the total 2270 grams (39 moles) of propylene oxide is charged to the reaction solution and temperature is raised gradually to about 100 °C. After addition of all of propylene oxide, the temperature is maintained at about 100 °C for 30 minutes. The product mixture is cooled down and washed with water to remove DMSO and further purified to remove potassium ions. The final polyol has hydroxyl number of 661 mg KOH/g and nominal functionality of 3.1.
  • Example 17 Propoxylation of iso-adipoguanamine in polyester polyols without using KOH
  • a mixture of 66.7 grams (0.23 moles) of iso-adipoguanamine, 600 grams of Terate ® HT 4020 polyol and 5 grams of imidazole is prepared in a 5-liter autoclave to form a homogeneous solution.
  • a small portion of the total 623 grams (11 moles) of propylene oxide is charged to the reaction solution and the temperature of the mixture is gradually raised to about 100 °C. After addition of all of propylene oxide, the temperature is maintained at 100 °C for 30 minutes.
  • the polyol product mixture is used directly without further purification steps.
  • the final polyol has hydroxyl number of 209 mg KOH/g and nominal functionality of 2.8.
  • Example 18 Propoxylation of iso-adipoguanamine in polyether polyols without using KOH [0135]
  • a mixture of 66.7 grams (0.23 moles) of iso-adipoguanamine, 600 grams of PPG-425 and 5 grams of imidazole is prepared in a 5-liter autoclave to form a homogeneous solution.
  • a small portion of the total 599 grams (10 moles) of propylene oxide is charged to the reaction mixture and the temperature is gradually raised to about 100 °C. After addition of all of propylene oxide, the temperature is maintained at 100 °C for 30 minutes.
  • the polyol product mixture is used directly without further purification steps.
  • the final polyol has hydroxyl number of 207 mg KOH/g and nominal functionality of 2.8.
  • Example 19 Propoxylation of iso-adipoguanamine in glycerin / Dytek ® A amine mixture with
  • a mixture of 32.4 grams (0.11 moles) of iso-adipoguanamine, 616.5 grams of 50/50 (w/w) glycerin / Dytek ® A amine mixture (6 moles of diamine) and 15 grams of 85 wt% aqueous KOH solution is prepared in a 5-liter autoclave to form a homogeneous solution. Water is removed by heating and overhead vaporization. A small portion of the total 3188 grams (55 moles) of propylene oxide is charged and the temperature of the reaction mixture is raised gradually to about 100 °C. After addition of all of propylene oxide, the temperature is maintained at 100 °C for 30 minutes. The product mixture is purified by removing potassium ion. The final polyol has hydroxyl number of 303 mg KOH/g and nominal functionality of 3.4.
  • Example 20 Propoxylation of iso-adipoguanamine in PEG / Dytek ® A amine mixture with
  • a mixture of 30.7 grams (0.11 moles) of iso-adipoguanamine, 584 grams of 50/50 (w/w) PEG600 / Dytek ® A amine mixture (3 moles of diamine) and 15 grams of 85 wt% aqueous KOH solution is prepared in a 5-liter autoclave to form a homogeneous solution. Water is removed by heating and overhead vaporization. A small portion of the total 1617 grams (28 moles) of propylene oxide is charged and the temperature of the reaction mixture is gradually raised to about 100 °C. After addition of all of propylene oxide, the temperature is maintained at 100 °C for 30 minutes. The product mixture is purified by removing potassium ion. The final polyol has hydroxyl number of 298 mg KOH/g and nominal functionality of 3.8.
  • Example 21 Propoxylation of benzoguanamine in glycerin/Dytek ® A amine mixture with KOH
  • a mixture of 313 grams (1.7 moles) of benzoguanamine, 313 grams of 50/50 (w/w) glycerin / Dytek ® A amine mixture (2 moles of diamine) and 15 grams of 85 wt% aqueous KOH solution is prepared in a 5-liter autoclave to form a homogeneous solution. Water is removed by heating and overhead vaporization. A small portion of the total 2479 grams (43 moles) of propylene oxide is charged and the mixture temperature is gradually raised to about 100 °C. After addition of all of propylene oxide, the temperature is maintained at 100 °C for 30 minutes. The product mixture is purified by removing potassium ion. The final polyol has hydroxyl number of 300 mg KOH/g and nominal functionality of 3.6.
  • Example 22 Propoxylation of benzoguanamine in PEG/Dytek ® A amine mixture with KOH
  • a mixture of 389 grams (2 moles) of benzoguanamine, 389 grams of 50/50 (w/w) PEG600 / Dytek ® A amine mixture (2 moles of diamine) and 15 grams of 85 wt% aqueous KOH solution is prepared in a 5-liter autoclave to form a homogeneous solution. Water is removed by heating and overhead vaporization. A small portion of the total 2109 grams (36 moles) of propylene oxide (36 moles) is charged and the mixture temperature is gradually raised to about 100 °C. After addition of all of propylene oxide, the temperature is maintained at 100 °C for 30 minutes. The product mixture is purified by removing potassium ion. The final polyol has hydroxyl number of 304 mg KOH/g and nominal functionality of 3.8.
  • Example 23 Preparation of Product A (shown in Drawing 1) without using KOH [0140]
  • a 2000 ml autoclave 290 grams (1.0 moles) of iso-adipoguanamine, and 300 grams of propanol are mixed to form a suspension.
  • the content is heated to about 90-100 °C and the autoclave pressure is adjusted to 5 psig.
  • 465 grams (8 moles) of propylene oxide is slowly and incrementally added to the reaction mixture so that the pressure in the reactor does not exceed 60 psig.
  • the mixture temperature is maintained at 100 °C for 30 minutes.
  • the propanol is stripped removed under vacuum.
  • the polyol product mixture is used directly without further purification steps.
  • the final polyol has hydroxyl number of approximately 583 mg KOH/g, 22% aromaticity, and nominal functionality of 8.
  • Example 24 Preparation of Product B (shown in Drawing 1) without using KOH [0141]
  • a 2000 ml autoclave 374 grams (2.0 moles) of benzoguanamine, and 300 grams of propanol are mixed to form a suspension.
  • the content is heated to about 90-100 °C and the autoclave pressure is adjusted to 5 psig.
  • 465 grams (8 moles) of propylene oxide is slowly and incrementally added to the reaction mixture so that the pressure in the reactor does not exceed 60 psig. After feeding all of propylene oxide the mixture temperature is maintained at 100 °C for 30 minutes.
  • the propanol is stripped removed under vacuum.
  • the polyol product mixture is used directly without further purification steps.
  • the final polyol has hydroxyl number of approximately 535 mg KOH/g, 37% aromaticity, and nominal functionality of 4.
  • Example 25 Preparation of Product A (shown in Drawing 1) in combination with Dytek ® A amine
  • Example 26 Preparation of Product B (shown in Drawing 1) in combination with Dytek ® A amine
  • Example 27 Propoxylation of benzoguanamine in polyester polyols
  • a mixture of 106 grams (0.57 moles) of benzoguanamine, 600 grams of Terate ® HT 4020 polyol is prepared in a 5-liter autoclave to form a solution.
  • a small portion of the total 131.4 grams (2.3 moles) of propylene oxide is charged and the mixture temperature is gradually raised to about 100 °C. After addition of all of propylene oxide, the mixture temperature is maintained at 100 °C for 30 minutes.
  • the polyol product mixture is used directly without further purification steps.
  • the final polyol has hydroxyl number of 392 mg KOH/g and nominal functionality of 2.7.
  • Example 30 mono-guanamine is prepared from 3-PN.
  • 25 mL of 3-pentenenitrile (0.26 mol), 26 g of dicyandiamide (0.31 mol), 5 wt% of hexamethyleneimine and 200 mL of n-butanol are combined and purged with nitrogen for 15 minutes.
  • the solution is refluxed for 5 hours under nitrogen.
  • the solvent is stripped and the resulting residue is analyzed via GC/MS.
  • the analysis shows a mixture of mono-guanamines from 2 and 3-pentenenitrile and 2-pentenenitrile dimer in a ratio of 69/31. Total conversion to mono-guanamines is 55%.
  • Polyurethane rigid foam can be made by reacting polyisocyanates with the “b-side” polyols containing either neat, blended or in-situ prepared alkoxylated guanamine/bis-guanamine polyols from any of the above examples.
  • the foam shows good appearance, improved reactivity profile, and improved physical properties such as improved compressive strength and flame resistance.
  • the above-prepared alkoxylated iso-adipobisguanamine polyol of Example 4 is incorporated into an APP polyol formulation, and the modified APP polyol is used as the “b-side” in the PUR foam production.
  • the foam prepared in this example shows better performance properties and improved flame retardancy properties.
  • Example 25 The above-prepared alkoxylated iso-adipobisguanamine polyol of Example 25 is used as neat into an APP polyol formulation, and the modified APP polyol is used as the “b-side” in the PUR foam production.
  • the foam prepared in this example shows improved performance properties and improved flame retardancy properties. Examples 36(A-L)
  • the disclosed Scheme (II) reaction chemistry is performed using two commercially available polyols [INVISTA TERATE ® HT 5350 and HT 5500] and benzoguanamine. Also, for comparison another commercial polyol [TERATE ® HT 1100] is reacted with melamine. The incorporation level of guanamine in the polyol via an amide linkage is varied up to about 15 % by wt. In each case, the polyol is mixed with the guanamine in a vessel and reacted at 140-235 °C temperature for about 2-4 hours.
  • Table 6 summarizes the properties of the Scheme (II) reaction products obtained in each case.
  • Examples 36A-E represent the TERATE ® HT 5350 polyol-benzoguanamine reacted system products;
  • Examples 36F-J represent the TERATE ® HT 5500 polyol-benzoguanamine reacted system products;
  • Examples 36K-L represent the TERATE ® HT 1100 polyol-melamine reacted system products.
  • a polyol premix is prepared by mixing the polyols, flame retardants, surfactant, catalysts, other additives, and water at ambient temperature. Blowing agent is cooled to 4 o C and then weighed into the polyol premix at desired amount. After gently shaking to blend the components, the formulated B-side blend is placed in a 10 0C bath overnight prior to foaming.
  • 300 grams of the polyol premix and equal weight of the polymeric MDI are mixed for 6.0 seconds using a Laboratory Dispersator (Manuf.: Premier Mill Corp; max. 10000 RPM) and then poured into a mold for curing.
  • a Format® machine Manuf.: Format Messtechnik GmbH) is used to record the rate of rise and reactivity profile data. The physical properties are measured after 24 hours aging at ambient temperature.
  • Example 37A is a control specimen that did not include the polyol products from Example 36. Also, note that in foam specimens of 37B-D, the polyether [280 OH #] and reactive Fire Retardant [250 OH#] components were absent. It is observed that, compared to the Control foam specimen [37 A], the overall foam performance is either similar or better in terms of reactivity profile, properties, smoke testing and fire resistance. More particularly, the compressive strength is significantly increased for 37B-D versus that measured for 37A.
  • a polyol premix is prepared by mixing the polyols, flame retardants, surfactant, catalysts, other additives, and water at ambient temperature. Blowing agent is cooled to 4°C and then weighed into the polyol premix at desired amount. After gently shaking to blend the components, the formulated B-side blend is placed in a 10°C bath overnight prior to foaming.
  • 300 grams of the polyol premix and equal weight of the polymeric MDI are mixed for 6.0 seconds using a Laboratory Dispersator (Manuf.: Premier Mill Corp; max. 10000 RPM) and then poured into a mold for curing.
  • a Format ® machine Manuf.: Format Messtechnik GmbH) is used to record the rate of rise and reactivity profile data. The physical properties are measured after 24 hours aging at ambient temperature.
  • Example 38A and 38B formulations represent Control specimens that do not contain the Example 36H Polyol Product.
  • Example 38G represents a Control specimens that does not contain the Example 36H Polyol Product and the poly ether (280 OH#) component.
  • Example 39 Propoxylation of bis(iso)adipoguanamine in polyester polyol without using
  • polyol functionality is 3.0 (calculated) and polyol yield is 90% based charging weights.
  • Skilled chemists should be able to use this example and by replacing propylene carbonate by ethylene carbonate, to make ethoxylated bisguanamines, or using other cyclocarbonates of interest for other alkoxylated bisguanamines, in polyester polyols without using KOH as a catalyst.
  • Example 40 Polyisocyanurate foam preparation
  • a polyisocyanurate foam is prepared using a polyol based on the following formulation: 100 g Aromatic polyester polyol, 26 g TCPP, 3.9 g of a mixture of amine and metal catalyst, 2.3 g silicon surfactant (Niax ® L-5122), 0.6 g water, 28.8 g of 50/50 n-pentane / isopentane, and 234 g Rubinate ® 1850.
  • the aromatic polyester polyol is designed as a series of polyol blends. Table 9 below represents the examples according to the present disclosure. In Tables and FIGs. “phpp” is parts of hundred per polyols.
  • Table 9 formulations are mixed mechanically with a high-speed mixer (Premier Mill Corp, Laboratory Dispensator) for 6 seconds and then poured into a box to make a foam. After curing at ambient temperature overnight, the foam properties are measured and summarized in Table 9.
  • FIG. 1 represents the Table 9 initial R-value data measured for “A-series” and Control “B- series” foam specimens at 4.5 °C and 23.5 °C temperatures, respectively.
  • the R-value of polyurethane / polyisocyanurate foam is a critical physical property that represents resistance to thermal conductivity when used as thermal insulation materials (the higher the R-value of a foam the better its insulation property).
  • FIG. 2 is a comparison of the aged R-value data at the 45 phpp loading level of the polyol from Example 39 and the comparison polyol.
  • Figure 2 shows that a foam that is prepared with the commercial Terate ® HT 5349 polyol has marginally higher R-value over the control at the tested temperature range with a peak value at about 12.5 °C.
  • the foam prepared with the disclosed polyol (Example 39) has much higher R-value over the control as well as the foams prepared with the commercial Terate ® HT 5349 polyol at the whole tested temperature range. Meanwhile, the highest R-value is now observed at a lower temperature (at 2.5 °C), which is an unexpected but very desirable improvement for thermal insulation foams.
  • polyisocyanurate foams prepared in Example 40 demonstrate that propoxylated bisguanamines can be made as additive blends with polyols or can be made with aromatic polyester polyols.

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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)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne des formulations de polyol comprenant des fractions de guanamine et de bis-guanamine. Les formulations de polyol peuvent être produites par réaction entre des polyols de polyester et des guanamines et des bis-guanamines de manière à produire des liens de liaison amide entre la fraction de guanamine et une fraction ester dans le polyol de polyester. De plus, les guanamines et les bis-guanamines peuvent être alcoxylées pour produire des polyols. Les polyols obtenus sont utiles pour fabriquer des produits en mousse.
PCT/US2020/053731 2019-10-04 2020-10-01 Guanamines et bis-guanamines utiles dans des polyols et des mousses WO2021067553A1 (fr)

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Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2381121A (en) 1945-08-07 Condensation products of triazines
US2748113A (en) 1953-04-17 1956-05-29 Univ Michigan Polymethyleneiminoalkanols
US3103515A (en) 1961-06-08 1963-09-10 Basic esters of i-benzoxacycloalkane-
GB1025571A (en) * 1962-08-28 1966-04-14 Olin Mathieson Oxyalkylation of amino-1,3,5-triazines
US3256281A (en) * 1963-01-04 1966-06-14 Olin Mathieson Alkoxylated mixtures of di- and triamino-1, 3, 5-triazine-polyols and a process for their production
US3265668A (en) * 1963-04-05 1966-08-09 Pittsburgh Plate Glass Co Reaction products of amino-s-triazine and alkylene carbonates
US3328321A (en) * 1966-01-27 1967-06-27 Wismer Marco Cellular polyurethanes prepared from polyhydroxy resinous reaction products of an amino-s-triazine and an alkylene carbonate or an alkylene oxide
US3399151A (en) 1963-04-25 1968-08-27 Olin Mathieson Polyurethane foam prepared from an oxyalkylated polyamino-1, 3, 5-triazine-organic polyisocyanate reaction product
US3438986A (en) * 1965-05-21 1969-04-15 Olin Mathieson Oxyalkylated nitrogen compounds
DE2003969A1 (de) * 1970-01-29 1971-08-12 Henkel & Cie Gmbh Schwachschaeumende Wasch-,Spuel- und Reinigungsmittel
US3812122A (en) * 1971-04-19 1974-05-21 Basf Wyandotte Corp Process for making oxyalkylated polyamino-1,3,5-triazines
DE2710992A1 (de) * 1977-03-14 1978-09-21 Henkel Kgaa Verfahren zur herstellung von waessrigen ueberzugsmitteln bzw. lacken
JPS6031528A (ja) * 1983-07-29 1985-02-18 Nippon Shokubai Kagaku Kogyo Co Ltd ポリエ−テルポリオ−ルの製造法
JPS6324254B2 (fr) 1981-05-01 1988-05-19 Asahi Glass Co Ltd
JPS63196626A (ja) * 1987-02-10 1988-08-15 Mitsubishi Rayon Co Ltd 共重合ポリエステル樹脂の製造方法
JPS63199241A (ja) * 1987-02-13 1988-08-17 Mitsubishi Rayon Co Ltd 接着剤組成物
JPS63256675A (ja) * 1987-04-15 1988-10-24 Mitsubishi Rayon Co Ltd 接着剤組成物
JPH01174582A (ja) * 1987-12-28 1989-07-11 Mitsubishi Rayon Co Ltd 接着剤組成物
EP0612797A2 (fr) * 1993-02-24 1994-08-31 MITSUI TOATSU CHEMICALS, Inc. Méthode de modification de résines
EP0612777A2 (fr) * 1993-02-24 1994-08-31 MITSUI TOATSU CHEMICALS, Inc. Compositions de moulage thermodurcissables et expansibles
JPH08209101A (ja) * 1995-10-30 1996-08-13 Mitsubishi Rayon Co Ltd 接着剤組成物
US20030045667A1 (en) * 2001-07-26 2003-03-06 Agrolinz Melamin Gmbh Polymers made from triazine derivatives
EP2128143A1 (fr) * 2008-05-30 2009-12-02 Basf Se Molécules amphiphiles avec un noyau de triazine
WO2009144274A2 (fr) * 2008-05-30 2009-12-03 Basf Se Molécules amphiphiles comportant un noyau triazine
US9944745B2 (en) 2015-05-28 2018-04-17 Coim Asia Pacific Pte. Ltd. Flame retardant and auto-catalytic polyesters for polyurethanes

Patent Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2381121A (en) 1945-08-07 Condensation products of triazines
US2748113A (en) 1953-04-17 1956-05-29 Univ Michigan Polymethyleneiminoalkanols
US3103515A (en) 1961-06-08 1963-09-10 Basic esters of i-benzoxacycloalkane-
GB1025571A (en) * 1962-08-28 1966-04-14 Olin Mathieson Oxyalkylation of amino-1,3,5-triazines
US3256281A (en) * 1963-01-04 1966-06-14 Olin Mathieson Alkoxylated mixtures of di- and triamino-1, 3, 5-triazine-polyols and a process for their production
US3265668A (en) * 1963-04-05 1966-08-09 Pittsburgh Plate Glass Co Reaction products of amino-s-triazine and alkylene carbonates
US3399151A (en) 1963-04-25 1968-08-27 Olin Mathieson Polyurethane foam prepared from an oxyalkylated polyamino-1, 3, 5-triazine-organic polyisocyanate reaction product
US3438986A (en) * 1965-05-21 1969-04-15 Olin Mathieson Oxyalkylated nitrogen compounds
US3328321A (en) * 1966-01-27 1967-06-27 Wismer Marco Cellular polyurethanes prepared from polyhydroxy resinous reaction products of an amino-s-triazine and an alkylene carbonate or an alkylene oxide
DE2003969A1 (de) * 1970-01-29 1971-08-12 Henkel & Cie Gmbh Schwachschaeumende Wasch-,Spuel- und Reinigungsmittel
US3812122A (en) * 1971-04-19 1974-05-21 Basf Wyandotte Corp Process for making oxyalkylated polyamino-1,3,5-triazines
DE2710992A1 (de) * 1977-03-14 1978-09-21 Henkel Kgaa Verfahren zur herstellung von waessrigen ueberzugsmitteln bzw. lacken
JPS6324254B2 (fr) 1981-05-01 1988-05-19 Asahi Glass Co Ltd
JPS6031528A (ja) * 1983-07-29 1985-02-18 Nippon Shokubai Kagaku Kogyo Co Ltd ポリエ−テルポリオ−ルの製造法
JPS63196626A (ja) * 1987-02-10 1988-08-15 Mitsubishi Rayon Co Ltd 共重合ポリエステル樹脂の製造方法
JPS63199241A (ja) * 1987-02-13 1988-08-17 Mitsubishi Rayon Co Ltd 接着剤組成物
JPS63256675A (ja) * 1987-04-15 1988-10-24 Mitsubishi Rayon Co Ltd 接着剤組成物
JPH01174582A (ja) * 1987-12-28 1989-07-11 Mitsubishi Rayon Co Ltd 接着剤組成物
EP0612797A2 (fr) * 1993-02-24 1994-08-31 MITSUI TOATSU CHEMICALS, Inc. Méthode de modification de résines
EP0612777A2 (fr) * 1993-02-24 1994-08-31 MITSUI TOATSU CHEMICALS, Inc. Compositions de moulage thermodurcissables et expansibles
JPH08209101A (ja) * 1995-10-30 1996-08-13 Mitsubishi Rayon Co Ltd 接着剤組成物
US20030045667A1 (en) * 2001-07-26 2003-03-06 Agrolinz Melamin Gmbh Polymers made from triazine derivatives
EP2128143A1 (fr) * 2008-05-30 2009-12-02 Basf Se Molécules amphiphiles avec un noyau de triazine
WO2009144274A2 (fr) * 2008-05-30 2009-12-03 Basf Se Molécules amphiphiles comportant un noyau triazine
US9944745B2 (en) 2015-05-28 2018-04-17 Coim Asia Pacific Pte. Ltd. Flame retardant and auto-catalytic polyesters for polyurethanes

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CAS , no. 4341-27-9
CAS, no. 108057-19-8
XIAOLIN LIZHENG FANGDONG JIZHIDONG WANKAI GUO: "The synthesis and application of a novel class of polyols for preparation of polyurethane", APPLIED MECHANICS AND MATERIALS, vol. 357-360, 2013, pages 1441 - 1445

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