WO2019099405A1 - Lignine alcoxylée pour applications de polyuréthane - Google Patents

Lignine alcoxylée pour applications de polyuréthane Download PDF

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Publication number
WO2019099405A1
WO2019099405A1 PCT/US2018/060827 US2018060827W WO2019099405A1 WO 2019099405 A1 WO2019099405 A1 WO 2019099405A1 US 2018060827 W US2018060827 W US 2018060827W WO 2019099405 A1 WO2019099405 A1 WO 2019099405A1
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WIPO (PCT)
Prior art keywords
lignin
polymer
diisocyanate
percent
weight percent
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PCT/US2018/060827
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English (en)
Inventor
Inc. Hexion
Anthony Maiorana
Srirama N. MADDIPATLA VENKATA
Ganapathy S. Viswanathan
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Hexion Research Belgium S.A.
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Priority claimed from US15/812,494 external-priority patent/US20190144595A1/en
Priority claimed from US15/812,408 external-priority patent/US20190144674A1/en
Application filed by Hexion Research Belgium S.A. filed Critical Hexion Research Belgium S.A.
Publication of WO2019099405A1 publication Critical patent/WO2019099405A1/fr

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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
    • C—CHEMISTRY; METALLURGY
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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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
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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
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • 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
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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    • 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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    • 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
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/141—Hydrocarbons

Definitions

  • This invention relates to processes for making polymers from polyisocyanates and polyisocyanate-reactive materials.
  • this invention relates to alkoxylated lignin useful as polyisocyanate-reactive materials.
  • the polyurethane industry currently sources the majority of its crosslinkers from petroleum-based polyols such as polyester polyols, aromatic polyester polyols, polyether polyols, and, to a lesser extent, novolacs.
  • Lignin is an attractive crosslinker for polyurethanes because it is sustainable, contains aromatic groups that can provide rigidity and fire retardance, and is multifunctional, which allows for fast curing and highly crosslinked networks.
  • lignin has not been able to be used as a polyurethane crosslinker because it is difficult to keep in solution with typical polyurethane crosslinkers and it does not behave as a thermoplastic. Therefore, development of a way to use lignin to manufacture polyurethanes would be desirable.
  • a process comprising, consisting of, or consisting essentially of: a) forming a reaction mixture containing at least one polyisocyanate and a polyisocyanate-reactive compound comprising at least one alkoxylated lignin dispersion; and b) curing the reaction mixture to form a polymer.
  • Lignin is a biopolymer which binds cellulose and hemicellulose together to help provide structural rigidity to plants and also acts as a protective barrier against fungi.
  • Compositions vary, but generally lignins are cross-linked phenolic polymers with a weight average molecular weight range between 1,000-20,000 grams/mole and are notoriously difficult to process once separated from cellulose during the pulping process. Lignin is typically burned to power the boilers of a pulping plant and is otherwise considered to have limited value.
  • Any suitable lignin can be used in the present invention.
  • suitable lignin include, but are not limited to lignosulfonate (obtained via the sulfite pulping process), kraft lignins (lignin obtained via the kraft process), pyrolytic lignins (lignin obtained via the pyrolysis process), steam explosion lignin (lignin obtained via the use of steam under high pressure), organosolv lignins (lignin obtained via the organosolv process), soda-ash lignins, dilute acid lignin (lignin obtained via treatment with dilute acids), biorefmery lignin (lignin obtained from any non-pulping process which converts biomass to other chemicals), and combinations thereof.
  • the lignin is dispersed into an alcohol-containing compound to form a lignin dispersion.
  • lignin dispersion is any dispersion of lignin in a solvent.
  • An alcohol-containing compound is any compound having one or more hydroxyl group per molecule.
  • the alcohol-containing compound typically has a boiling point in the range of l20°C to 300°C. In various embodiments, the alcohol-containing compound can have a boiling point in the range of from l50°C to 250°C. Any suitable alcohol-containing compound can be used.
  • the lignin is generally added to the alcohol-containing compound at a temperature in the range of from 25°C to 150°C. Any and all temperatures between 25°C and 150°C are included herein and disclosed herein; for example, the lignin can be added to the alcohol-containing compound at a temperature in the range of from 35°C to 135°C, from 50°C to l20°C or from 75°C to 105°C.
  • a suitable basic compound can be added before or after adding the lignin to the alcohol-containing compound.
  • suitable basic compound include, but are not limited to sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, triethanol amine, triethyl amine, melamine, benzoguanidine, diethanol amine, hexamethylene diamine, ethylene diamine and combinations thereof. If the lignin dispersion is already alkaline (defined as having a pH of 8 to 14), a basic compound does not need to be added.
  • the components after the lignin is added to the alcohol-containing compound, the components (along with a basic compound, if applicable) can be mechanically agitated for a period of time in the range of from 0.25 hours to 24 hours at any temperature between 120 °C and 200 °C. Any and all periods of time between 0.25 hours to 24 hours are included herein and disclosed herein; for example, the components can be mechanically agitated for a period of time in the range of from 3 hours to 20 hours, from 7 hours to 17 hours, or from 10 hours to 15 hours.
  • the lignin dispersion generally has a lignin to alcohol-containing compound weight ratio in the range of from 1 :0.3 to 1 :6. Any and all ratios in the between 1 :0.3 and 1 :6 are included herein and disclosed herein; for example the ratio of lignin to alcohol- containing compound can be in the range of from 1 :0.5 to 1 :5, 1 :0.5 to 1 :4, 1 :0.7 to 1 :3, or from 1 :1 to 1:2.
  • the lignin dispersion is reacted with an alkylene carbonate or mixture of alkylene carbonates to form the alkoxylated lignin dispersion.
  • the lignin dispersion is generally present in the reaction mixture in the range of from 10 weight percent to 80 weight percent, based on the total weight of components in the reaction mixture. Any and all weight percent ranges between 10 weight percent and 80 weight percent are included herein and disclosed herein; for example, the lignin dispersion can be present in the reaction mixture in the range of from 20 weight percent to 70 weight percent, from 25 weight percent to 60 weight percent, or from 30 weight percent to 50 weight percent. Any suitable reaction vessels can be used, in various embodiments, the vessel can be a batch reactor, a continuous reactor, or a semi-continuous to batch reactor.
  • 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:
  • 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 hydroxy group with 1 to 4 carbon atoms.
  • 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 hydroxy group with 1 to 4 carbon atoms.
  • alkylene carbonates that can be used include, but are not limited to ethylene carbonate, propylene carbonate, butylene carbonate, glycerin carbonate, vinyl ethylene carbonate, and combinations thereof.
  • the alkylene carbonate is present in the reaction mixture in the range of from
  • 20 weight percent to 90 weight percent based on the total weight of components in the reaction mixture. Any and all ranges between 20 weight percent and 90 weight percent are included herein and disclosed herein; for example, the alkylene carbonate can be present in the reaction mixture in the range of from 35 weight percent to 80 weight percent, from 40 weight percent to 70 weight percent, or from 45 weight percent to 60 weight percent.
  • an additional basic compound can be used in the reaction of the lignin dispersion with the alkylene carbonate to generate an alkoxylated lignin.
  • the basic compounds that can be used are those described above. If the reaction mixture is already alkaline, then adding an additional basic compound is optional.
  • the basic compound is generally present in the reaction mixture in an amount in the range of from 0.25 weight percent to 5 weight percent, based on the total weight of the components in the reaction mixture. Any and all ranges between 0.25 weight percent and 5 weight percent are included herein and disclosed herein; for example, the basic compound can be present in the reaction mixture in an amount in the range of from 0.5 weight percent to 3.5 weight percent, from 1 weight percent to 3 weight percent, or from 1.5 weight percent to 2.5 weight percent.
  • the alkylene carbonate can be added to the lignin dispersion/catalyst mixture over a period of time in the range of from 0.25 hours to 12 hours. Any and all ranges between 0.25 hours to 12 hours are included herein; for example, the alkylene carbonate can be added to the lignin dispersion/catalyst mixture over a period of time in the range of from 0.5 hours to 10 hours, from 2 hours to 8 hours, or from 3 hours to 6 hours.
  • the components in the reaction mixture can be reacted for a period of time in the range of from 0.25 hours to 24 hours. Any and all periods of time between 0.25 hours to 24 hours are included herein and disclosed herein; for example, the components can be mechanically agitated for a period of time in the range of from 3 hours to 20 hours, from 7 hours to 17 hours, or from 10 hours to 15 hours.
  • the alkoxylation reaction can optionally be neutralized with any mineral or organic acid.
  • acids examples include but are not limited to hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid, formic acid, acetic acid, trifluoro acetic acid, methane sulfonic acid, and p-toluenesulfonic acid.
  • 40 weight percent to 90 weight percent of the alcohol-containing compound is removed from the dispersion. Any and all weight percents between 40 and 90 weight percent are included herein and disclosed herein; for example, 45 to 80 weight percent of the alcohol-containing compound can be removed, or 55 to 80 weight percent of the alcohol- containing compound can be removed.
  • the alcohol-containing compound can be removed from the alkoxylated lignin dispersion in any suitable manner.
  • the alcohol-containing compound can be removed by distillation.
  • the alkoxylated lignin dispersion After removal of the alcohol-containing compound, the alkoxylated lignin dispersion generally contains from 40 weight percent to 80 weight percent of solids. Any and all ranges between 40 and 80 weight percent are included herein and disclosed herein; for example, the alkoxylated lignin dispersion can have from 50 to 75 weight percent of solids, or from 55 to 70 weight percent of solids.
  • a different polyisocyanate-reactive compound can be added to the alkoxylated lignin dispersion in order to reduce the dispersion’s viscosity.
  • polyisocyanate-reactive compounds include, but are not limited to polyether polyols, polyester polyols, and Mannich base polyols.
  • the polyisocyanate-reactive compound can be present in the alkoxylated lignin dispersion in the range of from 5 weight percent to 30 weight percent, from 8 weight percent to 25 weight percent, or from 10 weight percent to 20 weight percent, based on the total weight of the alkoxylated lignin dispersion.
  • the alkoxylated lignin 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 lignin 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, tetramethylene- 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’-dimethoxy-4, 4’ -biphenyl
  • 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 MDP products and the like.
  • the polyisocyanate can be a blocked isocyanate, where a standard polyisocyanate is prereacted with a blocking agent containing active hydrogen groups, which can then be deblocked at temperatures greater than 40°C (typically in the range of from 100°C to 190°C).
  • blocking agents include, but are not limited to g-caprolactam, phenol, methyl ketone oxime, 1,2,4-triazole, and dimethyl malonate.
  • Polyester polyols can also be used as part of the polyisocyanate-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 polyisocyanate-reactive compound.
  • the alkoxylated lignin is present in the polyisocyanate-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 lignin can be present in the polyisocyanate- reactive compound in a range of from 7 weight percent to 40 weight percent, from 10 weight percent to 30 weight percent, or from 15 weight percent to 25 weight percent.
  • the polyisocyanate and alkoxylated lignin mixture can also include a catalyst.
  • catalysts include, but are not limited to tertirary 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.
  • additional materials can be present during the reaction of the polyisocyanate compound with the alkoxylated lignin.
  • these materials include but are not limited to surfactants, blowing agents, cell openers, fillers, pigments and/or colorants, dessicants, reinforcing agents, biocides, preservatives, fragrances, antioxidants, flame retardants, and the like.
  • the flame retardant 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 phosphat
  • the relative amounts of polyisocyanate and polyisocyanate reactive compound 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 lignin dispersion.
  • 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 180, up to 600 or more.
  • the polyisocyanate compound and the polyisocyanate reactive compound are mixed and cured.
  • the curing step is achieved by subjecting the reaction mixture to conditions sufficient to cause the polyisocyanate compound and polyisocyanate reactive compound to react to form the polymer.
  • the polymer formed by the process of this invention can generally have a cream time in the range of from 3 percent to 10 percent lower than a polyurethane composition that was not prepared with an alkoxylated lignin, and from 4 percent to 9 percent lower in various other embodiments.
  • the polymer can also have a gel time in the range of from 15 percent to 20 percent lower than a polyurethane composition that was not prepared with an alkoxylated lignin, and from 16 percent to 18 percent lower in various other embodiments.
  • the polymer can have a rise time in the range of from 5 percent to 30 percent lower than a polyurethane composition that was not prepared with an alkoxylated lignin, and from 6 percent to 26 percent lower in various other embodiments.
  • the polymer can have a tack-free time in the range of from 7 percent to 30 percent lower than a polyurethane composition that was not prepared with an alkoxylated lignin, and from 9 percent to 25 percent in various other embodiments.
  • polymers can be made in accordance with the invention through the proper selection of particular alkoxylated lignins, 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 carpet 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.
  • Zero shear viscosity was determined by utilizing a shear sweep experiment on an ARES G2 rheometer (TA Instruments) equipped with 25 mm disposable stainless steel parallel plates at a gap of 1 mm. The shear rate was swept from 1-100 l/s and the zero shear viscosity was determined by averaging the Newtonian region of the viscosity curve. The Newtonian region of the viscosity curve is determined by viscosity remaining within a 2 Pa.s region i.e. 100 Pa.s +/- 2 Pa.s. Ten data points were measured for every magnitude change of shear rate such as 10 points between 0.1 and 1 1/s.
  • Glass transition temperature (7 g ) was determined from a Discovery differential scanning calorimeter (TA Instruments). Samples were about 5-7 mg and sealed in hermetic aluminum pans. A heating ramp program was used and temperature was swept from -80-200 °C at a heating rate of 10 °C/minute. The glass transition temperature was determined from the first heating scan through a midpoint analysis of the first inflection point of the heating curve.
  • Example 1 Synthesis of Alkoxylated Lignin (Sodium Lignosulfonate: Ethylene Carbonate [0048] 50 grams of sodium lignosulfonate, 125 grams of diethylene glycol, and 6 grams of potassium carbonate were charged to a reactor and were mechanically agitated at 140°C for a period of 20 minutes under reflux. The temperature was raised to 175°C and 50 grams of ethylene carbonate was charged to the lignin dispersion over a period of 30-45 minutes. The reactants were refluxed at 180°C until the C0 2 evolution ceased. The reaction was then neutralized to a pH between 6 and 8 with 38% phosphoric acid. The reaction mixture was vacuum distilled to obtain a target viscosity between 1-30 Pa.s.
  • Example 2 Synthesis of Alkoxylated Lignin (Sodium Lignosulfonate: Ethylene Carbonate
  • the reaction product was vacuum distilled to obtain a target viscosity between 1-30 Pa.s.
  • the alkoxylated lignin was then placed back into reflux mode and 30 grams of Terate 5350 was added to further adjust the viscosity to between 1-10 Pa.s.
  • Tables 1 and 2 show viscosity and glass transition temperature results for some of the examples above.
  • Table 1. Viscosity and Glass Transition Temperature of Alkoxylated Lignosulfonate
  • Example 13 Effect of Introducing Alkoxylated Lignin Into a Typical Polyurethane
  • the polyol components were prepared by the following method. For the Test Formulations, 7.5 parts of the alkoxylated lignin of Example 1 , 26.56 parts of Jeffol S-490, 6.44 parts of glycerine, and 7.5 parts of an aromatic polyol were preheated to l20°C and were blended by multiple agitation in the Speed Mixer DAC 400 FV (FlackTeck, Inc.) at 220 RPM until a homogeneous liquid was obtained. This polyol blend was then cooled to room temperature.
  • the polyol blend was then combined with Lumulse POE-7, Jeffcat PMDETA, Catalyst LB, Polycat 8, TCPP, TEP, Niax L-6000, water, and n-pentane in the amounts shown in Tables 3 and 4 using a high-torque mixer (CRAFTSMAN 10-inch Drill Press, Model No. 137.219000) for 2 minutes at 3100 rpm to form the polyol component.
  • the polyol component was immediately used for foam preparation by mixing with the isocyanate component according to the procedure below.
  • the polyol components were prepared by the method above, except that the preheating step was eliminated.
  • Foams were prepared using a high- torque mixer (CRAFSTMAN 10-Inch Drill Press, Model No. 137.219000) at 3,100 rpm speed. Polyol components and isocyanate components of the foam systems were mixed for 10 seconds. Afterwards, the mixtures were transferred into an open card boxes before the cream time and were allowed to free-rise. The foaming profde, including cream time, gel time, rise time, and tack-free time were measured on all foams as shown in Tables 3 and 4 below.
  • Foams were prepared with formulations selected for testing by pouring foam mix in card boxes without any liners to determine the adhesion of the foam to the card box as a substrate. Description of Materials:
  • Lumulse POE(7) Glycerine ethoxylate, with a hydroxyl value of 419.1 mg KOH/g, available from Vantage
  • Terol ® 250 Modified aromatic polyester polyol, available from Huntsman
  • Aromatic polyol Aromatic polyol with a hydroxyl value of 496 mg KOH/g
  • Catalyst LB Potassium acetate catalyst
  • Polycat 8 Dimethylcyclohexylamine catalyst
  • TCPP Trichloropropylphosphate, a flame retardant
  • TEP Triethylphosphate, a flame retardant
  • Niax L-6900 a polysiloxane surfactant, available from Momentive Performance Materials
  • Rubinate 9257 a polymeric MDI available from Huntsman
  • Rubinate M a polymeric MDI available from Huntsman
  • Test Formulation #2 containing alkoxylated lignin not only had a superior reactivity compared to Reference Formulation #2, but also resulted in a foam with a uniform cell structure, comparable friability, and good dimensional stability.
  • Test Formulation #2 was self-extinguishing as was Reference Formulation #2.
  • Both Reference Formulation #2 and Test Formulation #2 had compressive strain at yield values of less than 10%. Also, the difference between the compressive stress at yield values between the two formulations was not statistically significant.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne un procédé comprenant : a) la formation d'un mélange réactionnel contenant au moins un polyisocyanate et un composé réactif au polyisocyanate comprenant au moins une dispersion de lignine alcoxylée ; et b) le durcissement du mélange réactionnel pour former un polymère.
PCT/US2018/060827 2017-11-14 2018-11-13 Lignine alcoxylée pour applications de polyuréthane WO2019099405A1 (fr)

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US15/812,408 US20190144674A1 (en) 2017-11-14 2017-11-14 Alkoxylation of lignins

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CN113929857A (zh) * 2021-09-22 2022-01-14 南京林业大学 一种适用于阻燃聚氨酯硬泡的木质素多元醇的制备及其应用

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