EP2382251A1 - Mousse de pâte mécanique pour carton possédant un contenu d'origine biologique - Google Patents

Mousse de pâte mécanique pour carton possédant un contenu d'origine biologique

Info

Publication number
EP2382251A1
EP2382251A1 EP10736291A EP10736291A EP2382251A1 EP 2382251 A1 EP2382251 A1 EP 2382251A1 EP 10736291 A EP10736291 A EP 10736291A EP 10736291 A EP10736291 A EP 10736291A EP 2382251 A1 EP2382251 A1 EP 2382251A1
Authority
EP
European Patent Office
Prior art keywords
ester
acid
composition
oil
foam
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10736291A
Other languages
German (de)
English (en)
Inventor
Carina Araullo Mcadams
Eugen Gnedin
Leon J. Garcia
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Invista Technologies SARL Switzerland
Original Assignee
Invista Technologies SARL Switzerland
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Invista Technologies SARL Switzerland filed Critical Invista Technologies SARL Switzerland
Publication of EP2382251A1 publication Critical patent/EP2382251A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2115/00—Oligomerisation
    • C08G2115/02—Oligomerisation to isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof

Definitions

  • the disclosures herein relate to a polyisocyanurate (PIR) polymer with renewable (biobased) content and adapted for use in foam board stock applications.
  • PIR polyisocyanurate
  • Embodiments of the present disclosure can include polyurethane or polyisocyanurate board stock foams having a biobased content of 7% or greater as measured by ASTM D6866.
  • embodiments of the present disclosure relate to the use of renewable material for producing aromatic polyesters polyols and/or resins to generate foam products having biobased content.
  • Embodiments of the present disclosure can include polyurethane or polyisocyanurate board stock foam having a biobased content of 7% or greater as measured by ASTM D6866 that can be made from an aromatic polyol (e.g., a biobased polyol composition) and resin.
  • the polyurethane or polyisocyanurate board stock foam having a biobased content of 7% or greater as measured by ASTM D6866 includes a foam having an aromatic polyol provided by the reaction products of: a first composition comprising a hydroxylated material, wherein the hydroxylated material is at least difunctional; a second composition selected from the group consisting of: terephthalic acid, an ester of terephthalic acid, isophthalic acid, an ester of isophthalic acid, orthophthalic acid, an ester of orthophthalic acid, trimellitic acid, an ester of trimellitic acid, orthophthalic anhydride, an ester of orthophthalic anhydride, trimellitic anhydride, an ester of trimellitic anhydride, and a mixture thereof; and a third composition comprising of up to 50% of a hydrophobic material, wherein the hydrophobic material is selected from the group consisting of: a nonedible plant derived oil, a nonedible animal derived oil,
  • One exemplary polyol composition includes a first composition comprising a hydroxylated material, wherein the hydroxylated material is at least difunctional; a second composition selected from the group consisting of: terephthalic acid, an ester of terephthalic acid, isophthalic acid, an ester of isophthalic acid, orthophthalic acid, an ester of orthophthalic acid, trimellitic acid, an ester of trimellitic acid, orthophthalic anhydride, an ester of orthophthalic anhydride, trimellitic anhydride, an ester of trimellitic anhydride, and a mixture thereof; and a third composition comprising of up to 50% of a hydrophobic material, wherein the hydrophobic material is selected from the group consisting of: a nonedible plant derived oil, a nonedible animal derived oil, a fatty acid of a nonedible plant oil, a fatty acid of an animal derived oil, an ester of a nonedible plant oil, an ester of a nonedible
  • One exemplary resin blend includes an aromatic polyol, a surfactant, a catalyst and a blowing agent.
  • Figure 1 shows hydroxyl values and viscosity as a function of hydrophoblic modification for one composition of the invention.
  • Figure 2 is a boxplot of hydrocarbon solubility in various polyol resins including one aromatic polyol and two aliphatic polyols.
  • Figure 3 illustrates friability data as a function of aromatic vs. aliphatic content the polyol constituent of the isocyanurate foam.
  • Figure 4 shows the number of test cycles prior to 25% delamination for isocyanurate foams containing aromatic vs. aliphatic polyols.
  • Figure 5 is a matrix plot showing the effectof density and humid age on compressive strength of an isocyanurate foam.
  • Figure 6 is a matrix plot of initial k factor and the six-month k-factor change, both as a function of aromaticity of polyol in an isocyanurate foam, with k factor being inversely proportional to thermal insulating value.
  • Figure 7 is a matrix plot showing foam burn properties as a function of aromaticity of polyol in an isocyanurate foam.
  • Figure 8 is plot showing the effect of composition of three-component pentane isomer blowing agents in isocyanurate foam.
  • Figure 9 is a plot showing the density achievable as a function of composition of three-component pentane isomer blowing agents in isocyanurate foam.
  • Figure 10 is a plot showing the normalized average compressive strength as a function of composition of three-component pentane isomer blowing agents in isocyan urate foam.
  • Figure 11 is a plot showing the humidity aging as a function of composition of three-component pentane isomer blowing agents in isocyanurate foam.
  • Figure 12 is a plot showing k factor as a function of composition of three- component pentane isomer blowing agents in isocyanurate foam.
  • Figure 13 is a is a plot showing fire resistance under the standard FM- 4450 as a function of composition of three-component pentane isomer blowing agents in isocyanurate foam.
  • Figure 14 includes Table I.
  • Figure 15 includes Table II.
  • Figure 16 includes Table III.
  • a "board stock foam” is a product of a polyol composition and a polyisocyanate composition which are foamable.
  • the board stock foam can be a polyurethane or polyisocyanurate board stock foam.
  • Foamable means the resulting board stock has a cell structure produced by an expansion process. This process is known as "foaming" and provides a board stock product of comparatively low weight per unit volume and with low thermal conductivity. The foaming process can be carried out substantially simultaneously with the production of the board stock foam.
  • Board stock foam are often used as insulators for noise abatement 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.
  • cooling and heating technology e.g., household appliances
  • composite materials e.g., sandwich elements for roofing and siding
  • wood simulation material model-making material, and packaging.
  • hydroxyl functionality refers to the -OH group on a molecule; e.g., methanol (CH 3 OH) has a single hydroxyl functionality or functional group per molecule.
  • hydroxyl value refers to the concentration of hydroxyl groups, per unit weight of the polyol composition able to react with an isocyanate groups.
  • hydroxyl number formerly measured according to the standard ASTM D 1638 and reported as milligrams KOH/gram of the composition is measured according to ASTM D6342 - 08 Standard Practice for Polyurethane Raw Materials: Determining Hydroxyl Number of Polyols by Near Infrared (NIR) Spectroscopy
  • NIR Near Infrared
  • acid number correspondingly indicates the concentration of carboxylic acid groups present in the polyol, and is reported in terms of mg KOH/g and measured according to standard ASTM 4662-08.
  • isocyanate may also refer to a chemical compound containing an isocyanate functional group.
  • polyisocyanate refers to a chemical compound containing more than one isocyanate functional groups.
  • isocyanate index relates to a measure of the stoichiometric balance between the equivalents of isocyanate functionalities and hydroxyl functionalities in a mixture of reactants.
  • the isocyanate index is 100 times the number of isocyanate functionalities divided by the number of hydroxyl functionalities.
  • average functionality or "average hydroxyl functionality" of a polyol indicates the number of OH groups per molecule, on average.
  • average functionality of an isocyanate refers to the number of -NCO groups per molecule, on average.
  • aliphatic group refers to a saturated or unsaturated linear or branched hydrocarbon group and encompasses alkyl, alkenyl, and alkynyl groups, for example.
  • alk refers to straight or branched chain hydrocarbon groups having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, heptyl, n-octyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, and the like.
  • An alkyl group is optionally substituted, unless stated otherwise, with one or more groups, selected from aryl
  • aroyl optionally substituted
  • carboxy protected carboxy, cyano, nitro, amino, substituted amino, (monosubstituted)amino, (disubstituted)amino, protected amino, amido, lactam, urea, urethane, sulfonyl, and the like.
  • alkenyl refers to straight or branched chain hydrocarbon groups having 2 to 12 carbon atoms, preferably 2 to 4 carbon atoms, and at least one double carbon to carbon bond (either cis or trans), such as ethenyl.
  • alkenyl group is optionally substituted, unless stated otherwise,with one or more groups, selected from aryl (including substituted aryl), heterocyclo (including substituted heterocyclo), carbocyclo (including substituted carbocyclo), halo, hydroxy, alkoxy (optionally substituted), aryloxy (optionally substituted), alkylester (optionally substituted), arylester (optionally substituted), alkanoyl (optionally substituted), aroyl (optionally substituted), cyano, nitro, amino, substituted amino, amido, lactam, urea, urethane, sulfonyl, and the like.
  • alkynyl refers to straight or branched chain hydrocarbon groups having 2 to 12 carbon atoms, preferably 2 to 4 carbon atoms, and at least one triple carbon to carbon bond, such as ethynyl.
  • alkynyl group is optionally substituted, unless stated otherwise, with one or more groups, selected from aryl (including substituted aryl), heterocyclo (including substituted heterocyclo), carbocyclo (including substituted carbocyclo), halo, hydroxy, alkoxy (optionally substituted), aryloxy (optionally substituted), alkylester (optionally substituted), arylester (optionally substituted), alkanoyl (optionally substituted), aroyl (optionally substituted), cyano, nitro, amino, substituted amino, amido, lactam, urea, urethane, sulfonyl, and the like.
  • noncomesitble and “nonedible” refer to food or industrial sources where the item is not fit to be eaten by a mammal (specifically a human), not edible, is inedible, is not a foodstuff, or is not appropriate or safe to be eaten by a mammal (specifically a human). These terms do not mean that the item is poisonous to a human, although the item can be poisonous a human. These terms can include items that are not easily digested and/or tolerated by humans.
  • Embodiments of the present disclosure can include polyurethane or polyisocyanurate board stock foams having a biobased content of 7% or greater as measured by ASTM D6866.
  • embodiments of the present disclosure relate to the use of renewable material for producing aromatic polyesters polyols and/or resins to generate foam products having biobased content. More specifically, these renewable aforementioned aromatic polyester polyols are from nonfood (noncomesitble) grades sources and/or nonedible industrial sources.
  • Edible oils may include canola, corn, cottonseed, olive, peanut, rice bran, safflower seed, sesame seed, soybean, sunflower seed, coconut and palm.
  • Embodiments of the present disclosure include polyurethane or polyisocyanurate board stock foam having a biobased content of 7% or greater as measured by ASTM D6866, aromatic polyols (also referred to as biobased polyol or biobased polyol composition), methods of making biobased polyol compositions, methods of using biobased polyol compositions, biobased resin blend compositions, methods of making biobased resin blend compositions, methods of using biobased resin compositions, biobased board stock foam compositions, biobased board stock foams, and the like.
  • ASTM D6866-08 includes Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis.
  • Embodiments of the present disclosure can include polyurethane or polyisocyanurate board stock foam having a biobased content of 7% or greater as measured by ASTM D6866 that can be made from an aromatic polyol and resin.
  • the polyurethane or polyisocyanurate board stock foam having a biobased content of 7% or greater as measured by ASTM D6866 includes a foam having an aromatic polyol provided by the reaction products of: a first composition comprising a hydroxylated material, wherein the hydroxylated material is at least difunctional; a second composition selected from the group consisting of: terephthalic acid, an ester of terephthalic acid, isophthalic acid, an ester of isophthalic acid, orthophthalic acid, an ester of orthophthalic acid, trimellitic acid, an ester of trimellitic acid, orthophthalic anhydride, an ester of orthophthalic anhydride, trimellitic anhydride, an ester of trimellitic anhydride, and
  • an aromatic polyol e.g., aromatic polyester polyol (APP)
  • APP aromatic polyester polyol
  • the third composition may include a biobased component used to form the polyurethane or polyisocyanurate board stock foam.
  • a biobased polyol composition e.g., a biobased resin blend composition, or a biobased foamable product derived from any of these.
  • a third composition may be included in an appropriate amount to provide the end product, e.g., a biobased board stock foam, with a biobased content.
  • a biobased content may be chosen to be greater than 7% for a typical foam product.
  • the third composition can be about 15% to 50%, for example, or about 20% to 30% by weight of the polyol composition.
  • the third composition can be present in an amount so that the polyol composition has a biobased content of about 15% to 50%, for example, or about 20% to 30% by weight of the polyol composition.
  • the biobased component can be less than about 50%, less than about 40%, less than about 30%, or less than about 20%, by weight of the third composition.
  • the biobased component can be about 7% to 50%, for example, or about 7% to 30% by weight of the third composition.
  • the biobased component is covalently bonded to the backbone of the polyol.
  • the polyol is an aromatic polyester polyol having aromatic ester linkages.
  • the biobased component e.g., a natural oil
  • Such biobased natural oil components may include: castor, linseed, oiticica, rapeseed, tall oils and tung oils; and such materials as inedible tallow and grease or lard.
  • the third composition can include hydrophobic materials selected from the group of natural oils, as above, their corresponding fatty acids (e.g., tall oil fatty acid (TOFA), their corresponding fatty acid esters (e.g., methyl ester of TOFA) and mixtures thereof.
  • TOFA tall oil fatty acid
  • TOFA corresponding fatty acid esters
  • the hydrophobic material includes one or more of the following: nonedibile plant derived oils, e.g., tung oil, linseed oil, oiticica oil, dehydrated castor oil; animal derived oils, e.g., tallow; and edible plant derived oils, e.g., corn, cottonseed, olive, peanut, rice bran, safflower seed, sesame seed, soybean, sunflower seed, coconut, palm and canola (rapeseed oil).
  • nonedibile plant derived oils e.g., tung oil, linseed oil, oiticica oil, dehydrated castor oil
  • animal derived oils e.g., tallow
  • edible plant derived oils e.g., corn, cottonseed, olive, peanut, rice bran, safflower seed, sesame seed, soybean, sunflower seed, coconut, palm and canola (rapeseed oil).
  • the second composition can include includes compounds such as terephthalic acid, isophthalic acid, orthophthalic acid, trimellitic acid, orthophthalic anhydride, trimellitic anhydride, and their corresponding esters (e.g., esters of terephthalic acid, esters of isophthalic acid, and the like), and mixtures thereof.
  • the second composition can be about 10% to 60% or preferably about 30% to 45% by weight of the polyol composition.
  • the first composition can be a hydroxylated material having a functionality of at least 2 or about 2 to 10. In an embodiment, the hydroxylated material is difunctional.
  • the hydroxylated material can include ethylene glycol, diethylene glycol, triethylene glycol, tetraethyleneglycol, pentaethyleneglycol, dipropylene glycol, butanediol, and the like, or mixtures thereof.
  • the first composition is about 25% to 60% or preferably about 30% to 40% by weight of the polyol composition.
  • the first composition can contain monofunctional hydroxylated material from about 0 to 5% by weight of the polyol composition.
  • the polyol composition used to form the polyurethane or polyisocyanurate board stock foam can also include a reaction product with a hydroxylated crosslinker.
  • the hydroxylated crosslinker can include glycerin, trimethylol, pentaerythritol, sucrose, sorbitol, and a combination thereof.
  • the hydroxylated crosslinker is about 0% (or 0.01%) to 15% or about 0% (or 0.01%) to 6 % by weight of the polyol composition.
  • the polyol composition can be used in conjunction with a surfactant to form the polyurethane or polyisocyanurate board stock foam.
  • the surfactant can include silicone based surfactants, organic based surfactants, and a mixture thereof.
  • the silicone based surfactant can include, but is not limited to, polydimethylsiloxane-polyalkylene block copolymers and a combination thereof.
  • the surfactant serves 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 aromatic polyesterpolyol 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 (EVONIK) ether sulfates, fatty alcohol sulfates, sarcosinates, amine oxides, sulfonates, amides, sulfo-succinates, sulfonic acids, alkanol amides, ethoxylated fatty alcohol, and nonionics such as polyalkoxylated sorbitan, and a combination thereof, can be used.
  • the amount of surfactant in the composition can be about 1wt % to 4 wt %, based on the total weight of the mixture. In an embodiment, the amount of surfactant in the composition can be about 0.1 wt % to 5 wt %, based on the total weight of the mixture. In an embodiment, the amount of surfactant in the composition can be about 1 wt % to 2 wt %, based on the total weight of the mixture.
  • the polyol composition can be used in conjunction with a catalyst to form the polyurethane or polyisocyanurate board stock foam.
  • the catalyst can include a metal-based catalyst, amine-based catalyst, and a mixture thereof.
  • the metal-based catalyst can include, but is not limited to, potassium octoates, potassium acetates, organomercury, organolead, organoferric, organotin catalysts (e.g., stannous octoate and dibutyltin dilaurate), and/or combination thereof.
  • the amine-based catalyst can include, but is not limited to, triethylenediamine, N-methylmorpholine, pentamethyldiethylenetriamine, dimethylcyclohexylamine, tetra-methylethylenediamine, 1 -methyl-4- dimethylaminoethyl-pip- erazine, 3-methoxy-N-dimethyl-propylamine, N- ethylmorpholine, diethylethanolamine, N-cocomorpho-line, N,N-dimethyl-N',N'- dimethylisopropyl-propylene diamine, N , N-diethyl-3-diethyl aminopropylamine, dimethyl-benzyl amine, and a combination thereof.
  • the catalyst is about 1% to 5% of the mixture.
  • the polyol composition can be used in conjunction with a blowing agent to form the polyurethane or polyisocyanurate board stock foam.
  • the blowing agents can be a hydrocarbon having C 3 to C 7 carbon atoms, a hydrofluorocarbon, water, carbon dioxide, and a mixture thereof.
  • the hydrocarbon can include propane, butane, pentane (e.g., iso-pentane), hexane, and their corresponding isomers, alkene analogues, and/or a combination thereof.
  • the hydrofluorocarbon can include 1,1 ,1,3,3-pentafluoropropane (HFC-245fa), 1 ,1,1 ,2- tetrafluoroethane (HCF-134a), 1 ,1-dichloro-i-fluoroethane (HCFC 141-B), chlorodifluoromethane (HCFC R-22), HFC-365M and combinations thereof.
  • the blowing agent includes iso-pentane.
  • the blowing agent includes is about 50 to 100 weight percent of the mixture.
  • a wide variety of co-blowing agents can be employed in conjunction with the hydrogen-containing agents in preparing the foam compositions of the invention.
  • Co-blowing agents can include water, air, nitrogen, carbon dioxide, readily volatile organic substances, and compounds which decompose to liberate gases (e.g., azo compounds).
  • Typical co-blowing agents have a boiling point -5O 0 C to 100 0 C, preferably from -5O 0 C to 50 0 C.
  • iso-pentane, n-pentane, cyclopentane or combinations is the blowing agent.
  • 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: the HCFC/HFC or HCFC/HFC/water co-blown system; a water/hydrocarbon co-blown system; and a water blown system (also referred to in the art as a carbon dioxide blown system since CO 2 is derived from the water-isocyanate reaction).
  • HCFC/HFC system a liquid blowing agent is added to a mixture of aromatic polyesterpolyol, catalysts, and surfactants prior to adding a polyisocyanate.
  • water is added and mixed with an aromatic polyester polyol, catalyst, and surfactant mixture prior to adding a polyisocyanate.
  • both water and hydrocarbon blowing agents are added to an aromatic polyester polyol, catalyst surfactant premix prior to adding a polyisocyanate.
  • the full-scale production of these components may be metered directly in to the mixing head of the foam machine or premixed with an aromatic polyester polyol stream prior to injecting into the mixing head.
  • embodiments of the present disclosure include board stock foam compositions that include a reaction product of the biobased composition (or a mixture of components as noted above) with a polyfunctional isocyanate.
  • the polyol composition is present in an amount so that the board stock foam formed from the board stock foam composition can have a biobased value content of about 7% to 25% or 7%.
  • the polyisocyanate component employed in the foam forming process can be any of the polyisocyanates known to be useful in the art of polymer formation.
  • Typical polyisocyanates include m-phenylene diisocyanate; p-phenylene diisocyanate; polymethylene polyphenylisocyanate; 2,4-toluene diisocyanate; 2,6- tolylene diisocyanate; dianisidine diisocyanate; naphthalene 1 ,4 diisocyanate; diphenylene-4,4'-diisocyanate; aliphatic-aromatic diisocyanates, such as xylylene- 1,4-diisocyanate; xylylene-1 ,2-diisocyante; xylylene-1,3-diisocyanate; bis(4- isocyanatophenyl) methane; bis(3-methyl-4-isocyanatophenyl) methane; and
  • embodiments of the present disclosure include polyurethane (PU) and/or polyisocyanurate (PIR) foams to form polyurethane or polyisocyanurate board stock foam having a biobased content of 7 per cent or greater as measured by ASTM D6866.
  • the PU and/or PIR foam and products (board stock foam) can be produced at various volume ratios of polyol composition and/or other components, and polyisocyanate.
  • the ratios are normally referred to as A:B where "A" (or A-side component) is the polyisocyanate and "B" (or B-side component) is the polyol blend.
  • the ratio can be about 1:1 to 3:1.
  • the polyol composition is present in an amount so that the board stock foam produced from the PU and/or PIR foam has a biobased content of about 7% to 25% or 7%.
  • the board stock foam formed from the PU and/or PIR spray foam has a biobased content of 7 per cent and greater as measured by ASTM D6866.
  • Aromatic polyester polyols are polyols with aromatic ester linkages.
  • the "biobased" aromatic polyester polyol of the invention include aromatic polyester polyols with ester linkages containing structures from natural oils and/or an aliphatic group of natural oils.
  • a polyester polyol modified with tall oil fatty acid (TOFA) provides an ester linkage from natural source.
  • the TOFA is reacted with diethylene glycol (DEG) and 1 ,4- benzenedicarboxylic acid dimethyl ester, at a temperature of 235 degrees Celsius at atmospheric pressure in the presence of a catalyst.
  • DEG diethylene glycol
  • BV Biobased Value
  • an aromatic polyester polyol with higher levels of TOFA is provided.
  • the corresponding aromatic polyester polyol is blended with fire retardant package, known in the art, to make a polyol having a Biobased Value (BV) of about 26%.
  • a foam prepared from this polyol exhibits a Biobased Value of 9% according to ASTMD6866.
  • Table I Figure 14 below, the foam properties are comparable to that of a foam system which contained 0% biobased value.
  • the renewable or biobased component is allowed to react and thereby become a part of the aromatic ester polymer chain.
  • a polymer system of PIR (polyisocyanurate) prepared at an index of 2.5 the base aromatic polyester polyol containing about 23-28% BV will provide a foam system with a minimum %BV of 7%.
  • An alternative approach for a foam formulator seeking to provide a foam having a 7% minimum BV is to use conventional polyols, e.g., Terate® polyol 3510, or Terate® polyol 3512, (INVISTA S. a r.l.), post-blended with hydroxyl- containing natural oil or modified natural oil.
  • Table Il ( Figure 14) below shows the comparative compatibility of aromatic polyester polyols (APP) with renewable (biobased) material reacted into the aromatic ester linkages versus APP blends with castor oil.
  • the mixture of APP polyol from Example 2 below and a pentane blowing agent results in a single phase liquid, whereas pentane solution of conventional APP blended with castor oil results in multiphase layers.
  • the blowing agent comprises from 50 to 100 weight percent iso-pentane.
  • a designed study of blowing agent was carried out on APP containing 26% BV, similar to the polyol in Example 2. The simplex design from the study is represented in Figure 8, and the comparative data of laboratory generated foams made with different blowing agents using Polyol A are summarized in Table III and Figures 9-11.
  • iso-pentane enriched formulation with and without water provides optimum conditions when using APP with renewable material in boardstock applications. Measured improvements when using high iso- pentane include: blowing agent efficiency (represented in Figure 9); better compressives (represented in Figure 10); and better dimensional stability (represented in Figure 11).
  • Dimethyl ester manufactured from the byproducts of 1,4-benzenedicarboxylic acid - an aromatic feedstock used to make TERATE® polyols from INVISTA S. a r.l.
  • Tall oil fatty acid is available from Georgia Pacific.
  • Polymer grade diethylene glycol (>99%) was obtained from Equistar.
  • Pentane Isomers blowing agents are available from Exxon Chemical Company and/or Phillips Chemical Company.
  • Mondur 489 is a high functionality polymeric MDI available from Bayer Material Science.
  • TEGOSTAB® surfactants are silicone based surfactant available from Evonik Goldschmidt Corporation.
  • Catalysts such as Dabco® K-15, Polycat® 46, and Polycat® 5 are available from AirProducts, Inc.
  • the polyols were characterized for acidity, hydroxyl values, and viscosities at 25 0 C.
  • the total acid number (AN) and hydroxyl values (OH) were determined by using the standard titration methods. Dynamic viscosity measurements were done at 25 0 C on a Brookfield viscometer.
  • Foams presented in this application were generated via handmix preparations. Various foams were also generated from test laminations. Foam performance was monitored using procedures set forth in:
  • Calorimeter testing procedures are according to the reference: Dowling, K. C, Feske, E. F., Proceedings of the SPI Polyurethane Conference 1994, pp. 357-363.
  • results provided herein refer to the biobased component present in the material and not the amount of biobased used in the manufacturing process.
  • Polyol A a flame retardant package was added to the resulting polyol (Polyol A).
  • the Biobased Value (%BV) according to ASTM-D6866 was 26%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Des modes de réalisation de la présente invention peuvent concerner une mousse de pâte mécanique pour carton de polyuréthane ou de polyisocyanurate possédant un contenu d'origine biologique de 7 % ou plus, tel que mesuré par ASTM D6866. De plus, des modes de réalisation de la présente invention portent sur l'utilisation d'une matière renouvelable pour produire des polyesters polyols et/ou résines polyesters aromatiques pour générer des produits de mousse possédant un contenu d'origine biologique.
EP10736291A 2009-01-27 2010-01-26 Mousse de pâte mécanique pour carton possédant un contenu d'origine biologique Withdrawn EP2382251A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US14754609P 2009-01-27 2009-01-27
PCT/US2010/022058 WO2010088198A1 (fr) 2009-01-27 2010-01-26 Mousse de pâte mécanique pour carton possédant un contenu d'origine biologique

Publications (1)

Publication Number Publication Date
EP2382251A1 true EP2382251A1 (fr) 2011-11-02

Family

ID=42395966

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10736291A Withdrawn EP2382251A1 (fr) 2009-01-27 2010-01-26 Mousse de pâte mécanique pour carton possédant un contenu d'origine biologique

Country Status (3)

Country Link
EP (1) EP2382251A1 (fr)
CN (1) CN102300891A (fr)
WO (1) WO2010088198A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10534367B2 (en) 2014-12-16 2020-01-14 Aktiebolaget Electrolux Experience-based roadmap for a robotic cleaning device

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9181383B2 (en) 2010-08-13 2015-11-10 Dow Global Technologies Llc Polyisocyanurate composition
CN113195213A (zh) * 2018-12-28 2021-07-30 陶氏巴西东南工业有限公司 用于隔热器具的复合制品、包含复合制品的器具以及相关方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4758602A (en) * 1987-10-05 1988-07-19 Hercules Incorporated Polyols from tall oil and aromatic polyester polyols
US6359022B1 (en) * 1997-10-10 2002-03-19 Stepan Company Pentane compatible polyester polyols
CN1247656C (zh) * 2003-08-07 2006-03-29 烟台万华聚氨酯股份有限公司 一种聚酯多元醇与其改性原料的生产工艺和用途
CN101270203B (zh) * 2008-05-20 2010-08-25 上海中科合臣股份有限公司 一种用聚对苯二甲酸乙二醇酯废料制备聚酯多元醇的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010088198A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10534367B2 (en) 2014-12-16 2020-01-14 Aktiebolaget Electrolux Experience-based roadmap for a robotic cleaning device

Also Published As

Publication number Publication date
CN102300891A (zh) 2011-12-28
WO2010088198A1 (fr) 2010-08-05

Similar Documents

Publication Publication Date Title
US20100298453A1 (en) Board stock foam having biobased content
CN102300892B (zh) 芳族聚酯多元醇、异氰脲酸酯改性的聚氨酯泡沫体及其制备方法
CA2557193C (fr) Procede pour fabriquer des mousses de polyurethane rigides
WO2013030101A1 (fr) Mousses de polyuréthane rigides
CN102203154B (zh) 制备具有少量二噁烷废物的聚酯多元醇的方法
CA2725334A1 (fr) Procede pour la fabrication de mousses de polyisocyanurate rigides a l'aide de polyols d'huile naturelle
AU2011244310B2 (en) Method for producing polyurethane rigid foams
WO2010088198A1 (fr) Mousse de pâte mécanique pour carton possédant un contenu d'origine biologique
KR20220099982A (ko) 이미드 함유 폴리에스테르 폴리올 및 팽창 강성 발포체
US8399532B2 (en) Polyol compositions, resin blend compositions, spray compositions, and methods of using each, and methods of making each
CA3109540A1 (fr) Systemes de mousses polyurethanes en aerosol actionnes de maniere ecologique
US20030149123A1 (en) Polyol containing glycol adduct for use in producing rigid foam
ES2528757T3 (es) Elementos compuestos de metal y uso de espumas de PUR o de PIR que se obtienen de poliesterpolioles que se pueden obtener mediante procedimientos para la preparación de poliesterpolioles con pequeñas cantidades de residuo de dioxina, para la preparación de elementos compuestos de metal
EP3458491A1 (fr) Procédé de préparation de mousses de polyisocyanurate rigides
CA2909194A1 (fr) Polyester polyols a blocs de polyether polyols a chaine longue et leur utilisation dans des mousses dures de pur/pir
JP4449026B2 (ja) 独立気泡を有する硬質ポリウレタンフォームの製造方法
KR20240090526A (ko) 방향족 폴리에스테르 폴리올 및 에틸렌 옥시드계 폴리에테르 폴리올을 기초로 하는 개선된 경질 폴리이소시아누레이트 폼의 제조 방법
CN118103423A (zh) 基于芳香族聚酯多元醇和环氧乙烷基聚醚多元醇的改进型聚异氰脲酸酯硬质泡沫塑料的制备方法
EP4186936A1 (fr) Polyols de polyester d'origine biologique, mousse de polyuréthane polyol de polyester monocomposant d'origine biologique ou composition adhésive en mousse et utilisation de polyol de polyester d'origine biologique pour la fabrication d'une mousse de construction monocomposant ou adhésif en mousse

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20110701

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

DAX Request for extension of the european patent (deleted)
18W Application withdrawn

Effective date: 20120402