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WO2024261718A1 - Utilisation de polyols de polyester spécifiques en tant que phase molle pour la préparation d'adhésifs polyuréthane amovibles et utilisation desdits adhésifs - Google Patents

Utilisation de polyols de polyester spécifiques en tant que phase molle pour la préparation d'adhésifs polyuréthane amovibles et utilisation desdits adhésifs Download PDF

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Publication number
WO2024261718A1
WO2024261718A1 PCT/IB2024/056084 IB2024056084W WO2024261718A1 WO 2024261718 A1 WO2024261718 A1 WO 2024261718A1 IB 2024056084 W IB2024056084 W IB 2024056084W WO 2024261718 A1 WO2024261718 A1 WO 2024261718A1
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reaction
butanediol
methyl
heptanediol
polyurethane
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Inventor
Hermes Farina
Marco Aldo Ortenzi
Stefano ANTENUCCI
Stefano CAMAZZOLA
Stefano GAZZOTTI
Carolina Andrea PALMISANO
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GPS Tech Srl
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GPS Tech Srl
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/428—Lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6852—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C08G2230/00—Compositions for preparing biodegradable polymers

Definitions

  • Polyurethanes are known to be used in the textile industry, but not only, as hot-melt glues or materials that are able to impart functional or aesthetic properties to the products to which they are applied.
  • Polyurethanes for applications in the textile industry are generally constituted by a soft phase and a hard phase.
  • the soft phase imparts certain softness to the polyurethane
  • the hard phase imparts structural and physical properties such that polyurethane, for example, can be solid at room temperature.
  • the combination of soft phase and hard phase also gives elasticity properties to the polyurethanes.
  • polyurethanes are water repellency and waterproofing.
  • polyurethanes are often used in the form of thin films and are often multilayer films in which the polyurethane layer acting as a hot-melt glue often has the function of stably welding the multilayer product to a fabric. It is also often required that the multilayer product welded to the fabric does not come off after normal machine washing or dry cleaning. The more the resistance to machine washing is tested at higher temperatures, the better the product is generally considered to perform.
  • Polyurethanes that to date are mainly used for applications in the textile industry, but not only, can have a soft phase constituted by polyester polyols or, alternatively, poly ether polyols and a hard phase constituted by aliphatic or aromatic isocyanates.
  • Polyester polyol can be defined as a polyester-based polymer with hydroxyl functional groups capable of reacting with isocyanates in the process of polyurethane synthesis.
  • Polyether polyol can be defined as a polyether-based polymer with hydroxyl functional groups capable of reacting with isocyanates in the process of polyurethane synthesis.
  • polyols are generally difunctional, in order for the polyurethane to have, for example, elastic properties; thus, they are polymers with linear polymer chains and two hydroxyl groups at the ends of the polyol polymer chains.
  • polyols with >2 functionality can also be used, and this will clearly lead to the synthesis of polyurethanes with branched polymer chains.
  • the "hard phase”, constituted by aliphatic or aromatic isocyanates, is connected to the “soft phase” by reaction of the isocyanate with the hydroxyl groups of the polyol.
  • polyurethanes to date are used in a variety of technical fields including applications in the textile industry.
  • polyurethanes have a "hard phase” usually, but not exclusively, constituted by diisocyanates with two isocyanate groups (-NCO), said hard phase being generally constituted by sequences resulting from the reaction of said diisocyanates with a "chain extender” usually, but not exclusively, constituted by a dihydroxide (for example, a glycol).
  • Polyurethane with elastic properties commonly used in the textile industry, but not only, can be schematized as in Figure 1.
  • polyurethanes known to date have the disadvantage that they are not easily removable and this aspect is a drawback especially with regard to the possibility of recycling the products coupled, at the end of life, to such polyurethanes.
  • a fabric coupled to such polyurethanes, at the end of its life will not be able to be recycled in the recycling chain of the textile fabric, due to the coupling to such polyurethanes, with the result that the fabrics thus coupled will constitute non- reusable waste within the chain itself.
  • An object of the invention is to provide a novel use of a class of polyester polyols as a soft phase in the preparation of removable polyurethane adhesives.
  • a further object of the invention is to provide the use of polyurethanes containing the aforesaid class of polyester polyols as removable adhesives.
  • a further object of the invention is to provide recyclable items, particularly but not only, fabric items, comprising the removable polyurethane adhesives according to the invention.
  • Figure 1 shows the structure of polyurethane.
  • Figure 2 schematically shows the structures of a difunctional polyol and a trifunctional polyol.
  • Figures 3 to 12 show the NMR spectra of some synthesized polymers.
  • Figures 13 and 14 show the comparison of steric exclusion chromatography (SEC) spectra of some synthesized polymers.
  • subject-matter of the invention is the use of at least one polyester polyol comprising 1% to 90% monomeric units selected from:
  • glycolide and mixtures thereof; in the preparation of removable polyurethane adhesives.
  • polyester polyol comprising 1% to 90% monomeric units selected from
  • polyester polyol is prepared from one or more of said monomeric units, as will be described in more detail here below, the remaining percentage by weight being constituted by different monomeric units.
  • the percentage by weight of the monomeric units is expressed to the total weight of monomeric units of the polyester polyol.
  • polyester polyol for the use of the present invention is also referred to herein simply as "polyol of the present invention”.
  • the polyester polyol of the present invention is obtainable and/or obtained by the polymerization reaction of a mixture of monomers comprising at least one of the monomeric units (i) to (iv) above, or mixtures thereof, at the rate of 1-90% by weight to the total weight of the monomeric units of said polyester polyol.
  • the polyester polyol of the present invention is obtainable and/or obtained by a process comprising: a) a polycondensation reaction of:
  • AB-type monomers optionally partly in their cyclic form (lactones), and one or more chain-regulating compounds
  • II. a mixture comprising AB-type monomers, optionally also in their cyclic form (lactones), together with a mixture of AA+BB-type monomers and one or more chain-regulating compounds; wherein the AB-type monomers, optionally partly in their cyclic form (lactones), comprise at least lactic acid and/or lactide, and/or glycolic acid and/or glycolide, at the rate of 1-90% by weight to the total weight of the monomeric units of said polyester polyol; or b) a ring-opening polymerization reaction of a mixture comprising AB-type monomers in their cyclic form (lactones), said mixture comprising at least lactide or glycolide, at the rate of 1-90% by weight to the total weight of the monomeric units of said polyester polyol, and one or more chain-regulating compounds.
  • the polycondensation (a) and ring-opening polymerization (b) reactions can be carried out according to procedures known in the art and available to the skilled in art.
  • the AB-type monomers are hydroxy-acid monomers with a carboxylic acid group (-COOH) and a hydroxyl group (-OH).
  • Type AA monomers are diacid monomers with two carboxylic acid groups (-COOH); type BB monomers are dihydroxyl monomers (glycols), that is, with two hydroxyl groups (-OH).
  • lactone As well known, when an AB-type monomer is in its cyclic form it is called "lactone". Short-chain acids, such as the glycolic acid and lactic acid, are able to form lactones only in dimer form (glycolide and lactide). The term “lactones” here also includes lactide and glycolide.
  • the expression “optionally also”, referring to the cyclic form of AB monomers, is meant here to denote that said AB monomers may be partly or totally in cyclic form (lactones).
  • the expression "optionally partly”, referring to the cyclic form of AB monomers, is meant here to denote that said AB monomers may be partly, but not totally, in cyclic form (lactones).
  • RIO is a saturated or unsaturated, linear or branched aliphatic chain with a number of carbon atoms between 1 and 31, preferably between 1 and 17, even more preferably between 1 and 11 and even more preferably between 1 and 9, said hydroxy acids being preferably selected from glycolic acid, lactic acid, 4-hydroxy-butyric acid, 4-hydroxy-valeric acid, 5-hydroxy-valeric acid, 4-hydroxy-capric acid, 5-hydroxy-capric acid and 6-hydroxy-capric acid.
  • the AB-type monomers of the polymerization reaction (b) are selected from the cyclic derivatives (lactones) of the AB-type monomers of formula (V) and the preferred monomers set forth above.
  • the lactic acid monomers that can be used in the present invention comprise L-lactic acid and D- lactic acid.
  • the mixture of two or more AB-type monomers, optionally partly in their cyclic form (lactones), or AB-type monomers, optionally also in their cyclic form (lactones), together with a mixture of AA+BB-type monomers is characterized in that said mixture of monomers comprises 1 to 90% by weight lactic acid and/or lactide, and/or glycolic acid and/or glycolide.
  • the mixture of two or more AB-type monomers, optionally partly in their cyclic form (lactones), or AB-type monomers, optionally also in their cyclic form (lactones), and AA+BB-type monomers is characterized in that said mixture of monomers comprises 5 to 80% by weight lactic acid and/or lactide and/or glycolic acid, and/or glycolide.
  • the mixture of two or more AB-type monomers, optionally partly in their cyclic form (lactones), or AB-type monomers, optionally also in their cyclic form (lactones), and AA+BB-type monomers is characterized in that said mixture of monomers comprises 5 to 70%, or 5 to 60%, or 5% to 50%, or 5% to 40%, or 5% to 30%, or 5% to 20%, or 5 to 10% by weight lactic acid and/or lactide and/or glycolic acid and/or glycolide.
  • the mixture of two or more AB-type monomers, optionally partly in their cyclic form (lactones), or AB-type monomers, optionally also in their cyclic form (lactones), and AA+BB-type monomers is characterized in that said mixture of monomers comprises 1 to 80%, or 1% to 70%, or 1% to 60%, or 1% to 50%, or 1% to 40%, or 1% to 30%, or 1% to 20%, or 1 to 10% by weight lactic acid and/or lactide and/or glycolic acid, and/or glycolide.
  • the mixture of two or more AB-type monomers, optionally partly in their cyclic form (lactones), or AB-type monomers, optionally also in their cyclic form (lactones), and AA+BB-type monomers is characterized in that said mixture of monomers comprises 10 to 80%, or 10% to 70%, or 10% to 60%, or 10% to 50%, or 10% to 40%, or 10% to 30%, or 10% to 20% by weight lactic acid and/or lactide and/or glycolic acid, and/or glycolide.
  • the lactones of a mixture of AB-type monomers in their cyclic form, having a number of atoms per ring between 3 and 7, in addition to lactide and/or glycolide are selected from gamma-butyrolactone, gamma-valerolactone, delta- valerolactone, gamma-caprolactone, delta-caprolactone and epsilon-caprolactone; more preferably from epsilon- caprolactone (6-hydroxycaproic acid lactone) and delta-valerolactone (5-hydroxyvaleric acid lactone).
  • lactide and glycolide are preferred over lactic acid and glycolic acid, respectively.
  • the mixture of two or more lactones is characterized in that said mixture of lactone monomers comprises 1 to 90%, or 1 to 80%, or 1% to 70%, or 1% to 60%, or 1% to 50%, or 1% to 40%, or 1% to 30%, or 1% to 20%, or 1 to 10% by weight lactide and/or glycolide, the remaining monomers being preferably selected from gamma-butyrolactone, gamma- valerolactone, delta-valerolactone, gamma-caprolactone, delta-caprolactone and epsilon- caprolactone; more preferably from epsilon-caprolactone (6-hydroxycaproic acid lactone) and delta-valerolactone (5-hydroxyvaleric acid lactone).
  • the mixture of two or more lactones is characterized in that said mixture of lactone monomers comprises 5 to 80% by weight lactide and/or glycolide, the remaining monomers being preferably selected from gamma-butyrolactone, gamma- valerolactone, delta-valerolactone, gamma-caprolactone, delta-caprolactone and epsilon- caprolactone; more preferably from epsilon-caprolactone (6-hydroxycaproic acid lactone) and delta-valerolactone (5-hydroxyvaleric acid lactone).
  • the mixture of two or more lactones is characterized in that said mixture of lactone monomers comprises 5 to 70%, or 5 to 60%, or 5% to 50%, or 5% to 40%, or 5% to 30%, or 5% to 20%, or 5 to 10% by weight lactide and/or glycolide, the remaining monomers being preferably selected from gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, gamma-caprolactone, delta-caprolactone and epsilon-caprolactone; more preferably from epsilon- caprolactone (6-hydroxycaproic acid lactone) and delta-valerolactone (5-hydroxyvaleric acid lactone).
  • the mixture of two or more lactones is characterized in that said mixture of lactone monomers comprises 10 to 80%, or 10 to 70%, or 10 to 60%, or 10% to 50%, or 10% to 40%, or 10% to 30%, or 10% to 20% by weight lactide and/or glycolide, the remaining monomers being preferably selected from gamma-butyrolactone, gamma-valerolactone, delta- valerolactone, gamma-caprolactone, delta-caprolactone and epsilon-caprolactone; more preferably from epsilon-caprolactone (6-hydroxy caproic acid lactone) and delta- valerolactone (5- hydroxyvaleric acid lactone).
  • This result is particularly useful for the recycling of objects and items containing adhesives that couple different materials, because it allows the separation of these materials at the end of the object's life and their reuse.
  • polyurethanes containing, as soft phase, polyester polyols that do not contain any monomer selected from the monomers (i) to (iv) set forth above did not demonstrate to be removable.
  • the term "coupled” and derived terms is meant to denote the joining of different materials (in objects, items, fabrics, etc.) by the application of the adhesive according to the invention. Said different materials are therefore held together, coupled in fact, by said adhesive.
  • the polyester polyol of the invention in addition to the monomers as described above, comprises chain-regulating compounds.
  • the chain-regulating compounds are known in the art and are molecules comprising at least two functional groups, either the same or different from each other, selected from -OH, -NH2 and -NH. A representative and non-exhaustive list of such chain regulators is provided herein below.
  • the chain-regulating compound if it has two -OH functional groups (and thus exhibits the characteristics of a BB-type glycol), it must be present in such an amount that the total molar amount of BB-type compounds is greater than the total molar amount of AA compounds, and the molar amount of BB compounds in excess of AA compounds constitutes the effective moles of chain regulator, at the end of the reaction.
  • the polymerization reaction occurs by ring-opening and is carried out by the reaction between a chain-regulating compound comprising at least two functional groups, either the same or different from each other, selected from -OH, -NH2 and -NH, as defined above, and a mixture of two or more lactones having a number of atoms per ring between 3 and 7 atoms and comprising at least lactide and/or glycolide.
  • a chain-regulating compound comprising at least two functional groups, either the same or different from each other, selected from -OH, -NH2 and -NH, as defined above, and a mixture of two or more lactones having a number of atoms per ring between 3 and 7 atoms and comprising at least lactide and/or glycolide.
  • the polyester polyol obtained by the polycondensation reaction (a) of AB-type monomers, optionally partly in their cyclic form (lactones), or AB-type monomers, optionally also in their cyclic form (lactones), and AA+BB- type monomers or ring-opening polymerization (b) of lactones, will have a linear structure and will be a difunctional polyester polyol if the chain-regulating compound has two functional groups, whereas it will have a nonlinear structure and will be a polyester polyol with >2 functionality if the chain-regulating compound has three or more functional groups.
  • difunctional polyester polyol is meant that the resulting polyol has two hydroxyl groups (- OH) as end groups of the polyol chains.
  • polyester polyol with >2 functionality is meant that the resulting polyol has three or more hydroxyl groups (-OH) as end groups of the polyol chains.
  • chain regulators having a functional group selected from -OH, -NH2 and -NH are not excluded, but is not essential for the purposes of the present invention.
  • the chain regulators are selected from: compounds having general formula (I)
  • Ri is a saturated or unsaturated, linear or branched or cyclic aliphatic chain or a structure comprising aromatic rings with a number of carbon atoms between 1 and 44, preferably between 1 and 16 and even more preferably between 1 and 10;
  • R2 and R3, equal or different from each other, are H or saturated or unsaturated, linear or branched or cyclic aliphatic chains with a number of carbon atoms between 1 and 32, preferably between 1 and 18, even more preferably between 1 and 12, and even more preferably between 1 and 10;
  • R4 and R5, equal or different from each other, are saturated or unsaturated, linear or branched or cyclic aliphatic chains with a number of carbon atoms between 1 and 32, preferably between 1 and 18, even more preferably between 1 and 12 and even more preferably between 1 and 10;
  • n is between 0 and 10 when R2 and R3 are not H and between 1 and 10 when R2 and R3 are H;
  • m is between 0 and 10 when R2 and R3 are not H and between 1 and 10 when R2 and R3 are
  • m+n is between 1 and 11 when R2 and R3 are not H and between 2 and 11 when R2 and R3 are H; said polyamines being preferably selected from diethylenetriamine, triethylenetetramine, tetraethylenepentamine, higher oligomers of ethylenediamine, dipropylenetriamine, higher oligomers of propylenediamine, bis(hexamethylene)triamine), higher oligomers of hexamethylenediamine, spermidine and spermine; polyhydroxylates of general formula (III) wherein
  • Re and R7 are saturated or unsaturated, linear or branched or cyclic aliphatic chains with a number of carbon atoms between 1 and 32, preferably between 1 and 18, even more preferably between 1 and 12 and even more preferably between 1 and 10; x is between 1 and 10; y is between 1 and 10; x+y is between 2 and 11; p+q>l; said polyhydroxylates being preferably selected from diglycerol (glycerol dimer), higher oligomers of glycerol, dipentaerythritol (pentaerythritol dimer); dihydroxylates of general formula (IV) wherein
  • Rs and R9 are saturated or unsaturated, linear or branched or cyclic aliphatic chains with a number of carbon atoms between 1 and 32, preferably between 1 and 18, even more preferably between 1 and 12 and even more preferably between 1 and 10; z is between 1 and 10; w is between 1 and 10; z+w is between 2 and 11; said dihydroxylates being preferably selected from diethylene glycol (dimer of ethylene glycol), higher oligomers of ethylene glycol, dipropylene glycol (dimers of 1,2-propylene glycol or 1,3-propylene glycol), higher oligomers of 1,2-propylene glycol or 1,3-propylene glycol; polyhydroxylates of the monosaccharide and polysaccharide sugar family; said monosaccharides and polysaccharides being preferably selected from sorbitol, mannitol, xylitol, ribose, galactose, trehalose
  • the chain regulators are selected from: compounds having general formula (I)
  • Ri is a saturated or unsaturated, linear or branched or cyclic aliphatic chain or a structure comprising aromatic rings with a number of carbon atoms preferably between 1 and 10;
  • the chain regulator is selected from: dihydroxylates of general formula (IV) wherein Rs and R9, equal or different from each other, are saturated or unsaturated, linear or branched or cyclic aliphatic chains with a number of carbon atoms preferably between 1 and 10; z is between 1 and 10; w is between 1 and 10; z+w is between 2 and 11; said dihydroxylates being preferably selected from diethylene glycol (dimer of ethylene glycol), higher oligomers of ethylene glycol, dipropylene glycol (dimers of 1,2-propylene glycol or 1,3 -propylene glycol), higher oligomers of 1,2-propylene glycol or 1,3- propylene glycol.
  • diethylene glycol dimer of ethylene glycol
  • dipropylene glycol dimers of 1,2-propylene glycol or 1,3 -propylene glycol
  • higher oligomers of 1,2-propylene glycol or 1,3- propylene glycol 1,2-propylene glycol or
  • the chain regulators are selected from: amines with hydroxyl and/or ether functional groups, more preferably selected from ethanolamine, 4,9-dioxa-l,12-dodecanediamine (CAS RN 7300-34-7) and 4,7,10-trioxa- 1,13 -tridecanediamine (CAS RN 4246-51-9).
  • the chain regulators are selected from: ethylene glycol, 1,3- propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 2,2- dimethyl- 1,3 -propanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-l,3- cyclobutanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, ethylenediamine, 1,3-diaminopropane (propylenediamine), 1,4-diaminobutane, 1,6- diaminohexane, 1,2-cyclohexanediamine, 1,3 -cyclohexanediamine, 1,4-cyclohexanediamine,
  • the polyester polyol preferably has a number average molecular weight between 400 Daltons and 10000 Daltons, more preferably between 500 Daltons and 6000 Daltons, even more preferably between 800 Daltons and 5000 Daltons.
  • the polyester polyol preferably has a glass transition temperature lower than 30°C, more preferably lower than 20°C, even more preferably lower than 10°C.
  • the molecular weights of the polyester polyols can be measured by measuring the hydroxyl end groups according to ASTM method El 899-08. To calculate the molecular weight from the measurement of the hydroxyl end groups, the following Formula I can be applied: wherein:
  • P.M. KOH molecular weight of KOH (potassium hydroxide)
  • P. Mg molecular weight of individual monomeric “z” units.
  • the polycondensation (a) and ring-opening polymerization (b) reactions can be carried out in the presence of other components in addition to those described, for example, in the presence of catalysts and/or solvents and/or antioxidants and/or thermal stabilizers and/or other process additives normally used in the polymerization reactions and known to the skilled in the art.
  • An exemplary but not exhaustive list of catalysts comprises tin-based catalysts such as for example Sn octanoate, Sn 2-ethylhexanoate, Sn oxalate, butyl-Sn tris-2-ethylhexanoate, dibutyl-Sn diacetate, butyl-Sn hydroxide-oxide, butyl-Sn chloride-dihydroxide, dibutyl-Sn oxide, dibutyl-Sn dilaurate or catalysts such as for example Ti-tetrabutoxide, EGECat® Bismuth Octoate, EGECat® Bismuth-S, EGECat® Zinc-S, EGECat® Zircon-S, EGECat 8-S, considering that especially in the textile-fashion industry, the market often requires tin-free products.
  • tin-based catalysts such as for example Sn octanoate, Sn 2-ethylhexanoate, S
  • the polyester polyol can be used in the synthesis of polyurethanes by the common synthesis processes of said polyurethanes, which may comprise, by way of example but not limited to, the synthesis process from solvent-free bicomponent, the synthesis process in organic solvent solution and the synthesis process in aqueous emulsion.
  • the "hard phase" of the polyurethanes synthesized from the polyester polyol of the present invention is constituted by at least substances called aliphatic or aromatic isocyanates having two or more isocyanate groups and is connected to the "soft phase" by reaction of the isocyanate with the hydroxyl groups of the polyester polyol and generally is constituted by reaction sequences of said isocyanates with at least one chain extender constituted by a dihydroxide (glycol) or with a substance having more than two hydroxyl groups; in some cases diamines or substances having more than two amine groups can also be used as chain extenders and, in this specific case, the polyurethanes obtained will also be characterized by the presence of urea groups being polyurethanes/urea de facto.
  • Useful molecules as chain extenders can be selected from, for example, the chain regulators set forth above. All of these molecules may also comprise other functionalities that enable the formation of a polyurethane emulsion in water (emulsifying chain extenders). Such emulsifying chain extenders are known to the skilled in the art; for example, an emulsifying chain extender is dimethylolpropionic acid.
  • Said isocyanates are preferably diisocyanates with two isocyanate groups (-NCO) having general formula (VI)
  • the isocyanates with more than two isocyanate groups are preferably selected from the hexamethylene diisocyanate trimer (CAS Number: 3779-63-3), isophorone-diisocyanate trimer (CAS Number: 67873-91-0), diphenylmethane-diisocyanate trimer (CAS Number: 31107-36-5), toluene-diisocyanate trimer (26603-40-7).
  • the diisocyanates are preferably selected from 2,4-toluene- diisocyanate, 2,6-toluene-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane- 2,4'-diisocyanate, diphenylmethane-2,2'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, dicyclohexylmethane-2,2'-diisocyanate, hexamethylen- 1,6-diisocyanate, isophorone-diisocyanate, 2,2,4-trimethyl-hexamethylen-diisocyanate and 2,4,4- trimethyl-hexamethylen-diisocyanate.
  • the diisocyanates are preferably selected from diphenylmethane-4,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hexamethylen-1,6- dii socy anate, i sophorone-dii socy anate.
  • the synthesis of polyurethanes with the common synthesis processes of the said polyurethanes may be carried out in the presence of other components in addition to those described, for example, in the presence of catalysts and/or solvents and/or antioxidants and/or thermal stabilizers and/or other process additives normally used in polymerization reactions and known to the skilled in the art.
  • the expression "is between ... and ... " and similar expressions are intended to denote that the values set forth also include the extreme values of the range.
  • subject-matter of the invention is a removable polyurethane adhesive comprising, as a soft phase, one or more polyester polyols as defined above.
  • subject-matter of the invention is the use of a polyurethane comprising one or more polyester polyols as defined above as a removable adhesive, preferably, but not only, in the production of recyclable fabrics.
  • the recyclable objects and items such as fabrics comprising the removable polyurethane adhesive as defined herein, constitute an additional object of the invention.
  • the recyclable objects and items for example, fabric items, herein means objects and items constituted by different materials that can be recycled once the polyurethane portion according to the invention and the different material coupled to them are removed, by removal of the polyurethane.
  • fabric has a broad meaning here and includes any fabric (cloth) made of any material, whether of natural or synthetic origin, including woven-nonwoven fabrics.
  • the polyurethane of the invention can be easily removed, preferably under certain conditions of pH, temperature, time and liquid medium.
  • the liquid medium in which to carry out the removal is water.
  • the removal is carried out in aqueous solution at pH from 0 to 5 or from 8 to 14, more preferably from 0 to 4 or from 9 to 14, even more preferably from 0 to 3 or from 10 to 14 or from 10 to 13 or from 10 to 12.
  • a suitable medium for the removal at pH 11 can be obtained from an aqueous solution of sodium carbonate; a medium at pH 9 can be obtained from an aqueous solution of sodium bicarbonate/carbonate and a medium at pH 3 can be obtained from an aqueous solution of hydrochloric acid.
  • a medium at pH 9 can be obtained from an aqueous solution of sodium bicarbonate/carbonate and a medium at pH 3 can be obtained from an aqueous solution of hydrochloric acid.
  • the skilled in the art is perfectly capable of preparing other means of removal, at any desired pH.
  • the removal is carried out in aqueous solution at a temperature from 50°C to 150°C, more preferably from 60°C to 120°C, even more preferably from 70°C to 100°C or from 70°C to 95°C.
  • the time to carry out the removal is less than 50 hours and greater than 5 minutes, more preferably less than 25 hours and greater than 5 minutes, even more preferably less than 10 hours and greater than 5 minutes, even more preferably less than 6 hours and greater than 5 minutes or less than 6 hours and greater than 10 minutes or less than 6 hours and greater than 30 minutes, even more preferably less than 5 hours and greater than 5 minutes or less than 5 hours and greater than 10 minutes or less than 5 hours and greater than 30 minutes, for example, 5 hours, 4 hours, 3 hours, 2 hours, 1 hour or half an hour.
  • subject-matter of the invention is a method for removing the polyurethane according to the invention, that comprises implementing one or more of the pH, temperature, time and liquid medium conditions described above.
  • the invention represents a significant technical advance in the field of polyurethanes, particularly but not only, in the field of fabric-coupled polyurethanes.
  • the invention has applications in a variety of other technical fields, for example, the furniture, apparel, footwear, construction and automotive industries, and more generally in any industry where hot-melt glues are typically used.
  • the instrumental analyses used are: Nuclear Magnetic Resonance ( 'H-NMR) to confirm the correct structure of the synthesized polyester polyols, titration of the hydroxyl end groups to define the average molecular weight of the synthesized polyester polyols where a theoretical average molecular weight could not be calculated, steric exclusion chromatography (SEC) to evaluate the homogeneity of the distribution curve of the molecular weights of the synthesized polyester polyols to verify the correct course of the polymerization reaction, and polyurethane softening test to evaluate possible application as hot-melt as described below:
  • the film was flattened with a 25 mm-diameter plunger with a force of 10 N.
  • the temperature is raised from 50°C up to 150°C at 2°C/min and simultaneously the force equal to 10 N of piston pressure on the film is kept constant throughout the experiment by constantly measuring the film thickness.
  • the film softening temperature is considered to be the beginning of the piston penetration into the film, resulting in a decrease in the measured film thickness.
  • AB-type monomers or AB-type monomers with AA+BB-type monomers, a chain-regulating compound and a catalyst were loaded according to the amounts specified in the examples themselves.
  • the function of the chain-regulating compound is to adjust the molecular weight and structure (linear or branched) of the polyester polyol. If the chainregulating compound has two -OH functional groups (and thus exhibits the characteristics of a BB-type glycol), it must be present in such an amount that the molar amount of BB-type compounds is greater than the molar amount of AA compounds, and the molar amount of BB compounds in excess of AA compounds constitutes the effective moles of chain regulator, at the end of the reaction.
  • the reaction flask was equipped with a three-neck candelabra fitting: the central neck was equipped with a rod stirrer and the two side necks were equipped with two taps for the inlet and outlet of an inert gas stream, respectively, for the purpose of keeping the reaction atmosphere in the absence of oxygen and to allow the removal of water derived from the polycondensation reaction of AB-type monomers, or AB-type monomers with AA+BB-type monomers, or volatile reaction by-products.
  • reaction atmosphere was purged to remove the oxygen present with appropriate cycles of vacuum-inert gas. Then, the reaction environment was kept under continuous flow of inert gas at about 10 ml/min and the synthesis steps were started as described in the examples themselves.
  • the catalyst can be tin-based such as for example Sn octanoate, Sn 2-ethylhexanoate, Sn oxalate, butyl-Sn tris-2-ethylhexanoate, dibutyl-Sn diacetate, butyl-Sn hydroxide-oxide, butyl-Sn chloridedihydroxide, dibutyl-Sn oxide, dibutyl-Sn dilaurate or it can be a tin-free catalyst such as for example Ti-tetrabutoxide, EGECat® Bismuth Octoate, EGECat® Bismuth-S, EGECat® Zinc-S, EGECat® Zircon-S, EGECat 8-S, considering that especially in the textile-fashion industry, the market often requires tin-free products.
  • tin-based such as for example Sn octanoate, Sn 2-ethylhexanoate, Sn o
  • BB monomers neopentyl glycol and 1,4-butanediol monomers
  • the reaction system was returned to a nitrogen atmosphere (inert gas), and while keeping the nitrogen flow, the obtained polyol was allowed to cool to room temperature and then recovered.
  • the product obtained is a colorless transparent liquid at room temperature and was analyzed by NMR, SEC and end group titration.
  • the molecular weight of the polyester polyol was calculated from the number of end groups measured according to ASTM method El 899-08 and it was found to be about 1000 Daltons. SEC analysis showed a homogeneous distribution of molecular weights without alterations.
  • the 1,4-butanediol and neopentyl glycol monomers are in excess of the AA monomer and the molar amount of the BB monomers in excess of the AA monomer, at the end of the reaction, constitutes the actual moles of chain regulator.
  • the reaction system was returned to a nitrogen atmosphere (inert gas), and while keeping the nitrogen flow, the obtained polyol was allowed to cool to room temperature and then recovered.
  • the product obtained is a colorless transparent liquid at room temperature and was analyzed by NMR, SEC and end group titration.
  • the molecular weight of the polyester polyol was calculated from the number of end groups measured according to ASTM method El 899-08 and it was found to be about 2000 Daltons. SEC analysis showed a homogeneous distribution of molecular weights without alterations.
  • lactones In a 500 mL flask with one neck, lactones, a chain-regulating compound and a catalyst were loaded according to the amounts specified in the examples themselves.
  • the function of the chainregulating compound is to initiate the ring-opening polymerization reaction of the lactones and to adjust the molecular weight and structure (linear or branched) of the polyester polyol.
  • the reaction flask was equipped with a three-neck candelabra fitting: the central neck was equipped with a rod stirrer and the two side necks were equipped with two taps for the inlet and outlet of an inert gas stream, respectively, for the purpose of keeping the reaction atmosphere in the absence of oxygen and to allow the removal of any residual moisture or volatile reaction byproducts.
  • reaction atmosphere Before heating the reaction flask in a special oven, the reaction atmosphere was purged to remove the oxygen present with appropriate cycles of vacuum-inert gas. Then, the reaction environment was kept under continuous flow of inert gas at about 10 ml/min.
  • the reaction is carried out by heating to the temperature and for the time set forth in the examples themselves.
  • the obtained initiator was allowed to cool to room temperature and then recovered.
  • the catalyst can be tin-based such as for example Sn octanoate, Sn 2-ethylhexanoate, Sn oxalate, butyl-Sn tris-2-ethylhexanoate, dibutyl-Sn diacetate, butyl-Sn hydroxide-oxide, butyl-Sn chloridedihydroxide, dibutyl-Sn oxide, dibutyl-Sn dilaurate or it can be a tin-free catalyst such as for example Ti-tetrabutoxide, EGECat® Bismuth Octoate, EGECat® Bismuth-S, EGECat® Zinc-S, EGECat® Zircon-S, EGECat 8-S, considering that especially in the textile-fashion industry, the market often requires tin-free products.
  • tin-based such as for example Sn octanoate, Sn 2-ethylhexanoate, Sn o
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a white solid at room temperature.
  • Theoretical number average molecular weight 1000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature and was analyzed by
  • Theoretical number average molecular weight 1000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature and was analyzed by
  • Theoretical number average molecular weight 1000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature and was analyzed by
  • Theoretical number average molecular weight 2000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature.
  • Theoretical number average molecular weight 1000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature and was analyzed by
  • Theoretical number average molecular weight 2000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature.
  • Theoretical number average molecular weight 1000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature.
  • Theoretical number average molecular weight 2000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature.
  • Theoretical number average molecular weight 1000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature.
  • Theoretical number average molecular weight 2000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature.
  • Theoretical number average molecular weight 2000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature and was analyzed by
  • Theoretical number average molecular weight 2000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a waxy white solid at room temperature and was analyzed by NMR ( Figure 10) to confirm the successful polymerization reaction.
  • Theoretical number average molecular weight 2000 Daltons.
  • the reaction has been carried out for 3 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature and was analyzed by
  • Theoretical number average molecular weight 2000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature.
  • Theoretical number average molecular weight 2000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • Theoretical number average molecular weight 2000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a white solid at room temperature.
  • Theoretical number average molecular weight 10000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature.
  • Theoretical number average molecular weight 8000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature.
  • a polyester polyol is obtained from the following formulation: • 26.276 g LL-Lactide (lactone)
  • Theoretical number average molecular weight 500 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature.
  • Theoretical number average molecular weight 4000 Daltons.
  • the reaction has been carried out for 6 hours at 190°C.
  • the product obtained is a colorless transparent liquid at room temperature.
  • polyol polyesters synthesized as described above were analyzed by steric exclusion chromatography (SEC) in order to evaluate the homogeneity of the polyol distribution curve to verify the successful polymerization reaction.
  • SEC steric exclusion chromatography
  • the flask was equipped with a rod stirrer and the reagent mixture was homogenized with a maximum time of 60 seconds after the last component, the catalyst, was loaded into the flask.
  • the homogeneous mixture of reagents was then poured onto a non-adherent paper backing and leveled to a film by means of a doctor blade with thickness of 100 pm.
  • the leveling agent added in the reaction mixture is intended to ensure homogeneous leveling of the mixture itself on the non-adherent paper backing.
  • the non-adherent paper backing with the film leveled was then placed in a ventilated oven at the temperature specified in the examples themselves, in order to allow the reaction of polyurethane formation.
  • the non-adherent paper backing with the formed polyurethane film was allowed to rest for 48 h at room temperature before using the film for further testing.
  • the catalyst can be tin-based such as for example Sn octanoate, Sn 2-ethylhexanoate, Sn oxalate, butyl-Sn tris-2-ethylhexanoate, dibutyl-Sn diacetate, butyl-Sn hydroxide-oxide, butyl-Sn chloridedihydroxide, dibutyl-Sn oxide, dibutyl-Sn dilaurate or it can be a tin-free catalyst such as for example Ti-tetrabutoxide, EGECat® Bismuth Octoate, EGECat® Bismuth-S, EGECat® Zinc-S, EGECat® Zircon-S, EGECat 8-S, considering that especially in the textile-fashion industry, the market often requires tin-free products.
  • tin-based such as for example Sn octanoate, Sn 2-ethylhexanoate, Sn o
  • polyurethane is obtained from the following formulation:
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation: • 5.083 g PE05 (polyester polyol)
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish/ slightly yellow film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish/ slightly yellow film.
  • Example PU25b Using the synthesis method described above, polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish/ slightly yellow film.
  • polyurethane is obtained from the following formulation:
  • the reaction has been carried out at 150°C.
  • the product obtained is a whitish/ slightly yellow film.
  • a 500 mL flask with two necks was equipped with a magnetic stirrer, a condenser (fall back) engaged onto the central neck of the flask after charging the reagents of synthesis Step-1 and a dropping funnel engaged onto the side neck of the flask.
  • Said dropping funnel was itself equipped with a nitrogen inlet fitting in order to keep an inert, anhydrous atmosphere both during the reagent loading operations and during the polymerization synthesis.
  • the previously dried polyester polyol and anhydrous reaction solvent were loaded sequentially into the flask, according to the amounts specified in the examples themselves.
  • the system was stirred until the polyester polyol was completely solubilized in the reaction solvent and then isocyanate and catalyst were added.
  • an FT-IR analysis of the reaction mixture was performed at time zero so that the isocyanate consumption could be monitored during the course of the reaction.
  • the reaction was started at the temperature shown in the examples. The reaction was continued by monitoring the consumption of isocyanate (synthesis Step-1).
  • the leveling agent added to the polyurethane solvent solution is intended to ensure homogeneous leveling of the mixture itself on the non-adherent paper backing.
  • the non-adherent paper backing with the solution film leveled was then placed in a ventilated oven in order to allow the solvent to dry to obtain a polyurethane film.
  • the non-adherent paper backing with the polyurethane film was allowed to rest for 48 h at room temperature before using the film for further testing.
  • the catalyst can be tin-based such as for example Sn octanoate, Sn 2-ethylhexanoate, Sn oxalate, butyl-Sn tris-2-ethylhexanoate, dibutyl-Sn diacetate, butyl-Sn hydroxide-oxide, butyl-Sn chloridedihydroxide, dibutyl-Sn oxide, dibutyl-Sn dilaurate or it can be a tin-free catalyst such as for example Ti-tetrabutoxide, EGECat® Bismuth Octoate, EGECat® Bismuth-S, EGECat® Zinc-S, EGECat® Zircon-S, EGECat 8-S, considering that especially in the textile-fashion industry, the market often requires tin-free products.
  • tin-based such as for example Sn octanoate, Sn 2-ethylhexanoate, Sn o
  • polyurethane is obtained from the following formulation:
  • a 500 mL flask with two necks was equipped with a magnetic stirrer, a condenser (fall back) engaged onto the central neck of the flask after charging the reagents of synthesis Step-1, and a dropping funnel engaged onto the side neck of the flask.
  • the condenser was itself equipped with a nitrogen inlet fitting in order to keep an inert, anhydrous atmosphere both during the reagent loading operations of synthesis Step-2 and during the polymerization synthesis.
  • the previously dried polyester polyol, isocyanate and catalyst were loaded sequentially into the flask, according to the amounts specified in the examples themselves.
  • an FT-IR analysis of the reaction mixture was performed at time zero so that the isocyanate consumption could be monitored during the course of the reaction.
  • the reaction was started at the temperature shown in the examples.
  • the reaction was continued by monitoring the consumption of isocyanate (synthesis Step-1). After stability of the intensity of the FT-IR peak of the isocyanate was achieved, the temperature was raised to the value specified in the examples and then the anhydrous reaction solvent was added; after homogenization of the reaction mixture, the emulsifying chain extender and the chain extender were added, in smaller amounts than the stoichiometric amounts.
  • reaction was monitored until the intensity of the FT-IR peak of isocyanate (synthesis Step-2) was stable.
  • the reaction mixture was allowed to cool to room temperature and then slowly dripped into an aqueous solution of neutralizing agent of the emulsifying chain extender, if ionic, and amine chain extender, as specified in the examples, while keeping the system under vigorous agitation by means of an emulsifier (synthesis Step-3).
  • the solvent added in synthesis Step-2 was removed by evaporation in order to obtain an aqueous emulsion of the synthesized polyurethane.
  • a leveling agent was then added to the polyurethane emulsion in water and the solution was poured on a non-adherent paper backing and leveled to a film by means of a doctor blade with thickness of 200 pm.
  • the leveling agent added to the polyurethane emulsion in water is intended to ensure homogeneous leveling of the mixture itself on the non-adherent paper backing.
  • the non-adherent paper backing with emulsion film leveled was then placed in a ventilated oven in order to allow the water to dry to obtain a polyurethane film. At the end of the drying process, the non-adherent paper backing with the polyurethane film was allowed to rest for 48 h at room temperature before using the film for further testing.
  • the catalyst can be tin-based such as for example Sn octanoate, Sn 2-ethylhexanoate, Sn oxalate, butyl-Sn tris-2-ethylhexanoate, dibutyl-Sn diacetate, butyl-Sn hydroxide-oxide, butyl-Sn chloridedihydroxide, dibutyl-Sn oxide, dibutyl-Sn dilaurate or it can be a tin-free catalyst such as for example Ti-tetrabutoxide, EGECat® Bismuth Octoate, EGECat® Bismuth-S, EGECat® Zinc-S, EGECat® Zircon-S, EGECat 8-S, considering that especially in the textile-fashion industry, the market often requires tin-free products.
  • tin-based such as for example Sn octanoate, Sn 2-ethylhexanoate, Sn o
  • polyurethane is obtained from the following formulation:
  • aqueous solution constituted by:
  • the product obtained after removal of the solvent added in synthesis Step-2 is a whitish emulsion of polyurethane in water to which the leveling agent has been added:
  • polyurethane products obtained in the examples described were analyzed to determine their softening temperature.
  • the polyurethanes obtained in the examples were analyzed: PUOlb, PU04b, PUO5b, PU06b, PU13b, PU24b and for all of them the softening temperature is >80°C and ⁇ 150°C, making them for example suitable in applications such as hot- melt.
  • polyurethane film of about 10 cm 2 was placed in a 100 mL flask equipped with a magnetic stirrer, and then 60 mL of water-based treatment mixture with the characteristics as set forth in the examples themselves was added.
  • the flask was placed in an oil bath on a heating and stirring plate. Stirring was turned on at 200 rpm and then the oil bath was brought to the temperature and for the time specified in the examples themselves (Table-1) in order to test the removability of the polyurethanes.
  • Table-1 shows the numbers of Figures where a comparison of the SEC curves of the polyurethane film before and after removal at 24 hours can be observed; possible longer retention times point to lower molecular weights and thus the successful removal; conversely, similar retention times point to similar molecular weights and thus non-removal of the polyurethane.
  • This second surface of the polyurethane film was placed in contact with a second flap of fabric as specified in the examples in Table-2 and their hot coupling was carried out as already described, thus obtaining a Fabric/Polyurethane Film/Fabric coupled product with the two fabric flaps hot-melted together thanks to the polyurethane film placed in between.
  • the coupled product was allowed to rest for 48 h at room temperature before using it for further testing.
  • Polyester Jersey - 95% polyester, 5% linear Elastane • Polyamide: Lycra - 80% polyamide, 20% Elastane
  • the fabrics selected for the coupling procedure are only one example of application but do not limit the validity of the polyurethanes subject-matter of the present invention to the fabrics tested only.
  • Table-2 shows the coupled products made.
  • Table-2 Fabric/Polyurethane film/Fabric coupled products. The coupling was carried out at 140°C, with a pressure of 6 bars and a holding time of 20 seconds per application.
  • Fabric/Polyurethane film/Fabric coupled product of about 10 cm 2 was placed in a 100 mL flask equipped with a magnetic stirrer, and then 60 mL of water-based treatment mixture of the polyurethane, with the characteristics as set forth in the examples themselves, was added.
  • the flask was placed in an oil bath on a heating and stirring plate. Stirring was turned on at 200 rpm and then the oil bath was brought to the temperature and for the time specified in the examples themselves, in order to test the removability of the polyurethanes and the consequent release of the two previously coupled tissue flaps.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention a pour objet l'utilisation de polyols de polyester spécifiques en tant que phase molle dans la préparation d'adhésifs polyuréthane amovibles ; l'invention a également pour objet un procédé d'élimination desdits adhésifs polyuréthane et leur utilisation, en particulier mais de façon non limitative, pour l'industrie textile.
PCT/IB2024/056084 2023-06-22 2024-06-21 Utilisation de polyols de polyester spécifiques en tant que phase molle pour la préparation d'adhésifs polyuréthane amovibles et utilisation desdits adhésifs Pending WO2024261718A1 (fr)

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IT102023000012945A IT202300012945A1 (it) 2023-06-22 2023-06-22 Uso di specifici polioli poliesteri come fase soft per poliuretani facilmente degradabili e poliuretani degradabili così ottenuti

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WO1999064491A1 (fr) * 1998-06-05 1999-12-16 Polyganics B.V. Polyurethanne biomedical; obtention et utilisation
EP2251368A1 (fr) * 2008-03-04 2010-11-17 Mitsui Chemicals, Inc. Résine polyester, son procédé de fabrication et ses utilisations
WO2014147220A1 (fr) * 2013-03-22 2014-09-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. Composition adhésive à base d'un polyester d'uréthane et polyester d'uréthane
CN108148173A (zh) * 2017-12-18 2018-06-12 苏州浩洋聚氨酯科技有限公司 生物可降解医用聚氨酯及其制备方法
WO2018140912A1 (fr) * 2017-01-30 2018-08-02 Lubrizol Advanced Materials, Inc. Polyuréthannes thermoplastiques biodégradables et/ou bioabsorbables
CN110982474A (zh) * 2019-12-20 2020-04-10 北京工商大学 一种基于化学循环法制备可生物降解聚酯类胶黏剂的方法
WO2020124120A1 (fr) * 2018-12-21 2020-06-25 Polynovo Biomaterials Pty Limited Polyuréthanes biodégradables orientés
CN112225873A (zh) * 2020-09-15 2021-01-15 万华化学集团股份有限公司 一种高透明快成型的可降解热塑性聚氨酯弹性体及其制备方法
WO2021249749A1 (fr) * 2020-06-09 2021-12-16 Basf Se Procédé de recyclage d'articles collés
US20220403219A1 (en) * 2019-11-15 2022-12-22 Basf Se Moisture-curable polyurethane hotmelt adhesive having high initial strength
WO2023242421A1 (fr) * 2022-06-17 2023-12-21 Basf Se Matériaux pu compacts décollables

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4804691A (en) * 1987-08-28 1989-02-14 Richards Medical Company Method for making a biodegradable adhesive for soft living tissue
WO1999064491A1 (fr) * 1998-06-05 1999-12-16 Polyganics B.V. Polyurethanne biomedical; obtention et utilisation
EP2251368A1 (fr) * 2008-03-04 2010-11-17 Mitsui Chemicals, Inc. Résine polyester, son procédé de fabrication et ses utilisations
WO2014147220A1 (fr) * 2013-03-22 2014-09-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. Composition adhésive à base d'un polyester d'uréthane et polyester d'uréthane
WO2018140912A1 (fr) * 2017-01-30 2018-08-02 Lubrizol Advanced Materials, Inc. Polyuréthannes thermoplastiques biodégradables et/ou bioabsorbables
CN108148173A (zh) * 2017-12-18 2018-06-12 苏州浩洋聚氨酯科技有限公司 生物可降解医用聚氨酯及其制备方法
WO2020124120A1 (fr) * 2018-12-21 2020-06-25 Polynovo Biomaterials Pty Limited Polyuréthanes biodégradables orientés
US20220403219A1 (en) * 2019-11-15 2022-12-22 Basf Se Moisture-curable polyurethane hotmelt adhesive having high initial strength
CN110982474A (zh) * 2019-12-20 2020-04-10 北京工商大学 一种基于化学循环法制备可生物降解聚酯类胶黏剂的方法
WO2021249749A1 (fr) * 2020-06-09 2021-12-16 Basf Se Procédé de recyclage d'articles collés
CN112225873A (zh) * 2020-09-15 2021-01-15 万华化学集团股份有限公司 一种高透明快成型的可降解热塑性聚氨酯弹性体及其制备方法
WO2023242421A1 (fr) * 2022-06-17 2023-12-21 Basf Se Matériaux pu compacts décollables

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