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WO2013034867A1 - Improvement of the physical properties of polyurethane polymers - Google Patents

Improvement of the physical properties of polyurethane polymers Download PDF

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Publication number
WO2013034867A1
WO2013034867A1 PCT/FR2012/052011 FR2012052011W WO2013034867A1 WO 2013034867 A1 WO2013034867 A1 WO 2013034867A1 FR 2012052011 W FR2012052011 W FR 2012052011W WO 2013034867 A1 WO2013034867 A1 WO 2013034867A1
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Prior art keywords
compound
formula
polyurethane
chain extender
diol
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PCT/FR2012/052011
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French (fr)
Inventor
Georges Da Costa
Valérie DE SIMONE
Hervé Rolland
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Cecalc
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Publication of WO2013034867A1 publication Critical patent/WO2013034867A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-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
    • C08G18/3221—Polyhydroxy compounds hydroxylated esters of carboxylic acids other than higher fatty 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3324—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • 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
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/126—Copolymers block
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another

Definitions

  • the present invention relates to polyurethane polymers used as adhesive agents, coating agents, sealants or elastomers.
  • elastomeric polymers often implements chain extending compounds whose function is to improve certain physical properties of the final polymer, such as its hardness, heat resistance or resistance to hydrolysis.
  • chain extenders most used in the preparation of elastomeric polyurethanes are butane-1,4-diol or BDO:
  • the 1,4 butanediol nevertheless suffers from weaknesses for certain applications. For example, it leads to opaque products and is not based on renewable raw materials.
  • Isosorbide is cited in US6946539 as a possible initiator for the preparation of poly (trimethylene ether) glycol.
  • polyether diols, polyesters diols or polycarbonates diols are already widely used as diols and / or as chain extenders for reacting with isocyanates to prepare polyurethanes which are used in CASE applications (Coating, Adhesive, Sealant, Elastomer in English).
  • One of the objectives of the object of the present invention is to solve in particular the following problems:
  • An object of the present invention is to overcome all or part of the disadvantages of the prior art noted above.
  • the subject of the present invention is a compound of formula (I):
  • R 'and R " H, CH 3 , CH 2 -CH 3 or trimethylcyclohexane
  • n is an integer between 4 and 8, preferentially between 5 and 6, y + x> 0,
  • embodiments of the invention may include one or more of the following features:
  • the present invention also relates to a process for the preparation of a compound of formula (I) as defined above comprising at least the step of: a) reaction of a compound of formula (II):
  • Step a) of the process according to the present invention is preceded by a step of preparing an alkoxylated derivative of bisphenol of formula (II):
  • R is selected from the group consisting of hydrogen, methyl and ethyl
  • R 'and R " which are identical or different, represent, independently of one another, a hydrogen atom, a methyl radical or an ethyl radical;
  • the product of formula (IV) may be chosen from:
  • the product of formula (IV) is chosen from bisphenol A, bisphenol S, bisphenol F and bisphenol TMC.
  • the subject of the invention is a process as defined above in which the product (A) is chosen from ethylene oxide, propylene oxide and butylene oxide. , and their mixtures.
  • the propylene oxide is used.
  • embodiments of the invention may include one or more of the following features: - -
  • the molar ratio of the compound of formula (II) to the compound of formula (III) is between 1 / 0.5 and 1/20, preferably the ratio is between 1 / 1 and 1/3.
  • catalyst is tin octoate of formula Sn (Oct) 2 or tetra-n-butyltitanate of formula n-Bu 4 TiO 4 .
  • the present invention also relates to the use of the compound as defined above, as a chain extender in a polyurethane elastomer formulation.
  • the present invention also relates to a process for preparing a polyurethane elastomer formulation from isocyanate prepolymers and an effective amount of chain extender, characterized in that said chain extender is the compound such as than previously defined.
  • the present invention also relates to the use of the compound as defined above, as a monomer in the preparation of saturated or unsaturated polyesters, polycarbonates or epoxy resins.
  • the present invention also relates to a polyurethane polymer comprising a chain extender, characterized in that said chain extender is the compound as defined above.
  • the present invention also relates to the use of polyurethane polymer as defined above as an adhesive agent.
  • Hot melt adhesives are based on thermoplastic polymers. These polymers are solid at room temperature, heating makes it possible to obtain viscous liquid products which can therefore be applied as a melt. The application of hot melt adhesives is carried out at temperatures from
  • hot melt adhesive agents are so-called "reactive" adhesives.
  • Non-reactive hot melt adhesives have poor temperature resistance because after heating they soften or melt again.
  • the polyurethane compositions are excellently suitable for hot melt adhesives. They are often called PU-RHM ("PolyUrethane-Hot Melt Reactive" in English). They generally consist of polyurethane polymers having isocyanate groups and obtained by reaction of suitable polyols with an excess of diisocyanates.
  • Polyurethane hot melt adhesives have good adhesion to many materials, including materials having a good polar characteristic. On the other hand, the bonding of steel or apolar plastics is more problematic. However, the polyurethane agents obtained according to the present invention have the particularity of providing good adhesion properties on these materials.
  • the adhesion properties therefore depend on the structures of the polyols, isocyanates and additives used.
  • the reactive polyurethane adhesives are used mainly for laminating plastic films; packaging complexes polyethylene, polypropylene, polyamide, polyester, etc. ; PVC plasticized on wood, panels, metal; the building: manufacture of sandwich panels; structural bonding of reinforced plastics (SMC); glass-to-metal bonding (windshields), with partially flexible sealants; collages of various plastics; sticking of wood, panels, rigid insulating foams. - -
  • thermoplastic polyurethane adhesives in solution or in emulsion, used either in double sizing as contact glues (for gluing shoe soles for example); or by reactivation of the glue film after application and drying (for example: gluing of car parts or panels in the furniture).
  • Example 2 Bisphenol A + 2 OP (Dianol 320) + 2.6 moles of ⁇ -caprolactone.
  • Example 3 Bisphenol A + 2 OB + 2.6 moles of ⁇ -caprolactone.
  • Polyurethane elastomer materials are generally obtained by reaction:
  • TDI toluene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • HDI hexyldi-isocyanate
  • a long diol or mixture of long diols such as, for example, a polyether polyol, a polyester polyol, or a polybutadiene polyol;
  • the invention also relates to a process for preparing a polyurethane elastomer formulation from an isocyanate prepolymer and an effective amount of chain extender, characterized in that said lengthening agent of chains is the composition as defined above.
  • a pre-polymer pass process is employed. This is a two-step reaction. During the first stage we - reacting the long diol or mixture of long diols with an excess diisocyanate to obtain a "pre-polymer" having isocyanate functions.
  • essentially linear diols are used which, except for the hydroxyl groups at the ends, bear no other group reactive with isocyanates.
  • These diols have a molecular weight between 500 and 10,000 g / mol, preferably 700 and 5000 g / mol, with the special preference for the range of 1000 to 3000 g / mol. Molecular weight is meant as average molecular weight.
  • Polyesters for example polyethylene glycol, polypropylene glycol and / or poly-tetra-methylene glycol, are preferably used.
  • Poly-tetramethylene glycol also known as poly-tetrahydrofuran, can be produced by ionic polymerization of tetrahydrofuran with acid catalysts.
  • Suitable copolymers are also obtained by polymerizing tetrahydrofuran with a mixture of propylene oxide, ethylene oxide and glycols. This process is one of the most used and many commercial prepolymers are proposed, such as VIBRATHANE TM, BAYTEC TM, SUPRASEC TM, etc.
  • An isocyanate prepolymer is characterized by its percentage of NCO.
  • the "quasi prepolymer” process is similar to the “prepolymer” process, but in this case only a part of the long diol is reacted and not all of it.
  • All PUs contain the urethane unit: NHCO 2 , which results from the reaction of the isocyanate (NCO) (in general these NCO functions are at the origin of the adhesive properties of PU) with hydroxyl end groups (OH ). They are block copolymers with alternating rigid segments and flexible segments.
  • the hard phases, or segments, are created by the reaction of a diisocyanate with a short chain of dialcol (or glycol) (or extender of - - string). This results in a very strong urethane pattern, which is characteristic of hard elements, composed of repeating groups of diisocyanates and short dialkyl chains.
  • the flexible and flexible elements are generally polyalcohols ether or ester dispersed in the polymer chain and connected to the macromolecule by urethane units (NHCO 2 ). These flexible elements consist of repeating groups of diisocyanate and a long chain of dialcol (or polyalcohol).
  • the proportion and the molecular structure of these segments determine the specific characteristics of the various qualities of PU, ranging from rigid materials to flexible materials, extremely flexible.
  • the type and / or the relative percentage of the three basic constituent elements are modified: diisocyanate, polyalcohol and chain extender.
  • the morphology of the hard / soft phases is decisive for the toughness of the PUs. It is believed that it is the intramolecular and intermolecular hydrogen bonding that enhances the physical strength of a PU, but it is generally accepted that the length of the rigid segment, its volume fraction in the polymer and its "solubility" with the flexible segment are determining the resistance to stress and elongation of PUs. A percentage of hard segments too large will provide very brittle properties to the polymer.
  • Voranol 2000 L Polypropylene glycol molecular weight 2000 g / mol
  • Caprolactone (CAPA) (Molecular Weight ⁇ 700 g / mol)
  • ABS Thermoplastic Acrylonitrile Butadiene Styrene
  • AF it is about a rupture concerning the seal of glue, said rupture of adhesion (indeed a rupture of the adhesion between the surface of the support and the external surface of the layer of glue previously spread on the support is produced then).
  • CF this is a break with regard to the glue joint, known as cohesive failure (rupture occurs within the glue layer itself but the outer surface of the glue layer remains firmly bonded to the substrate).
  • prepolymer No. 1 which has not been prepared from alkoxylated bisphenol, unlike the prepolymers according to the present invention, does not have the same guarantees in terms of adhesive qualities.
  • the prepolymers prepared according to the present invention are not only good adhesives but in addition, there is a synergistic effect due to the combination of the alkoxylated bisphenol (product (II)) associated with caprolactone (product (III)).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

A compound of formula (I), in which: R = H, CH3 or CH2-CH3, R' and R" = H, CH3, CH2-CH3 or trimethylcyclohexane, n is an integer between 4 and 8, preferentially between 5 and 6, y + x > 0, a + b > 0.

Description

AMELIORATION DES PROPRIETES PHYSIQUES DE POLYMERES  IMPROVING THE PHYSICAL PROPERTIES OF POLYMERS
POLYURETHANES  Polyurethane
[0001] La présente invention concerne des polymères de polyuréthane mis en œuvre en tant qu'agents adhésifs, agents de revêtement, agents d'étanchéité ou élastomères. The present invention relates to polyurethane polymers used as adhesive agents, coating agents, sealants or elastomers.
[0002] La préparation de polymères élastomères met souvent en œuvre les composés allongeurs de chaînes qui ont pour fonction d'améliorer certaines propriétés physiques du polymère final, comme sa dureté, sa résistance à la chaleur ou sa résistance à l'hydrolyse.  The preparation of elastomeric polymers often implements chain extending compounds whose function is to improve certain physical properties of the final polymer, such as its hardness, heat resistance or resistance to hydrolysis.
[0003] Les allongeurs de chaînes les plus utilisés dans la préparation des polyuréthanes élastomères sont le butane-1 ,4-diol ou BDO :
Figure imgf000002_0001
The chain extenders most used in the preparation of elastomeric polyurethanes are butane-1,4-diol or BDO:
Figure imgf000002_0001
le 1 ,4-bis[(2-hydroxy-éthyl)oxy]benzène ou HQEE : 1,4-bis [(2-hydroxyethyl) oxy] benzene or HQEE:
Figure imgf000002_0002
Figure imgf000002_0002
ou le résorcinol diéthoxylé or resorcinol diethoxylated
Figure imgf000002_0003
Figure imgf000002_0003
[0004] L'utilisation de HQEE ou de HER par rapport au 1 ,4 Butanediol apporte à l'élastomère une plus grande dureté de part la géométrie de la molécule, mais également une meilleure résistance à la chaleur et à l'hydrolyse. — — The use of HQEE or HER with respect to 1, 4 butanediol gives the elastomer a greater hardness from the geometry of the molecule, but also a better resistance to heat and hydrolysis. - -
[0005] Malgré les bonnes performances mécaniques qu'il confère, le 1 ,4 butanediol souffre néanmoins de faiblesses pour certaines applications. Par exemple, il conduit à des produits opaques et n'est pas basé sur des matières premières renouvelables. Despite the good mechanical performance it gives, the 1,4 butanediol nevertheless suffers from weaknesses for certain applications. For example, it leads to opaque products and is not based on renewable raw materials.
[0006] La préparation et l'utilisation d'un mélange eutectique HER/Dianol 220® (i.e. le bisphénol A diéthoxylé) comme allongeur de chaînes sont décrites dans la demande EP 1496074. The preparation and use of a eutectic HER / Dianol 220 ® mixture (ie diethoxylated bisphenol A) as chain extender are described in EP 1496074.
[0007] Les avantages d'utilisation de la HER comme allongeur de chaînes dans les polyuréthanes sont mis en avant dans les publications « Lower Durometer TDI elastomers HER extended plasticizer free » - INDSPEC - PMA-CUMA Meeting Toronto (CA) 4-6 nov. 2001 et « Technical bulletin HER, 08.1997 et Technical bulletin HER UTECH 2000, 03.2000 » - INDSPEC.  The advantages of using HER as chain extender in polyurethanes are highlighted in the publications "Lower Durometer TDI elastomers HER extended plasticizer free" - INDSPEC - PMA-CUMA Meeting Toronto (CA) 4-6 Nov 2001 and "Technical bulletin HER, 08.1997 and Technical bulletin HER UTECH 2000, 03.2000" - INDSPEC.
[0008] Les exemples décrits dans la demande de brevet US2006/0293486 décrivent le 1 ,4 butanediol comme allongeur de chaînes.  The examples described in patent application US2006 / 0293486 describe 1,4 butanediol as chain extender.
[0009] Dans la demande de brevet US2007/0073030 est décrite l'originalité d'utilisation de diamines ou diimines comme allongeurs de chaînes dans le domaine des polyuréthanes.  In the patent application US2007 / 0073030 is described the originality of use of diamines or diimines as chain extenders in the field of polyurethanes.
[0010] L'isosorbide est cité, dans le brevet US6946539, comme initiateur possible pour la préparation du poly(triméthylène éther)glycol.  Isosorbide is cited in US6946539 as a possible initiator for the preparation of poly (trimethylene ether) glycol.
[0011] Il y a donc un besoin d'élaborer un allongeur de chaînes apportant une solution aux problèmes vus ci-dessus, tout en conférant des propriétés mécaniques équivalentes ou supérieures à celles obtenues jusqu'à présent en utilisant les allongeurs de chaînes existants sur le marché.  There is therefore a need to develop a chain extender providing a solution to the problems seen above, while imparting mechanical properties equivalent to or better than those obtained so far by using the extender chains existing on the market.
[0012] D'autre part, les polyéthers diols, polyesters diols ou polycarbonates diols sont déjà largement utilisés comme diols et/ou comme allongeurs de chaînes pour réagir avec des isocyanates afin de préparer des polyuréthanes qui sont utilisés dans des applications CASE (Coating, Adhesive, Sealant, Elastomer en anglais).  On the other hand, polyether diols, polyesters diols or polycarbonates diols are already widely used as diols and / or as chain extenders for reacting with isocyanates to prepare polyurethanes which are used in CASE applications (Coating, Adhesive, Sealant, Elastomer in English).
[0013] Aujourd'hui les diols et/ou allongeurs de chaînes connus les plus performants sont : Today the most effective known diols and / or chain extenders are:
des polypropylènes glycols et des polyéthylènes glycols dans le cas des applications des polyuréthanes en tant qu'agents adhésifs  polypropylenes glycols and polyethylenes glycols in the case of polyurethane applications as adhesive agents
du 1 ,4-butanediol dans le cas des polyuréthanes utilisés comme élastomères. — — 1,4-butanediol in the case of polyurethanes used as elastomers. - -
[0014] Un des objectifs de l'objet de la présente invention est de résoudre en particulier les problèmes suivants: One of the objectives of the object of the present invention is to solve in particular the following problems:
mettre en œuvre des agents adhésifs de type polyuréthane ayant des propriétés adhésives améliorées par rapport aux agents adhésifs de type polyuréthane de l'état de la technique;  implementing polyurethane adhesive agents having improved adhesive properties over polyurethane adhesive agents of the state of the art;
disposer d'élastomères et/ou de revêtements polyuréthanes ayant des propriétés thermiques et de résistance à l'hydrolyse améliorées par rapport aux agents adhésifs de type polyuréthane de l'état de la technique.  provide elastomers and / or polyurethane coatings having improved thermal and hydrolysis resistance properties compared to the polyurethane adhesive agents of the state of the art.
[0015] Un but de la présente invention est de pallier tout ou partie des inconvénients de l'art antérieur relevés ci-dessus. An object of the present invention is to overcome all or part of the disadvantages of the prior art noted above.
[0016] A cette fin, la présente invention a pour objet un composé de formule (I) :  For this purpose, the subject of the present invention is a compound of formula (I):
Figure imgf000004_0001
Figure imgf000004_0001
(I). (I).
dans laquelle:in which:
Figure imgf000004_0002
Figure imgf000004_0002
R' et R" = H, CH3, CH2-CH3 ou triméthylcyclohexane, R 'and R "= H, CH 3 , CH 2 -CH 3 or trimethylcyclohexane,
n est un nombre entier compris entre 4 et 8, préférentiellement entre 5 et 6, y + x > 0, n is an integer between 4 and 8, preferentially between 5 and 6, y + x> 0,
a + b > 0. a + b> 0.
[0017] Par ailleurs, des modes de réalisation de l'invention peuvent comporter l'une ou plusieurs des caractéristiques suivantes : Furthermore, embodiments of the invention may include one or more of the following features:
Composé tel que défini ci-dessus caractérisé en ce que x + y est compris entre 2 et 5.  Compound as defined above characterized in that x + y is between 2 and 5.
Composé tel que défini ci-dessus caractérisé en ce que x + y = 2.  Compound as defined above characterized in that x + y = 2.
Composé tel que défini ci-dessus caractérisé en ce que a + b est compris entre 2 et 9.  Compound as defined above characterized in that a + b is between 2 and 9.
Composé tel que défini ci-dessus caractérisé en ce que R' = R" = CH3. — — Compound as defined above characterized in that R '= R "= CH 3 . - -
Composé tel que défini ci-dessus caractérisé en ce que R = CH3. Compound as defined above characterized in that R = CH 3 .
[0018] La présente invention a également pour objet un procédé de préparation d'un composé de formule (I) tel que défini ci-dessus comprenant au moins l'étape : a) réaction d'un composé de formule (II) : The present invention also relates to a process for the preparation of a compound of formula (I) as defined above comprising at least the step of: a) reaction of a compound of formula (II):
Figure imgf000005_0001
Figure imgf000005_0001
R, R' et R" ayant la même définition que dans les revendications précédentes, avec un composé de formule (III) :  R, R 'and R "having the same definition as in the preceding claims, with a compound of formula (III):
O  O
O O
en présence d'un catalyseur. in the presence of a catalyst.
[0019] L'étape a) du procédé selon la présente invention est précédée d'une étape de préparation d'un dérivé alcoxylé du bisphénol de formule (II) : Step a) of the process according to the present invention is preceded by a step of preparing an alkoxylated derivative of bisphenol of formula (II):
Figure imgf000005_0002
Figure imgf000005_0002
dans laquelle R', R", R, x et y sont tels que définis précédemment, in which R ', R ", R, x and y are as defined above,
comprenant au moins l'étape : comprising at least the step:
de réaction d'un oxyde d'alkylène de formule (A) reaction of an alkylene oxide of formula (A)
R  R
7  7
O  O
(A),  (AT),
dans laquelle R est choisi parmi le groupe constitué par un atome d'hydrogène, un radical méthyle et un radical éthyle ; wherein R is selected from the group consisting of hydrogen, methyl and ethyl;
avec un dérivé du bisphénol de formule (IV) :
Figure imgf000006_0001
with a bisphenol derivative of formula (IV):
Figure imgf000006_0001
dans laquelle R' et R" identiques ou différents, représentent indépendamment l'un de l'autre un atome d'hydrogène, un radical méthyle ou un radical éthyle;  in which R 'and R ", which are identical or different, represent, independently of one another, a hydrogen atom, a methyl radical or an ethyl radical;
en présence d'un catalyseur et d'un solvant,  in the presence of a catalyst and a solvent,
[0020] Par exemple, le produit de formule (IV) peut être choisi parmi :  For example, the product of formula (IV) may be chosen from:
Figure imgf000006_0002
— —
Figure imgf000006_0002
- -
Figure imgf000007_0001
Figure imgf000007_0001
[0021] De manière préférée, le produit de formule (IV) est choisi parmi le bisphénol A, le bisphénol S, le bisphénol F et le bisphénol TMC. Preferably, the product of formula (IV) is chosen from bisphenol A, bisphenol S, bisphenol F and bisphenol TMC.
[0022] Selon un mode particulier, l'invention a pour objet un procédé tel que défini ci-dessus dans lequel le produit (A) est choisi parmi l'oxyde d'éthylène, l'oxyde de propylène, l'oxyde de butylène, et leurs mélanges. De préférence, l'oxyde de propylène est mis en œuvre.  According to a particular embodiment, the subject of the invention is a process as defined above in which the product (A) is chosen from ethylene oxide, propylene oxide and butylene oxide. , and their mixtures. Preferably, the propylene oxide is used.
[0023] Par ailleurs, des modes de réalisation de l'invention peuvent comporter l'une ou plusieurs des caractéristiques suivantes : — — Furthermore, embodiments of the invention may include one or more of the following features: - -
Procédé tel que défini ci-dessus caractérisé en ce que le rapport molaire du composé de formule (II) sur le composé de formule (III) est compris entre 1/0,5 et 1/20, de préférence le rapport est compris entre 1/1 et 1/3. Process as defined above characterized in that the molar ratio of the compound of formula (II) to the compound of formula (III) is between 1 / 0.5 and 1/20, preferably the ratio is between 1 / 1 and 1/3.
Procédé tel que défini ci-dessus caractérisé en ce que ledit catalyseur est l'octoate d'étain de formule Sn(Oct)2 ou le tétra-n-butyltitanate de formule n-Bu4TiO4. Process as defined above characterized in that said catalyst is tin octoate of formula Sn (Oct) 2 or tetra-n-butyltitanate of formula n-Bu 4 TiO 4 .
[0024] La présente invention a également pour objet l'utilisation du composé tel que défini précédemment, comme allongeur de chaîne dans une formulation élastomère de polyuréthane.  The present invention also relates to the use of the compound as defined above, as a chain extender in a polyurethane elastomer formulation.
[0025] La présente invention a également pour objet un procédé de préparation d'une formulation élastomère de polyuréthane à partir de prépolymère isocyanates et d'une quantité efficace d'allongeur de chaîne, caractérisé en ce que ledit allongeur de chaîne est le composé tel que défini précédemment.  The present invention also relates to a process for preparing a polyurethane elastomer formulation from isocyanate prepolymers and an effective amount of chain extender, characterized in that said chain extender is the compound such as than previously defined.
[0026] La présente invention a également pour objet l'utilisation du composé tel que défini précédemment, comme monomère dans la préparation de polyesters saturés ou insaturés, de polycarbonates ou de résines époxy.  The present invention also relates to the use of the compound as defined above, as a monomer in the preparation of saturated or unsaturated polyesters, polycarbonates or epoxy resins.
[0027] La présente invention a également pour objet un polymère de polyuréthane comprenant un allongeur de chaîne, caractérisé en ce que ledit allongeur de chaîne est le composé tel que défini précédemment.  The present invention also relates to a polyurethane polymer comprising a chain extender, characterized in that said chain extender is the compound as defined above.
[0028] La présente invention a également pour objet l'utilisation de polymère polyuréthane tel que défini ci-dessus comme agent adhésif.  The present invention also relates to the use of polyurethane polymer as defined above as an adhesive agent.
[0029] Les agents adhésifs thermofusibles (« hot melt » en langue anglaise) sont basés sur des polymères thermoplastiques. Ces polymères sont solides à température ambiante, le chauffage permet d'obtenir des produits liquides visqueux qui peuvent donc être appliqués comme une masse fondue. L'application des agents adhésifs thermofusibles s'effectue à des températures à partir de Hot melt adhesives ("hot melt" in English) are based on thermoplastic polymers. These polymers are solid at room temperature, heating makes it possible to obtain viscous liquid products which can therefore be applied as a melt. The application of hot melt adhesives is carried out at temperatures from
85°C. Suite à un refroidissement à température ambiante, ils se solidifient engendrant ainsi de la force d'adhérence. 85 ° C. Following cooling at room temperature, they solidify, thus generating adhesion strength.
[0030] En général les agents adhésifs thermofusibles sont des adhésifs dits « réactifs ». Les agents adhésifs thermofusibles non réactifs ont une mauvaise résistance à la température car après chauffage ils se ramollissent ou fondent à nouveau. — — In general, hot melt adhesive agents are so-called "reactive" adhesives. Non-reactive hot melt adhesives have poor temperature resistance because after heating they soften or melt again. - -
[0031] En outre, les thermofusibles classiques adhésifs ont souvent tendance à glisser, même à des températures bien en dessous du point de ramollissement (flux froid). In addition, conventional hot melt adhesives often tend to slip, even at temperatures well below the softening point (cold flow).
[0032] Ces inconvénients ont été sensiblement éliminés dans le cas des agents adhésifs thermofusibles dits réactifs par l'introduction dans la structure polymère de groupements réactifs, par exemple un groupement isocyanate pour les adhésifs polyuréthanes réactifs, procurant une réticulation avec l'eau du support ou l'effet de la température.  These disadvantages have been substantially eliminated in the case of hot melt adhesive agents called reactive by the introduction into the polymeric structure of reactive groups, for example an isocyanate group for reactive polyurethane adhesives, providing a crosslinking with the support water. or the effect of temperature.
[0033] En particulier, les compositions de polyuréthane conviennent de façon excellente pour les colles thermofusibles. Ils sont souvent appelés PU-RHM (« PolyUrethane-Hot Melt Reactive » en langue anglaise). Ils sont généralement constitués de polymères de polyuréthane, ayant des groupes isocyanate et obtenus par réaction de polyols adaptés avec un excès de diisocyanates.  In particular, the polyurethane compositions are excellently suitable for hot melt adhesives. They are often called PU-RHM ("PolyUrethane-Hot Melt Reactive" in English). They generally consist of polyurethane polymers having isocyanate groups and obtained by reaction of suitable polyols with an excess of diisocyanates.
[0034] Après leur application, ils vont rapidement engendrer et construire une grande force d'adhérence par refroidissement et acquièrent leurs propriétés finales, en particulier leur résistance à la distorsion thermique et aux influences environnementales, par réaction du groupement isocyanate en excès avec l'humidité. After their application, they will quickly generate and build a large adhesive strength by cooling and acquire their final properties, in particular their resistance to thermal distortion and environmental influences, by reaction of the excess isocyanate group with the humidity.
[0035] Les agents adhésifs thermofusibles polyuréthane ont une bonne adhérence sur de nombreux matériaux, notamment des matériaux présentant une bonne caractéristique polaire. En revanche le collage de l'acier ou de plastiques apolaires est plus problématique. Or les agents polyuréthanes obtenus selon la présente invention présentent la particularité de procurer de bonnes propriétés d'adhérence sur ces matériaux.  Polyurethane hot melt adhesives have good adhesion to many materials, including materials having a good polar characteristic. On the other hand, the bonding of steel or apolar plastics is more problematic. However, the polyurethane agents obtained according to the present invention have the particularity of providing good adhesion properties on these materials.
[0036] Les propriétés d'adhérence dépendent donc des structures des polyols, isocyanates et additifs utilisés.  The adhesion properties therefore depend on the structures of the polyols, isocyanates and additives used.
[0037] Les adhésifs polyuréthanes réactifs sont utilisés principalement pour le contre-collage de films plastiques ; les complexes d'emballages polyéthylène, polypropylène, polyamide, polyester, etc. ; les PVC plastifiés sur bois, panneaux, métal ; le bâtiment : fabrication de panneaux-sandwiches divers ; les collages structuraux de plastiques renforcés (SMC) ; le collage verre sur métal (pare- brises), avec des mastics partiellement souples ; les collages de plastiques divers ; le collage de bois, panneaux, mousses isolantes rigides. — — [0037] The reactive polyurethane adhesives are used mainly for laminating plastic films; packaging complexes polyethylene, polypropylene, polyamide, polyester, etc. ; PVC plasticized on wood, panels, metal; the building: manufacture of sandwich panels; structural bonding of reinforced plastics (SMC); glass-to-metal bonding (windshields), with partially flexible sealants; collages of various plastics; sticking of wood, panels, rigid insulating foams. - -
[0038] Il existe aussi des adhésifs polyuréthanes thermoplastiques en solution ou en émulsion, utilisés soit en double encollage comme des colles contact (pour le collage de semelles de chaussures par exemple) ; soit par réactivation à la chaleur du film de colle après application et séchage (par exemple : collage de garniture de pièces de voitures ou de panneaux dans le meuble). There are also thermoplastic polyurethane adhesives in solution or in emulsion, used either in double sizing as contact glues (for gluing shoe soles for example); or by reactivation of the glue film after application and drying (for example: gluing of car parts or panels in the furniture).
[0039] Les exemples qui suivent permettent d'illustrer davantage l'objet de la présente invention. The following examples illustrate further the object of the present invention.
Exemple 1 : Bisphénol A + 2 OE (Dianol 220) + 2,6 moles de ε-caprolactone.  Example 1 Bisphenol A + 2 EO (Dianol 220) + 2.6 moles of ε-caprolactone.
Figure imgf000010_0001
Figure imgf000010_0001
[0040] Protocole opératoire : [0040] Operating protocol:
Séchage de 1 mole de Dianol 220 (BPA + 2 OE (oxyde d'éthylène)) jusqu'à une teneur inférieure à 0,1 % en eau.  Drying of 1 mole of Dianol 220 (BPA + 2 EO (ethylene oxide)) to a content of less than 0.1% in water.
Ajout du catalyseur : 100 ppm de tétra-n-butyltitanate (TNBT).  Addition of the catalyst: 100 ppm of tetra-n-butyltitanate (TNBT).
Addition de 2,6 moles de caprolactone en 45 minutes à 160°C.  Addition of 2.6 moles of caprolactone in 45 minutes at 160 ° C.
Arrêt de la réaction au bout de 6 heures.  Stopping the reaction after 6 hours.
Exemple 2 : Bisphénol A + 2 OP (Dianol 320) + 2,6 moles de ε-caprolactone. Example 2: Bisphenol A + 2 OP (Dianol 320) + 2.6 moles of ε-caprolactone.
[0041] Les quantités utilisées et leurs stœchiométries sont exprimées dans le tableau suivant The quantities used and their stoichiometries are expressed in the following table
Figure imgf000010_0002
Figure imgf000010_0002
[0042] Protocole opératoire : [0042] Operating protocol:
Séchage de 1 mole de Dianol 320 (BPA + 2 OP (oxyde de propylène)) jusqu'à une teneur inférieure à 0,1 % en eau.  Drying of 1 mole of Dianol 320 (BPA + 2 OP (propylene oxide)) to a content of less than 0.1% in water.
Ajout du catalyseur : 100 ppm de tétra-n-butyltitanate (TNBT).  Addition of the catalyst: 100 ppm of tetra-n-butyltitanate (TNBT).
Addition de 2,6 moles de caprolactone en 45 minutes à 160°C.  Addition of 2.6 moles of caprolactone in 45 minutes at 160 ° C.
Arrêt de la réaction au bout de 6 heures. — — Stopping the reaction after 6 hours. - -
Exemple 3 : Bisphénol A + 2 OB + 2,6 moles de ε-caprolactone. Example 3: Bisphenol A + 2 OB + 2.6 moles of ε-caprolactone.
[0043] Les quantités utilisées et leurs stœchiométries sont exprimées dans le tableau suivant :  The amounts used and their stoichiometries are expressed in the following table:
Figure imgf000011_0001
Figure imgf000011_0001
[0044] Protocole opératoire :  [0044] Operating protocol:
Séchage de 1 mole de BPA + 2 OB (oxyde de butylène) jusqu'à une teneur inférieure à 0,1 % en eau.  Drying of 1 mole of BPA + 2 OB (butylene oxide) to a content of less than 0.1% in water.
Ajout du catalyseur : 190 ppm d'octoate d'étain (DABCO T-9).  Addition of the catalyst: 190 ppm of tin octoate (DABCO T-9).
Addition de 2,6 moles de caprolactone en 45 minutes à 160°C.  Addition of 2.6 moles of caprolactone in 45 minutes at 160 ° C.
Arrêt de la réaction au bout de 6 heures.  Stopping the reaction after 6 hours.
Applications : Adhésifs polyuréthanes Applications: Polyurethane Adhesives
[0045] Les matériaux élastomères polyuréthanes sont généralement obtenus par réaction :  Polyurethane elastomer materials are generally obtained by reaction:
d'un di-isocyanate, par exemple TDI (Toluène diisocyanate), MDI (4,4'- diphénylméthane diisocyanate), ou HDI (hexyldi-isocyanate) ;  a di-isocyanate, for example TDI (toluene diisocyanate), MDI (4,4'-diphenylmethane diisocyanate), or HDI (hexyldi-isocyanate);
d'un diol long ou mélange de diols longs, comme par exemple un polyéther polyol, un polyester polyol, ou un polybutadiène polyol ;  a long diol or mixture of long diols, such as, for example, a polyether polyol, a polyester polyol, or a polybutadiene polyol;
d'un allongeur de chaîne ;  a chain extender;
agent débullant, de catalyseurs et autres additifs.  debulking agent, catalysts and other additives.
[0046] Selon un autre aspect, l'invention a aussi pour objet, un procédé de préparation d'une formulation élastomère de polyuréthane à partir de prépolymère isocyanate et d'une quantité efficace d'allongeur de chaînes, caractérisé en ce que ledit allongeur de chaînes est la composition telle que définie précédemment. According to another aspect, the invention also relates to a process for preparing a polyurethane elastomer formulation from an isocyanate prepolymer and an effective amount of chain extender, characterized in that said lengthening agent of chains is the composition as defined above.
[0047] Pour obtenir des matériaux élastomères polyuréthanes, plusieurs procédés distincts sont possibles : To obtain elastomeric polyurethane materials, several different processes are possible:
un procédé dit « one-shot » est envisageable ; au cours de ce procédé tous les composants cités ci-dessus sont ajoutés en une seule étape ;  a so-called "one-shot" process is possible; during this process all the components mentioned above are added in a single step;
de manière préférée, un procédé avec passage par un pré-polymère est employé. Il s'agit d'une réaction en deux étapes. Au cours de la première étape on — — fait réagir le diol long ou mélange de diols longs avec un diisocyanate en excès pour obtenir un « Pré-polymère » possédant des fonctions isocyanates. preferably, a pre-polymer pass process is employed. This is a two-step reaction. During the first stage we - reacting the long diol or mixture of long diols with an excess diisocyanate to obtain a "pre-polymer" having isocyanate functions.
De préférence, sont utilisés les diols essentiellement linéaires qui, excepté les groupes d'hydroxyle aux extrémités, ne portent aucun autre groupe réagissant avec des isocyanates. Ces diols ont un poids moléculaire compris entre 500 et 10000 g/mol, de préférence 700 et 5000 g/mol, avec la préférence spéciale pour la gamme de 1000 à 3000 g/mol. Le poids moléculaire est signifié comme poids moléculaire moyen. Preferably, essentially linear diols are used which, except for the hydroxyl groups at the ends, bear no other group reactive with isocyanates. These diols have a molecular weight between 500 and 10,000 g / mol, preferably 700 and 5000 g / mol, with the special preference for the range of 1000 to 3000 g / mol. Molecular weight is meant as average molecular weight.
De manière préférée on utilise les polyesters, les polyéthers glycols, les glycols de polyalkylène, par exemple le polyéthylène glycol, le glycol de polypropylène et/ou glycol de poly-tétra-méthylène. Le glycol de Poly-tétra-méthylène, également connu sous le nom de poly-tétra-hydrofurane, peut être produit par polymérisation ionique de tétrahydrofurane avec des catalyseurs acides.  Polyesters, polyether glycols, polyalkylene glycols, for example polyethylene glycol, polypropylene glycol and / or poly-tetra-methylene glycol, are preferably used. Poly-tetramethylene glycol, also known as poly-tetrahydrofuran, can be produced by ionic polymerization of tetrahydrofuran with acid catalysts.
Des copolymères appropriés sont également obtenus en polymérisant le tétrahydrofurane avec un mélange d'oxyde de propylène, d'oxyde d'éthylène et de glycols. Ce procédé est l'un des plus utilisés et de nombreux pré-polymères commerciaux sont proposés, comme par exemple VIBRATHANE™, BAYTEC™, SUPRASEC™, etc. Un pré-polymère isocyanate se caractérise par son pourcentage de NCO.  Suitable copolymers are also obtained by polymerizing tetrahydrofuran with a mixture of propylene oxide, ethylene oxide and glycols. This process is one of the most used and many commercial prepolymers are proposed, such as VIBRATHANE ™, BAYTEC ™, SUPRASEC ™, etc. An isocyanate prepolymer is characterized by its percentage of NCO.
Le procédé « Quasi Pré-polymère » se rapproche du procédé « Prépolymère » mais dans ce cas on ne fait réagir qu'une partie du diol long et non la totalité.  The "quasi prepolymer" process is similar to the "prepolymer" process, but in this case only a part of the long diol is reacted and not all of it.
Structure moléculaire des polyuréthanes (PU) Molecular structure of polyurethanes (PU)
Matières premières Raw materials
[0048] Tous les PU contiennent le motif uréthane : NHCO2, qui résulte de la réaction de l'isocyanate (NCO) (en général ces fonctions NCO sont à l'origine des propriétés adhésives du PU) avec des groupes terminaux hydroxyle (OH). Ce sont des copolymères blocs avec alternance de segments rigides et de segments souples. All PUs contain the urethane unit: NHCO 2 , which results from the reaction of the isocyanate (NCO) (in general these NCO functions are at the origin of the adhesive properties of PU) with hydroxyl end groups (OH ). They are block copolymers with alternating rigid segments and flexible segments.
Réactions chimiques  Chemical reactions
[0049] Les phases dures, ou segments, sont créées par la réaction d'un diisocyanate avec une chaîne courte de dialcol (ou glycol) (ou allongeur de — — chaîne). Ceci entraîne un motif uréthanne très solide, qui est caractéristique des éléments durs, composés de groupes répétitifs de diisocyanates et de chaînes courtes de dialcool. The hard phases, or segments, are created by the reaction of a diisocyanate with a short chain of dialcol (or glycol) (or extender of - - string). This results in a very strong urethane pattern, which is characteristic of hard elements, composed of repeating groups of diisocyanates and short dialkyl chains.
[0050] Les éléments souples et flexibles sont généralement des polyalcools d'éther ou d'ester dispersés dans la chaîne polymère et reliés à la macromolécule par des motifs uréthanes (NHCO2). Ces éléments souples se composent de groupes répétitifs de diisocyanate et d'une chaîne longue de dialcol (ou de polyalcool). The flexible and flexible elements are generally polyalcohols ether or ester dispersed in the polymer chain and connected to the macromolecule by urethane units (NHCO 2 ). These flexible elements consist of repeating groups of diisocyanate and a long chain of dialcol (or polyalcohol).
[0051] La proportion et la structure moléculaire de ces segments déterminent les caractéristiques spécifiques des diverses qualités de PU, allant des matières rigides à des matières souples, extrêmement flexibles. Pour produire ces différents types de PU, on modifie le type et/ou le pourcentage relatif des trois éléments constitutifs de base : le diisocyanate, le polyalcool et l'allongeur de chaîne.  The proportion and the molecular structure of these segments determine the specific characteristics of the various qualities of PU, ranging from rigid materials to flexible materials, extremely flexible. In order to produce these different types of PU, the type and / or the relative percentage of the three basic constituent elements are modified: diisocyanate, polyalcohol and chain extender.
Résistance en traction  Tensile strength
[0052] La morphologie des phases dures/souples est déterminante pour la ténacité des PU. On pense que c'est la liaison hydrogène intramoléculaire et intermoléculaire qui renforce la résistance physique d'un PU, mais il est généralement admis que la longueur du segment rigide, sa fraction volumique dans le polymère et sa « solubilité » avec le segment souple sont déterminantes pour la résistance à la contrainte et à l'élongation des PU. Un pourcentage de segments durs trop important procurera des propriétés très cassantes au polymère.  The morphology of the hard / soft phases is decisive for the toughness of the PUs. It is believed that it is the intramolecular and intermolecular hydrogen bonding that enhances the physical strength of a PU, but it is generally accepted that the length of the rigid segment, its volume fraction in the polymer and its "solubility" with the flexible segment are determining the resistance to stress and elongation of PUs. A percentage of hard segments too large will provide very brittle properties to the polymer.
Synthèses de formulations Prépolymères Polyuréthanes - pourcentage NCO visé = 4% Synthesis of formulations Polyurethane prepolymers - target NCO percentage = 4%
Mode opératoire des synthèses :  Operating procedure syntheses:
Au préalable tous les diols courts ont été séchés en visant des teneurs en eau inférieure à 0,05%,  Beforehand, all the short diols were dried while aiming for water contents of less than 0.05%.
Chargement dans un réacteur sous azote de l'isocyanate fondu à l'étuve, Mise en chauffe et ajout du diol long : Voranol 2000 L (Polypropylène glycol poids moléculaire 2000 g/mol) à 50°C, durée de l'ajout d'environ 5 minutes.  Charge in a reactor under nitrogen the isocyanate melt in the oven, heating and addition of the long diol: Voranol 2000 L (Polypropylene glycol molecular weight 2000 g / mol) at 50 ° C, duration of the addition of about 5 minutes.
Montée en température : 85°C. — — Arrêt lorsque le pourcentage en fonction NCO visé est atteint. Temperature rise: 85 ° C. - - Stop when the target NCO percentage is reached.
Ajout du diol court en contrôlant l'exothermie : pendant 45 minutes environ. Suivi du pourcentage en fonctions NCO au cours du temps : Arrêt lorsque le pourcentage en NCO visé est atteint (4%).  Addition of the short diol controlling the exotherm: for about 45 minutes. NCO percentage percentage tracking over time: Stop when target NCO percentage is reached (4%).
Débullage du produit sous vide avant conditionnement.  Dewatering of the product under vacuum before conditioning.
Mise à l'étuve des cartouches PE de 350 ml.  Put in the oven 350 ml PE cartridges.
Conditionnement du produit dans les cartouches PE de 350 ml sous azote. Mesure du pourcentage en NCO après conditionnement.  Packaging of the product in 350 ml PE cartridges under nitrogen. Percentage measurement in NCO after conditioning.
[0053] Les tableaux récapitulatifs suivants comportent les résultats des tests mettant en évidence l'évaluation des performances adhésives de formulations de prépolymères polyuréthanes. The following summary tables include the results of tests highlighting the evaluation of the adhesive performance of polyurethane prepolymer formulations.
Tableau des valeurs de cisaillements sur éprouvettes des produits avec Table of shear values on test specimens of products with
Caprolactone (CAPA) (Poids Moléculaire~700 g/mol)  Caprolactone (CAPA) (Molecular Weight ~ 700 g / mol)
Prépolymère prepolymer
1 2 3 4 N°  1 2 3 4 No.
MDI MDI MDI MDI MDI MDI
MDI Polypropylène Polypropylène Polypropylène Polypropylène glycol 2000 glycol 2000 glycol 2000 compositions - glycol 2000 Dianol 320 + Dianol 220 + BPA + 2 OB + BDO + 5 CAPA 2,6 CAPA 2,6 CAPA 2,6 CAPA MDI Polypropylene Polypropylene Polypropylene Polypropylene glycol 2000 glycol 2000 glycol 2000 compositions - glycol 2000 Dianol 320 + Dianol 220 + BPA + 2 OB + BDO + 5 CAPA 2,6 CAPA 2,6 CAPA 2,6 CAPA
(exemple 2) (exemple 1 ) (exemple 3) (Example 2) (Example 1) (Example 3)
Poids Weight
moléculaire du g/mol 730 670 635 670 molecular weight of g / mol 730 670 635 670
diol court  short diol
Ratio en poids  Weight ratio
Diol long / Diol % 50/50 50/50 50/50 50/50 court Diol long / Diol% 50/50 50/50 50/50 50/50 short
Ratio molaire  Molar ratio
Diol long / Diol % 26,7/73,3 25/75 19,5/80,5 25,2/74,8 court Diol long / Diol% 26.7 / 73.3 25/75 19.5 / 80.5 25.2 / 74.8 short
Index segment  Index segment
% 28,8 41 ,7 42,7 41 ,6 dur  % 28.8 41, 7 42.7 41, 6 hard
Ratio molaire  Molar ratio
- 1 ,73 1 ,685 1 ,67 1 ,69 NCO/OH — — - 1, 73 1, 685 1, 67 1, 69 NCO / OH - -
Figure imgf000015_0001
Figure imgf000015_0001
ABS : thermoplastique sur Acrylonitrile Butadiène Styrène ABS: Thermoplastic Acrylonitrile Butadiene Styrene
Tableau des valeurs de cisaillements sur éprouvettes Table of shear values on specimens
des produits avec CAPA :  products with CAPA:
Prépolymère N° 5 6  Prepolymer No. 5 6
MDI MDI  MDI MDI
compositions - PPG 2000 PPG 2000  compositions - PPG 2000 PPG 2000
PPG1000 Dianol 3130 PPG1000 Dianol 3130
Ratio en poids Diol long / Diol court % 50/50 50/50 Weight ratio Diol long / Diol short% 50/50 50/50
Ratio molaire  Molar ratio
% 33,4/66,6 34,4/65,6 Diol long / Diol court  % 33.4 / 66.6 34.4 / 65.6 Diol long / Diol short
Index segment dur % 35,0 33,7 — — Hard segment index% 35.0 33.7 - -
Figure imgf000016_0001
Figure imgf000016_0001
[0054] Type de rupture (*) : Type of rupture (*):
AF : il s'agit d'une rupture concernant le joint de colle, dite rupture d'adhésion (en effet une rupture de l'adhésion entre la surface du support et la surface extérieure de la couche de colle préalablement répandue sur le support se produit alors). CF : il s'agit d'une rupture concernant le joint de colle, dite rupture de cohésion (la rupture a lieu au sein même de la couche de colle mais la surface extérieure de la couche de colle reste bien collée au support).  AF: it is about a rupture concerning the seal of glue, said rupture of adhesion (indeed a rupture of the adhesion between the surface of the support and the external surface of the layer of glue previously spread on the support is produced then). CF: this is a break with regard to the glue joint, known as cohesive failure (rupture occurs within the glue layer itself but the outer surface of the glue layer remains firmly bonded to the substrate).
[0055] Les tableaux comparatifs ci-dessus mettent ainsi en évidence que les composés selon la présente invention (prépolymères 2 à 4) possèdent de bien meilleures propriétés adhésives comparés aux prépolymères 5 et 6 n'ayant pas été obtenus à partir d'allongeurs de chaînes préparés à partir de caprolactone. D'autre part, le prépolymère n° 1 qui n'a pas été préparé à partir de Bisphénol alcoxylé, contrairement aux prépolymères selon la présente invention, ne présente pas les mêmes garanties en termes de qualités adhésives.  The above comparative tables thus demonstrate that the compounds according to the present invention (prepolymers 2 to 4) have much better adhesive properties compared to prepolymers 5 and 6 which have not been obtained from chains made from caprolactone. On the other hand, prepolymer No. 1 which has not been prepared from alkoxylated bisphenol, unlike the prepolymers according to the present invention, does not have the same guarantees in terms of adhesive qualities.
[0056] Par conséquent, il s'avère que les prépolymères préparés selon la présente invention son non seulement de bons adhésifs mais en plus, il existe un effet de synergie dû à l'association du bisphénol alcoxylé (produit (II)) associé à la caprolactone (produit (III)). Therefore, it turns out that the prepolymers prepared according to the present invention are not only good adhesives but in addition, there is a synergistic effect due to the combination of the alkoxylated bisphenol (product (II)) associated with caprolactone (product (III)).

Claims

REVENDICATIONS
1. Composé de formule (I) : 1. Compound of formula (I):
Figure imgf000017_0001
Figure imgf000017_0001
(l).  (L).
dans laquelle: in which:
Figure imgf000017_0002
Figure imgf000017_0002
R' et R" = H, CH3, CH2-CH3 ou triméthylcyclohexane, R 'and R "= H, CH 3 , CH 2 -CH 3 or trimethylcyclohexane,
n est un nombre entier compris entre 4 et 8, préférentiellement entre 5 et 6, y + x > 0,  n is an integer between 4 and 8, preferentially between 5 and 6, y + x> 0,
a + b > 0.  a + b> 0.
2. Composé selon la revendication 1 caractérisé, en ce que x + y est compris entre 2 et 5. 2. Compound according to claim 1, characterized in that x + y is between 2 and 5.
3. Composé selon la revendication 1 , caractérisé en ce que x + y = 2. 3. Compound according to claim 1, characterized in that x + y = 2.
4. Composé selon l'une des revendications 1 à 3, caractérisé en ce que a + b est compris entre 2 et 9. 4. Compound according to one of claims 1 to 3, characterized in that a + b is between 2 and 9.
5. Composé selon l'une des revendications précédentes, caractérisé en ce que R' = R" = CH3. 5. Compound according to one of the preceding claims, characterized in that R '= R "= CH 3 .
6. Composé selon l'une des revendications précédentes, caractérisé en ce que R = CH3. 6. Compound according to one of the preceding claims, characterized in that R = CH 3 .
7. Procédé de préparation d'un composé de formule (I) telle que défini à l'une des revendications précédentes comprenant au moins l'étape : 7. Process for the preparation of a compound of formula (I) as defined in one of the preceding claims comprising at least the step:
a) réaction d'un composé de formule (II) : a) reaction of a compound of formula (II):
Figure imgf000018_0001
Figure imgf000018_0001
R, R' et R" ayant la même définition que dans les revendications précédentes, avec un composé de formule (III) :  R, R 'and R "having the same definition as in the preceding claims, with a compound of formula (III):
O  O
O O
en présence d'un catalyseur. in the presence of a catalyst.
8. Procédé selon la revendication précédente, caractérisé en ce que le rapport molaire du composé de formule (II) sur le composé de formule (III) est compris entre 1/0,5 et 1/20, de préférence le rapport est compris entre 1/1 et 1/3. 8. Method according to the preceding claim, characterized in that the molar ratio of the compound of formula (II) to the compound of formula (III) is between 1 / 0.5 and 1/20, preferably the ratio is between 1/1 and 1/3.
9. Procédé selon l'une des revendications 7 ou 8, caractérisé en ce que ledit catalyseur est l'octoate d'étain de formule Sn(Oct)2 ou le Tétra n-butyltitanate de formule n-Bu4TiO4. 9. Method according to one of claims 7 or 8, characterized in that said catalyst is tin octoate of formula Sn (Oct) 2 or tetra n-butyltitanate of formula n-Bu 4 TiO 4 .
10. Utilisation du composé tel que défini à l'une des revendications 1 à 6, allongeur de chaîne dans une formulation élastomère de polyuréthane. 10. Use of the compound as defined in one of claims 1 to 6, chain extender in a polyurethane elastomer formulation.
11. Procédé de préparation d'une formulation élastomère de polyuréthane à partir de prépolymère isocyanate et d'une quantité efficace d'allongeur de chaîne, caractérisé en ce que ledit allongeur de chaîne est le composé tel que défini à l'une des revendications 1 à 6. 11. Process for the preparation of a polyurethane elastomer formulation from an isocyanate prepolymer and an effective amount of chain extender, characterized in that said chain extender is the compound as defined in one of claims 1. to 6.
12. Utilisation du composé tel que défini à l'une des revendications 1 à 6, comme monomère dans la préparation de polyesters saturés ou insaturés, de polycarbonates ou de résines époxy. 12. Use of the compound as defined in one of claims 1 to 6, as a monomer in the preparation of saturated or unsaturated polyesters, polycarbonates or epoxy resins.
13. Polymère de polyuréthane comprenant un allongeur de chaîne, caractérisé en ce que ledit allongeur de chaîne est le composé tel que défini à l'une des revendications 1 à 6. 13. Polyurethane polymer comprising a chain extender, characterized in that said chain extender is the compound as defined in one of claims 1 to 6.
14. Utilisation de polymère polyuréthane tel que défini à la revendication 13 comme agent adhésif. 14. Use of polyurethane polymer as defined in claim 13 as an adhesive agent.
PCT/FR2012/052011 2011-09-08 2012-09-07 Improvement of the physical properties of polyurethane polymers WO2013034867A1 (en)

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