EP3891202A1 - Polyurethane with (2-oxo-1,3-dioxolane-4-carboxylate) end groups - Google Patents

Polyurethane with (2-oxo-1,3-dioxolane-4-carboxylate) end groups

Info

Publication number
EP3891202A1
EP3891202A1 EP19842382.4A EP19842382A EP3891202A1 EP 3891202 A1 EP3891202 A1 EP 3891202A1 EP 19842382 A EP19842382 A EP 19842382A EP 3891202 A1 EP3891202 A1 EP 3891202A1
Authority
EP
European Patent Office
Prior art keywords
diisocyanate
polyurethane
compound
formula
chosen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19842382.4A
Other languages
German (de)
French (fr)
Inventor
Guillaume Michaud
Stéphane Fouquay
Frédéric Simon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bostik SA
Original Assignee
Bostik SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bostik SA filed Critical Bostik SA
Publication of EP3891202A1 publication Critical patent/EP3891202A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
    • C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • 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
    • C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group

Definitions

  • the present invention relates to a polyurethane with endings (2-oxo-1, 3-dioxolane-4-carboxylate), and to a process for its preparation.
  • the present invention also relates to a multicomponent system comprising said polyurethane.
  • the invention also relates to a method of assembling materials by gluing, using said polyurethane.
  • Adhesive compositions (glue or mastic), based on polyurethane, have long been known, in particular in the form of multicomponent systems (generally two-component) in which the (two) reactive components necessary for the synthesis of polyurethane are stored separately, and mixed at the last moment before using the adhesive composition.
  • the reactive components have on the one hand sufficient reactivity for the reaction to take place and take place quickly, and on the other hand a viscosity adapted to the temperature. of mixing so that it operates easily.
  • polyisocyanates are very sensitive compounds in the presence of atmospheric humidity and require taking appropriate measures to avoid their premature crosslinking, and therefore their loss of reactivity, during their handling and storage (anhydrous conditions).
  • some of these compounds such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (I PDI), toluene diisocyanate (TDI) or diphenyl methane diisocyanate (MDI) are known to present toxicological risks for humans and the environment, and can even generate toxic emissions for the most volatile.
  • HDI hexamethylene diisocyanate
  • I PDI isophorone diisocyanate
  • TDI toluene diisocyanate
  • MDI diphenyl methane diisocyanate
  • compositions in the form of a transportable kit in the form of a transportable kit, practical, easy and quick to implement on demand (“Do It Yourself”), the mixing of the reagents must be possible as much as possible on volumes restricted and at low temperature, especially at room temperature.
  • WO2015 / 140458 describes multi-component systems, and in particular two-component systems, obtained by mixing a component A comprising at least one polyurethane prepolymer functionalized with glycerol carbonate at the chain end, with a component B comprising at least two primary and / or secondary amine groups.
  • component A comprising at least one polyurethane prepolymer functionalized with glycerol carbonate at the chain end
  • component B comprising at least two primary and / or secondary amine groups.
  • compositions based on polyurethane available in the form of multicomponent system and in particular bicomponent, which are easier to use compared to the prior art, at mixing and reaction temperatures below 60 ° C. , preferably less than or equal to 35 ° C, and more preferably close to room temperature (23 ° C).
  • compositions available in the form of multicomponent systems in particular transportable (kits), respectful of man and the environment.
  • the number-average molar masses, expressed in grams per mole (g / mol) are determined by calculation by analyzing the content of terminal groups (NCO, OH and T functions) expressed in milliequivalents per gram (meq / g) and the functionality (number of NCO, OH function or T function per mole) of the compound (PP1), of the polyol, of the compound of formula (IV) or of the polyurethane comprising at least two terminal T functions (PP2) respectively);
  • the hydroxyl index of an alcoholic product represents the number of hydroxyl functions per gram of product, and is expressed in the form of the equivalent number of milligrams of potassium hydroxide (KOH) used in the determination of hydroxyl functions, per gram of product;
  • the viscosity measurement at 23 ° C can be done using a Brookfield viscometer according to ISO 2555.
  • the measurement carried out at 23 ° C can be done using a Brookfield RVT viscometer, a needle adapted to the viscosity range and at a rotation speed of 20 revolutions per minute (rpm);
  • the viscosity measurement at 60 ° C can be done using a Brookfield RVT viscometer coupled with a Thermosel type heating module from the Brookfield brand, a mobile adapted to the viscosity range and at a rotation speed 20 revolutions per minute.
  • the present invention relates to a polyurethane (PP2) comprising at least two, preferably two or three, T terminal functions of formula (I) below:
  • R 1 and R 2 identical or different, each represent:
  • alkyl group preferably being a C1-C22, preferably C1-C12 alkyl group,
  • alkylaryl group in which the linear or branched alkyl group comprises from 1 to 22 carbon atoms
  • alkyl or cycloalkyl groups optionally comprising one or more heteroatoms, preferably oxygen or sulfur.
  • the aforementioned polyurethane (PP2) is such that each of R 1 and R 2 represents, independently of one another, a hydrogen atom or a linear or branched, saturated or unsaturated alkyl group, said alkyl group preferably being a C1-C12 alkyl group, advantageously methyl or ethyl.
  • the polyurethane (PP2) is such that R 1 represents a hydrogen atom and R 2 represents a hydrogen atom, methyl or ethyl.
  • the aforementioned polyurethane (PP2) further comprises at least one of the following divalent radicals R 3 :
  • TDI 2,4-toluene diisocyanate and 2,2'-toluene diisocyanate
  • MDI 4,4'-methylene diphenyl diisocyanate and 4,4'-methylene diphenyl diisocyanate
  • - p is an integer ranging from 1 to 2;
  • - q is an integer ranging from 0 to 9;
  • - r is an integer equal to 5 or 6;
  • - R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms;
  • - R ’ represents a divalent hydrocarbon group, linear or branched, saturated, having 2 to 4 carbon atoms.
  • the aforementioned polyurethane (PP2) further comprises at least one of the following divalent radicals R 3 :
  • - p is an integer ranging from 1 to 2;
  • - q is an integer ranging from 0 to 9;
  • - r is an integer equal to 5 or 6;
  • - R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms;
  • - R ’ represents a divalent hydrocarbon group, linear or branched, saturated, having 2 to 4 carbon atoms.
  • the polyurethane (PP2) mentioned above comprises at least one radical R 3 chosen from the radicals d) derived from 2,4-TDI and / or from the radicals j) of formula (II) above mentioned.
  • the polyurethane (PP2) mentioned above comprises at least one repeating unit comprising at least one divalent radical R 3 mentioned above.
  • the aforementioned polyurethane (PP2) has the following formula (III):
  • R 1 and R 2 are as defined above, R 1 preferably being a hydrogen atom and R 2 preferably being a hydrogen atom, methyl or ethyl;
  • D and T represent, independently of one another, a hydrocarbon radical comprising from 2 to 66 carbon atoms, linear or branched, cyclic, alicyclic or aromatic, saturated or unsaturated, optionally comprising one or more heteroatoms;
  • - P 'and P being, independently of one another, a divalent radical derived from a polyol preferably chosen from polyether polyols, polydiene polyols, polyester polyols, polycarbonate polyols, the polyols preferably being those described below for step E1;
  • the aforementioned polyurethane (PP2) may have a viscosity measured at room temperature (23 ° C) less than or equal to 1,500 Pa.s, more preferably less than or equal to 600 Pa.s, and better still less than or equal to 400 Pa. s.
  • the polyurethane (PP2) according to the invention may have a viscosity measured at 60 ° C less than or equal to 50 Pa.s, more preferably less than or equal to 40 Pa.s, and better still less than or equal to 30 Pa.s.
  • the aforementioned polyurethane (PP2) has a viscosity measured at room temperature (23 ° C) less than or equal to 600 Pa.s and a viscosity measured at 60 ° C less than or equal to 40 Pa.s.
  • the polyurethane (PP2) comprising at least two T-terminal functions mentioned above can be obtained by reaction of a compound having at least two NCO groups (PP1) and at least one compound of the following formula (IV):
  • R 1 and R 2 identical or different, each represent: - a hydrogen atom
  • alkyl group preferably being a C1-C22 alkyl group, preferably a C1-C12 alkyl group,
  • alkylaryl group in which the linear or branched alkyl group comprises from 1 to 22 carbon atoms
  • alkyl or cycloalkyl groups optionally comprising one or more heteroatoms, preferably oxygen or sulfur.
  • the compounds of formula (IV) are those corresponding to the following formula (IV-1):
  • the compounds of formula (IV-1) are compounds of formula (IV) in which R 1 is a hydrogen atom.
  • the preferred compounds of formula (IV-1) are those having one of the following formulas (IV-1 a), (IV-1 b) and (IV-1 c):
  • the compounds of formula (IV-1 a), (I V-1 b) and (IV-c) can be obtained by reaction of the glyceric acid carbonate respectively with ethylene oxide (EO), the oxide propylene (OP) or butylene oxide (OB) according to the scheme (1) previously described.
  • EO ethylene oxide
  • OP oxide propylene
  • OB butylene oxide
  • the compound of formula (IV-1 a) is a compound of formula (IV) in which R 1 is a hydrogen atom, and R 2 is a hydrogen atom, namely 2-hydroxyethyl-2-oxo-1, 3 - dioxolane-4-carboxylate.
  • the compound of formula (I V-1 b) is a compound of formula (IV) in which R 1 is a hydrogen atom, and R 2 is a methyl, namely 2-hydroxypropyl-2-oxo-1, 3 -dioxolane-4-carboxylate.
  • the compound of formula (IV-1 c) is a compound of formula (IV) in which R 1 is a hydrogen atom, and R 2 is an ethyl, ie 2-hydroxybutyl-2-oxo-1, 3- dioxolane-4-carboxylate.
  • the present invention also relates to a process for the preparation of a polyurethane (PP2) mentioned above comprising at least two, preferably two or three, T terminal functions of formula (I) comprising a polyaddition reaction step (denoted E2):
  • r 2 is the NCO / OH molar ratio corresponding to the molar ratio of the number of isocyanate groups to the number of hydroxyl groups carried respectively by all of the isocyanate (s) (compound (s) (PP1) and optionally the unreacted polyisocyanate (s) at the end of a possible step E1), and alcohol (s) present in the reaction medium of step E2.
  • the calculation of the ratio r 2 notably takes into account on the one hand the NCO groups carried by all of the isocyanates present in the reaction medium during step E2 (compound (PP1) and optionally the unreacted polyisocyanates used for its synthesis. derived from a possible step E1) and on the other hand from the OH groups carried by the compound (s) of formula (IV).
  • the calculation of the ratio r2 takes account on the one hand of the NCO groups carried by the compound (PP1), but also the isocyanates optionally in mixture with the (s ) compound (s) (PP1) and / or on the other hand OH groups carried by the compound (s) of formula (IV), but also the polyol compound (s) optionally in mixture with the compound (s) of formula (IV).
  • Step E2 can be carried out at a temperature below 95 ° C, and preferably under anhydrous conditions.
  • the compound of formula (IV) which can be used to prepare the polyurethane (PP2) according to the invention can be used either pure or in the form of a mixture or composition of compounds of formula (IV) containing at least 95% by compound weight of formula (IV).
  • Step E2 can be carried out with a compound of formula (IV) or with a mixture of compounds of formula (IV) of different nature (for example with different R 1 , or else R 2 different, or else with R 1 and R 2 different).
  • the compound (s) (PP1) used can be used either pure or in the form of a composition essentially comprising the said compound (s) and a low content of residual polyisocyanate (s) resulting (s) in particular from the synthesis of said (said) compound (s).
  • the compound (s) (PP1) used (s) is (are) such that the content of NCO groups present in said composition preferably ranges from 0.5 to 15% by weight relative to the weight of said composition.
  • content of NCO groups is meant the content of isocyanate groups carried by all of the compounds present in the reaction medium, namely the compound (PP1) and other species carrying isocyanate group (s) which may be present, such as unreacted polyisocyanate monomers.
  • This content of NCO group can be calculated in a manner well known to those skilled in the art and is expressed as a percentage by weight relative to the total weight of the reaction medium.
  • the compound (s) (PP1) having at least two NCO groups can (wind) be:
  • HDI hexamethylene diisocyanate allophanate
  • - p is an integer ranging from 1 to 2;
  • - q is an integer ranging from 0 to 9;
  • - r is an integer equal to 5 or 6;
  • - R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms;
  • - R represents a divalent hydrocarbon group, linear or branched, saturated, having from 2 to 4 carbon atoms;
  • At least one polyisocyanate preferably chosen from diisocyanates, and in particular from the following diisocyanates:
  • polystyrene resin preferably chosen from polyether polyols, polyester polyols, polydiene polyols, polycarbonate polyols, and their mixtures, in amounts of polyisocyanate (s) and polyol (s) leading to a ratio NCO / OH molar, noted r 1 , strictly greater than 1, preferably ranging from 1.6 to 1.9, preferably ranging from 1.65 to 1.85.
  • the compounds (PP1) are chosen from:
  • n is the NCO / OH molar ratio corresponding to the molar ratio of the number of isocyanate groups (NCO) to the number of hydroxyl groups (OH) carried respectively by all of the polyisocyanates (s) and polyol (s) present in the reaction medium of step E1.
  • the HDI allophanate derivative of formula (NA) comprises a percentage by weight of isocyanate group ranging from 12 to 14% by weight relative to the weight of said derivative. More preferably,
  • - p is an integer ranging from 1 to 2;
  • - q is an integer ranging from 2 to 5;
  • - R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 6 to 14 carbon atoms;
  • R - R ' represents a divalent propylene group.
  • the compound (PP1) which can be used according to the invention can be used in the form of a composition comprising at least 99.5% by weight, preferably at least 99.8% by weight of derivative (s) of formula ( NA), and less than 0.5% by weight, preferably less than 0.2% by weight of HDI, relative to the total weight of said composition.
  • Such a composition can be obtained for example by:
  • the content of NCO groups (also denoted by “NCO level” and noted% NCO) present in the composition of derivative (s) of formula (MA) ranges from 12 to 14% by weight relative to the weight of said composition.
  • the reaction medium is preferably free of potentially toxic diisocyanate monomers (HDI, I PDI, TDI, MDI).
  • the polyurethane (PP2) according to the invention advantageously does not present toxicological risks linked to the presence of such monomers.
  • the aforementioned polyurethane (PP2) preferably has from 0.1 to 5 milliequivalents of T functions of formula (I) above per gram of said polyurethane (PP2).
  • the polyurethane (PP2) obtained preferably has from 0.1 to 3.0 milliequivalent (s) of T functions per gram of said polyurethane (PP2), preferably from 0.1 to 1.5 milliequivalents of T functions per gram of said polyurethane (PP2), more preferably from 0.15 to 1.0 milliequivalents of T functions of said polyurethane (PP2) and better still from 0.2 to 0.8 milliequivalents of T functions per gram of said polyurethane (PP2).
  • the polyol (s) which can be used according to the invention is (are) preferably chosen from polyether polyols, polyester polyols, polydiene polyols, polycarbonate polyols, and their mixtures.
  • the polyol (s) which can be used for preparing the polyurethane with NCO endings used according to the invention can be chosen from those whose number average molecular mass ranges from 200 to 20,000 g / mol, preferably from 250 to 18,000 g / mol, and better still from 2,000 to 12,000 g / mol.
  • the polyol (s) which can be used according to the invention has (s) a hydroxyl (IOH) ranging from 9 to 105 mg KOH / g, and preferably from 13 to 90 mg KOH / g, more preferably from 25 to 70 mg KOH / g, and better still from 40 to 65 mg KOH / g of polyol.
  • IOH hydroxyl
  • the polyether polyol (s) which can be used according to the invention is (are) preferably chosen from polyoxyalkylene polyol, the alkylene part of which, linear or branched, comprises from 1 to 4 carbon atoms , preferably from 2 to 3 carbon atoms.
  • the polyether polyol (s) which can be used according to the invention is (are) preferably chosen from polyoxyalkylene diols or polyoxyalkylene triols, and better still polyoxyalkylene diols, including the alkylene part , linear or branched, comprises from 1 to 4 carbon atoms, preferably from 2 to 3 carbon atoms, and whose number-average molar mass ranges from 200 to 20,000 g / mol, and preferably from 2,000 to 12,000 g / mol.
  • Polyoxypropylene diols or triols also designated by polypropylene glycols (PPG) diol or triol having a number average molecular weight ranging from 400 to 18,000 g / mol and preferably ranging from 400 to 4,000 g / mol;
  • polyoxyethylene diols or triols also designated by polyethylene glycols (PEG) diol or triol having a number average molecular weight ranging from 400 to 18,000 g / mol and preferably ranging from 400 to 4,000 g / mol;
  • PolyTHF polytetrahydrofuran diols or triols having a number average molecular weight ranging from 250 to 4,000 g / mol;
  • the polyether polyol (s) which can be used is (are) chosen from polyoxypropylene diols or triols with a polydispersity index ranging from 1 to 1, 4, in particular ranging from 1 to 1 , 3.
  • the polyether polyols raised can be prepared in a conventional manner, and are widely available commercially. They can be obtained by polymerization of the corresponding alkylene oxide in the presence of a catalyst based on a double metal-cyanide complex.
  • polyether diols By way of examples of polyether diols, mention may be made of the polyoxypropylene diols sold under the name "ACCLAIM®” by the company Bayer, such as the “ACCLAIM ® 12200" of average molecular weight neighbor number 1 1335 g / mol and whose hydroxyl number ranges from 9 to 1 of 1 mg KOH / g, the "Acclaim® 8200” of average molecular weight number close to 8,057 g / mol and with a hydroxyl number ranging from 13 to 15 mg KOH / g, and “ACCLAIM® 4200” with an average molecular weight close to 4,020 g / mol, and including hydroxyl number ranges from 26.5 to 29.5 mg KOH / g, or alternatively the polyoxypropylene diol sold under the name "VORANOL P2000" by the company DOW with an average molecular weight close to 2,004 g / mol and the hydroxyl number is approximately
  • polyether triol By way of examples of polyether triol, mention may be made of polyoxypropylene triol sold under the name "VORANOL CP3355" by the company Dow, with a number average molecular mass of around 3,554 g / mol and whose hydroxyl number ranges from 40 to 50 mg KOH / g.
  • the polydiene polyol (s) which can be used according to the invention is (are) preferably chosen from polydienes comprising terminal hydroxyl groups, and their corresponding hydrogenated or epoxidized derivatives.
  • the polydiene polyol (s) which can be used according to the invention is (are) chosen (s) from polybutadienes comprising terminal hydroxyl groups, optionally hydrogenated or epoxidized.
  • polydiene polyol (s) which can be used according to the invention is (are) chosen (s) from butadiene homopolymers comprising terminal hydroxyl groups, optionally hydrogenated or epoxidized.
  • terminals is meant that the hydroxyl groups are located at the ends of the main chain of the polydiene polyol.
  • the above-mentioned hydrogenated derivatives can be obtained by total or partial hydrogenation of the double bonds of a polydiene comprising terminal hydroxyl groups, and are therefore saturated (s) or unsaturated (s).
  • the epoxidized derivatives raised can be obtained by chemoselective epoxidation of the double bonds of the main chain of a polydiene comprising terminal hydroxyl groups, and therefore comprise at least one epoxy group in its main chain.
  • polybutadiene polyols mention may be made of butadiene homopolymers, saturated or unsaturated, comprising terminal hydroxyl groups, optionally epoxidized, such as for example those sold under the name POLY BD® or KRASOL® by the company CRAY VALLEY .
  • the polyester polyols can be chosen from polyester diols and polyester triols, and preferably from polyester diols.
  • polyester polyols there may be mentioned, for example:
  • aliphatic (linear, branched or cyclic) or aromatic polyols such as for example ethanediol, 1, 2-propanediol, 1, 3-propanediol, glycerol, trimethylolpropane, 1, 6- hexanediol, 1, 2,6-hexanetriol, butenediol, sucrose, glucose, sorbitol, pentaerythritol, mannitol, triethanolamine, N-methyldiethanolamine, and mixtures thereof, with
  • polycarboxylic acid or its ester or anhydride derivative such as 1, 6-hexanedioic acid, dodecanedioic acid, azelaic acid, sebacic acid, adipic acid, acid 1, 18- octadecanedioic acid, phthalic acid, succinic acid and mixtures of these acids, an unsaturated anhydride such as for example maleic or phthalic anhydride, or a lactone such as for example caprolactone.
  • polyester polyols raised can be prepared in a conventional manner, and are for the most part commercially available.
  • polyester polyols there may be mentioned, for example, the following products with hydroxyl functionality equal to 2:
  • TONE ® 0240 (available from Union Carbide) which is a medium molecular weight polycaprolactone of from about 2,000 g / mol and a melting point of 50 ° C,
  • polyester polyol having a viscosity of 180 Pa.s at 23 ° C, an average molecular mass in number Mn equal to 5500 g / mol, and a T g equal to -50 ° VS,
  • - KURARAY ® P-6010 polyester polyol having a viscosity of 68 Pa.s at 23 ° C, a number average molecular weight equal to 6000 g / mol, and a T g equal to -64 ° C
  • - KURARAY ® P-10010 polyester polyol having a viscosity of 687 Pa.s at 23 ° C, and a number average molecular weight equal to 10,000 g / mol.
  • polyester diol By way of example of a polyester diol, mention may also be made of REALKYD® XTR 10410 "sold by the company CRAY VALLEY with a number average molecular mass (Mn) close to 1000 g / mol and whose hydroxyl index ranges from 108 to 1 16 mg KOH / g. It is a product of the condensation of adipic acid, diethylene glycol and monoethylene glycol.
  • Mn number average molecular mass
  • the polycarbonate polyols can be chosen from polycarbonate diols or triols, in particular having a number-average molecular mass (M n ) ranging from 300 g / mol to 12,000 g / mol, preferably ranging from 400 to 4,000 g / mol .
  • M n number-average molecular mass
  • CONVERGE POLYOL 212-10 and CONVERGE POLYOL 212-20 marketed by the company NOVOMER respectively of molecular mass in number (M n ) equal to 1000 and 2000 g / mol whose hydroxyl indices are respectively 1 12 and 56 mg KOH / g,
  • KURARAY having a molecular weight in number (Mn) ranging from 500 to 3000 g / mol and a hydroxyl number ranging from 224 to 37 mg KOH / g.
  • reaction E1 is carried out in the presence of polyol (s) chosen (s) from polyether polyols, preferably polyether diols and / or polyether triols.
  • polyol chosen (s) from polyether polyols, preferably polyether diols and / or polyether triols.
  • the polyisocyanate (s) are preferably diisocyanate (s) in particular chosen from the following diisocyanates:
  • At least one polyisocyanate preferably chosen from diisocyanates, and in particular from the following diisocyanates:
  • H12MDI 2,4'-methylene dicyclohexyl diisocyanate and / or 4,4'-methylene dicyclohexyl diisocyanate
  • HDI hexamethylene diisocyanate allophanate
  • the diisocyanate is chosen from 2,4-TDI (or consisting essentially of 2,4-TDI), m-XDI, IPDI and the derivatives of formula (MA).
  • the polyisocyanates (in particular diisocyanate (s)) which can be used according to the invention (for example cited in a4) and a5) above) can (can) be used in the form of a mixture essentially containing the said polyisocyanate (s) (respectively diisocyanate (s)) and a low content of residual polyisocyanate compound (s) (respectively diisocyanate (s)) derived from the synthesis of said polyisocyanate (s) (respectively diisocyanate (s)).
  • the content of residual polyisocyanate compound (s) (respectively diisocyanate (s)) tolerated is such that the setting use of said mixture in the preparation of polyurethane with NCO endings used according to the invention advantageously has no impact on the final properties of said polyurethane.
  • the polyisocyanate (s) (for example diisocyanate (s)) which can be used according to the invention (in particular cited in a4) and a5) above) can (can) be used under the form of a mixture containing at least 99% by weight of polyisocyanate (s) (respectively diisocyanate (s)) and less than 1% by weight of compound (s) polyisocyanate (s) (respectively diisocyanate (s))) ( s), preferably in the form of a mixture containing at least 99.5% by weight of polyisocyanate (s) (respectively diisocyanate (s)) and less than 0.5% by weight of polyisocyanate compound (s) ) (respectively diisocyanate (s)) residual (s), more preferably in the form of a mixture containing at least 99.8% by weight of polyisocyanate (s) (respectively diisocyanate (s)) and less than 0.2% by weight of residual poly
  • the content of residual polyisocyanate compound (s) is such that the content by weight of isocyanate group in said mixture remains approximately equal to that indicated above relative to the weight of diisocyanate a4) and a5) alone.
  • 2,4-TDI as mentioned in a4) can be used in the form of a technical TDI, commercially available, corresponding to a composition whose content of 2,4-TDI is at least 99 % by weight, and preferably at least 99.5% by weight, relative to the weight of said composition.
  • 2,4'-MDI as mentioned in a5) can be used in the form of a technical MDI, commercially available, corresponding to a composition the content of which is 2,4'-MDI is at least 99% by weight, and preferably at least 99.5% by weight, relative to the weight of said composition.
  • the polyisocyanate (s) which can be used according to the invention are typically widely available commercially.
  • SCURANATE® T100 sold by the company VENCOREX, corresponding to a 2,4-TDI with a purity greater than 99% by weight
  • DESMODUR® I sold by the company COVESTRO, corresponding to an IPDI
  • TAKENATE TM 500 marketed by MITSUI CHEMICALS corresponding to an m-XDI
  • TAKENATE TM 600 marketed by MITSUI CHEMICALS corresponding to an m-H6XDI
  • VESTANAT® H12MDI marketed by EVONIK an H12MDI.
  • the derivative of formula (I IA) mentioned above is in particular marketed under the name of "TOLONATE®” by the company VENCOREX. Mention may in particular be made of "TOLONATE® X FLO 100" corresponding to a composition comprising at least 99.5% by weight of HDI allophanate derivative of formula (I IA) and less than 0.5% by weight of HDI relative to the weight of said composition.
  • Step E1 can be carried out at a temperature T1 below 95 ° C, preferably between 65 ° C and 80 ° C, and under anhydrous conditions.
  • the calculation of the NCO / OH molar ratio takes into account on the one hand the NCO groups carried by the polyisocyanate and the residual polyisocyanate compounds resulting from the synthesis of said polyisocyanate (s) possibly present in mixture, and on the other hand OH groups carried by the polyol (s) present in the reaction medium of step E1.
  • the polyaddition reaction of step E1 can be carried out in the presence or not of at least one reaction catalyst.
  • reaction catalyst (s) which can be used during the polyaddition reaction of step E1 can be any catalyst known to a person skilled in the art for catalyzing the formation of polyurethane by reaction d 'At least one polyisocyanate with at least one polyol preferably chosen from polyether polyols, polyester polyols, and polydiene polyols.
  • An amount ranging up to 0.3% by weight of catalyst (s) relative to the weight of the reaction medium of step E1 can be used. In particular, it is preferred to use from 0.02 to 0.2% by weight of catalyst (s) relative to the weight of the reaction medium of step E1.
  • the polyurethane with NCO endings (PP1) is obtained by polyaddition of at least one diisocyanate, preferably one or two diisocyanates chosen from those mentioned in a1), a2), a3) , a4), a5), a6), a7), a8 and a9) as described in any one of the preceding paragraphs with at least one, preferably one or two, polyol (s) chosen from polyether polyols and polydiene polyols, and preferably polyether polyols, such as for example polyether diols and / or polyether triols.
  • the compound having at least two NCO groups is such that its content of NCO groups preferably ranges from 0.5 to 5.7%, more preferably from 0.7 to 3 %, and better still from 1 to 2.5%.
  • the above-mentioned process may include a step of purifying the intermediate reaction products.
  • the process does not include a step for purifying the products of intermediate reactions, or a step for removing solvent.
  • said method does not include a step consisting in adding one or more solvent (s) and / or plasticizer (s).
  • a preparation process can thus advantageously be implemented without interruption, with very high production line speeds on an industrial scale.
  • the method according to the invention consists of a first step E1 and a second step E2, as defined in any one of the preceding paragraphs.
  • the present invention also relates to a polyurethane comprising at least two terminal T functions of formula (I) (PP2) capable of being obtained according to a preparation process according to the invention, as described in any one of the paragraphs previous.
  • the present invention also relates to a multicomponent system, preferably without solvent, comprising:
  • component A a composition comprising at least one polyurethane (PP2) as defined above, and
  • component B a composition comprising at least one amino compound (B1) comprising at least two amine groups chosen from primary amine groups, secondary amine groups and mixtures thereof, preferably comprising at least two primary amine groups.
  • the components of the multicomponent system are generally stored separately and are mixed at the time of use, at a mixing temperature T3, to form a composition, preferably adhesive, intended to be applied to the surface of a material.
  • the mixing of components of the multicomponent system, and in particular of components A and B, can be carried out under anhydrous conditions.
  • the amounts of polyurethane (s) (PP2) and of amino compound (s) (B1) present in the multicomponent system according to the invention lead to a molar ratio of the number of T functions of formula (I) on the number of primary and / or secondary amine groups noted r 3 , ranging from 0.5 to 1, in particular from 0.65 to 1, and preferably from 0.8 to 1.
  • the molar ratio noted r 3 throughout this application corresponds to the molar ratio of the total number of T functions of formula (I) present in the multicomponent system, over the total number of primary and / or secondary amine groups present in the multicomponent system.
  • ratio r 3 advantageously makes it possible to obtain, by a polyaddition reaction between the polyurethane (s) (PP2) mentioned above and the amino compound (s) (B1) preferably comprising at least two or three primary amine groups according to the invention, a composition, preferably adhesive, advantageously having good mechanical performance.
  • the amino compound (s) (B1) used according to the invention preferably has a viscosity adapted to the mixing temperature T3.
  • the amino compound (s) (B1) used according to the invention preferably have a primary alkalinity ranging from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g of amino compound.
  • Primary alkalinity is the number of primary NH 2 amine functions per gram of amino compound (B1), said number being expressed in the form of milliequivalents of HCl (or milliequivalents of NH 2 ) used in the determination of amine functions, determined by well known way by titrimetry.
  • the amino compound (s) (B1) used according to the invention can be monomeric or polymeric compounds.
  • the amino compound (s) (B1) may further comprise tertiary amine groups.
  • - cycloalkylene polyamines comprising at least two primary amine groups - NH 2 ,
  • polyamines comprising both alkyl and cycloalkyl groups and comprising at least two primary amine groups -NH 2 ,
  • polyether polyamines comprising at least two primary amine groups -NH 2 ,
  • the amino compound (s) (B1) used according to the invention has (s) two or three primary amine groups.
  • the amino compound (s) (B1) used according to the invention is (are) chosen from hydrocarbon compounds, linear, branched, cyclic or acyclic, saturated and comprising two or three primary amine groups -NH 2 , said compounds being optionally interrupted by one or more heteroatoms chosen from an oxygen atom -O- and a nitrogen atom -N- and / or one or more divalent secondary amine groups - NH-, and having a primary alkalinity ranging from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g of amino compound.
  • alkylene diamines and alkylene triamines comprising respectively two or three primary amine groups -NH 2 ,
  • cycloalkylene diamines and triamines comprising respectively two or three primary amine groups -NH 2
  • diamines and triamines comprising both alkyl and cycloalkyl groups, comprising respectively two or three primary amine groups -NH 2
  • diamines and triamines comprising both alkyl and cycloalkyl groups, comprising respectively two or three primary amine groups -NH 2
  • polyether diamines and polyether triamines comprising respectively two or three primary amine groups -NH 2 ,
  • EDA ethylene diamine
  • DETA diethylenetriamine
  • TAEA (2-aminoethyl) amine
  • x is an integer such that the primary alkalinity ranges from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g;
  • x is an integer such that the primary alkalinity is from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g;
  • x and y are whole numbers such that the primary alkalinity ranges from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g;
  • HMDA hexamethylene diamine
  • IPDA - isophorone diamine
  • polyether diamines are sold, for example, under the name JEFFAMINES EDR-148 and EDR-176 by the company HUNTSMAN and have respective primary alkalinities of 13.5 and 11.4 meq / g;
  • x is an integer ranging from 2 or 68, such that the primary alkalinity ranges from 0.5 to 8.7 meq / g;
  • polyether diamines are sold for example under the name JEFFAMINES D-230, D-400, D-2000 and D-4000 by the company HUNTSMAN and have respective primary alkalinities of 8.7, 5.0, 1.0 and 0.5 meq / g;
  • x, y and z are whole numbers, y ranging from 2 to 39 and x + z ranging from 1 to 6, such that the primary alkalinity ranges from 1.0 to 9.1 meq / g;
  • polyether diamines are marketed for example under the name JEFFAMINES HK-51 1, ED-600, ED-900 and ED-2003 by the company HUNTSMAN and have respective primary alkalinities of 9.1, 3.3, 2.2 and 1.0 meq / g;
  • - polyether diamines having a primary alkalinity ranging from 1 to 10 meq / g and corresponding to the following formula: in which X b is a linear or branched alkylene group, preferably comprising from 2 to 20 carbon atoms, preferably from 2 to 10 carbon atoms, m is an integer ranging from 1 to 20, and n is an integer ranging from 1 100 ;
  • R is a hydrogen atom or a C1 to C2 alkyl group
  • x, y, z and n are whole numbers, n ranging from 0 to 1 and x + y + z ranging from 5 to 85, such that the primary alkalinity ranges from 0.6 to 6.8 meq / g
  • polyether diamines are marketed for example under the name JEFFAMINES T-403, T-3000, and T-5000 by the company HUNTSMAN and have respective primary alkalinities of 6.8, 1.0 and 0.6 meq / g;
  • - dimer and trimer fatty amines comprising two or three primary amine groups of primary alkalinity ranging from 3.39 meq / g to 3.60 meq / g.
  • These fatty amines dimers and trimers can be obtained from corresponding dimerized and trimerized fatty acids.
  • dimeric fatty amines partially or completely hydrogenated, mention may be made of those corresponding to the following formulas:
  • the dimer and trimer fatty acids used to prepare the abovementioned fatty amines are obtained by high temperature polymerization under pressure of monocarboxylic unsaturated fatty acids (monomeric acid), comprising from 6 to 22 carbon atoms, preferably from 12 to 20 carbon atoms, and come from plant or animal sources.
  • monocarboxylic unsaturated fatty acids monomeric acid
  • unsaturated fatty acids include Cie acids having one or two double bonds (respectively oleic or linoleic acid) obtained from tall oil which is a by-product of the manufacture of paper pulp.
  • a technical mixture containing on average 30-35% by weight of monocarboxylic fatty acids often isomerized with respect to the starting monocarboxylic unsaturated fatty acids, 60-65% by weight of dicarboxylic acids ( dimer acids) comprising twice the number of carbon relative to the starting monocarboxylic unsaturated fatty acids and 5-10% by weight of tricarboxylic acids (trimer acids) having three times the carbon number relative to the starting monocarboxylic unsaturated fatty acids .
  • dimer acids dicarboxylic acids
  • trimer acids trimer acids having three times the carbon number relative to the starting monocarboxylic unsaturated fatty acids.
  • the compound (s) (B1) comprise at least two methylene amine groups (-CH2-NH 2 ).
  • the compound (s) (B1) are chosen from tris- (2-aminoethyl) amine (TAEA), hexamethylene diamine (HMDA), and their mixtures.
  • TAEA tris- (2-aminoethyl) amine
  • HMDA hexamethylene diamine
  • the multicomponent system according to the invention comprises at least two amino compounds (B1)
  • these can be included in two different components, for example a component (B) and a component (C).
  • the components (A), (B) and (C) are then stored separately before mixing at the time of use of said system, at a mixing temperature T3, to form a composition, preferably adhesive, intended to be applied to the surface of a material.
  • the multicomponent system according to the invention can comprise at least one crosslinking catalyst.
  • the crosslinking catalyst (s) can be any catalyst usually used to accelerate the ring-opening reaction of a compound comprising a T function with a primary amine and / or secondary.
  • crosslinking catalyst which can be used according to the invention, there may be mentioned:
  • BMEP 3,2-diazaphosphoride
  • tertiary amines such as:
  • DMDEE diethyl ether-2,2'-morpholine
  • crosslinking catalyst (s) An amount ranging from 0.05 to 1% by weight of crosslinking catalyst (s) relative to the total weight of the multicomponent system according to the invention can be used.
  • the crosslinking catalyst (s) can be distributed in one or more of the components forming the multicomponent system according to the invention.
  • the multicomponent system according to the invention can comprise at least one mineral filler.
  • the (or) mineral filler (s) that can be used is (are) advantageously chosen (s) so as to improve the mechanical performance of the composition according to the invention in the crosslinked state.
  • filler As an example of filler (s) which can be used, mention may be made, without limitation, of calcium carbonate, kaolin, silica, gypsum, microspheres and clays.
  • the mineral filler (s) has (s) a maximum particle size, in particular an external diameter, less than 100 mm and preferably less than 10 mm.
  • Such fillers can be selected in a manner well known to those skilled in the art using appropriate mesh screens.
  • the total content of filler (s) possibly present in the multicomponent system according to the invention does not exceed 70% by weight of the total weight of said system.
  • the load (s) can be distributed in one or more of the components forming the multicomponent system according to the invention.
  • the multicomponent system according to the invention may include less than 2% by weight of one or more additives advantageously chosen suitably so as not to deteriorate the properties of the composition according to the invention in the crosslinked state. Mention may be made, among the additives which can be used, of antioxidants or UV stabilizers (ultraviolet), pigments and dyes. These additives are preferably chosen from those usually used in adhesive compositions.
  • the additive (s) can be distributed in one or more of the components forming the multicomponent system according to the invention.
  • the aforementioned multicomponent system does not include any solvent and / or plasticizer.
  • the multicomponent system according to the invention can advantageously be used directly by mixing its various components, without adding solvent and / or plasticizer, viscosity reducers , in component (A) and / or without heating of said component to temperatures above 95 ° C.
  • the polyurethane (PP2) according to the invention has a viscosity measured at 23 ° C less than or equal to 600 Pa.s. and a viscosity measured at 60 ° C less than or equal to 40 Pa.s, allowing the multicomponent system according to the invention to be advantageously used without adding solvent and / or plasticizer to the component
  • (A) comprising said polyurethane (PP2), and / or without heating of said component.
  • the multicomponent system according to the invention comprises:
  • a composition comprising at least one polyurethane (PP2) according to the invention, and
  • composition comprising at least one or two amino compound (s) as described in one of the preceding paragraphs (B 1), and said multicomponent system being free of solvent and / or plasticizer.
  • the multicomponent system according to the invention can be a two-component system, that is to say a system consisting of two components (A) and (B), said components (A) and
  • the component (A) comprises at least 97% by weight, and more preferably at least 98% by weight of polyurethane to (PP2) according to the invention relative to the total weight of said component (A).
  • the multicomponent system is an adhesive composition, preferably an adhesive or mastic composition.
  • the invention also relates to the use of a polyurethane (PP2) according to the invention, for the manufacture of an adhesive composition, preferably without solvent, in particular in the form of a multicomponent system.
  • PP2 polyurethane
  • the manufacture of the adhesive composition is carried out without adding a compound intended to lower the viscosity of said composition, such as a solvent (aqueous, organic), a reactive diluent and / or a plasticizer.
  • a compound intended to lower the viscosity of said composition such as a solvent (aqueous, organic), a reactive diluent and / or a plasticizer.
  • the components of the multicomponent system according to the invention comprising the polyurethane (s) (PP2) according to the invention and the amino compound (s) (B1) according to the invention are mixed. at a temperature T3 as defined above.
  • the composition, preferably adhesive, according to the invention is produced by the use of the multicomponent system according to the invention, that is to say the mixture of the various components constituting it, at a mixing temperature T3 .
  • the subject of the invention is also a process for assembling materials using the polyurethane (PP2) according to the invention, in particular by means of the implementation of the multicomponent system according to the invention comprising the following steps:
  • the step of mixing at least one polyurethane (PP2) as described above and at least one amino compound (B1) as described above, can be carried out in particular by using the multicomponent system according to the invention , namely by mixing the components respectively comprising (s) polyurethane (s) (PP2) (component (A)) and the amino compound (s) (component (B)), as defined above .
  • This mixing step can be carried out at room temperature or hot, before coating.
  • the mixing is carried out at a temperature below the degradation temperature of the ingredients included in one or other of the components (A) and (B).
  • the mixing is carried out at a temperature T3 of less than 95 ° C, preferably ranging from 15 to 80 ° C, in order to advantageously avoid any thermal degradation.
  • the polyurethane with endings (PP2) and the amino compound (s) (B1) are mixed in amounts such as the molar ratio of the number of T functions to the number of primary and / or secondary amine groups present. in the mixture, noted ranges from 0.5 to 1, preferably from 0.8 to 1.0.
  • the coating of said mixture can be carried out on all or part of the surface of a material.
  • the coating of said mixture can be carried out in the form of a layer with a thickness ranging from 0.002 to 5 mm.
  • the crosslinking of said mixture on the surface of the material can be accelerated by heating the coated material (s) to a temperature less than or equal to 120 ° C.
  • the time required to complete this crosslinking reaction and thus ensure the required level of cohesion is generally on the order of 0.5 to 24 hours.
  • the coating and laminating of the second material are generally carried out in a time interval compatible with the coating process, as is well known to those skilled in the art, that is to say before the layer of adhesive loses its ability to glue the two materials together.
  • Suitable materials are, for example, inorganic substrates such as glass, ceramics, concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals) as well as metals and composites possibly coated with paint (as in the automotive field); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, epoxy resins and polyesters.
  • inorganic substrates such as glass, ceramics, concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals) as well as metals and composites possibly coated with paint (as in the automotive field); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, epoxy resins and polyesters.
  • the present invention also relates to the use of a polyurethane comprising at least two T terminal functions of formula (I) (PP2) according to the invention for the manufacture of an adhesive composition.
  • compositions according to the invention can be measured in accordance with the tests described in the examples which follow, namely once crosslinked.
  • the compositions according to the invention are advantageously adapted to a wide range of applications such as the food industry, cosmetics, hygiene, transport, housing, textiles, packaging.
  • the compositions according to the invention exhibit an intrinsic elongation force at break ranging from 0.3 to 10 MPa, as illustrated in the examples (measurement of mechanical performance).
  • the polyurethane (PP2) according to the invention advantageously exhibits improved reactivity with respect to amino compounds comprising at least two primary and / or secondary amine groups at a temperature close to ambient (ranging for example from 15 ° C to 35 ° C).
  • Examples 1 to 4 are prepared using the reagents indicated in Table 1 and according to the procedure described on the following pages.
  • the quantities indicated in table 1 are expressed in grams of commercial products.
  • - PPG diol the commercial product sold under the name VORANOL® P2000 by the company DOW, corresponding to polypropylene glycol diol, having a hydroxyl number approximately equal to 56 mg KOH / g,
  • - PPG triol the commercial product sold under the name VORANOL® CP3355 by the company DOW, corresponding to polypropylene glycol triol, having a hydroxyl number approximately equal to 45 mg KOH / g,
  • 2,4-TDI diisocyanate the commercial product sold under the name SCURANATE® T 100 by the company VENCOREX, corresponding to a TDI composition at 99% by weight of 2,4-TDI,
  • HDI hexamethylene allophanate diisocyanate
  • TOLONATE® X FLO the commercial product sold under the name TOLONATE® X FLO by the company VENCOREX, corresponding to a composition at 99.5% by weight minimum of derivative hexamethylene diisocyanate allophanate (HDI) of formula (MA) and less than 0.5% by weight of HDI, having an NCO group content equal to 13.4% by weight relative to the weight of TOLONATE® X FLO ,
  • the molar ratios r 1 and r 2 are calculated in a manner well known to those skilled in the art from the molar quantities of reagents used.
  • the number of mole (s) of diisocyanate used as a function of the molar mass of the latter the number of mole (s) of polyol used as a function of the hydroxyl number (mg KOH / g) and of the functionality of the latter, the number of mole (s) of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate used as a function of the hydroxyl number (mg KOH / g) of the latter and knowing that the mass KOH molar is 56.1 1 g / mol, we can write:
  • m1 (diisocyanate) corresponds to the mass of diisocyanate introduced (SCURANATE® T100 or TOLONATE X FLO according to the example considered)
  • diisocyanate corresponds to the molar mass of the diisocyanate introduced
  • IOH polyol
  • polyol corresponds to the hydroxyl index of the polyol used (VORANOL® P2000 or VORANOL® CP3355 according to the example considered),
  • m2 (polyol) corresponds to the mass of the polyol introduced
  • IOH (2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate) corresponds to the hydroxyl number of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate,
  • m3 (2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate) corresponds to the mass of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate introduced.
  • the diisocyanate is heated to 50 ° C. and then a mixture of polyol and reaction catalyst is introduced, with constant stirring, drop by drop, controlling the reaction temperature T1 so that it does not exceed 80 ° C, in accordance with the quantities indicated in Table 1.
  • This mixture is kept under constant stirring at 80 ° C., under nitrogen, until the NCO functions of the diisocyanate have completely reacted.
  • the reaction is monitored by measuring the change in the content of NCO groups in the mixture, for example by dosing dibutylamine in return, using hydrochloric acid according to standard NF T52-132.
  • the reaction is stopped when the "NCO level" (% NCO) measured is approximately equal to the desired NCO level.
  • Step E2 Synthesis of polyurethane (PP2) (component A)
  • step E1 the 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate is introduced into the reactor in the proportions indicated in the Table 1, with stirring and under nitrogen, ensuring that the reaction temperature T2 does not exceed 80 ° C.
  • the polyurethane mixture with NCO endings (PP1) - 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate is kept under constant stirring at 80 ° C., under nitrogen, until complete disappearance of the NCO functions visible in Infra-Red (IR) (about 2250 cm- 1 )
  • IR Infra-Red
  • the viscosity of the component (A) obtained is measured 24 hours after the end of the reaction (D + 1) at 23 ° C and 60 ° C and expressed in Pascal second (Pa.s). All the values measured for Examples 1 to 4 are grouped in Table 2 below.
  • the viscosity measurement at 23 ° C is carried out using a Brookfield RVT viscometer, with a needle suitable for the viscosity range and at a rotation speed of 20 revolutions per minute (rpm).
  • the viscosity measurement at 60 ° C. is done using a Brookfield RVT viscometer coupled with a Thermosel type heating module from the Brookfield brand, with a mobile adapted to the viscosity range and at a rotation speed of 20 revolutions. per minute.
  • the content of T functions in polyurethane (PP2) (denoted t cc (PP2)) (expressed in meq / g of polyurethane (PP2)) is calculated in a manner well known to those skilled in the art from the molar amount of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate introduced.
  • PP2 polyurethane
  • t cc polyurethane
  • IOH (2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate) corresponds to the hydroxyl number of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate,
  • m3 (2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate) corresponds to the mass of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate introduced,
  • m (PP2) corresponds to the mass of polyurethane (PP2), ie to the total mass of the ingredients used for the synthesis of polyurethane (PP2) (PPG diol or triol, diisocyanate, reaction catalyst).
  • TAEA (2-aminoethyl) amine
  • HMDA hexamethylene diamine
  • the molar ratio r3 is calculated in a manner well known to those skilled in the art from the molar quantities of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate and of amino compound (s) having at least two primary amine groups (-NH 2 ).
  • t cc is the content calculated as T functions in the polyurethane (PP2) (meq / g) as defined above,
  • m (PP2) corresponds to the mass of polyurethane (PP2) as defined above,
  • APk is the primary alkalinity of each amino compound
  • k is an integer greater than or equal to 1.
  • the component (A) is heated to between 65 and 80 ° C. then the component (B) consisting of the amino compound (s) (B1) is added. and optionally charging, with stirring. The mixing is carried out hot at the temperature T3 between indicated and is kept under constant stirring for 2 minutes under vacuum (for boiling).
  • Measurement of mechanical performance resistance and elongation at break of the compositions according to the invention in the crosslinked state Once crosslinked, the resistance and elongation at break are measured by tensile test of the adhesive composition according to the protocol described below.
  • the principle of the measurement consists in drawing in a tensile machine, the movable jaw of which moves at a constant speed equal to 100 mm / minute, a standard test piece consisting of the crosslinked adhesive composition; and record, at the time of the rupture of the test piece, the applied tensile stress (in MPa) as well as the elongation of the test piece (in%).
  • the standard test piece is dumbbell-shaped, as illustrated in international standard ISO 37.
  • the narrow part of the dumbbell used is 20 mm long, 4 mm wide and 500 mm thick.
  • the conditioned composition is heated to 95 ° C. as described above, then the quantity necessary is extruded onto an A4 sheet of silicone paper to form thereon a film having a thickness of 500 mm which is left for 7 days at 23 ° C and 50% relative humidity for crosslinking.
  • the dumbbell is then obtained by simply cutting out the crosslinked film using a cookie cutter.
  • the tensile strength test is repeated twice and gives the same results.
  • the applied applied tensile stress is expressed in Megapascal (MPa, ie 10 6 Pa) and the elongation at break in% relative to the initial length of the test piece. The values are collated in Table 4 below.
  • the adhesive compositions 1 ′, 2 ′, 4 ′, 5 ′ and 8 ′ according to the invention were moreover subjected to tests of bonding of two strips of powdered aluminum (each of size 100 mm ⁇ 25 mm) previously cleaned with a solvent (isopropanol).
  • the adhesive composition is applied to one of the surfaces of the strips using a spatula, in a space delimited by a window of 12.5 mm ⁇ 25 mm in Teflon.
  • the other strip is affixed over the surface coated with glue, pressing the two strips against each other. After crosslinking for seven days at 23 ° C. and 50% relative humidity, the shear force at break and the break face are measured. Table 5
  • the adhesive compositions according to the invention can be easily formulated, using a preparation process which is inexpensive in energy and respectful of man and his environment, using neither solvent nor plasticizer.
  • the adhesive compositions according to the invention lead to performance adhesives in terms of mechanical properties and / or adhesion strength, suitable for a wide range of applications.

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Abstract

The invention relates to a polyurethane (PP2) that has at least two, preferably two or three, terminal functions T of formula (I). The invention also relates to the uses of said polyurethanes (PP2) in the production of multicomponent systems.

Description

Polyuréthane à terminaisons (2-oxo-1 ,3-dioxolane-4-carboxylate) Polyurethane with endings (2-oxo-1, 3-dioxolane-4-carboxylate)
DOMAINE DE L’INVENTION FIELD OF THE INVENTION
La présente invention concerne un polyuréthane à terminaisons (2-oxo-1 ,3- dioxolane-4-carboxylate), et son procédé de préparation. The present invention relates to a polyurethane with endings (2-oxo-1, 3-dioxolane-4-carboxylate), and to a process for its preparation.
La présente invention concerne également un système multicomposant comprenant ledit polyuréthane. The present invention also relates to a multicomponent system comprising said polyurethane.
L’invention concerne également un procédé d’assemblage de matériaux par collage, mettant en oeuvre ledit polyuréthane. The invention also relates to a method of assembling materials by gluing, using said polyurethane.
ARRIERE-PLAN TECHNOLOGIQUE TECHNOLOGICAL BACKGROUND
On connaît depuis longtemps des compositions adhésives (de colle ou mastic), à base de polyuréthane, notamment sous la forme de systèmes multicomposants (généralement bicomposants) dans lesquels les (deux) composants réactifs nécessaires à la synthèse du polyuréthane sont stockés de manière séparée, et mélangés au dernier moment avant utilisation de la composition adhésive. Adhesive compositions (glue or mastic), based on polyurethane, have long been known, in particular in the form of multicomponent systems (generally two-component) in which the (two) reactive components necessary for the synthesis of polyurethane are stored separately, and mixed at the last moment before using the adhesive composition.
Pour qu’un tel système soit correctement mis en oeuvre, il est préférable que les composants réactifs présentent d’une part une réactivité suffisante pour que la réaction ait lieu et s’opère rapidement, et d’autre part une viscosité adaptée à la température de mélange pour que celui-ci s’opère aisément. For such a system to be correctly implemented, it is preferable that the reactive components have on the one hand sufficient reactivity for the reaction to take place and take place quickly, and on the other hand a viscosity adapted to the temperature. of mixing so that it operates easily.
Traditionnellement, la synthèse d’un polyuréthane a lieu par une réaction de polyaddition entre un polyol et un polyisocyanate. Traditionally, the synthesis of a polyurethane takes place by a polyaddition reaction between a polyol and a polyisocyanate.
Toutefois, les polyisocyanates sont des composés très sensibles en présence d’humidité atmosphérique et nécessitent de prendre des mesures appropriées pour éviter leur réticulation prématurée, et donc leur perte de réactivité, au cours de leur manipulation et de leur stockage (conditions anhydres). De plus, certains de ces composés, tels que l’hexaméthylène diisocyanate (HDI), l’isophorone diisocyanate (I PDI), le toluène diisocyanate (TDI) ou le diisocyanate de diphényle méthane (MDI) sont connus comme présentant des risques toxicologiques pour l’homme et l’environnement, et peuvent même générer des émissions toxiques pour les plus volatiles. However, polyisocyanates are very sensitive compounds in the presence of atmospheric humidity and require taking appropriate measures to avoid their premature crosslinking, and therefore their loss of reactivity, during their handling and storage (anhydrous conditions). In addition, some of these compounds, such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (I PDI), toluene diisocyanate (TDI) or diphenyl methane diisocyanate (MDI) are known to present toxicological risks for humans and the environment, and can even generate toxic emissions for the most volatile.
L’utilisation et le stockage de grande quantité de tels polyisocyanates est donc à éviter car cela nécessite de mettre en place des dispositifs de sécurité complexes et coûteux adaptés à leur utilisation et leur stockage. En particulier, on souhaite éviter d’avoir recours à de tels composés lors de la dernière étape de synthèse du polyuréthane, afin de pouvoir mettre à disposition du public des compositions adhésives à base de polyuréthane sous forme de systèmes multicomposants, plus respectueux de l’homme et son environnement et plus stable au stockage. The use and storage of large quantities of such polyisocyanates is therefore to be avoided since this necessitates setting up complex and costly safety devices adapted to their use and storage. In particular, it is desired to avoid using such compounds during the last polyurethane synthesis step, in order to be able to make available to the public adhesive compositions based on polyurethane in the form of multicomponent systems, more respectful of man and his environment and more stable in storage.
En outre, lorsqu’on désire formuler des compositions sous forme de kit transportable, pratique, facile et rapide à mettre en oeuvre à la demande (« Do It Yourself »), le mélange des réactifs doit pouvoir se faire autant que possible sur des volumes restreints et à basse température, notamment à température ambiante. In addition, when it is desired to formulate compositions in the form of a transportable kit, practical, easy and quick to implement on demand (“Do It Yourself”), the mixing of the reagents must be possible as much as possible on volumes restricted and at low temperature, especially at room temperature.
WO2015/140458 décrit des systèmes multi-composants, et en particulier bi- composant, obtenus par mélange d’un composant A comprenant au moins un prépolymère de polyuréthane fonctionnalisé par du carbonate de glycérol en bout de chaîne, avec un composant B comprenant au moins deux groupes amine primaire et/ou secondaire. Bien que ces compositions présentent l’avantage de ne pas utiliser de polyisocyanate lors du mélangeage des composants A et B, la réaction des groupes (2-oxo-1 ,3-dioxolan-4-yl) du composant A avec les groupes amine primaire et/ou secondaire du composant B est lente à basse température. Il est donc nécessaire de réaliser le mélange desdits composants à une température élevée, par exemple à plus de 80°C. Ainsi, de tels systèmes restent à améliorer en termes de réactivité. WO2015 / 140458 describes multi-component systems, and in particular two-component systems, obtained by mixing a component A comprising at least one polyurethane prepolymer functionalized with glycerol carbonate at the chain end, with a component B comprising at least two primary and / or secondary amine groups. Although these compositions have the advantage of not using polyisocyanate when mixing components A and B, the reaction of the (2-oxo-1, 3-dioxolan-4-yl) groups of component A with the primary amine groups and / or secondary of component B is slow at low temperature. It is therefore necessary to carry out the mixing of said components at a high temperature, for example at more than 80 ° C. Thus, such systems remain to be improved in terms of reactivity.
Par conséquent, il existe un besoin de mettre à disposition des compositions à base de polyuréthane ne présentant pas les inconvénients de l’art antérieur. Plus particulièrement, il existe un besoin de nouvelles compositions à base de polyuréthane présentant une meilleure réactivité à basse température, tout en conservant des propriétés adhésives satisfaisantes. Consequently, there is a need to provide polyurethane-based compositions which do not have the drawbacks of the prior art. More particularly, there is a need for new polyurethane-based compositions having better reactivity at low temperatures, while retaining satisfactory adhesive properties.
Il existe également un besoin de formuler des compositions à base de polyuréthane, disponibles sous forme de système multicomposants et notamment bicomposants, qui soient plus faciles à utiliser comparativement à l’art antérieur, à des températures de mélangeage et de réaction inférieure à 60°C, de préférence inférieure ou égale à 35°C, et plus préférentiellement proche de la température ambiante (23°C). There is also a need to formulate compositions based on polyurethane, available in the form of multicomponent system and in particular bicomponent, which are easier to use compared to the prior art, at mixing and reaction temperatures below 60 ° C. , preferably less than or equal to 35 ° C, and more preferably close to room temperature (23 ° C).
En particulier, il existe un besoin de trouver des compositions disponibles sous forme de systèmes multicomposants, notamment transportables (kits), respectueuses de l’homme et de l’environnement. In particular, there is a need to find compositions available in the form of multicomponent systems, in particular transportable (kits), respectful of man and the environment.
Il existe également un besoin de mettre à disposition des systèmes multicomposants dont la mise en oeuvre conduit à des compositions adhésives, notamment des compositions de colle ou de mastic, présentant des performances mécaniques (par exemple élongation et/ou module) adaptées à l’utilisation de la composition adhésive. There is also a need to make available multi-component systems, the implementation of which results in adhesive compositions, in particular adhesive or mastic compositions, exhibiting mechanical performance (for example elongation and / or module) suitable for use. of the adhesive composition.
Il existe en outre un besoin de mettre au point un procédé de préparation de telles compositions adhésives, qui soit économique, rapide à mettre en oeuvre, et/ou respectueux de l’homme et de l’environnement. Il est recherché notamment un procédé de préparation de telles compositions peu coûteux en énergie et ne mettant pas en oeuvre de grande quantité de solvant contrairement aux procédés de préparation existant. There is also a need to develop a process for preparing such adhesive compositions, which is economical, quick to use, and / or respectful of man and the environment. A process for the preparation of such compositions inexpensive in energy and not using a large amount of solvent unlike the existing preparation methods.
DESCRIPTION DE L’INVENTION DESCRIPTION OF THE INVENTION
Dans la présente demande, en l'absence d'indication contraire : In the present application, in the absence of an indication to the contrary:
- les quantités exprimées sous la forme de pourcentage correspondent à des pourcentages poids/poids ; - the quantities expressed as a percentage correspond to weight / weight percentages;
- les masses molaires moyennes en nombre, exprimées en gramme par mole (g/mol) sont déterminées par calcul par l’analyse de la teneur en groupes terminaux (NCO, OH et fonctions T) exprimée en milliéquivalent par gramme (méq/g) et la fonctionnalité (nombre de fonction NCO, OH ou fonction T par mole) du composé (PP1 ), du polyol, du composé de formule (IV) ou du polyuréthane comprenant au moins deux fonctions terminales T (PP2) respectivement) ; - the number-average molar masses, expressed in grams per mole (g / mol) are determined by calculation by analyzing the content of terminal groups (NCO, OH and T functions) expressed in milliequivalents per gram (meq / g) and the functionality (number of NCO, OH function or T function per mole) of the compound (PP1), of the polyol, of the compound of formula (IV) or of the polyurethane comprising at least two terminal T functions (PP2) respectively);
- l’indice hydroxyle d’un produit alcoolique représente le nombre de fonctions hydroxyles par gramme de produit, et est exprimé sous la forme du nombre équivalent de milligrammes de potasse (KOH) utilisés dans le dosage des fonctions hydroxyles, par gramme de produit ; - The hydroxyl index of an alcoholic product represents the number of hydroxyl functions per gram of product, and is expressed in the form of the equivalent number of milligrams of potassium hydroxide (KOH) used in the determination of hydroxyl functions, per gram of product;
- la mesure de viscosité à 23°C peut se faire à l’aide d’un viscosimètre Brookfield selon la norme ISO 2555. Typiquement, la mesure réalisée à 23°C peut se faire à l’aide d’un viscosimètre Brookfield RVT, d’une aiguille adaptée au domaine de viscosité et à une vitesse de rotation de 20 tours par minute (tr/mn) ; - the viscosity measurement at 23 ° C can be done using a Brookfield viscometer according to ISO 2555. Typically, the measurement carried out at 23 ° C can be done using a Brookfield RVT viscometer, a needle adapted to the viscosity range and at a rotation speed of 20 revolutions per minute (rpm);
- la mesure de viscosité à 60°C peut se faire à l’aide d’un viscosimètre Brookfield RVT couplé avec un module chauffant de type Thermosel de la marque Brookfield, d’un mobile adapté au domaine de viscosité et à une vitesse de rotation de 20 tours par minute. - the viscosity measurement at 60 ° C can be done using a Brookfield RVT viscometer coupled with a Thermosel type heating module from the Brookfield brand, a mobile adapted to the viscosity range and at a rotation speed 20 revolutions per minute.
A. Polyuréthane A. Polyurethane
La présente invention concerne un polyuréthane (PP2) comprenant au moins deux, de préférence deux ou trois, fonctions terminales T de formule (I) suivante : The present invention relates to a polyurethane (PP2) comprising at least two, preferably two or three, T terminal functions of formula (I) below:
dans laquelle R1 et R2, identiques ou différents, représentent chacun : in which R 1 and R 2 , identical or different, each represent:
- un atome d’hydrogène, - un groupe alkyle linéaire ou ramifié, saturé ou insaturé, ledit groupe alkyle étant de préférence un groupe alkyle en C1 -C22, préférentiellement en C1 -C12, - a hydrogen atom, a linear or branched, saturated or unsaturated alkyl group, said alkyl group preferably being a C1-C22, preferably C1-C12 alkyl group,
- un groupe (hétéro)aryle en C6-C12, - a C6-C12 (hetero) aryl group,
- un groupe cycloalkyle saturé ou instauré en C3-C8, préférentiellement en C5-C6, ou - a saturated or established cycloalkyl group at C3-C8, preferably at C5-C6, or
- un groupe alkylaryle dans lequel le groupe alkyle, linéaire ou ramifié, comprend de 1 à 22 atomes de carbone; an alkylaryl group in which the linear or branched alkyl group comprises from 1 to 22 carbon atoms;
lesdits groupes alkyles ou cycloalkyles comprenant éventuellement un ou plusieurs hétéroatomes, de préférence oxygène ou souffre. said alkyl or cycloalkyl groups optionally comprising one or more heteroatoms, preferably oxygen or sulfur.
Selon un mode de réalisation, le polyuréthane (PP2) susmentionné est tel que chacun de R1 et R2 représente, indépendamment l’un de l’autre, un atome d’hydrogène ou un groupe alkyle linéaire ou ramifié, saturé ou insaturé, ledit groupe alkyle étant de préférence un groupe alkyle en C1 -C12, avantageusement méthyle ou éthyle. According to one embodiment, the aforementioned polyurethane (PP2) is such that each of R 1 and R 2 represents, independently of one another, a hydrogen atom or a linear or branched, saturated or unsaturated alkyl group, said alkyl group preferably being a C1-C12 alkyl group, advantageously methyl or ethyl.
De préférence, le polyuréthane (PP2) est tel que R1 représente un atome d’hydrogène et R2 représente un atome d’hydrogène, un méthyle ou un éthyle. Preferably, the polyurethane (PP2) is such that R 1 represents a hydrogen atom and R 2 represents a hydrogen atom, methyl or ethyl.
Selon un mode de réalisation, le polyuréthane (PP2) susmentionné comprend en outre au moins l’un des radicaux divalents R3 suivants : According to one embodiment, the aforementioned polyurethane (PP2) further comprises at least one of the following divalent radicals R 3 :
a) radical divalent -(CH2)5- dérivé du pentaméthylène diisocyanate (PDI), a) divalent radical - (CH2) 5- derived from pentamethylene diisocyanate (PDI),
b) radical divalent -(CH2)6 -dérivé de l’hexaméthylène diisocyanate (HDI), b) divalent radical - (CH2) 6 - derivative of hexamethylene diisocyanate (HDI),
c) le radical divalent dérivé de l’isophorone : c) the divalent radical derived from isophorone:
d) le radical divalent dérivé des 2,4-toluène diisocyanate et 2,2’-toluène diisocyanate (TDI), e) le radical divalent dérivé des 4,4’-méthylène diphényl diisocyanate et 4,4’-méthylène diphényl diisocyanate (MDI), d) the divalent radical derived from 2,4-toluene diisocyanate and 2,2'-toluene diisocyanate (TDI), e) the divalent radical derived from 4,4'-methylene diphenyl diisocyanate and 4,4'-methylene diphenyl diisocyanate ( MDI),
f) le radical divalent dérivé du para-xylylène diisocyanate, méta-xylylène diisocyanate et ortho- xylylène diisocyanate (XDI), f) the divalent radical derived from para-xylylene diisocyanate, meta-xylylene diisocyanate and ortho-xylylene diisocyanate (XDI),
g) le radical divalent dérivé du 1 ,2-bis(isocyanatométhyl)cyclohexane, 1 ,3- bis(isocyanatométhyl)cyclohexane et 1 ,4-bis(isocyanatométhyl)cyclohexane (H6XDI) : g) the divalent radical derived from 1,2-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane (H6XDI):
h) les radicaux divalents dérivés des 2,4’- méthylène dicyclohexyl diisocyanate et 4,4'- méthylene dicyclohexyl diisocyanate (H12MDI) : h) divalent radicals derived from 2,4′-methylene dicyclohexyl diisocyanate and 4,4′-methylene dicyclohexyl diisocyanate (H12MDI):
[Chem 3] [Chem 3]
ou i) le radical divalent de formule (II) suivante: or i) the divalent radical of formula (II) below:
dans laquelle : in which :
- p est un nombre entier allant de 1 à 2 ; - p is an integer ranging from 1 to 2;
- q est un nombre entier allant de 0 à 9 ; - q is an integer ranging from 0 to 9;
- r est un nombre entier valant 5 ou 6 ; - r is an integer equal to 5 or 6;
- R représente une chaîne hydrocarbonée, saturée ou insaturée, cyclique ou acyclique, linéaire ou ramifiée, comprenant de 1 à 20 atomes de carbone ; et - R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms; and
- R’ représente un groupe divalent hydrocarboné, linéaire ou ramifié, saturé, ayant de 2 à 4 atomes de carbone. - R ’represents a divalent hydrocarbon group, linear or branched, saturated, having 2 to 4 carbon atoms.
De préférence, le polyuréthane (PP2) susmentionné comprend en outre au moins l’un des radicaux divalents R3 suivants : Preferably, the aforementioned polyurethane (PP2) further comprises at least one of the following divalent radicals R 3 :
a) le radical divalent -(CH2)5- dérivé du pentaméthylène diisocyanate (PDI) ; a) the divalent radical - (CH2) 5- derived from pentamethylene diisocyanate (PDI);
b) le radical divalent -(CH2)6- dérivé de l’hexaméthylène diisocyanate (HDI) ; b) the divalent radical - (CH2) 6- derived from hexamethylene diisocyanate (HDI);
c) le radical divalent dérivé de l’isophorone : c) the divalent radical derived from isophorone:
d) le radical divalent dérivé du 2,4-TDI d) the divalent radical derived from 2,4-TDI
e) le radical divalent dérivé du 2,4’-MDI: f) le radical divalent dérivé du méta-xylylène diisocyanate (m-XDI) : e) the divalent radical derived from 2,4'-MDI: f) the divalent radical derived from meta-xylylene diisocyanate (m-XDI):
g) le radical divalent dérivé du 1 ,3-bis(isocyanatométhyl)cyclohexane (m-H6XDI) : g) the divalent radical derived from 1,3-bis (isocyanatomethyl) cyclohexane (m-H6XDI):
h) les radicaux divalents dérivés des 2,4’- méthylène dicyclohexyl diisocyanate et 4,4'- méthylene dicyclohexyl diisocyanate (H12MDI) : h) divalent radicals derived from 2,4'-methylene dicyclohexyl diisocyanate and 4,4'-methylene dicyclohexyl diisocyanate (H12MDI):
i) le radical divalent de formule (II) suivante: i) the divalent radical of formula (II) below:
dans laquelle : in which :
- p est un nombre entier allant de 1 à 2 ; - p is an integer ranging from 1 to 2;
- q est un nombre entier allant de 0 à 9 ; - q is an integer ranging from 0 to 9;
- r est un nombre entier valant 5 ou 6 ; - r is an integer equal to 5 or 6;
- R représente une chaîne hydrocarbonée, saturée ou insaturée, cyclique ou acyclique, linéaire ou ramifiée, comprenant de 1 à 20 atomes de carbone ; et - R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms; and
- R’ représente un groupe divalent hydrocarboné, linéaire ou ramifié, saturé, ayant de 2 à 4 atomes de carbone. - R ’represents a divalent hydrocarbon group, linear or branched, saturated, having 2 to 4 carbon atoms.
De préférence, le polyuréthane (PP2) susmentionné comprend au moins un radical R3 choisi parmi les radicaux d) dérivé du 2,4-TDI et/ou parmi les radicaux j) de formule (II) susmentionnée. Preferably, the polyurethane (PP2) mentioned above comprises at least one radical R 3 chosen from the radicals d) derived from 2,4-TDI and / or from the radicals j) of formula (II) above mentioned.
Selon un mode de réalisation, le polyuréthane (PP2) susmentionné comprend au moins une unité répétitive comprenant au moins un radical divalent R3 susmentionné. According to one embodiment, the polyurethane (PP2) mentioned above comprises at least one repeating unit comprising at least one divalent radical R 3 mentioned above.
Selon un mode de réalisation, le polyuréthane (PP2) susmentionné a la formule (III) suivante : According to one embodiment, the aforementioned polyurethane (PP2) has the following formula (III):
dans laquelle : in which :
- R1 et R2 sont tels que définis ci-dessus, R1 étant de préférence un atome d’hydrogène et R2 étant de préférence un atome d’hydrogène, un méthyle ou un éthyle ; - R 1 and R 2 are as defined above, R 1 preferably being a hydrogen atom and R 2 preferably being a hydrogen atom, methyl or ethyl;
- P représente l’une des deux formules ci-dessous : - P represents one of the two formulas below:
dans lesquelles D et T représentent, indépendamment l’un de l’autre, un radical hydrocarboné comprenant de 2 à 66 atomes de carbone, linéaire ou ramifié, cyclique, alicyclique ou aromatique, saturé ou insaturé, comprenant éventuellement un ou plusieurs hétéroatomes ; in which D and T represent, independently of one another, a hydrocarbon radical comprising from 2 to 66 carbon atoms, linear or branched, cyclic, alicyclic or aromatic, saturated or unsaturated, optionally comprising one or more heteroatoms;
- P’ et P” étant, indépendamment l’un de l’autre, un radical divalent issu d’un polyol de préférence choisi parmi les polyéther polyols, les polydiène polyols, les polyester polyols, les polycarbonate polyols, les polyols étant préférentiellement ceux décrits ci- après pour l’étape E1 ; - P 'and P ”being, independently of one another, a divalent radical derived from a polyol preferably chosen from polyether polyols, polydiene polyols, polyester polyols, polycarbonate polyols, the polyols preferably being those described below for step E1;
- R3 étant tel que défini ci-dessus ; - R 3 being as defined above;
- m et f sont des nombres entiers tel que la masse moléculaire moyenne du polyuréthane va de 600 à 100 000 g/mol ; - m and f are whole numbers such that the average molecular weight of the polyurethane ranges from 600 to 100,000 g / mol;
- f est égal à 2 ou 3. - f is equal to 2 or 3.
Le polyuréthane (PP2) susmentionné peut avoir une viscosité mesurée à température ambiante (23°C) inférieure ou égale à 1 500 Pa.s, plus préférentiellement inférieure ou égale à 600 Pa.s, et mieux encore inférieure ou égale à 400 Pa.s. The aforementioned polyurethane (PP2) may have a viscosity measured at room temperature (23 ° C) less than or equal to 1,500 Pa.s, more preferably less than or equal to 600 Pa.s, and better still less than or equal to 400 Pa. s.
Le polyuréthane (PP2) selon l’invention peut avoir une viscosité mesurée à 60°C inférieure ou égale à 50 Pa.s, plus préférentiellement inférieure ou égale à 40 Pa.s, et mieux encore inférieure ou égale à 30 Pa.s. The polyurethane (PP2) according to the invention may have a viscosity measured at 60 ° C less than or equal to 50 Pa.s, more preferably less than or equal to 40 Pa.s, and better still less than or equal to 30 Pa.s.
De préférence, le polyuréthane (PP2) susmentionné possède une viscosité mesurée à température ambiante (23°C) inférieure ou égale à 600 Pa.s et une viscosité mesurée à 60°C inférieure ou égale à 40 Pa.s. Preferably, the aforementioned polyurethane (PP2) has a viscosity measured at room temperature (23 ° C) less than or equal to 600 Pa.s and a viscosity measured at 60 ° C less than or equal to 40 Pa.s.
Le polyuréthane (PP2) comprenant au moins deux fonctions terminales T susmentionné peut être obtenu par réaction d’un composé possédant au moins deux groupes NCO (PP1 ) et d’au moins un composé de formule (IV) suivante : The polyurethane (PP2) comprising at least two T-terminal functions mentioned above can be obtained by reaction of a compound having at least two NCO groups (PP1) and at least one compound of the following formula (IV):
dans laquelle R1 et R2, identiques ou différents, représentent chacun : - un atome d’hydrogène, in which R 1 and R 2 , identical or different, each represent: - a hydrogen atom,
- un groupe alkyle linéaire ou ramifié, saturé ou insaturé, ledit groupe alkyle étant de préférence un groupe alkyle en C1-C22, préférentiellement en C1-C12, a linear or branched, saturated or unsaturated alkyl group, said alkyl group preferably being a C1-C22 alkyl group, preferably a C1-C12 alkyl group,
- un groupe (hétéro)aryle en C6-C12, - a C6-C12 (hetero) aryl group,
- un groupe cycloalkyle saturé ou instauré en C3-C8, préférentiellement en C5-C6, ou - a saturated or established cycloalkyl group at C3-C8, preferably at C5-C6, or
- un groupe alkylaryle dans lequel le groupe alkyle, linéaire ou ramifié, comprend de 1 à 22 atomes de carbone; an alkylaryl group in which the linear or branched alkyl group comprises from 1 to 22 carbon atoms;
lesdits groupes alkyles ou cycloalkyles comprenant éventuellement un ou plusieurs hétéroatomes, de préférence oxygène ou souffre. said alkyl or cycloalkyl groups optionally comprising one or more heteroatoms, preferably oxygen or sulfur.
Les composés de formule (IV) peuvent être synthétisés tel que décrit dans WO 2015/132080, par exemple selon le schéma (1 ) suivant : The compounds of formula (IV) can be synthesized as described in WO 2015/132080, for example according to the following scheme (1):
Selon un mode de réalisation, les composés de formule (IV) sont ceux répondant à la formule (IV-1 ) suivante : According to one embodiment, the compounds of formula (IV) are those corresponding to the following formula (IV-1):
dans laquelle R2 est tel que défini précédemment. Les composés de formule (IV-1 ) sont des composés de formule (IV) dans laquelle R1 est un atome d’hydrogène. in which R 2 is as defined above. The compounds of formula (IV-1) are compounds of formula (IV) in which R 1 is a hydrogen atom.
Les composés de formule (IV-1 ) préférés sont ceux ayant l’une des formules (IV-1 a), (IV-1 b) et (IV-1 c) suivantes : The preferred compounds of formula (IV-1) are those having one of the following formulas (IV-1 a), (IV-1 b) and (IV-1 c):
Les composés de formule (IV-1 a), (I V-1 b) et (IV-c) peuvent être obtenus par réaction du carbonate d’acide glycérique respectivement avec l’oxyde d’éthylène (OE), l’oxyde de propylène (OP) ou l’oxyde de butylène (OB) selon le schéma (1 ) précédemment décrit. The compounds of formula (IV-1 a), (I V-1 b) and (IV-c) can be obtained by reaction of the glyceric acid carbonate respectively with ethylene oxide (EO), the oxide propylene (OP) or butylene oxide (OB) according to the scheme (1) previously described.
Le composé de formule (IV-1 a) est un composé de formule (IV) dans laquelle R1 est un atome d’hydrogène, et R2 est un atome hydrogène, soit le 2-hydroxyéthyl-2-oxo-1 ,3- dioxolane-4-carboxylate. The compound of formula (IV-1 a) is a compound of formula (IV) in which R 1 is a hydrogen atom, and R 2 is a hydrogen atom, namely 2-hydroxyethyl-2-oxo-1, 3 - dioxolane-4-carboxylate.
Le composé de formule (I V-1 b) est un composé de formule (IV) dans laquelle R1 est un atome d’hydrogène, et R2 est un méthyle, soit le 2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4- carboxylate. The compound of formula (I V-1 b) is a compound of formula (IV) in which R 1 is a hydrogen atom, and R 2 is a methyl, namely 2-hydroxypropyl-2-oxo-1, 3 -dioxolane-4-carboxylate.
Le composé de formule (IV-1 c) est un composé de formule (IV) dans laquelle R1 est un atome d’hydrogène, et R2 est un éthyle, soit le 2-hydroxybutyl-2-oxo-1 ,3-dioxolane-4- carboxylate. The compound of formula (IV-1 c) is a compound of formula (IV) in which R 1 is a hydrogen atom, and R 2 is an ethyl, ie 2-hydroxybutyl-2-oxo-1, 3- dioxolane-4-carboxylate.
B. Procédé B. Process
La présente invention concerne également un procédé de préparation d’un polyuréthane (PP2) susmentionné comprenant au moins deux, de préférence deux ou trois, fonctions terminales T de formule (I) comprenant une étape de réaction de polyaddition (notée E2) : The present invention also relates to a process for the preparation of a polyurethane (PP2) mentioned above comprising at least two, preferably two or three, T terminal functions of formula (I) comprising a polyaddition reaction step (denoted E2):
- d’au moins un composé (PP1 ) possédant au moins deux groupes NCO ; - at least one compound (PP1) having at least two NCO groups;
- avec au moins un composé de formule (IV) susmentionnée ; - with at least one compound of formula (IV) above;
dans des quantités de composé(s) (PP1 ) et de composé(s) de formule (IV) conduisant à un rapport molaire NCO/OH, noté r2, inférieur ou égal à 1 , de préférence allant de 0,8 à 1 , préférentiellement de 0,85 à 1 , avantageusement de 0,90 à 1 , et encore plus préférentiellement de 0,95 à 1 . Dans le cadre de l’invention, et sauf mention contraire, r2 est le rapport molaire NCO/OH correspondant au rapport molaire du nombre de groupes isocyanates sur le nombre de groupes hydroxyles portés respectivement par l’ensemble des isocyanate(s) (composé(s) (PP1 ) et éventuellement le(s) polyisocyanate(s) non réagi(s) à l’issue d’une éventuelle étape E1 ), et alcool(s) présents dans le milieu réactionnel de l’étape E2. in amounts of compound (s) (PP1) and compound (s) of formula (IV) leading to an NCO / OH molar ratio, denoted r2, less than or equal to 1, preferably ranging from 0.8 to 1, preferably from 0.85 to 1, advantageously from 0.90 to 1, and even more preferably from 0.95 to 1. In the context of the invention, and unless otherwise stated, r 2 is the NCO / OH molar ratio corresponding to the molar ratio of the number of isocyanate groups to the number of hydroxyl groups carried respectively by all of the isocyanate (s) (compound (s) (PP1) and optionally the unreacted polyisocyanate (s) at the end of a possible step E1), and alcohol (s) present in the reaction medium of step E2.
Le calcul du rapport r2 tient notamment compte d’une part des groupes NCO portés par l’ensemble des isocyanates présents dans le milieu réactionnel lors de l’étape E2 (composé (PP1 ) et éventuellement les polyisocyanates non réagis ayant servis à sa synthèse issus d’une éventuelle étape E1 ) et d’autre part des groupes OH portés par le(s) composé(s) de formule (IV). The calculation of the ratio r 2 notably takes into account on the one hand the NCO groups carried by all of the isocyanates present in the reaction medium during step E2 (compound (PP1) and optionally the unreacted polyisocyanates used for its synthesis. derived from a possible step E1) and on the other hand from the OH groups carried by the compound (s) of formula (IV).
Lorsque le composé (PP1 ) utilisé et/ou le composé de formule (IV) utilisé, est ou sont sous la forme d’une composition ou mélange comprenant essentiellement le(s)dit(s) composé(s) (PP1 ) et/ou composé(s) de formule (IV) respectivement, comme décrit plus haut, le calcul du rapport r2 tient compte d’une part des groupes NCO portés par le composé (PP1 ), mais également les isocyanates éventuellement en mélange avec le(s) composé(s) (PP1 ) et/ou d’autre part des groupes OH portés par le(s) composé(s) de formule (IV), mais également le(s) composé(s) polyol(s) éventuellement en mélange avec le(s) composé(s) de formule (IV). When the compound (PP1) used and / or the compound of formula (IV) used, is or are in the form of a composition or mixture essentially comprising the said compound (s) (PP1) and / or compound (s) of formula (IV) respectively, as described above, the calculation of the ratio r2 takes account on the one hand of the NCO groups carried by the compound (PP1), but also the isocyanates optionally in mixture with the (s ) compound (s) (PP1) and / or on the other hand OH groups carried by the compound (s) of formula (IV), but also the polyol compound (s) optionally in mixture with the compound (s) of formula (IV).
Etape E2 Step E2
L’étape E2 peut être mise en oeuvre à une température inférieure à 95°C, et de préférence dans des conditions anhydres. Step E2 can be carried out at a temperature below 95 ° C, and preferably under anhydrous conditions.
Le composé de formule (IV) utilisable pour préparer le polyuréthane (PP2) selon l’invention peut être mis en oeuvre soit pur, soit sous la forme d’un mélange ou composition de composés de formule (IV) contenant au moins 95% en poids composé de formule (IV). The compound of formula (IV) which can be used to prepare the polyurethane (PP2) according to the invention can be used either pure or in the form of a mixture or composition of compounds of formula (IV) containing at least 95% by compound weight of formula (IV).
L’étape E2 peut être réalisée avec un composé de formule (IV) ou avec un mélange de composés de formule (IV) de nature différente (par exemple avec des R1 différents, ou bien des R2 différents, ou alors avec des R1 et R2 différents). Step E2 can be carried out with a compound of formula (IV) or with a mixture of compounds of formula (IV) of different nature (for example with different R 1 , or else R 2 different, or else with R 1 and R 2 different).
A titre d’exemple de composé de formule (IV), on peut citer les composés (IV-1 a), (IV-1 b) et (IV-1 c) décrits précédemment. As an example of a compound of formula (IV), mention may be made of the compounds (IV-1 a), (IV-1 b) and (IV-1 c) described above.
Le(s) composé(s) (PP1 ) utilisé(s) peu(ven)t être mis en oeuvre soit pur, soit sous la forme d’une composition comprenant essentiellement le(s)dit(s) composé(s) et une faible teneur en polyisocyanate(s) résiduel(s) issu(s) notamment de la synthèse dudit (desdits) composé(s). Dans ce dernier cas, le(s) composé(s) (PP1 ) utilisé(s) est (sont) tel(s) que la teneur en groupes NCO présents dans ladite composition va de préférence de 0,5 à 15% en poids par rapport au poids de ladite composition. Par « teneur en groupes NCO » (aussi désigné par « taux de NCO », noté % NCO), on entend la teneur en groupes isocyanate portés par l’ensemble des composés présents dans le milieu réactionnel, à savoir le composé (PP1 ) et les autres espèces porteuses de groupe(s) isocyanate éventuellement présentes, tels que les monomères polyisocyanates non réagis. Cette teneur en groupe NCO est calculable de manière bien connue par l’homme du métier et est exprimé en pourcentage en poids par rapport au poids total du milieu réactionnel. The compound (s) (PP1) used can be used either pure or in the form of a composition essentially comprising the said compound (s) and a low content of residual polyisocyanate (s) resulting (s) in particular from the synthesis of said (said) compound (s). In the latter case, the compound (s) (PP1) used (s) is (are) such that the content of NCO groups present in said composition preferably ranges from 0.5 to 15% by weight relative to the weight of said composition. By “content of NCO groups” (also designated by “NCO content”, denoted% NCO), is meant the content of isocyanate groups carried by all of the compounds present in the reaction medium, namely the compound (PP1) and other species carrying isocyanate group (s) which may be present, such as unreacted polyisocyanate monomers. This content of NCO group can be calculated in a manner well known to those skilled in the art and is expressed as a percentage by weight relative to the total weight of the reaction medium.
Le(s) composé(s) (PP1 ) possédant au moins deux groupes NCO peut(vent) être : The compound (s) (PP1) having at least two NCO groups can (wind) be:
- choisi(s) parmi les dérivés d’allophanate d’hexaméthylène diisocyanate (HDI) de formule (I IA) suivante : - chosen from the derivatives of hexamethylene diisocyanate allophanate (HDI) of formula (I IA) below:
dans laquelle : in which :
- p est un nombre entier allant de 1 à 2 ; - p is an integer ranging from 1 to 2;
- q est un nombre entier allant de 0 à 9 ; - q is an integer ranging from 0 to 9;
- r est un nombre entier égal à 5 ou 6 ; - r is an integer equal to 5 or 6;
- R représente une chaîne hydrocarbonée, saturée ou insaturée, cyclique ou acyclique, linéaire ou ramifiée, comprenant de 1 à 20 atomes de carbone ; - R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms;
- R représente un groupe divalent hydrocarboné, linéaire ou ramifié, saturé, ayant de 2 à 4 atomes de carbone ; - R represents a divalent hydrocarbon group, linear or branched, saturated, having from 2 to 4 carbon atoms;
ou or
- choisi(s) parmi les polyuréthane(s) à terminaisons NCO obtenu(s) par une réaction de polyaddition (notée E1 ) : - chosen from polyurethane (s) with NCO endings obtained by a polyaddition reaction (denoted E1):
(i) d’au moins un polyisocyanate choisi de préférence parmi les diisocyanates, et en particulier parmi les diisocyanates suivants: (i) at least one polyisocyanate preferably chosen from diisocyanates, and in particular from the following diisocyanates:
a1 ) le pentaméthylène diisocyanate (PDI), a1) pentamethylene diisocyanate (PDI),
a2) l’hexaméthylèhne diisocyanate (HDI), a2) hexamethylene diisocyanate (HDI),
a3) l’isophorone diisocyanate (IPDI), a3) isophorone diisocyanate (IPDI),
a4) le 2,4-toluène diisocyanate (2,4-TDI), a4) 2,4-toluene diisocyanate (2,4-TDI),
a5) le 2,4’-diisocyanate de diphénylméthane (2,4’-MDI), a5) diphenylmethane 2,4’-diisocyanate (2,4’-MDI),
a6) le méta-xylylène diisocyanate (m-XDI), a6) meta-xylylene diisocyanate (m-XDI),
a7) le 1 ,3-Bis(isocyanatomethyl)cyclohexane (m-H6XDI), a8) le 2,4’- méthylène dicyclohexyl diisocyanate et/ou le 4,4'-méthylene dicyclohexyl diisocyanate (H12MDI) : a7) 1, 3-Bis (isocyanatomethyl) cyclohexane (m-H6XDI), a8) 2,4'-methylene dicyclohexyl diisocyanate and / or 4,4'-methylene dicyclohexyl diisocyanate (H12MDI):
a9) les dérivés d’allophanate d’hexaméthylène diisocyanate (HDI) de formule (MA) telle que décrite ci-dessus ; a9) derivatives of hexamethylene diisocyanate (HDI) allophanate of formula (MA) as described above;
a10) et leurs mélanges ; a10) and their mixtures;
(ii) avec au moins un polyol de préférence choisi parmi les polyéther polyols, les polyester polyols, les polydiène polyols, les polycarbonate polyols, et leurs mélanges, dans des quantités de polyisocyanate(s) et de polyol(s) conduisant à un rapport molaire NCO/OH, noté r1, strictement supérieur à 1 , de préférence allant de 1 ,6 à 1 ,9, préférentiellement allant de 1 ,65 à 1 ,85. (ii) with at least one polyol preferably chosen from polyether polyols, polyester polyols, polydiene polyols, polycarbonate polyols, and their mixtures, in amounts of polyisocyanate (s) and polyol (s) leading to a ratio NCO / OH molar, noted r 1 , strictly greater than 1, preferably ranging from 1.6 to 1.9, preferably ranging from 1.65 to 1.85.
De préférence, les composés (PP1 ) sont choisis parmi : Preferably, the compounds (PP1) are chosen from:
- les dérivés d’allophanate d’hexaméthylène diisocyanate (HDI) de formule (MA) susmentionnée ; ou - derivatives of allophanate hexamethylene diisocyanate (HDI) of formula (MA) above; or
- a4) le 2,4-toluène diisocyanate (2,4-TDI). - a4) 2,4-toluene diisocyanate (2,4-TDI).
Dans le cadre de l’invention, et sauf mention contraire, n est le rapport molaire NCO/OH correspondant au rapport molaire du nombre de groupes isocyanates (NCO) sur le nombre de groupes hydroxyles (OH) portés respectivement par l’ensemble des polyisocyanate(s) et polyol(s) présents dans le milieu réactionnel de l’étape E1. In the context of the invention, and unless otherwise stated, n is the NCO / OH molar ratio corresponding to the molar ratio of the number of isocyanate groups (NCO) to the number of hydroxyl groups (OH) carried respectively by all of the polyisocyanates (s) and polyol (s) present in the reaction medium of step E1.
De préférence, dans la formule (NA) susmentionnée p, q, R et R’ sont choisis tels que le dérivé d’allophanate de HDI de formule (NA) comporte un pourcentage en poids de groupe isocyanate allant de 12 à 14% en poids par rapport au poids dudit dérivé. Plus préférentiellement, Preferably, in the above-mentioned formula (NA) p, q, R and R ′ are chosen such that the HDI allophanate derivative of formula (NA) comprises a percentage by weight of isocyanate group ranging from 12 to 14% by weight relative to the weight of said derivative. More preferably,
- p est un nombre entier allant de 1 à 2 ; - p is an integer ranging from 1 to 2;
- q est un nombre entier allant de 2 à 5 ; - q is an integer ranging from 2 to 5;
- R représente une chaîne hydrocarbonée, saturée ou insaturée, cyclique ou acyclique, linéaire ou ramifiée, comprenant de 6 à 14 atomes de carbone ; - R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 6 to 14 carbon atoms;
- R’ représente un groupe divalent propylène. - R ' represents a divalent propylene group.
Le composé (PP1 ) utilisable selon l’invention peut être mis en oeuvre sous la forme d’une composition comprenant au moins 99,5% en poids, de préférence au moins 99,8% en poids de dérivé(s) de formule (NA), et moins de 0,5% en poids, de préférence moins de 0,2% en poids de HDI, par rapport au poids total de ladite composition. The compound (PP1) which can be used according to the invention can be used in the form of a composition comprising at least 99.5% by weight, preferably at least 99.8% by weight of derivative (s) of formula ( NA), and less than 0.5% by weight, preferably less than 0.2% by weight of HDI, relative to the total weight of said composition.
Une telle composition peut être obtenue par exemple par : Such a composition can be obtained for example by:
- réaction de carbamatation allant de 80 à 100°C d’un mono alcool saturé ou insaturé, acyclique, linéaire ou ramifié, comprenant de 1 à 20 atomes de carbone, et oxyalkylé dont la partie alkylène est linéaire ou ramifiée et comprend de 1 à 4 atomes de carbone, avec un premier monomère de HDI, dans un rapport molaire NCO/OH supérieur à 2, avantageusement supérieur à 4, de préférence supérieur à 8, puis - carbamation reaction ranging from 80 to 100 ° C of a saturated or unsaturated, acyclic, linear or branched mono alcohol, comprising from 1 to 20 carbon atoms, and oxyalkylated in which the alkylene part is linear or branched and comprises from 1 to 4 carbon atoms, with a first HDI monomer, in an NCO / OH molar ratio greater than 2, advantageously greater than 4, preferably greater than 8, then
- réaction d’allophanatation à une température allant de 100 à 180°C, de préférence autour de 140°C, du composé carbamate obtenu possédant une fonction hydroxyle, avec un deuxième monomère de HDI, dans un rapport molaire NCO/OH compris de 5 à 20, et - Allophanation reaction at a temperature ranging from 100 to 180 ° C, preferably around 140 ° C, of the carbamate compound obtained having a hydroxyl function, with a second HDI monomer, in an NCO / OH molar ratio of 5 at 20, and
- distillation des monomères de HDI non réagis, afin d’obtenir un réactif comprenant moins de 0,5% en poids de HDI, de préférence moins de 0,2% en poids de HDI. - Distillation of the unreacted HDI monomers, in order to obtain a reagent comprising less than 0.5% by weight of HDI, preferably less than 0.2% by weight of HDI.
De préférence, la teneur en groupes NCO (aussi désigné par « taux de NCO » et noté % NCO) présents dans la composition de dérivé(s) de formule (MA) va de 12 à 14% en poids par rapport au poids de ladite composition. Preferably, the content of NCO groups (also denoted by “NCO level” and noted% NCO) present in the composition of derivative (s) of formula (MA) ranges from 12 to 14% by weight relative to the weight of said composition.
A l’issue de l’étape E2, le milieu réactionnel est de préférence exempt de monomères diisocyanates potentiellement toxiques (HDI, I PDI, TDI, MDI). Dans ce cas, le polyuréthane (PP2) selon l’invention ne présente avantageusement pas de risques toxicologiques liés à la présence de tels monomères. At the end of step E2, the reaction medium is preferably free of potentially toxic diisocyanate monomers (HDI, I PDI, TDI, MDI). In this case, the polyurethane (PP2) according to the invention advantageously does not present toxicological risks linked to the presence of such monomers.
A l’issue de l’étape E2, le polyuréthane (PP2) susmentionné présente de préférence de 0,1 à 5 milliéquivalent de fonctions T de formule (I) susmentionnée par gramme dudit polyuréthane (PP2). At the end of step E2, the aforementioned polyurethane (PP2) preferably has from 0.1 to 5 milliequivalents of T functions of formula (I) above per gram of said polyurethane (PP2).
Dans le cas où le composé (PP1 ) est un polyuréthane à terminaisons NCO issu de l’étape E1 , le polyuréthane (PP2) obtenu présente de préférence de 0,1 à 3,0 milliéquivalent(s) de fonctions T par gramme dudit polyuréthane (PP2), de préférence de 0,1 à 1 ,5 milliéquivalent(s) de fonctions T par gramme dudit polyuréthane (PP2), plus préférentiellement de 0,15 à 1 ,0 milliéquivalent de fonctions T dudit polyuréthane (PP2) et mieux encore de 0,2 à 0,8 milliéquivalent de fonctions T par gramme dudit polyuréthane (PP2). In the case where the compound (PP1) is a polyurethane with NCO endings resulting from step E1, the polyurethane (PP2) obtained preferably has from 0.1 to 3.0 milliequivalent (s) of T functions per gram of said polyurethane (PP2), preferably from 0.1 to 1.5 milliequivalents of T functions per gram of said polyurethane (PP2), more preferably from 0.15 to 1.0 milliequivalents of T functions of said polyurethane (PP2) and better still from 0.2 to 0.8 milliequivalents of T functions per gram of said polyurethane (PP2).
Etape E1 Step E1
Polvol(s) Polvol (s)
Le(s) polyol(s) utilisable(s) selon l’invention est(sont) de préférence choisi(s) parmi les polyéther polyols, les polyester polyols, les polydiène polyols, les polycarbonate polyols, et leurs mélanges. The polyol (s) which can be used according to the invention is (are) preferably chosen from polyether polyols, polyester polyols, polydiene polyols, polycarbonate polyols, and their mixtures.
Le(s) polyol(s) utilisable(s) pour préparer le polyuréthane à terminaisons NCO utilisé selon l’invention peu(ven)t être choisi(s) parmi ceux dont la masse moléculaire moyenne en nombre va de 200 à 20 000 g/mol, de préférence de 250 à 18 000 g/mol, et mieux encore de 2 000 à 12 000 g/mol. The polyol (s) which can be used for preparing the polyurethane with NCO endings used according to the invention can be chosen from those whose number average molecular mass ranges from 200 to 20,000 g / mol, preferably from 250 to 18,000 g / mol, and better still from 2,000 to 12,000 g / mol.
De préférence, leur fonctionnalité hydroxyle va de 2 à 3. La fonctionnalité hydroxyle est le nombre moyen de fonction hydroxyle par mole de polyol. De préférence, le(s) polyol(s) utilisable(s) selon l’invention présente(nt) un hydroxyle (IOH) allant de 9 à 105 mg KOH/g, et de préférence de 13 à 90 mg KOH/g, plus préférentiellement de 25 à 70 mg KOH/g, et mieux encore de 40 à 65 mg KOH/g de polyol. Preferably, their hydroxyl functionality ranges from 2 to 3. The hydroxyl functionality is the average number of hydroxyl functions per mole of polyol. Preferably, the polyol (s) which can be used according to the invention has (s) a hydroxyl (IOH) ranging from 9 to 105 mg KOH / g, and preferably from 13 to 90 mg KOH / g, more preferably from 25 to 70 mg KOH / g, and better still from 40 to 65 mg KOH / g of polyol.
Le(s) polyéther polyol(s) utilisable(s) selon l’invention est (sont) de préférence choisi(s) parmi les polyoxyalkylène-polyol, dont la partie alkylène, linéaire ou ramifiée, comprend de 1 à 4 atomes de carbone, de préférence de 2 à 3 atomes de carbone. The polyether polyol (s) which can be used according to the invention is (are) preferably chosen from polyoxyalkylene polyol, the alkylene part of which, linear or branched, comprises from 1 to 4 carbon atoms , preferably from 2 to 3 carbon atoms.
Plus préférentiellement, le(s) polyéther polyol(s) utilisable(s) selon l’invention est (sont) de préférence choisi(s) parmi les polyoxyalkylène-diols ou polyoxyalkylène triols, et mieux encore des polyoxyalkylène diols, dont la partie alkylène, linéaire ou ramifiée, comprend de 1 à 4 atomes de carbone, de préférence de 2 à 3 atomes de carbone, et dont la masse molaire moyenne en nombre va de 200 à 20000 g/mol, et de préférence de 2000 à 12000 g/mol. More preferably, the polyether polyol (s) which can be used according to the invention is (are) preferably chosen from polyoxyalkylene diols or polyoxyalkylene triols, and better still polyoxyalkylene diols, including the alkylene part , linear or branched, comprises from 1 to 4 carbon atoms, preferably from 2 to 3 carbon atoms, and whose number-average molar mass ranges from 200 to 20,000 g / mol, and preferably from 2,000 to 12,000 g / mol.
A titre d’exemple de polyoxyalkylène diols ou triols utilisables selon l’invention, on peut citer : By way of example of polyoxyalkylene diols or triols which can be used according to the invention, there may be mentioned:
- les polyoxypropylène diols ou triols (aussi désignés par polypropylène glycols (PPG) diol ou triol) ayant une masse moléculaire moyenne en nombre allant de 400 à 18 000 g/mol et de préférence allant de 400 à 4 000 g/mol ; - Polyoxypropylene diols or triols (also designated by polypropylene glycols (PPG) diol or triol) having a number average molecular weight ranging from 400 to 18,000 g / mol and preferably ranging from 400 to 4,000 g / mol;
- les polyoxyéthylène diols ou triols (aussi désignés par polyéthylène glycols (PEG) diol ou triol) ayant une masse moléculaire moyenne en nombre allant de 400 à 18 000 g/mol et de préférence allant de 400 à 4 000 g/mol ; - polyoxyethylene diols or triols (also designated by polyethylene glycols (PEG) diol or triol) having a number average molecular weight ranging from 400 to 18,000 g / mol and preferably ranging from 400 to 4,000 g / mol;
- les copolymères de PPG/PEG diols ou triols ayant une masse moléculaire moyenne en nombre allant de 400 à 18 000 g/mol et de préférence allant de 400 à 4 000 g/mol ; - PPG / PEG diol or triol copolymers having a number-average molecular mass ranging from 400 to 18,000 g / mol and preferably ranging from 400 to 4,000 g / mol;
- les polytétrahydrofurane (PolyTHF) diols ou triols ayant une masse moléculaire moyenne en nombre allant de 250 à 4 000 g/mol ; - polytetrahydrofuran (PolyTHF) diols or triols having a number average molecular weight ranging from 250 to 4,000 g / mol;
- et leurs mélanges. - and their mixtures.
De préférence, le(s) polyéther polyol(s) utilisable(s) est (sont) choisi(s) parmi les polyoxypropylène diols ou triols avec un indice de polydispersité allant de 1 à 1 ,4, en particulier allant de 1 à 1 ,3. Cet indice correspond au rapport de la masse molaire moyenne en poids à la masse moléculaire moyenne en nombre du polyéther polyol (Ip =Mw/Mn) déterminées par GPC. Preferably, the polyether polyol (s) which can be used is (are) chosen from polyoxypropylene diols or triols with a polydispersity index ranging from 1 to 1, 4, in particular ranging from 1 to 1 , 3. This index corresponds to the ratio of the average molar mass by weight to the average molecular mass by number of the polyether polyol (Ip = Mw / Mn) determined by GPC.
Les polyéther polyols suscités peuvent être préparés de manière conventionnelle, et sont largement disponibles dans le commerce. Ils peuvent être obtenus par polymérisation de l’oxyde d’alkylène correspondant en présence d’un catalyseur à base d’un double complexe métal-cyanure. The polyether polyols raised can be prepared in a conventional manner, and are widely available commercially. They can be obtained by polymerization of the corresponding alkylene oxide in the presence of a catalyst based on a double metal-cyanide complex.
A titre d’exemples de polyéther diols, on peut citer les polyoxypropylène diols commercialisés sous la dénomination « ACCLAIM® » par la société BAYER, tels que l' « ACCLAIM® 12200 » de masse moléculaire moyenne en nombre voisine de 1 1 335 g/mol et dont l’indice hydroxyle va de 9 à 1 1 mg KOH/g, l’« ACCLAIM® 8200 » de masse moléculaire moyenne en nombre voisine de 8 057 g/mol et dont l’indice hydroxyle va de 13 à 15 mg KOH/g, et l’« ACCLAIM® 4200 » de masse moléculaire moyenne en nombre voisine de 4 020 g/mol, et dont l’indice hydroxyle va de 26,5 à 29,5 mg KOH/g, ou encore le polyoxypropylène diol commercialisé sous la dénomination « VORANOL P2000 » par la société DOW de masse moléculaire moyenne en nombre voisine de 2 004 g/mol et dont l’indice hydroxyle est de 56mg KOH/g environ. By way of examples of polyether diols, mention may be made of the polyoxypropylene diols sold under the name "ACCLAIM®" by the company Bayer, such as the "ACCLAIM ® 12200" of average molecular weight neighbor number 1 1335 g / mol and whose hydroxyl number ranges from 9 to 1 of 1 mg KOH / g, the "Acclaim® 8200" of average molecular weight number close to 8,057 g / mol and with a hydroxyl number ranging from 13 to 15 mg KOH / g, and “ACCLAIM® 4200” with an average molecular weight close to 4,020 g / mol, and including hydroxyl number ranges from 26.5 to 29.5 mg KOH / g, or alternatively the polyoxypropylene diol sold under the name "VORANOL P2000" by the company DOW with an average molecular weight close to 2,004 g / mol and the hydroxyl number is approximately 56 mg KOH / g.
A titre d’exemples de polyéther triol, on peut citer le polyoxypropylène triol commercialisés sous la dénomination « VORANOL CP3355 » par la société Dow, de masse moléculaire moyenne en nombre voisine de 3554 g/mol et dont l’indice hydroxyle va de 40 à 50 mg KOH/g. By way of examples of polyether triol, mention may be made of polyoxypropylene triol sold under the name "VORANOL CP3355" by the company Dow, with a number average molecular mass of around 3,554 g / mol and whose hydroxyl number ranges from 40 to 50 mg KOH / g.
Le(s) polydiène polyol(s) utilisable(s) selon l’invention est(sont) choisi(s) de préférence parmi les polydiènes comportant des groupes hydroxyles terminaux, et leurs dérivés correspondants hydrogénés ou époxydés. The polydiene polyol (s) which can be used according to the invention is (are) preferably chosen from polydienes comprising terminal hydroxyl groups, and their corresponding hydrogenated or epoxidized derivatives.
Plus préférentiellement, le(s) polydiène polyol(s) utilisable(s) selon l’invention est (sont) choisi(s) parmi les polybutadiènes comportant des groupes hydroxyles terminaux, éventuellement hydrogénés ou époxydés. More preferably, the polydiene polyol (s) which can be used according to the invention is (are) chosen (s) from polybutadienes comprising terminal hydroxyl groups, optionally hydrogenated or epoxidized.
Mieux encore, le(s) polydiène polyol(s) utilisable(s) selon l’invention est (sont) choisi(s) parmi les homopolymères de butadiène comportant des groupes hydroxyles terminaux, éventuellement hydrogénés ou époxydés. Better still, the polydiene polyol (s) which can be used according to the invention is (are) chosen (s) from butadiene homopolymers comprising terminal hydroxyl groups, optionally hydrogenated or epoxidized.
Par terminaux, on entend que les groupes hydroxyles sont situés aux extrémités de la chaîne principale du polydiène polyol. By terminals is meant that the hydroxyl groups are located at the ends of the main chain of the polydiene polyol.
Les dérivés hydrogénés suscités peuvent être obtenus par hydrogénation totale ou partielle des doubles liaisons d’un polydiène comportant des groupes hydroxyles terminaux, et sont donc saturé(s) ou insaturé(s). The above-mentioned hydrogenated derivatives can be obtained by total or partial hydrogenation of the double bonds of a polydiene comprising terminal hydroxyl groups, and are therefore saturated (s) or unsaturated (s).
Les dérivés époxydés suscités peuvent être obtenus par époxydation chémiosélective des doubles liaisons de la chaîne principale d’un polydiène comportant des groupes hydroxyles terminaux, et comportent donc au moins un groupe époxy dans sa chaîne principale. The epoxidized derivatives raised can be obtained by chemoselective epoxidation of the double bonds of the main chain of a polydiene comprising terminal hydroxyl groups, and therefore comprise at least one epoxy group in its main chain.
A titre d’exemples de polybutadiène polyols, on peut citer les homopolymères de butadiène, saturé ou insaturé, comprenant des groupes hydroxyles terminaux, éventuellement époxydés, tels que par exemple ceux commercialisés sous la dénomination POLY BD® ou KRASOL® par la société CRAY VALLEY. As examples of polybutadiene polyols, mention may be made of butadiene homopolymers, saturated or unsaturated, comprising terminal hydroxyl groups, optionally epoxidized, such as for example those sold under the name POLY BD® or KRASOL® by the company CRAY VALLEY .
Les polyester polyols peuvent être choisis parmi les polyester diols et les polyester triols, et de préférence parmi les polyester diols. Parmi les polyester polyols, on peut par exemple citer : The polyester polyols can be chosen from polyester diols and polyester triols, and preferably from polyester diols. Among the polyester polyols, there may be mentioned, for example:
- les polyesters polyols d’origine naturelle tel que l’huile de ricin ; - polyesters polyols of natural origin such as castor oil;
- les polyesters polyols résultant de la condensation : - polyester polyols resulting from condensation:
- d’un ou plusieurs polyols aliphatiques (linéaires, ramifiés ou cycliques) ou aromatiques tels que par exemple l’éthanediol, le 1 ,2-propanediol, le 1 ,3-propanediol, le glycérol, le triméthylolpropane, le 1 ,6-hexanediol, le 1 ,2,6-hexanetriol, le butènediol, le sucrose, le glucose, le sorbitol, le pentaérythritol, le mannitol, la triéthanolamine, la N- méthyldiéthanolamine, et leurs mélanges, avec - one or more aliphatic (linear, branched or cyclic) or aromatic polyols such as for example ethanediol, 1, 2-propanediol, 1, 3-propanediol, glycerol, trimethylolpropane, 1, 6- hexanediol, 1, 2,6-hexanetriol, butenediol, sucrose, glucose, sorbitol, pentaerythritol, mannitol, triethanolamine, N-methyldiethanolamine, and mixtures thereof, with
- un ou plusieurs acide polycarboxylique ou son dérivé ester ou anhydride tel que l’acide 1 ,6-hexanedioïque, l’acide dodécanedioïque, l’acide azélaïque, l’acide sébacique, l’acide adipique, l’acide 1 ,18-octadécanedioïque, l’acide phtalique, l’acide succinique et les mélanges de ces acides, un anhydride insaturé tel que par exemple l’anhydride maléique ou phtalique, ou une lactone telle que par exemple la caprolactone. - one or more polycarboxylic acid or its ester or anhydride derivative such as 1, 6-hexanedioic acid, dodecanedioic acid, azelaic acid, sebacic acid, adipic acid, acid 1, 18- octadecanedioic acid, phthalic acid, succinic acid and mixtures of these acids, an unsaturated anhydride such as for example maleic or phthalic anhydride, or a lactone such as for example caprolactone.
Les polyester polyols suscités peuvent être préparés de manière conventionnelle, et sont pour la plupart disponibles commercialement. The polyester polyols raised can be prepared in a conventional manner, and are for the most part commercially available.
Parmi les polyesters polyols, on peut par exemple citer les produits suivants de fonctionnalité hydroxyle égale à 2 : Among the polyester polyols, there may be mentioned, for example, the following products with hydroxyl functionality equal to 2:
-le TONE® 0240 (disponible auprès de UNION CARBIDE) qui est une polycaprolactone de masse moléculaire moyenne en nombre d’environ 2000 g/mol, et un point de fusion de 50°C environ, -the TONE ® 0240 (available from Union Carbide) which is a medium molecular weight polycaprolactone of from about 2,000 g / mol and a melting point of 50 ° C,
- le DYNACOLL®7381 (disponible auprès d’EVONIK) de masse moléculaire moyenne en nombre d’environ 3500 g/mol, et un point de fusion de 65°C environ, - DYNACOLL ® 7381 (available from EVONIK) with a number average molecular mass of around 3500 g / mol, and a melting point of around 65 ° C,
- le DYNACOLL®7360 (disponible auprès d’EVONIK) qui résulte de la condensation de l’acide adipique avec l’hexane diol, et a une masse moléculaire moyenne en nombre d’environ 3500 g/mol, et un point de fusion de 55°C environ, - DYNACOLL ® 7360 (available from EVONIK) which results from the condensation of adipic acid with hexane diol, and has a number average molecular weight of around 3500 g / mol, and a melting point of 55 ° C approximately,
- le DYNACOLL®7330 (disponible auprès d’EVONIK) de masse moléculaire moyenne en nombre d’environ 3500 g/mol, et un point de fusion de 85°C environ, - DYNACOLL ® 7330 (available from EVONIK) with a number-average molecular mass of around 3500 g / mol, and a melting point of around 85 ° C,
- le DYNACOLL® 7363 (disponible auprès d’EVONIK) qui résulte également de la condensation de l’acide adipique avec l’hexane diol, et a une masse moléculaire moyenne en nombre d’environ 5500 g/mol, et un point de fusion de 57°C environ, - DYNACOLL ® 7363 (available from EVONIK) which also results from the condensation of adipic acid with hexane diol, and has a number average molecular weight of around 5500 g / mol, and a melting point about 57 ° C,
- le DYNACOLL ® 7250 (commercialisé par EVONIK) : polyester polyol ayant une viscosité de 180 Pa.s à 23°C, une masse moléculaire moyenne en nombre Mn égale à 5 500 g/mol, et une Tg égale à -50°C, - DYNACOLL ® 7250 (marketed by EVONIK): polyester polyol having a viscosity of 180 Pa.s at 23 ° C, an average molecular mass in number Mn equal to 5500 g / mol, and a T g equal to -50 ° VS,
- le KURARAY ® P-6010 (commercialisé par KURARAY) : polyester polyol ayant une viscosité de 68 Pa.s à 23°C, une masse moléculaire moyenne en nombre égale à 6 000 g/mol, et une Tg égale à -64°C, - le KURARAY ® P-10010 (commercialisé par KURARAY) : polyester polyol ayant une viscosité de 687 Pa.s à 23°C, et une masse moléculaire moyenne en nombre égale à 10 000 g/mol. - KURARAY ® P-6010 (marketed by KURARAY): polyester polyol having a viscosity of 68 Pa.s at 23 ° C, a number average molecular weight equal to 6000 g / mol, and a T g equal to -64 ° C, - KURARAY ® P-10010 (marketed by KURARAY): polyester polyol having a viscosity of 687 Pa.s at 23 ° C, and a number average molecular weight equal to 10,000 g / mol.
A titre d’exemple de polyester diol, on peut également citer le REALKYD® XTR 10410 » commercialisé par la société CRAY VALLEY de masse moléculaire moyenne en nombre (Mn) voisine de 1000 g/mol et dont l’indice hydroxyle va de 108 à 1 16 mg KOH/g. Il s’agit d’un produit issu de la condensation d’acide adipique, de diéthylèneglycol et de monoéthylèneglycol. By way of example of a polyester diol, mention may also be made of REALKYD® XTR 10410 "sold by the company CRAY VALLEY with a number average molecular mass (Mn) close to 1000 g / mol and whose hydroxyl index ranges from 108 to 1 16 mg KOH / g. It is a product of the condensation of adipic acid, diethylene glycol and monoethylene glycol.
Les polycarbonate polyols peuvent être choisis parmi les polycarbonate diols ou triols, ayant en particulier une masse moléculaire moyenne en nombre (Mn) allant de 300 g/mol à 12 000 g/mol, de préférence allant de 400 à 4 000 g/mol. The polycarbonate polyols can be chosen from polycarbonate diols or triols, in particular having a number-average molecular mass (M n ) ranging from 300 g / mol to 12,000 g / mol, preferably ranging from 400 to 4,000 g / mol .
A titre d’exemple de polycarbonate diol, on peut citer : As an example of a polycarbonate diol, there may be mentioned:
- le CONVERGE POLYOL 212-10 et CONVERGE POLYOL 212-20 commercialisés par la société NOVOMER respectivement de masse moléculaire en nombre (Mn) égales à 1 000 et 2 000 g/mol dont les indices hydroxyles sont respectivement de 1 12 et 56 mg KOH/g,- CONVERGE POLYOL 212-10 and CONVERGE POLYOL 212-20 marketed by the company NOVOMER respectively of molecular mass in number (M n ) equal to 1000 and 2000 g / mol whose hydroxyl indices are respectively 1 12 and 56 mg KOH / g,
- le DESMOPHEN® C XP 2716 commercialisé par COVESTRO de masse moléculaire en nombre (Mn) égale à 326 g/mol dont l’indice hydroxyle est de 344 mg KOH/g, - DESMOPHEN® C XP 2716 marketed by COVESTRO with a molecular mass in number (M n ) equal to 326 g / mol, the hydroxyl number of which is 344 mg KOH / g,
- les POLYOL C-590, C1090, C-2090 et C-3090 commercialisés par KURARAY ayant une masse moléculaire en nombre (Mn) allant de 500 à 3000 g/mol et un indice hydroxyle allant de 224 à 37 mg KOH/g. - POLYOL C-590, C1090, C-2090 and C-3090 marketed by KURARAY having a molecular weight in number (Mn) ranging from 500 to 3000 g / mol and a hydroxyl number ranging from 224 to 37 mg KOH / g.
De préférence, la réaction E1 est réalisée en présence de polyol(s) choisi(s) parmi les polyéther polyols, de préférence les polyéther diols et/ou les polyéther triols. Preferably, the reaction E1 is carried out in the presence of polyol (s) chosen (s) from polyether polyols, preferably polyether diols and / or polyether triols.
Polvisocvanate(s) Polvisocvanate (s)
Le(s) polyisocyanate(s) sont de préférence des diisocyanate(s) en particulier choisi(s) parmi les diisocyanates suivants: The polyisocyanate (s) are preferably diisocyanate (s) in particular chosen from the following diisocyanates:
d’au moins un polyisocyanate choisi de préférence parmi les diisocyanates, et en particulier parmi les diisocyanates suivants: at least one polyisocyanate preferably chosen from diisocyanates, and in particular from the following diisocyanates:
a1 ) le pentaméthylène diisocyanate (PDI), a1) pentamethylene diisocyanate (PDI),
a2) l’hexaméthylèhne diisocyanate (HDI), a2) hexamethylene diisocyanate (HDI),
a3) l’isophorone diisocyanate (IPDI), a3) isophorone diisocyanate (IPDI),
a4) le 2,4-toluène diisocyanate (2,4-TDI), a4) 2,4-toluene diisocyanate (2,4-TDI),
a5) le 2,4’-diisocyanate de diphénylméthane (2,4’-MDI), a5) diphenylmethane 2,4’-diisocyanate (2,4’-MDI),
a6) le méta-xylylène diisocyanate (m-XDI), a6) meta-xylylene diisocyanate (m-XDI),
a7) le 1 ,3-Bis(isocyanatomethyl)cyclohexane (m-H6XDI), a7) 1, 3-Bis (isocyanatomethyl) cyclohexane (m-H6XDI),
a8) le 2,4’- méthylène dicyclohexyl diisocyanate et/ou le 4,4'-méthylene dicyclohexyl diisocyanate (H12MDI) : a9) les dérivés d’allophanate d’hexaméthylène diisocyanate (HDI) de formule (MA) telle que décrite ci-dessus ; a8) 2,4'-methylene dicyclohexyl diisocyanate and / or 4,4'-methylene dicyclohexyl diisocyanate (H12MDI): a9) derivatives of hexamethylene diisocyanate allophanate (HDI) of formula (MA) as described above;
a10) et leurs mélanges. a10) and their mixtures.
Selon un mode de réalisation, le diisocyanate est choisi parmi le 2,4-TDI (ou constitué essentiellement de 2,4-TDI), le m-XDI, l’IPDI et les dérivés de formule (MA). According to one embodiment, the diisocyanate is chosen from 2,4-TDI (or consisting essentially of 2,4-TDI), m-XDI, IPDI and the derivatives of formula (MA).
Le(s) polyisocyanates (en particulier diisocyanate(s)), utilisable(s) selon l’invention (par exemple cités en a4) et a5) ci-dessus) peu(ven)t être mis en oeuvre sous la forme d’un mélange contenant essentiellement le(s)dit(s) polyisocyanate(s) (respectivement diisocyanate(s)) et une faible teneur en composé(s) polyisocyanates (respectivement diisocyanate(s)) résiduel(s) issu(s) de la synthèse dudit (desdits) polyisocyanate(s) (respectivement diisocyanate(s)). La teneur en composé(s) polyisocyanate(s) (respectivement diisocyanate(s)) résiduel(s) tolérée (correspondant notamment aux isomères du 2,4-TDI, et du 2,4’-MDI respectivement) est telle que la mise en oeuvre dudit mélange dans la préparation du polyuréthane à terminaisons NCO utilisé selon l’invention n’a avantageusement pas d’impact sur les propriétés finales dudit polyuréthane. The polyisocyanates (in particular diisocyanate (s)) which can be used according to the invention (for example cited in a4) and a5) above) can (can) be used in the form of a mixture essentially containing the said polyisocyanate (s) (respectively diisocyanate (s)) and a low content of residual polyisocyanate compound (s) (respectively diisocyanate (s)) derived from the synthesis of said polyisocyanate (s) (respectively diisocyanate (s)). The content of residual polyisocyanate compound (s) (respectively diisocyanate (s)) tolerated (corresponding in particular to the isomers of 2,4-TDI, and 2,4'-MDI respectively) is such that the setting use of said mixture in the preparation of polyurethane with NCO endings used according to the invention advantageously has no impact on the final properties of said polyurethane.
Par exemple, le(s) polyisocyanate(s) (par exemple diisocyanate(s)) utilisable(s) selon l’invention (notamment cités en a4) et a5) ci-dessus) peu(ven)t être mis en oeuvre sous la forme d’un mélange contenant au moins 99% en poids de polyisocyanate(s) (respectivement diisocyanate(s)) et moins de 1 % en poids de composé(s) polyisocyanate(s) (respectivement diisocyanate(s)) résiduel(s), de préférence sous la forme d’un mélange contenant au moins 99,5% en poids de polyisocyanate(s) (respectivement diisocyanate(s)) et moins de 0,5% en poids de composé(s) polyisocyanate(s) (respectivement diisocyanate(s)) résiduel(s), plus préférentiellement sous la forme d’un mélange contenant au moins 99,8% en poids de polyisocyanate(s) (respectivement diisocyanate(s)) et moins de 0,2% en poids de composé(s) polyisocyanate(s) (respectivement diisocyanate(s)) résiduel(s), par rapport au poids dudit mélange. For example, the polyisocyanate (s) (for example diisocyanate (s)) which can be used according to the invention (in particular cited in a4) and a5) above) can (can) be used under the form of a mixture containing at least 99% by weight of polyisocyanate (s) (respectively diisocyanate (s)) and less than 1% by weight of compound (s) polyisocyanate (s) (respectively diisocyanate (s))) ( s), preferably in the form of a mixture containing at least 99.5% by weight of polyisocyanate (s) (respectively diisocyanate (s)) and less than 0.5% by weight of polyisocyanate compound (s) ) (respectively diisocyanate (s)) residual (s), more preferably in the form of a mixture containing at least 99.8% by weight of polyisocyanate (s) (respectively diisocyanate (s)) and less than 0.2% by weight of residual polyisocyanate compound (s) (respectively diisocyanate (s)), relative to the weight of said mixture.
De préférence, la teneur en composé(s) polyisocyanate(s) (en particulier diisocyanate(s)) résiduel(s) est telle que la teneur pondérale en groupe isocyanate dans ledit mélange reste environ égale à celle indiquée ci-dessus par rapport au poids du diisocyanate a4) et a5) seul. Preferably, the content of residual polyisocyanate compound (s) (in particular diisocyanate (s)) is such that the content by weight of isocyanate group in said mixture remains approximately equal to that indicated above relative to the weight of diisocyanate a4) and a5) alone.
Ainsi, le 2,4-TDI tel que cité en a4) peut être mis en oeuvre sous la forme d’un TDI technique, disponible commercialement, correspondant à une composition dont la teneur en 2,4-TDI est d’au moins 99% en poids, et de préférence d’au moins 99,5% en poids, par rapport au poids de ladite composition. Thus, 2,4-TDI as mentioned in a4) can be used in the form of a technical TDI, commercially available, corresponding to a composition whose content of 2,4-TDI is at least 99 % by weight, and preferably at least 99.5% by weight, relative to the weight of said composition.
Le 2,4’-MDI tel que cité en a5) peut être mis en oeuvre sous la forme d’un MDI technique, disponible commercialement, correspondant à une composition dont la teneur en 2,4’-MDI est d’au moins 99% en poids, et de préférence d’au moins 99,5% en poids, par rapport au poids de ladite composition. 2,4'-MDI as mentioned in a5) can be used in the form of a technical MDI, commercially available, corresponding to a composition the content of which is 2,4'-MDI is at least 99% by weight, and preferably at least 99.5% by weight, relative to the weight of said composition.
Le(s) polyisocyanate(s) utilisable(s) selon l’invention sont typiquement largement disponibles dans le commerce. A titre d’exemple, on peut citer le « SCURANATE® T100 » commercialisé par la société VENCOREX, correspondant à un 2,4-TDI de pureté supérieure à 99% en poids, le « DESMODUR® I » commercialisé par la société COVESTRO, correspondant à un IPDI, le « TAKENATE™ 500 » commercialisé par MITSUI CHEMICALS correspondant à un m-XDI, le « TAKENATE™ 600 » commercialisé par MITSUI CHEMICALS correspondant à un m-H6XDI, le « VESTANAT® H12MDI » commercialisé par EVONIK correspondant à un H12MDI. The polyisocyanate (s) which can be used according to the invention are typically widely available commercially. By way of example, mention may be made of “SCURANATE® T100” sold by the company VENCOREX, corresponding to a 2,4-TDI with a purity greater than 99% by weight, “DESMODUR® I” sold by the company COVESTRO, corresponding to an IPDI, the "TAKENATE ™ 500" marketed by MITSUI CHEMICALS corresponding to an m-XDI, the "TAKENATE ™ 600" marketed by MITSUI CHEMICALS corresponding to an m-H6XDI, the "VESTANAT® H12MDI" marketed by EVONIK an H12MDI.
Le dérivé de formule (I IA) susmentionné est notamment commercialisé sous le nom de « TOLONATE® » par la société VENCOREX. On peut citer en particulier le « TOLONATE® X FLO 100 » correspondant à une composition comprenant au moins 99,5% en poids de dérivé d’allophanate de HDI de formule (I IA) et moins de 0,5% en poids de HDI par rapport au poids de ladite composition. The derivative of formula (I IA) mentioned above is in particular marketed under the name of "TOLONATE®" by the company VENCOREX. Mention may in particular be made of "TOLONATE® X FLO 100" corresponding to a composition comprising at least 99.5% by weight of HDI allophanate derivative of formula (I IA) and less than 0.5% by weight of HDI relative to the weight of said composition.
Conditions Conditions
L’étape E1 peut être réalisée à une température T1 inférieure à 95°C, de préférence entre 65°C et 80°C, et dans des conditions anhydres. Step E1 can be carried out at a temperature T1 below 95 ° C, preferably between 65 ° C and 80 ° C, and under anhydrous conditions.
Lorsque le polyisocyanate utilisé lors de l’étape E1 est sous la forme d’une composition ou mélange comme décrit plus haut, le calcul du rapport molaire NCO/OH, noté n et allant de 1 ,6 à 1 ,9 et préférentiellement de 1 ,65 à 1 ,85, tient compte d’une part des groupes NCO portés par le polyisocyanate et les composés polyisocyanates résiduels issus de la synthèse dudit (desdits) polyisocyanate(s) éventuellement présents en mélange, et d’autre part des groupes OH portés par les polyol(s)) présents dans le milieu réactionnel de l’étape E1 . When the polyisocyanate used during step E1 is in the form of a composition or mixture as described above, the calculation of the NCO / OH molar ratio, noted n and ranging from 1.6 to 1.9, and preferably from 1 , 65 to 1, 85, takes into account on the one hand the NCO groups carried by the polyisocyanate and the residual polyisocyanate compounds resulting from the synthesis of said polyisocyanate (s) possibly present in mixture, and on the other hand OH groups carried by the polyol (s) present in the reaction medium of step E1.
La réaction de polyaddition de l’étape E1 peut être mise en oeuvre en présence ou non d’au moins un catalyseur de réaction. The polyaddition reaction of step E1 can be carried out in the presence or not of at least one reaction catalyst.
Le(s) catalyseur(s) de réaction utilisable(s) au cours de la réaction de polyaddition de l’étape E1 peu(ven)t être tout catalyseur connu de l'homme du métier pour catalyser la formation de polyuréthane par réaction d’au moins un polyisocyanate avec au moins un polyol choisi de préférence parmi les polyéther polyols, les polyester polyols, et les polydiène polyols. The reaction catalyst (s) which can be used during the polyaddition reaction of step E1 can be any catalyst known to a person skilled in the art for catalyzing the formation of polyurethane by reaction d 'At least one polyisocyanate with at least one polyol preferably chosen from polyether polyols, polyester polyols, and polydiene polyols.
Une quantité allant jusque 0,3% en poids de catalyseur(s) par rapport au poids du milieu réactionnel de l’étape E1 peut être utilisée. En particulier, on préfère utiliser de 0,02 à 0,2% en poids de catalyseur(s) par rapport au poids du milieu réactionnel de l’étape E1 . Selon un mode de réalisation préféré, le polyuréthane à terminaisons NCO (PP1 ) est obtenu par polyaddition d’au moins un diisocyanate, de préférence d’un ou deux diisocyanates choisi(s) parmi ceux cités en a1 ), a2), a3), a4), a5), a6), a7), a8 et a9) tels que décrits dans l’un quelconque des paragraphes précédents avec au moins un, de préférence un ou deux, polyol(s) choisi(s) parmi les polyéther polyols et les polydiène polyols, et de préférence les polyéther polyols, tels que par exemple les polyéther diols et/ou les polyéther triols. An amount ranging up to 0.3% by weight of catalyst (s) relative to the weight of the reaction medium of step E1 can be used. In particular, it is preferred to use from 0.02 to 0.2% by weight of catalyst (s) relative to the weight of the reaction medium of step E1. According to a preferred embodiment, the polyurethane with NCO endings (PP1) is obtained by polyaddition of at least one diisocyanate, preferably one or two diisocyanates chosen from those mentioned in a1), a2), a3) , a4), a5), a6), a7), a8 and a9) as described in any one of the preceding paragraphs with at least one, preferably one or two, polyol (s) chosen from polyether polyols and polydiene polyols, and preferably polyether polyols, such as for example polyether diols and / or polyether triols.
A l’issue de l’étape E1 , le composé possédant au moins deux groupes NCO (PP1 ) est tel que sa teneur en groupes NCO va de préférence de 0,5 à 5,7 %, plus préférentiellement de 0,7 à 3 %, et mieux encore de 1 à 2,5 %. At the end of step E1, the compound having at least two NCO groups (PP1) is such that its content of NCO groups preferably ranges from 0.5 to 5.7%, more preferably from 0.7 to 3 %, and better still from 1 to 2.5%.
Autres étapes Other steps
Le procédé susmentionné peut comprendre une étape de purification des produits de réaction intermédiaire. The above-mentioned process may include a step of purifying the intermediate reaction products.
De préférence, le procédé ne comprend pas d’étape de purification des produits de réactions intermédiaires, ou d’étape d'élimination de solvant. Preferably, the process does not include a step for purifying the products of intermediate reactions, or a step for removing solvent.
Selon un mode de réalisation, ledit procédé ne comprend pas d’étape consistant à ajouter un ou plusieurs solvant(s) et/ou plastifiant(s). Un tel procédé de préparation peut ainsi être avantageusement mis en oeuvre sans interruption, avec des vitesses de ligne de production très élevées à l’échelle industrielle. According to one embodiment, said method does not include a step consisting in adding one or more solvent (s) and / or plasticizer (s). Such a preparation process can thus advantageously be implemented without interruption, with very high production line speeds on an industrial scale.
Selon un mode de réalisation préféré le procédé selon l’invention consiste en une première étape E1 et en une deuxième étape E2, telles que définies dans l’un quelconque des paragraphes précédents. According to a preferred embodiment, the method according to the invention consists of a first step E1 and a second step E2, as defined in any one of the preceding paragraphs.
La présente invention a également pour objet un polyuréthane à comprenant au moins deux fonctions terminales T de formule (I) (PP2) susceptible d’être obtenu selon un procédé de préparation selon l’invention, tel que décrit dans l’un quelconque des paragraphes précédents. The present invention also relates to a polyurethane comprising at least two terminal T functions of formula (I) (PP2) capable of being obtained according to a preparation process according to the invention, as described in any one of the paragraphs previous.
C. Système multicomposant C. Multicomponent system
La présente invention a également pour objet un système multicomposant, de préférence sans solvant, comprenant : The present invention also relates to a multicomponent system, preferably without solvent, comprising:
- comme premier composant (composant A), une composition comprenant au moins un polyuréthane (PP2) tel que défini précédemment, et as first component (component A), a composition comprising at least one polyurethane (PP2) as defined above, and
- comme deuxième composant (composant B), une composition comprenant au moins un composé aminé (B1 ) comprenant au moins deux groupes amine choisis parmi les groupes amine primaire, les groupes amine secondaire et leurs mélanges, de préférence comprenant au moins deux groupes amine primaire. as second component (component B), a composition comprising at least one amino compound (B1) comprising at least two amine groups chosen from primary amine groups, secondary amine groups and mixtures thereof, preferably comprising at least two primary amine groups.
Les composants du système multicomposants sont généralement stockés séparément et sont mélangés au moment de l’emploi, à une température de mélange T3, pour former une composition, de préférence adhésive, destinée à être appliquée sur la surface d’un matériau. The components of the multicomponent system are generally stored separately and are mixed at the time of use, at a mixing temperature T3, to form a composition, preferably adhesive, intended to be applied to the surface of a material.
Le mélange des composants du système multicomposants, et en particulier des composants A et B, peut être réalisé en conditions anhydres. The mixing of components of the multicomponent system, and in particular of components A and B, can be carried out under anhydrous conditions.
De préférence, les quantités de polyuréthane(s) (PP2) et de composé(s) aminé(s) (B1 ) présents dans le système multicomposant selon l’invention conduisent à un rapport molaire du nombre de fonctions T de formule (I) sur le nombre de groupes amine primaire et/ou secondaire noté r3, allant de 0,5 à 1 , en particulier de 0,65 à 1 , et préférentiellement de 0,8 à 1 . Preferably, the amounts of polyurethane (s) (PP2) and of amino compound (s) (B1) present in the multicomponent system according to the invention lead to a molar ratio of the number of T functions of formula (I) on the number of primary and / or secondary amine groups noted r 3 , ranging from 0.5 to 1, in particular from 0.65 to 1, and preferably from 0.8 to 1.
Le rapport molaire noté r3 dans l’ensemble de la présente demande correspond au rapport molaire du nombre total de fonctions T de formule (I) présentes dans le système multicomposant, sur le nombre total de groupes amine primaire et/ou secondaire présents dans le système multicomposant. The molar ratio noted r 3 throughout this application corresponds to the molar ratio of the total number of T functions of formula (I) present in the multicomponent system, over the total number of primary and / or secondary amine groups present in the multicomponent system.
L’utilisation d’un tel rapport r3 permet avantageusement d’obtenir par une réaction de polyaddition entre le(s) polyuréthane(s) (PP2) susmentionnés et le(s) composé(s) aminés (B1 ) comportant de préférence au moins deux ou trois groupes amine primaire selon l’invention, une composition, de préférence adhésive, présentant avantageusement de bonnes performances mécaniques. The use of such a ratio r 3 advantageously makes it possible to obtain, by a polyaddition reaction between the polyurethane (s) (PP2) mentioned above and the amino compound (s) (B1) preferably comprising at least two or three primary amine groups according to the invention, a composition, preferably adhesive, advantageously having good mechanical performance.
Le(s) composé(s) aminé(s) (B1 ) utilisé(s) selon l’invention possède(nt) de préférence une viscosité adaptée à la température de mélange T3. The amino compound (s) (B1) used according to the invention preferably has a viscosity adapted to the mixing temperature T3.
Le(s) composé(s) aminés (B1 ) utilisé(s) selon l’invention possède(nt) de préférence une alcalinité primaire allant de 0,4 à 34 méq/g, plus préférentiellement de 3,0 à 34 méq/g de composé aminé. The amino compound (s) (B1) used according to the invention preferably have a primary alkalinity ranging from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g of amino compound.
L’alcalinité primaire est le nombre de fonctions amine primaire NH2 par gramme de composé aminé (B1 ), ledit nombre étant exprimé sous la forme de milliéquivalents de HCl (ou milliéquivalents de NH2) utilisé dans le dosage des fonctions amines, déterminé de manière bien connue par titrimétrie. Primary alkalinity is the number of primary NH 2 amine functions per gram of amino compound (B1), said number being expressed in the form of milliequivalents of HCl (or milliequivalents of NH 2 ) used in the determination of amine functions, determined by well known way by titrimetry.
Le(s) composé(s) aminé(s) (B1 ) utilisé(s) selon l’invention peu(ven)t être des composés monomériques ou des polymériques. The amino compound (s) (B1) used according to the invention can be monomeric or polymeric compounds.
Le(s) composé(s) aminé(s) (B1 ) peuvent comprendre en outre des groupes amine tertiaires. Le(s) composé(s) aminé(s) (B1 ) utilisé(s) selon l’invention peu(ven)t être choisie(s) parmi des composés hydrocarbonés, linéaires, ramifiés, cycliques ou acycliques, saturés ou insaturés, et comportant au moins deux groupes amine choisis parmi les groupes amine primaires, les groupes amine secondaires et leurs mélanges, de préférence comportant au moins deux groupes amine primaire -NH2, la chaîne hydrocarbonée entre les fonctions amine (ou avantageusement -CH2-NH2) étant éventuellement interrompue par un ou plusieurs hétéroatomes choisi parmi O, N, S et/ou éventuellement interrompue par un ou plusieurs groupes divalents -NH- (amine secondaire), -COO- (ester), -CONH- (amide), -NHCO- (carbamate), -C=N- (imine), -CO- (carbonyle) et -SO- (sulfoxyde), le(s)dit(s) composé(s) aminé(s) présentant de préférence une alcalinité primaire allant de 0,4 à 34 méq/g, plus préférentiellement de 3,0 à 34 méq/g de composé aminé. The amino compound (s) (B1) may further comprise tertiary amine groups. The amino compound (s) (B1) used according to the invention can be chosen from hydrocarbon compounds, linear, branched, cyclic or acyclic, saturated or unsaturated, and comprising at least two amine groups chosen from primary amine groups, secondary amine groups and mixtures thereof, preferably comprising at least two primary amine groups -NH 2 , the hydrocarbon chain between the amine functions (or advantageously -CH2-NH 2 ) being optionally interrupted by one or more heteroatoms chosen from O, N, S and / or possibly interrupted by one or more divalent groups -NH- (secondary amine), -COO- (ester), -CONH- (amide), - NHCO- (carbamate), -C = N- (imine), -CO- (carbonyl) and -SO- (sulfoxide), the said amino compound (s) preferably having alkalinity primary ranging from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g of amino compound.
A titre d’exemple de tels composés, on peut citer par exemple: Examples of such compounds that may be mentioned include:
- les alkylène polyamines comportant au moins deux groupes amine primaire -NH2,- alkylene polyamines comprising at least two primary amine groups -NH 2 ,
- les cycloalkylène polyamines comportant au moins deux groupes amine primaire - NH2, - cycloalkylene polyamines comprising at least two primary amine groups - NH 2 ,
- les polyamines comprenant à la fois des groupes alkyles et cycloalkyles et comportant au moins deux groupes amine primaire -NH2, polyamines comprising both alkyl and cycloalkyl groups and comprising at least two primary amine groups -NH 2 ,
- les polyéther polyamines comportant au moins deux groupes amine primaire -NH2,polyether polyamines comprising at least two primary amine groups -NH 2 ,
- les polyéthylène imines comportant au moins deux groupes amine primaire -NH2,- polyethylene imines comprising at least two primary amine groups -NH 2 ,
- les polypropylène imines comportant au moins deux groupes amine primaire -NH2,- polypropylene imines comprising at least two primary amine groups -NH 2 ,
- les polyamidoamines comportant au moins deux groupes amine primaire -NH2.- polyamidoamines comprising at least two primary amine groups -NH 2 .
De préférence, le(s) composé(s) aminé(s) (B1 ) utilisé(s) selon l’invention possède(nt) deux ou trois groupes amines primaires. Preferably, the amino compound (s) (B1) used according to the invention has (s) two or three primary amine groups.
Plus préférentiellement, le(s) composé(s) aminé(s) (B1 ) utilisé(s) selon l’invention est (sont) choisi(s) parmi des composés hydrocarbonés, linéaires, ramifiés, cycliques ou acycliques, saturés et comportant deux ou trois groupes amines primaires -NH2, lesdits composés étant éventuellement interrompus par un ou plusieurs hétéroatomes choisis parmi un atome d’oxygène -O- et un atome d’azote -N- et/ou un ou plusieurs groupes divalents amine secondaire -NH-, et présentant une alcalinité primaire allant de 0,4 à 34 méq/g, plus préférentiellement de 3,0 à 34 méq/g de composé aminé. More preferably, the amino compound (s) (B1) used according to the invention is (are) chosen from hydrocarbon compounds, linear, branched, cyclic or acyclic, saturated and comprising two or three primary amine groups -NH 2 , said compounds being optionally interrupted by one or more heteroatoms chosen from an oxygen atom -O- and a nitrogen atom -N- and / or one or more divalent secondary amine groups - NH-, and having a primary alkalinity ranging from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g of amino compound.
A titre d’exemple de tels composés, on peut citer par exemple: Examples of such compounds that may be mentioned include:
- les alkylène diamines et alkylène triamines, comportant respectivement deux ou trois groupes amines primaires -NH2, the alkylene diamines and alkylene triamines, comprising respectively two or three primary amine groups -NH 2 ,
- les cycloalkylène diamines et triamines, comportant respectivement deux ou trois groupes amines primaires -NH2, - les diamines et triamines comprenant à la fois des groupes alkyles et cycloalkyles, comportant respectivement deux ou trois groupes amines primaires -NH2, the cycloalkylene diamines and triamines, comprising respectively two or three primary amine groups -NH 2 , diamines and triamines comprising both alkyl and cycloalkyl groups, comprising respectively two or three primary amine groups -NH 2 ,
- les polyéther diamines et polyéther triamines, comportant respectivement deux ou trois groupes amines primaires -NH2, polyether diamines and polyether triamines, comprising respectively two or three primary amine groups -NH 2 ,
- les polyéthylène imines comportant deux ou trois groupes amines primaires -NH2,- polyethylene imines comprising two or three primary amine groups -NH 2 ,
- les polypropylène imines comportant deux ou trois groupes amines primaires -NH2,- polypropylene imines comprising two or three primary amine groups -NH 2 ,
- les polyamidoamines comportant deux ou trois groupes amines primaires -NH2. - polyamidoamines comprising two or three primary amine groups -NH 2 .
Plus particulièrement, on peut citer : More particularly, we can cite:
- l’éthylène diamine (EDA) ayant une alcalinité primaire de 33,28 méq/g : - ethylene diamine (EDA) having a primary alkalinity of 33.28 meq / g:
- la diéthylènetriamine (DETA) ayant une alcalinité primaire de 19,39 méq/g : - diethylenetriamine (DETA) having a primary alkalinity of 19.39 meq / g:
HH . HH.
- la tris(2-aminoéthyl)amine (TAEA) ayant une alcalinité primaire de 20,52 méq/g : - tris (2-aminoethyl) amine (TAEA) having a primary alkalinity of 20.52 meq / g:
- les polyéthylène imines répondant aux formules ci-dessous: - polyethylene imines corresponding to the formulas below:
dans lesquelles x est un nombre entier tel que l’alcalinité primaire va de 0,4 à 34 méq/g, plus préférentiellement de 3,0 à 34 méq/g ; in which x is an integer such that the primary alkalinity ranges from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g;
- les polypropylène imines répondant aux formules ci-dessous : - polypropylene imines corresponding to the formulas below:
dans lesquelles x est un nombre entier tel que l’alcalinité primaire est va de 0,4 à 34 méq/g, plus préférentiellement de 3,0 à 34 méq/g ; in which x is an integer such that the primary alkalinity is from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g;
- les poly(éthylène-propylène) imines répondant aux formules ci-dessous : - poly (ethylene-propylene) imines corresponding to the formulas below:
dans lesquelles x et y sont des nombres entiers tel que l’alcalinité primaire va de 0,4 à 34 méq/g, plus préférentiellement de 3,0 à 34 méq/g ; in which x and y are whole numbers such that the primary alkalinity ranges from 0.4 to 34 meq / g, more preferably from 3.0 to 34 meq / g;
- l’hexaméthylène diamine (HMDA) ayant une alcalinité primaire de 17,1 1 méq/g - hexamethylene diamine (HMDA) having a primary alkalinity of 17.1 1 meq / g
- l’isophorone diamine (IPDA) ayant une alcalinité primaire de 11 ,73 méq/g - isophorone diamine (IPDA) having a primary alkalinity of 11.73 meq / g
- les polyéther diamines possédant une alcalinité primaire allant de 1 1 ,4 à 13,5 méq/g et répondant à la formule ci-dessous : - polyether diamines having a primary alkalinity ranging from 11.4 to 13.5 meq / g and corresponding to the formula below:
dans laquelle x = 2 ou 3; de telles polyéther diamines sont commercialisées par exemple sous la dénomination JEFFAMINES EDR-148 et EDR-176 par la société HUNTSMAN et présentent des alcalinités primaires respectives de 13,5 et 11 ,4 méq/g ; in which x = 2 or 3; such polyether diamines are sold, for example, under the name JEFFAMINES EDR-148 and EDR-176 by the company HUNTSMAN and have respective primary alkalinities of 13.5 and 11.4 meq / g;
- les polyéther diamines possédant une alcalinité primaire allant de 0,5 à 8,7 méq/g et répondant à la formule ci-dessous : - polyether diamines having a primary alkalinity ranging from 0.5 to 8.7 meq / g and corresponding to the formula below:
dans laquelle x est un nombre entier allant de 2 ou 68, tel que l’alcalinité primaire va de 0,5 à 8,7 méq/g ; de telles polyéther diamines sont commercialisées par exemple sous la dénomination JEFFAMINES D-230, D-400, D-2000 et D-4000 par la société HUNTSMAN et présentent des alcalinités primaires respectives de 8,7, 5,0, 1 ,0 et 0,5 méq/g ; in which x is an integer ranging from 2 or 68, such that the primary alkalinity ranges from 0.5 to 8.7 meq / g; such polyether diamines are sold for example under the name JEFFAMINES D-230, D-400, D-2000 and D-4000 by the company HUNTSMAN and have respective primary alkalinities of 8.7, 5.0, 1.0 and 0.5 meq / g;
- les polyéther diamines possédant une alcalinité primaire allant de 1 ,0 à 9,1 méq/g et répondant à la formule ci-dessous : - polyether diamines having a primary alkalinity ranging from 1.0 to 9.1 meq / g and corresponding to the formula below:
dans laquelle x, y et z sont des nombres entiers, y allant de 2 à 39 et x + z allant de 1 à 6, tel que l’alcalinité primaire va de 1 ,0 à 9,1 méq/g ; de telles polyéther diamines sont commercialisées par exemple sous la dénomination JEFFAMINES HK-51 1 , ED- 600, ED-900et ED-2003 par la société HUNTSMAN et présentent des alcalinités primaires respectives de 9,1 , 3,3, 2,2 et 1 ,0 méq/g ; in which x, y and z are whole numbers, y ranging from 2 to 39 and x + z ranging from 1 to 6, such that the primary alkalinity ranges from 1.0 to 9.1 meq / g; such polyether diamines are marketed for example under the name JEFFAMINES HK-51 1, ED-600, ED-900 and ED-2003 by the company HUNTSMAN and have respective primary alkalinities of 9.1, 3.3, 2.2 and 1.0 meq / g;
- les polyétherdiamines possédant une alcalinité primaire allant de 1 à 10 méq/g et répondant à la formule suivante : dans laquelle Xb est un groupe alkylène linéaire ou ramifié, comprenant de préférence de 2 à 20 atomes de carbone, préférentiellement de 2 à 10 atomes de carbone, m est un entier allant de 1 à 20, et n est un entier allant de 1 à 100 ; - polyether diamines having a primary alkalinity ranging from 1 to 10 meq / g and corresponding to the following formula: in which X b is a linear or branched alkylene group, preferably comprising from 2 to 20 carbon atoms, preferably from 2 to 10 carbon atoms, m is an integer ranging from 1 to 20, and n is an integer ranging from 1 100 ;
- les polyéther triamines possédant une alcalinité primaire allant de 0,6 à 6,8 méq/g et répondant à la formule ci-dessous : - polyether triamines having a primary alkalinity ranging from 0.6 to 6.8 meq / g and corresponding to the formula below:
dans laquelle R est un atome d’hydrogène ou un groupe alkyl en C1 à C2, x, y, z et n sont des nombres entiers, n allant de 0 à 1 et x + y + z allant de 5 à 85, tel que l’alcalinité primaire va de 0,6 à 6,8 méq/g ; de telles polyéther diamines sont commercialisées par exemple sous la dénomination JEFFAMINES T-403, T-3000, et T-5000 par la société HUNTSMAN et présentent des alcalinités primaires respectives de 6,8, 1 ,0 et 0,6 méq/g ; in which R is a hydrogen atom or a C1 to C2 alkyl group, x, y, z and n are whole numbers, n ranging from 0 to 1 and x + y + z ranging from 5 to 85, such that the primary alkalinity ranges from 0.6 to 6.8 meq / g; such polyether diamines are marketed for example under the name JEFFAMINES T-403, T-3000, and T-5000 by the company HUNTSMAN and have respective primary alkalinities of 6.8, 1.0 and 0.6 meq / g;
- les amines grasses dimères et trimères comportant deux ou trois groupes amines primaire d’alcalinité primaire allant de 3,39 méq/g à 3,60 méq/g. Ces amines grasses dimères et trimères peuvent être obtenues à partir d’acides gras dimérisés et trimérisés correspondants. A titre d’exemple de telles amines grasses dimères, partiellement ou totalement hydrogénées, on peut citer celles répondant aux formules suivantes : - dimer and trimer fatty amines comprising two or three primary amine groups of primary alkalinity ranging from 3.39 meq / g to 3.60 meq / g. These fatty amines dimers and trimers can be obtained from corresponding dimerized and trimerized fatty acids. By way of example of such dimeric fatty amines, partially or completely hydrogenated, mention may be made of those corresponding to the following formulas:
Les acides gras dimères et trimères utilisés pour préparer les amines grasses sus-cités sont obtenus par polymérisation à haute température et sous pression d'acides gras insaturés monocarboxyliques (acide monomère), comprenant de 6 à 22 atomes de carbone, de préférence de 12 à 20 atomes de carbone, et proviennent de sources végétales ou animales. On peut citer comme exemple de tels acides gras insaturés, les acides en Cie ayant une ou deux doubles liaisons (respectivement l'acide oléïque ou linoléïque) obtenus à partir de tallol qui est un sous-produit de la fabrication de la pâte à papier. Après polymérisation de ces acides gras insaturés, on obtient un mélange technique contenant en moyenne 30-35 % en poids d'acides gras monocarboxyliques souvent isomérisés par rapport aux acides gras insaturés monocarboxyliques de départ, 60-65 % en poids d'acides dicarboxyliques (acides dimères) comprenant le double du nombre de carbone par rapport aux acides gras insaturés monocarboxyliques de départ et 5-10 % en poids d'acides tricarboxyliques (acides trimères) ayant le triple du nombre de carbone par rapport aux acides gras insaturés monocarboxyliques de départ. Par purification de ce mélange, on obtient les différents grades commerciaux d'acides dimères, monomères ou trimères. Ces acides gras dimères et trimères sont ensuite soumis à une réaction d’ammoniation réductrice (NH3/H2) en présence d’un catalyseur, permettant d’obtenir les amines grasses dimérisées. The dimer and trimer fatty acids used to prepare the abovementioned fatty amines are obtained by high temperature polymerization under pressure of monocarboxylic unsaturated fatty acids (monomeric acid), comprising from 6 to 22 carbon atoms, preferably from 12 to 20 carbon atoms, and come from plant or animal sources. Examples of such unsaturated fatty acids that may be mentioned include Cie acids having one or two double bonds (respectively oleic or linoleic acid) obtained from tall oil which is a by-product of the manufacture of paper pulp. After polymerization of these unsaturated fatty acids, a technical mixture is obtained containing on average 30-35% by weight of monocarboxylic fatty acids often isomerized with respect to the starting monocarboxylic unsaturated fatty acids, 60-65% by weight of dicarboxylic acids ( dimer acids) comprising twice the number of carbon relative to the starting monocarboxylic unsaturated fatty acids and 5-10% by weight of tricarboxylic acids (trimer acids) having three times the carbon number relative to the starting monocarboxylic unsaturated fatty acids . By purification of this mixture, the various commercial grades are obtained of dimeric, monomeric or trimeric acids. These dimer and trimer fatty acids are then subjected to a reductive ammoniation reaction (NH 3 / H2) in the presence of a catalyst, making it possible to obtain the dimerized fatty amines.
Selon un mode de réalisation, le(s) composé(s) (B1 ) comprennent au moins deux groupes méthylène amine (-CH2-NH2). According to one embodiment, the compound (s) (B1) comprise at least two methylene amine groups (-CH2-NH 2 ).
Selon un mode de réalisation préféré, le(s) composé(s) (B1 ) sont choisis parmi la tris-(2-aminoéthyl)amine (TAEA), l’hexaméthylène diamine (HMDA), et leurs mélanges. According to a preferred embodiment, the compound (s) (B1) are chosen from tris- (2-aminoethyl) amine (TAEA), hexamethylene diamine (HMDA), and their mixtures.
Lorsque le système multicomposant selon l’invention comprend au moins deux composés aminés (B1 ), ceux-ci peuvent être compris dans deux composants différents, par exemple un composant (B) et un composant (C). Les composants (A), (B) et (C) sont alors stockés séparément avant mélange au moment de l’emploi dudit système, à une température de mélange T3, pour former une composition, de préférence adhésive, destinée à être appliquée sur la surface d’un matériau. When the multicomponent system according to the invention comprises at least two amino compounds (B1), these can be included in two different components, for example a component (B) and a component (C). The components (A), (B) and (C) are then stored separately before mixing at the time of use of said system, at a mixing temperature T3, to form a composition, preferably adhesive, intended to be applied to the surface of a material.
Le système multicomposant selon l’invention peut comprendre au moins un catalyseur de réticulation. The multicomponent system according to the invention can comprise at least one crosslinking catalyst.
Le(s) catalyseur(s) de réticulation peu(ven)t être n’importe quel catalyseur habituellement utilisé(s) pour accélérer la réaction d’ouverture de cycle d’un composé comportant une fonction T par une amine primaire et/ou secondaire. The crosslinking catalyst (s) can be any catalyst usually used to accelerate the ring-opening reaction of a compound comprising a T function with a primary amine and / or secondary.
A titre d’exemple de catalyseur de réticulation utilisable selon l’invention, on peut citer : By way of example of a crosslinking catalyst which can be used according to the invention, there may be mentioned:
- les alcoolates, tels que le tert-butylate de potassium ou le méthanolate de sodium ; - alcoholates, such as potassium tert-butoxide or sodium methanolate;
- les bases fortes choisis parmi : - strong bases chosen from:
- les phosphazènes tel que le 2-tert-butylimino-2-diéthylamino-1 ,3- diméthylperhydro-1 ,3,2-diazaphosphorure (BMEP), - phosphazenes such as 2-tert-butylimino-2-diethylamino-1, 3-dimethylperhydro-1, 3,2-diazaphosphoride (BMEP),
- les guanidines telles que : - guanidines such as:
le 1 ,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) 1, 5,7-triazabicyclo [4.4.0] dec-5-ene (TBD)
le N-méthyl triazabicyclodécène (Me-TBD) N-methyl triazabicyclodecene (Me-TBD)
des amines tertiaires telles que : tertiary amines such as:
le 1 ,8-diazabicyclo[5.4.0]undec-7-ène (DBU) 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU)
le 1 ,5-diazabicyclo[4.3.0]non-5-ène (DBN) 1,5-diazabicyclo [4.3.0] non-5-ene (DBN)
l'éther diéthylique-2,2’-morpholine (DMDEE) diethyl ether-2,2'-morpholine (DMDEE)
le 1 ,4-diazabicyclo[2.2.2]octane (DABCO) 1, 4-diazabicyclo [2.2.2] octane (DABCO)
Une quantité allant de 0,05 à 1 % en poids de catalyseur(s) de réticulation par rapport au poids total du système multicomposant selon l’invention peut être utilisée. An amount ranging from 0.05 to 1% by weight of crosslinking catalyst (s) relative to the total weight of the multicomponent system according to the invention can be used.
Le(s) catalyseur(s) de réticulation peu(ven)t être réparti(s) dans un ou plusieurs des composants formant le système multicomposant selon l’invention. The crosslinking catalyst (s) can be distributed in one or more of the components forming the multicomponent system according to the invention.
Avantageusement, le système multicomposant selon l’invention peut comprendre au moins une charge minérale. Advantageously, the multicomponent system according to the invention can comprise at least one mineral filler.
La (ou les) charge(s) minérale(s) utilisable(s) est (sont) avantageusement choisie(s) de manière à améliorer les performances mécaniques de la composition selon l’invention à l’état réticulée. The (or) mineral filler (s) that can be used is (are) advantageously chosen (s) so as to improve the mechanical performance of the composition according to the invention in the crosslinked state.
A titre d’exemple de charge(s) utilisable(s), on peut citer de manière non limitative le carbonate de calcium, le kaolin, la silice, le gypse, les microsphères et les argiles. As an example of filler (s) which can be used, mention may be made, without limitation, of calcium carbonate, kaolin, silica, gypsum, microspheres and clays.
De préférence, la (ou les) charge(s) minérale(s) possède(nt) une taille de particule maximale, notamment un diamètre externe, inférieur(e) à 100 mm et de préférence inférieur(e) à 10 mm. De telles charges peuvent être sélectionnées de manière bien connue par l’homme du métier en utilisant des tamis de mailles appropriées. De préférence, la teneur totale en charge(s) éventuellement présente(s) dans le système multicomposant selon l’invention ne dépasse pas 70% en poids du poids total dudit système. Preferably, the mineral filler (s) has (s) a maximum particle size, in particular an external diameter, less than 100 mm and preferably less than 10 mm. Such fillers can be selected in a manner well known to those skilled in the art using appropriate mesh screens. Preferably, the total content of filler (s) possibly present in the multicomponent system according to the invention does not exceed 70% by weight of the total weight of said system.
Le(s) charge(s) peu(ven)t être répartie(s) dans un ou plusieurs des composants formant le système multicomposant selon l’invention. The load (s) can be distributed in one or more of the components forming the multicomponent system according to the invention.
Le système multicomposant selon l'invention peut inclure moins de 2% en poids d’un ou plusieurs additifs choisis avantageusement de manière appropriée pour ne pas détériorer les propriétés de la composition selon l’invention à l’état réticulé. On peut citer parmi les additifs utilisables des antioxydants ou stabilisants UV (ultra-violet), des pigments, et des colorants. Ces additifs sont de préférence choisis parmi ceux habituellement utilisés dans des compositions adhésives. The multicomponent system according to the invention may include less than 2% by weight of one or more additives advantageously chosen suitably so as not to deteriorate the properties of the composition according to the invention in the crosslinked state. Mention may be made, among the additives which can be used, of antioxidants or UV stabilizers (ultraviolet), pigments and dyes. These additives are preferably chosen from those usually used in adhesive compositions.
Le(s) additif(s) peu(ven)t être répartie(s) dans un ou plusieurs des composants formant le système multicomposant selon l’invention. The additive (s) can be distributed in one or more of the components forming the multicomponent system according to the invention.
De préférence, le système multicomposant susmentionné ne comprend pas de solvant et/ou plastifiant. Preferably, the aforementioned multicomponent system does not include any solvent and / or plasticizer.
Du fait de la faible viscosité du polyuréthane (PP2) selon l’invention, le système multicomposant selon l’invention peut avantageusement être mis en oeuvre directement par mélange de ses différents composants, sans ajout de solvant et/ou de plastifiant, réducteurs de viscosité, dans le composant (A) et/ou sans chauffage dudit composant à des températures au-delà de 95°C. Due to the low viscosity of the polyurethane (PP2) according to the invention, the multicomponent system according to the invention can advantageously be used directly by mixing its various components, without adding solvent and / or plasticizer, viscosity reducers , in component (A) and / or without heating of said component to temperatures above 95 ° C.
De préférence, le polyuréthane (PP2) selon l’invention possède une viscosité mesurée à 23°C inférieure ou égale à 600 Pa.s. et une viscosité mesurée à 60°C inférieure ou égale à 40 Pa.s, permettant au système multicomposant selon l’invention d’être avantageusement mis en oeuvre sans ajout de solvant et/ou de plastifiant dans le composant Preferably, the polyurethane (PP2) according to the invention has a viscosity measured at 23 ° C less than or equal to 600 Pa.s. and a viscosity measured at 60 ° C less than or equal to 40 Pa.s, allowing the multicomponent system according to the invention to be advantageously used without adding solvent and / or plasticizer to the component
(A) comprenant ledit polyuréthane (PP2), et/ou sans chauffage dudit composant. (A) comprising said polyurethane (PP2), and / or without heating of said component.
Selon un mode de réalisation, le système multicomposant selon l’invention comprend: According to one embodiment, the multicomponent system according to the invention comprises:
- comme premier composant (A), une composition comprenant au moins un polyuréthane (PP2) selon l’invention, et - As the first component (A), a composition comprising at least one polyurethane (PP2) according to the invention, and
- comme deuxième composant (B), une composition comprenant au moins un ou deux composé(s) aminé(s) tel(s) que décrit(s) dans l’un des paragraphes précédents (B 1 ), et ledit système multicomposant étant dépourvu de solvant et/ou de plastifiant. - As the second component (B), a composition comprising at least one or two amino compound (s) as described in one of the preceding paragraphs (B 1), and said multicomponent system being free of solvent and / or plasticizer.
Le système multicomposant selon l’invention peut être un système bicomposant, c’est-à-dire un système constitué de deux composants (A) et (B), lesdits composants (A) et The multicomponent system according to the invention can be a two-component system, that is to say a system consisting of two components (A) and (B), said components (A) and
(B) étant tels que décrits dans l’un des paragraphes précédents. De préférence, le composant (A) comprend au moins 97% en poids, et plus préférentiellement au moins 98% en poids de polyuréthane à (PP2) selon l’invention par rapport au poids total dudit composant (A). (B) being as described in one of the preceding paragraphs. Preferably, the component (A) comprises at least 97% by weight, and more preferably at least 98% by weight of polyurethane to (PP2) according to the invention relative to the total weight of said component (A).
Selon un mode de réalisation, le système multicomposant est une composition adhésive, de préférence une composition de colle ou de mastic. According to one embodiment, the multicomponent system is an adhesive composition, preferably an adhesive or mastic composition.
L’invention porte également sur l’utilisation d’un polyuréthane (PP2) selon l’invention, pour la fabrication d’une composition adhésive, de préférence sans solvant, notamment sous la forme d’un système multicomposant. The invention also relates to the use of a polyurethane (PP2) according to the invention, for the manufacture of an adhesive composition, preferably without solvent, in particular in the form of a multicomponent system.
De préférence, la fabrication de la composition adhésive est réalisée sans ajout de composé destiné à abaisser la viscosité de ladite composition, tel qu’un solvant (aqueux, organique), un diluant réactif et/ou un plastifiant. Preferably, the manufacture of the adhesive composition is carried out without adding a compound intended to lower the viscosity of said composition, such as a solvent (aqueous, organic), a reactive diluent and / or a plasticizer.
De préférence, les composants du système multicomposant selon l’invention comprenant le(s) polyuréthane(s) (PP2) selon l’invention et le(s) composé(s) aminé(s) (B1 ) selon l’invention sont mélangés à une température T3 telle que définie précédemment. Preferably, the components of the multicomponent system according to the invention comprising the polyurethane (s) (PP2) according to the invention and the amino compound (s) (B1) according to the invention are mixed. at a temperature T3 as defined above.
De préférence, la composition, de préférence adhésive, selon l’invention est fabriquée par la mise en oeuvre du système multicomposant selon l’invention, c’est-à-dire le mélange des différents composants le constituant, à une température de mélange T3. Preferably, the composition, preferably adhesive, according to the invention is produced by the use of the multicomponent system according to the invention, that is to say the mixture of the various components constituting it, at a mixing temperature T3 .
D. Utilisations D. Uses
L’invention a également pour objet un procédé d’assemblage de matériaux mettant en oeuvre le polyuréthane (PP2) selon l’invention, notamment par l’intermédiaire de la mise en oeuvre du système multicomposant selon l’invention comprenant les étapes suivantes : The subject of the invention is also a process for assembling materials using the polyurethane (PP2) according to the invention, in particular by means of the implementation of the multicomponent system according to the invention comprising the following steps:
- le mélange d’au moins un polyuréthane (PP2) tel que décrit précédemment et d’au moins un composé aminé (B1 ), puis - the mixture of at least one polyurethane (PP2) as described above and at least one amino compound (B1), then
- l’enduction dudit mélange sur la surface d’un premier matériau, puis - coating said mixture on the surface of a first material, then
- le contrecollage de la surface d’un second matériau sur ladite surface enduite, puis - laminating the surface of a second material on said coated surface, then
- la réticulation dudit mélange. - crosslinking of said mixture.
L’étape de mélange d’au moins un polyuréthane (PP2) tel que décrit précédemment et d’au moins un composé aminé (B1 ) tel que décrit précédemment, peut être réalisée notamment par la mise en oeuvre du système multicomposant selon l’invention, à savoir par mélange des composants comprenant respectivement le(s) polyuréthane(s) (PP2) (composant (A)) et le(s) composé(s) aminé(s) (composant (B)), tel que définis précédemment. The step of mixing at least one polyurethane (PP2) as described above and at least one amino compound (B1) as described above, can be carried out in particular by using the multicomponent system according to the invention , namely by mixing the components respectively comprising (s) polyurethane (s) (PP2) (component (A)) and the amino compound (s) (component (B)), as defined above .
Cette étape de mélange peut être réalisée à température ambiante ou à chaud, avant enduction. De préférence, le mélange est réalisé à une température inférieure à la température de dégradation des ingrédients compris dans l’un ou l’autre des composants (A) et (B). En particulier, le mélange est réalisé à une température T3 inférieure à 95°C, de préférence allant de 15 à 80°C, afin d’éviter avantageusement toute dégradation thermique. This mixing step can be carried out at room temperature or hot, before coating. Preferably, the mixing is carried out at a temperature below the degradation temperature of the ingredients included in one or other of the components (A) and (B). In particular, the mixing is carried out at a temperature T3 of less than 95 ° C, preferably ranging from 15 to 80 ° C, in order to advantageously avoid any thermal degradation.
De préférence, on mélange le polyuréthane à terminaisons (PP2) et le(s) composé(s) aminé (B1 ) dans des quantités telles que le rapport molaire du nombre de fonctions T sur le nombre de groupes amine primaire et/ou secondaire présents dans le mélange, noté va de 0,5 à 1 , préférentiellement de 0,8 à 1 ,0. Preferably, the polyurethane with endings (PP2) and the amino compound (s) (B1) are mixed in amounts such as the molar ratio of the number of T functions to the number of primary and / or secondary amine groups present. in the mixture, noted ranges from 0.5 to 1, preferably from 0.8 to 1.0.
Dans chacune de ces variantes, l’enduction dudit mélange peut être réalisée sur tout ou partie de la surface d’un matériau. En particulier, l’enduction dudit mélange peut être réalisée sous la forme d’une couche d’épaisseur allant de 0,002 à 5 mm. In each of these variants, the coating of said mixture can be carried out on all or part of the surface of a material. In particular, the coating of said mixture can be carried out in the form of a layer with a thickness ranging from 0.002 to 5 mm.
Eventuellement, la réticulation dudit mélange sur la surface du matériau peut être accélérée en chauffant le(s) matériau(x) enduit(s) à une température inférieure ou égale à 120°C. Le temps requis pour compléter cette réaction de réticulation et assurer ainsi le niveau de cohésion requis est en général de l’ordre de 0,5 à 24 heures. Optionally, the crosslinking of said mixture on the surface of the material can be accelerated by heating the coated material (s) to a temperature less than or equal to 120 ° C. The time required to complete this crosslinking reaction and thus ensure the required level of cohesion is generally on the order of 0.5 to 24 hours.
L’enduction et le contrecollage du second matériau sont généralement effectués dans un intervalle de temps compatible avec le procédé d’enduction, comme il est bien connu de l’homme du métier, c’est-à-dire avant que la couche d’adhésif perde sa capacité à fixer par collage les deux matériaux. The coating and laminating of the second material are generally carried out in a time interval compatible with the coating process, as is well known to those skilled in the art, that is to say before the layer of adhesive loses its ability to glue the two materials together.
Les matériaux appropriés sont, par exemple, des substrats inorganiques tels que le verre, les céramiques, le béton, les métaux ou les alliages (comme les alliages d’aluminium, l’acier, les métaux non-ferreux et les métaux galvanisés) ainsi que les métaux et les composites éventuellement revêtus de peinture (comme dans le domaine automobile); ou bien des substrats organiques comme le bois, des plastiques tel que le PVC, le polycarbonate, le PMMA, les résines époxy et les polyesters. Suitable materials are, for example, inorganic substrates such as glass, ceramics, concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals) as well as metals and composites possibly coated with paint (as in the automotive field); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, epoxy resins and polyesters.
La présente invention concerne également l'utilisation d’un polyuréthane comprenant au moins deux fonctions terminales T de formule (I) (PP2) selon l’invention pour la fabrication d’une composition adhésive. The present invention also relates to the use of a polyurethane comprising at least two T terminal functions of formula (I) (PP2) according to the invention for the manufacture of an adhesive composition.
Les performances mécaniques et le pouvoir adhésif des compositions selon l’invention peuvent être mesurés conformément aux tests décrits dans les exemples qui suivent, à savoir une fois réticulées. Les compositions selon l’invention sont avantageusement adaptées à un large panel d’applications telles que l’agroalimentaire, la cosmétique, l’hygiène, le transport, l’habitat, les textiles, l’emballage. En particulier, les compositions selon l’invention présentent une force d’élongation à la rupture intrinsèque allant de 0,3 à 10 MPa, tel qu’illustré dans les exemples (mesure des performances mécaniques). Il a été observé que le polyuréthane (PP2) selon l’invention présente avantageusement une réactivité améliorée vis-à-vis des composés aminés comprenant au moins deux groupes amine primaire et/ou secondaire à une température proche de l’ambiante (allant par exemple de 15°C à 35°C). The mechanical performances and the adhesive power of the compositions according to the invention can be measured in accordance with the tests described in the examples which follow, namely once crosslinked. The compositions according to the invention are advantageously adapted to a wide range of applications such as the food industry, cosmetics, hygiene, transport, housing, textiles, packaging. In particular, the compositions according to the invention exhibit an intrinsic elongation force at break ranging from 0.3 to 10 MPa, as illustrated in the examples (measurement of mechanical performance). It has been observed that the polyurethane (PP2) according to the invention advantageously exhibits improved reactivity with respect to amino compounds comprising at least two primary and / or secondary amine groups at a temperature close to ambient (ranging for example from 15 ° C to 35 ° C).
Il a été observé par ailleurs qu’en utilisant le polyuréthane (PP2) selon l’invention, on pouvait avantageusement fabriquer des compositions adhésives sans solvant présentant de bonnes propriétés de mouillabilité et de bonnes performances mécaniques, adaptées au revêtement de surface, et des propriétés adhésives satisfaisantes pour l’assemblage par collage d’au moins deux matériaux. It has also been observed that by using the polyurethane (PP2) according to the invention, it is possible advantageously to manufacture adhesive compositions without solvent having good wettability properties and good mechanical performance, suitable for the surface coating, and properties satisfactory adhesives for bonding at least two materials.
Tous les modes de réalisation décrits ci-dessus peuvent être combinés les uns avec les autres. All of the embodiments described above can be combined with each other.
Dans le cadre de l’invention, par « comprise entre x et y », ou « allant de x à y », on entend un intervalle dans lequel les bornes x et y sont incluses. Par exemple, la gamme «comprise entre 0% et 25% » inclus notamment les valeurs 0% et 25%. In the context of the invention, by "lying between x and y", or "ranging from x to y", is meant an interval in which the limits x and y are included. For example, the range "between 0% and 25%" includes in particular the values 0% and 25%.
Les exemples suivants sont donnés à titre purement illustratif de l'invention et ne sauraient être interprétés pour en limiter la portée. The following examples are given purely by way of illustration of the invention and should not be interpreted to limit its scope.
PARTIE EXPERIMENTALE EXPERIMENTAL PART
A - Synthèse de polyuréthanes comprenant au moins deux fonctions terminales T (PP2) (composant A) A - Synthesis of polyurethanes comprising at least two terminal functions T (PP2) (component A)
Les composants (A) des exemples 1 à 4 selon l’invention sont préparés à l’aide des réactifs indiqués dans le tableau 1 et selon le mode opératoire décrit dans les pages suivantes. Les quantités indiquées dans le tableau 1 sont exprimées en gramme de produits commerciaux. The components (A) of Examples 1 to 4 according to the invention are prepared using the reagents indicated in Table 1 and according to the procedure described on the following pages. The quantities indicated in table 1 are expressed in grams of commercial products.
Tableau 1 Table 1
N.A. : non applicable N.A.: not applicable
Dans le tableau 1 , on utilise comme: In Table 1, we use as:
- PPG diol, le produit commercial vendu sous la dénomination VORANOL® P2000 par la société DOW, correspondant à du polypropylène glycol diol, ayant un indice d’hydroxyle environ égal à 56 mg KOH/g, - PPG diol, the commercial product sold under the name VORANOL® P2000 by the company DOW, corresponding to polypropylene glycol diol, having a hydroxyl number approximately equal to 56 mg KOH / g,
- PPG triol, le produit commercial vendu sous la dénomination VORANOL® CP3355 par la société DOW, correspondant à du polypropylène glycol triol, ayant un indice d’hydroxyle environ égal à 45 mg KOH/g, - PPG triol, the commercial product sold under the name VORANOL® CP3355 by the company DOW, corresponding to polypropylene glycol triol, having a hydroxyl number approximately equal to 45 mg KOH / g,
- diisocyanate 2,4-TDI, le produit commercial vendu sous la dénomination SCURANATE® T 100 par la société VENCOREX, correspondant à une composition de TDI à 99% en poids de 2,4-TDI, - 2,4-TDI diisocyanate, the commercial product sold under the name SCURANATE® T 100 by the company VENCOREX, corresponding to a TDI composition at 99% by weight of 2,4-TDI,
- diisocyanate dérivé d’allophanate d’hexaméthylène diisocyanate (HDI) de formule (I IA), le produit commercial vendu sous la dénomination TOLONATE® X FLO par la société VENCOREX, correspondant à une composition à 99,5% en poids minimum de dérivé d’allophanate d’hexaméthylène diisocyanate (HDI) de formule (MA) et moins de 0,5% en poids de HDI, ayant une teneur en groupe NCO égale à 13,4 % en poids par rapport au poids de TOLONATE® X FLO, - diisocyanate derived from hexamethylene allophanate diisocyanate (HDI) of formula (I IA), the commercial product sold under the name TOLONATE® X FLO by the company VENCOREX, corresponding to a composition at 99.5% by weight minimum of derivative hexamethylene diisocyanate allophanate (HDI) of formula (MA) and less than 0.5% by weight of HDI, having an NCO group content equal to 13.4% by weight relative to the weight of TOLONATE® X FLO ,
- catalyseur de réaction, le produit commercial vendu sous la dénomination BORCHI KAT® 315 par la société BORCHERS, correspondant au néodécanoate de bismuth, - reaction catalyst, the commercial product sold under the name BORCHI KAT® 315 by the company BORCHERS, corresponding to bismuth neodecanoate,
- 2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4-carboxylate synthétisé selon la demande de brevet WO 2015/132080 (pureté de 99% en poids) et présentant un indice d’hydroxyle IOH de 295 mg KOH/g. - 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate synthesized according to patent application WO 2015/132080 (purity of 99% by weight) and having a hydroxyl number IOH of 295 mg KOH / g .
Les rapports molaires r1 et r2 sont calculés de manière bien connue par l’homme du métier à partir des quantités molaires en réactifs utilisés. En exprimant le nombre de mole(s) de diisocyanate utilisé en fonction de la masse molaire de ce dernier, le nombre de mole(s) de polyol utilisé en fonction de l’indice hydroxyle (mg KOH/g) et de la fonctionnalité de ce dernier, le nombre de mole(s) de 2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4-carboxylate utilisé en fonction de l’indice hydroxyle (mg KOH/g) de ce dernier et sachant que la masse molaire de KOH est de 56,1 1 g/mol, on peut écrire : The molar ratios r 1 and r 2 are calculated in a manner well known to those skilled in the art from the molar quantities of reagents used. By expressing the number of mole (s) of diisocyanate used as a function of the molar mass of the latter, the number of mole (s) of polyol used as a function of the hydroxyl number (mg KOH / g) and of the functionality of the latter, the number of mole (s) of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate used as a function of the hydroxyl number (mg KOH / g) of the latter and knowing that the mass KOH molar is 56.1 1 g / mol, we can write:
et and
m1 (diisocyanate) correspond à la masse de diisocyanate introduit (SCURANATE® T100 ou TOLONATE X FLO selon l’exemple considéré) m1 (diisocyanate) corresponds to the mass of diisocyanate introduced (SCURANATE® T100 or TOLONATE X FLO according to the example considered)
M (diisocyanate) correspond à la masse molaire du diisocyanate introduit, M (diisocyanate) corresponds to the molar mass of the diisocyanate introduced,
IOH (polyol) correspond à l’indice hydroxyle du polyol utilisé (VORANOL® P2000 ou du VORANOL® CP3355 selon l’exemple considéré), IOH (polyol) corresponds to the hydroxyl index of the polyol used (VORANOL® P2000 or VORANOL® CP3355 according to the example considered),
m2 (polyol) correspond à la masse du polyol introduit, m2 (polyol) corresponds to the mass of the polyol introduced,
IOH (2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4-carboxylate) correspond à l’indice d’hydroxyle du 2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4-carboxylate, IOH (2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate) corresponds to the hydroxyl number of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate,
m3 (2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4-carboxylate) correspond à la masse de 2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4-carboxylate introduit. m3 (2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate) corresponds to the mass of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate introduced.
Exemples 1 à 3 : synthèse de polyuréthanes (PP2) (composant A) en deux étapesExamples 1 to 3: synthesis of polyurethanes (PP2) (component A) in two stages
(E1 et E2) (E1 and E2)
Etape E1 : Synthèse du composé (PP1 ) Step E1: Synthesis of the compound (PP1)
Dans un réacteur placé sous atmosphère d’azote, on chauffe le diisocyanate à 50°C puis on introduit sous agitation constante au goutte à goutte un mélange de polyol et de catalyseur de réaction en contrôlant la température de réaction T1 de manière à ce qu’elle ne dépasse pas 80°C, conformément aux quantités indiquées dans le tableau 1 . In a reactor placed under a nitrogen atmosphere, the diisocyanate is heated to 50 ° C. and then a mixture of polyol and reaction catalyst is introduced, with constant stirring, drop by drop, controlling the reaction temperature T1 so that it does not exceed 80 ° C, in accordance with the quantities indicated in Table 1.
Ce mélange est maintenu sous agitation constante à 80°C, sous azote, jusqu'à réaction complète des fonctions NCO du diisocyanate. This mixture is kept under constant stirring at 80 ° C., under nitrogen, until the NCO functions of the diisocyanate have completely reacted.
Le suivi de la réaction est réalisé en mesurant l’évolution de la teneur en groupes NCO dans le mélange, par exemple par un dosage de dibutylamine en retour, à l’aide d’acide chlorhydrique selon la norme NF T52-132. La réaction est stoppée lorsque le « taux de NCO » (%NCO) mesuré est environ égal au taux de NCO souhaité. The reaction is monitored by measuring the change in the content of NCO groups in the mixture, for example by dosing dibutylamine in return, using hydrochloric acid according to standard NF T52-132. The reaction is stopped when the "NCO level" (% NCO) measured is approximately equal to the desired NCO level.
Etape E2 : Synthèse du polyuréthane (PP2) (composant A) Step E2: Synthesis of polyurethane (PP2) (component A)
Une fois la réaction de l’étape E1 terminée, on introduit dans le réacteur le 2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4-carboxylate dans les proportions indiquées dans le tableau 1 , sous agitation et sous azote, en veillant à ce que la température de réaction T2 ne dépasse pas 80°C. Le mélange polyuréthane à terminaisons NCO (PP1 ) - 2-hydroxypropyl-2- oxo-1 ,3-dioxolane-4-carboxylate est maintenu sous agitation constante à 80 °C, sous azote, jusqu'à disparition complète des fonctions NCO visibles en Infra-Rouge (IR) (environ 2250 cm- 1)· Once the reaction of step E1 is complete, the 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate is introduced into the reactor in the proportions indicated in the Table 1, with stirring and under nitrogen, ensuring that the reaction temperature T2 does not exceed 80 ° C. The polyurethane mixture with NCO endings (PP1) - 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate is kept under constant stirring at 80 ° C., under nitrogen, until complete disappearance of the NCO functions visible in Infra-Red (IR) (about 2250 cm- 1 )
Exemple 4 : synthèse de polyuréthane (PP2) (composant A) en une étape E2)Example 4 Synthesis of Polyurethane (PP2) (Component A) in Step E2)
Dans un réacteur placé sous atmosphère d’azote, on chauffe le diisocyanate (composé (PP1 ) = dérivé de formule (lia)) à 50°C puis on introduit le 2-hydroxypropyl -2-oxo-1 ,3- dioxolane-4-carboxylate dans les proportions indiquées dans le tableau 1 . Le mélange est ensuite porté à 80°C et le catalyseur est ajouté. Ce mélange est maintenu sous agitation constante à 80°C, sous azote, jusqu'à disparition complète des fonctions NCO visibles en Infra-Rouge (IR) (environ 2250 cm-1). In a reactor placed under a nitrogen atmosphere, the diisocyanate (compound (PP1) = derivative of formula (IIa)) is heated to 50 ° C. and then 2-hydroxypropyl -2-oxo-1, 3-dioxolane-4 is introduced. -carboxylate in the proportions indicated in table 1. The mixture is then brought to 80 ° C. and the catalyst is added. This mixture is kept under constant stirring at 80 ° C., under nitrogen, until complete disappearance of the NCO functions visible in Infra-Red (IR) (approximately 2250 cm -1 ).
Mesure de viscosité : Viscosity measurement:
La viscosité du composant (A) obtenu est mesurée 24 heures après la fin de réaction (J+1 ) à 23°C et 60°C et exprimée en Pascal seconde (Pa.s). L’ensemble des valeurs mesurées pour les exemples 1 à 4 sont regroupés dans le tableau 2 suivant. The viscosity of the component (A) obtained is measured 24 hours after the end of the reaction (D + 1) at 23 ° C and 60 ° C and expressed in Pascal second (Pa.s). All the values measured for Examples 1 to 4 are grouped in Table 2 below.
La mesure de viscosité à 23°C se fait à l’aide d’un viscosimètre Brookfield RVT, avec une aiguille adaptée au domaine de viscosité et à une vitesse de rotation de 20 tours par minute (tr/mn). The viscosity measurement at 23 ° C is carried out using a Brookfield RVT viscometer, with a needle suitable for the viscosity range and at a rotation speed of 20 revolutions per minute (rpm).
La mesure de viscosité à 60°C se fait à l’aide d’un viscosimètre Brookfield RVT couplé avec un module chauffant de type Thermosel de la marque Brookfield, avec un mobile adapté au domaine de viscosité et à une vitesse de rotation de 20 tours par minute. The viscosity measurement at 60 ° C. is done using a Brookfield RVT viscometer coupled with a Thermosel type heating module from the Brookfield brand, with a mobile adapted to the viscosity range and at a rotation speed of 20 revolutions. per minute.
Tableau 2 Table 2
La teneur en fonctions T dans le polyuréthane (PP2) (notée tcc (PP2)) (exprimée en méq/g de polyuréthane (PP2)) est calculée de manière bien connue de l’homme du métier à partir de la quantité molaire de 2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4-carboxylate introduit. En exprimant le nombre de mole(s) de 2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4-carboxylate introduit en fonction de l’indice hydroxyle (mg KOH/g) de ce dernier et de la masse molaire de KOH égale à 56,11 g/mol, on peut écrire : The content of T functions in polyurethane (PP2) (denoted t cc (PP2)) (expressed in meq / g of polyurethane (PP2)) is calculated in a manner well known to those skilled in the art from the molar amount of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate introduced. By expressing the number of moles of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate introduced as a function of the hydroxyl index (mg KOH / g) of the latter and of the molar mass of KOH equal to 56.11 g / mol, we can write:
où : or :
IOH (2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4-carboxylate) correspond à l’indice d’hydroxyle du 2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4-carboxylate, IOH (2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate) corresponds to the hydroxyl number of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate,
m3 (2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4-carboxylate) correspond à la masse de 2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4-carboxylate introduit, m3 (2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate) corresponds to the mass of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate introduced,
m (PP2) correspond à la masse de polyuréthane (PP2), soit à la masse totale des ingrédients utilisés pour la synthèse du polyuréthane (PP2) (PPG diol ou triol, diisocyanate, catalyseur de réaction). m (PP2) corresponds to the mass of polyurethane (PP2), ie to the total mass of the ingredients used for the synthesis of polyurethane (PP2) (PPG diol or triol, diisocyanate, reaction catalyst).
B - Préparation des compositions adhésives par mélange des composants (A) et (B) Les compositions adhésives 1’ à 8’ sont préparées par mélangeage des différents ingrédients indiqués dans le tableau 3 suivant, en suivant le mode opératoire décrit ci-après. Les quantités indiquées dans le tableau 3 sont exprimées en grammes. B - Preparation of the adhesive compositions by mixing the components (A) and (B) The adhesive compositions 1 ′ to 8 ’are prepared by mixing the various ingredients indicated in table 3 below, by following the procedure described below. The amounts indicated in table 3 are expressed in grams.
Tableau 3 Table 3
Dans le tableau 3, on utilise : In Table 3, we use:
- la tris(2-aminoéthyl)amine (TAEA) d’alcalinité primaire = 20,52 méq/g de TAEA, - the tris (2-aminoethyl) amine (TAEA) of primary alkalinity = 20.52 meq / g of TAEA,
- l’hexaméthylène diamine (HMDA) d’alcalinité primaire = 17,21 méq/g de HMDA, - hexamethylene diamine (HMDA) of primary alkalinity = 17.21 meq / g of HMDA,
- l’amine grasse dimère commercialisée sous le nom PRIAMINE® 1071 par la société CRODA, d’alcalinité primaire = 3,65 méq/g de Priamine, - the fatty dimer amine sold under the name PRIAMINE® 1071 by the company CRODA, of primary alkalinity = 3.65 meq / g of Priamine,
- le carbonate de calcium de taille de particule maximale = 100 mm. - calcium carbonate with maximum particle size = 100 mm.
Le rapport molaire r3 est calculé de manière bien connue par l’homme du métier à partir des quantités molaires en 2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4-carboxylate et en composé(s) aminé(s) possédant au moins deux groupes amines primaires (-NH2). En exprimant le nombre de mole(s) de 2-hydroxypropyl-2-oxo-1 ,3-dioxolane-4-carboxylate en fonction de la teneur en fonctions T dans le polyuréthane (PP2) précédemment calculée ; et le nombre de mole(s) de composé(s) aminé(s) utilisé(s) en fonction de l’alcalinité primaire (méq/g) de ce dernier, on peut écrire : The molar ratio r3 is calculated in a manner well known to those skilled in the art from the molar quantities of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate and of amino compound (s) having at least two primary amine groups (-NH 2 ). By expressing the number of mole (s) of 2-hydroxypropyl-2-oxo-1, 3-dioxolane-4-carboxylate as a function of the content of T functions in polyurethane (PP2) previously calculated; and the number of mole (s) of amino compound (s) used according to the primary alkalinity (meq / g) of the latter, we can write:
où : or :
tcc est la teneur calculée en fonctions T dans le polyuréthane (PP2) (méq/g) comme définie précédemment, t cc is the content calculated as T functions in the polyurethane (PP2) (meq / g) as defined above,
m (PP2) correspond à la masse de polyuréthane (PP2) comme définie précédemment,m (PP2) corresponds to the mass of polyurethane (PP2) as defined above,
APk est l’alcalinité primaire de chaque composé aminé, APk is the primary alkalinity of each amino compound,
Sk[mk (composé aminé)x APk (composé aminé)] correspond pour k=1 au produit de la masse du composé aminé utilisé par l’alcalinité primaire dudit composé aminé, et pour k>1 à la somme des produits de la masse de chaque composé aminé utilisé par leur alcalinité primaire respective, S k [m k (amino compound) x AP k (amino compound)] corresponds for k = 1 to the product of the mass of the amino compound used by the primary alkalinity of said amino compound, and for k> 1 to the sum of the products the mass of each amino compound used by their respective primary alkalinity,
k est un nombre entier supérieur ou égal à 1 . k is an integer greater than or equal to 1.
Dans un réacteur en polypropylène placé sous atmosphère d’azote, on chauffe le composant (A) entre 65 et 80°C puis on ajoute le composant (B) constitué du (ou des) composé(s) aminé(s) (B1 ) et éventuellement de charge, sous agitation. Le mélange est effectué à chaud à la température T3 comprise entre indiquée et est maintenu sous agitation constante pendant 2 minutes sous vide (pour débullage). In a polypropylene reactor placed under a nitrogen atmosphere, the component (A) is heated to between 65 and 80 ° C. then the component (B) consisting of the amino compound (s) (B1) is added. and optionally charging, with stirring. The mixing is carried out hot at the temperature T3 between indicated and is kept under constant stirring for 2 minutes under vacuum (for boiling).
Puis, on laisse agiter le mélange jusqu’à disparition complète des fonctions T visibles en Infra-Rouge (signal à 1800 cm-1). Then, the mixture is allowed to stir until complete disappearance of the T functions visible in Infra-Red (signal at 1800 cm -1 ).
Mesure des performances mécaniques : résistance et allongement à la rupture des compositions selon l’invention à l’état réticulé Une fois réticulée, on mesure la résistance et de l’allongement à la rupture par essai de traction de la composition adhésive selon le protocole décrit ci-après. Measurement of mechanical performance: resistance and elongation at break of the compositions according to the invention in the crosslinked state Once crosslinked, the resistance and elongation at break are measured by tensile test of the adhesive composition according to the protocol described below.
Le principe de la mesure consiste à étirer dans une machine de traction, dont la mâchoire mobile se déplace à une vitesse constante égale à 100 mm/minute, une éprouvette standard constituée de la composition adhésive réticulée ; et à enregistrer, au moment où se produit la rupture de l’éprouvette, la contrainte de traction appliquée (en MPa) ainsi que l’allongement de l’éprouvette (en %). The principle of the measurement consists in drawing in a tensile machine, the movable jaw of which moves at a constant speed equal to 100 mm / minute, a standard test piece consisting of the crosslinked adhesive composition; and record, at the time of the rupture of the test piece, the applied tensile stress (in MPa) as well as the elongation of the test piece (in%).
L’éprouvette standard est en forme d’haltère, comme illustré dans la norme internationale ISO 37. La partie étroite de l’haltère utilisée a pour longueur 20 mm, pour largeur 4 mm et pour épaisseur 500 mm. The standard test piece is dumbbell-shaped, as illustrated in international standard ISO 37. The narrow part of the dumbbell used is 20 mm long, 4 mm wide and 500 mm thick.
Pour préparer l’haltère, on chauffe à 95°C la composition conditionnée comme décrit précédemment, puis on extrude sur une feuille A4 de papier siliconé la quantité nécessaire pour former sur celle-ci un film ayant une épaisseur de 500 mm qui est laissé durant 7 jours à 23°C et 50% d’humidité relative pour réticulation. L’haltère est alors obtenue par simple découpe dans le film réticulé à l’aide d’un emporte-pièce. To prepare the dumbbell, the conditioned composition is heated to 95 ° C. as described above, then the quantity necessary is extruded onto an A4 sheet of silicone paper to form thereon a film having a thickness of 500 mm which is left for 7 days at 23 ° C and 50% relative humidity for crosslinking. The dumbbell is then obtained by simply cutting out the crosslinked film using a cookie cutter.
Le test de résistance à la traction est répété deux fois et donne les mêmes résultats. La contrainte à la traction appliquée enregistrée est exprimée en Mégapascal (MPa, soit 106 Pa) et l’allongement à la rupture en % par rapport à la longueur initiale de l’éprouvette. Les valeurs sont regroupées dans le tableau 4 ci-dessous. The tensile strength test is repeated twice and gives the same results. The applied applied tensile stress is expressed in Megapascal (MPa, ie 10 6 Pa) and the elongation at break in% relative to the initial length of the test piece. The values are collated in Table 4 below.
Tableau 4 Table 4
Pouvoir adhésif : Mesure de la force de cisaillement sous contrainte (en anglais Lap Shear) Adhesion: Measurement of the shear force under stress (in English Lap Shear)
Les compositions adhésives 1’, 2’, 4’, 5’ et 8’ selon l’invention ont été soumises par ailleurs à des tests de collage de deux lamelles en aluminium poudré (chacune de taille 100 mm x 25 mm) préalablement nettoyée avec un solvant (isopropanol). On applique la composition adhésive sur une des surfaces des lamelles à l’aide d’une spatule, dans un espace délimité par une fenêtre de 12,5 mm x 25 mm en téflon. On appose par-dessus la surface enduite de colle l’autre lamelle, en pressant les deux lamelles l’une contre l’autre. Après réticulation de sept jours à 23°C et 50% d’humidité relative, on mesure la force de cisaillement à la rupture ainsi que le faciès de rupture. Tableau 5 The adhesive compositions 1 ′, 2 ′, 4 ′, 5 ′ and 8 ′ according to the invention were moreover subjected to tests of bonding of two strips of powdered aluminum (each of size 100 mm × 25 mm) previously cleaned with a solvent (isopropanol). The adhesive composition is applied to one of the surfaces of the strips using a spatula, in a space delimited by a window of 12.5 mm × 25 mm in Teflon. The other strip is affixed over the surface coated with glue, pressing the two strips against each other. After crosslinking for seven days at 23 ° C. and 50% relative humidity, the shear force at break and the break face are measured. Table 5
On note « RC » pour rupture cohésive, signifiant que l’on observe qu’une partie du joint adhésif est collé sur les deux faces des lamelles contrecollées. We note "RC" for cohesive rupture, meaning that we observe that part of the adhesive joint is glued on both sides of the laminated lamellae.
Ainsi, les compositions adhésives selon l’invention, peuvent être formulées aisément, à l’aide d’un procédé de préparation peu coûteux en énergie et respectueux de l’homme et de son environnement, ne mettant pas en oeuvre de solvant, ni de plastifiant. Thus, the adhesive compositions according to the invention can be easily formulated, using a preparation process which is inexpensive in energy and respectful of man and his environment, using neither solvent nor plasticizer.
En outre, les compositions adhésives selon l’invention ainsi obtenues conduisent à des adhésifs performants en termes de propriétés mécaniques et/ou de force d’adhésion, adaptés à un large panel d’applications. In addition, the adhesive compositions according to the invention thus obtained lead to performance adhesives in terms of mechanical properties and / or adhesion strength, suitable for a wide range of applications.

Claims

REVENDICATIONS
1. Polyuréthane (PP2) comprenant au moins deux, de préférence deux ou trois, fonctions terminales T de formule (I) suivante : 1. Polyurethane (PP2) comprising at least two, preferably two or three, T terminal functions of formula (I) below:
dans laquelle R1 et R2, identiques ou différents, représentent chacun : in which R 1 and R 2 , identical or different, each represent:
- un atome d’hydrogène, - a hydrogen atom,
- un groupe alkyle linéaire ou ramifié, saturé ou insaturé, ledit groupe alkyle étant de préférence un groupe alkyle en C1-C22, préférentiellement en C1-C12, a linear or branched, saturated or unsaturated alkyl group, said alkyl group preferably being a C1-C22 alkyl group, preferably a C1-C12 alkyl group,
- un groupe (hétéro)aryle en C6-C12, - a C6-C12 (hetero) aryl group,
- un groupe cycloalkyle saturé ou instauré en C3-C8, préférentiellement en C5-C6, ou - a saturated or established cycloalkyl group at C3-C8, preferably at C5-C6, or
un groupe alkylaryle dans lequel le groupe alkyle, linéaire ou ramifié, comprend de 1 à 22 atomes de carbone; an alkylaryl group in which the linear or branched alkyl group comprises from 1 to 22 carbon atoms;
lesdits groupes alkyles ou cycloalkyles comprenant éventuellement un ou plusieurs hétéroatomes, de préférence oxygène ou souffre. said alkyl or cycloalkyl groups optionally comprising one or more heteroatoms, preferably oxygen or sulfur.
2. Polyuréthane selon la revendication 1 , comprenant en outre au l’un des radicaux divalents R3 suivants : 2. Polyurethane according to claim 1, further comprising one of the following divalent radicals R 3 :
a) radical divalent -(CH2)5- dérivé du pentaméthylène diisocyanate (PDI), a) divalent radical - (CH2) 5- derived from pentamethylene diisocyanate (PDI),
b) radical divalent -(CH2)6 -dérivé de l’hexaméthylène diisocyanate (HDI), b) divalent radical - (CH2) 6 - derivative of hexamethylene diisocyanate (HDI),
c) le radical divalent dérivé de l’isophorone (IPDI) : c) the divalent radical derived from isophorone (IPDI):
d) le radical divalent dérivé des 2,4-toluène diisocyanate et 2,2’-toluène diisocyanate d) the divalent radical derived from 2,4-toluene diisocyanate and 2,2'-toluene diisocyanate
(TDI), e) le radical divalent dérivé des 4,4’-méthylène diphényl diisocyanate et 4,4’-méthylène diphényl diisocyanate (MDI), (TDI), e) the divalent radical derived from 4,4'-methylene diphenyl diisocyanate and 4,4'-methylene diphenyl diisocyanate (MDI),
f) le radical divalent dérivé du para-xylylène diisocyanate, méta-xylylène diisocyanate et ortho-xylylène diisocyanate (XDI), f) the divalent radical derived from para-xylylene diisocyanate, meta-xylylene diisocyanate and ortho-xylylene diisocyanate (XDI),
g) le radical divalent dérivé du 1 ,2-bis(isocyanatométhyl)cyclohexane, 1 ,3- bis(isocyanatométhyl)cyclohexane et 1 ,4-bis(isocyanatométhyl)cyclohexane (H6XDI) : g) the divalent radical derived from 1,2-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane (H6XDI):
h) les radicaux divalents dérivés des 2,4’- méthylène dicyclohexyl diisocyanate et 4,4'- méthylène dicyclohexyl diisocyanate (H12MDI) : h) divalent radicals derived from 2,4'-methylene dicyclohexyl diisocyanate and 4,4'-methylene dicyclohexyl diisocyanate (H12MDI):
ou i) le radical divalent de formule (II) suivante : or i) the divalent radical of formula (II) below:
dans laquelle : in which :
- p est un nombre entier allant de 1 à 2 ; - p is an integer ranging from 1 to 2;
- q est un nombre entier allant de 0 à 9 ; - q is an integer ranging from 0 to 9;
- r est un nombre entier valant 5 ou 6 ; - r is an integer equal to 5 or 6;
- R représente une chaîne hydrocarbonée, saturée ou insaturée, cyclique ou acyclique, linéaire ou ramifiée, comprenant de 1 à 20 atomes de carbone ; et - R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms; and
- R’ représente un groupe divalent hydrocarboné, linéaire ou ramifié, saturé, ayant de 2 à 4 atomes de carbone. - R ’represents a divalent hydrocarbon group, linear or branched, saturated, having 2 to 4 carbon atoms.
3. Polyuréthane selon l’une quelconque des revendications 1 ou 2, ayant la formule (III) suivante 3. Polyurethane according to any one of claims 1 or 2, having the following formula (III)
dans laquelle : in which :
- R1 et R2 sont tels que définis dans la revendication 1 , R1 étant de préférence un atome d’hydrogène et R2 étant de préférence un atome d’hydrogène, un méthyle ou un éthyle ;- R 1 and R 2 are as defined in claim 1, R 1 preferably being a hydrogen atom and R 2 preferably being a hydrogen atom, methyl or ethyl;
- P représente l’une des deux formules ci-dessous : - P represents one of the two formulas below:
dans lesquelles D et T représentent, indépendamment l’un de l’autre, un radical hydrocarboné comprenant de 2 à 66 atomes de carbone, linéaire ou ramifié, cyclique, alicyclique ou aromatique, saturé ou insaturé, comprenant éventuellement un ou plusieurs hétéroatomes ; in which D and T represent, independently of one another, a hydrocarbon radical comprising from 2 to 66 carbon atoms, linear or branched, cyclic, alicyclic or aromatic, saturated or unsaturated, optionally comprising one or more heteroatoms;
- P’ et P” étant, indépendamment l’un de l’autre, un radical divalent issu d’un polyol de préférence choisi parmi les polyéther polyols, les polydiène polyols, les polyester polyols, les polycarbonate polyols ; - P ’and P” being, independently of one another, a divalent radical derived from a polyol preferably chosen from polyether polyols, polydiene polyols, polyester polyols, polycarbonate polyols;
- R3 étant tel que défini dans la revendication 2; - R 3 being as defined in claim 2;
- m et f sont des nombres entiers tel que la masse moléculaire moyenne du polyuréthane va de 600 à 100 000 g/mol ; - m and f are whole numbers such that the average molecular weight of the polyurethane ranges from 600 to 100,000 g / mol;
- f est égal à 2 ou 3. - f is equal to 2 or 3.
4. Polyuréthane selon l’une quelconque des revendications 1 à 3, caractérisé en ce qu’il est obtenu par réaction d’un composé comprenant au moins deux groupes NCO (PP1 ) et d’au moins un composé de formule (IV) suivante : 4. Polyurethane according to any one of claims 1 to 3, characterized in that it is obtained by reaction of a compound comprising at least two NCO groups (PP1) and at least one compound of formula (IV) below :
dans laquelle R1 et R2, identiques ou différents, représentent chacun : in which R 1 and R 2 , identical or different, each represent:
- un atome d’hydrogène, - a hydrogen atom,
- un groupe alkyle linéaire ou ramifié, saturé ou insaturé, ledit groupe alkyle étant de préférence un groupe alkyle en C1 -C22, préférentiellement en C1 -C12, a linear or branched, saturated or unsaturated alkyl group, said alkyl group preferably being a C1-C22, preferably C1-C12 alkyl group,
- un groupe (hétéro)aryle en C6-C12, - a C6-C12 (hetero) aryl group,
- un groupe cycloalkyle saturé ou instauré en C3-C8, préférentiellement en C5-C6, ou - a saturated or established cycloalkyl group at C3-C8, preferably at C5-C6, or
- un groupe alkylaryle dans lequel le groupe alkyle, linéaire ou ramifié, comprend de 1 à 22 atomes de carbone; an alkylaryl group in which the linear or branched alkyl group comprises from 1 to 22 carbon atoms;
lesdits groupes alkyles ou cycloalkyles comprenant éventuellement un ou plusieurs hétéroatomes, de préférence oxygène ou souffre. said alkyl or cycloalkyl groups optionally comprising one or more heteroatoms, preferably oxygen or sulfur.
5. Procédé de préparation d’un polyuréthane (PP2) tel que défini selon l’une quelconque des revendications 1 à 4, comprenant la réaction d’au moins un composé comprenant au moins deux groupes NCO (PP1 ) et d’au moins un composé de formule (IV) telle que définie dans la revendication 4, ledit composé (PP1 ) étant choisi : 5. Process for the preparation of a polyurethane (PP2) as defined in any one of claims 1 to 4, comprising the reaction of at least one compound comprising at least two NCO groups (PP1) and at least one compound of formula (IV) as defined in claim 4, said compound (PP1) being chosen:
- parmi les dérivés d’allophanate d’hexaméthylène diisocyanate (HDI) de formule (MA) suivante : - from the derivatives of hexamethylene diisocyanate (HDI) allophanate of formula (MA) below:
dans laquelle : in which :
- p est un nombre entier allant de 1 à 2 ; - p is an integer ranging from 1 to 2;
- q est un nombre entier allant de 0 à 9 ; - q is an integer ranging from 0 to 9;
- r est un nombre entier égal à 5 ou 6 ; - R représente une chaîne hydrocarbonée, saturée ou insaturée, cyclique ou acyclique, linéaire ou ramifiée, comprenant de 1 à 20 atomes de carbone ; - r is an integer equal to 5 or 6; - R represents a hydrocarbon chain, saturated or unsaturated, cyclic or acyclic, linear or branched, comprising from 1 to 20 carbon atoms;
- R représente un groupe divalent hydrocarboné, linéaire ou ramifié, saturé, ayant de 2 à 4 atomes de carbone ; - R represents a divalent hydrocarbon group, linear or branched, saturated, having from 2 to 4 carbon atoms;
ou or
- parmi les polyuréthanes à terminaisons NCO obtenus par une réaction de polyaddition (notée E1 ) : - among the polyurethanes with NCO endings obtained by a polyaddition reaction (denoted E1):
(i) d’au moins un polyisocyanate choisi de préférence parmi les diisocyanates, et en particulier parmi les diisocyanates suivants: (i) at least one polyisocyanate preferably chosen from diisocyanates, and in particular from the following diisocyanates:
a1 ) le pentaméthylène diisocyanate (PDI), a1) pentamethylene diisocyanate (PDI),
a2) l’hexaméthylène diisocyanate (HDI), a2) hexamethylene diisocyanate (HDI),
a3) l’isophorone diisocyanate (IPDI), a3) isophorone diisocyanate (IPDI),
a4) le 2,4-toluène diisocyanate (2,4-TDI), a4) 2,4-toluene diisocyanate (2,4-TDI),
a5) le 2,4’-diisocyanate de diphénylméthane (2,4’-MDI), a5) diphenylmethane 2,4’-diisocyanate (2,4’-MDI),
a6) le méta-xylylène diisocyanate (m-XDI), a6) meta-xylylene diisocyanate (m-XDI),
a7) le 1 ,3-Bis(isocyanatomethyl)cyclohexane (m-H6XDI), a7) 1, 3-Bis (isocyanatomethyl) cyclohexane (m-H6XDI),
a8) le 2,4’- méthylène dicyclohexyl diisocyanate et/ou le 4,4'-méthylene dicyclohexyl diisocyanate (H12MDI) : a8) 2,4'-methylene dicyclohexyl diisocyanate and / or 4,4'-methylene dicyclohexyl diisocyanate (H12MDI):
a9) les dérivés d’allophanate d’hexaméthylène diisocyanate (HDI) de formule (MA); a10) et leurs mélanges ; a9) derivatives of hexamethylene diisocyanate (HDI) allophanate of formula (MA); a10) and their mixtures;
(ii) avec au moins un polyol de préférence choisi parmi les polyéther polyols, les polyester polyols, les polydiène polyols, les polycarbonate polyols, et leurs mélanges, dans des quantités de polyisocyanate(s) et de polyol(s) conduisant à un rapport molaire NCO/OH, noté r1, strictement supérieur à 1 , de préférence allant de 1 ,6 à 1 ,9, préférentiellement allant de 1 ,65 à 1 ,85. (ii) with at least one polyol preferably chosen from polyether polyols, polyester polyols, polydiene polyols, polycarbonate polyols, and their mixtures, in amounts of polyisocyanate (s) and polyol (s) leading to a ratio NCO / OH molar, noted r 1 , strictly greater than 1, preferably ranging from 1.6 to 1.9, preferably ranging from 1.65 to 1.85.
6. Procédé de préparation selon la revendication 5, caractérisé en ce que le composé (PP1 ) est choisi parmi : 6. Preparation process according to claim 5, characterized in that the compound (PP1) is chosen from:
- les dérivés d’allophanate d’hexaméthylène diisocyanate (HDI) de formule (I IA) susmentionnée ; ou - derivatives of hexamethylene diisocyanate allophanate (HDI) of formula (I IA) above; or
- les polyuréthanes à terminaisons NCO obtenus par une réaction de polyaddition (notée E1 ) d’au moins le 2,4-toluène diisocyanate (2,4-TDI) avec au moins un polyol. - NCO-terminated polyurethanes obtained by a polyaddition reaction (denoted E1) of at least 2,4-toluene diisocyanate (2,4-TDI) with at least one polyol.
7. Procédé de préparation selon l’une quelconque des revendications 5 ou 6, caractérisé en ce qu’il ne comprend pas d’étape consistant à ajouter un ou plusieurs solvant(s) et/ou plastifiant(s). 7. Preparation process according to any one of claims 5 or 6, characterized in that it does not comprise a step consisting in adding one or more solvent (s) and / or plasticizer (s).
8. Procédé de préparation selon l’une quelconque des revendications 5 à 7, caractérisé en ce que le polyol est choisi parmi : 8. Preparation process according to any one of claims 5 to 7, characterized in that the polyol is chosen from:
- les polyéther polyols choisis parmi les polyoxyalkylène polyols, dont la partie alkylène, linéaire ou ramifiée, comprend de 1 à 4 atomes de carbone, the polyether polyols chosen from polyoxyalkylene polyols, the alkylene part of which, linear or branched, comprises from 1 to 4 carbon atoms,
- les polybutadiènes comportant des groupes hydroxyles terminaux éventuellement hydrogénés ou époxydés, et polybutadienes containing terminal hydroxyl groups which may be hydrogenated or epoxidized, and
- leurs mélanges. - their mixtures.
9. Procédé de préparation selon l’une quelconque des revendications 5 à 8, caractérisé en ce que le(s) polyol(s) est(sont) choisi(s) parmi ceux ayant une masse moléculaire moyenne en nombre allant de 200 à 20 000 g/mol. 9. Preparation process according to any one of claims 5 to 8, characterized in that the polyol (s) is (are) chosen (s) from those having a number average molecular weight ranging from 200 to 20 000 g / mol.
10. Système multicomposant comprenant : 10. Multicomponent system comprising:
- comme premier composant (composant A), une composition comprenant au moins un polyuréthane (PP2) tel que défini selon l’une quelconque des revendications 1 à 4, et - As the first component (component A), a composition comprising at least one polyurethane (PP2) as defined according to any one of claims 1 to 4, and
- comme deuxième composant (composant B), une composition comprenant au moins un composé aminé (B1 ) comprenant au moins deux groupes amine choisis parmi les groupes amine primaire, les groupes amine secondaire et leurs mélanges, de préférence comprenant au moins deux groupes amine primaire. - As second component (component B), a composition comprising at least one amino compound (B1) comprising at least two amine groups chosen from primary amine groups, secondary amine groups and their mixtures, preferably comprising at least two primary amine groups .
1 1 . Système multicomposant selon la revendication 10, caractérisé en ce que le(s)dit(s) composé(s) aminé(s) (B1 ) possède(nt) une alcalinité primaire allant de 0,4 à 34 méq/g de composé aminé. 1 1. Multicomponent system according to claim 10, characterized in that the said amino compound (s) (B1) has (s) a primary alkalinity ranging from 0.4 to 34 meq / g of amino compound .
12. Système multicomposant selon l’une quelconque des revendications 10 ou 1 1 , caractérisé en ce que le(s) composé(s) aminé(s) (B1 ) comprennent au moins deux groupes méthylène amine (-CH2-NH2). 12. Multicomponent system according to any one of claims 10 or 1 1, characterized in that the compound (s) amino (s) (B1) comprise at least two methylene amine groups (-CH2-NH 2 ).
13. Système multicomposant selon l’une quelconque des revendications 10 à 12, caractérisé en ce que les quantités de polyuréthane(s) (PP2) et de composé(s) aminé(s) (B1 ) présents dans le système multicomposant conduisent à un rapport molaire du nombre de fonctions T de formule (I) sur le nombre de groupes amine primaire et/ou secondaire noté allant de 0,5 à 1 . 13. Multicomponent system according to any one of claims 10 to 12, characterized in that the amounts of polyurethane (s) (PP2) and of amino compound (s) (B1) present in the multicomponent system lead to a molar ratio of the number of T functions of formula (I) to the number of primary and / or secondary amine groups noted ranging from 0.5 to 1.
14. Système multicomposant selon l’une quelconque des revendications 10 à 13, caractérisé en ce qu’il comprend au moins une charge minérale. 14. Multicomponent system according to any one of claims 10 to 13, characterized in that it comprises at least one mineral filler.
15. Procédé d’assemblage de matériaux mettant en oeuvre le polyuréthane (PP2) tel que défini à l’une quelconque des revendications 1 à 4, comprenant les étapes suivantes : 15. Method of assembling materials using polyurethane (PP2) as defined in any one of claims 1 to 4, comprising the following steps:
- le mélange d’au moins un e polyuréthane (PP2) tel que défini à l’une quelconque des revendications 1 à 4, et d’au moins un composé aminé (B1 ) comprenant au moins deux groupes amine choisis parmi les groupes amine primaire, les groupes amine secondaire et leurs mélanges, de préférence comprenant au moins deux groupes amine primaire ; - the mixture of at least one polyurethane (PP2) as defined in any one of claims 1 to 4, and of at least one amino compound (B1) comprising at least two amine groups chosen from primary amine groups , secondary amine groups and mixtures thereof, preferably comprising at least two primary amine groups;
- l’enduction dudit mélange sur la surface d’un premier matériau, puis - coating said mixture on the surface of a first material, then
- le contrecollage de la surface d’un second matériau sur ladite surface enduite, puis - laminating the surface of a second material on said coated surface, then
- la réticulation dudit mélange. - crosslinking of said mixture.
16. Utilisation d’un polyuréthane comprenant au moins deux fonctions terminales T de formule (I) (PP2) tel que défini selon l’une quelconque des revendications 1 à 4, pour la fabrication d’une composition adhésive. 16. Use of a polyurethane comprising at least two terminal T functions of formula (I) (PP2) as defined according to any one of claims 1 to 4, for the manufacture of an adhesive composition.
EP19842382.4A 2018-12-05 2019-12-04 Polyurethane with (2-oxo-1,3-dioxolane-4-carboxylate) end groups Pending EP3891202A1 (en)

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FR1872340A FR3089514B1 (en) 2018-12-05 2018-12-05 Terminated polyurethane (2-oxo-1,3-dioxolane-4-carboxylate)
PCT/FR2019/052912 WO2020115430A1 (en) 2018-12-05 2019-12-04 Polyurethane with (2-oxo-1,3-dioxolane-4-carboxylate) end groups

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US9556304B2 (en) * 2012-08-28 2017-01-31 Covestro Deutschland Ag Binder with cyclic carbonate structures
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FR3018815B1 (en) * 2014-03-19 2016-03-04 Bostik Sa POLYURETHANE PREPOLYMER WITH LOW VISCOSITY CYCLOCARBONATE TERMINATIONS AND USE THEREOF IN THE MANUFACTURE OF A MULTICOMPONENT ADHESIVE COMPOSITION
FR3018816B1 (en) 2014-03-19 2017-07-28 Bostik Sa POLYURETHANE PREPOLYMER WITH LOW VISCOSITY CYCLOCARBONATE TERMINATIONS AND USE THEREOF IN THE MANUFACTURE OF A MULTICOMPONENT ADHESIVE COMPOSITION
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