Classifications

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  • 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
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
  • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
  • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
  • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
• • 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
  • C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
• • 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
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/10—Definition of the polymer structure
  • C08G2261/12—Copolymers
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/10—Definition of the polymer structure
  • C08G2261/13—Morphological aspects
  • C08G2261/135—Cross-linked structures
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/10—Definition of the polymer structure
  • C08G2261/16—End groups
  • C08G2261/164—End groups comprising organic end groups
  • C08G2261/1644—End groups comprising organic end groups comprising other functional groups, e.g. OH groups, NH groups, COOH groups or boronic acid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
  • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
  • C08G2261/3323—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other monocyclic systems
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
  • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
  • C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/40—Polymerisation processes
  • C08G2261/41—Organometallic coupling reactions
  • C08G2261/418—Ring opening metathesis polymerisation [ROMP]
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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/70—Post-treatment
  • C08G2261/74—Further polymerisation of the obtained polymers, e.g. living polymerisation to obtain block-copolymers
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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/70—Post-treatment
  • C08G2261/76—Post-treatment crosslinking
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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/70—Post-treatment
  • C08G2261/80—Functional group cleavage, e.g. removal of side-chains or protective groups

Definitions

• the present invention relates to hydrocarbon polymers comprising two alkoxysilane end groups, their preparation and their use.
• Silane-modified polymers (MS Polymers or MS Polymers for "Modified Silane Polymers”) are known in the field of adhesives. They are used for bonding a wide variety of objects (or substrates).
• the compositions based on polymers MS are applied, in combination with a catalyst, in the form of an adhesive layer on at least one of two surfaces belonging to two substrates to be assembled and intended to be brought into contact with one another. with each other in order to assemble them.
• the polymer MS reacts by crosslinking with the water of the ambient medium and / or the water provided by the substrates, which leads to the formation of a cohesive adhesive seal ensuring the strength of the assembly of these two substrates.
• This adhesive seal consists mainly of MS polymer crosslinked in a three-dimensional network formed by the polymer chains interconnected by siloxane type bonds.
• the crosslinking may take place before or after contacting the two substrates and the application, if any, of a pressure at their tangency surface.
• the MS polymers must most often be used in the form of adhesive compositions comprising other constituents, for example tackifying resins, one or more additives with a reinforcing effect, for example at least one mineral filler, or else one or more additives to improve setting time (i.e. the time after which crosslinking can be considered complete) or other characteristics such as rheology or mechanical performance (elongation, modulus). .).
• other constituents for example tackifying resins, one or more additives with a reinforcing effect, for example at least one mineral filler, or else one or more additives to improve setting time (i.e. the time after which crosslinking can be considered complete) or other characteristics such as rheology or mechanical performance (elongation, modulus). .).
• CA 2242060 discloses the possibility of employing a polymer-based adhesive seal composition containing at least a cycloolefin, a catalyst for chain-opening metathesis polymerization, a feedstock and a compound which comprises only a single silane function.
• patent application EP 2468783 describes the preparation of a polyurethane-polyether and polyurethane-polyester block polyurethane with at least two polyurethane-polyester terminal blocks connected to an alkoxysilane terminal group, as well as an adhesive composition comprising this polyurethane and a crosslinking catalyst.
• the silane terminal group is derived from an isocyanatosilane which comprises only one silane functional group.
• telechelic polymers comprising a repeating unit derived from cyclic monomer such as, for example, norbornene.
• patent application WO 01/047173 describes the catalytic ring-opening copolymerization by metathesis of branched cycloolefins comprising the same cycloolefin.
• Said cycloolefin is preferably norbornene.
• patent application WO 201 1/038057 describes the ring-opening polymerization by metathesis of dicarboxylic anhydrides of norbornene and optionally of 7-oxanorbornene dicarboxylic anhydrides.
• patent application GB 2238791 describes a method for the polymerization of 7-oxanorbornene by ring opening polymerization by metathesis.
• the object of the present invention is to propose novel polymers with two alkoxysilane end groups. These polymers can lead, after crosslinking, to the formation of an adhesive seal having improved mechanical properties, and in particular a higher cohesion compared with those of the state of the art.
• the present invention relates to a hydrocarbon polymer comprising two alkoxysilane end groups, said hydrocarbon polymer being of formula (1) below:
• F 1 is (R'O) 3 -ZRzSi- (CH 2 ) p 1 and F 2 is - (CH 2 ) qi-SiR z (OR ') 3 . z ; or F 1 is (R'0) 3-zRzSi-R "-OOC- (CH 2) p2 and F 2 is - (CH 2) q 2 -COO-R" Rz -Si (OR ') 3 -z ; where z is an integer equal to 0, 1, 2 or 3; p1 and q1 are independently an integer of 1, 2 or 3; p2 and q2 are independently an integer of 0, 1, 2 or 3; the groups R and R 'are independently an alkyl group, preferably linear, comprising from 1 to 4, preferably from 1 to 2, carbon atoms; the group R "is an alkylene group, preferably linear, comprising from 1 to 4 carbon atoms, and in which:
• each carbon-carbon bond of the noted chain is a double bond or a single bond, in accordance with the valence rules of organic chemistry
• the groups R1, R2, R3, R4, R5, R6, R7 and R8 are independently hydrogen, halogen, alkyl, heteroalkyl, alkenyl, alkoxycarbonyl or heteroalkoxycarbonyl; at least one of the groups R1 to R8 being part of the same ring or saturated or unsaturated heterocycle with at least one other of the groups R1 to R8, according to the valence rules of the organic chemistry and at least one of the pairs
• X and y are integers independently within a range of 0 to 5, preferably 0 to 2, more preferably more preferably x is 1 and y is 1, the sum x + y being preferably in a range of 0 to 4 and even more preferably 0 to 2;
• the groups R14, R15, R16 and R17 are independently hydrogen, halogen, alkyl, heteroalkyl, alkenyl, alkoxycarbonyl or heteroalkoxycarbonyl, wherein forming part of the same ring or saturated or unsaturated heterocycle with at least one other of the groups R14 to R17, according to the valence rules of organic chemistry;
• N is an integer greater than or equal to 2 and m is an integer strictly greater than 0, the molar ratio m: n being between 0 and 0.5, preferably between 0.25 and 0.5; n and m being further such that the number average molar mass Mn of the hydrocarbon polymer of formula (1) is in the range of 400 to 50,000 g / mol, preferably 600 to 20,000 g / mol, and the The polydispersity (PDI) of the hydrocarbon polymer of formula (1) is in a range from 1.0 to 3.0, preferably from 1.0 to 2.0, more preferably from 1.45 to 1.85. .
• the main chain of the polymer of formula (1) therefore comprises two types of repeating units, a first type of repeated repetition unit n times and a second type of repetition units repeated m times.
• m: n between 0 and 0.5 we therefore mean that m: n is in a range of 0 to 0.5, excluded limits.
• terminal groups F1 and F2 are generally substantially symmetrical with respect to the main chain, that is, they correspond substantially, with the exception of the indices p1 and p2, and q1 and q2.
• alkyl group is meant a saturated monovalent hydrocarbon compound linear or branched, cyclic, acyclic, heterocyclic or polycyclic, and comprising unless generally indicated generally from 1 to 22 carbon atoms. Such an alkyl group most often comprises from 1 to 14, preferably from 1 to 8, carbon atoms.
• heteroalkyl group is meant according to the invention an alkyl group in which at least one of the carbon atoms is substituted with a heteroatom chosen from the group formed by O and S.
• alkylene group is meant a divalent saturated hydrocarbon compound linear or branched, cyclic, acyclic, heterocyclic or polycyclic, and comprising unless otherwise indicated generally from 1 to 22 carbon atoms. Such an alkylene group most often comprises from 1 to 14, preferably from 1 to 8, carbon atoms.
• alkenyl group is meant an unsaturated hydrocarbon compound (that is to say comprising at least one double bond) linear or branched, cyclic, acyclic, heterocyclic or polycyclic, and generally comprising from 1 to 22 carbon atoms. Such an alkenyl group most often comprises from 1 to 14, preferably from 1 to 8, carbon atoms.
• alkoxycarbonyl group is meant a linear or branched, saturated or partially unsaturated (monovalent) alkyl group comprising from 1 to 22, preferably from 1 to 14, carbon atoms, as well as a divalent group -COO- .
• heteroalkoxycarbonyl group is meant according to the invention an alkoxycarbonyl group in which at least one of the carbon atoms is substituted by a heteroatom selected from the group formed by O and S.
• halogen atom is meant an iodine, chlorine, bromine or fluorine atom, preferably chlorine.
• heterocycle is meant a hydrocarbon ring which may comprise another atom than carbon in the ring chain, such as, for example, oxygen, sulfur or nitrogen.
• alkoxysilane group is meant a group comprising a linear or branched, saturated or partially unsaturated alkyl group comprising from one to four, preferably from one to two, carbon atoms and, in addition, a divalent group -Si O-.
• At least one of the groups R1 to R8 which may form part of the same ring or saturated or unsaturated heterocycle with at least one other of the groups R1 to R8, according to the valence rules of organic chemistry means according to the invention that these two groups, whether or not they are borne by the same carbon, are linked together by a hydrocarbon-based chain optionally comprising at least one heteroatom such as S or O.
• a cycle consists of R 1 -0 -R8. This is also applicable to groups R14 to R17.
• the pair (R1, R2) is such that where C is the carbon that supports the two groups forming the pair (R1, R2). This is also applicable to pairs (R3, R4), (R5, R6) and (R7, R8).
• terminal group is meant a group located at the end of the chain (or end) of the polymer.
• the polymer according to the invention comprises a main chain, i.e. a longer chain, both ends of which are the terminal groups of the polymer according to the invention.
• PDI polymolecularity (or D M dispersity) is defined as the ratio Mw / Mn, that is to say the ratio of the weight average molar mass to the number average molar mass of the polymer.
• the two average molar masses Mn and Mw are measured according to the invention by Size Exclusion Chromatography (SEC), usually with PEG (PolyEthyleneGlycol) or PS (Polystyrene) calibration, preferably PS.
• SEC Size Exclusion Chromatography
• the groups R5 to R8 are each hydrogen.
• R17 and R20 have the meanings given above and the --NjN ° bond is a geometrically oriented bond on one side or the other with respect to the double bond (cis or trans).
• all the bonds " -" of the formula (1) are carbon-carbon single bonds, and the formula (1) then becomes the formula (1 H) which is described below. after.
• Each of the double bonds of the polymer of formula (1 ') is oriented geometrically cis or trans, preferably is of cis orientation.
• the geometric isomers of the polymer of formula (1 ') are generally present in variable proportions, with most often a majority of cis (Z) - cis (Z) - cis (Z) - cis (Z). It is preferred according to the invention to have mixtures whose double bonds are predominantly oriented cis (Z), and preferably all oriented cis (Z). It is also possible according to the invention to obtain only one of the geometric isomers, according to the reaction conditions and in particular according to the nature of the catalyst used.
• the invention also relates to a polymer of formula (1 H) below:
• the formula (1 H) illustrates the case where the main chain of the polymer of formula (1) is saturated, that is to say contains only saturated bonds.
• the polymer of formula (1 H) may for example be derived from the hydrogenation of the unsaturated polymer of formula (1 ').
• F1 is (R'0) 3 - z R z Si- (CH 2 ) P -
• F1 is (R'0) 3 -zRzSi-R "-OOC- (CH 2 ) p2 - and F 2 is
• R' is a methyl
• the polymers of formulas (1), (1 ') and (1H) according to the invention are particularly homogeneous and temperature-stable. They are preferably packaged and stored away from moisture.
• the polymers of formulas (1), (1 ') and (1H) according to the invention can form, after crosslinking with the water of the ambient medium and / or the water provided by at least one substrate, generally at room temperature.
• atmospheric humidity for example for a relative humidity of the air (also called degree of hygrometry) usually included in a range of 25 to 65%, and in the presence of a suitable crosslinking catalyst, an adhesive joint which has values high cohesion, in particular greater than 3 MPa.
• Such values of cohesion allow use as an adhesive, for example as a seal on a usual support (concrete, glass, marble), in the field of building, or for gluing glazing in the automotive and naval industry. .
• the non-crosslinked polymers of the invention are solid or liquid polymers at room temperature (i.e., about 20 ° C).
• they are liquid polymers having a viscosity at 23 ° C. ranging from 1 to 500,000 mPa.s, preferably from 1 to 150,000 mPa.s and even more preferably from 1 to 50,000 mPa.s.
• the molar ratio m: n is between 0.25 and 0.5 and / or at least one of the groups R 1 to R 8 and / or R 14 to R 17 comprises an alkyl group
• the non-crosslinked polymers according to the invention are preferably liquid polymers having a viscosity at 23 ° C ranging from 1 to 500,000 mPa.s.
• the uncrosslinked polymer according to the invention When solid at ambient temperature, it is generally thermoplastic (in anhydrous medium), that is to say deformable and heat fusible (i.e. at a temperature above ambient temperature). It can therefore be used as a hot-melt adhesive and hot-applied on the interface of substrates to be assembled at their tangency surface. By solidification at room temperature, an adhesive seal solidarisant the substrates is thus immediately created, giving the adhesive advantageous properties of reduced setting time.
• the adhesive composition which comprises may comprise at least one additional component such as a tackifying resin or a filler.
• the invention also relates to a method for preparing at least one hydrocarbon polymer comprising two alkoxysilane end groups according to the invention, said process comprising at least one metathesis ring opening polymerization step (or "Ring Opening Metathesis”). ), in the presence of:
• At least one metathesis catalyst preferably a catalyst comprising ruthenium, more preferably a Grubbs catalyst,
• At least one alkoxysilane chain transfer agent for the following formula (C): wherein the -RJ bond is a geometrically oriented bond on one side or the other with respect to the double bond (cis or trans); F is (RO) 3 -zRzSi- (CH 2 ) p 1 and F 2 is - (CH 2 ) qi-SiRz (OR ') 3 -z, or F 1 is (R'O) 3-zRzSi-R "-OOC- (CH 2 ) p 2 - and F 2 is - (CH 2 ) q 2 -COO-R" -SiR z (OR ') 3 -z; where z is an integer equal to 0, 1, 2 or 3; p1 and q1 are independently an integer of 1, 2 or 3; p2 and q2 are independently an integer of 0, 1, 2 or 3; the groups R and R 'are independently an alkyl group, preferably linear, comprising from 1 to 4, preferably
• the groups R1, R2, R3, R4, R5, R6, R7 and R8 are independently hydrogen, halogen, alkyl, heteroalkyl, alkenyl, alkoxycarbonyl or heteroalkoxycarbonyl; at least one of the groups R1 to R8 being part of the same ring or saturated or unsaturated heterocycle with at least one other of the groups R1 to R8, according to the valence rules of the organic chemistry and at least one of the pairs (R1, R2 ), (R3, R4), (R5, R6) and (R7, R8) being an oxo group;
• X and y are integers independently within a range of 0 to 5, preferably 0 to 2, even more preferably x is 1 and y is 1, the sum x + y being preferably in a range of 0 to 4 and even more preferably 0 to 2;
• the groups R14, R15, R16 and R17 are independently hydrogen, halogen, alkyl, heteroalkyl, alkenyl, alkoxycarbonyl or heteroalkoxycarbonyl, wherein forming part of the same ring or saturated or unsaturated heterocycle with at least one other of the groups R14 to R17, according to the valence rules of organic chemistry; and
• the duration and temperature for a given reaction generally depend on the reaction conditions and in particular the catalytic loading rate. The skilled person is able to adapt them depending on the circumstances.
• (A) and (B) is in the range of 0.01 to 0.10, preferably 0.05 to 0.10.
• the compounds of formula (A) generally comprise from 6 to 30, preferably from 6 to 22, carbon atoms.
• the compounds of formula (B) generally comprise from 6 to 30, preferably from 6 to 22, carbon atoms.
• the ring opening polymerization by metathesis is a reaction well known to those skilled in the art, which is implemented here in the presence of a particular CTA compound of formula (C) comprising two silane functions.
• the cyclic compounds of formula (A) are preferably according to the invention chosen from the group formed by cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, 1,5-cyclooctadiene, cyclononadiene, 1,5,9-cyclodecatriene.
• R is an alkyl group comprising from 1 to 22, preferably 1 to 14, carbon atoms
• cyclooctene being very particularly preferred.
• R is n-hexyl.
• cyclic compounds of formula (B) are preferably according to the invention chosen from the group formed by norbornene, norbornadiene, dicyclopentadiene, 7-oxanorbornene and 7-oxanorbornadiene which are respectively of the following formulas:
• Norbornene and 7-oxanorbornene are particularly preferred.
• the cyclic compounds of formula (B) may also be chosen from the group formed by the compounds of formulas:
• R is an alkyl group comprising from 1 to 22, preferably 1 to 14, carbon atoms.
• R is n-hexyl.
• the cyclic compounds of formula (B) may also be chosen from the group formed by the addition products (or adducts in English) resulting from the Diels-Alder reaction using cyclopentadiene or furan as starting material, as well as the compounds derived from norbornene such as branched norbornenes as described in WO 2001/04173 (such as: isobornyl norbornene carboxylate, phenyl norbornene carboxylate, ethylhexyl norbornene carboxylate, phenoxyethyl norbornene carboxylate and alkyl dicarboxymide norbornene, the alkyl comprising most often from 3 to 8 carbon atoms) and branched norbornenes as described in WO 201 1/038057 (norbornene dicarboxylic anhydrides and optionally 7-oxanorbornene dicarboxylic anhydrides).
• the CTA has the following formula (C1):
• the CTA has the following formula (C2):
• R ' is methyl
• q 2 0.
• the CTA may be chosen from the group formed by the compounds of formulas (C1) and the compounds of formula (C2).
• the CTA is selected from the group consisting of bis (propyltrimethoxysilyl) fumarate and transi, 4-bis (trimethoxysilyl) but-2-ene.
• the step of polymerization by ring opening by metathesis is carried out most often in the presence of at least one solvent, generally chosen from the group formed by aqueous solvents. or organic compounds typically used in polymerization reactions and which are inert in polymerization conditions, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water or mixtures thereof.
• a preferred solvent is selected from the group consisting of benzene, toluene, para-xylene, methylene chloride, dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, hexane heptane, methanol, ethanol, water or mixtures thereof.
• the solvent is selected from the group consisting of benzene, toluene, para-xylene, methylene chloride, dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, hexane, heptane, methanol, ethanol or their mixtures. Even more preferably, the solvent is toluene, heptane, or a mixture of toluene and methylene chloride.
• the solubility of the polymer formed during the polymerization reaction depends generally and mainly on the choice of solvent and the molar weight of the polymer obtained. It is also possible that the reaction is carried out without solvent.
• the metathesis catalyst such as for example a Grubbs catalyst, is generally a commercial product.
• the metathesis catalyst is most often a transition metal catalyst including a catalyst comprising ruthenium most often in the form of complex (s) of ruthenium such as a ruthenium-carbene complex.
• the Grubbs catalysts can thus be used in a particularly preferred manner.
• the term "Grubbs catalyst” generally means, according to the invention, a Grubbs 1 st or 2 nd generation catalyst, but also any other Grubbs type catalyst (ruthenium-carbene type) accessible to a person skilled in the art, such as for example the substituted Grubbs catalysts described in US Pat. No. 5,849,851.
• a Grubbs catalyst 1 st generation is generally of the formula (8): (8), wherein Ph is phenyl and Cy is cyclohexyl.
• the I UPAC name for this compound is: benzylidenebis (tricyclohexylphosphine) dichlororuthenium (CAS number 172222-30-9).
• a Grubbs 2 nd generation catalyst (or G2) is generally of the formula (9):
• the IUPAC name of the second generation of this catalyst is benzylidene [1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (tricyclohexylphosphine) ruthenium (CAS number 246047-72-3).
• the method for preparing a hydrocarbon polymer according to the invention may further comprise at least one additional step of hydrogenation of double bonds.
• This step is generally carried out by catalytic hydrogenation, most often under hydrogen pressure and in the presence of a hydrogenation catalyst such as a palladium catalyst supported by carbon (Pd / C). It more particularly makes it possible to form a compound of formula (1H) from an unsaturated compound of formula (1 ').
• a hydrogenation catalyst such as a palladium catalyst supported by carbon (Pd / C). It more particularly makes it possible to form a compound of formula (1H) from an unsaturated compound of formula (1 ').
• the invention also relates to an adhesive composition comprising a polymer according to the invention and from 0.01 to 3% by weight, preferably from 0.1 to 1% by weight, of a crosslinking catalyst, relative to the weight of the adhesive composition.
• the polymer according to the invention is a polymer of formula (1), (1 ') or (1 H).
• the crosslinking catalyst can be used in the composition according to the invention and can be any catalyst known to those skilled in the art for the silanol condensation. Examples of such catalysts include:
• organic titanium derivatives such as di (acetylacetonate) - titanium diisopropylate (IV) (commercially available under the name
• organic derivatives of aluminum such as the aluminum chelate commercially available under the name K-KAT® 5218 from King Industries;
• organic tin derivatives such as dibutyl dilaurate tin
• amines such as 1,8-DiazaBicyclo [5.4.0] undec-7-ene (DBU) and 1,5-diazabicyclo [4.3.0] non-5-ene (DBN).
• DBU 1,8-DiazaBicyclo [5.4.0] undec-7-ene
• DBN 1,5-diazabicyclo [4.3.0] non-5-ene
• UV stabilizers such as amines or antioxidants may also be included in the composition according to the invention.
• Antioxidants may include primary antioxidants that scavenge free radicals and are generally substituted phenols like Irganox ® 1010 from Ciba. Primary antioxidants may be used alone or in combination with other antioxidants such as phosphites such as Ciba Irgafos ® 168.
• the adhesive composition according to the invention is packaged in an airtight package prior to its final use, so as to protect it from ambient humidity.
• a package may advantageously be formed of a multilayer sheet which typically comprises at least one aluminum layer and / or at least one layer of high density polyethylene.
• the package is formed of a layer of polyethylene coated with a aluminum foil.
• Such a package may in particular take the form of a cylindrical cartridge.
• the invention finally relates to a method of bonding by assembling two substrates comprising:
• the adhesive composition in liquid form is either the (naturally) liquid adhesive composition or the melted adhesive composition.
• the skilled person is able to proceed so that the adhesive composition used in liquid form at the time of use.
• the coating and the contacting must be carried out within a compatible time interval, as is well known to those skilled in the art, that is to say before the adhesive layer applied to the substrate loses its ability to bond this substrate to another substrate.
• the crosslinking of the polymer of the adhesive composition in the presence of the catalyst and the water of the ambient medium and / or the water provided by at least one of the substrates, begins to occur during the coating, then continues to occur during the step of contacting the two substrates.
• water usually results from the relative humidity of the air.
• Suitable substrates are, for example, inorganic substrates such as glass, ceramics, concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and paint-coated composites (as in the automotive field).
• inorganic substrates such as glass, ceramics, concrete, metals or alloys (such as aluminum alloys, steel, non-ferrous metals and galvanized metals); or organic substrates such as wood, plastics such as PVC, polycarbonate, PMMA, polyethylene, polypropylene, polyesters, epoxy resins; metal substrates and paint-coated composites (as in the automotive field).
• the synthesis reactions of the examples were carried out in two or three stages, with a step of synthesis of the cycloolefin, a step of synthesis of the transfer agent (CTA) of formula (C) and a stage of polymerization by ring opening.
• CTA transfer agent
• DCM dichloromethane
• bond is a geometrically oriented bond on one side or the other with respect to the double bond (cis or trans);
• chain transfer agent CTA is of formula (C)
• cycloolefins are of formulas (A) and (B)
• G2 is the metathesis catalyst of formula (9):
• F1 and F2 groups are symmetrical and correspond respectively to the -COO (CH 2 ) 3 Si (OCH 3 ) 3 group (in which the CTA is bis (propyltrimethoxysilyl) fumarate) and to -CH 2 -Si (OCH 3 ) 3 (where CTA is trans, 4-bis (trimethoxysilyl) but-2-ene);
• n is the number of moles of cycloolefins of formula (A)
• m is the number of moles of cycloolefins of formula (B)
• x is the number of moles of CTA of formula (C).
• the number of monomer units in the polymer is equal to n + m.
• CTA chain transfer agent
• Cyclooctene (COE) of purity greater than 95% and norbornene (NBN) of greater than 99% purity were commercial products of Sigma AIdrich. They were previously distilled on CaH 2 .
• the raw materials, reagents and solvents used in these syntheses were commercial products from Sigma AIdrich.
• the cycloolefins of formulas (A) and (B), respectively COE (5.4 mmol) and NBN (5.4 mmol) described above, and dry CH 2 CI 2 (5 ml) were placed in a flask. of 100 ml in which was also placed a magnetic stir bar coated Teflon ® . The flask and its contents were then put under argon. The compound of formula CTA 1 or CTA 2 (1.08 mmol) was then introduced into the flask by syringe.
• the resulting polymer was liquid at room temperature.
• the resulting polymer was liquid at room temperature.
• An adhesive composition comprising 0.2% by weight of a crosslinking catalyst consisting of tin dioctyl dideodecanoate (Tib kat 223 product from Tib Chemicals) was produced, and the polymer according to the invention obtained in the example 1, by mixing.
• the mixture thus obtained was left under reduced stirring (20 mbar or 2000 Pa) for 15 minutes before the composition thus obtained was packaged in an aluminum cartridge.
• the measurement of the tensile strength and elongation at break was performed according to the protocol described below.
• the principle of the measurement consists in stretching in a tensile machine, whose moving jaw moves at a constant speed equal to 100 mm / min, a standard specimen consisting of the crosslinked adhesive composition and recording, at the moment when the rupture of the specimen, the tensile stress applied (in MPa) and the elongation of the specimen (in%).
• the standard test piece is dumbbell-shaped, as shown in International Standard ISO 37.
• the narrow part of the dumbbell used has a length of 20 mm, a width of 4 mm and a thickness of 500 ⁇ .
• the composition packaged as described above was heated to 100 ° C., then the amount necessary to form a film having a thickness of 300 ⁇ which was left on a sheet of silicone paper was extruded on a sheet of silicone paper. during 7 days at 23 ° C. and 50% relative humidity for crosslinking.
• the dumbbell is then obtained by simple cutting in the crosslinked film.
• dumbbell of the adhesive composition then has a breaking stress of 8 MPa with an elongation at break of 10%. This test is repeated twice and gives the same result.
• the adhesive composition was then subjected to bonding tests of two wooden strips (each size 20 mm x 20 mm x 2 mm) to conduct after crosslinking for seven days at 23 ° C to a breaking strength of 2 MPa adhesive rupture.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

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• 2015
  • 2015-01-08 FR FR1550160A patent/FR3031517B1/fr not_active Expired - Fee Related
• 2016
  • 2016-01-07 WO PCT/FR2016/050023 patent/WO2016110653A1/fr active Application Filing
  • 2016-01-07 US US15/541,600 patent/US20170349698A1/en not_active Abandoned
  • 2016-01-07 EP EP16702174.0A patent/EP3242902A1/de not_active Withdrawn

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