Classifications

• • 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J11/00—Recovery or working-up of waste materials
  • C08J11/04—Recovery or working-up of waste materials of polymers
  • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
  • C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
• • 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
  • C08G2261/16—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
  • C08G2261/3324—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]
• • 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
  • C08G2261/70—Post-treatment
  • C08G2261/73—Depolymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers

Definitions

• the present invention relates to hydrocarbon copolymers comprising two alkoxysilane end groups which are liquid at room temperature.
• the invention also relates to the preparation and use of said copolymers.
• the silane-modified polymers are liquid hydrocarbon polymers having 2 alkoxysilane end groups which 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 in the presence of water (from the ambient medium and / or 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, such as, for example, tackifying resins, one or more additives with a reinforcing effect, such as a mineral filler, or one or more additives. aiming to improve the setting time (that is to say the time after which the crosslinking can be considered as completed) or other characteristics such as rheology or mechanical performance (elongation, module ).
• thermoplastic that is, deformable and heat fusible
• hydrocarbon polymers with alkoxysilane end groups which are themselves liquid at room temperature.
• liquid hydrocarbon polymers particularly low viscosity at room temperature
• cyclooctene or substituted derivatives of cyclooctene generally requires the implementation of cyclooctene or substituted derivatives of cyclooctene.
• these products correspond to raw materials that are not accessible industrially or that are difficult to achieve.
• the object of the present invention is to propose novel polymers with two alkoxysilane end groups which remedy these disadvantages.
• Another object of the present invention is to provide liquid polymers at room temperature which can lead, after crosslinking, to the formation of an adhesive seal having improved mechanical properties.
• Another object of the present invention is to provide polymers with liquid alkoxysilane terminations, in particular of lower temperature viscosity. ambient, which can also be manufactured by a process which uses industrially widely available raw materials.
• Another object of the present invention is to provide such polymers, which can, in addition, be manufactured industrially by a process whose exotherm is easier to control.
• the present invention relates to a hydrocarbon-based copolymer P comprising 2 alkoxysilane end groups F 1 and F 2 connected respectively to each of the two ends of the main chain, having the formulas:
• F 1 (R'O) 3-tRtSi-R "-NH-C (O) O- (CH 2 ) g- and F 2 : - (CH 2 ) di-OC (O) -NH-R" -SiR t (OR ') 3- t; or
• - 1 is an integer equal to 0, 1 or 2;
• - g1 and d1 identical or different, represent an integer equal to 1, 2 or 3;
• - g2 and d2 identical or different, represent an integer equal to 0, 1, 2 or 3;
• R and R ' which may be identical or different, represent an alkyl radical comprising from 1 to 4 carbon atoms;
• R is an alkylene radical comprising from 1 to 4 carbon atoms
• R '" represents a hydrogen atom, a phenyl radical, a branched or cyclic linear alkyl radical comprising from 1 to 6 carbon atoms, or a succinate radical of formula:
• the main chain of the copolymer P comprises: a unit (I) of formula (I) repeated p times, p being an integer different from 0:
• R ° represents the methyl radical or one of the 3 radicals of following formula:
• R 1 , R 2 , R 3 and R 4 identical or different, represent:
• a radical comprising from 1 to 22 carbon atoms and chosen from alkyl, alkenyl, alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy and alkylcarbonyloxyalkyl, the hydrocarbon chain of said radical possibly being interrupted by at least one oxygen atom or one sulfur atom; ; in addition: at least one of the groups R 1 to R 4 can form, together with at least one other group R 1 to R 4 and with the carbon atom or atoms to which the said groups are connected, a saturated or unsaturated hydrocarbon ring or heterocycle, optionally substituted, and comprising from 3 to 10 members; and
• the carbon atom carrying one of the groups of the pair (R 1 , R 2 ) can be connected to the carbon atom carrying one of the groups of the pair (R 3 , R 4 ) by a double bond, it being understood that, according to the valence rules, only one of the groups of each of these 2 pairs is then present;
• R 5 represents:
• R 6 is an alkyl or alkenyl radical comprising from 1 to 22 carbon atoms
• n, p and m are such that the number-average molecular weight Mn of the copolymer P is in a range of from 400 to 100,000 g / mol and its polymolecularity index is in a range from 1.5 to 3; , 0.
• the units (I), (II) and, optionally, (III) are divalent radicals which are randomly distributed in the main chain of the copolymer P, with the exception of 2 units (I) which are directly connected to F 1 and F 2 .
• the copolymer P is therefore a random copolymer.
• the main chain of the copolymer P therefore comprises two or three repeating units:
• the copolymer P can be a bipolymer (presence of the 2 repeating units (I) and (II)) or a terpolymer (presence of the 3 repeating units (I), (II) and (III)).
• terminal groups F 1 and F 2 are generally symmetrical with respect to the main chain, that is to say that they correspond substantially, with the exception of the indices g1 and g2 , and d1 and d2.
• 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 atoms.
• terminal group is meant a group located at one of the two ends of the main chain of the polymer.
• copolymer means a polymer resulting from the copolymerization of at least two comonomers, that is to say two chemically different monomers.
• the main chain of a copolymer comprises at least 2 chemically distinct repeating units.
• terpolymer means a copolymer resulting from the copolymerization of three comonomers, and whose main chain consists essentially of 3 distinct repeating units.
• bipolymer a copolymer resulting from the copolymerization of two comonomers, and whose main chain consists essentially of 2 distinct repeating units.
• Polymolecularity index (also referred to as polydispersity index or PDI) is defined as the Mw / Mn ratio, that is to say the ratio of the weight average molecular weight to the number average molecular weight of the polymer.
• Mn and Mw are measured by Size Exclusion Chromatography (SEC), which is also referred to as gel permeation chromatography (or the term "Size Exclusion Chromatography”). by the corresponding English acronym GPC).
• SEC Size Exclusion Chromatography
• GPC Gel permeation chromatography
• the calibration implemented is usually a PEG (PolyEthyleneGlycol) or PS (Polystyrene) calibration, preferably PS.
• the copolymer P according to the invention is particularly homogeneous and stable in temperature. It is advantageously at room temperature in the form of a viscous liquid whose Brookfield viscosity at 23 ° C is between 1 mPa.s and 150 Pa.s, preferably between 1 and 50 Pa.s.
• the copolymer P may form, after a crosslinking reaction in the presence of water and a catalyst, an adhesive seal resulting from the formation of Si-O-Si siloxane bonds between the polymer chains.
• the water used in the crosslinking reaction is the water of the ambient medium and / or the water supplied by at least one substrate, generally the atmospheric humidity, corresponding for example to a relative humidity of the air (called also degree of hygrometry) usually in a range of 25 to 65%.
• the formed adhesive seal exhibits high cohesion values, in particular greater than 2 MPa.
• cohesive values allow a use of said polymer 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 industry and naval.
• the copolymer P is preferably packaged and stored protected from moisture.
• the main chain of the copolymer P consists essentially of the repeating unit (I) of formula (I), the repeating unit (II) of formula (II) and, optionally, the repeating unit (III) of formula (III).
• the number of units (I), (II) and optionally (III) advantageously represents at least 90% of the total number of units constituting the main chain of the copolymer P, and even more advantageously at least 95%.
• the relative proportion of units of formula (I) and units of formula (II) present in the main chain of copolymer P corresponds to an excess of units of formula (I). More particularly, the number p of units (I) and the number n of units (II) are such that:
• p / (n + p) is between 45 and 95%
• n / (n + p) is between 5 and 55%.
• the main chain of the copolymer P is thus such that:
• R ° represents the methyl radical or one of the 3 radicals of following formula:
• the unit (III) also has the formula ( ⁇ ):
• the bond is a single bond geometrically oriented on one side or the other with respect to the double bond (cis or trans).
• the main chain of the copolymer P is such that:
• n also correspond to formula (II"), n "being an integer different from 0, lower than n and such that nV is greater than 0.9:
• m is equal to 0, and the main chain of P does not include a pattern of formula ( ⁇ ).
• the main chain of the copolymer P is therefore such that:
• the unit (I) also has the formula (l H ):
• the pattern (II) also has the formula (II H )
• R ° represents the methyl radical or one of the 3 radicals of following formula:
• the unit (III) has the formula (III H ):
• Copolymer P according to this second embodiment is for example from the hydrogenation of the copolymer P according to the embodiment 1 described above.
• the radical R ° of the unit (II) represents the methyl radical.
• F 1 is (RO) 3 -tRtSi-R "-NH-C ( O) O- (CH 2 ) g i- and F 2 is - (CH 2 ) di-OC (O) -NH-R "-SiRt (OR ') 3- t, with:
• F 1 and F 2 are each: -CH 2 -OC (O) -NH- (CH 2 ) 3 -Si (OCH 3 ) 3
• F 1 is (R'O) 3 -tRtSi-R "-NH-C (O) O- (CH 2 ) g- and F 2 is - (CH 2 ) di-OC (O) -NH-R "-SiRt (OR ') 3- t, with:
• F 1 and F 2 are each: -CH 2 -OC (O) -NH-CH 2 -SiCH 3 (OCH 3 ) 2 .
• F 1 is (RO) 3-t RtSi-R "-NH-C (O) -NR"'- (CH 2 ) g- and F 2 is
• F 1 and F 2 are each: -CH 2 -NH-C (O) -NH- (CH 2 ) 3 -Si (OCH 3 ) 3 .
• F 1 is (RO) 3-tRtSi-R "-NR"'- C (O) -NR "" - (CH 2) g - and F 2 is
• F 1 and F 2 are each: -CH 2 -NH-C (O) -NH-CH 2 -SiCH 3 (OCH 3 ) 2.
• F 1 is (RO) 3-tRtSi-R "-NR"'- C (O) - (CH 2 ) g 2 - and F 2 is - ( CH2) d2-C (O) -NR , "-R" -SiRt (OR ') 3- t, with:
• F 1 and F 2 are each -C (O) -NH- (CH 2 ) 3 -Si (OCH 3 ) 3.
• F 1 and F 2 are each -C (O) -NH-CH 2 -SiCH 3 (OCH 3 ) 2.
• R "' represents a hydrogen atom.
• the invention also relates to a process for preparing the hydrocarbon-based copolymer P as defined above, said process comprising:
• a random bipolymer A selected from poly (butadiene-isoprene), poly (butadiene-myrcene) and poly (butadiene-farnesene);
• step (ii) a step of heating the product formed in step (i) to a temperature in a range of 20 to 60 ° C, in the presence of a chain transfer agent (also called CTA) of formula (C ) : (VS)
• a chain transfer agent also called CTA
• the bond is a single bond geometrically oriented on one side or the other with respect to the double bond (cis or trans);
• each of steps (i) and (ii) is carried out in the presence of a metathesis catalyst and a solvent.
• Step (i) implements a depolymerization reaction of bipolymer A and intramolecular cydization, which leads to the formation of one or more macrocyclic cooligomer O comprising:
• p '°, n' ° and m ' 0 are such that the number-average molecular mass Mn of the cyclic cooligomer (s) O is in the range from 162 to 5000 g / mol, preferably from 1000 to 3000 g / mole.
• the formation and structure of the O-macrocyclic cooligomer (s) can be characterized by size exclusion chromatography techniques (or SEC) and mass spectrometry.
• SEC size exclusion chromatography techniques
• mass spectrometry mass spectrometry.
• the distribution in the macrocycle of the units of formulas ( ⁇ ), ( ⁇ ) and optionally ( ⁇ ) is statistical.
• a preferred temperature range for heating the bipolymer A and optionally compound B according to step (i) is from 30 ° C to 60 ° C.
• the corresponding heating time is adapted to obtain a yield close to 100% relative to the molar amount of bipolymer A used, as well as that of the other reactants present.
• Bipolymer A is a copolymer consisting essentially of 2 monomers and is selected from poly (butadiene-isoprene), poly (butadiene-myrcene), and poly (butadiene-farnesene).
• the bipolymer A implemented in step (i) is a poly (butadiene-isoprene).
• a hydrocarbon-based copolymer P according to the invention the main chain comprising:
• Poly (butadiene-isoprene) are copolymers which constitute an industrially advantageous raw material, in particular because of their availability and properties in terms of industrial hygiene.
• Polybutadiene-isoprene is generally obtained by various polymerization processes:
• 1,3-butadiene can be carried out in either a 1,4-trans-addition or a 1,4-cis-addition, resulting in a repeating unit in the copolymer chain (referred to as a trans-butadiene unit, respectively).
• 1, 4 and cis-1, 4 which is in the form of the two geometric isomers of the respective formula: butadiene trans-1,4)
• the cis-1,4 butadiene unit is identical to the unit of formula (I ") defined previously.
• the polymerization of 1,3-butadiene can also be carried out according to a 1,2-addition, resulting in a repeating unit in the copolymer chain (designated 1,2-vinyl butadiene unit) which has the formula:
• poly (butadiene-isoprene) generally comprises in its chain the 3 repeating units above, hereinafter referred to generically as "butadiene derived units”.
• the cis-1,4 isoprene unit is identical to the unit of formula (II ") in which R ° is methyl, as defined above.
• the polymerization of isoprene can also be carried out in an addition-1, 2, resulting in a repeating unit in the copolymer chain (designated by isoprene vinyl-1, 2 unit) which has the formula:
• the polymerization of the isoprene can finally be carried out according to a 3,4-addition, resulting in a repeating unit in the copolymer chain (designated by 3,4-vinylisoprene unit) which has the formula:
• polybutadiene-isoprene generally comprises in its chain the 4 repeating units above, hereinafter referred to generically as "isoprene derived units”.
• the poly (butadiene-isoprene) used in step (i) may have a number-average molecular weight (Mn) ranging from 3,000 to 100,000 g / mol, preferably from 3,000 to 50,000 g / mol, and a glass transition temperature (Tg) of from -1 to -60 ° C.
• Mn number-average molecular weight
• Tg glass transition temperature
• It preferably comprises from 45 to 95% of number of units derived from butadiene and from 5 to 55% of number of units derived from isoprene, said percentages being expressed on the basis of the total number of constituent units of the poly chain. (butadiene-isoprene).
• the poly (butadiene-isoprene) chain implemented in step (i) comprises:
• the poly (butadiene-isoprene) chain implemented in step (i) comprises:
• 1, 2, isoprene vinyl-3,4, butadiene cis-1,4 and isoprene cis-1,4 defined above can be determined by NMR of 1 H and 13 C.
• poly (butadiene-isoprene) is KURAPRENE® LIR-390 which is commercially available from KURARAY.
• This liquid poly (butadiene-isoprene) has a number-average molecular weight (Mn) of 48,000 g / mole. It comprises 92% number of units derived from butadiene and 8% number of units derived from isoprene, said percentages being expressed on the basis of the total number of units derived from butadiene and isoprene constituting the chain.
• Mn number-average molecular weight
• KURAPRENE® LIR-340 also commercially available from KURARAY.
• This poly (butadiene-isoprene) has a number-average molecular weight (Mn) of 34,000 g / mole. It comprises 46% number of units derived from butadiene and 54% number of units derived from isoprene, said percentages being expressed on the basis of the total number of units constituting the chain. It has, moreover, the same characteristics as those indicated above for the KURAPRENE® LIR-390.
• the bipolymer A is either a poly (butadiene-myrcene) or a poly (butadiene-farnesene).
• Myrcene is a naturally occurring organic compound belonging to the chemical class of monoterpenes and is an important intermediate in the perfume industry. It is produced semi-synthetic from plants of the genus Myrcia. It is in the form of two geometric isomers:
• Farnesene or ⁇ -farnesene is a natural isoprenoid compound that can be chemically synthesized by isoprene oliogomerization or by dehydration of neridol. It is used mainly as perfume or intermediate and meets the developed formula: Reference is made to application EP 2810963 for the processes for the preparation of copoly (butadiene-myrcene) and copoly (butadiene-farnesene).
• a hydrocarbon-based copolymer P according to the invention comprising:
• the main chain comprises the additional unit of formula ( ⁇ ), as defined above.
• the compound of formula (B) generally comprises from 6 to 30, preferably from 6 to 22, carbon atoms.
• R 1 , R 2 , R 3 and R 4 represent a hydrogen atom or an alkyl or alkoxycarbonyl radical comprising from 1 to 14 carbon atoms, and even more preferably from 1 to 8;
• the radical R 6 included in the group -NR 6 which is one of the meanings of R 5 , is a linear radical comprising from 1 to 14 carbon atoms.
• At most one of the groups selected from (R 1 , R 2 , R 2 and R 4 ) is a C 1 -C 6 alkoxycarbonyl radical and all the others represent a hydrogen atom; and or
• R 5 represents a radical -Ch - or an oxygen atom.
• the compound of formula (B) is in particular chosen from:
• 7-oxanorbornene of the following formula 7-oxanorbornadiene, of the following formula: 5-Ethidene-2-norbornene, of the following formula:
• the compound of formula (B) may also be chosen from the following compounds:
• R is an alkyl radical comprising from 1 to 22 carbon atoms, preferably from 1 to 14 carbon atoms.
• the compound of formula (B) can 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 norbornene derivatives 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 having the more often 3 to 8 carbon atoms) and substituted norbornenes as described in WO 201 1/038057 (norbornene dicarboxylic anhydrides and optionally 7-oxanorbornene dicarboxylic anhydrides).
• norbornene and dicyclopentadiene are particularly preferred.
• the macrocyclic cooligomers O corresponding to the product formed in step (i) are polymerized by heating at a temperature in a range of 20 to 60 ° C., in the presence of a chain transfer agent (also called CTA) of formula (VS) :
• CTA chain transfer agent
• the bond is a single bond oriented geometrically on one side or the other with respect to the double bond (cis or trans).
• this step implements macrocycle O opening polymerization and cross-metathesis with CTA.
• This step (ii) advantageously has a low exothermicity, so that the industrial implementation of the method according to the invention does not pose difficulties in controlling the temperature.
• the molar amount of CTA to be introduced in the present step (ii) is related to the molar amount of bipolymer A and, optionally, to the molar amount of compound B introduced in step (i).
• the bipolymer A is a poly (butadiene-isoprene), said ratio r is equal to the ratio of the number of moles of the CTA:
• the ratio r defined above is in the range of 0.0020 to 0.3.
• the CTA has the formula (C) in which F 1 is (R'O) 3-tRtSi-R "-NH-C (O) O- (CH 2 ) and F 2 is - (CH 2 ) di-OC (O) -NH-R "-SiRt (OR ') 3- t.
• a ⁇ -isocyanatosilane such as 3-isocyanatopropyltrimethoxysilane
• an ⁇ -isocyanatosilane such as
• the CTA has the formula (C) in which F 1 is (R'O) 3-tRtSi-R "-NH-C (O) -NR '" - (CH 2 ) g- and F 2 is - (CH 2 ) di-NR " , -C (O) -NH-R" -SiRt (OR ') 3- t.
• a ⁇ -isocyanatosilane such as 3-isocyanatopropyltrimethoxysilane
• an ⁇ -isocyanatosilane such as
• 1,4-diamino-2-butene 1 mole of unsaturated linear diamine (for example 1,4-diamino-2-butene) which may be synthesized by conversion of 1,4-dibromo-2-butene according to WO 92/21235 or according to Koziara et al., Synthesis 1985, 202 or, from 1, 4-dibromo-2-butene according to LH Amundsen et al., J. Am. Chem. Soc. 1951, 73, 21 18).
• unsaturated linear diamine for example 1,4-diamino-2-butene
• the CTA has the formula (C) in which F 1 is (RO) 3 -tRtSi-R "-NR"'- C (O) - (CH 2 ) g2- and F 2 is - (CH2) d2-C (O) -NR "'- R” -SiRt (OR') 3- t.
• These 2 compounds can be synthesized by amidification of unsaturated linear carboxylic diacids or corresponding anhydrides with 2 moles, respectively, of a ⁇ -aminosilane (such as 3-aminopropyltrimethoxysilane) or an ⁇ -aminosilane (such as (aminomethyl) methyldimethoxysilane), marketed by WACKER Chemie under the GENIOSIL® brand.
• a ⁇ -aminosilane such as 3-aminopropyltrimethoxysilane
• an ⁇ -aminosilane such as (aminomethyl) methyldimethoxysilane
• Steps (i) and (ii) of the process according to the invention each implement a metathesis catalyst and a solvent which may be identical or different, and preferably identical in each of these two steps.
• the metathesis catalyst is preferably a catalyst comprising ruthenium, and even more preferably a Grubbs catalyst,
• Such a 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.
• Grubbs catalyst is generally defined according to the invention a Grubbs catalyst 1 st or 2 nd generation, but also any other Grubbs catalyst (such as ruthenium carbene) or Hoveyda-Grubbs accessible to the skilled person , 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 (G1):
• Ph is phenyl
• Cy is cyclohexyl
• P (Cy) 3 is a tricyclohexylphosphine group.
• the IUPAC name for this compound is: benzylidene-bis (tricyclohexylphosphine) dichlororuthenium (CAS number 172222-30-9).
• a catalyst is available in particular from Aldrich.
• a preferred catalyst is the 2nd generation Grubbs (or G2) catalyst is generally of formula (G2):
• 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).
• This catalyst is also available from Aldrich.
• the solvent is generally chosen from the group formed by the aqueous or organic solvents typically used in the polymerization reactions and which are inert under the conditions of the polymerization, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water or their mixtures.
• a preferred solvent is selected from the group consisting of benzene, toluene, para-xylene, methylene chloride (or dichloromethane), 1,2-dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, hexane, heptane, a mixture of liquid isoparaffins (for example Isopar®), methanol, ethanol, water or their mixtures.
• the solvent is selected from the group consisting of benzene, toluene, paraxylene, methylene chloride, 1,2-dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, hexane, heptane, methanol, ethanol or mixtures thereof.
• the solvent is dichloromethane, 1,2-dicholoroethane, toluene, heptane or a mixture of toluene and 1,2-dichloroethane.
• each of the steps (i) and (ii) is carried out without solvent.
• the main chain of the hydrocarbon copolymer P according to the invention which is obtained directly after steps (i) and (ii) is unsaturated, and, more precisely, comprises - according to the first embodiment described above for said copolymer - a repeating unit (I) of formula ( ⁇ ), a repeating unit (II) of formula ( ⁇ ) and, optionally, a repeating unit (III) of formula ( ⁇ ).
• the process for the preparation of the hydrocarbon copolymer P which has just been described may also comprise, in addition to the steps (i) and (ii), an additional step of hydrogenation of the 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 obtain for the hydrocarbon copolymer P - according to the second embodiment previously described for said copolymer - a main chain which is saturated, and which therefore comprises a repeating unit (I) of formula (I H ), a repeating unit (II) of formula (II H ) n times and possibly a pattern (III) of formula (III H ) repeated m times.
• a hydrogenation catalyst such as a palladium catalyst supported by carbon
• the invention also relates to an adhesive composition
• an adhesive composition comprising a copolymer P according to the invention and from 0.01 to 3% by weight, preferably from 0.1 to 1% by weight, of a crosslinking catalyst.
• Said adhesive composition is advantageously in the form of a viscous liquid.
• the crosslinking catalyst that may be used in the composition according to the invention may be any catalyst known to those skilled in the art for the condensation of silanols. Examples of such catalysts include:
• titanium (IV) di (acetylacetonate) diisopropylate commercially available under the name TYZORR® AA75 from Dupont;
• 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 dibutyltin dilaurate (DBTL); and
• 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 polyethylene layer coated with aluminum foil.
• Such a package may in particular take the form of a cylindrical cartridge.
• the invention finally relates to a method of assembling two substrates by gluing, comprising:
• an adhesive composition as defined above preferably in the form of a layer of thickness in a range of 0.3 to 5 mm, preferably of 1 to 3 mm, on at least 1 one of the two surfaces which respectively belong to the two substrates to be assembled, and which are intended to be brought into contact with one another according to a tangent surface; then
• 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 does not lose its ability to fix by bonding this substrate to another substrate.
• the crosslinking of the copolymer of the adhesive composition in the presence of the catalyst and of 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 comes 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).
• copolymers P illustrated have a Brookfield viscosity at 23.degree.
• EXAMPLE 1 depolymerization / cyclization by heating of a liquid poly (butadiene-isoprene), followed by a hot cross metathesis in the presence of CTA 1 :
• KURAPRENE® LIR-390 as defined above is used as liquid poly (butadiene-isoprene) and CTA 1 of the formula:
• This mixture is heated in an oil bath for 3 hours at 40 ° C with stirring until disappearance of KURAPRENE® LIR-390 and formation of a mixture of macrocyclic cooligomers O attested by steric exclusion chromatography.
• the compound CTA 1 (0.27 mmol) is added by syringe and with stirring into the mixture contained in the flask of step (i) and the temperature of 40 ° C. is maintained by heating.
• the ratio r as defined previously, is: 0.27 / 81, 00 is 0.003
• the number-average molecular weight M n and the polydispersity index are respectively 17 200 g / mol and 2.7.
• EXAMPLE 2 depolymerization / cyclization by heating of a poly (butadiene-isoprene) in the presence of norbornene, followed by a cross-metathesis in the presence of CTA 1 :
• Example 1 is repeated, replacing in step (i) the 81.00 mmol of poly (butadiene-isoprene) with a mixture of 41.00 mmol of polybutadiene-isoprene and 40.00 mmol of norbornene of formula :
• the ratio r of the reagents, as defined above, is equal to 0.27 mmol divided by 41.00 mmol + 40.00 mmol, ie 0.003.
• the product in the flask is removed after evaporation of the solvent in vacuo.
• the product is then recovered in the form of a liquid at ambient temperature, after precipitation in methanol, filtration and drying at 23 ° C. under vacuum.
• the number-average molecular weight Mn and the polydispersity index are 22,800 g / mol and 2.80, respectively.
• EXAMPLE 3 depolymerization / cyclization by heating of a liquid poly (butadiene-isoprene), followed by a hot cross metathesis in the presence of CTA 2 :
• Example 1 is repeated, replacing, as a chain transfer agent, CTA 1 with CTA 2 , of formula:
• the number-average molecular weight Mn and the polydispersity index are 22,800 g / mol and 2.80, respectively.
• EXAMPLE 4 depolymerization / cyclization by heating of a liquid poly (butadiene-isoprene), followed by a hot cross-metathesis in the presence of CTA 3 :
• Example 1 is repeated, replacing, as a chain transfer agent, CTA 1 with CTA 3 , of formula:
• a polymer is also recovered in the form of a colorless liquid whose 1 H / 13 C NMR analysis gives the following values:
• the number-average molecular weight Mn and the polydispersity index are respectively 17 100 g / mol and 2.7.
• EXAMPLE 5 depolymerization / cyclization by heating poly (butadiene-isoprene) in the presence of dicyclopentadiene, followed by cross-metathesis in the presence of CTA 1
• Example 2 is repeated, replacing norbornene with dicyclopentadiene, of formula:
• the number average molecular weight Mn and the polydispersity index are 28,500 g / mol and 2.80, respectively.
• An adhesive composition consisting of 0.2% by weight of a crosslinking catalyst consisting of tin dioctyl dideodecanoate (TIB KAT® 223 product from TIB Chemicals) and 99.8% by weight is prepared by simple mixing. of copolymer according to the invention obtained in Example 1.
• the measurement of the tensile strength and elongation at break is carried out according to the protocol described below.
• 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 conditioned as described above is heated to 100 ° C., then the amount necessary to form a film having a thickness of 300 ⁇ , which is left during a film, is extruded on an A4 sheet of silicone paper. 7 days at 23 ° C and 50% relative humidity for crosslinking. The dumbbell is then obtained by simple cutting in the crosslinked film.
• a tensile stress greater than 0.7 MPa and an elongation at break greater than 200% are measured.
• Said adhesive composition is also subjected to bonding tests of two wooden strips (each size 20 mm ⁇ 20 mm ⁇ 2 mm) to conduct, after crosslinking for seven days at 23 ° C. and forming an adhesive seal of 1 mm thick on a surface of 12.5 mm X 20 mm, with a breaking stress greater than 2 MPa in adhesive breaking.

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