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  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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  • 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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  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
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  • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
  • C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
  • C08C19/40—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with epoxy radicals
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  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F236/06—Butadiene
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  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/22—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having three or more carbon-to-carbon double bonds
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  • 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
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  • 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
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  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
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Definitions

• the present invention relates to hydrocarbon polymers comprising two end groups of cyclocarbonate or similar type, their method of preparation and their use for the manufacture of coating compositions, mastics or adhesives.
• compositions may be in the form of one-component or two-component compositions.
• the reagents necessary for the synthesis of the polyurethane are stored separately, optionally in the presence of other ingredients (additives), and are intended to be mixed before use of the composition, to synthesize the polyurethane at the last moment. .
• polyurethanes The synthesis of polyurethanes is traditionally done by reaction of a diisocyanate with a diol.
• diisocyanates are toxic compounds as such, and are generally obtained from phosgene, itself very toxic by inhalation or by contact.
• the manufacturing process used in industry generally involves the reaction of an amine with an excess of phosgene to form an isocyanate.
• polyisocyanates are very sensitive compounds in the presence of atmospheric moisture and require taking appropriate measures to prevent their premature crosslinking, and therefore their loss of reactivity, during handling and storage (anhydrous conditions).
• polyurethane polymers that can react with amines or oligomers of amines to form polyurethanes or derivatives structurally close to polyurethanes, such as poly (thio) urethanes, which will be generically referred to herein as "polyurethane polymers".
• hydrocarbon polymers comprising two end groups containing 2-oxo-1,3-dioxolan-4-yl (also called cyclocarbonate) which can be obtained by ring opening polymerization by metathesis. from a cycloolefin, and in the presence of a chain transfer agent and a metathesis catalyst.
• polyurethane-type polymers can then react with a (poly) amine to form polyurethane-type polymers, without the use of isocyanate, and which can be used to formulate coating, sealant or adhesive compositions.
• this reaction is relatively long and remains to be improved.
• Patent application WO 2016/162627 also describes hydrocarbon polymers comprising two end-vinylene cyclocarbonate-terminated end groups which are also capable of being obtained by ring opening polymerization by metathesis from a cycloolefin, and in the presence of a chain transfer agent and a metathesis catalyst.
• Patent application WO 2016/185106 describes hydrocarbon polymers comprising two dithiocyclocarbonate (or 2-thione-1, 3-oxathiolan-4-yl) terminated end groups, which are also capable of being obtained by ring opening polymerization. by metathesis from a cycloolefin, and in the presence of a chain transfer agent and a metathesis catalyst. These latter polymers can then react with a (poly) amine to form poly (thio) urethanes without isocyanate which can also be used to formulate coating, putty or adhesive compositions.
• the hydrocarbon polymer as described by these references and the amine compound, used as hardener are each included in a component of a two-component composition which is made available to the user. .
• the latter thus proceeds, just at the time of use of the adhesive, the mixture of these 2 components, optionally hot, so as to obtain a liquid adhesive composition.
• This one is applied on at least one of two surfaces belonging to two substrates to be assembled, which are put in contact to proceed with their assembly.
• This adhesive seal is therefore mainly composed of the product of said reaction, and therefore of a polyurethane or a poly (thio) urethane, depending on the case.
• hydrocarbon polymer as described by these references in the form of a composition
• a composition comprising other constituents, such as, for example, tackifying resins, plasticizers, adhesion promoters, one or a number of additives with a reinforcing effect, such as a mineral filler, or one or more additives to improve setting time (ie the time after which crosslinking can be considered complete) or other characteristics like the rheology or the mechanical performances (elongation, module ).
• hydrocarbon polymers described by the previously cited references of the prior art may be liquid, but they are then obtained from substituted cycloolefins which are difficult to access as an industrial raw material.
• Said described hydrocarbon polymers are more generally solid, and must therefore be applied hot for their mixing with the hardener.
• compositions that can be applied at room temperature by the end user and which can also be manufactured industrially, also at room temperature, by simple mixture of the hydrocarbon polymer and additional components mentioned above.
• hydrocarbon polymers with cyclocarbonate or similar end groups which are themselves liquid at room temperature.
• the object of the present invention is to propose novel polymers with two end groups of the cyclocarbonate type or the like, which remedy these drawbacks.
• Another object of the present invention is to provide liquid polymers at room temperature which can, after mixing with a hardener, lead to the formation of an adhesive seal having improved mechanical properties.
• Another object of the present invention is to provide liquid polymers at room temperature, the synthesis of which does not use isocyanates, and which are capable of reacting with a polyamine in a short time to form polymers.
• polyurethane type is a polyurethane type.
• Another object of the present invention is to provide polymers with terminations of the type cyclocarbonate or the like which are liquid, in particular of lower viscosity at ambient temperature, and which can also be manufactured by a process which implements raw materials largely. available at the industrial level.
• 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 copolymer P comprising 2 end groups F 1 and F 2 of cyclocarbonate type and the like, having the following formulas:
• g and d identical or different, represent an integer equal to 1, 2 or
• G and D are 2 monovalent radicals such that the pair (G, D) is chosen from the pairs:
• a 2 is an alkylene group having 1 to 9 carbon atoms
• a 3 and A 4 identical or different, each represent a hydrogen atom, an alkyl radical, linear or branched, comprising from 1 to 6 carbon atoms, a cycloalkyl radical comprising 5 or 6 carbon atoms, a phenyl radical; or an alkylphenyl group whose alkyl chain comprises from 1 to 4 carbon atoms;
• a 3 and A 4 may further be bonded together to form a - (CH 2 -) q - group in which q is an integer from 3 to 5;
• 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, 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 g and d. .
• 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 and advantageously liquid at room 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.
• a primary and / or secondary polyamine can react with a primary and / or secondary polyamine, according to a polyaddition reaction, at a temperature of less than or equal to 80 ° C. and even at ambient temperature, to form, at the end of a reaction time advantageously reduced, a polymer polyurethane type that can constitute an adhesive seal.
• the adhesive seal thus formed has high cohesion values, in particular greater than 2 MPa.
• Such 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 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 main chain of the copolymer P consists essentially of the repeating unit (I) of formula (I) and of the repeating unit (II) of formula (II).
• the relative proportion of units of formula (I) and of units of formula (II) present in the main chain of the 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, less than n and such that n is greater than 0.9:
• At least 80% of the units of formula ( ⁇ ) are of cis configuration, represented by formula (I "), and at least 90% of units of formula ( ⁇ ) are also of cis configuration, represented by the formula (II ").
• the corresponding percentages can be determined by 1 H and 13 C NMR.
• m is equal to 0, and the main chain of P does not include a pattern of formula ( ⁇ ).
• all the bonds which are represented in the formulas (I), (II) and, optionally, (III) as well as in the formulas giving the meaning of R ° are simple carbon-carbon bonds.
• 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: G 1 -O-CH 2) g - and also has the formula:
• F 2 is: -CH 2) d-O-D 1 and also has the formula: corresponding to a terminal cyclocarbonate (or 2-oxo-1,3-dioxolan-4-yl) group.
• a 1 is a methylene group.
• g and d are equal to 1.
• F 1 is: G 2 -O-CH 2 ) g - and also has the formula:
• F 2 is: CH 2 ) d -O- D 2 and also has formula corresponding to a terminal dithiocyclocarbonate (or 2-thione-1,3-oxathiolan-4-yl) group.
• a 2 is a methylene group.
• g and d are equal to 1.
• F 1 is: G 3 -O- (CH 2) g - and also has the formula:
• F 2 is: -CH 2) d -O-D 3 and also has the formula:
• g and d are equal to 1.
• F 1 is: G 4 -O- (CH 2) g - and also has the formula:
• F 2 is: -CH 2) d -O-D 4 and also has the formula:
• a 3 is a methyl and A 4 is a hydrogen atom.
• g and d are equal to 1.
• 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 known as CTA), being specified that :
• a chain transfer agent also known as CTA
• F 1 and F 2 are such that the pair (G, D) corresponds to the corresponding definition (G1, D1), (G3, D3) or (G4, D4);
• the bond is a single carbon-carbon bond oriented geometrically on one side or the other with respect to the double bond (cis or trans);
• the bond is a single carbon-carbon bond oriented geometrically on one side or the other with respect to the double bond (cis or trans); it being further specified that 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 steric exclusion chromatography (SEC) and mass spectrometry techniques.
• SEC steric exclusion chromatography
• 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 is obtained:
• the main chain of P comprises according to this same variant:
• 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:
• the polymerization of 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: tif 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:
• this double upper limit of 5 mol% is lowered to 2%.
• the poly (butadiene-isoprene) chain implemented in step (i) comprises:
• the percentages of 1,2-butadiene vinyl-1,2-isoprene vinyl-1,2-isoprene vinyl-3,4-butadiene cis-1,4 and isoprene cis-1,4 units defined above can be determined by 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
• poly (butadiene-isoprene) is 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 iso-oligomerization or dehydration. neridol. It is mainly used as perfume or intermediate and meets the formula developed:
• 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 especially chosen from: norbornene, of 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 stage (i) are polymerized by heating to a temperature comprised in a 20 to 60 ° C, in the presence of a chain transfer agent (also known as CTA).
• a chain transfer agent also known as CTA
• F 1 and F 2 are such that the pair (G, D) corresponds to the corresponding definition (G1,
• the bond is a single carbon-carbon bond oriented geometrically on one side or the other with respect to the double bond (cis or trans).
• hydrocarbon P according to the invention.
• the bond is a single carbon-carbon bond oriented geometrically on one side or the other with respect to the double bond (cis or trans).
• an intermediate hydrocarbon-based copolymer I comprising the two terminal groups F ' 1 e and F' 2 e and whose main chain is identical to that of the copolymer P according to the invention, is obtained directly at the end of step (ii). 'invention.
• the CTA has the formula (C) in which F 1 and F 2 are such that the torque (G, D) is (G1, D1).
• the CTA then has the formula:
• a 1 is a methylene group.
• g and d are equal to 1.
• CTA 1 1,4-Bis [(1,3-dioxolan-2-one-4-yl) -) methyloxy] -2-butene. It is hereinafter referred to as CTA 1 .
• CTA 1 was synthesized according to the procedure described in patent application WO 2016/188875 of HENKEL by carbonation with carbon dioxide of the compound of formula:
• the CTA has the formula (C) in which F 1 and F 2 are such that the pair (G, D) is (G3, D3).
• g and d are equal to 1.
• the CTA corresponding to this last variant is designated: 1,4-Bis [(1,3-dioxolan-2-one-4-carboxylate], 2-butene and is designated hereinafter by CTA 3 .
• CTA 3 can be prepared from an unsaturated linear diol (eg 2-butene-1,4-diol available from ALDRICH) and 2-oxo-1,3-dioxolan-4-carboxylic acid depending on the mode. 3-step operating procedure described below which has been adapted from WO 2014/206636 to CONSTRUCTION RESEARCH & TECHNOLOGY.
• unsaturated linear diol eg 2-butene-1,4-diol available from ALDRICH
• 2-oxo-1,3-dioxolan-4-carboxylic acid depending on the mode.
• Step 1 gentle oxidation of glycerol carbonate to 2-oxo-1,3-dioxolan-4-carboxylic acid
• the CTA has the formula (C) in which F 1 and F 2 are such that the pair (G, D) is (G4, D4).
• the CTA then has the formula:
• a 3 is a methyl and A 4 is a hydrogen atom.
• g and d are equal to 1.
• CTA 4 is designated 1,4-Bis [(1,3-dioxol-2-one-5-methyl-4-yl) methyloxy] -2-butene. It is hereinafter referred to as CTA 4 .
• CTA of formula (C4) can be obtained according to scheme (1) below, following the procedure described in US 8,653,126 DAIICHI SANKYO:
• X is a chlorine or bromine atom
• a 2 is a methylene group.
• g and d are equal to 1.
• the TA resulting from the combination of these 2 variants has the formula:
• CTA 2 diglycidyl ether
• this compound can be synthesized according to the procedure described in patent application EP 0,91 1,326 to KYOWA YUKA, by reaction of 2 moles of epichlorohydrin with one mole of 1,4-butenediol in the presence a phase transfer catalyst.
• step (ii) implements macrocycle O opening polymerization and CTA cross-metathesis.
• 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.
• 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 Grubbs 2nd Generation (or G2) catalyst of formula (G2):
• Ph is phenyl and Cy is cyclohexyl.
• 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 mixtures thereof.
• 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 ( ⁇ ).
• step (ii) the di-epoxidized CTA of formula (C).
• an intermediate hydrocarbon-based copolymer I comprising the two terminal groups F ' 1 e and F' 2 e and whose main chain is identical to that of the copolymer P is obtained directly in this case. according to the invention.
• Said intermediate copolymer I is then reacted, according to the present step (iii), according to a dithiocarbonation reaction with carbon disulfide (CS2) in the presence of a halogenated lithium compound, at a temperature ranging from 10 to 45 ° C. .
• CS2 carbon disulfide
• the hydrocarbon-based copolymer P such that the pair (G, D) is (G 2, D 2) is then obtained.
• the process for the preparation of the hydrocarbon copolymer P which has just been described may also comprise, besides the steps (i) and (ii) (and, where appropriate, (iii)), 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 described above for said copolymer - a main chain which is saturated, and which therefore comprises a unit (I) of formula (I H ) repeated p times. , a unit (II) of formula (II H ) repeated n times and, optionally, a unit (III) of formula (III H ) repeated m times.
• a hydrogenation catalyst such as a palladium catalyst supported by carbon (Pd / C).
• said process consists essentially of steps (i), (ii) and, where appropriate, (iii).
• This variant makes it possible to obtain, for the hydrocarbon copolymer P, according to the first embodiment described above for said copolymer, an unsaturated main chain, which therefore comprises a unit (I) of formula ( ⁇ ), a unit (II) of formula ( ⁇ ) and, optionally, a unit (III) of formula ( ⁇ ').
• the invention also relates to the use as adhesive of the hydrocarbon copolymer comprising two end groups of cyclocarbonate type or the like, as defined above, in a mixture with an amine compound comprising at least two amino groups, for example chosen from diamines, triamines and higher homologs.
• the amounts of the hydrocarbon polymer and the amine compound correspond to stoichiometric amounts, that is to say that the molar ratio of the number of cyclocarbonate groups (or the like) to the number of amine groups ranges from 0.8 to 1.2. preferably from 0.9 to 1.1 or even about 1.0.
• the hydrocarbon polymer and the amine compound, used as hardener are advantageously each comprised in a component of a two-component composition which is made available to the user.
• the latter thus proceeds, at the time of the use of the adhesive, to the mixture of these 2 components, optionally hot, so as to obtain a liquid adhesive composition of appropriate viscosity.
• the invention also relates to a method of assembling two substrates by gluing, comprising:
• liquid adhesive composition obtained by mixing an amine compound comprising at least two amino groups with the hydrocarbon polymer comprising two end groups of cyclocarbonate or similar type as defined above ; then
• the liquid adhesive composition is either the adhesive composition comprising said compound and polymer in the liquid state at room temperature, or the hot melt adhesive composition. Those skilled in the art are able to proceed so that the adhesive composition used is in a liquid form and at an appropriate viscosity, at the time of its use.
• the coating of the liquid adhesive composition is preferably made in the form of a layer of thickness in a range of 0.3 to 5 mm, preferably 1 to 3 mm, on at least one two surfaces which belong respectively to the two substrates to be assembled, and which are intended to be brought into contact with one another according to a tangent surface. The effective contact of the two substrates is then implemented according to their tangency surface.
• 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 polycondensation of the hydrocarbon polymer with the amino compound begins to occur during the coating, and then continues to occur during the step of contacting the two substrates.
• 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.
• 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 1 is repeated replacing, as a chain transfer agent, CTA 1 by 2 , of formula:
• the number-average molecular weight Mn and the polydispersity index are respectively 17,050 g / mol and 2.80.
• EXAMPLE 3 depolymerization / cyclization by heating of a liquid poly (butadiene-isoprene), followed by a hot cross metathesis in the presence of CTA 3 and obtaining a copolymer P such that (G, D) is (G3, D3):
• Example 1 is repeated, replacing, as a chain transfer agent, CTA 1 with CTA 3 , of formula:
• the number average molecular weight Mn and the polydispersity index are respectively 22 700 g / mol and 2.80.
• Example 1 is repeated, replacing, as chain transfer agent, CTA 1 with CTA 4 , of formula:
• the number-average molecular weight Mn and the polydispersity index are respectively 17 020 g / mol and 2.80.
• EXAMPLE 5 depolymerization / cyclization by heating of poly (butadiene-isoprene) in the presence of norbornene followed by cross-metathesis in the presence of CTA 4
• Example 4 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 : and available from Sigma Aldrich.
• 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 present in the flask is removed after evaporation of the solvent in vacuo.
• the product is then recovered in the form of a liquid at room temperature, after precipitation in methanol, filtration and drying at 23 ° C. under vacuum, with a yield greater than 90%.
• the number-average molecular weight Mn and the polydispersity index are respectively 22 390 g / mol and 2.80.
• Example 6 Synthesis of a Polyurethane from the Unsaturated Liquid Polyolefin of the End-Group Cyclocarbonate of Example 1
• the polyolefin of Example 1 was reacted at 80 ° C. in a stoichiometric ratio with a primary diamine of the polyether diamine type (JEFFAMINE EDR 176, Huntsman) until complete disappearance of the characteristic infrared band. 1,3-dioxolan-2-one groups (at 1800 cm -1 ) and appearance of the characteristic bands of the carbamate bond (band at 1700 cm -1 ).
• reaction time recorded during the complete disappearance of the infrared band characteristic of the 1,3-dioxolan-2-one groups was approximately 3 hours.
• Example 7 Synthesis of a Poly (thio) urethane from the Dithiocyclocarbonate End Group Liquid Unsaturated Polyolefin of Example 2: The unsaturated liquid polyolefin was reacted at 23 ° C. in a stoichiometric ratio.
• CS band infrared band characteristic of the 2-thione-1,3-oxathiolan-4-yl groups
• C S band at 1530 cm -1 in Infra-Red
• thiol and disulfide functions HS band at 2500 cm "1 and SS band at 510 cm " 1 in Raman).
• the reaction time was about 3 hours.
• Example 8 Synthesis of a Polyurethane from the Hydrocarbonated End Group Liquid Unsaturated Polyolefin of Example 3
• Example 7 is repeated replacing the polyolefin of Example 2 with the liquid unsaturated polyolefin end group cyclocarbonate of Example 3.
• Example 9 Synthesis of a Polyurethane from the Liquid Unsaturated Polyolefin with 2-Oxo-1,3-dioxolen-4-yl End Group of Example 4
• Example 7 is repeated, replacing the polyolefin of Example 2 with the liquid unsaturated polyolefin end-group 2-oxo-1,3-dioxol-4-yl of Example 4, until complete disappearance of the infrared band characteristic of the 1, 3-dioxol-2-one groups (at 1800 cm -1 ) and appearance of the characteristic bands of the 2-oxazolidinone groups (band between 1770 and 1780 cm -1 ) resulting from rapid post-cyclization keto-carbamates previously obtained.
• the reaction time was about 3 hours.

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