Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C409/00—Peroxy compounds
  • C07C409/16—Peroxy compounds the —O—O— group being bound between two carbon atoms not further substituted by oxygen atoms, i.e. peroxides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C409/00—Peroxy compounds
  • C07C409/20—Peroxy compounds the —O—O— group being bound to a carbon atom further substituted by singly—bound oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
  • C07D303/02—Compounds containing oxirane rings
  • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
  • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals

Definitions

• the subject of the present invention is macromonomer compounds, one of the ends of which has a three-atom ring, among which is a heteroatom, as well as diene compounds having a terminal function of the peroxy or disulfide type.
• the present invention likewise relates to a process for the preparation of the above-mentioned macromonomer compounds from said diene compounds, by radical polymerization.
• H 2 C C (R 1 ) (CX2-OOR 2 ), formula in which the radical R 1 represents a hydrogen atom, a chlorine atom, an alkyl group or a group capable of activating the double bond, and R 2 represents a hydrogen atom, alkyl groups. alkenyl, aryl, optionally substituted, or a group -CO-Z for which Z corresponds to a group R of the type of alkyl, alkenyl, aryl, optionally substituted, or a group -OR in which R has the same meaning as previously.
• the radical R 1 is a group activating the double bond, of the aryl, cyano or even ester type.
• the polymers obtained by radical polymerization in the presence of the abovementioned transfer agents with unsaturated monomers have a terminal epoxy group.
• This terminal epoxy group is however disubstituted due to the presence of the abovementioned radical R 1 , which happens to be different from a hydrogen atom.
• the present invention therefore relates to the preparation of macromonomer compounds comprising at one of their ends a three-atom ring, one of which is an oxygen or sulfur atom.
• macromonomer compounds have the unexpected advantage of being more reactive in polymerization than their counterparts described in the prior art.
• these new macromonomer compounds are more reactive with monomers, polymers or copolymers comprising at least one function of the carboxylic, carboxylate, amino, alcohols and / or thiol type.
• R 4 - [A] n -CH 2 -CR 1 CH-CH-C (R 2 ) (R 3 )
• alkyl, aryl, arylalkyl or alkylaryl radical these radicals being possibly substituted by at least one carboxy, alkoxycarbonyl, acyloxy, carbamoyl or cyano group,
• R 2 and R 3 identical or different, represent a hydrogen atom, a halogen atom, an alkyl, aryl, alkylaryl, arylalkyl, or alkoxy radical,
• alkyl radical an aryl, alkylaryl or arylalkyl radical, these radicals being optionally substituted by at least one carboxy, alkoxy ⁇ carbonyl, acyloxy, carbamoyl, cyano, or
• R 5 representing a hydrogen atom, an alkyl, aryl, alkylaryl or arylalkyl radical, these radicals being optionally substituted by at least one carboxy, alkoxycarbonyl, acyloxy, carbamoyl, cyano group,
• ° X represents an oxygen atom or a sulfur atom
• ° A corresponds to a unit derived from at least one ethylenically unsaturated monomer, and ° n is between 1 and 10000.
• Another subject of the present invention relates to diene compounds of formula (II) below:
• alkyl, aryl, alkylaryl or arylalkyl radical these radicals being optionally substituted with at least one carboxy, alkoxy ⁇ carbonyl, acyloxy, carbamoyl, cyano group,
• R 7 representing an alkyl, aryte, alkylaryl or arylalkyl radical, - a hydrogen atom, and when R 2 and R 3 represent a methyl group, R 6 does not represent a hydrogen atom.
• the present invention also relates to the use of the compounds of formula (II) for the preparation of the macromonomer compounds of formula (I). Finally, the invention relates to the use of the macromonomer compounds of formula (I) for the preparation of copolymers.
• diene compounds are compounds of formula (II) below:
• the radical R 1 represents a hydrogen atom, a carboxy, alkoxycarbonyl, acyloxy, carbamoyl or cyano group.
• the radical R 1 represents a hydrogen atom.
• the radicals R 2 and R 3 which are identical or different, represent a hydrogen atom, an alkyl radical, linear or branched at C r C 6 .
• R 5 more particularly represents a hydrogen atom, an alkyl radical. aryl, alkylaryl or arylalkyl, these radicals being optionally substituted with at least one carboxy, alkoxycarbonyl, acyloxy, carbamoyl, or cyano group. According to an advantageous embodiment of the present invention, R 5 more particularly represents an alkyl, aryl, alkylaryl or arylalkyl radical.
• R 6 represents more particularly an alkyl, aryl, alkylaryl or arylalkyl radical, these radicals being optionally substituted with at least one carboxy, alkoxycarbonyl, acyloxy, carbamoyl or cyano group.
• the diene compounds of formula (II) are such that X represents an oxygen atom.
• Such compounds can be synthesized from their halogen derivatives which are brought into contact with a derivative of the peroxide or disulfide type.
• This reaction is usually carried out in a solvent medium.
• suitable solvents mention may be made of cyclic ethers such as tetrahydrofuran or all the compounds capable of dissolving the intermediate cations of the reaction, such as the hydroperoxide or disulfide salts, or the halogen derivative present.
• the reaction is carried out at a temperature such that the degradation reactions by thermoyysis of the reactants and of the products obtained are negligible.
• the reaction temperature is lower than room temperature and more particularly below 10 ° C.
• the macromonomer compounds of formula (I), which are the subject of the present invention, have radicals R 1 , R 2 , R 3 , R 4 and X as defined above.
• the radical R 1 represents a hydrogen atom, a carboxy, alkoxycarbonyl, acyloxy, carbamoyl or cyano group.
• the radical R 1 represents a hydrogen atom.
• the radicals R 2 and R 3 which are identical or different, represent a hydrogen atom, an alkyl radical, linear or branched at C r C 6 .
• the radical R 5 more particularly represents a hydrogen atom, an alkyl, aryl, alkylaryl or arylalkyl radical, these radicals being optionally substituted by at least one carboxy, alkoxycarbonyl, acyloxy, carbamoyl or cyano group.
• R 5 more particularly represents an alkyl, aryl, alkylaryl or arylalkyl radical.
• R 6 more particularly represents an alkyl, aryl, alkylaryl or arylalkyl radical, these radicals being optionally substituted with at least one carboxy, alkoxycarbonyl, acyloxy, carbamoyl or cyano group.
• the macromonomer compounds of formula (I) are such that X represents an oxygen atom.
• the macromonomer compounds (I) according to the invention further comprise in their structure n groups A, with A corresponding to a unit derived from an ethylenically unsaturated monomer and n of between 1 and 10000.
• n is between 1 and 5000.
• (meth) acrylic esters is meant the esters of acrylic acid and of methacrylic acid with C r C 12 , preferably C r C 8, alcohols.
• Vinyl nitriles more particularly include those having 3 to 12 carbon atoms, such as in particular acrylonitrile and methacrylonitrile.
• styrene can be replaced in whole or in part by derivatives such as alphamethylstyrene or vinyltoluene.
• the other ethylenically unsaturated monomers which can be used alone or as a mixture, or which can be copolymerized with the above monomers are in particular:
• ethylenic monomers comprising a sulfonic acid group and its alkali or ammonium salts, for example vinylsulfonic acid, vinylbenzene sulfonic acid, alpha-acrylamido methylpropane-sulfonic acid, 2-sulfoethylene-methacrylate,
• ethylenic unsaturated monomers comprising a secondary, tertiary or quaternary amino group, or a heterocyclic group containing nitrogen such as for example vinylpyridines, vinylimidazole, aminoalkyl (meth) acrylates and (meth) acrylamides) aminoalkyl such as dimethylaminoethylacrylate or -methacrylate, ditertiobutylaminoethylacrylate or -methacrylate, dimethylamino methylacrylamide or -methacrylamide. It is likewise possible to use zwitterionic monomers such as, for example, sulfopropyl (dimethyl) aminopropyl acrylate.
• the macromonomer compounds of formula (I) are obtained from the diene compounds of formula (II).
• the formula of the diene compounds of formula (II) includes, in addition, R 6 equal to a hydrogen atom when R 2 and R 3 both represent a methyl radical. More particularly for the preparation of said monomers (1), radical polymerization is carried out with at least one aforementioned ethylenically unsaturated monomer and at least one diene compound of formula (II).
• the polymerization is carried out in a manner known per se, in solution, in bulk, in aqueous emulsion when the monomer (s) used are not miscible with water, in the presence of at least one radical initiator and at least one compound. diene of formula (II).
• initiators include hydroperoxides such as hydrogen peroxide, diisopropylbenzene hydroperoxide, sodium, potassium or ammonium persulfates, and azo initiators such as azobis (isobutyronitrile), 4-4 ' azobis (4-cyano valeric acid).
• hydroperoxides such as hydrogen peroxide, diisopropylbenzene hydroperoxide, sodium, potassium or ammonium persulfates
• azo initiators such as azobis (isobutyronitrile), 4-4 ' azobis (4-cyano valeric acid).
• These initiators can be associated with a reducing agent such as, for example, bisulfite.
• the amount is generally between 0.05 and 2% by weight relative to the amount of the monomers.
• the amount of diene compound of formula (II) depends on the molecular weight desired for the macromonomer of formula (I). As an indication, this amount is generally between 0.05 and 10%, preferably between 0.1 and 3% by weight relative to the total weight of the monomers.
• the diene compound can be introduced into the reaction medium either entirely at the start of the reaction, or in continuous solution in the main monomers, or even partially initially and partly continuously.
• the solubility of the product in the monomers is low, it can be introduced in the form of a suspension simultaneously with the said monomers.
• the polymerization temperature is a function of the nature of the initiator and the skilled person is able, with his only knowledge of the field to determine the appropriate temperature. More particularly, the reaction is carried out at a temperature such that the degradation reactions by thermolysis of the reactants and of the products obtained are negligible. As an indication, the reaction is carried out at temperatures below 100 ° C.
• the conversion of the diene compound to the macromonomer is not limited and quantitative conversions of the latter can be achieved without degrading the macromonomer obtained.
• the stabilization of the particles is ensured, if necessary, by any colloidal stabilization system known as anionic, cationic, amphoteric and nonionic emulsifiers.
• the polymerization can be carried out continuously, batchwise or semi-continuously with the introduction of a portion of the monomers continuously and be of the "seeded" or “incremental” type according to any known variant for obtaining particles of homogeneous and heterogeneous structure .
• the compounds of general formulas (I) make it possible to synthesize copolymers having particular structures such as copolymers with grafted or comb structure.
• the graft or comb copolymers are obtained (i) by reacting the macromonomer compounds (I) with at least one ethylenically unsaturated monomer having at least one carboxylic, carboxylate, amine, alcohol or thiol function, then (ii) by radical copolymerizing the macromonomers (I) thus modified with at least one other ethylenically unsaturated monomer.
• Radical polymerization takes place in the presence, generally, of an effective amount of a free radical initiator or initiator.
• a free radical initiator or initiator The lists indicated above concerning the monomers and initiating agents, remain valid and will not be repeated here.
• the relative amounts of monomers and macromonomer compounds used in the second step are variable and depend on the percentage of grafting of the graft copolymer that it is desired to obtain. A person skilled in the art knows how to adapt these relative quantities as a function of the desired result.
• the macromonomer compounds (I) according to the invention can be used to prepare copolymers of comb or graft structure in a simple and effective manner.
• At least one polymer or copolymer is reacted comprising functions capable of reacting with the three-atom ring comprising sulfur, and more particularly oxygen.
• functions of this type mention may be made of polymers or copolymers having at least one carboxylic, carboxylate, amine, alcohol and / or thiol function.
• Such a reaction is generally carried out in the presence of a catalyst such as, for example, a quaternary ammonium salt in the case of the addition of a group to the oxirane ring of the macromonomer.
• a catalyst such as, for example, a quaternary ammonium salt in the case of the addition of a group to the oxirane ring of the macromonomer.
• the macromonomer compounds according to the invention can lead to comb copolymers by carrying out a polymerization by ring opening.
• the reaction can be catalyzed by strong bases, for example sodium methylate, or by Lewis acids, for example BF 3 , (C ⁇ H ⁇ O.
• copolymers obtained by the process of the invention have numerous applications.
• They can for example be used as counting agents in polymer blends, adhesion agents on substrates, dispersing agents, agents for aging resistance and for improving the gloss in polymer coatings.
• gums for example: guar, xanthan, etc.
• associative polymers for example: guar, xanthan, etc.
• sequestering polymers for example: guar, xanthan, etc.
• surface-active polymers for example: elastomeric thermoplastic polymers.
• reaction temperature is kept below 0 ° C.
• reaction mixture is then brought to ambient temperature and filtered.
• the filtrate is concentrated by vacuum evaporation then mixed with 10 ml of water and then extracted with 3 times 30 ml of heptane.
• the organic phases are dried over MgSO4 and then distilled under vacuum to remove the solvent.
• the product is purified by solid liquid chromatography on a silica gel column, by gel permeation.
• the tubes are deaerated and sealed under vacuum.
• the reactions are carried out at 60 ° C. for a time such that the conversion remains below 10%. Thus it is 1 hour for the styrene and methyl methacrylate monomers, and 10 minutes for the butyl acrylate and methyl acrylate monomers.
• the reactions are then stopped by adding hydroquinone and then cooling by immersion of the tubes in an ice and isopropanol bath.
• the resulting polymers are precipitated in heptane or methanol and then dried.
• the conversions of the monomers are measured by gravimetry from the weights of the polymers and from the initial quantity of macromonomer.
• the polymer obtained is precipitated and washed in methanol to remove any trace of remaining reagent.
• the RM N 1 H spectrum of the polymer obtained has the characteristics according to the table below. This NMR spectrum reveals the existence of a vinyloxirane group at the chain end.
• Example 5 Preparation of the macromonomeric polystyrene compounds from the TBPDP of Example 4.
• the 1 H NMR spectrum of the polymer obtained has the same characteristics as those of the polymer of Example 3, which reveal the existence of a vinyloxirane group at the chain end.
• Acetal 3,3-dimethoxy-1-propene is obtained by reaction of 2,4-hexadienal (1.92 g, 0.0020 mole) with trimethyl orthoformate (0.021 mole, 2.23 g) and in the presence of paratoluenesulfonic acid (25 mg, 0.001 mole). Then, to the acetal obtained, the cumyl hydroperoxide (94%, 3.40 g, 0.021 mole) is added dropwise at room temperature.
• the initiator 2,2'-azo-bis-isobutyronitrile (40 g, 2.44.10 ⁇ 4 mole at 60 ° C) is dissolved in distilled MMA (40 ml).
• a fixed volume (5 ml) of this solution is placed in clean, dry Pyrex tubes.
• a solution of 6-cumylperoxy-6-methoxy-2,4-hexadiene (5.10 "4 mole) in MMA (10 ml) is also prepared and a variable amount is added to the various ampoules.
• the polymerization is carried out at seven concentrations in transfer agent different from 0 to 2.5 E-2 mole / l.
• reaction media are degassed three times, then the tubes are sealed under reduced pressure (0.01 mm Hg).
• the polymerizations are carried out at a temperature of 60 ° C., for a period of 60 minutes.
• the transfer constant Ctr measured is 0.09.
• Example 7A The preparation is similar to that of Example 7A, the methyl methacrylate is replaced by styrene.
• a solution of 100 mg of macromonomer prepared in Example 5, 210 mg of methacrylic acid and 35 mg of ethanol in 1 ml of THF is heated at 60 ° C for 1 hour. After addition of 2 ml of THF, the polymers are precipitated in 50 ml of methanol, and they are recovered after filtration on a frit and drying under vacuum.

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• 1996
  • 1996-01-17 FR FR9600466A patent/FR2743563B1/fr not_active Expired - Fee Related
• 1997
  • 1997-01-15 WO PCT/FR1997/000067 patent/WO1997026282A1/fr not_active Application Discontinuation
  • 1997-01-15 AU AU13138/97A patent/AU1313897A/en not_active Abandoned
  • 1997-01-15 JP JP9525738A patent/JP2000503696A/ja active Pending
  • 1997-01-15 EP EP97900647A patent/EP0874865A1/fr not_active Ceased

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