EP3601293A1 - Acrylic derivatives of 1,4:3,6-dianhydrohexitol - Google Patents

Acrylic derivatives of 1,4:3,6-dianhydrohexitol

Info

Publication number
EP3601293A1
EP3601293A1 EP18722094.2A EP18722094A EP3601293A1 EP 3601293 A1 EP3601293 A1 EP 3601293A1 EP 18722094 A EP18722094 A EP 18722094A EP 3601293 A1 EP3601293 A1 EP 3601293A1
Authority
EP
European Patent Office
Prior art keywords
diisocyanate
formula
branched
compound
compound according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18722094.2A
Other languages
German (de)
French (fr)
Inventor
Clothilde Buffe
Jean-Marc Corpart
Vincent Wiatz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roquette Freres SA
Original Assignee
Roquette Freres SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Roquette Freres SA filed Critical Roquette Freres SA
Publication of EP3601293A1 publication Critical patent/EP3601293A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C08F220/365—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate containing further carboxylic moieties

Definitions

  • the invention relates to novel acrylic derivatives of 1: 4, 3: 6 dianhydrohexitol which are particularly useful for the manufacture of polymers.
  • compositions for making polymers for example in the form of bulk materials or coatings. In the latter case, it may be for example protective coatings, decorative, or surface treatment.
  • crosslinkable compositions for this use in the literature and in commerce. These compositions consist for the most part of a mixture of polymerizable monomers manufactured by the chemical industry from petroleum derivatives.
  • the polymers can either be dissolved or suspended with a crosslinking agent, then applied to the substrate, and finally crosslinked after evaporation of the solvent, either deposited by standard "powder coating” techniques, or melted to be deposited. In all cases, these deposition techniques require a post-crosslinking step. The fact that the realization of the coating requires several successive steps is binding.
  • di (meth) acrylic derivatives of isosorbide as crosslinked monomers has been proposed. The acrylate and methacrylate derivatives of isosorbide have been described for the first time by Wiggins et al. in 1946 (GB 586141).
  • Patent application WO 2014/147340 A1 in the name of the Applicant describes crosslinkable compositions comprising isosorbide diacrylate or isosorbide dimethacrylate.
  • Patent application WO 2015/004381 A1 also in the name of the Applicant, described by an isosorbide caprolactate diacrylate which would be useful in the manufacture of polymers.
  • These diacrylates and isosorbide dimethacrylate have the disadvantage that the resins obtained therewith have a high degree of crosslinking which results in brittle coatings.
  • Isosorbide mono (meth) acrylate derivatives whose second hydroxyl function is substituted or not are also known.
  • the patent application US 2016/0139526 A1 for example describes resins based on (meth) acrylate isosorbide and their use in toner compositions, this (methacrylate) may be monosubstituted.
  • the patent application US 2013/0017484 relates to monoacrylate derivatives of very specific isosorbide whose second hydroxyl group is substituted by an acid-labile group or an acetal function. These compounds are useful for the preparation of polymers transparent to radiation ⁇ 500 nm.
  • One of the objectives of the present invention is to provide novel mono (meth) acrylate derivatives of 1: 4, 3: 6 dianhydrohexitol.
  • R 1 is a linear or branched C 1 -C 6 alkyl group
  • R 2 is H or C 1 or C 2 alkyl
  • L is O, -OCH 2 -CH (OH) -CH 2 -O-, -O-C (O) -NH-L 1 -O- where L 1 is selected from alkylene, linear or branched, or -O- C (O) -NH-L 2 -O-L 3 -O- where -OC (O) -NH-L 2 - is a residue of a reagent selected from isophorone diisocyanate (IPDI), isocyanurate d IPDI, polymeric IPDI, 1,5-naphthalene diisocyanate (NDI), methylene bis-cyclohexyl isocyanate, methylene diphenyl diisocyanate (MDI), polymeric MDI, toluene diisocyanate (TDI), TDI isocyanurate , the adduct of TDI-trimethylolpropane, polymeric TDI, hexamethylene diisocyanate (HD
  • Preferred compounds of formulas I are those in which one, more or even each of R 1 , R 2 is L is defined as follows:
  • R 1 is a linear or branched C 1 to C 4 alkyl group, preferably R 1 is methyl or ethyl, more preferably R 1 is methyl;
  • R 2 is H or methyl
  • L is O, -O-CH 2 -CH (OH) -CH 2 -O-, -O-C (O) -NH-L 1 -O- where L 1 is selected from C 2 -C 4 alkylene, linear or branched, or -O-C (O) -NH-L 2 -O-L 3 -O- where -O-C (O) -NH-L 2 - is a residue of a reagent selected from isophorone diisocyanate (IPDI), IPDI isocyanurate, polymeric IPDI, 1,5-naphthalene diisocyanate (NDI), methylene bis-cyclohexylisocyanate, methylene diphenyl diisocyanate (MDI), polymeric MDI, toluene diisocyanate (TDI), TDI isocyanaurate, TDI-trimethylolpropane adduct, polymeric TDI, hexamethylene diiso
  • the compounds of formula I described above exist in different conformations due to the presence of the 1: 4, 3: 6 dianhydrohexitol nucleus.
  • the compounds of formula I may be derivatives of isosorbide (1: 4, 3: 6 dianhydro-D-glucidol), isoidide (1: 4, 3: 6 dianhydro-L-iditol) or isomannide (1: 4, 3: 6 dianhydro-D-mannitol).
  • the present invention therefore covers the compounds of formulas Ia, Ib, Ia and Id:
  • the compound of formula I is selected from compounds according to formula Ia, Ib and mixtures thereof.
  • the compound of formula I has formula II:
  • R 1 and R 2 are as defined above with respect to formula I.
  • R 2 is methyl.
  • the compound of formula II may be chosen from compounds of formula IIa, IIb and IIe
  • R 1 and R 2 are as defined above with respect to formula II, as well as among their mixtures.
  • the compound of formula II is selected from compounds according to formula IIa, Mb and mixtures thereof.
  • the compound of formula I has formula III:
  • R 2 is methyl
  • the compound of formula III may be chosen from the compounds of formula Nia, IIIb and II and
  • R 1 and R 2 are as defined above with respect to formula III.
  • the compound of formula III is chosen from the compounds according to formula Nia, IIIb or mixtures thereof.
  • the compound according to the invention is a compound according to one of the formulas defined above in which, when L is O, R 1 can not be a C 4 to C 6 tertiary alkyl group, especially -butyl and / or when L is O and R 2 is H, R 1 can not be methylated.
  • the compounds of the invention may be prepared according to synthesis methods known to those skilled in the art. They may for example be prepared by a two-step synthesis process starting from 1: 4, 3: 6 dianhydrohexitol comprising a first step of protecting a hydroxyl group of 1: 4, 3: 6 dianhydrohexitol with an ether function and a second step of functionalization of the other hydroxyl group by an acrylate function.
  • the compounds of formula I may be prepared by a process comprising the following steps: a) preparation of a linear or branched C1 to C6 aliphatic monoether of 1: 4, 3: 6 dianhydrohexitol by reacting 1 : 4, 3: 6 dianhydrohexitol with an alkylating agent;
  • step b) functionalization of the free hydroxyl group of the monoether obtained in step a) with an acrylate, methacrylate, epoxy-acrylate, epoxy-methacrylate, isocyanate-acrylate or isocyanate-methacrylate function.
  • the 1: 4, 3: 6 dianhydrohexitol may be chosen from isosorbide (1: 4, 3: 6 dianhydro-D-glucidol), isoidide (1: 4, 3: 6 dianhydro-L-iditol) and isomannide (1: 4, 3: 6 dianhydro-D-mannitol).
  • the preferred 1: 4, 3: 6 dianhydrohexitol is isosorbide.
  • a compound of formula la, Ib or a mixture of the two is obtained. In the case where a mixture of compounds of formulas Ia and Ib, this mixture can be separated by the techniques known to those skilled in the art, for example by column chromatography.
  • the preparation of the monoether in step a) can be carried out according to the methods known to those skilled in the art, for example starting from 1: 4, 3: 6 dianhydrohexitol and a linear to linear C 1 to C 6 alkylating agent. branched.
  • the linear or branched C1-C6 alkyl residue of the alkylating agent is advantageously chosen from linear or branched C1-C4 alkyl radicals, preferably from methyl and ethyl.
  • the rest alkyl is methyl. Examples of etherification reactions that can be used are described in patent applications WO2014023902 A1, WO 2014/168698 A1 and WO 2016/156505 A1.
  • the alkylating agent may especially be chosen from C1 to C6 linear or branched aliphatic alcohols, linear or branched C1 to C6 aliphatic alkyl halides, linear or branched C1 to C6 aliphatic esters of sulfuric acids. linear or branched C1 to C6 aliphatic dialkylcarbonates or linear or branched C1 to C6 aliphatic dialkoxymethans.
  • the C1-C6 alkyl radicals are advantageously chosen from linear or branched C1-C4 alkyl radicals, preferably from methyl and ethyl radicals. More preferably, the alkyl radical is methyl.
  • the alcohols that can be used as alkylating agent include, in particular, methanol, ethanol, isopropanol and f-butanol, methanol being preferred.
  • the alkyl halides that can be used as alkylating agents include, in particular, methyl, ethyl, isopropyl and n-butyl halides, with methyl halides being preferred.
  • the linear or branched C 1 to C 6 aliphatic esters of sulfuric acids may, for example, be chosen from methyl, ethyl, isopropyl and t-butyl esters, methyl esters, in particular dimethyl sulphate, being preferred.
  • the dialkyl carbonates may for example be selected from dimethyl carbonate, diethyl carbonate, diisopropyl carbonate and di-t-butyl carbonate, dimethyl carbonate being preferred.
  • the dialkoxymethanes that can be used as alkylating agent include dimethoxymethane, diethoxymethane, diisopropoxymethane and di-t-butoxymethane, dimethoxymethane being preferred.
  • the 1: 4, 3: 6 dianhydrohexitol may be chosen from isosorbide (1: 4, 3: 6 dianhydro-D-glucidol), isoidide (1: 4, 3: 6 dianhydro-L-iditol) and isomannide (1: 4, 3: 6 dianhydro-D-mannitol).
  • the preferred 1: 4, 3: 6 dianhydrohexitol is isosorbide.
  • the 1: 4, 3: 6 dianhydrohexitol isosorbide, is obtained at the end of step b) a compound of formula la, Ib (or subformula Ma and Mb or Nia and Mb) or a mixture both.
  • this mixture can be separated by the techniques known to those skilled in the art, for example by column chromatography.
  • step a) a mixture of monoalkyl ether, dialkyl ether and dianhydrohexitol is generally obtained which can be used directly in step b) or the mixture can be separated by distillation with rectification under reduced pressure before step b ).
  • step b) the free hydroxyl group is functionalized with an acrylate, methacrylate, epoxy-acrylate, epoxy-methacrylate, isocyanate-acrylate or isocyanate-methacrylate function, preferably with an acrylate, methacrylate, epoxy-acrylate or epoxy function. methacrylate.
  • the functionalization of the free hydroxyl group by an acrylate, methacrylate, epoxy-acrylate, epoxy-methacrylate, isocyanate-acrylate or isocyanate-methacrylate function can be carried out according to the methods known to those skilled in the art. It is possible, for example, to use acrylic and methacrylic acids, acrylic and methacrylic acid esters, acrylic and methacrylic anhydrides, glycidyl acrylate, glycidyl methacrylate, alkyl isocyanate acrylates and methacrylates, or diisocyanates with hydroxyalkyl acrylates or hydroxyalkyl methacrylates.
  • the free hydroxyl group When the free hydroxyl group is functionalized with an acrylate or methacrylate function, compounds of formula II are obtained.
  • the free hydroxyl group can be reacted with acrylic or methacrylic acid, an acrylic or methacrylic acid ester, or an acrylic or methacrylic anhydride,
  • the hydroxyl group may also be functionalized with an isocyanate-acrylate or isocyanate-methacrylate function.
  • the free hydroxyl group can be reacted with a linear or branched alkylisocyanate acrylate or methacrylate, especially C 2 -C 4, preferably with an acrylate or ethylisocyanate methacrylate. It is also possible to proceed in two stages by first reacting the free hydroxyl group with a diisocyanate and then reacting the product thus obtained with a hydroxyalkyl acrylate, a hydroxyalkyl methacrylate, a poly (propylene glycol) acrylate or a poly (propylene glycol) methacrylate. .
  • diisocyanate as used herein is meant a compound comprising at least two isocyanate functional groups.
  • This diisocyanate may, for example, be chosen from isophorone diisocyanate (IPDI), IPDI isocyanurate, polymeric IPDI, 1,5-naphthalene diisocyanate (NDI), methylene bis-cyclohexylisocyanate and methylene diphenyl diisocyanate.
  • MDI polymeric MDI, toluene diisocyanate
  • TDI TDI isocyanurate
  • TDI-trimethylolpropane adduct polymer TDI
  • HDI hexamethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • HDI hexamethylene diisocyanurate
  • HDI biurate polymeric HDI
  • xylylene diisocyanate hydrogenated xylylene diisocyanate
  • tetramethyl xylylene diisocyanate 7-phenylene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate (DDDI), 2,2 , 4-trimethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NDI) and 4,4'-dibenzyl diisocyanate (DBDI),
  • the compounds of the invention can be used for the preparation of thermoplastic acrylic resins.
  • they may partially or completely replace the methylmethacrylate in polymers of the PMMA (polymethylmethacrylate) type, better known under the name of PLEXIGLAS®.
  • PMMA polymethylmethacrylate
  • They can be used alone or in combination with many other monomers capable of integrating into a radical polymerization process, for example acrylic and methacrylic monomers, (methyl methacrylate, butyl acrylate, glycidyl methacrylate, etc.). styrene and vinyl acetate.
  • these resins can then be used to produce films or materials that can be used in the field of coatings (paint, ink, etc.) adhesives, dental prostheses, optical materials, excipients for pharmacy, etc.
  • thermosetting resins can also be used as reactive diluent and / or flexibilizing agent in the preparation of thermosetting resins in combination optionally with other monomers and in particular mono and / or multifunctional acrylates and / or styrene.
  • the medium is brought to 95 ° C. and then 172.4 g of sodium hydroxide are introduced in 2 hours using a peristaltic pump. The reaction medium is then stirred at 95 ° C. for at least 3 hours.
  • the product After filtration and concentration on a rotary evaporator, the product is obtained in liquid form, contains 19.7% of isosorbide, 20.5% of 5-O-monomethylether of isosorbide A (MMI A- functionalization in the endo position), 24 , 8% isosorbide 2-O-monomethyl ether (MMI B - functionalization in the exo position) and 25% isosorbide dimethyl ether (DMI).
  • the percentages correspond to mass percentages measured by NMR analysis.
  • the medium is brought to 95 ° C. and then 172.4 g of sodium hydroxide are introduced in 2 hours using a peristaltic pump.
  • the reaction medium is then stirred at 95 ° C. for at least 3 hours. After filtration and concentration on a rotary evaporator, the product is obtained in liquid form, contains 18% of isosorbide, 21.4% of 5-O-monoethylether of isosorbide (MEI A), 26.2% of 2-O- isosorbide monoethyl ether (MEI B) and 25.6% isosorbide diethyl ether (IED). The percentages correspond to mass percentages measured by NMR analysis.
  • Example? Monomethylsiloxane solution of 1641.9 g of the product obtained according to Example 1 is introduced into a jacketed reactor of 2L surmounted by a rectification column, a reflux head, a condenser and recovery recipes.
  • the grinding column is filled with 10 Sulzer type EX packing elements.
  • the assembly is put under reduced pressure (15m Bar) and the product is heated at 150 ° C under total reflux until stabilization of the temperatures at the top of the column.
  • the acid number is 19 mg KOH / g of crude.
  • the product is purified by liquid-liquid extraction. A first wash with a 6% sodium hydroxide solution is carried out and then 2 washes with water. The organic phase is dried using anhydrous magnesium sulphate, filtered and concentrated using a rotary evaporator after adding 10 mg of hydroquinone monomethyl ether.
  • Example 6 synthesis of isosorbide monomethyl methacrylate (mixture A and B)
  • reaction medium is then stirred at room temperature for at least 6 hours.
  • reaction medium is filtered and then purified by successive washings with saturated aqueous NaHCO 3 solution, NaOH (1M) and NaCl.
  • the organic phase is dried using anhydrous magnesium sulphate, filtered and concentrated on a rotary evaporator after addition of 10 mg of hydroquinone monomethyl ether.
  • the product obtained is a slightly colored liquid.
  • the structure is confirmed by NMR analysis with a mass purity greater than 85%.
  • reaction medium is heated at 75 ° C. and kept stirring for at least 4 hours. 21.4 g of 2-hydroxyethyl methacrylate are then introduced and the medium is stirred for at least 3 h at 60 ° C.
  • the reaction is monitored by NMR analysis.
  • the medium is purified by liquid / liquid water / dichloromethane extraction.
  • the organic phase is then dried using magnesium sulfate anhydride and concentrated in a rotavapor.
  • the crude product is then purified by chromatography on a silica column (eluent ethyl acetate / cyclohexane).
  • the product obtained is a slightly colored liquid.
  • the structure is confirmed by NMR analysis.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a compound of formula (I), the production thereof and the use of same as a monomer in the production of polymers.

Description

DÉRIVÉS ACRYLIQUES DE 1 ,4:3,6-DIANHYDROHEXITOL  ACRYLIC DERIVATIVES OF 1, 4: 3,6-DIANHYDROHEXITOL
Domaine de l'Invention Field of the Invention
L'invention a pour objet de nouveaux dérivés acryliques de 1 :4, 3 :6 dianhydrohexitol qui sont notamment utiles pour la fabrication de polymères. The invention relates to novel acrylic derivatives of 1: 4, 3: 6 dianhydrohexitol which are particularly useful for the manufacture of polymers.
Etat de la technique State of the art
De nombreuses industries ont besoin de compositions permettant de fabriquer des polymères, par exemple sous forme de matériaux massifs ou de revêtements. Dans ce dernier cas, il peut s'agir par exemple de revêtements protecteurs, décoratifs, ou de traitement de surface. Il existe déjà un grand nombre de compositions réticulables pour cet usage dans la littérature et dans le commerce. Ces compositions consistent pour la plupart en un mélange de monomères polymérisables fabriqués par l'industrie chimique à partir de dérivés du pétrole. Many industries require compositions for making polymers, for example in the form of bulk materials or coatings. In the latter case, it may be for example protective coatings, decorative, or surface treatment. There are already a large number of crosslinkable compositions for this use in the literature and in commerce. These compositions consist for the most part of a mixture of polymerizable monomers manufactured by the chemical industry from petroleum derivatives.
Cependant, dans le contexte actuel de la diminution progressive des ressources en produits pétroliers, il est de plus en plus intéressant de remplacer les produits d'origine pétrolière par des produits d'origine naturelle. However, in the current context of the gradual decline in petroleum product resources, it is increasingly interesting to replace products of petroleum origin with products of natural origin.
L'utilisation de polymères biosourcés, c'est-à-dire réalisés à partir de matières premières d'origine naturelle, a déjà été décrite. En particulier, la publication de L. Jasinska et de C. E. Koning (« Unsaturated, biobased polyesters and their cross-linking via radical copolymerization », Journal of Polymer Science Part A: Polymer Chemistry, Volume 48, Issue 13, pages 2885-2895, 1 Juillet 2010) décrit la préparation de polyesters insaturés ayant des températures de transition vitreuse (Tg) relativement élevées, i.e. supérieures à 45°C, ces polyesters étant particulièrement utiles à la fabrication de revêtements. Ces polyesters insaturés sont obtenus par polymérisation d'isosorbide avec de l'anhydride maléique et optionnellement de l'acide succinique. Pour pouvoir être utilisés en tant que revêtement, ces polyesters insaturés doivent cependant être réticulés. Les polymères peuvent soit être mis en solution ou en suspension avec un agent réticulant, puis appliqués sur le substrat, et enfin réticulés après évaporation du solvant, soit déposés par des techniques usuelles de type « powder coating », soit fondus pour être déposés. Dans tous les cas, ces techniques de dépôt nécessitent une étape de post-réticulation. Le fait que la réalisation du revêtement nécessite plusieurs étapes successives est contraignant. Pour surmonter ces inconvénients, l'utilisation de dérivés di(méth)acryliques d'isosorbide en tant que monomères réticu labiés a été proposée. Les dérivés acrylates et méthacrylates d'isosorbide ont été décrit pour la première fois par Wiggins et al. en 1946 (GB 586141 ).La demande de brevet WO 2014/147340 A1 au nom de la Demanderesse décrit des compositions réticulables comprenant du diacrylate d'isosorbide ou du diméthacrylate d'isosorbide. La demande de brevet WO 2015/004381 A1 , également au nom de la Demanderesse, décrit par un diacrylate de caprolactate d'isosorbide qui serait utile dans la fabrication de polymères. Ces diacrylates et diméthacrylate d'isosorbide présentent toutefois l'inconvénient que les résines obtenues avec ceux-ci ont un haut degré de réticulation ce qui résulte en des revêtements cassants. The use of biosourced polymers, that is to say made from raw materials of natural origin, has already been described. In particular, the publication of L. Jasinska and CE Koning ("Unsaturated, biobased polyesters and their cross-linking via radical copolymerization", Journal of Polymer Science Part A: Polymer Chemistry, Volume 48, Issue 13, pages 2885-2895, 1 July 2010) describes the preparation of unsaturated polyesters having relatively high glass transition temperatures (T g ), ie above 45 ° C, these polyesters being particularly useful in the manufacture of coatings. These unsaturated polyesters are obtained by polymerization of isosorbide with maleic anhydride and optionally succinic acid. To be used as a coating, however, these unsaturated polyesters must be crosslinked. The polymers can either be dissolved or suspended with a crosslinking agent, then applied to the substrate, and finally crosslinked after evaporation of the solvent, either deposited by standard "powder coating" techniques, or melted to be deposited. In all cases, these deposition techniques require a post-crosslinking step. The fact that the realization of the coating requires several successive steps is binding. To overcome these drawbacks, the use of di (meth) acrylic derivatives of isosorbide as crosslinked monomers has been proposed. The acrylate and methacrylate derivatives of isosorbide have been described for the first time by Wiggins et al. in 1946 (GB 586141). The patent application WO 2014/147340 A1 in the name of the Applicant describes crosslinkable compositions comprising isosorbide diacrylate or isosorbide dimethacrylate. Patent application WO 2015/004381 A1, also in the name of the Applicant, described by an isosorbide caprolactate diacrylate which would be useful in the manufacture of polymers. These diacrylates and isosorbide dimethacrylate, however, have the disadvantage that the resins obtained therewith have a high degree of crosslinking which results in brittle coatings.
On connaît également des dérivés mono(méth)acrylates d'isosorbide dont la deuxième fonction hydroxyle est substitué ou non. La demande de brevet US 2016/0139526 A1 décrit par exemple des résines à base de (méth)acrylate d'isosorbide et leur utilisation dans des composition de toner, ce (méthacrylate) pouvant être monosubstitué. La demande de brevet US 2013/0017484 porte sur des dérivés monoacrylates d'isosorbide très spécifique dont le deuxième groupement hydroxyle est substitué par un groupement labile vis-à-vis des acides ou une fonction acétal. Ces composés sont utiles pour la préparation de polymères transparents à la radiation < 500 nm. Isosorbide mono (meth) acrylate derivatives whose second hydroxyl function is substituted or not are also known. The patent application US 2016/0139526 A1 for example describes resins based on (meth) acrylate isosorbide and their use in toner compositions, this (methacrylate) may be monosubstituted. The patent application US 2013/0017484 relates to monoacrylate derivatives of very specific isosorbide whose second hydroxyl group is substituted by an acid-labile group or an acetal function. These compounds are useful for the preparation of polymers transparent to radiation <500 nm.
La demande de brevet US 2016/0229863 A1 et l'article de Gallagher et al. (ACS Sustainable Chem. Eng. 2015, 3, 662-667) décrivent la synthèse de dérivés monoacétate monométhacrylate d'isosorbide. Ils sont préparés via réaction entre le monoacétate d'isosorbide et l'anhydride méthacrylique en présence de triflate de scandium. Les produits, purifiés par chromatographie sur colonne, sont des liquides visqueux. Aucune différence significative n'a été observé entre les deux isomères monoacétates exo et endo. La polymérisation de ces monomères a conduit à des matériaux ayant une température de transition vitreuse (Tg) élevée (130 °C) et une stabilité thermique similaire au PMMA. U.S. Patent Application 2016/0229863 A1 and the article by Gallagher et al. (ACS Sustainable Chem Eng., 2015, 3, 662-667) describe the synthesis of isosorbide monoacetate monomethacrylate derivatives. They are prepared by reaction between isosorbide monoacetate and methacrylic anhydride in the presence of scandium triflate. The products, purified by column chromatography, are viscous liquids. No significant difference was observed between the two exo and endo monoacetate isomers. Polymerization of these monomers resulted in materials having a high glass transition temperature (Tg) (130 ° C) and a thermal stability similar to PMMA.
Un des objectifs de la présente invention est de proposer de nouveaux dérivés mono(méth)acrylates de 1 :4, 3 :6 dianhydrohexitol. One of the objectives of the present invention is to provide novel mono (meth) acrylate derivatives of 1: 4, 3: 6 dianhydrohexitol.
Résumé de l'invention Ainsi, l'invention a pour objet un composé de formule I : (I)SUMMARY OF THE INVENTION Thus, the subject of the invention is a compound of formula I: (I)
dans laquelle in which
R1 est un groupement alkyle en C1 à C6, linéaire ou ramifié, R2 est H ou alkyle en C1 ou C2, R 1 is a linear or branched C 1 -C 6 alkyl group, R 2 is H or C 1 or C 2 alkyl,
L est O, -OCH2-CH(OH)-CH2-0-, -0-C(0)-NH-L1-0- où L1 est choisi parmi alkylène, linéaire ou ramifié, ou -0-C(0)-NH-L2-0-L3-0- où -O-C(0)-NH-L2- est un résidu d'un réactif choisi parmi l'isophorone diisocyanate (IPDI), l'isocyanaurate d'IPDI, de l'IPDI polymère, le 1 ,5- naphthalène diisocyanate (NDI), le méthylène bis-cyclohexylisocyanate, le méthylène diphényl diisocyanate (MDI), du MDI polymère, le toluène diisocyanate (TDI), l'isocyanaurate de TDI, l'adduct de TDI- triméthylolpropane, du TDI polymérique, l'hexaméthylène diisocyanate (HDI), HDI isocyanaurate, HDI biurate, du HDI polymère, xylylène diisocyanate, du xylylène diisocyanate hydrogéné, le tetraméthyl xylylène diisocyanate, /7-phenylene diisocyanate, le 3,3'- diméthyldiphényl-4,4' -diisocyanate (DDDI), le 2,2,4-triméthylhexaméthylène diisocyanate (TMDI), le norbornane diisocyanate (NDI) et le 4,4'-dibenzyl diisocyanate (DBDI), et L3 est choisi parmi alkylène , linéaire ou ramifié, et poly(propylèneglycol). L is O, -OCH 2 -CH (OH) -CH 2 -O-, -O-C (O) -NH-L 1 -O- where L 1 is selected from alkylene, linear or branched, or -O- C (O) -NH-L 2 -O-L 3 -O- where -OC (O) -NH-L 2 - is a residue of a reagent selected from isophorone diisocyanate (IPDI), isocyanurate d IPDI, polymeric IPDI, 1,5-naphthalene diisocyanate (NDI), methylene bis-cyclohexyl isocyanate, methylene diphenyl diisocyanate (MDI), polymeric MDI, toluene diisocyanate (TDI), TDI isocyanurate , the adduct of TDI-trimethylolpropane, polymeric TDI, hexamethylene diisocyanate (HDI), HDI isocyanurate, HDI biurate, HDI polymer, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, 7-phenylene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate (DDDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NDI) and 4,4'-dibenzyl diisocyanate (DBDI), and L3 is selected from alkylene, linear or branched and poly (propylene glycol).
Description détaillée de l'Invention Detailed description of the invention
Des composés préférés de formules I sont ceux dans lesquelles un, plusieurs, voire chacun de R1, R2 est L est défini de manière suivante : Preferred compounds of formulas I are those in which one, more or even each of R 1 , R 2 is L is defined as follows:
R1 est un groupement alkyle en C1 à C4, linéaire ou ramifié, de préférence R1 est méthyle ou éthyle, de préférence encore R1 est méthyle ; R 1 is a linear or branched C 1 to C 4 alkyl group, preferably R 1 is methyl or ethyl, more preferably R 1 is methyl;
R2 est H ou méthyle ; R 2 is H or methyl;
L est O, -0-CH2-CH(OH)-CH2-0-, -0-C(0)-NH-L1-0- où L1 est choisi parmi alkylène en C2 à C4, linéaire ou ramifié, ou -0-C(0)-NH-L2-0-L3-0- où -0-C(0)-NH-L2- est un résidu d'un réactif choisi parmi l'isophorone diisocyanate (IPDI), l'isocyanaurate d'IPDI, de l'IPDI polymère, le 1 ,5-naphthalène diisocyanate (NDI), le méthylène bis-cyclohexylisocyanate, le méthylène diphényl diisocyanate (MDI), du MDI polymère, le toluène diisocyanate (TDI), l'isocyanaurate de TDI, l'adduct de TDI- triméthylolpropane, du TDI polymère, l'hexaméthylène diisocyanate (HDI), HDI isocyanaurate, HDI biurate, du HDI polymère, xylylène diisocyanate, du xylylène diisocyanate hydrogéné, le tetraméthyl xylylène diisocyanate, /7-phenylene diisocyanate, le 3,3'- diméthyldiphényl-4,4' -diisocyanate (DDDI), le 2,2,4-triméthylhexaméthylène diisocyanate (TMDI), le norbornane diisocyanate (NDI) et le 4,4'-dibenzyl diisocyanate (DBDI), et L3 est choisi parmi alkylène, linéaire ou ramifié, de préférence en C2 à C4, et poly(propylèneglycol), de préférence L est O, -0-CH2-CH(OH)-CH2-0- ou -C(0)-NH-L1-0- où L1 est alkylène en C2 à C4, linéaire ou ramifié, de préférence encore L est O, -O-CH2- CH(OH)-CH2-0- ou -0-C(0)-NH-(CH2)2-0-, et plus préférentiellement encore L est O ou -O- CH2-CH(OH)-CH2-0-. L is O, -O-CH 2 -CH (OH) -CH 2 -O-, -O-C (O) -NH-L 1 -O- where L 1 is selected from C 2 -C 4 alkylene, linear or branched, or -O-C (O) -NH-L 2 -O-L 3 -O- where -O-C (O) -NH-L 2 - is a residue of a reagent selected from isophorone diisocyanate (IPDI), IPDI isocyanurate, polymeric IPDI, 1,5-naphthalene diisocyanate (NDI), methylene bis-cyclohexylisocyanate, methylene diphenyl diisocyanate (MDI), polymeric MDI, toluene diisocyanate (TDI), TDI isocyanaurate, TDI-trimethylolpropane adduct, polymeric TDI, hexamethylene diisocyanate (HDI), HDI isocyanaurate, HDI biurate, HDI polymer, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, 7-phenylene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate (DDDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NDI) and 4,4'-dibenzyl diisocyanate (DBDI), and L3 is selected from alkylene, linear or branched, preferably C2 to C4, and poly (propylene glycol), preferably L is O, -O-CH 2 -CH (OH) -CH 2 -O- or -C (O) -NH-L 1 -O- where L 1 is C 2 -C 4 alkylene, linear or branched, more preferably L is O, -O-CH 2 -CH (OH) -CH 2 -O- or -O-C (O) -NH- (CH 2 ) 2 -O-, and even more preferably L is O or -O - CH 2 -CH (OH) -CH 2 -O-.
Les composés de formule I décrits ci-dessus existent sous différentes conformations en raison de la présence du noyau 1 :4, 3 :6 dianhydrohexitol. Ainsi, les composés de formule I peuvent être des dérivés d'isosorbide (1 :4, 3 :6 dianhydro-D-glucidol), d'isoidide (1 :4, 3 :6 dianhydro-L-iditol) ou d'isomannide (1 :4, 3 :6 dianhydro-D-mannitol). La présente invention couvre donc les composés de formules la, Ib, le et Id : The compounds of formula I described above exist in different conformations due to the presence of the 1: 4, 3: 6 dianhydrohexitol nucleus. Thus, the compounds of formula I may be derivatives of isosorbide (1: 4, 3: 6 dianhydro-D-glucidol), isoidide (1: 4, 3: 6 dianhydro-L-iditol) or isomannide (1: 4, 3: 6 dianhydro-D-mannitol). The present invention therefore covers the compounds of formulas Ia, Ib, Ia and Id:
(la), dans lesquelles R1, R2 et L sont tels que définis ci-dessus par rapport à la formule I, ainsi que parmi leurs mélanges. De préférence le composé de formule I est choisi parmi les composés selon la formule la, Ib et leurs mélanges. (the), in which R 1 , R 2 and L are as defined above with respect to formula I, as well as among their mixtures. Preferably the compound of formula I is selected from compounds according to formula Ia, Ib and mixtures thereof.
Dans un mode de réalisation, le composé de formule I répond à la formule II : In one embodiment, the compound of formula I has formula II:
(II) dans laquelle R1 et R2 sont tels que définis ci-dessus par rapport à la formule I. De préférence, R2 est méthyle. (II) wherein R 1 and R 2 are as defined above with respect to formula I. Preferably, R 2 is methyl.
Le composé de formule II peut être choisi parmi les composés de formule lia, llb et Ile The compound of formula II may be chosen from compounds of formula IIa, IIb and IIe
(lld), dans lesquelles R1 et R2 sont tels que définis ci-dessus par rapport à la formule II, ainsi que parmi leurs mélanges. De préférence le composé de formule II est choisi parmi les composés selon la formule lia, Mb et leurs mélanges. (IId), wherein R 1 and R 2 are as defined above with respect to formula II, as well as among their mixtures. Preferably the compound of formula II is selected from compounds according to formula IIa, Mb and mixtures thereof.
Dans un autre mode de réalisation, le composé de formule I répond à la formule III : In another embodiment, the compound of formula I has formula III:
dans laquelle R1 et R2 sont tels que définis ci-dessus par rapport à la formule I. in which R 1 and R 2 are as defined above with respect to formula I.
De préférence, R2 est méthyle. Preferably, R 2 is methyl.
Le composé de formule III peut être choisi parmi les composés de formule Nia, lllb et II le et  The compound of formula III may be chosen from the compounds of formula Nia, IIIb and II and
dans lesquelles R1 et R2 sont tels que définis ci-dessus par rapport à la formule III. De préférence le composé de formule III est choisi parmi les composés selon la formule Nia, lllb ou leurs mélanges. in which R 1 and R 2 are as defined above with respect to formula III. Preferably, the compound of formula III is chosen from the compounds according to formula Nia, IIIb or mixtures thereof.
Selon un mode de réalisation, le composé selon l'invention est un composé selon l'une des formules définies ci-dessus dans lequel, quand L est O, R1 ne peut pas être un groupement alkyle tertiaire en C4 à C6, notamment f-butyl et/ou quand L est O et R2 est H, R1 ne peut pas être méthyle. According to one embodiment, the compound according to the invention is a compound according to one of the formulas defined above in which, when L is O, R 1 can not be a C 4 to C 6 tertiary alkyl group, especially -butyl and / or when L is O and R 2 is H, R 1 can not be methylated.
Les composés de l'invention peuvent être préparés selon des modes de synthèse connus de l'homme du métier. Ils peuvent par exemple être préparés par un procédé de synthèse en deux étapes à partir de 1 :4, 3 :6 dianhydrohexitol comprenant une première étape de protection d'un groupement hydroxyle du 1 :4, 3 :6 dianhydrohexitol par une fonction éther et une deuxième étape de fonctionnalisation de l'autre groupement hydroxyle par une fonction acrylate. The compounds of the invention may be prepared according to synthesis methods known to those skilled in the art. They may for example be prepared by a two-step synthesis process starting from 1: 4, 3: 6 dianhydrohexitol comprising a first step of protecting a hydroxyl group of 1: 4, 3: 6 dianhydrohexitol with an ether function and a second step of functionalization of the other hydroxyl group by an acrylate function.
Plus particulièrement, les composés de formule I peuvent être préparés par un procédé comprenant les étapes suivantes : a) préparation d'un monoéther aliphatique en C1 à C6, linéaire ou ramifié, de 1 :4, 3 :6 dianhydrohexitol en faisant réagir du 1 :4, 3 :6 dianhydrohexitol avec un agent d'alkylation ; More particularly, the compounds of formula I may be prepared by a process comprising the following steps: a) preparation of a linear or branched C1 to C6 aliphatic monoether of 1: 4, 3: 6 dianhydrohexitol by reacting 1 : 4, 3: 6 dianhydrohexitol with an alkylating agent;
b) fonctionnalisation du groupement hydroxyle libre du monoéther obtenu à l'étape a) par une fonction acrylate, méthacrylate, époxy-acrylate, époxy-méthacrylate, isocyanate-acrylate, ou isocyanate-méthacrylate.  b) functionalization of the free hydroxyl group of the monoether obtained in step a) with an acrylate, methacrylate, epoxy-acrylate, epoxy-methacrylate, isocyanate-acrylate or isocyanate-methacrylate function.
Le 1 :4, 3 :6 dianhydrohexitol peut être choisi parmi l'isosorbide (1 :4, 3 :6 dianhydro-D- glucidol), l'isoidide (1 :4, 3 :6 dianhydro-L-iditol) et l'isomannide (1 :4, 3 :6 dianhydro-D- mannitol). Le 1 :4, 3 :6 dianhydrohexitol préféré est l'isosorbide. Lorsque le 1 :4, 3 :6 dianhydrohexitol est l'isosorbide, on obtient à l'issue de l'étape b) un composé de formule la, Ib ou un mélange des deux., Dans le cas où on obtient un mélange de composés de formules la et Ib, ce mélange peut être séparé par les techniques connues de l'homme du métier, comme par exemple par chromatographie sur colonne. The 1: 4, 3: 6 dianhydrohexitol may be chosen from isosorbide (1: 4, 3: 6 dianhydro-D-glucidol), isoidide (1: 4, 3: 6 dianhydro-L-iditol) and isomannide (1: 4, 3: 6 dianhydro-D-mannitol). The preferred 1: 4, 3: 6 dianhydrohexitol is isosorbide. When the 1: 4, 3: 6 dianhydrohexitol is isosorbide, at the end of step b) a compound of formula la, Ib or a mixture of the two is obtained. In the case where a mixture of compounds of formulas Ia and Ib, this mixture can be separated by the techniques known to those skilled in the art, for example by column chromatography.
La préparation du monoéther à l'étape a) peut être réalisée selon les méthodes connues de l'homme du métier, par exemple à partir de 1 :4, 3 :6 dianhydrohexitol et un agent d'alkylation en C1 à C6, linéaire ou ramifié. Le reste alkyle en C1 à C6, linéaire ou ramifié, de l'agent d'alkylation est avantageusement choisi parmi les restes alkyles en C1 à C4, linéaire ou ramifié, de préférence parmi méthyle et éthyle. De préférence encore, le reste alkyle est méthyle. Des réactions d'étherification pouvant être utilisées sont par exemple décrites dans les demandes de brevet WO2014023902 A1 , WO 2014/168698 A1 et WO 2016/156505 A1. The preparation of the monoether in step a) can be carried out according to the methods known to those skilled in the art, for example starting from 1: 4, 3: 6 dianhydrohexitol and a linear to linear C 1 to C 6 alkylating agent. branched. The linear or branched C1-C6 alkyl residue of the alkylating agent is advantageously chosen from linear or branched C1-C4 alkyl radicals, preferably from methyl and ethyl. Preferably again, the rest alkyl is methyl. Examples of etherification reactions that can be used are described in patent applications WO2014023902 A1, WO 2014/168698 A1 and WO 2016/156505 A1.
L'agent d'alkylation peut notamment être choisi parmi les alcools aliphatiques linéaires ou ramifiés en C1 à C6, les halogénures d'alkyles aliphatiques linéaires ou ramifiés en C1 à C6, les esters aliphatiques linéaires ou ramifiés en C1 à C6 d'acides sulfuriques, les dialkylcarbonates aliphatiques linéaires ou ramifiés en C1 à C6 ou les dialkoxyméthanes aliphatiques linéaires ou ramifiés en C1 à C6. Comme précisé précédemment, les restes alkyles en C1 à C6 sont avantageusement choisis parmi les restes alkyles en C1 à C4, linéaire ou ramifié, de préférence parmi méthyle et éthyle. De préférence encore, le reste alkyle est méthyle. The alkylating agent may especially be chosen from C1 to C6 linear or branched aliphatic alcohols, linear or branched C1 to C6 aliphatic alkyl halides, linear or branched C1 to C6 aliphatic esters of sulfuric acids. linear or branched C1 to C6 aliphatic dialkylcarbonates or linear or branched C1 to C6 aliphatic dialkoxymethans. As specified above, the C1-C6 alkyl radicals are advantageously chosen from linear or branched C1-C4 alkyl radicals, preferably from methyl and ethyl radicals. More preferably, the alkyl radical is methyl.
Les alcools pouvant être utilisés comme agent d'alkylation comprennent notamment le méthanol, l'éthanol, l'isopropanol et le f-butanol, le méthanol étant préféré. Les halogénures d'alkyles pouvant être utilisés comme agent d'alkylation comprennent notamment les halogénures de méthyle, d'éthyle, d'isopropyle et de f-butyle, les halogénures de méthyle étant préférés. Les esters aliphatiques linéaires ou ramifiés en C1 à C6 d'acides sulfuriques peuvent par exemple être choisis parmi les esters de méthyle, d'éthyle, d'isopropyle et de t- butyle, les esters de méthyle, notamment le diméthylsulfate, étant préférés. Les dialkylcarbonates peuvent par example être choisis parmi le diméthylcarbonate, le diéthylcarbonate, diisopropylcarbonate et de di-f-butylcarbonate, le diméthylcarbonate étant préféré. Les dialkoxyméthanes pouvant être utilisés comme agent d'alkylation comprennent notamment le diméthoxyméthane, le diéthoxyméthane, diisopropoxyméthane et le di-f- butoxyméthane, le diméthoxyméthane étant préféré. The alcohols that can be used as alkylating agent include, in particular, methanol, ethanol, isopropanol and f-butanol, methanol being preferred. The alkyl halides that can be used as alkylating agents include, in particular, methyl, ethyl, isopropyl and n-butyl halides, with methyl halides being preferred. The linear or branched C 1 to C 6 aliphatic esters of sulfuric acids may, for example, be chosen from methyl, ethyl, isopropyl and t-butyl esters, methyl esters, in particular dimethyl sulphate, being preferred. The dialkyl carbonates may for example be selected from dimethyl carbonate, diethyl carbonate, diisopropyl carbonate and di-t-butyl carbonate, dimethyl carbonate being preferred. The dialkoxymethanes that can be used as alkylating agent include dimethoxymethane, diethoxymethane, diisopropoxymethane and di-t-butoxymethane, dimethoxymethane being preferred.
Le 1 :4, 3 :6 dianhydrohexitol peut être choisi parmi l'isosorbide (1 :4, 3 :6 dianhydro-D- glucidol), l'isoidide (1 :4, 3 :6 dianhydro-L-iditol) et l'isomannide (1 :4, 3 :6 dianhydro-D- mannitol). Le 1 :4, 3 :6 dianhydrohexitol préféré est l'isosorbide. Lorsque le 1 :4, 3 :6 dianhydrohexitol est l'isosorbide, on obtient à l'issue de l'étape b) un composé de formule la, Ib (ou sous-formules Ma et Mb ou Nia et Mb) ou un mélange des deux. Dans le cas où on obtient un mélange de composés de formules la et Ib (ou sous-formules Ma et llb ou I lia et Illb), ce mélange peut être séparé par les techniques connus de l'homme du métier, comme par exemple par chromatographie sur colonne. The 1: 4, 3: 6 dianhydrohexitol may be chosen from isosorbide (1: 4, 3: 6 dianhydro-D-glucidol), isoidide (1: 4, 3: 6 dianhydro-L-iditol) and isomannide (1: 4, 3: 6 dianhydro-D-mannitol). The preferred 1: 4, 3: 6 dianhydrohexitol is isosorbide. When the 1: 4, 3: 6 dianhydrohexitol is isosorbide, is obtained at the end of step b) a compound of formula la, Ib (or subformula Ma and Mb or Nia and Mb) or a mixture both. In the case where a mixture of compounds of formulas Ia and Ib (or sub-formulas Ma and IIb or IIa and IIIb) is obtained, this mixture can be separated by the techniques known to those skilled in the art, for example by column chromatography.
A l'issue de l'étape a) on obtient généralement un mélange de monoalkyléther, dialkyléther et dianhydrohexitol qui peut être utilisé directement à l'étape b) ou le mélange peut être séparé par distillation avec rectification sous pression réduite avant l'étape b). A l'étape b), le groupement hydroxyle libre est fonctionnalisé par une fonction acrylate, méthacrylate, époxy-acrylate, époxy-méthacrylate, isocyanate-acrylate ou isocyanate- méthacrylate, de préférence par une fonction acrylate, méthacrylate, époxy-acrylate ou époxy-méthacrylate. At the end of step a), a mixture of monoalkyl ether, dialkyl ether and dianhydrohexitol is generally obtained which can be used directly in step b) or the mixture can be separated by distillation with rectification under reduced pressure before step b ). In step b), the free hydroxyl group is functionalized with an acrylate, methacrylate, epoxy-acrylate, epoxy-methacrylate, isocyanate-acrylate or isocyanate-methacrylate function, preferably with an acrylate, methacrylate, epoxy-acrylate or epoxy function. methacrylate.
La fonctionnalisation du groupement hydroxyle libre par une fonction acrylate, méthacrylate, époxy-acrylate, époxy-méthacrylate, isocyanate-acrylate ou isocyanate-méthacrylate peut être effectuée selon les méthodes connues de l'homme du métier. On peut par exemple utiliser les acides acrylique et méthacrylique, les esters d'acide acrylique et méthacrylique, les anhydrides acryliques et méthacrylique, l'acrylate de glycidyle, le méthacrylate de glycidyle, des acrylates et méthacrylates d'alkylisocyanate, ou des diisocyantes avec des hydroxyalkyl acrylates ou des hydroxyalkyl méthacrylates. The functionalization of the free hydroxyl group by an acrylate, methacrylate, epoxy-acrylate, epoxy-methacrylate, isocyanate-acrylate or isocyanate-methacrylate function can be carried out according to the methods known to those skilled in the art. It is possible, for example, to use acrylic and methacrylic acids, acrylic and methacrylic acid esters, acrylic and methacrylic anhydrides, glycidyl acrylate, glycidyl methacrylate, alkyl isocyanate acrylates and methacrylates, or diisocyanates with hydroxyalkyl acrylates or hydroxyalkyl methacrylates.
Lorsque le groupement hydroxyle libre est fonctionnalisé avec une fonction acrylate ou méthacrylate, on obtient des composés de formule II. Dans ce cas, on peut faire réagir le groupement hydroxyle libre avec de l'acide acrylique ou méthacrylique, un ester d'acide acrylique ou méthacrylique, ou un anhydride acrylique ou méthacrylique, When the free hydroxyl group is functionalized with an acrylate or methacrylate function, compounds of formula II are obtained. In this case, the free hydroxyl group can be reacted with acrylic or methacrylic acid, an acrylic or methacrylic acid ester, or an acrylic or methacrylic anhydride,
Lorsque le groupement hydroxyle libre est fonctionnalisé avec une fonction époxy-acrylate ou époxy-méthacrylate, on obtient des composés de formule III. Dans ce cas, on peut faire réagir le groupement hydroxyle libre avec de l'acrylate de glycidyle et du méthacrylate de glycidyle. When the free hydroxyl group is functionalized with an epoxy-acrylate or epoxy-methacrylate function, compounds of formula III are obtained. In this case, the free hydroxyl group can be reacted with glycidyl acrylate and glycidyl methacrylate.
Le groupement hydroxyle peut également être fonctionnalisé avec une fonction isocyanate - acrylate ou isocyanate-méthacrylate. Dans ce cas, on peut faire réagir le groupement hydroxyle libre avec un acrylate ou méthacrylate d'alkylisocyanate, notamment en C2 à C4, linéaire ou ramifié, de préférence avec un acrylate ou méthacrylate d'éthylisocyanate. On peut également procéder en deux étapes en faisant d'abord réagir le groupement hydroxyle libre avec un diisocyanate puis en faisant réagir le produit ainsi obtenu avec un hydroxyalkyl acrylate, un hydroxyalkyl méthacrylate, un poly(propylèneglycol) acrylate ou un poly(propylèneglycol) méthacrylate. Pour ce qui est des hydroxyalkyl acrylates et méthacrylates, on utilisera avantageusement ceux en C2 à C4, linéaires ou ramifiés, de préférence l'hydroxyéthyl acrylate ou méthacrylate. On entend par diisocyanate tel qu'utilisé ici, un composé comprenant aux moins deux fonctions isocyanate. Ce diisocyanate peut par exemple être choisi parmi l'isophorone diisocyanate (IPDI), l'isocyanaurate d'IPDI, de l'IPDI polymère, le 1 ,5-naphthalène diisocyanate (NDI), le méthylène bis-cyclohexylisocyanate, le méthylène diphényl diisocyanate (MDI), du MDI polymère, le toluène diisocyanate (TDI), l'isocyanaurate de TDI, l'adduct de TDI- triméthylolpropane, du TDI polymère, l'hexaméthylène diisocyanate (HDI), HDI isocyanaurate, HDI biurate, du HDI polymérique, xylylène diisocyanate, du xylylène diisocyanate hydrogéné, le tetraméthyl xylylène diisocyanate, /7-phenylene diisocyanate, le 3,3'- diméthyldiphényl-4,4' -diisocyanate (DDDI), le 2,2,4-triméthylhexaméthylène diisocyanate (TMDI), le norbornane diisocyanate (NDI) et le 4,4'-dibenzyl diisocyanate (DBDI), The hydroxyl group may also be functionalized with an isocyanate-acrylate or isocyanate-methacrylate function. In this case, the free hydroxyl group can be reacted with a linear or branched alkylisocyanate acrylate or methacrylate, especially C 2 -C 4, preferably with an acrylate or ethylisocyanate methacrylate. It is also possible to proceed in two stages by first reacting the free hydroxyl group with a diisocyanate and then reacting the product thus obtained with a hydroxyalkyl acrylate, a hydroxyalkyl methacrylate, a poly (propylene glycol) acrylate or a poly (propylene glycol) methacrylate. . With regard to the hydroxyalkyl acrylates and methacrylates, use will advantageously be those C2 to C4, linear or branched, preferably hydroxyethyl acrylate or methacrylate. By diisocyanate as used herein is meant a compound comprising at least two isocyanate functional groups. This diisocyanate may, for example, be chosen from isophorone diisocyanate (IPDI), IPDI isocyanurate, polymeric IPDI, 1,5-naphthalene diisocyanate (NDI), methylene bis-cyclohexylisocyanate and methylene diphenyl diisocyanate. (MDI), polymeric MDI, toluene diisocyanate (TDI), TDI isocyanurate, TDI-trimethylolpropane adduct, polymer TDI, hexamethylene diisocyanate (HDI), HDI isocyanurate, HDI biurate, polymeric HDI, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, 7-phenylene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate (DDDI), 2,2 , 4-trimethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NDI) and 4,4'-dibenzyl diisocyanate (DBDI),
Les composés de l'invention peuvent être utilisés pour la préparation de résines acryliques thermoplastiques. Ils peuvent notamment remplacer partiellement ou intégralement le méthylméthacrylate, dans des polymères de type PMMA (polyméthylméthacrylate) plus connus sous le nom de PLEXIGLAS®. Ils peuvent être utilisé seuls ou en association avec de nombreux autres monomères capables de s'intégrer dans un processus de polymérisation radicalaire, par exemple les monomères acryliques et méthacryliques, (méthacrylate de méthyle, acrylate de butyle, méthacrylate de glycidyle, etc.) le styrène et l'acétate de vinyle. The compounds of the invention can be used for the preparation of thermoplastic acrylic resins. In particular, they may partially or completely replace the methylmethacrylate in polymers of the PMMA (polymethylmethacrylate) type, better known under the name of PLEXIGLAS®. They can be used alone or in combination with many other monomers capable of integrating into a radical polymerization process, for example acrylic and methacrylic monomers, (methyl methacrylate, butyl acrylate, glycidyl methacrylate, etc.). styrene and vinyl acetate.
Préparées en masse, en solution ou en dispersion (émulsion, suspension, etc.) ces résines peuvent alors être utilisées pour réaliser des films ou de matériaux pouvant être utilisés dans le domaine des revêtements (peinture, encre,..) des adhésifs, des prothèses dentaires, des matériaux optiques, des excipients pour la pharmacie, etc. Prepared in bulk, in solution or in dispersion (emulsion, suspension, etc.) these resins can then be used to produce films or materials that can be used in the field of coatings (paint, ink, etc.) adhesives, dental prostheses, optical materials, excipients for pharmacy, etc.
Ces composés peuvent également être utilisés en tant que diluant réactif et/ou agent de flexibilisation dans la préparation de résines thermodurcissables en association éventuellement avec d'autres monomères et notamment des acrylates mono et/ou multifonctionnels et/ou le styrène. These compounds can also be used as reactive diluent and / or flexibilizing agent in the preparation of thermosetting resins in combination optionally with other monomers and in particular mono and / or multifunctional acrylates and / or styrene.
L'invention va maintenant être illustrée dans les exemples ci-après. Il est précisé que ces exemples ne limitent en rien la présente invention. The invention will now be illustrated in the examples below. It is specified that these examples do not limit the present invention.
Exemples : Examples:
Exemple 1 : Synthèse de méthvléther d'isosorbide Example 1 Synthesis of Isosorbide Methyl Ether
HO HO
Dans un réacteur de 2L double enveloppe surmonté d'un réfrigérant, équipé d'une agitation mécanique et d'un thermomètre, 500g d'isosorbide et 125g d'eau sont chargés. Le milieu est chauffé à 50°C puis 258,9g de diméthylsulfate et 172,4 d'hydroxyde de sodium à 50% sont introduits simultanément à l'aide de pompes péristaltiques et en veillant à ne pas dépasser 65°C dans le milieu. L'addition dure 2h. In a reactor of 2L double jacket surmounted by a refrigerant, equipped with a mechanical stirrer and a thermometer, 500g of isosorbide and 125g of water are charged. The medium is heated at 50 ° C. and then 258.9 g of dimethyl sulphate and 172.4 of 50% sodium hydroxide are introduced simultaneously with peristaltic pumps and taking care not to exceed 65 ° C in the medium. The addition lasts 2 hours.
Dès la fin de l'addition, le milieu est porté à 95°C puis 172,4g d'hydroxyde de sodium sont introduit en 2h à l'aide d'une pompe péristaltique. Le milieu réactionnel est ensuite maintenu sous agitation à 95°C pendant au moins 3h. As soon as the addition is complete, the medium is brought to 95 ° C. and then 172.4 g of sodium hydroxide are introduced in 2 hours using a peristaltic pump. The reaction medium is then stirred at 95 ° C. for at least 3 hours.
Après filtration et concentration au évaporateur rotatif, le produit est obtenu sous forme liquide, contient 19,7% d'isosorbide, 20,5% de 5-O-monométhylether d'isosorbide A (MMI A- fonctionnalisation en position endo), 24,8% de 2-O-monométhylether d'isosorbide (MMI B - fonctionnalisation en position exo) et 25% de diméthyléther d'isosorbide (DMI). Les pourcentages correspondent à des pourcentages massiques mesurés par analyse RMN. After filtration and concentration on a rotary evaporator, the product is obtained in liquid form, contains 19.7% of isosorbide, 20.5% of 5-O-monomethylether of isosorbide A (MMI A- functionalization in the endo position), 24 , 8% isosorbide 2-O-monomethyl ether (MMI B - functionalization in the exo position) and 25% isosorbide dimethyl ether (DMI). The percentages correspond to mass percentages measured by NMR analysis.
Exemple 2 : Synthèse d'éthvléther d'isosorbide Example 2 Synthesis of Isosorbide Ethyl Ether
Dans un réacteur de 2L double enveloppe surmonté d'un réfrigérant, équipé d'une agitation mécanique et d'un thermomètre, 500g d'isosorbide et 125g d'eau sont chargés. Le milieu est chauffé à 50°C puis 316,1g de diéthylsulfate et 172,4 d'hydroxyde de sodium à 50% sont introduits simultanément à l'aide de pompes péristaltiques et en veillant à ne pas dépasser 65°C dans le milieu. L'addition dure 2h. In a reactor of 2L double jacket surmounted by a refrigerant, equipped with a mechanical stirrer and a thermometer, 500g of isosorbide and 125g of water are charged. The medium is heated to 50 ° C. and then 316.1 g of diethyl sulphate and 172.4 of 50% sodium hydroxide are introduced simultaneously using peristaltic pumps and taking care not to exceed 65 ° C. in the medium. The addition lasts 2 hours.
Dès la fin de l'addition, le milieu est porté à 95°C puis 172,4g d'hydroxyde de sodium sont introduit en 2h à l'aide d'une pompe péristaltique. As soon as the addition is complete, the medium is brought to 95 ° C. and then 172.4 g of sodium hydroxide are introduced in 2 hours using a peristaltic pump.
Le milieu réactionnel est ensuite maintenu sous agitation à 95°C pendant au moins 3h. Après filtration et concentration au évaporateur rotatif, le produit est obtenu sous forme liquide, contient 18% d'isosorbide, 21,4% de 5-O-monoéthylether d'isosorbide (MEI A), 26,2% de 2-O-monoéthylether d'isosorbide (MEI B) et 25,6% de diéthyléther d'isosorbide (DEI). Les pourcentages correspondent à des pourcentages massiques mesurés par analyse RMN. The reaction medium is then stirred at 95 ° C. for at least 3 hours. After filtration and concentration on a rotary evaporator, the product is obtained in liquid form, contains 18% of isosorbide, 21.4% of 5-O-monoethylether of isosorbide (MEI A), 26.2% of 2-O- isosorbide monoethyl ether (MEI B) and 25.6% isosorbide diethyl ether (IED). The percentages correspond to mass percentages measured by NMR analysis.
Exemple ? : Qbjenflon de monomfthYllsosorblde 1641.9g du produit obtenu selon l'exemple 1 sont introduit dans un réacteur de 2L double enveloppe surmonté d'une colonne de rectification, d'une tête de reflux, d'un condenseur et de recettes de récupération. La colonne de rectification est remplie de 10 éléments de garnissage Sulzer type EX. Example? Monomethylsiloxane solution of 1641.9 g of the product obtained according to Example 1 is introduced into a jacketed reactor of 2L surmounted by a rectification column, a reflux head, a condenser and recovery recipes. The grinding column is filled with 10 Sulzer type EX packing elements.
Dans un premier temps le montage est mis sous pression réduite (15m Bar) et le produit est chauffé à 150°C sous reflux total jusqu'à stabilisation des températures en tête de colonne. At first the assembly is put under reduced pressure (15m Bar) and the product is heated at 150 ° C under total reflux until stabilization of the temperatures at the top of the column.
Dès stabilisation des températures, une première fraction de distillation est obtenue avec un taux de reflux imposé supérieure à 1. As soon as the temperatures are stabilized, a first distillation fraction is obtained with an imposed reflux ratio of greater than 1.
Durant la conduite de la rectification, la pression est réduite progressivement jusqu'à 0.4mBar et la température du milieu est augmentée jusqu'à 200°C. Les températures de distillation en tête de colonne et les pressions de distillation de chaque composé sont rassemblées dans le tableau : During the conduct of the grinding, the pressure is gradually reduced to 0.4mBar and the temperature of the medium is increased to 200 ° C. The distillation temperatures at the top of the column and the distillation pressures of each compound are collated in the table:
Exemple 4 : synthèse de monométhvl méthacrvlate d'Isosorblde A Dans un ballon tricol de 250mL surmonté d'un Dean-Stark, chauffé à l'aide d'un chauffe ballon et muni d'une agitation magnétique, 40g de MMI A (produit 3), 23,7g d'acide méthacrylique et 150g de xylènes sont introduit. EXAMPLE 4 Synthesis of Isosorblde A Monomethyl Methacrylate In a 250mL three-necked flask surmounted by a Dean-Stark, heated with a balloon heater and equipped with magnetic stirring, 40 g of MMI A (product 3 ), 23.7g of methacrylic acid and 150g of xylenes are introduced.
64mg de phénothiazine, 1040mg d'acide méthanesulfonique à 70% et 110mg d'acide hypophosphoreux à 50% sont ajoutés. Le milieu réactionnel est ensuite chauffé à la température d'ébullition du solvant pendant au moins 24h. L'eau est éliminée en continu par distillation azéotropique. 64 mg of phenothiazine, 1040 mg of 70% methanesulfonic acid and 110 mg of 50% hypophosphorous acid are added. The reaction medium is then heated to the boiling point of the solvent for at least 24 hours. Water is continuously removed by azeotropic distillation.
Après 24h de réaction, l'indice d'acide est de 19mgKOH/g de brut. Le produit est purifié par extraction liquide-liquide. Un premier lavage à l'aide d'une solution de soude à 6% est effectué puis 2 lavages à l'eau. La phase organique est séchée à l'aide de sulfate de magnésium anhydre, filtrée et concentrée à l'aide d'un évaporateur rotatif après ajout de 10mg de monomethylether d'hydroquinone. After 24 hours of reaction, the acid number is 19 mg KOH / g of crude. The product is purified by liquid-liquid extraction. A first wash with a 6% sodium hydroxide solution is carried out and then 2 washes with water. The organic phase is dried using anhydrous magnesium sulphate, filtered and concentrated using a rotary evaporator after adding 10 mg of hydroquinone monomethyl ether.
35g de monométhyl méthacrylate A sont obtenus sous forme liquide. La structure est confirmé par analyse RMN ( avec une pureté massique supérieure à 85% Exemple 5 : synthèse de monométhvl méthacrvlate d'isosorbide B 35 g of monomethyl methacrylate A are obtained in liquid form. The structure is confirmed by NMR analysis (with a mass purity greater than 85% EXAMPLE 5 Synthesis of Isosorbide B monomethyl methacrylate
Suivant le protocole identique à celui de l'exemple 4 en remplaçant le MMI A par le MMI B (produit 2). 36g de monométhyl méthacrylate B sont obtenus sous forme solide. La structure est confirmée par analyse RMN avec une pureté massique supérieure à 85%. Exemple 6 : synthèse de monométhvl méthacrvlate d'isosorbide (mélange A et B) Following the protocol identical to that of Example 4, replacing MMI A with MMI B (product 2). 36 g of monomethyl methacrylate B are obtained in solid form. The structure is confirmed by NMR analysis with a mass purity greater than 85%. Example 6: synthesis of isosorbide monomethyl methacrylate (mixture A and B)
Dans un réacteur double enveloppe de 500ml_ surmonté d'un réfrigérant, et muni d'une agitation magnétique, 11g de MMI A (produit 3), 11g de MMI B (produit 2), 100mL de dichloromethane sont introduit. Le milieu est refroidi à 0°C. In a 500ml jacketed reactor surmounted by a condenser and provided with a magnetic stirrer, 11 g of MMI A (product 3), 11 g of MMI B (product 2), 100 ml of dichloromethane are introduced. The medium is cooled to 0 ° C.
Une solution de triméthylamine ( 16.7g dans 50m L de dichlorométhane) est alors ajouté au milieu réactionnel. Puis une solution de chlorure de méthacryloyle (17.3g) dans le dichlorométhane (100mL) est ajouté goutte à goutte à l'aide d'une pompe péristaltique en veillant à ne pas dépasser 5°C dans le milieu. A solution of trimethylamine (16.7 g in 50 ml of dichloromethane) is then added to the reaction medium. Then a solution of methacryloyl chloride (17.3g) in dichloromethane (100mL) is added dropwise using a peristaltic pump taking care not to exceed 5 ° C in the medium.
Le milieu réactionnel est ensuite maintenu sous agitation à température ambiante pendant au moins 6h. En fin de réaction le milieu réactionnel est filtré puis purifié par lavages successifs à l'aide de solution aqueuse de NaHC03 saturée, NaOH (1 M) et NaCI. The reaction medium is then stirred at room temperature for at least 6 hours. At the end of the reaction, the reaction medium is filtered and then purified by successive washings with saturated aqueous NaHCO 3 solution, NaOH (1M) and NaCl.
La phase organique est séchée à l'aide de sulfate de magnésium anhydre, filtrée et concentrée au évaporateur rotatif après ajout de 10mg de monomethylether d'hydroquinone. The organic phase is dried using anhydrous magnesium sulphate, filtered and concentrated on a rotary evaporator after addition of 10 mg of hydroquinone monomethyl ether.
Le produit obtenu est un liquide légèrement coloré. La structure est confirmée par analyse RMN avec une pureté massique supérieure à 85%. The product obtained is a slightly colored liquid. The structure is confirmed by NMR analysis with a mass purity greater than 85%.
Exemple 7 : synthèse de monométhvl urethane-methacrvlate d'isosorbide B EXAMPLE 7 Synthesis of Isosorbide B-monomethyl-urethane-methacrylate
Dans un réacteur double enveloppe de 250mL, est introduit 36.4g de diisocyanate d'isophorone, 25g de MMIB et 0.1g de dilaurate de dibutylétain. In a 250mL jacketed reactor, 36.4 g of isophorone diisocyanate, 25 g of MMIB and 0.1 g of dibutyltin dilaurate are introduced.
Le milieu réactionnel est chauffé à 75°C et maintenu sous agitation au moins 4h. 21.4g de méthacrylate de 2-hydroxyethyl sont ensuite introduit et le milieu est maintenu sous agitation au moins 3h à 60°C. The reaction medium is heated at 75 ° C. and kept stirring for at least 4 hours. 21.4 g of 2-hydroxyethyl methacrylate are then introduced and the medium is stirred for at least 3 h at 60 ° C.
La disparition du groupement NCO est suivi par analyse Infra-Rouge (pic à 2200cm-1). Exemple 8 : synthèse de monométhyl epoxy-méthacrylate d'isosorbide B The disappearance of the NCO group is monitored by Infra-Red analysis (peak at 2200cm-1). EXAMPLE 8 Synthesis of Isosorbide B Monomethyl Epoxy Methacrylate
Dans un réacteur double enveloppe de 250mL, équipé d'une agitation mécanique et d'un réfrigérant, est introduit 20g de Monométhylether d'isosorbide MMIB (0,125mol, 1eq) et 12,65g de triéthylamine (0,125mol 1eq) dans 180g de dichlorométhane. Le montage est placé sous léger flux d'azote. 250 g of a double jacketed reactor equipped with mechanical stirring and a condenser are charged with 20 g of isosorbide Monomethylether MMIB (0.125 mol, 1 eq) and 12.65 g of triethylamine (0.125 mol Ieq) in 180 g of dichloromethane. . The assembly is placed under light nitrogen flow.
17,8g de méthacrylate de glycidyle (0,125mol, 1eq) sont ensuite introduit goutte à goutte. Dès la fin de l'addition, le milieu est chauffé à 70°C par l'intermédiaire d'un bain thermostaté. 17.8 g of glycidyl methacrylate (0.125 mol, 1 eq) are then introduced dropwise. As soon as the addition is complete, the medium is heated to 70 ° C. by means of a thermostatic bath.
Le suivi de la réaction est effectué par analyse RMN. En fin de réaction, le milieu est purifié par extraction liquide/liquide eau/dichlorométhane. La phase organique est ensuite séchée à l'aide de sulfate de magnésium anhydride et concentrée au rotavapor. The reaction is monitored by NMR analysis. At the end of the reaction, the medium is purified by liquid / liquid water / dichloromethane extraction. The organic phase is then dried using magnesium sulfate anhydride and concentrated in a rotavapor.
Le produit brut est ensuite purifié par chromatographie sur colonne de silice (éluant acétate d'éthyle/cyclohexane). The crude product is then purified by chromatography on a silica column (eluent ethyl acetate / cyclohexane).
Le produit obtenu est un liquide légèrement coloré. La structure est confirmée par analyse RMN. The product obtained is a slightly colored liquid. The structure is confirmed by NMR analysis.

Claims

REVENDICATIONS
1. Composé de formule I 1. Compound of formula I
(I) dans laquelle (I) in which
R1 est un groupement alkyle en C1 à C6, linéaire ou ramifié, R2 est H ou alkyle en C1 ou C2, R 1 is a linear or branched C 1 -C 6 alkyl group, R 2 is H or C 1 or C 2 alkyl,
L est O, -0-CH2-CH(OH)-CH2-0-, -0-C(0)-NH-L1-0- où L1 est choisi parmi alkylène, linéaire ou ramifié, ou -0-C(0)-NH-L2-0-L3-0- où -0-C(0)-NH-L2- est un résidu d'un réactif choisi parmi l'isophorone diisocyanate (IPDI), l'isocyanaurate d'IPDI, de l'IPDI polymérique, le 1 ,5- naphthalène diisocyanate (NDI), le méthylène bis-cyclohexylisocyanate, le méthylène diphényl diisocyanate (MDI), du MDI polyméric, le toluène diisocyanate (TDI), l'isocyanaurate de TDI, l'adduct de TDI- triméthylolpropane, du TDI polymérique, l'hexaméthylène diisocyanate (HDI), HDI isocyanaurate, HDI biurate, du HDI polymérique, xylylène diisocyanate, du xylylène diisocyanate hydrogéné, le tetraméthyl xylylène diisocyanate, /7-phenylene diisocyanate, le 3,3'- diméthyldiphényl^,^ -diisocyanate (DDDI), le 2,2,4-triméthylhexaméthylène diisocyanate (TMDI), le norbornane diisocyanate (NDI) et le 4,4'-dibenzyl diisocyanate (DBDI), et L3 est choisi parmi alkylène en C2 à C4, linéaire ou ramifié, et poly(propylèneglycol). L is O, -O-CH 2 -CH (OH) -CH 2 -O-, -O-C (O) -NH-L 1 -O- where L 1 is selected from alkylene, linear or branched, or - 0-C (O) -NH-L 2 -O-L 3 -O- where -O-C (O) -NH-L 2 - is a residue of a reagent selected from isophorone diisocyanate (IPDI), IPDI isocyanurate, polymeric IPDI, 1,5-naphthalene diisocyanate (NDI), methylene bis-cyclohexylisocyanate, methylene diphenyl diisocyanate (MDI), polymeric MDI, toluene diisocyanate (TDI), TDI isocyanurate, TDI-trimethylolpropane adduct, polymeric TDI, hexamethylene diisocyanate (HDI), HDI isocyanurate, HDI biurate, polymeric HDI, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, / 7 -phenylene diisocyanate, 3,3'-dimethyldiphenyl-diisocyanate (DDDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NDI) and 4,4'-dibenzyl diisocyanate (DBDI) ), and L3 is selected from C2 to C4 alkylene, branched or branched, and poly (propylene glycol).
2. Composé selon la revendication 1 , dans lequel 2. The compound of claim 1, wherein
R1 est un groupement alkyle en C1 à C6, linéaire ou ramifié, R2 est H ou alkyle en C1 ou C2, R 1 is a linear or branched C 1 -C 6 alkyl group, R 2 is H or C 1 or C 2 alkyl,
L est O, -0-CH2-CH(OH>-CH2-0- ou -0-C(0)-NH-(CH2)2-0-. L is O, -O-CH 2 -CH (OH) -CH 2 -O- or -O-C (O) -NH- (CH 2) 2-O-.
3. Composé selon la revendication 1 ou 2, dans lequel R1 est méthyle. The compound of claim 1 or 2, wherein R 1 is methyl.
4. Composé selon l'une quelconque des revendications 1 à 3, dans lequel R2 est H ou méthyle. The compound of any one of claims 1 to 3, wherein R 2 is H or methyl.
5. Composé selon l'une quelconque des revendications 1 à 4, dans lequel L est O O-CHz-CHiOHVCHz-O-. 5. A compound according to any one of claims 1 to 4, wherein L is OO-CH 2 -CHiOHVCH 2 -O-.
6. Composé selon l'une quelconque des revendications 1 à 5 choisi parmi les composés de formules la, Ib, le, Id : 6. Compound according to any one of claims 1 to 5 selected from compounds of formulas la, Ib, le, Id:
Composé selon l'une quelconque des revendications 1 à 6 ayant la formule II Compound according to any one of claims 1 to 6 having formula II
(II). (II).
(llb), (IIb)
9. Composé selon la revendication 7 choisi parmi les composés de formule Ha, Mb et leurs mélanges. 9. Compound according to claim 7 selected from compounds of formula Ha, Mb and mixtures thereof.
Composé selon l'une quelconque des revendications 1 à 6 ayant la formule III Compound according to any one of Claims 1 to 6 having the formula III
(III).  (III).
Composé selon la revendication 9 choisi parmi les composés de formules llla, lllb,  Compound according to Claim 9 chosen from compounds of formulas IIIa, IIIb,
(Nia), (Nia),
(lllb), (IIIb)
(lllc), (IIIc),
(llld),(IIId),
et leurs mélanges. and their mixtures.
12. Composé selon la revendication 10 choisi parmi les composés de formule I lia, lllb et leurs mélanges. 12. A compound according to claim 10 selected from the compounds of formula I IIa, IIIb and mixtures thereof.
13. Procédé de fabrication d'un composé de formule I tel que défini à la revendication 1 comprenant les étapes suivantes : a) on prépare un monoéther d'alkyle en C1 à C6, linéaire ou ramifié, de 1 :4, 3 :6 dianhydrohexitol en faisant réagir un 1 :4, 3 :6 dianhydrohexitol avec un agent d'alkylation ; b) on fonctionnalise le groupement hydroxyle libre du monoéther obtenu à l'étape a) par une fonction acrylate, méthacrylate, époxy-acrylate, époxy-méthacrylate, isocyanate-acrylate, ou isocyanate-méthacrylate. 13. A process for preparing a compound of formula I as defined in claim 1 comprising the following steps: a) a linear or branched C1-C6 alkyl monoether of 1: 4, 3: 6 is prepared; dianhydrohexitol by reacting a 1: 4, 3: 6 dianhydrohexitol with an alkylating agent; b) the free hydroxyl group of the monoether obtained in step a) is functionalized with an acrylate, methacrylate, epoxy-acrylate, epoxy-methacrylate, isocyanate-acrylate or isocyanate-methacrylate function.
14. Utilisation d'un composé selon l'une quelconque des revendications 1 à 11 ou obtenu selon le procédé de la revendication 12 en tant que monomère pour la préparation de polymères. 14. Use of a compound according to any one of claims 1 to 11 or obtained according to the process of claim 12 as a monomer for the preparation of polymers.
EP18722094.2A 2017-03-28 2018-03-27 Acrylic derivatives of 1,4:3,6-dianhydrohexitol Pending EP3601293A1 (en)

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