EP2496625A1 - Procédé de fabrication d'une résine époxy - Google Patents

Procédé de fabrication d'une résine époxy

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Publication number
EP2496625A1
EP2496625A1 EP10771757A EP10771757A EP2496625A1 EP 2496625 A1 EP2496625 A1 EP 2496625A1 EP 10771757 A EP10771757 A EP 10771757A EP 10771757 A EP10771757 A EP 10771757A EP 2496625 A1 EP2496625 A1 EP 2496625A1
Authority
EP
European Patent Office
Prior art keywords
halogenated
equal
aromatic
process according
aromatic alcohol
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.)
Withdrawn
Application number
EP10771757A
Other languages
German (de)
English (en)
Inventor
Patrick Gilbeau
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.)
Solvay SA
Original Assignee
Solvay 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
Priority claimed from FR0957793A external-priority patent/FR2952060B1/fr
Priority claimed from FR0959590A external-priority patent/FR2954772B1/fr
Application filed by Solvay SA filed Critical Solvay SA
Publication of EP2496625A1 publication Critical patent/EP2496625A1/fr
Withdrawn legal-status Critical Current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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/022—Polycondensates containing more than one epoxy group per molecule characterised by the preparation process or apparatus used

Definitions

  • the present invention relates to a process for manufacturing an epoxy resin.
  • Epoxy resins may be used in "coating” applications or "structural” applications.
  • Coating applications may be found in the marine field (corrosion- resistant coating for boats, for example), in the field of metal containers (cans for food use, for example), in the coil coating field, and in the field of coatings for motor vehicles, to name but a few of them.
  • fibres based on glass, boron or graphite for example in the civil engineering field, in the fields of floor coverings, of construction, of electrical laminates (printed circuits), of electrical and electronic applications
  • the epoxy resin is a liquid epoxy resin
  • a critical step of the manufacture lies in the difficulty of recovering said resin from a mixture containing the resin and inorganic salts, owing to the presence of solid organic by-products in the mixture.
  • the recovery is generally carried out by treating the mixture containing the resin and the inorganic salts with a mixture of water and of an organic solvent, the solubility of which in water is limited.
  • the organic phase obtained, which contains the liquid epoxy resin, and the aqueous phase obtained, which contains the salts, are separated by settling. The presence of a solid third phase at the interface of the organic and aqueous phases makes their separation difficult.
  • the resin is recovered by adding, to the mixture containing the resin and the inorganic salts, firstly toluene and then, after a minimum period of 15 min, water.
  • This multi-step procedure does not completely solve the problem linked to the presence of the solid third phase and furthermore, it lengthens the time of the resin recovery step which reduces the productivity of the resin manufacturing process.
  • the objective of the invention is to solve the aforementioned problem by providing a process for manufacturing an epoxy resin, in which epichlorohydrin is reacted with at least one aromatic polyol so as to obtain the epoxy resin and a salt, and in which use is made of at least one non-halogenated, non-aromatic alcohol, as an additive, added to at least one step of the process or formed in at least one step of the process, in an additional amount relative to the amount of non-halogenated, non-aromatic alcohol possibly present as an impurity in the epichlorohydrin and/or in the aromatic polyol.
  • step of the process by step of the process, one intends to denote any step including the supply of the raw materials and the recovery of the epoxy resin.
  • the steps of the process can for instance be:
  • One of the essential features of the invention consists in using a non- halogenated, non-aromatic alcohol in the process for manufacturing the epoxy resin.
  • a non-halogenated, non-aromatic alcohol is an alcohol in which the molecule does not contain a bond between an aromatic carbon atom and a hydroxyl group -OH and does not contain a halogen atom.
  • the addition of the non-halogenated, non-aromatic alcohol makes it possible to carry out the reaction under conditions such that the recovery of the resin may be performed easily, for example by adding to the mixture containing the resin and inorganic salts, a mixture of water and of an organic solvent, the solubility of which in water is limited, and by separating the aqueous and organic phases obtained by settling.
  • epoxy resin is understood to mean Type I Grade 1 Classes A to H, Type II Grade 1 Classes A to F and Type VI Grade 1 Class A resins, as defined in the ASTM D 1763 - 00 (2005) standard entitled "Standard Specifications for Epoxy Resins".
  • the epoxy resin is preferably a liquid epoxy resin.
  • liquid epoxy resin is understood to mean Type I Grade 1 Classes A and B, Type II Grade 1 Classes A, B and C and Type VI Grade 1 Class A resins, as defined in the ASTM D 1763 - 00 (2005) standard entitled "Standard Specifications for Epoxy Resins".
  • Bisphenol A diglycidyl ether is one example of an epoxy resin.
  • the epoxy resin may be a polymer, the chemical formula of which contains at least one oxirane group, preferably a 2,3- epoxypropyloxy group.
  • polymer is understood to mean molecules comprising several units joined to one another by covalent bonds, often in a repeating manner, these units being referred to as repeating units. The number of repeating units is greater than zero.
  • a polymer contains at least one type of repeating unit. When the polymer contains only a single type of repeating unit, it is known as a homopolymer. When the polymer contains more than a single type of repeating unit, it is known as a copolymer.
  • the copolymer may be of statistical, alternating or block type, as described in "Polymer Science Dictionary, M.S.M., Elsevier Applied Science, London and New York, 1989, page 86".
  • the non-halogenated, non- aromatic alcohol preferably has a solubility in water that is greater than or equal to 10 g/kg at 25°C, more preferably greater than or equal to 50 g/kg, even more preferably greater than or equal to 100 g/kg, more preferably still greater than or equal to 150 g/kg, yet preferably greater than or equal to 200 g/kg, very particularly preferably greater than or equal to 500 g/kg.
  • a non-halogenated, non-aromatic alcohol that is miscible with water in all proportions at 25°C is particularly suitable.
  • the non-halogenated, non- aromatic alcohol preferably has a boiling point at a pressure of 1 bar absolute that is less than or equal to 100°C, more preferably less than or equal to 90°C, and most preferably lower than or equal to 80 °C.
  • the non-halogenated, non- aromatic alcohol preferably forms a binary azeotrope with water, the boiling point of which at a pressure of 1 bar absolute is generally less than or equal to 100°C, and preferably less than 95 °C.
  • the non-halogenated, non- aromatic alcohol comprises at least 1 carbon atom, preferably at least 2 carbon atoms and more preferably at least 3 carbon atoms.
  • This non-halogenated, non- aromatic alcohol preferably comprises at most 12 carbon atoms, more preferably at most 8 carbon atoms and even more preferably at most 6 carbon atoms.
  • the non-halogenated, non- aromatic alcohol may be of linear, branched, cyclic or branched cyclic structure.
  • the non-halogenated, non- aromatic alcohol may be selected from non-halogenated, non-aromatic monoalcohols, non-halogenated, non-aromatic polyols and mixtures of at least two of them.
  • the non-halogenated, non aromaticalcohol is preferably a non halogenated, non aromatic polyol.
  • the non-halogenated, non- aromatic monoalcohol is preferably selected from methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, iert-butanol, 1-pentanol, 2- pentanol, 3-pentanol, 3 -methyl- 1-butanol, 2 -methyl- 1-butanol, 2-methyl-2- butanol, 3-methyl-2-butanol, 2,2-dimethyl- 1-propanol, cyclopentanol, cyclohexanol, hydroxy acetone, allyl alcohol, glycidol and any mixture thereof.
  • the non-halogenated, non- aromatic polyol is preferably selected from ethylene glycol, 1 ,2-propanediol, 1,3- propanediol, 1 ,2-butanediol, 1,2,3-propanetriol (glycerol), sorbitol, mannitol, maltitol, erythritol, xylitol, glycerol methyl ether, glycerol ethyl ether, linear glycerol oligomers, branched glycerol oligomers, cyclic glycerol oligomers, glyceraldehyde, erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, dihydroxy acetone, erythr
  • linear glycerol oligomers is 3-(2,3- dihydroxypropoxy)propan-l,2-diol.
  • Branched diglycerol oligomers are, for example, 3-(2-hydroxy-l-hydroxymethylethoxy)propan-l,2-diol and 2-(2- hydroxy-l-hydroxymethylethoxy)propan-l,3-diol).
  • Branched glycerol oligomers are, for example, cis- and trans-2,5-bis(hydroxymethyl)-l,4-dioxane, cis- and trans-2,6-bis(hydroxymethyl)-l,4-dioxane, cis- and trans-6-hydroxy-2- hydroxymethyl-l,4-dioxepane and cis- and trans-3,7-dihydroxy-l,5-dioxocane.
  • the non-halogenated, non- aromatic alcohol is preferably a non-halogenated, non-aromatic monoalcohol, such as isopropanol and glycidol, for example. Glycidol is most preferred.
  • the non-halogenated, non- aromatic alcohol is preferably a non-halogenated, non-aromatic polyol of linear structure, such as glycerol or sorbitol, for example. Glycerol is most preferred.
  • the aromatic polyol and the non-halogenated, non-aromatic alcohol use may also be made of at least one basic compound.
  • the aromatic polyol and the non-halogenated, non- aromatic alcohol use is also preferably made of at least one basic compound.
  • the basic compound may be an organic or inorganic basic compound.
  • Organic basic compounds are for example amines, phosphines and ammonium, phosphonium or arsonium hydroxides. Inorganic basic compounds are preferred.
  • the expression "inorganic compounds” is understood to mean compounds which do not contain a carbon-hydrogen bond.
  • the inorganic basic compound may be chosen from alkali and alkaline-earth metal oxides, hydroxides, carbonates, hydrogen carbonates, phosphates, hydrogen phosphates and borates, and mixtures thereof. Alkali and alkaline-earth metal oxides and hydroxides are preferred.
  • the preferred basic compounds are in the form of concentrated aqueous solutions or suspensions of sodium hydroxide or calcium hydroxide or in the form of purified caustic brine.
  • purified caustic brine here means sodium hydroxide which contains sodium chloride such as, for example, that produced in a diaphragm electrolysis process.
  • the aromatic polyol and the non-halogenated, non-aromatic alcohol use may also be made of at least one monovalent substituted onium salt.
  • the monovalent substituted onium salt may be chosen from the group constituted of quaternary ammonium, phosphonium or arsonium halides, phosphates, sulphates and arsenates, and mixtures of at least two of them.
  • the aromatic polyol is preferably selected from the group constituted of bisphenol A (4,4'-dihydroxy-2,2- diphenylpropane, 4,4'-isopropylidenediphenol), tetrabromobisphenol A (4,4'- isopropylidenebis(2,6-dibromophenol)), bisphenol AF (4,4'-[2,2,2-trifluoro-l- (trifluoromethyl)ethylidene]bisphenol), hexafluorobisphenol A (4,4'-dihydroxy- 2,2-diphenyl- 1,1,1 ,3,3,3-hexafluoropropane), 1 , 1 ,2,2-tetra(p- hydroxyphenyl)ethane, tetramethylbisphenol (4,4 ' -dihydroxy-3 ,3 ',5,5'- tetramethylbisphenol), 1,5-dihydroxynaphthalene, 1,1 ',7,7'
  • condensation product of phenol with formaldehyde preferably bisphenol F (mixture of ⁇ , ⁇ ', ⁇ , ⁇ ' and ⁇ , ⁇ ' isomers of dihydroxydiphenylmethane), a condensation product of cresol with formaldehyde (mixture of ⁇ , ⁇ ', ⁇ , ⁇ ' and ⁇ , ⁇ ' isomers of methylhydroxydiphenylmethane), an alkylation product of phenol and of dicyclopentadiene (2,5-bis[(hydroxyphenyl]octahydro-4,7-methano-5H- indene), a condensation product of phenol and of glyoxal (tetrakis(4- hydroxyphenyl)ethane), a condensation product of phenol and of a
  • hydroxybenzaldehyde e.g. tris(4-hydroxyphenyl)methane), l,l,3-tris(p- hydroxyphenyl)propane, and mixtures of at least two of them.
  • Bisphenol A is more particularly preferred.
  • the aromatic polyol is more preferably selected from the group constituted by bisphenol A, a condensation product of phenol with formaldehyde, a condensation product of cresol with formaldehyde and mixtures of at least two of them.
  • the aromatic polyol is bisphenol A and the epoxy resin is a liquid epoxy resin of Type I Grade 1 Classes A and B, as defined in the ASTM D 1763 - 00 (2005) standard entitled "Standard Specifications for Epoxy Resins”.
  • This resin generally has a viscosity at 25°C greater than or equal to 3000 cP and less than or equal to 40 000 cP, often greater than or equal to 3000 cP and less than or equal to 20 000 cP and frequently greater than or equal to 15 000 cP and less than or equal to 40 000 cP.
  • This resin generally has an epoxide equivalent weight greater than or equal to 170 and less than or equal to 226, often greater than or equal to 170 and less than or equal to 200, and frequently greater than or equal to 190 and less than or equal to 226.
  • the epoxide equivalent weight is defined as the weight in grams of resin that contains one molar equivalent of epoxide functional group.
  • This embodiment is used in the process known under the name of the Phase Transfer Catalyst Process for manufacturing a liquid epoxy resin, and as described in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Completely Revised Edition, Vol. A9, pages 548-549.
  • the various steps of the process according to the invention may be carried out in continuous mode or in batch mode.
  • the non-halogenated, non- aromatic alcohol is used as an additive, added to at least one step of the process or formed in at least one step of the process, in an additional amount relative to the amount of this non-halogenated, non-aromatic alcohol possibly present as an impurity in the epichlorohydrm and/or in the aromatic polyol.
  • the non-halogenated, non-aromatic alcohol may be present or may not be present as an impurity in the
  • the non-halogenated, non-aromatic alcohol may be present as an impurity in the epichlorohydrm and/or in the aromatic polyol.
  • the amount of this non-halogenated, non-aromatic alcohol as an impurity in the epichlorohydrm and/or in the aromatic polyol is insufficient to inhibit the adsorption of hydroxylated organic by-products, for example hydrolysis products of epoxy resins, on the salt formed, which would be responsible for the aforementioned separation difficulties when the epoxy resin is a liquid epoxy resin, for example, and that it is needed to add or form an extra amount of that non-halogenated, non-aromatic alcohol.
  • the non-halogenated, non-aromatic alcohol may not be present as an impurity in the epichlorohydrm and/or in the aromatic polyol.
  • the expression "not be present” is understood to mean situations where the content of non- halogenated, non-aromatic alcohol in the epichlorohydrm and/or in the aromatic polyol is less than 1 mg of non-halogenated, non-aromatic alcohol per kg of epichlorohydrm and/or less than 1 mg of non-halogenated, non-aromatic alcohol per kg of aromatic polyol.
  • the non-halogenated, non-aromatic alcohol may be added to or formed in at least one of the steps of the process according to the invention.
  • epichlorohydrm and the aromatic polyol is generally carried out in a reaction medium.
  • the non- halogenated, non-aromatic alcohol is formed during the epichlorohydrm pretreatment step.
  • This pretreatment step may consist of a partial hydrolysis of the epichlorohydrm. This partial hydrolysis may be carried out by addition of a defined amount of water or a defined amount of an aqueous mixture containing at least one basic agent as defined above.
  • the non-halogenated, non- aromatic alcohol is, for example, glycidol or glycerol, preferably glycerol.
  • the non- halogenated, non-aromatic alcohol is added to at least one of the compounds chosen from epichlorohydrin, the aromatic polyol, the basic agent, the quaternary ammonium salt and mixtures of at least two of them.
  • the non- halogenated, non-aromatic alcohol is added to the reaction medium.
  • the non-halogenated, non- aromatic alcohol is added during the reaction between the epichlorohydrin and the aromatic polyol.
  • the expression “during the reaction” one intends to denote during any step where both the epichlorohydrin and the aromatic polyol are present.
  • said reaction is preferably carried out at a
  • the non-halogenated, non-aromatic alcohol is added when the degree of conversion of the aromatic polyol, expressed as mol% of this compound, is greater than or equal to 50 mol%, preferably greater than or equal to 55 mol%, more preferably greater than or equal to 60 mol%, still more preferably greater than or equal to 65 mol%, yet more preferably preferably greater than or equal to 70 mol%, particularly preferably greater than or equal to 75 mol %, very particularly preferably greater than or equal to 80 mol%, most preferably greater than or equal to 85 %. and yet most preferably greater than or equal to 90 mol%.
  • That degree of conversion of the aromatic polyol, expressed as mol% of this compound, is preferably lower than or equal to 99.9 mol%, more preferably lower than or equal to 99 mol%, still more preferably lower than or equal to 97.5 mol%, yet more preferably lower than or equal to 95 mol% and particularly preferably lower than or equal to 92.5 mol %.
  • This degree of conversion is the ratio between the amount of aromatic polyol that has been converted into epoxy resin in the process and the amount of aromatic polyol introduced during the process, before the addition of the non- halogenated, non-aromatic alcohol. This applies to continuous processes, semi- continuous processes and batch processes, whatever the number of steps to go from the raw materials to the final products.
  • the non- halogenated, non-aromatic alcohol is used as an additive, added to at least one step of the process or formed in at least one step of the process, when the degree of conversion of the aromatic polyol expressed as mol% of this compound is greater than or equal to 50 mol %, preferably greater than or equal to 55 mol%, more preferably greater than or equal to 60 mol%, still more preferably greater than or equal to 65 mol%, yet more preferably greater than or equal to 70 mol%, particularly preferably greater than or equal to 75 mol %, very particularly preferably greater than or equal to 80 mol%, still very particularly preferably greater than or equal to 80 mol%, most preferably greater than or equal to 85 % and yet most preferably greater than or equal to 90 mol%.
  • the degree of conversion of the aromatic polyol, expressed as mol% of this compound is preferably lower than or equal to 99.9 mol%, more preferably lower than or equal to 99
  • the non-halogenated, non- aromatic alcohol is used as an additive, added to at least one step of the process.
  • the at least one step is a chemical reaction step.
  • the at least one step is a physical treatment for removing reactants and/or products of the reaction.
  • a treatment is for instance an operation to separate the epoxy resin from the other components of reaction medium, like for instance unreacted raw materials, reaction intermediates, and other products of the reaction.
  • the separation operation can for instance be a liquid-liquid extraction of the reaction medium with a mixture of water and a solvent, preferably organic, with a limited solubility in water.
  • the non-halogenated, non- aromatic alcohol is used as an additive, formed to at least one step of the process.
  • this approach makes it possible to prevent a degradation of the non-halogenated, non-aromatic alcohol which would limit its role of inhibiting the adsorption of hydroxylated organic by-products, for example hydrolysis products of epoxy resins, on the salt formed, which would be responsible for the aforementioned separation difficulties when the epoxy resin is a liquid epoxy resin for example.
  • the reaction between the epichlorohydrin and the aromatic polyol is carried out in a reaction medium and at least one portion of this reaction medium is subjected to at least one separation operation during which at least a first fraction containing unconverted epichlorohydrin and at least a second fraction, concentrated in epoxy resin and in salt, are obtained, in which said second fraction is subjected to at least one subsequent treatment, and in which at least one portion of the non-halogenated, non-aromatic alcohol is added to said second fraction before the subsequent treatment and/or during said subsequent treatment of said second fraction.
  • At least one portion of the reaction medium is subjected to at least one separation operation during which at least a first fraction containing unconverted epichlorohydrin and at least a second fraction, concentrated in epoxy resin and in salt, are obtained, and at least one portion of the non-halogenated, non-aromatic alcohol is added to said second fraction.
  • the second fraction, to which the non-halogenated, non-aromatic alcohol has been added is mixed with water and at least one organic solvent, the solubility of which in water is limited, so as to separate, by settling, a first part comprising the organic solvent and most of the epoxy resin included in the second fraction, to which the non-halogenated, non-aromatic alcohol has been added, before mixing and a second part comprising the water and most of the salt included in the second fraction, to which the non-halogenated, non-aromatic alcohol has been added, before mixing.
  • the water and the organic solvent may be added to the second fraction, to which the non-halogenated, non-aromatic alcohol has been added, in any sequence, such as the water before the organic solvent, the organic solvent before the water, and the organic solvent at the same time as the water.
  • the solubility of which in water is limited means that the solubility of the organic solvent in water at 25°C is less than 300 g of solvent per kg of water.
  • At least one portion of the reaction medium is subjected to at least one separation operation during which at least a first fraction containing unconverted epichlorohydrin and at least a second fraction, concentrated in epoxy resin and in salt, are obtained, and said second fraction is subjected to at least one subsequent treatment, and at least one portion of the non-halogenated, non-aromatic alcohol is added to said second fraction during said subsequent treatment.
  • the second fraction is mixed with water and at least one organic solvent, the solubility of which in water is limited, and a first part, comprising the organic solvent and most of the epoxy resin included in the medium before mixing, and a second part, comprising the water and most of the salt included in the medium before mixing, are separated by settling.
  • the organic solvent the solubility of which in water is limited, may be selected from the group constituted by toluene, xylene, benzene, methyl isobutyl ketone, methyl ethyl ketone and mixtures of at least two of them.
  • the water and the organic solvent may be added to the second fraction in any sequence, such as the water before the organic solvent, the organic solvent before the water, and the organic solvent at the same time as the water.
  • non-halogenated, non-aromatic alcohol may be added as is, or as a mixture with water, or as a mixture with the organic solvent or in any mixture with water and with at least one organic solvent.
  • the weight ratio between the amount of water added to the second fraction, concentrated in epoxy resin and in salt, and the amount of salt in said concentrated fraction is generally greater than or equal to 3 and preferably greater than or equal to 4. This ratio is generally less than or equal to 50, preferably less than or equal to 20 and more preferably less than or equal to 10.
  • the weight ratio between the amount of organic solvent added to the second fraction, concentrated in epoxy resin and in salt, and the amount of epoxy resin in said concentrated fraction is generally greater than or equal to 0.1 and preferably greater than or equal to 0.5 and more preferably greater than or equal to 0.8. This ratio is generally less than or equal to 10, preferably less than or equal to 5 and more preferably less than or equal to 2.
  • the additional amount of the non- halogenated, non-aromatic alcohol preferably corresponds to at least one of the following conditions:
  • the additional amount of the non-halogenated, non-aromatic alcohol relative to the total amount of epichlorohydrin used in the process expressed as g of non-halogenated, non-aromatic alcohol per kg of epichlorohydrin is greater than or equal to 0.005 and less than or equal to 500
  • the additional amount of the non-halogenated, non-aromatic alcohol relative to the total amount of aromatic polyol used in the process expressed as g of non-halogenated, non-aromatic alcohol per kg of aromatic polyol is greater than or equal to 0.005 and less than or equal to 500.
  • This additional amount of the non-halogenated, non-aromatic alcohol relative to the total amount of epichlorohydrin used in the process expressed as g of non-halogenated, non-aromatic alcohol per kg of epichlorohydrin is more preferably greater than or equal to 0.01, even more preferably greater than or equal to 0.1, more preferably still greater than or equal to 1 and very particularly preferably greater than or equal to 10.
  • This content is more preferably less than or equal to 200, even more preferably less than or equal to 100, more preferably still less than or equal to 50, yet more preferably less than or equal to 30, particularly preferably less than or equal to 25, very particularly preferably less than or equal to 20 and most preferably less than or equal to 12.
  • a content of less than or equal to 5 is also particularly convenient.
  • This additional amount of the non-halogenated, non-aromatic alcohol relative to the total amount of aromatic polyol used in the process expressed as g of non-halogenated, non-aromatic alcohol per kg of aromatic polyol is more preferably greater than or equal to 0.01, even more preferably greater than or equal to 0.1, more preferably still greater than or equal to 1 and very particularly preferably greater than or equal to 10.
  • This content is more preferably less than or equal to 200, even more preferably less than or equal to 100, and more preferably still less than or equal to 50, yet more preferably less than or equal to 30, particularly preferably less than or equal to 25, very particularly preferably less than or equal to 20 and most preferably less than or equal to 12.
  • the non-halogenated, non-aromatic alcohol may be added continuously or in batch mode.
  • the epichlorohydrin may have been manufactured by any process.
  • the epichlorohydrin may originate, for example, from a process for dehydrochlorination of dichloropropanol, for example via a basic compound, from an allyl chloride epoxidation process, or from the two processes.
  • a process for dehydrochlorination of dichloropropanol for example via a basic compound
  • an allyl chloride epoxidation process or from the two processes.
  • the process for epoxidation via hydrogen peroxide is preferred.
  • At least one portion of the epichlorohydrin is obtained by reaction between dichloropropanol and at least one basic compound.
  • the basic compound may be as defined above.
  • dichloropropanol may itself be obtained by any process.
  • the dichloropropanol may originate, for example, from an allyl chloride hypochlorination process, from a glycerol hydrochlorination process, from an allyl alcohol chlorination process, from a 1,3-dichloroacetone reduction process, from a 2,3- dichloropropanal reduction process or from a combination of at least two of these processes.
  • the dichloropropanol is preferably obtained by a glycerol hydrochlorination process, by an allyl chloride hypochlorination process, or by a combination of the two.
  • At least one portion of the dichloropropanol is more preferably obtained by a glycerol hydrochlorination process, and more specifically by reaction between glycerol and hydrogen chloride.
  • At least one portion of the epichlorohydrin is preferably obtained by dehydrochlorination of
  • dichloropropanol via a basic compound, and at least one portion of said dichloropropanol being obtained by hydrochlorination of glycerol.
  • At least one portion of the epichlorohydrin is more preferably obtained by a process for
  • dehydrochlorination of dichloropropanol and at least one portion of said dichloropropanol is preferably obtained by hydrochlorination of glycerol, the dehydrochlorination and hydrochlorination processes possibly being carried out at the same manufacturing site as the process according to the invention or at different manufacturing sites.
  • the epichlorohydrin is more preferably obtained by reaction between dichloropropanol and at least one basic compound, and at least one portion of said dichloropropanol is preferably obtained by reaction between glycerol and hydrogen chloride, and preferably at least one part of the glycerol has been obtained from renewable raw materials, such as in the production of biodiesel.
  • the processes for preparing the dichloropropanol and the epichlorohdyrin can be such as disclosed in International applications WO2005/054167, WO2006/100311, WO2006/100312, WO2006/100313, WO2006/100314, WO2006/100315, WO2006/100316, WO2006/100317, WO2006/106153, 2007054505, WO 2006/100318, WO2006/100319, WO2006/100320,
  • dichloropropanol having been obtained by hydrochlorination of glycerol using hydrogen chloride, 1 mol of commercial bisphenol A diglycidyl ether of 95% purity and 2 mol of sodium chloride, was heated at 90°C, with stirring, for 20 min and under a nitrogen atmosphere.
  • the epichlorohydrin contained less than 50 ppm by weight of glycerol and less than 50 ppm by weight of glycidol.
  • This mixture was then cooled to 85°C, and 0.025 mol of bisphenol A and 0.05 mol of sodium hydroxide, in the form of an aqueous solution containing 33% by weight of NaOH, were added thereto. The resulting mixture continued to be stirred for 1 hour at 85 °C.
  • the epichlorohydrin was then evaporated by gradually reducing the pressure from 1 bar to around 200 mbar absolute, while gradually increasing the temperature of the mixture to 113°C.
  • the temperature of the mixture resulting from the evaporation of the epichlorohydrin was then reduced to 55°C and a weight amount of methyl isobutyl ketone identical to the amount of bisphenol A diglycidyl ether used was added, with vigorous stirring,
  • the mixture obtained was then transferred to a separatory funnel and the three phases were separated after settling at 25°C for 20 h.
  • the densest phase was a solution containing most of the salt present in the mixture before settling.
  • the least dense phase was a solution containing most of the epoxy resin present in the mixture before settling.
  • the phase of intermediate density contained a suspended solid. This phase was filtered under pressure through a polytetrafluoroethylene filter having a porosity of 5 ⁇ . On the filter, 4 g of wet solid were recovered per 100 g of bisphenol A diglycidyl ether used. The solid recovered was analysed by high performance liquid chromatography and contained 18.4% by weight of epoxy resin.
  • Example 2 The operations from Example 1 were repeated except that, added to the mixture cooled to 85°C and containing the epichlorohydrin, the bisphenol A diglycidyl ether and the sodium chloride, were the bisphenol A, the 33% sodium hydroxide solution and 1.73 g of glycerol per mol of bisphenol A diglycidyl ether.
  • Example 2 The operations from Example 1 were repeated except that, added to the mixture cooled to 85°C and containing the epichlorohydrin, the bisphenol A diglycidyl ether and the sodium chloride, were the bisphenol A and 1.86 g of glycidol per mol of bisphenol A diglycidyl ether, and then the 33% sodium hydroxide solution.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Compounds (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'une résine époxy, dans lequel de l'épichlorohydrine est mise à réagir avec au moins un polyol aromatique afin d'obtenir la résine époxy et un sel, et dans lequel est utilisé au moins un alcool non halogéné et non aromatique, comme additif, ajouté dans au moins une étape du procédé ou formé dans au moins une étape du procédé, en quantité supplémentaire par rapport à la quantité de l'alcool non halogéné non aromatique éventuellement présent sous la forme d'une impureté dans l'épichlorohydrine et/ou dans le polyol aromatique.
EP10771757A 2009-11-04 2010-10-29 Procédé de fabrication d'une résine époxy Withdrawn EP2496625A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0957793A FR2952060B1 (fr) 2009-11-04 2009-11-04 Procede de fabrication d'un produit derive de l'epichlorhydrine
FR0959590A FR2954772B1 (fr) 2009-12-24 2009-12-24 Procede de fabrication d'une resine epoxy
PCT/EP2010/066533 WO2011054770A1 (fr) 2009-11-04 2010-10-29 Procédé de fabrication d'une résine époxy

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EP2496625A1 true EP2496625A1 (fr) 2012-09-12

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EP (1) EP2496625A1 (fr)
CN (1) CN102712738A (fr)
TW (1) TW201124438A (fr)
WO (1) WO2011054770A1 (fr)

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EP1687248B1 (fr) 2003-11-20 2011-06-01 SOLVAY (Société Anonyme) Procédé de production de dichloropropanol à partir de glycérol et d'un agent chlorant en la présence d'un catalyseur choisit parmi l' acide adipique ou glutarique
TWI478875B (zh) 2008-01-31 2015-04-01 Solvay 使水性組成物中之有機物質降解之方法
FR2935968B1 (fr) 2008-09-12 2010-09-10 Solvay Procede pour la purification de chlorure d'hydrogene
FR2963338B1 (fr) 2010-08-02 2014-10-24 Solvay Procede d'electrolyse
FR2964096A1 (fr) 2010-08-27 2012-03-02 Solvay Procede d'epuration d'une saumure
EP2621911A1 (fr) 2010-09-30 2013-08-07 Solvay Sa Dérivé d'épichlorhydrine d'origine naturelle
FR2966825B1 (fr) 2010-10-29 2014-05-16 Solvay Procede de fabrication d'epichlorhydrine
EP2794484A1 (fr) 2011-12-19 2014-10-29 Solvay SA Procédé pour la réduction du carbone organique total de compositions aqueuses
EP2669306B1 (fr) * 2012-06-01 2015-08-12 Solvay Sa Procédé de fabrication d'une résine époxy
EP2669307A1 (fr) * 2012-06-01 2013-12-04 Solvay Sa Processus de fabrication dýune époxyde
CN103526328B (zh) * 2013-10-14 2015-10-07 江苏恒力化纤股份有限公司 一种抗蠕变聚酯的安全气囊工业丝及其制备方法
CN103570917B (zh) * 2013-10-24 2017-01-25 安徽善孚新材料科技股份有限公司 一种脂肪族羟基化合物改性固体环氧树脂及其制备方法
KR102090992B1 (ko) * 2013-11-20 2020-03-20 솔베이(소시에떼아노님) 에폭시 수지의 제조 방법
CN110591054B (zh) * 2019-09-17 2021-05-18 江苏泰特尔新材料科技股份有限公司 一种总氯含量低、无重金属残留的环氧化物及其合成工艺

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WO2011054770A1 (fr) 2011-05-12
CN102712738A (zh) 2012-10-03

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