EP2496626A2 - Procédé de fabrication d'un produit dérivé de l'épichlorohydrine - Google Patents

Procédé de fabrication d'un produit dérivé de l'épichlorohydrine

Info

Publication number
EP2496626A2
EP2496626A2 EP10776334A EP10776334A EP2496626A2 EP 2496626 A2 EP2496626 A2 EP 2496626A2 EP 10776334 A EP10776334 A EP 10776334A EP 10776334 A EP10776334 A EP 10776334A EP 2496626 A2 EP2496626 A2 EP 2496626A2
Authority
EP
European Patent Office
Prior art keywords
epichlorohydrin
alkylating agent
process according
substituted
mixture
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Withdrawn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
EP10776334A
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
Application filed by Solvay SA filed Critical Solvay SA
Publication of EP2496626A2 publication Critical patent/EP2496626A2/fr
Withdrawn legal-status Critical Current

Links

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
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • 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 a product derived from epichlorohydrin.
  • Products derived from epichlorohydrin find uses in various fields such as protective coatings, binders, adhesives, inks, food applications, paper manufacture, flame retardants, detergency and elastomers, for example.
  • 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, in steps, the organic solvent, the solubility of which in water is limited, and water, the solvent being added first and the water then being added after a minimum period of 15 min.
  • 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 a product derived from epichlorohydrin by conversion of epichlorohydrm starting from a raw material comprising epichlorohydrm, in which use is made of an alkylating agent as an additive, said alkylating agent being added to at least one step of the process or formed in at least one step of the process, for instance added to the conversion of the epichlorohydrm, in an additional amount relative to the amount of this alkylating agent possibly present as an impurity in the raw material, said alkylating agent being chosen from halogen-substituted, sulphate-substituted, sulphonate- substituted, carbonate-substituted and phosphate-substituted organic compounds and mixtures of at least two of them.
  • step of the process one intends to denote any step from the supply of the raw materials to the recovery of the final product derived from epichlorohydrm.
  • steps are for instance, pretreatment of the raw materials, supply of the raw materials to the reaction medium, reaction to give the product derived from epichlorohydrm, treatments of the constituents of the reaction medium like for example separation of unconverted raw materials, intermediates of reaction, products and by-products of the reaction, recycling of the unconverted raw materials, purification of the product derived from epichlorohydrm, etc.
  • conversion of epichlorhydrin one intends to denote any step or combination of steps of the process wherein the epichlorohydrm is converted into the product derived from epichlorohydrm.
  • One essential feature of the invention consists in using an alkylating agent as additive, said alkylating agent being added to at least one step of the process or formed in at least one step of the process.
  • the epichlorohydrin derivative is a liquid epoxy resin
  • the use of the alkylating agent as additive 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.
  • an alkylating agent as additive inhibits the formation of solid organic by-products, for example of higher molecular weight epoxy resins, which could be responsible for the aforementioned separation difficulties when the epoxy resin is a liquid epoxy resin.
  • the product derived from epichlorohydrin may be chosen from epoxy resins, monoglycidyl ethers, diglycidyl ethers, glycidyl esters, glycidyl amides, glycidyl imides, glycidyl amines, products that can be used as coagulants, water-resistant resins, cationizing agents, flame retardants, detergent ingredients, epichlorohydrin elastomers, halogenated polyether polyols, monochloropropanediol and mixtures of at least two of them.
  • the product derived from epichlorohydrin may be as described in international application WO 2008/152044 in the name of SOL V AY, the content of which, and more specifically the passage from page 13, line 10, to page 44, line 8, is incorporated herein by reference, and in international application PCT/ EP2009/053766 in the name of SOL V AY, the content of which, and more specifically the passage from page 27, line 26, to page 33, line 18, is
  • the product derived from epichlorohydrin is preferably an epoxy resin.
  • epoxy resin is understood to mean 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 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, Type IV Grade 1 Classes A to D, Type V Grade 1 Classes A and B 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 product derived from epichlorohydrin is an epoxy resin
  • this resin can possibly be further cured.
  • the curing process and the curing agents can be such described in International application WO 2008/153044 in the name of SOLVAY SA, the content of which is hereby incorporated by reference, more specifically the passage from page 22, line 20 to page 24, line 16.
  • the expression "raw material” is understood to mean all of the chemicals used for carrying out the conversion of the epichlorohydrin. Besides the epichlorohydrin, the raw material may be a coreactant, a solvent, a catalyst, or a mixture of at least two of them.
  • the raw material may comprise at least one compound other than epichlorohydrin, selected from monoalcohols, monocarboxylic acids, polyols, polyamines, amino alcohols, polyimides, polyamides, polycarboxylic acids, ammonia, amines, polyaminoamides, polyimines, amine salts, phosphoric acid, phosphoric acid salts, phosphorus oxychlorides, phosphoric acid esters, phosphonic acids, esters of phosphonic acids, salts of phosphonic acids, phosphinic acids, esters of phosphinic acids, salts of phosphinic acids, phosphine oxides, phosphines, ethoxylated alcohols, alkylene oxides, phenylene oxides such as arylalkylene oxides, water and dihydroxylated or polyhydroxylated compounds that may optionally be halogenated and/or have ether-oxide bonds and/or have double bonds capable of
  • the raw material may comprise at least one compound other than epichlorohydrin, selected from monoalcohols, monocarboxylic acids, polyamines, amino alcohols, polyimides, polyamides, polycarboxylic acids, ammonia, amines, polyaminoamides, polyimines, amine salts, phosphoric acid, phosphoric acid salts, phosphorus oxychlorides, phosphoric acid esters, phosphonic
  • polyhydroxylated compounds that may optionally be halogenated and/or have ether-oxide bonds and/or have double bonds capable of being halogenated in a subsequent step .
  • the raw material may comprise 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 raw material may comprise 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 compound other than epichlorohydrin may be as described in international application WO 2008/152044 in the name of SOL V AY, the content of which, and more specifically the passage from page 13, line 10, to page 44, line 8, is incorporated herein by reference, and in international application PCT/ EP2009/053766 in the name of SOL V AY, the content of which, and more specifically the passage from page 27, line 26, to page 33, line 18, is
  • the compound other than epichlorohydrin may be a monoalcohol, preferably chosen from the group constituted of 1-butanol, a C 12 to C 14 primary alcohol, a cresol and any mixture of at least two of them.
  • the product derived from epichlorhydrin is selected from monoglycidyl ethers, and any mixtures thereof.
  • the compound other than epichlorohydrin may be a monocarboxylic acid, preferably chosen from the group constituted of neodecanoic acid, acrylic acid, methacrylic acid and any mixture of at least two of them.
  • the compound other than epichlorohydrin may be an amino alcohol, preferably p-aminophenol.
  • the raw material comprises at least one compound other than epichlorohydrin which is preferably a polyol.
  • the polyol is preferably chosen in the group consisting of a diol, a triol, a tetraol, and any mixture of at least two of them.
  • the process according to the invention when the product derived from epichlorohydrin is an epoxy resin, the process according to the invention generally comprises at least one of the following steps:
  • the compound other than epichlorohydrin is a polyol and more specifically a diol
  • it 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-d
  • condensation product of bisphenol A with formaldehyde bisphenol A novolac
  • a 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
  • 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 compound other than epichlorohydrin is bisphenol A and the product derived from epichlorohydrin 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.
  • the raw material may also comprise at least one basic compound, as defined above.
  • This particularly preferred embodiment is used in the process known under the name of the Caustic Coupling 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 raw material generally comprises at least one monovalent substituted onium salt, as defined above.
  • the raw material may also comprise at least one basic compound and at least one monovalent substituted onium salt as defined above.
  • 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
  • the alkylating agent may be a halogen-substituted organic compound chosen from halogen-substituted alkyl derivatives, halogen-substituted cycloalkyl derivatives, halogen-substituted cycloalkylalkyl derivatives, halogen-substituted arylalkyl derivatives, halogen- substituted aryl derivatives, halogen-substituted alkylvmyl derivatives, halogen- substituted vinyl derivatives, halogen-substituted arylvin l derivatives, halogen- substituted a Iky iaryl vinyl derivatives, halogen-substituted alkyl epoxides other than epichiorohydrin, halogen-substituted alkylaryl epoxides, halogen- substituted cycloalkyl epoxides, halogen-substituted e
  • the alkyl groups generally comprise linear or branched alkyl chains of 1 to 6 carbon atoms including, but not limited to, ethyl, ethyl, n-propyS, isopropyi, n -butyl, isobutyl, sec-butyl, i-butyl, n-pentyl, 1-methylbutyl, 2,2-dimethylbutyl, 2-methylpentyl, 2,2-dimethy [propyl, n-hexyl and the like.
  • the alkylating agent is preferably a halogen-substituted organic compound.
  • the halogen-substituted organic compound may be monohalogenated or polyhalogenated.
  • the halogen atom in the halogen- substituted organic compound may be chosen from fluorine, chlorine, bromine and iodine.
  • the halogen-substituted organic compound may contain several different halogen atoms chosen from those mentioned above.
  • the halogen-substituted organic compound may also comprise at least one heteroatom other than the halogen.
  • the halogen-substituted organic compound is an alkyl, alkenyl, cycloalkyl or cycloalkenyl monochloride or polychloride. More preferably, the halogen-substituted organic compound is an alkyl or alkenyl monochloride or polychloride.
  • the halogen-substituted organic compound is preferably chosen from the following compounds and mixtures of at least two of them:
  • chloromethane often dichloromethane, frequently trichloromethane, usually tetrachloromethane, and any mixture of at least two of them;
  • chloropropane often 2-chloropropane, frequently 1-chloropropane, and any mixture of at least two of them;
  • dichloropropane preferably 1,3-dichloropropane, 1,2-dichloropropane, 2,2- dichloropropane, and any mixture of at least two of them;
  • trichloropropane preferably 1,2,2-trichloropropane, 1 , 1 ,2-trichloropropane, 1,2,3-trichloropropane, and any mixture of at least two of them;
  • chloropropene often 2-chloro-l-propene, frequently ds-l-chloro-l -propene, usually mms-l-chloro-l -propene, specifically 3-chloro-l-propene, and any mixture of at least two of them;
  • dichloropropene often ds-l ⁇ -dichloropropene, frequently trans-1,3- dichloropropene, usually 3,3-dichloro-l-propene, frequently 2,3-dichloro-l- propene, usually cis- 1 ,3-dichloro- 1 -propene, specifically trans- 1 ,3-dichloro-
  • ⁇ trichloropropene often ds-l ⁇ -trichloro-l-propene, frequently trans-1,3,3- trichloro-1 -propene, usually ds-l ⁇ -trichloropropene, specifically trans- 1,2,3-trichloropropene, and any mixture of at least two of them;
  • chloroalkyl ethers of empirical formula RO(CH 2 ) p Cl where p is greater than or equal to 1 frequently chloromethyl ethers of empirical formula ROCH 2 Cl, more specifically methyl chloromethyl ether, bis(chloromethyl) ether, benzyl chloromethyl ether, i-butyl chloromethyl ether, methoxyethoxy chloromethyl ether, and any mixture of at least two of them;
  • chloropropenol often 2-chloro-2-propen-l-ol, frequently cis-3-chioro-2- propen-l-ol, and specifically iraws-S-chloro- -propen-l-ol, and any mixture of at least two of them;
  • dichloropropanol often l,3-dichloropropan-2-ol, 2,3-dichloropropan-l-ol, and any mixture thereof;
  • chloroethers preferably chosen from the chloroethers of empirical chemical formula: C6H10CI2O2 , C6H12CI2O, C6H9CI3O2, C6H11CI3O2, and any mixture of at least two of them;
  • the halogen-substituted organic compound is more preferably chosen from dichloropropenes, trichloropropenes, trichloropropanes, benzyl chloride, chloroacetone, and mixtures of at least two of them.
  • the sulphate-substituted organic compound may be dimethyl sulphate, diethyl sulphate, dihexyl sulphate, diallyl sulphate, dibenzyl sulphate and any mixture thereof.
  • Dimethyl sulphate, diallyl sulphate, dibenzyl sulphate and mixtures of at least two of them are very suitable.
  • the sulphonate-substituted organic compound may be methyl tosylate, ethyl tosylate, allyl tosylate, benzyl tosylate, methyl methanesulphonate, ethyl methanesulphonate, allyl
  • methanesulphonate benzyl methanesulphonate, and any mixture thereof.
  • Methyl methanesulphonate, allyl methanesulphonate, benzyl methanesulphonate and mixtures of at least two of them are very suitable.
  • the carbonate-substituted organic compound may be dimethyl carbonate, diethyl carbonate, diallyl carbonate, dibenzyl carbonate and any mixture thereof.
  • the phosphate-substituted organic compound may be trimethyl phosphate, triethyl phosphate, triallyl phosphate, tribenzyl phosphate and any mixture thereof.
  • the alkylating agent is used as an additive added to at least one step of the process or formed in at least one step of the process, for instance added to the conversion of the epichlorohydrin, in an additional amount relative to the amount of this alkylating agent possibly present as an impurity in the raw material.
  • the alkylating agent may be present or may not be present as an impurity in the raw material containing the epichlorohydrin.
  • the alkylating agent may be present as an impurity in the raw material containing the epichlorohydrin, in particular as an impurity in the
  • the alkylating agent may not be present as an impurity in the raw material containing the epichlorohydrin, in particular as an impurity of the
  • epichlorohydrin By “not being present”, one intends to denote situations where the content of the alkylating agent in the raw material, in particular in the epichlorohydrin, is lower than 1 mg of alkylating agent per kg of raw material, in particular par kg of epichlorohydrin.
  • the alkylating agent can be added at or formedand preferably added during at least one step of the process according to the invention.
  • the alkylating agent used as an additive is formed during a step of pretreatment of the epichlorohydrin.
  • This pretreatment step can consist of a partial hydrolysis of epichlorohydrin.
  • This hydrolysis can be carried out by adding a defined quantity of water or a defined quantity of a aqueous mixture containing at least one mineral acid, such as hydrogen chloride for instance, to the epichlorohydrin.
  • the alkylating agent is for example a monochloropropanediol or a dichloropropanol or any mixture thereof.
  • the alkylating agent used as an additive is added to one or more of the chemicals that make up the raw material.
  • the alkylating agent is added to the epichlorohydrin.
  • the alkylating agent is added to this chemical.
  • the alkylating agent is added for one part to that chemical and for another part to the epichlorohydrin.
  • the alkylating agent is added or formed to the medium in which the epichlorohydrin conversion takes place.
  • This medium is generally a liquid reaction medium.
  • the alkylating agent is added to the medium in which the epichlorohydrin conversion takes place.
  • the alkylating agent is formed to the medium in which the epichlorohydrin conversion takes place.
  • the alkylating agent may be added or formed continuously or in batch mode.
  • the alkylating agent is often added continuously or in batch mode.
  • the alkylating agent is preferably added to the epichlorohydrin conversion medium.
  • this approach makes it possible to prevent degradation of the alkylating agent which would limit its role of inhibiting the formation of solid organic by-products, such as higher molecular weight epoxy resins.
  • the alkylating agent may be judicious to add the alkylating agent to the epichlorohydrin conversion medium when the degree of conversion of the diol, expressed as mol% of diol, is generally greater than or equal to 50 mol%, usually greater than or equal to 60%, in many cases greater than or equal to 70%, often greater than or equal to 80%, frequently greater than or equal to 90%, and specifically greater than or equal to 95%. It may be judicious to add the alkylating agent to the epichlorohydrin conversion medium when the degree of conversion of the diol, expressed as mol % of diol, is usually lower than or equal to 99.9 % and often lower than or equal to 99 %.
  • This variant is suitable when the product derived from epichlorohydrin is a liquid epoxy resin obtained by conversion of epichlorohydrin starting from a raw material comprising epichlorohydrin, a diol and a basic compound.
  • the diol is preferably bisphenol A.
  • the ratio of the additional amount of alkylating agent to the amount of alkylating agent present as an impurity in the raw material is generally greater than or equal to 0.01, often greater than or equal to 0.1, frequently greater than or equal to 1 and specifically greater than or equal to 10. This ratio is habitually less than or equal to 1000, often less than or equal to 500, frequently less than or equal to 100 and specifically less than or equal to 50.
  • the additional amount of alkylating agent relative to the amount of epichlorohydrin in the raw material and expressed as g of alkylating agent per kg of epichlorohydrin is generally greater than or equal to 0.005, often greater than or equal to 0.02, frequently greater than or equal to 0.05 and in particular greater than or equal to 0.1.
  • This additional amount is generally less than or equal to 5, often less than or equal to 1, frequently less than or equal to 0.7 and in particular less than or equal to 0.5.
  • the product derived from epichlorohydrin is a liquid epoxy resin obtained by conversion of epichlorohydrin starting from a raw material comprising epichlorohydrin, bisphenol A and a basic compound
  • the ratio of the additional amount of alkylating agent to the amount of bisphenol A, expressed as g of alkylating agent per kg of bisphenol A is generally greater than or equal to 0.03, often greater than or equal to 0.1 and in particular greater than or equal to 0.3. This ratio is habitually less than or equal to 25, frequently less than or equal to 5, and specifically less than or equal to 3.
  • the epichlorohydrin present in the raw material may have been manufactured by any process.
  • 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.
  • allyl chloride epoxidation processes the process for epoxidation via hydrogen peroxide is preferred. It is preferred that at least one part of the epichlorohydrin is obtained by dehydrochlorination of dichloropropanol, preferably by dehydrochlorination of dichloropropanol with a basic compound.
  • At least one portion of the epichlorohydrin is preferably 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 alcohol chlorination 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.
  • the glycerol can be obtained by any process. That process can be starting from renewable raw materials, fossil raw materials, or any combination thereof. It is preferred that at least one part of said glycerol has been prepared in a conversion process of renewable raw materials.
  • Glycerol obtained from renewable raw materials is for instance glycerol which has been prepared in the process selected from the group consisting of hydrolysis, saponification, transesterification, aminolysis and hydrogenation of oils and/or fats of animal and/or plant and/or algae origin, of fermentation, hydrogenation and
  • Glycerol which has been obtained during the manufacture of biodiesel, i.e. during the transesterification of oils and/or fats of animal and/or plant and/or algae, and preferably during the transesterification of oils and/or fats of plant origin, is particularly convenient.
  • the processes for preparing the dichloropropanol and the epichlorohydrin 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, WO 2006/106154, WO2006/106155, WO 2007/144335, WO 2008/107468, WO 2008/101866, WO 2008/145729, WO 2008/110588, WO 2008/152045, WO 2008/152043, WO 2009/000773, WO 2009/043796, WO 2009/121853, WO 2008/152044, WO 2009/077528, WO 2010/066660, WO 2010/029039 and WO 2010/029153, filed in the name of SOLVAY, the contents of which are
  • 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.
  • 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 obtained by reaction between glycerol and hydrogen chloride.
  • the process according to the invention may comprise a step at the end of which a mixture is recovered that comprises the epoxy resin and a salt, in which said mixture is treated with water and at least one organic solvent, the solubility of which in water is limited, and in which a first fraction comprising the organic solvent and most of the epoxy resin included in the mixture before the treatment and a second fraction comprising the water and most of the salt included in the mixture before the treatment are separated by settling.
  • the organic solvent the solubility of which in water is limited, may be chosen from the group constituted by toluene, xylene, benzene, methyl isobutyl ketone, methyl ethyl ketone and mixtures of at least two of them.
  • the epichlorohydrin contains, as impurities, 3-chloro-l-propene, 3,3-dichloro-l-propene, chloroacetone, 3,3- dichloro-l-propene, 1 ,2-dichloropropane, 2,3-dichloro-l-propene, cis-1 ,3- dichloro-l-propene, iraws-l ⁇ -dichloro-l-propene, 2-chloro-2-propen-l-ol, 1 ,3- dichloropropane, 1 ,1 ,2-trichloropropane, chlorobenzene, l ,3-dichloropropan-2-ol and glycerol alpha-monochlorohydrin.
  • the sum of the amounts of these impurities relative to the amount of epichlorohydrin is 0.1 1 g of impurities/kg of epichlorohydrin.
  • a water/epichlorohydrin mixture is drawn off continuously by distillation. The water/epichlorohydrin mixture is cooled and an aqueous phase and epichlorohydrin are separated by settling. The epichlorohydrin is returned to the resulting mixture. When all of the sodium hydroxide is consumed, the excess epichlorohydrin is removed by distillation. Added in sequence to the residue of this distillation are methyl isobutyl ketone and water. The whole mixture is stirred and then left to settle.
  • Example 2 The operations from Example 1 are repeated except that added to the epichlorohydrin are 3-chloro-l-propene, 3,3-dichloro-l-propene, chloroacetone, 3,3-dichloro-l-propene, 1 ,2-dichloropropane, 2,3-dichloro-l-propene, as- 1 ,3- dichloro-l-propene, iraws-l ⁇ -dichloro-l-propene, 2-chloro-2-propen-l-ol, 1 ,3- dichloropropane, 1 ,1 ,2-trichloropropane, chlorobenzene, l ,3-dichloropropan-2-ol and glycerol alpha-monochlorohydrin (alkylating agents) before mixing with the bisphenol A, so as to obtain a sum of the amounts of these impurities relative to the amount of epichlorohydrin of 1.34 g/kg
  • the amount of solid phase present after settling of the water/methyl isobutyl ketone mixture is smaller than in Example 1.
  • BADGE has been reconstituted by mixing 147.3 g of commercial BADGE (0.43 mol) and 50.9 g of sodium chloride (0.87 mol). The mixture has been stirred during 10 min at 90°C and under nitrogen at atmospheric pressure before the addition of 160.3 g of epichlorohydrin (1.73 mol).
  • the epichlorohydrin contains, as impurities, chloroacetone, ds-l ⁇ -dichloro-l-propene, trans- 1 ,3- dichloro-l-propene, 2-chloro-2-propen-l-ol, 1 ,3 -dichloropropane, 1 ,1 ,2- trichloropropane, 1,2,3-trichloropropane, chlorobenzene and 1,3-dichloropropan- 2-ol.
  • the sum of the amounts of the impurities relative to the amount of epichlorohydrin is 0.12 g of impurities/kg of epichlorohydrin.
  • the temperature of the mixture has then been regulated at 86°C and 2.52 g of bisphenol A (0.01 mol) has been added after 25 min.
  • a solution of 0.93 g of sodium hydroxide in 1.84 g of water has been added after 10 min and the resulting mixture has been stirred during 1 h.
  • the epichlorohydrin has then been evaporated under vacuum to reach a residue temperature of 114° C under 230 torr. 151.3 g of methyl butyl ketone have been added in 20 min at a constant rate flow in the stirred residue at 50°C. 281.7 g of water have finally been added in 10 min under agitation at a temperature of 46° C.
  • the mixture has then been put in a separatory funnel to give 3 fractions after decantation during 48 h : a clear liquid upper phase, an intermediate liquid phase containing a solid, and a clear liquid lower phase.
  • 4.72 g of a wet solid has been recovered by filtration of the intermediate liquid phase on a 5 ⁇ porosity polytetrafluoroethylene (PTFE) filter and by centrifugation of the filtrate.
  • the weight of the wet solid is equivalent to 3.2 % of the weight of the initial quantity of BADGE.
  • a final reaction mixture of a synthesis of bisphenol A diglycidyl ether (BADGE) has been reconstituted by mixing 149.2 g of commercial BADGE
  • epichlorohydrin quality is the same as for example 3 except that 2,3-dichloropropene has been added to reach a 500 mg/kg concentration. The mixture has been stirred during 12 min at 84°C and under nitrogen at
  • the mixture has then been put in a separatory funnel to give 3 fractions after decantation during 24 h : a clear liquid upper phase, an intermediate liquid phase containing a solid, and a clear liquid lower phase.
  • 3.49 g of a wet solid has been recovered by filtration of the intermediate liquid phase on a 5 ⁇ porosity PTFE filter.
  • the weight of the wet solid is equivalent to 2.3 % of the weight of the initial quantity of BADGE.
  • a final reaction mixture of a synthesis of bisphenol A diglycidyl ether (BADGE) has been reconstituted by mixing 151.6 g of commercial BADGE
  • the epichlorohydrin contains, as impurities, 3,3-dichloro-l-propene, 2,3-dichloro-l-propene, chloroacetone, ds-l ⁇ -dichloro-l-propene, trans-1,3- dichloro-l-propene, 2-chloro-2-propen-l-ol, 3-chloro-2-propen-l-ol, 1,3- dichloropropane, 1,1,2-trichloropropane, 1,2,3-trichloropropane, 1,3,3- trichloropropene, 1,2,3-trichloropropene, chlorobenzene, l,3-dichloropropan-2- ol and 3-chloro-l, 2, -propanediol.
  • the sum of the amounts of the impurities relative to the amount of epichlorohydrin is 0.71 g of impurities/kg of epichlorohydrin. .
  • the mixture has been stirred during 25 min at 84°C and under nitrogen at atmospheric pressure.
  • the temperature of the mixture has then been regulated at 85°C and 2.51 g of bisphenol A (0.01 mol) has been added.
  • a solution of 0.92 g of sodium hydroxide in 1.83 g of water has been added after 10 min and the resulting mixture has been stirred during 1 h.
  • epichlorohydrin has then been evaporated under vacuum to reach a residue temperature of 114° C under 263 torr. 152.7 g of methyl butyl ketone have been added in 19 min at a constant rate flow in the stirred residue at 53°C. 286.1 g of water have finally been added in 10 min under agitation at a temperature of 49°C.
  • the mixture has then been put in a separatory funnel to give 3 fractions after decantation during 48 h : a clear liquid upper phase, an intermediate liquid phase containing a solid, and a clear liquid lower phase. 5.27 g of a wet solid has been recovered by filtration of the intermediate liquid phase on a 5 ⁇ porosity PTFE filter and by centrifugation of the filtrate. The weight of the wet solid is equivalent to 3.5 % of the weight of the initial quantity of BADGE.
  • BADGE has been reconstituted by mixing 150.1 g of commercial BADGE (0.44 mol), 51.8 g of sodium chloride (0.89 mol) and 165.1 g of epichlorohydrin (1.78 mol).
  • the epichlorohydrin quality is the same as for example 5 except that 3-chloro-l,2-propanediol has been added to reach a 5 g/kg concentration. The mixture has been stirred during 20 min at 83°C and under nitrogen at
  • the mixture has then been put in a separatory funnel to give 3 fractions after decantation during 24 h : a clear liquid upper phase, an intermediate liquid phase containing a solid, and a clear liquid lower phase.
  • 2.51 g of a wet solid has been recovered by filtration of the intermediate liquid phase on a 5 ⁇ porosity PTFE filter.
  • the weight of the wet solid is equivalent to 1.7 % of the weight of the initial quantity of BADGE.

Landscapes

  • 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'un produit dérivé de l'épichlorohydrine par conversion de l'épichlorohydrine à partir d'une matière première comprenant de l'épichlorohydrine, consistant à utiliser un agent d'alkylation comme additif, ledit agent d'alkylation étant 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 cet agent d'alkylation éventuellement présent sous forme d'impureté dans la matière première, ledit agent d'alkylation étant choisi parmi des composés organiques à substitution halogène, sulfate, sulfonate, carbonate et phosphate et des mélanges d'au moins deux d'entre eux.
EP10776334A 2009-11-04 2010-10-29 Procédé de fabrication d'un produit dérivé de l'épichlorohydrine Withdrawn EP2496626A2 (fr)

Applications Claiming Priority (2)

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
PCT/EP2010/066532 WO2011054769A2 (fr) 2009-11-04 2010-10-29 Procédé de fabrication d'un produit dérivé de l'épichlorohydrine

Publications (1)

Publication Number Publication Date
EP2496626A2 true EP2496626A2 (fr) 2012-09-12

Family

ID=41668261

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10776334A Withdrawn EP2496626A2 (fr) 2009-11-04 2010-10-29 Procédé de fabrication d'un produit dérivé de l'épichlorohydrine

Country Status (5)

Country Link
EP (1) EP2496626A2 (fr)
CN (1) CN102686632A (fr)
FR (1) FR2952060B1 (fr)
TW (1) TW201124439A (fr)
WO (1) WO2011054769A2 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1752436A1 (fr) 2003-11-20 2007-02-14 SOLVAY (Société Anonyme) Compositions pseudo-azeotropiques contenant du dichloropropanol et leur procédé de fabrication
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
JP6049087B2 (ja) 2010-09-30 2016-12-21 ソルヴェイ（ソシエテ アノニム） 天然起源のエピクロロヒドリンの誘導体
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
CN106630083B (zh) * 2015-10-29 2021-05-14 中国石油化工股份有限公司 一种环氧化废水的无害化处理方法

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD216471A1 (de) * 1983-06-30 1984-12-12 Leuna Werke Veb Verfahren zur aufarbeitung von epoxidharzhaltigen reaktionsgemischen
JPS61112066A (ja) * 1984-11-05 1986-05-30 Dainippon Ink & Chem Inc エポキシ樹脂の製法
US6794478B2 (en) * 2001-09-28 2004-09-21 Dainippon Ink And Chemicals, Inc. Preparing epoxy resin by distilling two fractions to recover and reuse epihalohydrin without glycidol
EP1752436A1 (fr) 2003-11-20 2007-02-14 SOLVAY (Société Anonyme) Compositions pseudo-azeotropiques contenant du dichloropropanol et leur procédé de fabrication
JP5419446B2 (ja) 2005-05-20 2014-02-19 ソルヴェイ（ソシエテ アノニム） 耐腐食性装置内でのクロロヒドリンの調製方法
CA2628684A1 (fr) 2005-11-08 2007-05-18 Solvay (Societe Anonyme) Procede de fabrication de dichloropropanol par chloration de glycerol
US8124814B2 (en) 2006-06-14 2012-02-28 Solvay (Societe Anonyme) Crude glycerol-based product, process for its purification and its use in the manufacture of dichloropropanol
US20100032617A1 (en) 2007-02-20 2010-02-11 Solvay (Societe Anonyme) Process for manufacturing epichlorohydrin
FR2913421B1 (fr) 2007-03-07 2009-05-15 Solvay Procede de fabrication de dichloropropanol.
FR2913684B1 (fr) 2007-03-14 2012-09-14 Solvay Procede de fabrication de dichloropropanol
TW200911740A (en) 2007-06-01 2009-03-16 Solvay Process for manufacturing a chlorohydrin
JP5188777B2 (ja) 2007-06-11 2013-04-24 ナブテスコ株式会社 舶用制御装置及びその表示器
TWI500609B (zh) 2007-06-12 2015-09-21 Solvay 含有環氧氯丙烷的產品，其製備及其不同應用中的用途
TW200911693A (en) 2007-06-12 2009-03-16 Solvay Aqueous composition containing a salt, manufacturing process and use
FR2918058A1 (fr) 2007-06-28 2009-01-02 Solvay Produit a base de glycerol, procede pour sa purification et son utilisation dans la fabrication de dichloropropanol
KR20100089835A (ko) 2007-10-02 2010-08-12 솔베이(소시에떼아노님) 용기의 내부식성 향상을 위한 실리콘-함유 조성물의 용도
FR2925045B1 (fr) 2007-12-17 2012-02-24 Solvay Produit a base de glycerol, procede pour son obtention et son utilisation dans la fabrication de dichloropropanol
CN101980995B (zh) 2008-04-03 2014-06-18 索尔维公司 包含甘油的组合物、获得该组合物的方法以及它们在二氯丙醇生产中的用途
FR2935699A1 (fr) 2008-09-10 2010-03-12 Solvay Procede de fabrication d'un produit chimique
FR2935968B1 (fr) 2008-09-12 2010-09-10 Solvay Procede pour la purification de chlorure d'hydrogene
FR2939434B1 (fr) 2008-12-08 2012-05-18 Solvay Procede de traitement de glycerol.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011054769A2 *

Also Published As

Publication number Publication date
FR2952060B1 (fr) 2011-11-18
TW201124439A (en) 2011-07-16
CN102686632A (zh) 2012-09-19
FR2952060A1 (fr) 2011-05-06
WO2011054769A2 (fr) 2011-05-12
WO2011054769A3 (fr) 2011-06-30

Similar Documents

Publication Publication Date Title
EP2496626A2 (fr) Procédé de fabrication d'un produit dérivé de l'épichlorohydrine
TWI406855B (zh) 表氯醇的製造方法
EP2268596B1 (fr) Composition comprenant du glycérol, son procédé d'obtention et son utilisation dans la fabrication de dichloropropanol
JP5878293B2 (ja) エピクロロヒドリンを含有する生成物、その調製および種々の用途におけるその使用
EP2496625A1 (fr) Procédé de fabrication d'une résine époxy
JP5575793B2 (ja) グリセロール処理方法
TWI335323B (en) Process for preparing an epoxide
KR20080037613A (ko) 폴리히드록실화 지방족 탄화수소의 클로로히드린으로의전환 방법
EP2669305A1 (fr) Procédé de fabrication d'une résine époxy
KR101558633B1 (ko) 액체 에폭시 수지의 제조 방법
KR102090992B1 (ko) 에폭시 수지의 제조 방법
CA1118433A (fr) Obtention de polyglycidylethers de phenols polyhydriques
EP2669307A1 (fr) Processus de fabrication dýune époxyde
EP2669308A1 (fr) Procédé de fabrication d'une résine époxy
EP2669306B1 (fr) Procédé de fabrication d'une résine époxy
TW201427934A (zh) 汽提液體介質的方法
EP2669247A1 (fr) Procédé de fabrication de dichloropropanol
WO2024209710A1 (fr) Procédé de production d'une résine époxyde, procédé de production d'une composition de résine époxyde, procédé de production d'un produit durci, procédé de production d'une composition de résine époxyde contenant des fibres, procédé de production de carbonate de diphényle et procédé de production de résine de polycarbonate
JP2024149214A (ja) エポキシ樹脂及び再生繊維の製造方法、繊維含有エポキシ樹脂組成物の製造方法、並びに繊維含有エポキシ樹脂硬化物の製造方法
FR2954772A1 (fr) Procede de fabrication d'une resine epoxy

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120604

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20130115