EP2496626A2

EP2496626A2 - Process for manufacturing a product derived from epichlorohydrin

Info

Publication number: EP2496626A2
Application number: EP10776334A
Authority: EP
Inventors: Patrick Gilbeau
Original assignee: Solvay SA
Current assignee: Solvay SA
Priority date: 2009-11-04
Filing date: 2010-10-29
Publication date: 2012-09-12
Also published as: CN102686632A; FR2952060A1; WO2011054769A2; FR2952060B1; WO2011054769A3; TW201124439A

Abstract

Process for manufacturing a product derived from epichlorohydrin by conversion of epichlorohydrin starting from a raw material comprising epichlorohydrin, 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, 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.

Description

Process for manufacturing a product derived from epichlorohydrin

The present application claims benefit of French patent application n° 0957793 filed on November 04 2009, the content of which is incorporated herein by reference.

Should the disclosure of any of the patents, patent applications, and publications that are incorporated herein by reference conflict with the present specification to the extent that it might render a term unclear, the present specification shall take precedence.

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.

When the product derived from epichlorohydrin is a liquid epoxy resin, 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.

In patent application DD 216 471 Al, 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.

In the process according to the invention, by 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. Such 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. By 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.

There are many advantages linked to the use of such an agent as additive: ■ easy control of the epichlorohydrm conversion reaction;

■ increase in the selectivity of the process for the product derived from

epichlorohydrm;

■ possibility of choosing from several procedures for recovery of the product derived from epichlorohydrm;

■ better use of the raw material;

■ reduction in the amount of by-products formed;

■ reduction in the amount of releases to be treated and removed;

■ overall reduction in the cost of the process;

■ improvement in the productivity of the process;

■ simplification of the equipment. More specifically, when 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.

Without wishing to be tied to any one theoretical explanation, it is believed that the use of 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.

In the process according to the invention, 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

incorporated herein by reference.

In the process according to the invention, the product derived from epichlorohydrin is preferably an epoxy resin.

The expression "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.

The term "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".

Examples of chemical formulae of epoxy resins are presented in Figure 1 , when n is other than zero.

In the process according to the invention, the epoxy resin is preferably a liquid epoxy resin. The expression "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".

In the process according to the invention, when 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.

In the process according to the invention, 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.

In the process according to the invention, 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 being halogenated in a subsequent step.

In the process according to the invention, when the product derived from epichlorohydrin is selected from monoglycidyl 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 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 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, 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 being halogenated in a subsequent step .

In the process according to the invention, 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. The expression "purified caustic brine" here means sodium hydroxide which contains sodium chloride such as, for example, that produced in a diaphragm electrolysis process.

In the process according to the invention, 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

incorporated herein by reference.

In the process according to the invention, when the product derived from epichlorohydrin is selected from monoglycidyl ethers, 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.

In the process according to the invention, when the compound other than epichlorohydrin is a monoalcohol, the product derived from epichlorhydrin is selected from monoglycidyl ethers, and any mixtures thereof.

In the process according to the invention, 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.

In the process according to the invention, the compound other than epichlorohydrin may be an amino alcohol, preferably p-aminophenol.

In the process according to the invention, when the product derived from epichlorohydrin is a diglycidyl ether or an epoxy resin or a mixture thereof, 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.

In 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:

■ pretreatment of the reactants, such as the epichlorohydrin, the aromatic polyol and the basic agent for example;

■ chemical reactions that make it possible to change from the reactants to the epoxy resin, such as neutralization, condensation and dehydrochlorination reactions, for example;

■ physical treatments for removing reactants and/or products of the reaction, such as the azeotropic removal of the water by distillation, the removal of the unreacted epichlorohydrin by distillation, the filtration of the salt formed, the addition of solvents in order to dissolve the salt and the resin, the settling of the resulting solutions of epoxy resins and salt, for example.

In the process according to the invention when 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-dihydroxynaphthalene, 1,1 ',7,7'- tetrahydroxydinaphthylmethane, 4,4 ' -dihydroxy-a-methylstilbene, a

condensation product of bisphenol A with formaldehyde (bisphenol A novolac), a condensation product of phenol with formaldehyde, preferably bisphenol F (mixture of ο,ο', ο,ρ' and ρ,ρ' isomers of dihydroxydiphenylmethane), a condensation product of cresol with formaldehyde (mixture of ο,ο', ο,ρ' and ρ,ρ' 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.

In one particularly preferred embodiment of the process according to the invention, 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.

In this particularly preferred embodiment, 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.

In this particularly preferred embodiment, the raw material generally comprises at least one monovalent substituted onium salt, as defined above.

In this particularly preferred embodiment, 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

Chemistry, Fifth Completely Revised Edition, Vol. A9, pages 548-549.

In the process according to the invention, 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 eycloaikyiaikyi epoxides, halogen-substituted heterocyclic compounds or halogen-substituted alkylated heterocyclic compounds other than epichiorohydrin, and mixtures of at least two of them.

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. In the process according to the invention, 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. Preferably, 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.

In the process according to the invention, 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;

■ chloroethane;

■ chloropropane, often 2-chloropropane, frequently 1-chloropropane, and any mixture of at least two of them;

■ dichloroethane, often 1 ,2-dichloroethane;

■ 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-

1-propene, and any mixture of at least two of them;

■ 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(CH₂)_pCl where p is greater than or equal to 1 , frequently chloromethyl ethers of empirical formula ROCH₂Cl, 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;

■ aromatic compounds substituted by a chloromethyl group, often benzyl chloride; ■ chloroethanol, often 2-chloroethanol;

■ chloropropanol, often 3-chloro-l-propanol;

■ 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;

■ monochloropropanediol, often 3-chloro-l,2-propanediol, frequently 2-chloro- 1,3-propanediol, and mixtures thereof;

■ 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;

■ compounds of empirical chemical formula: C4H7CIO2, C6H9CI3, C6H9CI3O2, C9H17CI3O4, C9H15CI5O, C3H3CI3, and any mixture of at least two of them; ■ dichloroepoxypropane, epibromohydrin, and mixtures thereof; and

■ chloroacetone, dichloroacetone, preferably 1,3-dichloroacetone, and mixtures thereof.

In the process according to the invention, the halogen-substituted organic compound is more preferably chosen from dichloropropenes, trichloropropenes, trichloropropanes, benzyl chloride, chloroacetone, and mixtures of at least two of them.

In the process according to the invention, 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.

In the process according to the invention, 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.

In the process according to the invention, the carbonate-substituted organic compound may be dimethyl carbonate, diethyl carbonate, diallyl carbonate, dibenzyl carbonate and any mixture thereof. In the process according to the invention, the phosphate-substituted organic compound may be trimethyl phosphate, triethyl phosphate, triallyl phosphate, tribenzyl phosphate and any mixture thereof.

In the process according to the invention, 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.

By possibly present as an impurity in the raw material, one intends to denote that 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

epichlorohydrin. In this case and without wishing to be tied to any one theoretical explanation, it is believed that the amount of alkylating agent as an impurity in the raw material is insufficient to inhibit the formation of solid organic by-products, and that it is needed to add or form an extra amount of that alkylating agent.

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.

In a first embodiment according to the process of 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. In this case, the alkylating agent is for example a monochloropropanediol or a dichloropropanol or any mixture thereof. In a second embodiment according to the process of the invention, the alkylating agent used as an additive is added to one or more of the chemicals that make up the raw material.

In a first variant of this second embodiment, the alkylating agent is added to the epichlorohydrin.

In a second variant of this second embodiment, when the raw material comprises at least one chemical other than the epichlorohydrin, such as those described above, the alkylating agent is added to this chemical.

In a third variant of this second embodiment, when the raw material comprises at least one chemical other than epichlorohydrin, such as those described above, the alkylating agent is added for one part to that chemical and for another part to the epichlorohydrin.

In a third embodiment, 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.

In a first variant of the third embodiment, the alkylating agent is added to the medium in which the epichlorohydrin conversion takes place.

In a second variant of the third embodiment, 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.

In one particularly preferred embodiment of the process according to the invention, in which the compound other than epichlorohydrin is a diol, the alkylating agent is preferably added to the epichlorohydrin conversion medium. Without wishing to be tied to one theoretical explanation, it is believed that 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.

In a variant of this particularly preferred embodiment, 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 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. In this variant, the diol is preferably bisphenol A.

In the process according to the invention, 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.

In the process according to the invention, 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.

In the variant of the embodiment of the process according to the invention, in which 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.

In the process according to the invention, the epichlorohydrin present in the raw material 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. Among the 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.

In the process according to the invention, 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.

In the process according to the invention, when the epichlorohydrin originates from a dichloropropanol dehydrochlorination process, the

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.

In the process according to the invention, 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

hydrogenolysis of mono- and polysaccharides and derived alcohols, derived from or occurring naturally in the biomass, and any combination thereof. 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 incorporated herein by reference.

In the process according to the invention, 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.

In the process according to the invention, 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.

When the epichlorohydrin derivative is an epoxy resin, 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 examples below are intended to illustrate the invention without, however, limiting it.

Example 1 (comparative)

The procedure is carried out as follows.

Added gradually to a mixture containing 10 mol of an epichlorohydrin obtained by dehydrochlorination of dichloropropanol by a basic compound, the dichloropropanol being obtained by hydrochlorination of glycerol using hydrogen chloride, and 1 mol of bisphenol A, are 2 mol of NaOH from an aqueous solution containing 40% by weight of NaOH. The procedure is carried out at the boiling point of the resulting mixture. 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. The presence of three phases is observed, a light organic phase containing most of the epoxy resin formed in the reaction between the epichlorohydrin and the bisphenol A, a dense aqueous phase containing most of the sodium chloride formed in said reaction, and a diffuse solid phase at the interface of the organic and aqueous phases. The amount of this solid phase is sizeable (visual estimate).

Example 2 (according to the invention)

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.

Example 3 (comparative)

A final reaction mixture of a synthesis of bisphenol A diglycidyl ether

(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 μιη 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.

Example 4 (according to the invention)

A final reaction mixture of a synthesis of bisphenol A diglycidyl ether (BADGE) has been reconstituted by mixing 149.2 g of commercial BADGE

(0.44 mol), 51.7 g of sodium chloride (0.88 mol) and 163.4 g of epichlorohydrin (1.77 mol). The 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

atmospheric pressure. 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. A solution of 0.89 g of sodium hydroxide in 1.79 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 109° C under 225 torr. 150.1 g of methyl butyl ketone have been added in 15 min at a constant rate flow in the stirred residue at 55°C. 286.1 g of water have finally been added in 10 min under agitation at a temperature of 48°C. 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 μιη porosity PTFE filter. The weight of the wet solid is equivalent to 2.3 % of the weight of the initial quantity of BADGE.

Example 5 (comparative)

A final reaction mixture of a synthesis of bisphenol A diglycidyl ether (BADGE) has been reconstituted by mixing 151.6 g of commercial BADGE

(0.45 mol), 51.7 g of sodium chloride (0.88 mol) and 163.7 g of epichlorohydrin (1.77 mol). 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. The

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 μιη 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.

Example 6 (according to the invention)

A final reaction mixture of a synthesis of bisphenol A diglycidyl ether

(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

atmospheric pressure. The temperature of the mixture has then been regulated at 85°C and 2.52 g of bisphenol A (0.01 mol) has been added. A solution of 0.87 g of sodium hydroxide in 1.75 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 45 torr. 150.6 g of methyl butyl ketone have been added in 19 min at a constant rate flow in the stirred residue at 56°C. 286.1 g of water have finally been added in 10 min under agitation at a temperature of 50°C. 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 μιη porosity PTFE filter. The weight of the wet solid is equivalent to 1.7 % of the weight of the initial quantity of BADGE.

Claims

C L A I M S

1 - Process for manufacturing a product derived from epichlorohydrin by conversion of epichlorohydrin starting from a raw material comprising epichlorohydrin, 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, 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.

2 - Process according to claim 1 wherein the alkylating agent is present as an impurity in the raw material comprising epichlorohydrin, and 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, in an additional amount relative to the amount of this alkylating agent present as an impurity in the raw material.

3 - Process according to claims 1 or 2, wherein the alkylating agent is used as an additive added to at least one step of the process.

4 - Process according to claim 3, wherein the alkylating agent is used as an additive added to the conversion of the epichlorohydrin.

5 - Process according to any one of Claims 1 to 4, in which the alkylating agent is a halogen-substituted organic compound chosen from dichloropropenes, trichloropropenes, trichloropropanes, benzyl chloride, chloroacetone and mixtures of at least two of them.

6 - Process according to any one of Claims 1 to 5, in which the additional amount of the alkylating agent relative to the amount of epichlorohydrin in the raw material and expressed as g of alkylating agent per kg of epichlorohydrin is greater than or equal to 0.005 and less than or equal to 5.

7 - Process according to any one of Claims 1 to 6, in which the product derived from epichlorohydrin is 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.

8 - Process according to any one of Claims 1 to 7, in which the product derived from epichlorohydrin is chosen from 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, and wherein the raw material comprises 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, water and dihydroxylated or 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.

9 - Process according to any one of Claim 1 to 7, in which the product derived from epichlorohydrin is a diglycidyl ether or an epoxy resin or a mixture thereof and the raw material comprises at least one compound other than epichlorohydrin 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- 1 -(trifluoromethyl)ethylidene]bisphenol),

hexafluorobisphenol A (4,4'-dihydroxy-2,2-diphenyl-l, 1,1,3, 3,3- hexafluoropropane), 1 , 1 ,2,2-tetra(p-hydroxyphenyl)ethane, tetramethylbisphenol (4,4'-dihydroxy-3,3',5,5'-tetramethyl bisphenol), 1,5-dihydroxynaphthalene, 1,1 ',7,7'-tetrahydroxydinaphthylmethane, 4,4'-dihydroxy-a-methylstilbene, a condensation product of bisphenol A with formaldehyde (bisphenol A novolac), a condensation product of phenol with formaldehyde, preferably bisphenol F (mixture of ο,ο', ο,ρ' and ρ,ρ' isomers of dihydroxydiphenylmethane), a condensation product of cresol with formaldehyde (mixture of ο,ο', ο,ρ' and ρ,ρ' 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.

10 - Process according to Claim 9, in which the alkylating agent is added to the conversion of the epichlorohydrin when the degree of conversion of the diol, expressed as mol% of diol, is greater than or equal to 50 mol%. 11 - Process according to any one of Claims 1 to 10, in which at least one portion of the epichlorohydrin has been obtained by reaction between dichloropropanol and at least one basic compound, and at least one portion of said dichloropropanol ha been obtained by reaction between glycerol and hydrogen chloride. 12 - Process according to claim 11 wherein at least part of the glycerol has been obtained in the manufacture of biodiesel.

13 - Process according to any one of Claims 9 to 12, in which the epichlorohydrin derivative is an epoxy resin and which comprises 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 medium before the treatment and a second fraction comprising the water and most of the salt included in the medium before the treatment are separated by settling. 14 - Process according to Claim 13, in which the organic solvent is selected from the group constituted by toluene, xylene, benzene, methyl isobutyl ketone, methyl ethyl ketone and mixtures of at least two of them.