CN1976886A - Conversion of a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin - Google Patents

Abstract

The present invention relates to a process for converting a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin, by contacting the multihydroxylated-aliphatic hydrocarbon or ester thereof starting material with a source of a superatmospheric partial pressure of hydrogen chloride for a sufficient time and at a sufficient temperature, and wherein such contracting step is carried out without substantial removal of water, to produce the desired chlorohydrin product; wherein the desired product or products can be made in high yield without substantial formation of undesired overchlorinated byproducts. In addition, certain catalysts of the present invention may be used in the present process at superatmospheric, atmospheric and subatmospheric pressure conditions with improved results.

Description

Multihydroxylated-aliphatic hydrocarbon or its ester are to the conversion of chloropharin

Background of invention

The present invention relates to multihydroxylated-aliphatic hydrocarbon or its ester are transformed into the method for chloropharin.Chloropharin can be used for preparing epoxide such as epoxy chloropropane.

Epoxy chloropropane is the widely-used precursor of Resins, epoxy.Epoxy chloropropane is to be generally used for the alkylating monomer of dihydroxyphenyl propane; The diepoxide that obtains can proceed to high molecular weight resin as free monomer or oligopolymer diepoxide, and this high molecular weight resin for example is used for electrical laminate material, jar coating, automobile top coat and knows coating.

The currently known methods of making epoxy chloropropane comprises that the hypochlorination of chlorallylene is to form dichlorohydrin.The dichlorohydrin mixture provides epoxy chloropropane by the closed loop of causticity thing, and this epoxy chloropropane is distilled high purity (＞99.6%).These chloropharin processing requirement two equivalent chlorine and the every moles of epichlorohydrin of monovalent causticity thing (caustic).

In producing the another kind of currently known methods of epoxy chloropropane, first step comprises by the palladium catalyzed reaction of molecular oxygen in acetate, in the allylic positions of propylene oxygen is set.Then with the allyl acetate hydrolysis, the chlorination that obtain with subsequently initial dichlorohydrin is become epoxy chloropropane by causticity thing closed loop.This method is avoided the generation of chlorallylene and is therefore used less chlorine (only monovalent).

Above-mentioned two kinds of methods of making epoxy chloropropane require the sacrifices of chlorine to use, and can amplify and known these methods produce the chlorinated secondary product of remarkable quantity in technical scale with using with the industry of hypochlorous acid (HOCl) and producing relevant complicacy.Especially, the hypochlorination of known chlorallylene produces glyceryl trichloride and other not required chlorinated ether and oligopolymer (RCl).The RCl problem is considered the manufacturing cost of increase.Owing to add new fund, must increase capital investment that the downstream processes to adapt to and to remedy these undesirable by products to adapt to bigger worldwide production.These identical problems are being similar and these approach of less enforcement in the HOCl approach of propylene and ethene chloropharin.

In a kind of alternative method, it avoids the generation of HOCl, for example at WO 2002092586 and U.S. patent No.6, describes in 288,248, comprises the direct epoxidation of chlorallylene that uses titanosilicate catalysis to adopt hydrogen peroxide.Though have and reduce the advantage that HOCl produces but chlorallylene remains intermediate.Using the shortcoming of chlorallylene is two aspects: (1) propylene to the free radical chlorination of chlorallylene be not very optionally with the suitable vast scale of generation (＞15mol%) 1, the 2-propylene dichloride.(2) propylene is a hydrocarbon feed and for the secular price of propylene, and world projection continues progressively to raise.Need to produce the new economically viable method of epoxy chloropropane, it is complicated that this method avoids that controlled chlorine class oxidation chemistry and RCl produce.Need to produce the method for epoxy chloropropane in the industry, this method comprises the renewable raw material of nonhydrocarbon.

Glycerine is thought of as low cost, renewable raw material, and it is a by product of making the biofuel oil method of fuel dope.Known other renewable raw material such as fructose, glucose and sorbyl alcohol can hydrogenolysis to produce vicinal two pure and mild triols, as glycerine, ethylene glycol, 1,2-propylene glycol, 1, the mixture of ammediol etc.

Adopt in a large number and glycerine or mix glycol cheaply, glycerine or the attractive economically method of mixing the glycol hydrochlorinate are needed.If such method is that highly chemistry optionally and does not produce RCl to forming the vicinal chloropharin, then is favourable.

Known glycerine (being also referred to as " glycerine " at this) is changed into the method for the mixture of dichlorohydrine (being also referred to as " dichlorohydrin " at this), Compound I and II, shown in following scheme 1.Being reflected at anhydrous HCl and acetate (HOAc) catalyzer carries out under existing and removes water.Two kinds of Compound I and II then can be by adopting the epoxy chloropropane that is processed into of causticity thing.

Scheme 1: the hydrochlorinate of glycerine

The whole bag of tricks of above chemistry has report in the prior art in the operational version 1.For example, epoxy chloropropane can be by making dichlorohydrine as 2,3-propylene dichloride-1-alcohol or 1, and 3-propylene dichloride-2-alcohol prepares with alkali reaction.Dichlorohydrine successively can be under atmospheric pressure from glycerine, anhydrous hydrochloric acid and acid catalyst preparation.Recommend big excessive hydrogen chloride (HCl) gas to remove with the azeotropic of the water that promotes in reaction process, to produce.

For example, Gibson, G.P., Chemistry and Industry 1931,20,949-975; With people, Organic Synthesis CV 1,292-294 and Organic SynthesisCV 1,295-297 such as Conant; The stirred solution of having reported by glycerine and organic acid catalyst purges big excessive anhydrous HCl (7 equivalents at the most), at surpass 70% the dichlorohydrin distillation yield of above scheme 1 for dichlorohydrin, Compound I and II.The method of describing in the above reference requires to use the HCl of barometric point, and it is used as entrainer to remove cumulative water.Other azeotrope is known.For example, U.S. patent No.2,144,612 have described use n-butyl ether and excessive hydrogen chloride (HCl) gas removing with promotion reaction distillation and water.

Really, all prior art instruction azeotrope and evaporation of water remove to finish water high conversion and arts demand to be provided to be lower than normal atmosphere or to equal the atmospheric pressure condition.U.S. patent No.2,144,612 advocate advantageously to use the entrainers (for example, n-butyl ether) that add to promote the elimination of reaction component distillation and water, use excessive HCl once more under atmospheric pressure.Use the similar scheme of vacuum removal water to instruct in German Patent No.1075103.

German Patent No.197308 has instructed the method that is prepared chloropharin by anhydrous hydrogen chloride by the catalysis hydrochlorinate of glycerine.This reference teaches under atmospheric pressure, adopt the method for water sepn.German Patent No.197308 is not taught in and carries out hydrochlorination technology under the high pressure.

Produce all known prior aries of chloropharin and reported hydrochlorinate technology, wherein water is removed from technology as common product.Especially, WO2005/021476 has instructed a series of hydrochlorinations, wherein with the water of reaction at normal atmosphere or be lower than in the normal atmosphere technology and remove by reaction distillation.Similar technology is instructed in the WO2005/054167 with following other instruction: the reaction of carrying out under high total pressure more (the HCl dividing potential drop is not stipulated) can improve speed of reaction.Yet, the use of unexposed HCl dividing potential drop and the effect in this technology thereof in WO2005/054167.WO2005/054167 also illustration need remove water with at normal atmosphere or be lower than under the atmospheric pressure and realize high conversion and selectivity.WO2005/021476 and WO2005/054167 are not taught in any advantage that stays water in their technology, or remove water and cause the formation of not wishing cloroecther and RCl ' s.

The use of big especially excessive hydrogen chloride (HCl) gas is problematic economically, and unreacted hydrogen chloride causes being not easy the moisture hydrogen chloride flow of round-robin to the intrinsic pollution of water.In addition, require reaction times of 24-48 hour to reach transforming fully of glycerine far away; Yet product generally includes the not required excessive chlorination trichloropropane and the chlorinated ether of remarkable quantity.Other method of also known use reagent, this method are converted into muriate with alcohol but former bit clear water.For example, thionyl chloride can be used for the transformation of glycerol pentasol, as described in Carre, the Mauclere C.R.Hebd.Seances Acad.Sci 1930,192 and be to select, but produces the SO of stoichiometric ₂The cost of this reagent and expenditure are unacceptable for epoxy chloropropane or derived from the industrial production of any other chloropharin of multihydroxylated-aliphatic hydrocarbon.Equally, appropriateness and effectively other hydrochlorinate reagent be considered expensively with external for this transformation, as at Gomez, wait described in people Tetrahedron Letters 2000,41, the 6049-6052.Other low temperature process (for example changes into better leavings group with alcohol; the methylsulfonyl thing) and by the ionic liquid that uses with molar excess provide muriatic solvability form; as at Leadbeater, wait described in people Tetrahedron 2003,59, the 2253-58.Once more, the muriatic demand for anhydrous condition, stoichiometry reagent and expensive form has stoped above technology to become the object that industry is considered.In addition, these reagent can cause the thorough chlorination of multihydroxylated-aliphatic hydrocarbon, cause not required RCl by product, as at Viswanathan, wait among people Current Science, 1978,21, the 802-803 and instruct.

In a word, there are at least five kinds of main drawbacks for all above known arrangement that prepare chloropharin from glycerine or any other vicinal-glycol, triol or multihydroxylated-aliphatic hydrocarbon: the big excessive HCl of the atmospheric pressure processing requirement of (1) glycerine or any glycol hydrochlorinate, 7-10 times of molar excess usually.In the atmospheric pressure technology, excessive anhydrous HCl pollutes by water subsequently.(2) variant of above currently known methods is very slow, the batch type reaction, and it is changing into required chloropharin product above needing under 100 ℃ the temperature 24-48 hour and being no more than 80-90%.(3) external hydrochlorinate reagent can be produced inconsistent by product but produce with commodity economy usually by removing driving a reaction.(4) all above schemes produce the higher levels of RCl that do not wish, define for glycerol hydrochlorination as above.When (5) operation is with the evaporation of controlling reactor content under being reflected at high pressure, the speed of reaction that the low dividing potential drop of HCl causes low-conversion or is obstructed.

Prior art infers that requiring to carry out water removes to promote the fully conversion of glycerine to dichlorohydrin.Remove requirement for adapting to this water, prior art is reflected under azeotropic or reaction distillation or the extraction conditions carries out, and this requires solubility promoter or expellant and the capital addition suitable to technology.All prior aries are inferred because there is equilibrium-limited in the existence of water in reaction mixture to this conversion.

Industrial needs provide from the hydrochlorinate method of polyhydroxylated aliphatic hydrocrbon production high purity chloropharin, and it is inappropriate that this method can overcome all of prior art.Therefore, the progress in the chloropharin chemical field is simple and cost effective ways of finding to change two pure and mild triol pentasols.

Summary of the invention

An aspect of of the present present invention relates to the method for producing chloropharin, chloropharin ester or its mixture, and this method comprises the steps: to make the ester of multihydroxylated-aliphatic hydrocarbon, multihydroxylated-aliphatic hydrocarbon or its mixture contacts with production chloropharin, chloropharin ester or its mixture with the hydrogenchloride source of super-atmospheric pressure dividing potential drop and significantly do not remove water." super-atmospheric pressure pressure " is pressed in more than the atmospheric pressure at this expression hydrogenchloride (HCl) branch, i.e. 15psia or bigger.

The objective of the invention is to use method of the present invention to minimize the formation of undesirable RCl or chlorination glycerin oligomer.

One embodiment of the invention use hydrogen chloride gas to originate to produce chloropharin as hydrogenchloride.

In second aspect, the present invention relates to prepare the method for chloropharin, this method comprises the steps: to depress at the super-atmospheric pressure branch of HCl, under the about 1000psia of for example about 20psia-; With under sufficient temp, contact following material under for example about 25 ℃-Yue 300 ℃ together: (a) polyhydroxylated aliphatic hydrocrbon, for example 1,2-glycol or 1,2,3-triol; (b) promote polyhydroxylated aliphatic hydrocrbon to change into the catalyzer of chloropharin, for example carboxylic acid, ester, lactone, acid amides or lactan; With its mixture; (c) hydrogenchloride source, for example hydrogen chloride gas; During contact procedure, remove water when wherein carrying out this method indistinctively.

In the third aspect, the present invention relates to prepare the method for chloropharin, this method comprises the steps: to depress at the super-atmospheric pressure branch of HCl, under the about 1000psia of for example about 20psia-; With under sufficient temp, contact following material under for example about 25 ℃-Yue 300 ℃ together: (a) ester of polyhydroxylated aliphatic hydrocrbon, for example glyceryl monoacetate; (b) hydrogenchloride source, for example hydrogenchloride; Wherein carry out described method and during contact procedure, remove water indistinctively.

In a fourth aspect of the present invention, can produce novel composition by aforesaid method.

Super-atmospheric pressure pressure method of the present invention for example comprises with respect to the advantage of the atmospheric methods of prior art: (1) the inventive method is simplified, and cashes and is not require that water removes and do not require solubility promoter/expellant." super-atmospheric pressure pressure method " in this method that is expressed as follows, and promptly wherein is reflected at hydrogenchloride (HCl) and divides and be pressed on the atmospheric pressure, promptly carries out under 15psia or the bigger condition.Method of the present invention can be carried out and do not had other additive, as entrainer.(2) be used for the catalyzer/HCl dividing potential drop/temperature range of the inventive method and do not have water to remove multihydroxylated-aliphatic hydrocarbon has been improved almost 20 times to the conversion rate of chloropharin.Because by the demand that prior art processes removes for water, prior art is far away to the influence of using super-atmospheric pressure HCl dividing potential drop to produce.(3) unexpectedly, permission cumulative water in the reaction under high pressure mixture makes it possible to obtain the selectivity technology of compared with prior art higher conversion rate and Geng Gao, promptly with the chlorinated ether of comparing in prior art normal atmosphere HCl technology still less, RCl still less forms in technology of the present invention.(4) therefore the catalyzer demonstration that is used for technology of the present invention makes that selectivity is higher and increases process rate with respect to other catalyzer that is used for prior art such as the improvement of acetate.(5) comparing super-atmospheric pressure pressure method of the present invention with the atmospheric pressure technology of prior art uses the HCl of much less to reach even bigger transformation efficiency (for example, the excessive 700-1400% to prior art of 1-25%HCl of the present invention is excessive).

That the super-atmospheric pressure pressure method allow to use is rough, wet glycerine begins material as multihydroxylated-aliphatic hydrocarbon, also still reaches compared with prior art higher selectivity and transformation efficiency and do not require that other water removes faster.

Another benefit of using catalyzer of the present invention is from using low volatility, the simplification technology of catalyzer capable of circulation and so improved process economy.

Super-atmospheric pressure pressure method of the present invention passes through with high once through yield (for example greater than 90mol%) and highly selective (for example, greater than 90mol%) provide fast (for example, less than about 12 hours) measure that multihydroxylated-aliphatic hydrocarbon or its ester are changed into chloropharin to solve the demand of this area.Astoundingly, method of the present invention can be carried out and do not had the azeotropic of water or original position to remove.

Although above aspect of the present invention relates to the super-atmospheric pressure pressure method, find that some catalyzer work also works and adopts or do not adopt water to remove equaling normal atmosphere and be lower than the atmospheric pressure condition astoundingly in the super-atmospheric pressure pressure method.Therefore, a fifth aspect of the present invention relates to the production chloropharin, the method of chloropharin ester or its mixture, this method comprises the steps: to make multihydroxylated-aliphatic hydrocarbon in the presence of catalyzer, the ester of multihydroxylated-aliphatic hydrocarbon or its mixture contacts with the production chloropharin with the hydrogenchloride source that equals normal atmosphere or be lower than the normal atmosphere dividing potential drop, chloropharin ester or its mixture, wherein said catalyzer: (i) be the carboxylate radical derivative that contains about 20 carbon atoms of 2-and comprise at least one functional group, this functional group comprises amine, alcohol, halogen, sulfydryl, ether, ester, or its combination, wherein said functional group closer is connected to acid functional group unlike α carbon; Or its precursor; (ii) volatility is not as chloropharin, chloropharin ester or its mixture; (iii) comprise hetero atom substituents.

Of the present invention this aspect the 5th in, briefly by general formula (a) expression of following demonstration, wherein functional group " R ' " comprising an embodiment of catalyst structure of the present invention: the functional group that comprises amine, alcohol, halogen, sulfydryl, ether, ester; Or alkyl, aryl or the alkaryl of about 20 carbon atoms of the 1-that comprises this functional group; Or its combination; Wherein functional group " R " can comprise hydrogen, alkali, alkaline earth or transition metal or hydrocarbon functional groups.

General formula (a)

The accompanying drawing summary

To be explanation be called the process flow sheet of an embodiment of the technology of the present invention of one way circulation, no circulation technology at this to Fig. 1.

Fig. 2 is that explanation is called the process flow sheet of another embodiment of the technology of the present invention of catalyzer and middle circulation technology at this.

To be explanation be called the process flow sheet of another embodiment of the technology of the present invention of catalyzer with transesterify and middle circulation technology at this to Fig. 3.

Figure A is the quantity that shows in mol%, as the function of time, uses the illustrating to the result of the transformation efficiency of the pure and mild dichlorohydrin of monochloro that be not the glycerine that carries out of the embodiment of a part of the present invention.

Detailed Description Of The Invention

Of the present invention one wide aspect, the present invention is the method that multihydroxylated-aliphatic hydrocarbon or its ester is changed into chloropharin or its ester, and this method comprises the steps: to depress and multihydroxylated-aliphatic hydrocarbon or its ester and hydrogenchloride source contact with production chloropharin or its ester do not have water to remove substantially at the super-atmospheric pressure branch." do not have water to remove substantially " and mean during the reaction process step, during the hydrochlorinate step, do not adopt any method with the water that exists in the removing process product (for example, the water of reaction or the water introduced by feed component) at this.These methods can comprise any reactive, freezing point, extraction, azeotropic, absorption or evaporate original position or the technology or be used for any known technology that water removes of offing normal.

Term " multihydroxylated-aliphatic hydrocarbon " expression comprises the hydrocarbon of at least two hydroxyls as used herein, and this hydroxyl is connected to independent saturated carbon atom.Described multihydroxylated-aliphatic hydrocarbon can comprise, but therefore is not limited to about 60 carbon atoms of 2-.

Any single carbon that has a multihydroxylated-aliphatic hydrocarbon of hydroxyl (OH) functional group must have a no more than OH group and must be sp3 hydridization.The carbon atom that has the OH group can be primary, the second month in a season or uncle.Be used for multihydroxylated-aliphatic hydrocarbon of the present invention and must comprise at least two sp3 hydridization carbon, each has the OH group this hydridization carbon.Multihydroxylated-aliphatic hydrocarbon comprises: the hydrocarbon that contains any vicinal-glycol (1, the 2-glycol) or triol (1,2, the 3-triol) that comprises more high-grade vicinity or vicinal repeating unit.It is for example one or more 1 that the definition of multihydroxylated-aliphatic hydrocarbon also comprises, 3-1,4-, 1,5-and 1,6-functionalized with glycols group.Multihydroxylated-aliphatic hydrocarbon also can be polymkeric substance such as polyvinyl alcohol.As an example, glycol should be got rid of from the multihydroxylated-aliphatic hydrocarbon compound of this type in pairs.

Should be appreciated that described multihydroxylated-aliphatic hydrocarbon can comprise aromatics part or heteroatoms, this heteroatoms comprises for example halogen, sulphur, phosphorus, nitrogen, oxygen, silicon and boron heteroatoms; With its mixture.

" chloropharin " is used herein to describe and comprises at least one hydroxyl and at least one is connected to the compound of the chlorine atom of independent saturated carbon atom.The chloropharin that comprises at least two hydroxyls also is a multihydroxylated-aliphatic hydrocarbon.Therefore, beginning material of the present invention and product can all be chloropharins; Under these circumstances, the product chloropharin is more highly chlorinated than the beginning chloropharin, promptly contains more chlorine atom and hydroxyl still less than the beginning chloropharin.Preferred chloropharin is for example as the chloropharin that begins material.Preferred highly chlorinated chloropharin such as dichlorohydrin can be the products of the inventive method for example.

Be used for multihydroxylated-aliphatic hydrocarbon of the present invention and comprise for example 1; 1, the 2-propylene glycol; 1, ammediol; 1-chloro-2, ammediol; Glycerin; 1, the 4-butyleneglycol; 1, the 5-pentanediol; Cyclohexane diol; 1, the 2-butyleneglycol; 1, the 2-cyclohexanedimethanol; 1,2,3-glycerol (also be known as and can exchange be " glycerine ", " glycerine " or " glycerine " at this); With its mixture.Preferably, be used for multihydroxylated-aliphatic hydrocarbon of the present invention and comprise for example 1; 1, the 2-propylene glycol; 1, ammediol; With 1,2, the 3-glycerol; And most preferably be 1,2, the 3-glycerol.

The example that is used for the ester of multihydroxylated-aliphatic hydrocarbon of the present invention comprises for example ethylene glycol acetate, propylene glycol monoacetate, glyceryl monoacetate, Zerol, glyceryl diacetate and its mixture.In one embodiment, such ester can be from the mixture of multihydroxylated-aliphatic hydrocarbon with thorough esterification multihydroxylated-aliphatic hydrocarbon, for example mixture of triacetin and glycerine preparation.

Multihydroxylated-aliphatic hydrocarbon of the present invention can adopt any required non-limiting concentration to use.Usually, because the preferably higher concentration of economic reasons.Can comprise the about 99.99mol% of for example about 0.01mol%-, the about 99.5mol% of preferably about 1mol%-, the more preferably from about about 99mol% of 5mol%-and the most preferably from about about 95mol% of 10mol%-for useful concentrations of the present invention.

To be used for hydrogenchloride of the present invention source preferably as gas, liquid or at solution or mixture or its mixture, introduce as the mixture of for example hydrogenchloride and nitrogen, as long as provide the dividing potential drop that requires of hydrogenchloride to be used for method of the present invention.

Most preferred hydrogenchloride source is a hydrogen chloride gas.The hydride of other form can be used for the present invention, and condition is to meet the dividing potential drop that requires that produces hydrogenchloride.Muriate can adopt the positively charged ion of any number to introduce especially, and this positively charged ion comprises those relevant with microcosmic salt (for example chlorination tetrabutyl phosphorus) with phase transfer reagent such as quaternary ammonium.Perhaps, ionic liquid such as chlorination normal-butyl-glyoxal ethyline can be as synergistic agent to promote the acid catalysis displacement of OH from multihydroxylated-aliphatic hydrocarbon.

Also known these other halide sources can be used as the promotor of the hydrochlorinate of alcohol.The iodide of catalytic quantity or bromide can be used for promoting these reactions in this regard.These reagent can be used as gas, liquid or use phase transition or ionic liquid form to introduce as gegenion.Reagent can be introduced as metal-salt, wherein alkali or transition metal gegenion do not promote the oxidation of multihydroxylated-aliphatic hydrocarbon yet.Because the possibility that RCl forms can reduce, must be careful when in the controlled hydrogen chlorination, using these promotors.Can adopt the halogenide of different sources, for example hydrogen chloride gas and ion muriate are as the mixture of chlorination tetra-allkylammonium or metal halide.For example, metal halide can be sodium-chlor, potassiumiodide, Potassium Bromide etc.

Multihydroxylated-aliphatic hydrocarbon is in embodiment of the present invention of beginning material therein, and as relative with the ester of the multihydroxylated-aliphatic hydrocarbon of material to start with, the formation of preferred chloropharin is promoted by the existence of catalyzer.In another embodiment of the invention, wherein the ester of multihydroxylated-aliphatic hydrocarbon is as the beginning material, and preferred part ester, catalyzer exist in ester inherently and the use of therefore independent catalyst component is selectable.Yet other catalyzer can still comprise in the method the conversion with the required product of further promotion.Other catalyzer also can be used for wherein beginning the situation that material comprises the combination of esterification and non-esterified multihydroxylated-aliphatic hydrocarbon.

When catalyzer was used for super-atmospheric pressure pressure process of the present invention, catalyzer can be for example carboxylic acid, acid anhydrides, acyl chlorides, ester, lactone, lactan, acid amides, organometallics such as sodium acetate; Or its combination.Also can use any compound that under reaction conditions of the present invention, can change into carboxylic acid or functionalized carboxylic acid.

The optimization acid who is used for the super-atmospheric pressure pressure method is the acid with following functional group: halogen, amine, alcohol, alkylated amines, sulfydryl, aryl or alkyl, or its combination, wherein this part can the steric restriction hydroxy-acid group.The preferred acid that is used for this purpose is an acetate.

The example that is used as the carboxylic acid of catalyzer among the present invention comprises acetate, propionic acid, 4-methylvaleric acid, hexanodioic acid, 4-hydroxyphenyl acetic acid, 6-chlorine caproic acid, 4-aminobutyric acid, caproic acid, enanthic acid, 4-dimethylaminobutyricacid acid, 6-aminocaprolc acid, 6 hydroxycaproic acid, 4-aminophenyl acetate, 4-trimethyl ammonium butyryl chloride, polyacrylic acid, the polyethylene by acrylic acid-grafted, Vinylstyrene/Sipacril 2739OF and its mixture.The example of acid anhydrides comprises diacetyl oxide, maleic anhydride and its mixture.The example of acyl chlorides comprises Acetyl Chloride 98Min., 6-chlorine caproyl chloride, 6-hydroxyl caproyl chloride and its mixture.The example of ester comprise methyl acetate, methyl propionate, methyl pivalate, methyl-butyrate, ethylene glycol acetate, glycol diacetate, propylene glycol monoacetate, propylene-glycol diacetate, glyceryl monoacetate, glyceryl diacetate, triacetin, short and long-chain acyl triglyceride molecules (comprise the glycerine list-, two-, with three-ester) and its combination.Most preferably the example of lactone comprises 6-caprolactone, gamma-butyrolactone, δ-Wu Neizhi and its mixture.The example of lactan is a ε-Ji Neixianan.Zinc acetate is metal-organic example.

Being used for preferred catalyst of the present invention is carboxylic acid, carboxylicesters, or its combination, and boiling point is higher than the ester or the acid of the required maximum boiling point chloropharin that forms in the reaction mixture especially, makes can to remove chloropharin and do not remove catalyzer.Satisfy this definition and be used for catalyzer of the present invention and for example comprise, polyacrylic acid, short and long-chain acyl triglyceride molecules (comprise the glycerine list-, two-, with three-ester), by acrylic acid-grafted polyethylene, 6-chlorine caproic acid, 4-chloro-butyric acid, caprolactone, enanthic acid, 4-hydroxyphenyl acetate, 4-aminophenyl acetate, 6 hydroxycaproic acid, 4-aminobutyric acid, 4-trimethyl ammonium butyryl chloride, stearic acid, 5-chloro pentane acid, 6 hydroxycaproic acid, 4-aminophenyl acetate and its mixture.

Carboxylic acid (RCOOH) catalysis multihydroxylated-aliphatic hydrocarbon is to the hydrochlorinate of chloropharin.Selection is used for the concrete carboxylic acid catalyst of the object of the invention can be based on many factors, this factor for example comprise it as the effectiveness of catalyzer, it cost, it is to the stability of reaction conditions and its physicals.Wherein will adopt the special process of catalyzer and process program also can be the factor of selecting in the special catalyst of present method." R " of carboxylic acid can be selected from hydrogen or alkyl, comprises alkyl, aryl, aralkyl, and alkaryl.Alkyl can be linearity, branching or cyclic and can be replacement or unsubstituted.Admissible substituting group comprises any functional group that does not disturb catalyst performance nocuously, and can comprise heteroatoms.Can allow the non-limitative example of functional group to comprise chlorine root, bromine root, iodine root, hydroxyl, phenol, ether, acid amides, primary amine, secondary amine, tertiary amine, quaternary ammonium, sulfonate radical, sulfonic acid, phosphonate radical and phosphonic acids.

Be used for carboxylic acid of the present invention and can be monoprotic acid such as acetate, formic acid, propionic acid, isopropylformic acid, caproic acid, enanthic acid, oleic acid, or stearic acid; Or polyprotonic acid such as succsinic acid, hexanodioic acid, or terephthalic acid.Aralkyl carboxylic acid's example comprises phenylacetic acid and 4-aminophenyl acetate.The example of substituted carboxylic acid comprises 4-aminobutyric acid, 4-dimethylaminobutyricacid acid, 6-aminocaprolc acid, 4-aminophenyl acetate, 4-hydroxyphenyl acetate, lactic acid, oxyacetic acid, 4-dimethylaminobutyricacid acid and 4-trimethyl ammonium butyric acid.In addition, under reaction conditions, can change into the material of carboxylic acid, comprise for example acid halide, as Acetyl Chloride 98Min.; Carboxylic acid anhydride such as diacetyl oxide; Carboxylicesters such as methyl acetate; Multihydroxylated-aliphatic hydrocarbon acetic ester such as glycerine 1, the 2-diacetate esters; Carboxylic acid amide such as ε-Ji Neixianan and butyrolactam; Also can be used for the present invention with carboxylic acid lactone such as gamma-butyrolactone, δ-Wu Neizhi and 6-caprolactone.The mixture of carboxylic acid also can be used for the present invention.

It is effective not as other material in hydrochlorinate method of the present invention to can be used for carboxylic acid catalysts more of the present invention, described other material for example have near the space requirement of hydroxy-acid group substituent those, for example 2,2-acid dimethyl, steric hindrance 2-substituted benzoic acid such as 2-benzaminic acid and 2-methylamino phenylformic acid.Reason thus is more preferably at the not interrupted carboxylic acid of hydroxy-acid group surrounding space.

In the inventive method that adopts super-atmospheric pressure HCl partial pressure conditions, be used for preferred acid catalyzer of the present invention and comprise for example acetate, propionic acid, butyric acid, isopropylformic acid, caproic acid, enanthic acid, 4-hydroxyphenyl acetate, 4-aminophenyl acetate, 4-aminobutyric acid, 4-dimethylaminobutyricacid acid, 4-trimethyl ammonium butyryl chloride, succsinic acid, 6-chlorine caproic acid, 6 hydroxycaproic acid and its mixture.

In another aspect of this invention, the catalyzer more of the present invention that work in above-mentioned super-atmospheric pressure pressure method also can equal normal atmosphere and being lower than astoundingly and work under the atmospheric pressure condition and adopt or do not adopt water to remove.Therefore, a fifth aspect of the present invention relates to the production chloropharin, the method of chloropharin ester or its mixture, this method comprises the steps: to make multihydroxylated-aliphatic hydrocarbon in the presence of catalyzer, the ester of multihydroxylated-aliphatic hydrocarbon or its mixture and super-atmospheric pressure, the hydrogenchloride source contact that equals normal atmosphere or be lower than the normal atmosphere dividing potential drop is to produce chloropharin, chloropharin ester or its mixture, wherein said catalyzer (i) is the carboxylate radical derivative that contains about 20 carbon atoms of 2-and comprise at least one functional group, this functional group comprises amine, alcohol, halogen, sulfydryl, ether, ester, or its combination, wherein said functional group closer is connected to acid functional group unlike α carbon; Or its precursor; (ii) volatility is not as chloropharin, chloropharin ester or its mixture; (iii) comprise hetero atom substituents.

Of the present invention this aspect the 5th in, an embodiment of catalyst structure of the present invention is by general formula (a) expression of following demonstration, wherein functional group " R ' " comprising: the functional group of containing amine, alcohol, halogen, sulfydryl, ether, ester; Or alkyl, aryl or the alkaryl of about 20 carbon atoms of the 1-that comprises this functional group; Or its combination; Wherein functional group " R " can comprise hydrogen, alkali, alkaline earth or transition metal or hydrocarbon functional groups.

General formula (a)

According to this 5th aspect of the present invention, some catalyzer also can be advantageously super-atmospheric pressure, equal normal atmosphere or be lower than under the atmospheric pressure and following therein especially situation under adopt: wherein water is removed conversion is driven into required higher level from reaction mixture continuously or periodically.For example, can be by hydrogen chloride gas be sprayed the hydrochlorination of implementing glycerine by multihydroxylated-aliphatic hydrocarbon and mixture of catalysts.Under these circumstances, volatile catalyst (as acetate) can be removed and can be lost from reaction medium by the hydrogen chloride gas that sprays by solution from reaction to small part.Owing to reduced catalyst concn, therefore multihydroxylated-aliphatic hydrocarbon can slow down to the conversion of required chloropharin.Under these circumstances, it may be preferred using less volatile catalyst, and described catalyzer for example is 6 hydroxycaproic acid, 4-aminobutyric acid, dimethyl 4-aminobutyric acid, 6-chlorine caproic acid, caprolactone, carboxylic acid amide such as ε-Ji Neixianan and butyrolactam, carboxylic acid lactone such as gamma-butyrolactone, δ-Wu Neizhi and 6-caprolactone, hexanolactam, 4-hydroxyphenyl acetate, 6-aminocaprolc acid, 4-aminophenyl acetate, lactic acid, oxyacetic acid, 4-dimethylaminobutyricacid acid, 4-trimethyl ammonium butyric acid and its combination etc.What need most is to equal normal atmosphere or be lower than to use volatility to be lower than the catalyzer of the required chloropharin that is produced under the atmospheric pressure at these.In addition, the multihydroxylated-aliphatic hydrocarbon complete miscibility that needs catalyzer and employing.If catalyzer is not a complete miscibility, it may form second phase and can not realize catalytic effect completely.Reason may need catalyzer to comprise polarity hetero atom substituents such as hydroxyl, amino or substituted-amino or halogen foundation group for this reason, and they make catalyzer and multihydroxylated-aliphatic hydrocarbon, and for example glycerine is miscible.

Catalyzer (for example carboxylic acid catalyst) also can be by the concrete process program domination that is used for the multihydroxylated-aliphatic hydrocarbon hydrochlorinate to the selection that is used for the inventive method.For example, in the one way flow-through process, wherein multihydroxylated-aliphatic hydrocarbon is reacted to the high as far as possible transformation efficiency to required chloropharin, it further change into other product then and not with the separating of catalyzer, further do not utilize the carboxylic acid catalyst subsequently.In such process program, except that effectively, also need carboxylic acid cheap.Optimization acid's catalyzer in the situation is an acetate for example like this.

In circulation technology, for example wherein the chloropharin of producing is further being separated before processing or the use with the carboxylic acid catalyst, the carboxylic acid catalyst according to catalyzer and its ester and reaction product, selects from the separation of required chloropharin product in addition easily.Under these circumstances, can preferably adopt heavily (promptly than low volatility) acid to make it easily to be recycled to reactor and be used for further reaction with unreacted glycerine or intermediate monochloro alcohol.Be used for suitable heavy acid of the present invention and comprise for example 4-hydroxyphenyl acetate, enanthic acid, 4-aminobutyric acid, caprolactone, 6 hydroxycaproic acid, 6-chlorine caproic acid, 4-dimethylaminobutyricacid acid, 4-trimethyl ammonium butyryl chloride and its mixture.

Also preferred acid, or its ester and multihydroxylated-aliphatic hydrocarbon be by hydrochlorinate, or its ester and reaction intermediate or reaction product are miscible in reaction soln.Reason can need to consider these solubility limit and select the carboxylic acid catalyst for this reason.Therefore, if be unusual polar by the multihydroxylated-aliphatic hydrocarbon of hydrochlorinate for example, as glycerine, some carboxylic acid catalysts demonstrate less than solubleness completely, and ice forms two-phase when mixing.Under these circumstances, can need more miscible acid catalyst, as acetate or 4-aminobutyric acid.

Can be used for catalyzer of the present invention is effective in wide concentration range, for example based on the about 99.9mol% of about 0.01mol%-of multihydroxylated-aliphatic hydrocarbon mole number, the preferred about 67mol% of about 0.1mol%-, the more preferably from about about 50mol% of 0.5mol%-and the most preferably from about about 40mol% of 1mol%-.Be used for the concrete concentration of catalyzer of the present invention and can be dependent on the process program that is used for concrete catalyzer of the present invention and wherein adopts such catalyzer.

For example, in the one way flow-through process, wherein catalyzer only uses once and subsequently and abandons, and preferably adopts the high activity catalyzer of lower concentration.In addition, may need to adopt cheap catalyzer.Under these circumstances for example, can use the about 10mol% of about 0.01mol%-, the about 6mol% of preferably about 0.1mol%-, the more preferably from about concentration of the about 5mol% of 1mol%-based on multihydroxylated-aliphatic hydrocarbon.

In process program,, may need to adopt the concentration higher than the catalyzer of abandoning for example wherein with catalyst recirculation and repeated use.Can use the about 99.9mol% of the about 1mol%-of such recycling catalyst, based on multihydroxylated-aliphatic hydrocarbon, the about 70mol% of preferably about 5mol%-, more preferably from about the about 50mol% of 5mol%-is nonrestrictive but these concentration should be thought of as.The formation that higher catalyst concn can be used to reduce the size of reaction times, minimization of process equipment requiredly and reduce not required uncatalyzed by product.

Usually, preferred method of the present invention is carried out under the super-atmospheric pressure pressure condition." super-atmospheric pressure pressure " is pressed in more than the atmospheric pressure at this expression hydrogenchloride (HCl) branch, i.e. 15psia or bigger.Usually, the hydrogenchloride dividing potential drop that is used for the inventive method is at least about 15psia HCl or bigger.Preferably, the pressure of present method is not less than about 25psia, more preferably is not less than about 35psia HCl and most preferably is not less than about 55psia; Preferably be not more than about 1000psia HCl, more preferably no more than about 600psia with most preferably be not more than about 150psia.

It most preferably is anhydrous being used for HCl of the present invention.HCl forms can be from 100 volume % hydrogenchloride to about 50 volume % hydrogenchloride.Preferably, the HCl feed composition is greater than about 50 volume %HCl, more preferably greater than about 90 volume %HCl with most preferably greater than about 99 volume %HCl.

The temperature that can be used for the inventive method should be enough to obtain economic speed of reaction, but not high feasible beginning material, product or catalyst stability are undermined.In addition, high temperature can increase not required uncatalyzed reaction, as non-selective excessive chlorating speed, and can cause the equipment corrosion speed that increases.Useful temperature among the present invention can be about 25 ℃-Yue 300 ℃ usually, preferred about 25 ℃-Yue 200 ℃, and more preferably from about 30 ℃-Yue 160 ℃, even more preferably from about 40 ℃-Yue 150 ℃ and most preferably from about 50 ℃-Yue 140 ℃.

The reaction of super-atmospheric pressure pressure method of the present invention preferably less than about 5 hours, is more preferably less than about 3 hours and most preferably less than about 2 hours time advantageously fast and can carry out less than about 12 hours.In the longer reaction times, as greater than under about 12 hours, technology begins to form RCl and other excessive chlorinated secondary product.

Astoundingly, find that high once through yield and highly selective can use super-atmospheric pressure pressure method of the present invention to reach.For example, for chloropharin based on multihydroxylated-aliphatic hydrocarbon greater than about 80%, be preferably greater than about 85%, more preferably greater than about 90% with most preferably can reach by the present invention greater than about 93% once through yield.For example, chloropharin greater than about 80%, be preferably greater than about 85%, more preferably greater than about 90% with most preferably can reach by method of the present invention greater than about 93% highly selective.Certainly, can increase yield by the circulating reaction intermediate.

For example, when being used for multihydroxylated-aliphatic hydrocarbon of the present invention and being glycerine, the ultimate yield of the dichlorohydrin that intercycle body monochloro alcohol can have increased access to.In addition, do not resemble many methods of prior art, it is not the necessary characteristic of the inventive method that water removes in the reaction that forms chloropharin.In fact, reaction of the present invention preferably removes azeotropic as water at water and removes and carry out under not existing.

In super-atmospheric pressure pressure method of the present invention, not the beginning material that must use and do not have pollutent (organic impurity beyond Ru Shui, salt or the multihydroxylated-aliphatic hydrocarbon).Therefore, the beginning material can comprise usually, is not more than this pollutant of about 50wt%.For example, comprise thick 1 of water (the about 25wt% of about 5%-), alkali (for example, sodium or potassium) or alkaline earth (for example, calcium or magnesium) metal-salt (the about 20wt% of about 1%-) and/or alkali carboxylate salt (the about 5wt% of about 1%-), 2,3-glycerol (raw glycerine) also can be used for the present invention with the required product of effective production.So method of the present invention is economic especially scheme.

In an embodiment of the inventive method, with 1,2,3-glycerol (glycerine) is put into encloses container, and in heating and pressurization in the presence of the carboxylic acid of above-mentioned catalytic quantity or its ester under the HCl gas atmosphere.Under preferred processing condition, principal product is 1,3-propylene dichloride-2-alcohol (for example,＞90% yield) and a small amount of () following product for example,＜10% total recovery: 1-chloro-2, ammediol, glycerin and 2,3-propylene dichloride-1-alcohol; With the glyceryl trichloride that detects less than quantity (less than 200ppm).Advantageously, both all are precursors of epoxy chloropropane to a small amount of dichloride product of advocating peace (1,3-two chloro-propane-2-are pure and mild 2,3-propylene dichloride-1-alcohol).The dichloride product can easily change into epoxy chloropropane by the reaction with alkali, as known in the art.

The present invention can comprise various process programs, comprises for example intermittence, semi-batch or successive process program.In one embodiment, for example the present invention includes hydrochlorinate by the multihydroxylated-aliphatic hydrocarbon of carrying out with the reaction of hydrogenchloride.Multihydroxylated-aliphatic hydrocarbon can adopt or dilution use in appropriate solvent with pure substance.Such solvent can comprise for example water and alcohol.Can preferably make with extra care multihydroxylated-aliphatic hydrocarbon by removing pollutent before it is used for hydrochlorination before using, described pollutent comprises water, organic materials or inorganic materials.This is refining can to comprise known purification techniques such as distillation, extraction, absorption, centrifugal, or other appropriate means.Usually multihydroxylated-aliphatic hydrocarbon is delivered to technology as liquid, although this is not absolute necessary.

The hydrogenchloride that is used for technology is gasiform preferably.Yet, as needs, hydrogenchloride can solvent as alcohol (for example methyl alcohol) in; Or in carrier gas such as nitrogen, dilute.Randomly, hydrogenchloride can be refining to remove any not required pollutent before using.Preferred hydrogenchloride is anhydrous substantially, although some quantity (for example less than about 50mol%, preferably less than about 20mol%, are more preferably less than about 10mol%, even be more preferably less than about 5mol%, and most preferably less than about 3mol%) water that exists in the hydrogenchloride is not too deleterious.Adopt any way that hydrogenchloride is fed to processing unit.The preferred design processing unit is to guarantee that hydrogenchloride is being used for the whole good distribution of hydrochlorination device of present method.Therefore, single or multiple sprinker, baffle plate and effective stirring mechanism are required.

Can be with catalyzer charging as follows: add individually, or add, or add processing unit as the component of multihydroxylated-aliphatic hydrocarbon or hydrogenchloride charging as mixture with multihydroxylated-aliphatic hydrocarbon or hydrogenchloride.

The equipment that is used for hydrochlorination of the present invention can be any equipment well known in the art and should comprise reaction mixture under the hydrochlorinate condition.Suitable device can be made by the corrosive material of anti-technology component, and for example can comprise metal (as tantalum, suitable metal alloy such as Hastalloy C ), or glass-lined equipment.Suitable device can comprise, for example single or multiple stirred pot, pipeline or pipe, or its combination.

In an illustrative batch technology, multihydroxylated-aliphatic hydrocarbon and hydrochlorinate catalyzer are added reactor.Then hydrogenchloride is added to required pressure and reactor content is heated to temperature required required time span down.Then reactor content is discharged and refining or deliver to miscellaneous equipment and be used for further processing from reactor, or deliver to storage.

In an illustrative semi-batch technology, one or more reagent are added to reactor within a certain period of time in entire reaction, and other reagent is only added when reaction begins.In such technology, for example multihydroxylated-aliphatic hydrocarbon and catalyzer can be added to the hydrochlorination device in single batch, then it is remained on the time suitable under the reaction conditions, simultaneously hydrogenchloride is added under desired rate in entire reaction continuously, described desired rate can be the constant flow amount, or under the constant pressure.After reaction, the hydrogenchloride charging can stop and reactor content can be discharged and be used for storing refining or further processing.

In the scale operation of chemical, usually need to adopt continuous processing, this be since like this economical advantage of operation usually greater than batch process.Continuous processing can be for example single process or circulation technology.In single process, one or more reagent by processing unit once, and subsequently in the future the effluent that obtains of autoreactor send and be used for refining or further processing.In such scheme, multihydroxylated-aliphatic hydrocarbon and catalyzer can be delivered to equipment and as required hydrogenchloride be added in whole processing unit at single point or a plurality of, and it can comprise continuous-stirring reactor, pipeline, pipe or its combination.

Perhaps, the catalyzer of employing can be a solid, and it is retained in the processing unit by strainer or equal equipment.Reagent and catalyzer are added the residence time that makes in the processing unit under given pace be suitable to reach the required transformation efficiency of multihydroxylated-aliphatic hydrocarbon to product.To leave the material of processing unit as needs and deliver to storage, be used for refining or further processing.Under these circumstances, need usually to transform multihydroxylated-aliphatic hydrocarbon as much as possible to required product.

In continuous circulation process, one or more unreacted multihydroxylated-aliphatic hydrocarbon, reaction intermediate, hydrogenchloride or the catalyst recirculation of leaving processing unit are returned point more preceding in the technology.Adopt this mode, maximize starting material efficient or re-use catalyzer.Because catalyzer is used further to such process program, may need to be used for single process and compare higher concentration employing catalyzer with them, in single process, abandon them usually.This can cause reacting faster, or littler processing unit, and they cause the lower fund cost for the equipment that adopts.

Required product can adopt variety of way to reach from removing of catalyzer or other technology component.Can reach separation in the following way, for example adopt the evaporation of continuous mode, directly from the hydrochlorination device, or an independent equipment such as vaporizer or distillation tower.Under these circumstances, adopt the catalyzer of volatility, make catalyzer be retained in the processing unit not as required product.Perhaps, can adopt solid catalyst, with separate can by for example filter, centrifugal or evaporation reaches.Liquid extraction absorbs or chemical reaction also can be used for recycling catalyst or reaction intermediate in some cases.

In one embodiment of the invention, use the hydrochlorinate catalyzer to come the hydrochlorinate multihydroxylated-aliphatic hydrocarbon, select this catalyzer to make not hydrochlorinate product as required of its volatility.After hydrochlorination, other multihydroxylated-aliphatic hydrocarbon is added in reaction product, excessive beginning material, reaction intermediate and the catalyzer.Think that this discharges some required hydrochlorinate products, the ester that they can be used as catalyzer exists, and makes required product to be reclaimed from reaction soln by evaporation more completely.After reclaiming required hydrochlorinate product, remaining process flow can be recycled to the hydrochlorinate logistics.This process program also can have the advantage of the hydrogenchloride quantity of minimum losses, this be since after adding multihydroxylated-aliphatic hydrocarbon, keep in the process flow many by with the reaction consumes of initiate multihydroxylated-aliphatic hydrocarbon.

The special process scheme that adopts can be dependent on many factors, and this factor comprises that what for example the concrete processing condition of the characteristic of the multihydroxylated-aliphatic hydrocarbon of hydrochlorinate, cost and purity, employing, refined products required separates and other factors.The example of method described herein is not thought of as restriction the present invention.

Fig. 1,2 and 3 shows three non-limiting embodiments of hydrochlorinate method of the present invention.The example of the explanation the inventive method that shows among Fig. 1,2 and 3 only is the preferred embodiments of the invention.

For example Fig. 1 shows the inventive method of being indicated by numeral 10 usually, wherein multihydroxylated-aliphatic hydrocarbon such as glycerine feed stream 11 is introduced reaction vessel 15.Reaction vessel 15 can for example comprise for any known adequate types, one or more agitator tank reactors (CSTR) or tubular reactor; Or its combination.

What also be introduced into container 15 is hydrogenchloride incoming flow 12 and carboxylic acid or carboxylic acid precursor catalyst charge stream 13.Logistics 12 and 13 can be separately or is introduced container 15 together.In addition, randomly, all logistics 11,12 and 13 can be combined into an incoming flow together.Any logistics 11,12 or 13 can be introduced at the single point of container 15 or at a plurality of points.In container 15, with glycerine by carboxylic acid catalyst, the pure and mild dichlorohydrin of monochloro and their ester moiety or change into its ester fully.Comprise for example logistics 14 of dichlorohydrin, monochloro alcohol, unreacted glycerine and their ester, water, unreacted hydrogen chloride and catalyzer and leave container 15, and can send to storage, send to further processing as refining or deliver to miscellaneous equipment and be used for further reaction.

For example, in one embodiment, logistics 14 can with alkali reaction to form epoxy chloropropane.Carboxylic acid catalyst in this quadrat method can select according to its efficient under lower concentration and its low cost.For example, described carboxylic acid can be acetate or propionic acid.

Fig. 2 shows common another embodiment by digital 20 the inventive method of indicating, and container 26 is delivered in the incoming flow 21 that wherein will comprise multihydroxylated-aliphatic hydrocarbon such as glycerine, and it can be one or many CSTR or tubular reactor, or its combination.What also add container 26 is the incoming flow 22 that comprises hydrogenchloride.What also add container 26 is from container 27 circulation, comprises pure and mild their cycling stream 25 of ester and catalyzer (it also circulates in this logistics 25) of for example unreacted glycerine, monochloro.

In container 26, transformation of glycerol is become pure and mild their ester of monochloro; And monochloro alcohol is changed into the ester of dichlorohydrin and they.Comprise for example logistics 23 of dichlorohydrin, monochloro alcohol, unreacted glycerine and their ester and carboxylic acid catalyst, water, unreacted hydrogen chloride and catalyzer and leave container 26, and be sent to container 27.In container 27, at least some required dichlorohydrin, water and unreacted hydrogen chloride be as logistics 24, and as pure and mild their ester, unreacted glycerine and its ester and the catalyst separating of the monochloro of cycling stream 25, wherein said cycling stream 25 is recycled to container 26.Logistics 25 also can randomly comprise some dichlorohydrin and their ester.

Container 27 can comprise any known appropriate separation container, and this separation vessel comprises one or more distillation towers, flash chamber, extraction or absorption tower, or any suitable known separating device known in the art.Product logistics 24 can be delivered to storage, it is for example refining to deliver to further processing, or delivers to further reaction, for example changes into epoxy chloropropane.In an example of this process program, can selecting catalyst make its chemistry or the physicals separate easily that causes catalyzer or its ester and required dichlorohydrin.For example, the catalyzer of selecting for this process program can be 6-chlorine caproic acid, caprolactone, 4-chloro-butyric acid, stearic acid, or 4-hydroxyphenyl acetate.

Fig. 3 shows common another embodiment by digital 30 the inventive method of indicating, and wherein adds the incoming flow 31 that comprises hydrogenchloride by logistics 35 in container 36; With by comprise glycerine, glyceryl ester, monochloro pure and mild they ester and the cycling stream of catalyzer.(it can comprise one or more CSTR, one or more tubular reactor or its combination) changes into dichlorohydrin with glycerine and monochloro alcohol in container 36.Comprising for example logistics 32 of dichlorohydrin, monochloro alcohol, glycerine and their ester, catalyzer, unreacted hydrogen chloride and water leaves container 36 and delivers to container 37.What also add container 37 is the incoming flow 33 that comprises glycerine.

In container 37, the reaction of the ester of glycerine and the pure and mild dichlorohydrin of monochloro is with the pure and mild dichlorohydrin of basic release free monochloro and form glyceryl ester.In addition, at least some unreacted hydrogen chloride that enter container 37 by logistics 32 also obtain consuming with main formation monochloro alcohol.Container 37 also can be used as the mechanism that separates required dichlorohydrin and pure and mild glycerine of unreacted monochloro and their ester.Container 37 can comprise, for example one or more distillation towers, flash chamber, extractor, or any other separating device; Or container 37 can be for example combination of stirred pot, tubular reactor or similar container and above-mentioned separating device.Leave product logistics 34 container 37 and that comprise dichlorohydrin, water and remaining hydrogenchloride and can send to storage, send to further processing, for example deliver to reaction process and be used to prepare epoxy chloropropane as refining or deliver to technology and be used for further reaction.Comprise pure and mild their ester and the catalyst stream 35 of glycerine and monochloro and leave container 37 to be recycled to container 36 as logistics 35.

In the Process configuration of Fig. 3, can need to use the catalyzer of relatively large number amount, for example based on the about 70mol% of about 10mol%-of glycerine, make that hydrochlorination speed in the container 36 is very quick and equipment is therefore less.Also preferred in the Process configuration of Fig. 3 catalyzer have suitable chemistry or physicals and make and can promote separation in the container 37 that for example can preferably use ebullient catalyzer under the temperature that is lower than following temperature substantially when separation method is distillation: the dichlorohydrin of minimum boiling point seethes with excitement under this temperature.The example of catalyzer comprises 6-chlorine caproic acid, enanthic acid and 4-hydroxyphenyl acetate like this.

The present invention also comprises the composition by method preparation of the present invention.Composition of the present invention by present method preparation for example comprises, from the dichlorohydrin of glycerine preparation.Why useful by such dichlorohydrin of present method preparation is to be that they comprise the dichlorohydrin of high density, (promptly 1,3-propylene dichloride-2-pure and mild 2,3-propylene dichloride-1-alcohol) two kinds of dichlorohydrin isomer and their ester are at high proportion, promptly 1, the pure and mild ester of 3-propylene dichloride-2-is to 2, the pure and mild ester of 3-propylene dichloride-1-at high proportion, the ester and the monochloro alcohol of glycerine and it, promptly the 2-chloro-1, ammediol and 1-chloro-2, the lower concentration and the not required by product of the ester of ammediol and they, promptly 1,2,3-trichloropropane and chlorination glycerin oligomer ether are as the lower concentration of two (3-chloro-2-hydroxypropyl) ethers and their ester.

Composition of the present invention is used to make epoxy chloropropane, obtains the high purity epoxy chloropropane and the low-level chlorinated secondary product of high yield, the difficult treatment of this by product or costliness in the time at short reaction.

As an embodiment and explanation of the present invention, but can't help theory constraint, can useful composition prepared in accordance with the present invention (getting rid of water and inorganic impurity), can for example prepare from glycerol hydrochlorination.Following abbreviation is used for following table: " 1, the 3-dichlorohydrin " is 1,3-propylene dichloride-2-alcohol; " 2, the 3-dichlorohydrin " are 2,3-propylene dichloride-1-alcohol; " monochloro alcohol " comprising: 1-chloro-2, ammediol and glycerin and its mixture.Usually, such composition comprises for example following component, gets rid of fatty acid methyl ester, etc.:

Component	Mol％
		Glycerine and ester thereof	0.1-1
Monochloro alcohol and ester thereof	4-10
		1,3-dichlorohydrin and ester thereof	Greater than 80
2,3-dichlorohydrin and ester thereof	1-4
		Glyceryl trichloride	Less than 1
Chlorination glyceryl ether and ester thereof	Less than 0.3

In the above composition 1, the 3-dichlorohydrin is to 2, and 3-dichlorohydrin ratio is generally about 8: about 100: 1 of 1-.Preferably, composition of the present invention can be as follows:

Component	Mol％
		Glycerine and ester thereof	0.01-0.1
Monochloro alcohol and ester thereof	3-8
		1,3-dichlorohydrin and ester thereof	Greater than 85
2,3-dichlorohydrin and ester thereof	1-3
		Glyceryl trichloride	Less than 0.1
Chlorination glyceryl ether and ester thereof	Less than 0.2

More preferably, composition of the present invention can be as follows:

Component	Mol％
		Glycerine and ester thereof	0.001-0.01
Monochloro alcohol and ester thereof	2-7
		1,3-dichlorohydrin and ester thereof	Greater than 87
2,3-dichlorohydrin and ester thereof	1-2
		Glyceryl trichloride	Less than 0.05
Chlorination glyceryl ether and ester thereof	Less than 0.15

Most preferably, composition of the present invention can be as follows:

Component	Mol％
		Glycerine and ester thereof	Less than 0.1
Monochloro alcohol and ester thereof	1-5
		1,3-dichlorohydrin and ester thereof	Greater than 90
2,3-dichlorohydrin and ester thereof	0.1-2
		Glyceryl trichloride	Less than 0.02
Chlorination glyceryl ether and ester thereof	Less than 0.1

Above composition of the present invention is used to make epoxy chloropropane.With respect to 2, the selectivity of 3-dichlorohydrin and ester thereof, to 1, the highly selective of 3-dichlorohydrin and ester thereof causes the more effective and quick formation of epoxy chloropropane with the reaction of causticity thing the time.In addition, the low-level of trichloropropane in this composition (TCP) is required, and this is because it minimizes the cost of disposing and handling TCP.By the high conversion to required dichlorohydrin, glycerine and monochloro alcohol low-level also is required with maximization glycerine starting material efficient in this composition.

Following embodiment only is used for illustration purpose and is not intended to limit the scope of the invention.

Embodiment 1-prepares chloropharin from glycerine

100mL HastelloyC to assembling agitator of magnetic drive, inner spiral coil cooling tube and thermopair ^TMAdd glycerine (30.0g is available from Sigma-Aldrich ChemicalCorporation) and glacial acetic acid (4.5g is available from JT Baker Corporation) in the Parr reactor.With reactor sealing, adopt anhydrous hydrogen chloride gas (Airgas Corporation) to be pressurized to 90psig and be heated to 93 ℃ following 90 minutes and adopt anhydrous hydrogen chloride gas to remain on 90psig, thereafter with reactor cooling and in room temperature (about 25 ℃) exhaust down.Collect reactor content (65.9g), analyze, and find to comprise following product by gas-chromatography (GC): 1,3-propylene dichloride-2-alcohol and acetic ester thereof (amounting to 92.6mol%) and 2,3-propylene dichloride-1-alcohol and acetic ester thereof (amounting to 1.7mol%).In addition, detect many monochloro compounds (amounting to 4.4mol%) and unreacted glycerine and ester (amounting to 1.0mol%) thereof.Do not detect trichloropropane (limit of detection is 200ppm).

Embodiment 2-prepares chloropharin from glycerine/glyceride mixture

To 200mL Hastelloy C ^TMAdd 10mL glass measuring bottle in the high-pressure reactor, this measuring bottle comprise dry glycerine (Aldrich, predrying by molecular sieve, 91mg, 0.99mmol) and triacetin (Aldrich, the triacetate of glycerine, 457mg, 2.10mmole).Reactor is sealed and adopted nitrogen pressure adopts stirring to reach 110 ℃ to 40psig (three pressure cycling) and after the nitrogen exhaust.Anhydrous HCl introduced under the constant pressure of 76psig and make reaction carry out 3 hours.With the reactor exhaust, product is provided, find that this product comprises 1 of 25.90 area %, 1 of 3-propylene dichloride-2-alcohol, 68.34 area %, 1 of 3-two chloro-2-acetoxy-propanes, 1.57 area %, the 2 cbloropropane isopropyl chloride-1 of 2-two chloro-3-acetoxy-propanes, 2.86 area %, 3-diacetoxy propane and do not have can detected glycerine, triacetin or 1,2, the 3-trichloropropane is as being measured by GC flame ionization check and analysis.

Embodiment 3-prepares chloropharin from raw glycerine

To the 100mLHastelloy that is equipped with agitator of magnetic drive, inner spiral coil cooling tube and thermopair ^TMAdd raw glycerine (30.0g is available from InterwestCorporation) and glacial acetic acid (0.6g is available from JT Baker Corporation) in the C Parr reactor.With reactor sealing, adopt anhydrous hydrogen chloride gas (Airgas Corporation) to be pressurized to 120psig, and be heated to 120 ℃ following 90 minutes, keep-up pressure at 120psig by anhydrous hydrogen chloride gas simultaneously.After at this moment, with reactor cooling and exhaust at room temperature.Reactor content (57.2g) is collected as the moving liquid that comprises the suspension white solid.

Repeat said process and react the reactor content of collecting 58.0g from second.Then in conjunction with two reaction product (57.2g and 58.0g).

After filtering with the sodium and sylvite that remove white solid, introduce by raw glycerine, filtrate comprises 1 by gas chromatographic analysis and discovery, 3-propylene dichloride-2-alcohol (95.3wt%), 2,3-propylene dichloride-1-alcohol (2.6wt%), 2-acetoxyl group-1,3-propylene dichloride (0.7wt%), with 1-acetoxyl group-2,3-propylene dichloride (0.1wt%).In addition, detect a certain amount of acetoxyl group propylene chlorohydrin (0.87wt%).Do not detect unreacted glycerine and do not detect ester yet, do not detect trichloropropanol yet.

Embodiment 4-41

Following embodiment is at the Hastalloy C of the 100mL of assembling agitator of magnetic drive, thermopair and inner spiral coil cooling tube ^TMCarry out in the Parr autoclave.With glycerine (30g, 326mmol, Aldrich 99%) and catalyzer (10mmol) or other additive of describing in the Table I down, and water (3.0g, 167mmol) adds reactor, and sealed reactor subsequently.The quality of record reactor and content.Stirred reactor and by spiral coil cooling tube circulation ice cold water.Hydrogen chloride gas under the required pressure of 110psig (Airgas Corporation) adds reactor, typically causes 15-25 ℃ of heat release.Reactor is heated to 110 ℃ temperature required, and makes reaction carry out 4 hours, under setting pressure, add hydrogen chloride gas during by reaction consumes continuously at hydrogen chloride gas simultaneously.The hydrogenchloride quality that adds reactor by the weight measurement of cylinder in the record whole reactor.

After past in four hours required reaction times, the hydrogenchloride charging stops, and with reactor and content cool to room temperature.Then with the reactor exhaust and write down reactor and the quality of content.Reaction product is by gas chromatographic analysis.The selectivity of dichlorohydrin is reported to the glycerine mole number of 100%x dichlorohydrin mole number/adding.

Use following abbreviation at this: " 1,3-DCH " is 1,3-propylene dichloride-2-alcohol; " 2,3-DCH " is 2,3-propylene dichloride-1-alcohol; " 1-MCH " is 1-chloro-2, ammediol; " 2-MCH " is glycerin; " BZMBr " is the positive Methylimidazole of bromination; " BZIMCl " is the positive Methylimidazole of chlorination; " Bu4NCl.H2O " is the tetrabutylammonium chloride hydrate; " C16Me3NCl " is the n-hexadecyl trimethyl ammonium chloride.

Amberlite IRC-50 and IRP-64 are weak-acid ion exchange resins.</entry></row></tbody></tgroup></table></tables>

Comparative example A-employing HCl, acetate and toluene are being lower than under the atmospheric pressure glycerine to the reaction of dichlorohydrin as entrainer

In the 500mL Wharton of assembling top air agitator, HCl inlet glaze, Dean Stark steam separator and condenser adds 3 neck flasks of baffle plate, add glycerine (92.0g, 1.00mol), 5mL acetate (HOAc) and 200mL toluene.Just be reflected under (positive) nitrogen gas stream, adopt the slow purging of anhydrous HCl to be heated to backflow (not having the flow of determining or flow control).After 5 hours refluxed, analysis showed that the bottom that obtains is＞85% monochloro alcohol mutually with NMR to collect the moisture HCl of some 23mL 6N.After 3 hours, add other 5mL HOAc and adding in 6 hours once more; Elutriation goes out very fast (in the steam separator 1-2mL/15 minute) after reinforced at every turn.Heat is miscible and the time be separated into two-phase in cooling subsequently after 6 hours.The product that obtains is confirmed standard substance by NMR and the residuum that removes most of toluene is used to provide the 122g specimen material.Use gas chromatography/mass spectrometry (GC/MS) to analyze analytic sample.

Analytical results and chemical scheme are seen following scheme 2.

Scheme 2

Comparative Examples B-adopts excessive HCl purging, acetate and does not have azeotropic water to remove and the reaction to dichlorohydrin of the glycerine of atmospheric pressure

In this Comparative Examples, do not attempt strictly removing water.To assembling top air agitator, HCl inlet glaze and be connected to add in the 500mL Wharton 3 neck flasks of outlet of washer 4A sieve exsiccant glycerine (138.0g, 1.50mol), 3.8g HOAc (2.75% based on glycerine).This outlet pipe is made of 16 inches direct-cooled condensers (glass) of the non-chilling that is connected to 1/16 inch polyethylene outlet pipe (about 7 feet), and this outlet pipe is coupled to by nodular by flange, 3 feet water wash column that ceramic saddle is filled.Be reflected under the positive nitrogen gas stream, be heated to 100 ℃ and begin to adopt the slow purging (approximately 200mg/ minute) of anhydrous HCl then.Speed and the total quantity of the HCl that adds are monitored by weight cell (cell).The little aliquots containig (for example 300mg) of sample is taken out to finish coarse motion mechanics conversion situation by the side arm in appropriate intervals, obtain transformation period from this conversion situation.The reaction internal reaction temperature keeps isothermal (100 ℃ ± 2 ℃) by temperature regulator.In 24 hours time, amount to the anhydrous HCl of 700g and pass through solution.Use wt%GC determination and analysis sample and also analyze the water of final sample and HCl content with acquisition total mass balance by the potentiometric titration mode.The burgundy reaction product (subtracting the 200mg retainer) that obtains after 23.75 hours purge is 218.5g.

Analytical results and chemical scheme are seen following scheme 3.Glycerine is to conversion graphic presentation in figure A of the pure and mild dichlorohydrin of monochloro.In figure A, " MCH " is monochloro alcohol 3-chloro-2, total mol% of ammediol and glycerin; " MCH-OAc " is total mol% of the acetic ester of MCH; " DCH " is dichlorohydrin 1, and 3-propylene dichloride-2-is pure and mild 2, total mol% of 3-propylene dichloride-1-alcohol.

Scheme 3

Embodiment 42-adopts pressure HCl, acetate and does not have glycerine reaction that azeotropic water removes to dichlorohydrin

At nitrogen purging (two 40psig pressure/exhaust cycle) afterwards, the dry glycerine (30.0g, 0.320 mole) that will comprise the 4wt% acetate (1.2g Aldrich) as catalyzer adopts to drive at magnetic and stirs in the 100mL Hasteloy-C Parr reactor and heating and experience the static pressure 90-96psig of anhydrous HCl.The internal heat galvanic couple of this reactor alignment measurement internal solution temperature.Indirect heating to reactor is provided by impregnation bath, by temperature regulator control impregnation bath.Under 90 ℃ initial internal temperature, almost heat release immediately then takes place and in 10 minutes, internal reaction temperature is 120-123 ℃.Heat release is accompanied by the rapid absorption of HCl.Impregnation bath is provided under this temperature 1.5-2 hour and monitors HCl by heavy pond (cylinder) and computer control system.After at this moment, in fact not having more HCl to absorb is obvious (approximately 32.1g absorbs).Reactor cooling to room temperature, carefully is vented to the HCl purge column, opens and content (68.0g) is transferred to the vial with polyethylene thread cap.Accurate H ₂O, HCl and wt% are organic balanced to be obtained on this and other sample.

Analytical results and chemical scheme are seen following scheme 4.

The Table II more as follows of embodiment 42 and Comparative Examples B.

Table II

Component	Embodiment 42 pressure HCl 32.1g HCl (wt%)	Comparative Examples B atmosphere HCl 700g HCl (wt%)
			Acetate	3.6	0.44
1，3-DCH	53.74	57.78
			2，3-DCH	1	1.11
3-chloro-1, the 2-propylene glycol	ND *	9.98
			Glycerin	1.88	4.03
Glycerine	ND	ND
			2-acetoxyl group-2, the 3-propylene dichloride	4.75	0.34
1-acetoxyl group-2, the 3-propylene dichloride	0.43	ND
			1-acetoxy-3-chloro-2-propyl alcohol	ND	0.42
The acetoxyl group propylene chlorohydrin	1.25	0.23
			The diacetoxy propylene chlorohydrin	0.3	ND
Chlorine ether dimer (RCl)	0.08	0.3
			Water	16.8	17.65
HCl	14.97	7.7
			The total mass balance	99.3	99.98

^*ND=does not detect

Comparative Examples B is presented among the embodiment that equals atmospheric pressure with respect to having occurred the reaction times and the catalyst loss that prolong in the super-atmospheric pressure pressure method.Same unexpected ground, monochloro alcohol experiences in the super-atmospheric pressure situation and produces less chlorine ether (RCl) to the bigger transformation efficiency of dichlorohydrin.The main loss of HCl is experienced in Comparative Examples B.

Embodiment 43

With ethylene glycol (501mg, 8.07mmol), 1, the 2-propylene glycol (519mg, 6.82mmol) and glacial acetic acid (102mg 1.715mmol) puts into vial with stirring rod.Bottle is placed on the Hastelloy C of 200mL ^TMIn the pressurized vessel.Then pressurized vessel is adopted the anhydrous HCl gas pressurization of 40psig.Bottle bottom is immersed down and kept stirring and pressure 45 minutes at 72-74 ℃ in water-bath.When reaction finishes, the solution in the bottle be transparent and color clear.Reaction obtains 1.893g and wraps aqueous crude product, and this crude product detects gas Chromatographic Determination by flame ionization.Measure following product according to the retention time of known commercial standard substance: chloroethanol (35.62 area %), n-propyl chloride-2-alcohol (40.47 area %), 2 cbloropropane isopropyl chloride-1-alcohol (6.47 area %), unconverted propylene glycol (3.00 area %), 2-chloro-1-acetoxyl group ethane (5.09 area %), 1-chloro-2-acetoxy-propane (4.45 area %) and 2-chloro-1-acetoxy-propane (0.75 area %).

Embodiment 44-51

Check that hydrogenchloride pressure uses 30g glycerine, 3g water, 12.6mol% acetate to carry out to the following test of the influence of glycerol hydrochlorination.It is 120 minutes with the reaction times that temperature of reaction is 90 ℃.Hydrogenchloride pressure as shown in Table III and as follows to the selectivity of dichlorohydrin and acetic ester thereof.

Table III

Embodiment No.	Pressure (HCl) (psig)	1,3-DCH yield (mol%)	1,3-DCH acetic ester yield (mol%)	2,3-DCH yield (mol%)
					44	15	0.2	0.0	0.0
45	20	3.2	0.1	0.1
					46	25	5.0	0.0	0.1
47	30	10.2	0.1	0.2
					48	40	33.5	0.4	0.6
49	55	49.4	0.1	0.9
					50	80	82.0	2.2	1.4
51	100	88.7	2.5	1.5

Embodiment 52

Following embodiment shows the formation of novel composition of the present invention.With glycerine (30g, 326mmol), water (3.0g, 167mmol) and 6-caprolactone (1.14g, 10.0mmol) be added to 100ml Parr reactor, be heated to 110 ℃ and adopt anhydrous hydrogen chloride to be pressurized to 110psig.After 4 hours, reaction mixture absorbs 34.0 gram hydrogenchloride under these conditions.Reactor content discharge and analysis and discovery are had following composition (get rid of water and remaining hydrogenchloride.

Table IV

Component	Mole number	Mol％
			1, and the 3-dichlorohydrin (1,3-DCH)	0.3052	98.414
1-acetoxyl group-2,3-propylene dichloride (2, the 3-DCH acetic ester)	0	0
			1-acetoxy-3-chloropropane-2-alcohol (1-MCH acetic ester)	0	0
2, and the 3-dichlorohydrin (2,3-DCH)	0.0063	1.9197
			2-acetoxyl group-1,3-propylene dichloride (1, the 3-DCH acetic ester)	0	0
2-monochloro alcohol (2-MCH)	0.0122	3.7294
			Acetoxyl group propylene chlorohydrin (MCH acetic ester)	0	0
1-monochloro alcohol (1-MCH)	0.0018	0.5545
			Glyceryl diacetate (glyceryl diacetate)	0	0
Diacetoxy chloropropane (MCH diacetate esters)	0.0011	0.3347
			Glycerine	0	0
Glycerol acetate 1 (glyceryl acetate)	0	0
			Glycerol acetate 2 (glyceryl acetate)	0	0
Glyceryl trichloride (TCP)	0	0
			Vanay (triacetin)	0	0
Chlorination two glycerine	0.0002	0.0005
Summation (all organic constituents)	0.3267	99.9527
			The summation of glycerine and acetic ester	0	0
The summation of the pure and mild acetic ester of monochloro	0.0151	4.6186
			1,3-dichlorohydrin and acetic ester	0.3052	93.414
2,3-dichlorohydrin and acetic ester	0.0063	1.9197
			Trichloropropane	0	0
Chlorination two glycerine and ester	0.0002	0.0477

Embodiment 53-chloropharin is used to prepare the purposes of epoxy chloropropane

Be used for this embodiment from dichlorohydrin (DCH) product of above embodiment 3 preparations.The apparatus for reactive distillation of being made up of 1 liter of strap clamp cover still is used in this test, this strap clamp cover still has outlet at bottom, is equipped with 30 tower tray Oldershaw sections at the top, is used for feed points, 6 tower tray Oldershaw sections, the moisture condenser that returns feed points and be connected to phase separator of 10% causticity thing/DCH charging.Preheating and the mixing before next-door neighbour's drawing-in system more than the 30 tower tray Oldershaw sections with DCH and 10% causticity thing.Operational condition is pressure 250mm Hg, 75-77 ℃ of still temperature, head temperature 65-67 ℃ and feeding temperature 68-76 ℃.Regulate DCH feeding rate and causticity thing feeding rate to reach causticity thing 10% molar excess with respect to DCH.The thick epoxy chloropropane sample of producing in the reaction/distillation plant has following composition the (area %) by the gas chromatographic analysis with flame ionization detector:

Component	Area %
		Epoxy chloropropane	99.00
Racemic glycidol	0.04
		1，3-DCH	0.13
2，3-DCH	0.35
		MCH	0.05

Embodiment 54 and 55 and Comparative Examples C and D

With hydrogenchloride by glycerine (30g), water (3.0g) and 10mmol mixture of catalysts under atmospheric pressure 110 ℃ of following bubblings four (4) hours.In four (4) little the reaction times, hydrogenchloride at 20-25g is per hour flowed rate-controlling.After at this moment, with reaction mixture cooling and by gas chromatographic analysis to measure to measure the concentration of dichlorohydrin, the pure and mild unreacted glycerine of monochloro.Table V shows the result who uses acetate, 6 hydroxycaproic acid, phenylacetic acid and 4-hydroxyphenyl acetate to obtain as catalyzer.

Table V

Embodiment	Comparative Examples C	Embodiment 54	Comparative Examples D	Embodiment 55
					Catalyzer	Acetate	6 hydroxycaproic acid	Phenylacetic acid	4-hydroxyphenyl acetate
The HCl (g) that uses	86.3	92.2	90	101
					Reaction mass (g)	50.75	51.78	48.4	52.5
Initial glycerine (g)	30	30	30	30
					Product
The DCH mole number	0.0502	0.0651	0.0332	0.0363
					The MCH mole number	0.2432	0.2365	0.2221	0.2399
Transformation efficiency
					Transformation efficiency to DCH	15.4	20	10.2	11.1
Transformation efficiency to MCH	74.7	72.6	68.2	73.6
					Unconverted certain oil	6.9	8.1	17.5	17.5

Claims (59)

1. method of producing chloropharin, chloropharin ester or its mixture, comprise the steps: in the presence of catalyzer, to make ester or its mixture of multihydroxylated-aliphatic hydrocarbon, multihydroxylated-aliphatic hydrocarbon contacts with production chloropharin, chloropharin ester or its mixture, carry out this contact procedure and remove water indistinctively with the hydrogenchloride source of super-atmospheric pressure dividing potential drop.

2. method according to claim 1 is carried out in the presence of catalyzer and promotor.

3. method according to claim 2, wherein said promotor are the sources of muriate, bromide or iodide.

4. method according to claim 1, wherein said hydrogenchloride source are 50mol% hydrogenchloride at least.

5. method according to claim 1, wherein said hydrogenchloride source is a hydrogen chloride gas.

6. method according to claim 1, wherein said chloropharin are dichlorohydrin, dichloro alcohol ester or its mixture.

7. method according to claim 6, wherein said dichlorohydrin is 1,3-propylene dichloride-2-alcohol or 2,3-propylene dichloride-1-alcohol or its mixture.

8. method according to claim 1, wherein said multihydroxylated-aliphatic hydrocarbon is a raw glycerine.

9. method according to claim 8, wherein said raw glycerine comprise less than the water of 25wt% with less than basic metal or the alkaline earth salt of 25wt%.

10. method according to claim 1, wherein said multihydroxylated-aliphatic hydrocarbon is 1,2, the 3-glycerol.

11. method according to claim 1, wherein said multihydroxylated-aliphatic hydrocarbon is selected from 1,1,2-propylene glycol, 1, ammediol, 1-chloro-2, ammediol, glycerin and 1,2,3-glycerol and its mixture.

12. method according to claim 1, wherein said catalyzer are selected from carboxylic acid, acid anhydrides, acyl chlorides, ester, lactone, lactan, acid amides, organometallics, metal-salt, can change into any compound or its combination of carboxylic acid under the technological reaction conditions.

13. method according to claim 1, wherein said catalyzer are carboxylic acid or its precursors that comprises about 60 carbon atoms of 1-.

14. method according to claim 1, wherein said catalyzer is the carboxylates derivatives that contains about 20 carbon atoms of 2-and comprise at least one functional group, described functional group comprises amine, alcohol, halogen, sulfydryl, ether, ester or its combination, and wherein said functional group closer is connected to acid functional group unlike α carbon; Or its precursor.

15. method according to claim 1, wherein said catalyzer is selected from acetate, propionic acid, caproic acid, enanthic acid, stearic acid, butyric acid, valeric acid, the 4-methylvaleric acid, phenylacetic acid, styracin, succsinic acid, polyacrylic acid, by acrylic acid-grafted polyethylene, 6-caprolactone, δ-Wu Neizhi, gamma-butyrolactone, ε-Ji Neixianan, 6-chlorine caproic acid, 4-hydroxyphenyl acetate, the 4-aminobutyric acid, the 4-dimethylaminobutyricacid acid, 4-trimethyl ammonium butyryl chloride, 4-hydroxyphenyl acetate, 4-aminophenyl acetate, the 5-chloro pentane acid, the 5-hydroxypentanoic acid, 4 hydroxybutyric acid, the 4-chloro-butyric acid, 5-chloro pentane acid or its mixture.

16. method according to claim 1, wherein said catalyzer are selected from acetate, propionic acid, butyric acid, 4-methylvaleric acid, caproic acid, enanthic acid, stearic acid, 6-caprolactone, gamma-butyrolactone, 6-chlorine caproic acid, 4-aminobutyric acid, 4-dimethylaminobutyricacid acid, 4-trimethyl ammonium butyryl chloride, 4-hydroxyphenyl acetate, 4-aminophenyl acetate or its mixture.

17. method according to claim 1, wherein said catalyzer are selected from acetate, ε caprolactone, 6-chlorine caproic acid, δ-Wu Neizhi, 5-chloro pentane acid, 4-chloro-butyric acid, 4-hydroxyphenyl acetate, 4-aminophenyl acetate, 4-aminobutyric acid or its mixture.

18. method according to claim 1, wherein said catalyzer are acetate or acetogenin.

19. method according to claim 1, wherein said catalyzer are caprolactone or caprolactone derivative.

20. method according to claim 1, wherein said catalyzer are from being selected from the glyceryl ester that following compound obtains, glycol ester or propylene glycol ester: acetate, propionic acid, caproic acid, enanthic acid, stearic acid, butyric acid, valeric acid, the 4-methylvaleric acid, phenylacetic acid, styracin, succsinic acid, phenylformic acid, polyacrylic acid, by acrylic acid-grafted polyethylene, the ε caprolactone, δ-Wu Neizhi, gamma-butyrolactone, ε-Ji Neixianan, 6-chlorine caproic acid, 4-hydroxyphenyl acetate, the 4-aminobutyric acid, the 4-dimethylaminobutyricacid acid, 4-trimethyl ammonium butyryl chloride, 4-hydroxyphenyl acetate, 4-aminophenyl acetate, the 5-chloro pentane acid, the 5-hydroxypentanoic acid, 4 hydroxybutyric acid, the 4-chloro-butyric acid, 5-chloro pentane acid or its mixture.

21. method according to claim 1, wherein said catalyzer are to be selected from following ester: glyceryl monoacetate, glyceryl diacetate, distearin, 1-chloro-2, ammediol monoacetate, poly carboxylic acid glyceryl ester or its mixture.

22. method according to claim 1, wherein said catalyzer are the insoluble polymers that comprises carboxylic moiety or its ester.

23. method according to claim 22, wherein said insoluble polymer or multipolymer are polyester, polyacrylic acid, polymeric amide, polyacrylic ester and its multipolymer and its mixture.

24. method according to claim 1, the vapour pressure of wherein said catalyzer are lower than the azeotrope of chloropharin or itself and water.

25. method according to claim 1, its hydrogenchloride branch at the about 1000psia of about 15psia-is depressed and is carried out.

26. method according to claim 1, its hydrogenchloride branch at the about 600psia of about 35psia-is depressed and is carried out.

27. method according to claim 1, its hydrogenchloride branch at the about 150psia of about 55psia-is depressed and is carried out.

28. method according to claim 1, its hydrogenchloride branch at the about 120psia of about 20psia-is depressed and is carried out.

29. method according to claim 1, it carries out under about 25 ℃-Yue 300 ℃ temperature.

30. method according to claim 1, it carries out under about 25 ℃-Yue 200 ℃ temperature.

31. method according to claim 1, it carries out under about 30 ℃-Yue 160 ℃ temperature.

32. method according to claim 1, it carries out under about 40 ℃-Yue 150 ℃ temperature.

33. method according to claim 1, it carries out under about 50 ℃-Yue 140 ℃ temperature.

34. a method for preparing chloropharin, the hydrogenchloride branch that is included in the about 1000psia of about 15psia-are depressed and under about 25 ℃-Yue 300 ℃ temperature with (a) multihydroxylated-aliphatic hydrocarbon; (b) promote the catalyzer that multihydroxylated-aliphatic hydrocarbon transforms to chloropharin; (c) step that contacts together of hydrogen chloride gas; Wherein carry out this contact procedure and remove water indistinctively.

35. a method for preparing chloropharin, the hydrogenchloride branch that is included in the about 1000psia of about 15psia-are depressed and under about 25 ℃-Yue 300 ℃ temperature with the ester of (a) multihydroxylated-aliphatic hydrocarbon; (b) step that contacts together of hydrogenchloride; Carry out this contact procedure and remove water indistinctively.

36. a method for preparing epoxide comprises the steps:

(a) ester of multihydroxylated-aliphatic hydrocarbon, multihydroxylated-aliphatic hydrocarbon or its mixture contacts with the production chloropharin with the hydrogenchloride source, wherein carry out this contact procedure and remove water indistinctively; With

(b) chloropharin that forms in the above step (a) is contacted to form epoxide with alkali.

37. a method for preparing epoxy chloropropane comprises the steps:

(a) glycerine, glyceryl ester or its mixture and hydrogenchloride source contact with the production dichlorohydrin, carry out this contact procedure and remove water indistinctively; With

(b) dichlorohydrin that forms in the above step (a) is contacted to form epoxy chloropropane with alkali.

38. a method for preparing epoxide comprises the steps:

(a) ester of multihydroxylated-aliphatic hydrocarbon, multihydroxylated-aliphatic hydrocarbon or its mixture are contacted to produce required chloropharin with the hydrogenchloride source, carry out this contact procedure and remove water indistinctively;

(b) make required chloropharin and unreacted multihydroxylated-aliphatic hydrocarbon, not required chloropharin and its ester and catalyst separating; With

(c) isolating required chloropharin is contacted to form epoxide with alkali.39. according to the described method of claim 38, comprise the steps: with isolating unreacted multihydroxylated-aliphatic hydrocarbon, monochloro pure and mild they ester and catalyst recirculation to step (a).

40. a method for preparing epoxy chloropropane comprises the steps:

(a) glycerine, glyceryl ester or its mixture and hydrogenchloride source contact with the production dichlorohydrin, carry out this contact procedure and remove water indistinctively;

(b) make pure and mild their ester of dichlorohydrin and unreacted glycerine, monochloro, and catalyst separating; With

(c) isolating dichlorohydrin is contacted to form epoxy chloropropane with alkali.

41. a method for preparing epoxide comprises the steps:

(a) ester of multihydroxylated-aliphatic hydrocarbon, multihydroxylated-aliphatic hydrocarbon or its mixture are contacted to produce required chloropharin and its ester with the chloride ion source, carry out this contact procedure and remove water indistinctively;

(b) product of step (a) and multihydroxylated-aliphatic hydrocarbon are reacted so that required chloropharin ester is changed into required chloropharin;

(c) make required chloropharin and unreacted multihydroxylated-aliphatic hydrocarbon, not required chloropharin and their ester, and catalyst separating; With

(d) isolating required chloropharin is contacted to form epoxide with alkali.

42. a method for preparing epoxy chloropropane comprises the steps:

(a) glycerine, glyceryl ester or its mixture are contacted to produce dichlorohydrin and its ester with the chloride ion source, carry out this contact procedure and remove water indistinctively;

(b) make the product of step (a) and glycerine reaction so that the dichloro alcohol ester is converted into dichlorohydrin;

(c) make pure and mild their ester of dichlorohydrin and unreacted glycerine, monochloro, and catalyst separating; With

(d) isolating dichlorohydrin is contacted to form epoxy chloropropane with alkali.

43. according to the described method of claim 40, wherein said alkali is carbonate, supercarbonate or oxyhydroxide or its mixture of sodium, potassium, calcium, magnesium.

44. according to the described method of claim 34-43, wherein said multihydroxylated-aliphatic hydrocarbon is a raw glycerine.

45. according to the described method of claim 34-43, wherein said multihydroxylated-aliphatic hydrocarbon is 1,2, the 3-glycerol.

46. a method of producing high yield chloropharin, chloropharin ester or its mixture comprises the steps: to make the ester of multihydroxylated-aliphatic hydrocarbon, multihydroxylated-aliphatic hydrocarbon or its mixture contacts with the hydrogenchloride source of super-atmospheric pressure dividing potential drop and remove water indistinctively with production chloropharin, chloropharin ester or its mixture in the presence of catalyzer.

47. method that comprises the steps: the ester of multihydroxylated-aliphatic hydrocarbon, multihydroxylated-aliphatic hydrocarbon or its mixture are contacted with hydrochloric acid gas to produce chloropharin, carry out this contact procedure and remove water indistinctively.

48. a composition that comprises dichlorohydrin comprises:

Glycerine and the ester thereof of the about 1mol% of about 0.1mol%-; Monochloro alcohol and the ester thereof of the about 10mol% of about 4mol%-; Greater than 1 of about 80mol%, 3-dichlorohydrin and ester thereof; 2 of the about 4mol% of about 1mol%-, 3-dichlorohydrin and ester thereof; Glyceryl trichloride less than about 1mol%; With chlorination glyceryl ether and ester thereof less than 0.3mol%; And wherein in the composition 1, the 3-dichlorohydrin is to 2, and the ratio of 3-dichlorohydrin was greater than about 8: 1.

49. according to the described composition of claim 48, wherein said chlorination glyceryl ether and ester thereof are less than about 0.2mol%.

50. according to the described composition of claim 48, wherein said chlorination glyceryl ether and ester thereof are less than about 0.15mol%.

51. according to the described composition of claim 48, wherein chlorination glyceryl ether and ester thereof are less than about 0.1mol%.

52. according to the described composition of claim 48, wherein said glyceryl trichloride is less than about 0.1mol%.

53. according to the described composition of claim 48, wherein said glyceryl trichloride is less than about 0.05mol%.

54. according to the described composition of claim 48, wherein said glyceryl trichloride is less than about 0.02mol%.

55. produce chloropharin for one kind, the method of chloropharin ester or its mixture, comprise the steps: in the presence of catalyzer, to make multihydroxylated-aliphatic hydrocarbon, the ester of multihydroxylated-aliphatic hydrocarbon or its mixture and super-atmospheric pressure, the hydrogenchloride source contact that equals normal atmosphere or be lower than the normal atmosphere dividing potential drop is to produce chloropharin, chloropharin ester or its mixture, catalyzer wherein: (i) be the carboxylate radical derivative that contains about 20 carbon atoms of 2-and comprise at least one functional group, this functional group comprises amine, alcohol, halogen, sulfydryl, ether, ester or its combination, wherein said functional group closer is connected to acid functional group unlike α carbon; Or its precursor; (ii) volatility is not as required chloropharin, chloropharin ester or its mixture; (iii) comprise hetero atom substituents.

56. according to the described method of claim 55, wherein said carboxylate radical derivative catalyst has following general formula (a):

General formula (a)

Wherein " R ' " comprising: the functional group that comprises amine, alcohol, halogen, sulfydryl, ether, ester; Or alkyl, aryl or the alkaryl of about 20 carbon atoms of the 1-that comprises described functional group; Or its combination; Wherein " R " comprises hydrogen, alkali, alkaline earth or transition metal or hydrocarbon functional groups.

57. according to the described method of claim 55, wherein said carboxylate radical derivative catalyst is selected from lactone, ester, lactan, acid amides or functionalized carboxylic acid.

58. according to the described method of claim 55, wherein said carboxylate radical derivative catalyst select oneself lactone, carboxylic acid amide, carboxylic acid lactone, hexanolactam or its combination.

59. according to the described method of claim 55, wherein said carboxylate radical derivative catalyst is selected from 6 hydroxycaproic acid, 6-chlorine caproic acid, caprolactone, ε-Ji Neixianan or butyrolactam; Gamma-butyrolactone, δ-Wu Neizhi or 6-caprolactone; 6-aminocaprolc acid; 4-aminophenyl acetate, 4-aminobutyric acid, 4-dimethylaminobutyricacid acid, 4-hydroxyphenyl acetate, 4-dimethylaminophenyl acetate, aminophenyl acetate, lactic acid, oxyacetic acid, 4-dimethylaminobutyricacid acid, 4-trimethyl ammonium butyric acid or its combination.

60. according to the described method of claim 55, wherein said multihydroxylated-aliphatic hydrocarbon is glycerine or raw glycerine.

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