CN101010283B - Process for production of alpha,beta-unsaturated carboxylic esters and alpha, beta-unsaturated carboxylic esters - Google Patents
Process for production of alpha,beta-unsaturated carboxylic esters and alpha, beta-unsaturated carboxylic esters Download PDFInfo
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Abstract
A process for the production of alpha,beta-unsaturated carboxylic esters by reacting (A) an alcohol with (B) an alpha,beta-unsaturated carboxylic acid or a lower alkyl ester thereof in the presence of (alpha) an inorganic porous substance carrying sulfonic acid groups; and alpha,beta-unsaturated carboxylic esters obtained by the process which each have a sulfur content of 50ppm or below based on the weight of the carboxylic ester and each contain by-product ethers and by-product adducts in amounts of as small as 2 % by mole or below and as small as 1 % by mole or below respectively based on the molar amount of the carboxylic ester. Thus, the invention provides a process for the production of alpha,beta-unsaturated carboxylic esters which is not accompanied by the generation of a large amount of waste; a process for the production of high-purity alpha,beta-unsaturated carboxylic esters which little brings about by-products; and high-purity alpha,beta-unsaturated carboxylic esters which little contain a catalyst residue and are reduced in the corrosiveness on metals.
Description
Technical field
The present invention relates to α, the method for manufacture of beta-unsaturated carboxylic acid ester and α, beta-unsaturated carboxylic acid ester.At length say, relate to the α of solid acid as catalyzer, the method for manufacture of beta-unsaturated carboxylic acid ester and resulting α, beta-unsaturated carboxylic acid ester.
Background technology
In the past, as being used to make pure and mild α, beta-unsaturated carboxylic acid or its lower member ester reacted and made α, and the acid catalyst of beta-unsaturated carboxylic acid ester uses mineral acid (sulfuric acid, phosphoric acid etc.) and sulfonic acid (p-toluenesulphonic acids, methylsulfonic acid, trifluoromethanesulfonic acid etc.) usually.
But; When these Brs are used as catalyzer; After reaction, need to neutralize, washing or adsorption treatment etc. are numerous and diverse removes the catalyzer operation, produce a large amount of wastes; And have following problems: residual in the carboxylicesters that obtains have a catalyst residue, sometimes the metal of contact produced corrosion according to its purposes.
In order to address these problems, proposed to use the α of various " solid acid " catalyzer, the method for manufacture of beta-unsaturated carboxylic acid ester.These methods can suppress the waste that produces because of neutralization, washing etc. at an easy rate with reaction product and catalyst separating through using " solid acid " as heterogeneous catalyst.
As these solid acid catalysts, proposed solid super-strong acids (with reference to following patent documentation 3) such as ion exchange resin (sulfonated bodies of styrene diethylene benzene copoly mer etc.) (with reference to following patent documentation 1 and 2), phospho-wolframic acid, contained the fluorine resin (Du-Pont company " Nafion " etc.) of sulfonic acid etc.
But these solid acid catalysts are as being used for α, and the catalyzer of beta-unsaturated carboxylic acid ester not only all can not satisfy catalytic activity, and is easy to generate by product.As by product; Elimination reaction product (sloughing water and the alkene that generates by the alcohol of a molecule), etherate (ether that is generated by the dehydration of alcohols condensation of two molecules) and adduct are arranged (to α; β-unsaturated group addition alcohol and the affixture that generates etc.); The α that obtains, beta-unsaturated carboxylic acid ester have the low problem of purity.
And, though to compare problem few with the situation of Br, also have the problem that is easy to the residual sour compositions such as oxysulfide that wash-out goes out through catalyst decomposes.
Patent documentation 1: No. 6087527 specification sheets of USP
Patent documentation 2:WO90/08127 pph
Patent documentation 3: No. 5827939 specification sheets of USP
Summary of the invention
The purpose of this invention is to provide the α that does not produce a large amount of wastes, the method for manufacture of beta-unsaturated carboxylic acid ester.
Another object of the present invention provides the few and highly purified α of by product, the method for manufacture of beta-unsaturated carboxylic acid ester.
A further object of the present invention provides few and few to the corrosion of metal property α of catalyst residue, the method for manufacture of beta-unsaturated carboxylic acid ester.
Of the present inventionly advance a purpose and provide the highly purified α that obtains by above-mentioned method of manufacture, beta-unsaturated carboxylic acid ester.
α of the present invention, the method for manufacture of beta-unsaturated carboxylic acid ester comprises: support sulfonic inorganic porous body (α) in the presence of make alcohol (A) and α, the reaction of beta-unsaturated carboxylic acid or its lower alkyl esters (B).
α of the present invention; The beta-unsaturated carboxylic acid ester be through support sulfonic inorganic porous body (α) in the presence of make alcohol (A) and α; Beta-unsaturated carboxylic acid or its lower alkyl esters (B) reaction obtain, and its sulphur atom content is based on α, and the weight of beta-unsaturated carboxylic acid ester is below the 50ppm; By-product ether compound and by-product adduct be based on α, and the mole number of beta-unsaturated carboxylic acid ester is respectively below 2 moles of % and 1 mole below the %.
Embodiment
Among the present invention,, can enumerate out the polyvalent alcohol (A2) more than monohydroxy-alcohol (A1) and the binary as alcohol (A) (below, simply be designated as (A) sometimes).
As (A1), can enumerate out following compound.
(A11) representative examples of saturated aliphatic monohydroxy-alcohol [carbonatoms is the straight or branched alcohol of 1-36, for example methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, 2-Ethylhexyl Alcohol, octanol, nonyl alcohol, decyl alcohol, hendecanol, dodecanol, tridecyl alcohol, tetradecanol, cetyl alcohol, Stearyl alcohol, nonadecanol, 2-decyl tetradecanol, 2-tetradecyl Stearyl alcohol etc.];
(A12) unsaturated aliphatic-unit's alcohol [carbonatoms is the straight or branched alcohol of 2-36, for example vinyl alcohol, (methyl) allyl alcohol, octenol, decenol, lanolin alcohol, tridecylene alcohol, 15 carbenes alcohol, oleyl alcohol, gadoleyl alcohol, inferior oleyl alcohol etc.];
(A13) ester ring type monohydroxy-alcohol [total carbon atom number with alicyclic radical is the alcohol of 6-36, for example ethyl cyclohexyl alcohol, propyl group cyclohexyl alcohol, octyl group cyclohexyl alcohol, nonyl cyclohexyl alcohol, adamantanol etc.];
(A14) monobasic phenols [total carbon atom number with phenol ring is the phenols of 6-36, for example phenol, cresols, tert.-butyl phenol, styrenated phenol, bromophenol etc.];
(A15) has the monohydroxy-alcohol [replacing the part of above-mentioned (A11)-(A14) and the alcohol that forms with the group that contains nitrogen-atoms, sulphur atom and/or halogen atom, for example dimethylaminoethanol, diethylaminoethanol, morpholinyl ethanol, ethylene chlorhydrin etc.] of nitrogen-atoms, sulphur atom and/or halogen atom;
(A16) alkylene oxide of above-mentioned alcohol (A11)-(A15) (below; Brief note is AO) [carbonatoms is the compound of 2-8; For example oxyethane (below, note by abridging be EO), propylene oxide (below, note by abridging be PO), 1; 2-or 2,3-butylene oxide ring, THF and Styrene oxide 98min. etc.] affixture (the addition mole number is 1-50).
As the object lesson of (A2), can enumerate out:
(A21) [carbonatoms is the alkylene glycol (terepthaloyl moietie, 1 of 2-12 to divalent alcohol; 2-Ucar 35,1; Ammediol, 1; 4-butyleneglycol and 1; 6-pinakons etc.), the polymerization degree is AO affixture (the addition mole number is 1-50) and the AO affixture (the addition mole number is 2-30) (AO is same as described above) of bisphenols (dihydroxyphenyl propane, Bisphenol F and bisphenol S etc.) of polyalkylene glycol (Diethylene Glycol, triethylene glycol, dipropylene glycol, polyoxyethylene glycol, W 166 and polytetramethylene glycol etc.), ester ring type glycol (total carbon atom number with alicyclic radical is the glycol of 6-36, for example 1,4 cyclohexane dimethanol and Hydrogenated Bisphenol A 99 etc.) and these divalent alcohol of 2-1000];
(A22) 3-8 unit or above aliphatic polyol [the AO affixture (the addition mole number is 1-50) of alkane polyol and its intramolecularly or intermolecular dehydrate (glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder, sorbitan, poly-glycerol and Dipentaerythritol), carbohydrate and its verivate (sucrose and methyl glucoside etc.) and above-mentioned aliphatic polyol];
(A23) 3-8 unit or the above polyvalent alcohol that contains aromatic nucleus [the AO affixture (the addition mole number is 2-50) of the AO affixture of three phenols (triphenol PA etc.) (the addition mole number is 2-50), novolac resin (phenol novolac resin and cresols novolac resin etc.) etc.].
(A) preferred compound is the polyvalent alcohol of monohydroxy-alcohol (A1) or 2-8 unit and their AO affixture in, more preferably (A1).
(A1) preferred compound is (A11), (A12), (A15) and their AO affixture in; From being easy to obtain the viewpoint consideration of highly purified product, the carbonatoms that particularly preferably is in (A11) is the representative examples of saturated aliphatic monohydroxy-alcohol and its AO (particularly EO) affixture of 8-32.
In addition,, can enumerate out primary hydroxyl and secondary hydroxyl, preferred primary hydroxyl as the hydroxyl that contains in (A).
As α of the present invention; Beta-unsaturated carboxylic acid or its lower alkyl esters (B) (below; Sometimes simply be designated as (B)) in α, beta-unsaturated carboxylic acid (B1) can be enumerated out aliphatic alpha; β-unsaturated monocarboxylic acid [(methyl) vinylformic acid and Ba Dousuan etc.] and aliphatic alpha, β-unsaturated dicarboxylic acid (toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid etc.).
In addition, as α, the lower alkyl esters of beta-unsaturated carboxylic acid (B2) can be enumerated out by (B1) and to have carbonatoms be the ester (methyl esters, ethyl ester and isopropyl ester etc.) that the alcohol of the alkyl of 1-4 obtains.
Among (B), consider preferably (B1) from the viewpoint that obtains the high ester of purity; The amount of adduct is few from by product viewpoint considers, aliphatic alpha more preferably, β-unsaturated monocarboxylic acid; From the α that obtains, the excellent viewpoint of the polymerizability of beta-unsaturated carboxylic acid ester is considered, particularly preferably is vinylformic acid and methylacrylic acid.
Of the present invention to have supported sulfonic inorganic porous body (α) (below, simply be designated as (α) sometimes) fixing and support and contain sulfonic compound and obtain on inorganic porous body, is the catalyzer of (A) and esterification (B).
As inorganic porous body, can use known inorganic porous body, for example can enumerate out the inorganic porous body that constitutes by more than one the inorganics that is selected among silicon-dioxide, aluminum oxide, titanium oxide, Natural manganese dioxide and the zirconium white.
Specifically, as the inorganic porous body that constitutes by silicon-dioxide, can enumerate out silica gel; As the inorganic porous body that constitutes by aluminum oxide, can enumerate out alumina gel etc.; As the inorganic porous body that constitutes by silicon-dioxide and aluminum oxide, can enumerate out zeolite etc.; As other inorganic porous body, can enumerate out the silica-alumina class porous insert " KYOWAAD " (consonance chemistry (strain) system) sold as sorbent material and zeyssatite etc.
Wherein, consider that preferably silicon-dioxide, aluminum oxide, zeolite and " KYOWAAD " particularly preferably are silica gel and " KYOWAAD " from the viewpoint of catalytic activity.
Inorganic porous body is saccharoid normally, as its shape, can enumerate out amorphous particle, spherical particle or particulate state etc.
Wherein, from make through after the little viewpoint of flow method when reaction pressure-losses stated consider preferred spherical particle and particulate state, especially preferred spherical particle.
When the particle diameter of inorganic porous body is represented with d50 (median size), be preferably 1-8000 μ m, more preferably 10-6000 μ m is preferably 40-500 μ m especially.If be set in 1 μ m when above, then processing ease is preferably below the 8000 μ m with regard to the catalytic activity aspect.D50 can measure according to the particle size distribution measurement method of JIS K1150 regulation among the present invention.
When the specific surface area of inorganic porous body is represented with the BET specific surface area, be preferably 30m
2More than/the g, 50-1500m more preferably
2/ g is preferably 100-800m especially
2/ g.Consider from the viewpoint that catalytic activity improves and side reaction reduces, be preferably 30m
2More than/the g.The BET specific surface area can be measured according to the specific surface area method of masurement of JIS K1150 regulation among the present invention.
The long-width ratio of inorganic porous body is preferably 1.0-1.25, and more preferably 1.0-1.18 is preferably 1.0-1.11 especially.In addition, so-called long-width ratio is meant the longest diameter and the shortest diameter ratio of particle, and it approaches 1.0 more, shows to approach spherical shape more.From make through after the little viewpoint of flow method when reaction pressure-losses stated consider that long-width ratio is that the scope of 1.0-1.25 is preferred.
Long-width ratio can be through using the microscopic examination particle among the present invention, instrumentation its shortest diameter and longest diameter, and 100 particles are averaged measure.
As making inorganic porous body support sulfonic method; Can enumerate send as an envoy to inorganic porous body with contain the compound (s) that can change sulfonic sulfonic acid precursor base into (below; Sometimes simply be designated as (s)) reaction, make sulfonic acid precursor base change sulfonic method etc. into then.
(s) be the group and the compound that can change sulfonic group into that in its molecule, has with the reaction of the surface functional group of inorganic porous body.
As the surface functional group of inorganic porous body, can enumerate out hydroxyl, amino and carboxyl etc.Consider preferred hydroxyl from the viewpoint on the surface that is easy to modify inorganic porous body.
On the other hand, as contain in (s) and with the group of the surface functional group of inorganic porous body reaction, be can enumerate out trialkoxysilyl, glycidyl and carboxyl etc. under hydroxyl or the amino situation at surface functional group; Be to enumerate out trialkoxysilyl, glycidyl and amino etc. under the situation of carboxyl at surface functional group.
Wherein consider preferred trialkoxysilyl and glycidyl, preferred especially trialkoxysilyl from the viewpoint that is easy to react with the functional group on surface.
Sulfonic sulfonic acid precursor base can be changed into as what contain in (s), sulfydryl (is sulfonic group through oxidotranstormation) and phenyl (changing sulfophenyl into) etc. can be enumerated out through sulfonation.
As the object lesson of (s), can enumerate out the silane coupling agent (sulfydryl propyl trimethoxy silicane and sulfydryl propyl-triethoxysilicane etc.) that contains sulfydryl, contain the silane coupling agent (phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane etc.) of phenyl and contain the glycidyl compound (phenyl glycidyl ether, nonyl phenyl glycidyl ether etc.) of phenyl.The silane coupling agent that wherein preferably contains sulfydryl.
The reaction of silane coupling agent and inorganic porous body can be carried out under various reaction conditionss.For example; With the weight based on inorganic porous body is the ratio adding silane coupling agent of 30-60 weight %; In the presence of solvent, carry out heated and stirred, make surface functional group (hydroxyl etc.) reaction of trialkoxysilyl and inorganic porous body in the silane coupling agent, refining then and obtain.
The solvent that adopts during as reaction, with an organic solvent (toluene, YLENE, vinyl acetic monomer, methylethylketone, acetone and/or carbonatoms are the lower alcohol of 1-4 etc.) also can be the mixed solvent of water and these organic solvents.
For the hydroxyl that promotes inorganic porous surface and the activity of silane coupling agent, preferably make water on a small quantity, the ratio of water is to be preferably 3 times especially more than the mole with respect to silane coupling agent.
In addition the usage quantity of the above-mentioned solvent weight that is based on inorganic porous body be generally 80-300% (below, only if % is special limit outside, all represent weight %), be preferably 100-250%.
Temperature of reaction is generally 60-150 ℃, can remove the material from alkoxyl group (for example lower alcohol such as methyl alcohol, ethanol) of generation in the limit, and react on the limit.
Saccharoid is separated, reclaimed in the reaction back through filter or use separating centrifuge etc.; In order to remove unreacted reactant (unreacted silane coupler etc.); With above-mentioned organic solvent washing for several times after, carry out drying under reduced pressure (under 100-120 ℃, 10-20mmHg, carrying out 3-5 hour usually).
After making the silane coupling agent reaction that contains sulfydryl, make sulfydryl change sulfonic group into, in the presence of solvent, carry out oxidizing reaction.As the oxygenant that uses, can enumerate out various oxygenants, for example nitric acid, hydrogen peroxide, hypochlorite, potassium permanganate, chromic acid or superoxide etc., preferably hydrogen peroxide.As above-mentioned solvent, use acetone, carbonatoms lower alcohol, acetonitrile, pyridine, chloroform and/or methylene dichloride etc. usually as 1-4.Temperature of reaction is generally 0-100 ℃.Oxidizing reaction by hydrogen peroxide produces also can be carried out under the reaction conditions of No. 5912385 specification sheets records of USP.
After making the silane coupling agent reaction that contains phenyl, make the phenyl sulfonation, can use various method of sulfonating.Can enumerate and send as an envoy to the for example vitriol oil, oleum, sulphur trioxide, chlorsulfonic acid, fluosulfonic acid or thionamic acid etc. as the method for sulphonating agent.As the solvent of this situation, can use acetic acid, acetic anhydride, vinyl acetic monomer, acetonitrile, ethylene dichloride and/or tetracol phenixin etc.Temperature of reaction is generally-10～180 ℃.
Under any situation of oxidizing reaction or sulfonation reaction, can obtain having supported sulfonic inorganic porous body (α) as reacted refinement treatment operation through carrying out operation same as described above (separate, reclaim, wash and drying).
After preferably making the silane coupling agent and inorganic porous precursor reactant that contains sulfydryl in the method for manufacture (α), change sulfonic method into.
(α) preferably have 5-250mgKOH/g, more preferably have 10-150mgKOH/g, especially preferably have the acid number of 15-100mgKOH/g.
At acid number is 5mgKOH/g when above, and catalytic activity is improved, and just can carry out esterification with a spot of catalyzer, is that 250mgKOH/g is difficult for producing side reaction when following at acid number.
The measurement of acid number (α) can be used (α) is immersed in the ion exchanged water, adds excessive sodium hydroxide and stirs, and carries out the method for neutralization titration with the 0.1N aqueous hydrochloric acid and measures.
(α) be and support the identical in fact shape of inorganic porous body before the sulfonic group that the preferable range of its d50, BET specific surface area and long-width ratio is also identical.
(α) preferably have 1-8000 μ m, more preferably have 10-6000 μ m, especially preferably have the d50 of 40-500 μ m.Processing ease when 1 μ m is above is preferably below the 8000 μ m with regard to the catalytic activity aspect.
(α) preferably has 30m
2More than/the g, more preferably has 50-1500m
2/ g especially preferably has 100-800m
2The BET specific surface area of/g.Consider to be preferably 30m from catalytic activity height and the few viewpoint of side reaction
2More than/the g.
(α) preferably have 1.0-1.25, more preferably have 1.0-1.18, especially preferably have the spherical particle of the long-width ratio of 1.0-1.11.
From make through after the little viewpoint of flow method when reaction pressure-losses stated consider that long-width ratio is that the spherical particle of 1.0-1.25 is preferred.
In the method for manufacture of esters of unsaturated carboxylic acids of the present invention, make (A) and (B) (A) in when reaction and equivalence ratio (B) be generally 1: 3-3: 1, be preferably 1: 2-2: 1, more preferably 1: 1.5-1.5: 1, be preferably 1 especially: 1.5-1: 1.02.
Consider from the viewpoint that improves reactivity, advantageously: (A) or the excessive use of a side that is easy to (B) remove, after the reaction completion, remove with excessive (A) or (B).
In the method for manufacture of esters of unsaturated carboxylic acids of the present invention, also can add polymerization retarder in order to prevent the unsaturated group polymerization.
As polymerization retarder, can enumerate out phenols polymerization retarder (quinhydrones, hydroquinone monomethyl ether, pyrocatechol, cresols, DBMP, DI-tert-butylphenol compounds, tri-butyl-phenol etc.) and amine polymerization retarder (thiodiphenylamine, pentanoic, alkylated diphenylamine etc.) etc.
Wherein preferred phenols polymerization retarder.
The addition of polymerization retarder is based on (A) and gross weight (B) is generally 0.001-2%, is preferably 0.01-1%, and more preferably 0.01-0.5% is preferably 0.01-0.2% especially.
Usage quantity (α) is to be generally 0.1-70% with respect to (A) and gross weight (B), is preferably 1-60%, and more preferably 2-50% is preferably 3-40% especially.
Consider from carrying out the esterification aspect effectively, preferably use more than 0.1%; And consider from economic aspect, be preferably below 70%.
In addition, (α) usage quantity is that the ratio of the equivalent of sulfonic equivalent and employed (A) in feasible (α) is preferably 0.005-0.3,0.01-0.2 more preferably.Consider from the viewpoint of speed of response, be preferably more than 0.005; Consider from the viewpoint that suppresses side reaction, be preferably below 0.3.
As the form of esterification, also can carry out with any method of batch process or flow method.
Under the situation of batch process, (α), (A), (B) and the solvent that just adds are as required packed in the reactive tank, heated and stirred, the limit is removed the water or the lower alcohol limit of generation and is reacted.After reaction is accomplished, separate reaction product and (α) through decant, filtration, spinning etc.Under excessive use (A) or situation (B), remove excessive raw material after can or separating before (α) separated, thereby obtain esters of unsaturated carboxylic acids.
Esterification reaction temperature is generally 60-180 ℃, is preferably 80-160 ℃, more preferably 100-140 ℃.Consider from the viewpoint of speed of response, be preferably more than 60 ℃; Consider from the viewpoint that suppresses side reaction, be preferably below 180 ℃.
Reaction times was generally 10 minutes-24 hours, was preferably 30 minutes-10 hours, was preferably 1-5 hour especially.
As solvent, can use varsol (aromatic hydrocarbonss such as toluene, YLENE etc.), ketones solvent (methylethylketone, MIBK etc.) and ether solvent (THF etc.) etc.In these reaction solvents, from being easy to separate and remove the viewpoint consideration of water generation reaction, preferred hydrocarbons kind solvent.
Method as the water of removing generation or lower alcohol; Can enumerate out the method that distillation is removed under normal pressure or decompression; The method of separatory and spinning, the method that contacts with dewatering agents such as molecular sieve, sal epsom, selective membranes such as water separatory membrane carry out the method for membrane sepn etc.Under the situation of above-mentioned batch process, the method that preferably distillation is removed under normal pressure or decompression.
Under the situation of flow method, can make (A) that be adjusted into specified temperature and mixture (B) from post, fixed bed or the thermopnore etc. of having filled (α) through carrying out esterification.
Also can be with obtaining esters of unsaturated carboxylic acids through the distillation of the reaction mixture after once, and consider from the viewpoint that can improve reactivity, the method for manufacture of following operation preferably comprised: in the presence of (α), make (A) and the operation (1) of (B) reacting; With from reaction mixture, remove by (A) and (B) water that generates of reaction or the operation (2) of lower alcohol.
Especially, can be through repetition operation (1) and operation (2) and further improve reactivity.(A) that passes through in the operation (1) and the temperature of mixture (B) are generally 60-180 ℃, are preferably 80-160 ℃, more preferably 100-140 ℃.Consider from the viewpoint of speed of response, be preferably more than 60 ℃, consider, be preferably below 180 ℃ from the viewpoint that suppresses side reaction.
The mean transit time (average contact time of catalyzer and reaction solution) of per pass is generally 0.1-60 minute in the operation (1), is preferably 0.2-10 minute, more preferably 0.5-5 minute.Anhydrate or the method for lower alcohol as removing in the operation (2); Can enumerate out the method for removing with the distillation of continous way vaporizer; Use has the methods that distillation is removed under normal pressure or decompression such as the reactive tank of condensing surface, and carries out dehydration method etc. through water sepn film, spinning or dewatering agent.Wherein, consider, preferred continous way vaporizer, have the reactive tank of condensing surface and their combinations are used from the viewpoint of production efficiency.
The multiplicity of operation (1) and operation (2) is generally 1-500 time, is preferably more preferably 5-100 time 3-200 time.
In method of manufacture of the present invention,, also can make dissolved oxygen in the reaction solution in order to forbid the polymerization of (B) and product.As the supply source of oxygen, can enumerate out mixed gas (below, abbreviate " mixed gas " sometimes as) of oxygen, air and air and nitrogen etc.These gases are fed in the reaction solution, thereby make dissolved oxygen in the reaction solution.Wherein consider preferred air and mixed gas, preferred especially mixed gas from the viewpoint of security.
The mixed volume ratio of the air of mixed gas and nitrogen is generally 1: 9-9: 1, be preferably 1: 9-5: and 5, be preferably 2 especially: 8-4: 6.Consider from the viewpoint that improves polymerization-inhibiting effects, preferably improve the ratio of air, and consider, preferably improve the ratio of nitrogen from the painted viewpoint that tails off of product.
The air flow of air or mixed gas is 1-5000mL/ minute with respect to (A) and the every 1kg of summation (B) preferably, more preferably 20-1000mL/ minute, is preferably 30-500mL/ minute especially.
As the method for bubbling air or mixed gas, under the situation of batch process, can enumerate out the method for constantly to esterification, ventilating from the reactive tank bottom.
Under the situation of flow method, can enumerate out the method for in operation (1), operation (2) and their pipe arrangements midway, ventilating, from having speed of response concurrently and suppressing the consideration of polymeric viewpoint, particularly preferably in the method for ventilation in the operation (2).In operation (2), preferred constantly bubbling air or mixed gas.
The purity of the esters of unsaturated carboxylic acids that is obtained by the present invention is generally more than 95%, is preferably more than 98%.
As impurity; Can enumerate out unreacting alcohol, elimination reaction product (sloughing water and the alkene that generates etc.), by-product ether compound (ether that generates by the dehydration of alcohols condensation of two molecules), by-product adduct (to α, β-unsaturated group addition alcohol and the affixture that generates etc.) and contain the compound (oxysulfide that wash-out goes out through catalyst decomposes etc.) etc. of sulphur atom by the alcohol of a molecule.In addition, comprise and be not impurity but as the polymerization retarder of additive.
The content of unreacting alcohol is based on α, and the mole number of beta-unsaturated carboxylic acid ester is generally 5 moles below the %, is preferably 2 moles below the %.
The content of elimination reaction product is based on α, and the mole number of beta-unsaturated carboxylic acid ester is generally 2 moles below the %, is preferably below 0.1 mole of % (detection limit).
The content of by-product ether compound and by-product adduct is based on α, and the mole number of beta-unsaturated carboxylic acid ester is preferably (more preferably 1.5 moles of % are following) below 2 moles of % and 1 mole of % following (more preferably 0.8 mole of % is following) respectively.
The sulphur atom content (being designated hereinafter simply as S content) that contains the compound of sulphur atom is based on α, and the weight of beta-unsaturated carboxylic acid ester is generally below the 50ppm, is preferably below the 20ppm (detection limit).
As polymerization retarder, can enumerate out being selected from above-mentioned phenols polymerization retarder and more than one the polymerization retarder among the amine polymerization retarder.
The content of polymerization retarder is based on α, and the weight of beta-unsaturated carboxylic acid ester is 0.001-0.2%, is preferably 0.01-0.06%.
In addition, α, the content of beta-unsaturated carboxylic acid ester, unreacting alcohol, elimination reaction product, by-product ether compound and by-product adduct can be through measuring and resolve the H of product
1-NMR comes quantitatively.In addition, S content can use jigger coupling high frequency plasma apparatus for analyzing luminosity (being designated hereinafter simply as the ICP measuring apparatus) " ICPS-8000 " (Shimadzu Seisakusho Ltd.'s system) to carry out quantitatively.
Because α of the present invention, beta-unsaturated carboxylic acid ester purity is high, and has the polymerizability unsaturated group, so can suit as various polymer raw material monomers.
With α of the present invention, the beta-unsaturated carboxylic acid ester as a kind of monomer and the polymkeric substance that obtains can be used as various resins, modifier, used in pressure sensitive adhesive tackiness agent, coating with paint vehicle, lubricating oil with viscosity index rising agent, lubricating oil with flow point depressant or various additive.
Embodiment
Through embodiment the present invention is described at length below, but the present invention is not limited to this.In addition, part is all represented weight part.
<supporting the manufacturing example of sulfonic inorganic porous body (α) >
(making example 1)
In reaction vessel with whipping appts, heating-cooling device, TM and return line; The silica gel of using IX water washing after drying in advance (" Wakogel C-100 ": Wako Pure Chemical Industries, Ltd.'s system) 200 parts and, be warming up to 100-110 ℃ then of packing into as 400 parts of the toluene of solvent and 10 parts in water.Then add 100 parts of 3-sulfydryl propyl trimethoxy silicanes, stirring reaction is 8 hours under refluxing.And then add 15 parts of entry and reacted 8 hours.From reaction mixture, leach solid state component,, wash three times for 400 parts,, obtain supporting 190 parts of the inorganic porous bodies of silane coupling agent then 120 ℃ of following drying under reduced pressure 5 hours with Virahol successively with 400 parts of toluene washing three times.
With 150 parts among the inorganic porous body that supports silane coupling agent, add in the reaction vessel same as described above for 150 parts as the aquae hydrogenii dioxidi of 450 parts of the methyl alcohol of solvent and 30%, reacted 8 hours at 70 ℃ down refluxing.From reaction mixture, leach solid state component; This solid state component is washed three times for 400 parts with methyl alcohol successively; Once and with ion exchanged water wash three times for 400 parts with 400 parts of washings of 0.1N sulfuric acid; Then 120 ℃ of following drying under reduced pressure 5 hours, obtain by supporting 140 parts of the catalyzer (α-1) that sulfonic inorganic porous body constitutes.(α-1) structure of sulfopropyl that has been loaded by silica gel, its d50 is 230 μ m, the BET specific surface area is 222m
2/ g, acid number are 37mgKOH/g, and long-width ratio is 1.89.
(making example 2)
Except using 200 parts of phenyl triethoxysilanes to replace the 3-sulfydryl propyl trimethoxy silicanes, use and make 190 parts of the inorganic porous bodies that example 1 identical method obtains supporting silane coupling agent.
With in 150 parts among the inorganic porous body that supports silane coupling agent, 180 parts of adding reaction vessels of ethylene dichloride as solvent; Under water cooling; Drip 10 parts of sulphur trioxides down through 5 hours at 17-23 ℃, stir 3 hours to carry out sulfonation down at 40-50 ℃ then.Add 4 parts of ion exchanged waters; Make unreacted sulphur trioxide change sulfuric acid into; From reaction mixture, leach solid state component then; This solid state component is washed three times for 400 parts with 400 parts of Virahols washing three times with ion exchanged water successively,, thereby obtain 140 parts of catalyzer (α-2) then 120 ℃ of following drying under reduced pressure 5 hours.(α-2) structure of sulfophenyl that has been loaded by silica gel, its d50 is 230 μ m, the BET specific surface area is 215m
2/ g, acid number are 45mgKOH/g, and long-width ratio is 1.82.
(making example 3)
Except use 200 parts of silica-alumina class porous inseries (" KYOWAAD ": Kyowa Chemical Industry Co., Ltd's system) the carrier as catalyzer, use with make the example 1 identical method obtain 140 parts of catalyzer (α-3).(α-3) is the structure that silica-alumina class porous insert has supported sulfopropyl, and its d50 is 216 μ m, and the BET specific surface area is 197m
2/ g, acid number are 85mgKOH/g, and long-width ratio is 1.12.
(making example 4)
Except use 200 parts of aluminum oxide (" activated alumina 200 ": Nacalai Tesque Co., Ltd. system) the carrier as catalyzer, use with make the example 1 identical method obtain 140 parts of catalyzer (α-4).(α-4) is the structure that aluminum oxide has supported sulfopropyl, and its d50 is 68 μ m, and the BET specific surface area is 231m
2/ g, acid number are 52mgKOH/g, and long-width ratio is 1.14.
(making example 5)
Except use 200 parts of silica gel (CARiACT Q-6, the particle size range that contains particle is 75-500 μ m: Silysia KCC of Fuji system) beyond the carrier as catalyzer, use with make the example 1 identical method obtain 140 parts of catalyzer (α-5).(α-5) structure of sulfopropyl that has been loaded by silica gel, its d50 is 220 μ m, the BET specific surface area is 287m
2/ g, acid number are 43mgKOH/g, and long-width ratio is 1.02.
(making example 6)
Except use 200 parts of silica gel (CARiACT Q-6, the particle size range that contains particle is 45-75 μ m: Silysia KCC of Fuji system) beyond the carrier as catalyzer, use with make the example 1 identical method obtain 140 parts of catalyzer (α-6).(α-6) structure of sulfopropyl that has been loaded by silica gel, its d50 is 58 μ m, the BET specific surface area is 320m
2/ g, acid number are 34mgKOH/g, and long-width ratio is 1.02.
< α, the manufacturing of beta-unsaturated carboxylic acid ester >
(embodiment 1)
In reaction vessel with whipping appts, heating-cooling device, TM and distributive pipe; Add 1800 parts of dodecanols and 1100 parts of methylacrylic acids (mol ratio is 1: 1.3), to wherein adding 580 parts of catalyzer (α-1) and as 0.3 part of the quinhydrones of polymerization retarder.To generate water in temperature of reaction 115-125 ℃ bottom with distributive pipe and be rejected to continuously outside the system, esterification was carried out 2 hours in the limit.Under the decompression of 250-300mmHg, reacted 1 hour down again at 115-125 ℃; Then remove excessive methylacrylic acid in 10-20mmHg, a 120-130 ℃ following distillation; Cooling is removed catalyzer through decant, thereby is obtained 2500 parts of esters of unsaturated carboxylic acids of the present invention (E-1) then.
Use H
1-NMR resolves, and the result finds, (E-1) contains 99.8 moles of % of methylacrylic acid dodecyl alcohol ester and 0.2 mole of % of unreacting alcohol of target, and elimination reaction product, by-product ether compound and by-product adduct are all at (0.1 mole below the %) below the detection limit.
In addition, for to studying from the amount of sulfonic composition from the catalyzer wash-out to product, with ICP measuring apparatus " ICPS-8000 " (Shimadzu Seisakusho Ltd.'s system) S content is carried out quantitatively, the result finds at (below the 20ppm) below the detection limit.
(embodiment 2-5)
Except the umber with record in the below table 1 uses the raw material of record in the table 1, make the α of embodiment 2-5 with embodiment 1, beta-unsaturated carboxylic acid ester (E-2), (E-3), (E-4) and (E-5) identically.
The analytical results of product is as shown in table 2.
(embodiment 6)
Be blown in the stainless steel reactive tank of 12L of mouth, condensing surface, pore to having whipping appts, heating-cooling device, TM, gas, add carbonatoms and be 12 and 13 alkyl alcohol mixture (" Dobanol 23 "; Mitsubishi chemical Co., Ltd's system) 5.7kg, methylacrylic acid 3.3kg (mol ratio is 1: 1.3) and as the quinhydrones 1g of polymerization retarder, the mixed gas (1: 2) with air-nitrogen in whole operation fed with 500ml/ minute.After temperature of reaction is warming up to 115-125 ℃; With surge pump the reaction solution in the reactive tank was fed with flow velocity 1.1L/ minute continuously and to have filled in the stainless steel fixed bed of 1.8kg catalyzer (α-5); Make output liquid loop back original reactive tank; In reactive tank, under 115-125 ℃ of following normal pressure, the water distillation that generates is removed and dewater, the limit is circulated reaction solution, and react and dehydration procedure 1 hour simultaneously continuously on the limit.
Then,, carry out identical reaction again and dewatered 2 hours, esterification is finished reducing pressure into 250-300mmHg in the reactive tank.Then, entire reaction liquid is returned reactive tank, under 10-20mmHg, 120-130 ℃ condition, excessive methacrylic acid distillation is removed, thereby obtained 7.6kg unsaturated carboxylic acid ester composition of the present invention (E-6).
In addition, the average retention time of the reaction solution of per pass is 2.5 minutes in fixed bed.
And the cycle repeats number of times of entire reaction liquid is calculated as about 18 times by the flow velocity in the fixed bed in the esterification.
The analytical results of product is as shown in table 2.
(embodiment 7)
Except make the flow velocity that feeds liquid be 3.1L/ minute and in fixed bed the average retention time of per pass be 0.8 minute, make the α of embodiment 7, beta-unsaturated carboxylic acid ester composition (E-7) with embodiment 6 identically.
The cycle repeats number of times of entire reaction liquid is calculated as about 50 times by flow velocity in the fixed bed and average retention time under the normal pressure.
The analytical results of product is as shown in table 2.
(comparative example 1)
Except using polystyrolsulfon acid type ion exchange resin " AMBERLYST-16 " (Rohm & Hass Company system) as the catalyzer, make the α of comparative example 1, beta-unsaturated carboxylic acid ester (H-1) with embodiment 1 with record umber in the table 1 identically.The d50 of " AMBERLYST-16 " is 720 μ m, and the BET specific surface area is 35m
2/ g, acid number are 280mgKOH/g, and long-width ratio is 1.05.
The analytical results of product is as shown in table 2.
(comparative example 2)
Except the umber with record in the table 1 uses vinylformic acid as (B), make the α of comparative example 2, beta-unsaturated carboxylic acid ester (H-2) with comparative example 1 identically.
The analytical results of product is as shown in table 2.
(comparative example 3)
Except the umber with record in the table 1 uses sulfuric acid as the catalyzer; Carry out esterification with embodiment 1 identically, again with aqueous sodium hydroxide solution neutralize, separatory, with ion exchanged water wash, separatory handles; Thereby obtain the α of comparative example 3, beta-unsaturated carboxylic acid ester (H-3).
The analytical results of product is as shown in table 2.
[table 1]
[table 2]
N.D.: do not detect (below the detection limit)
As can knowing by table 2, α of the present invention, the by product of beta-unsaturated carboxylic acid ester is few, and purity is high, and catalyst residue is also few.
The present invention can provide the α that does not produce a large amount of wastes; The method of manufacture of beta-unsaturated carboxylic acid ester; And provide by product few and highly purified α; The method of manufacture of beta-unsaturated carboxylic acid ester, and then provide catalyst residue few and little α to corrosion of metal property, the method for manufacture of beta-unsaturated carboxylic acid ester.In addition, the present invention can provide the highly purified α that is obtained by above-mentioned method of manufacture, beta-unsaturated carboxylic acid ester.Therefore, the present invention can be effectively applied to make α, the beta-unsaturated carboxylic acid ester.
Claims (10)
1. α, the method for manufacture of beta-unsaturated carboxylic acid ester, it comprises following operation:
(1) support sulfonic inorganic porous body (α) in the presence of make alcohol (A) and α through flow method, beta-unsaturated carboxylic acid or by this α, beta-unsaturated carboxylic acid is ester (B) reaction that the alcohol of 1～4 alkyl obtains with having carbonatoms; (2) from the reaction mixture of above-mentioned gained, removing the water that generated by the reaction of said composition (A) and said composition (B) or carbonatoms is 1～4 alcohol,
Wherein, the multiplicity of said operation (1) and said operation (2) is 3-200 time.
2. the α that puts down in writing according to claim 1, the method for manufacture of beta-unsaturated carboxylic acid ester, wherein said composition (A) is monohydroxy-alcohol or the polyvalent alcohol of 2-8 unit or their alkylene oxide affixture.
3. the α that puts down in writing according to claim 1 or 2, the method for manufacture of beta-unsaturated carboxylic acid ester, wherein said composition (B) is acrylic or methacrylic acid.
4. the α that puts down in writing according to claim 1 or 2; The method of manufacture of beta-unsaturated carboxylic acid ester, wherein said inorganic porous body (α) are to make the inorganic porous body that is made up of more than one the inorganics that is selected among silicon-dioxide, aluminum oxide, titanium oxide, Natural manganese dioxide and the zirconium white support sulfonic group and the saccharoid that forms.
5. the α that puts down in writing according to claim 1 or 2; The method of manufacture of beta-unsaturated carboxylic acid ester, wherein said inorganic porous body (α) be make inorganic porous body obtain with compound (s) reaction that contains sulfonic acid precursor base supporting the inorganic porous body of sulfonic acid precursor base, then make sulfonic acid precursor base change sulfonic group into and obtain supported sulfonic inorganic porous body.
6. the α that puts down in writing according to claim 1 or 2, the method for manufacture of beta-unsaturated carboxylic acid ester, wherein said inorganic porous body (α) is the saccharoid with median size of 1-8000 μ m.
7. the α that puts down in writing according to claim 1 or 2, the method for manufacture of beta-unsaturated carboxylic acid ester, wherein said inorganic porous body (α) has 30m
2The BET specific surface area that/g is above.
8. the α that puts down in writing according to claim 1 or 2, the method for manufacture of beta-unsaturated carboxylic acid ester, wherein said inorganic porous body (α) has the acid number of 5-250mgKOH/g.
9. the α that puts down in writing according to claim 1 or 2, the method for manufacture of beta-unsaturated carboxylic acid ester, wherein said inorganic porous body (α) is the spherical particle with long-width ratio of 1.0-1.25.
10. the α that puts down in writing according to claim 1 or 2, the method for manufacture of beta-unsaturated carboxylic acid ester, wherein in said operation (2), the mixed gas that air perhaps is made up of air and nitrogen feeds in the said reaction mixture.
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| PCT/JP2005/014325 WO2006025182A1 (en) | 2004-08-30 | 2005-08-04 | PROCESS FOR PRODUCTION OF α,β-UNSATURATED CARBOXYLIC ESTERS AND α,β-UNSATURATED CARBOXYLIC ESTERS |
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| DE102008054611A1 (en) * | 2008-12-15 | 2010-06-17 | Evonik Röhm Gmbh | Process for the preparation of methacrylated benzophenones |
| CN104610059A (en) * | 2015-01-15 | 2015-05-13 | 吉林化工学院 | Method for synthesizing methyl-acrylate through ester exchange and adsorption removal of methanol |
| EP3898584A1 (en) * | 2018-12-20 | 2021-10-27 | DSM IP Assets B.V. | Improved process to produce specific alpha,beta-unsaturated carboxylates |
| CN110845331A (en) * | 2019-10-10 | 2020-02-28 | 天津利安隆新材料股份有限公司 | Preparation method of benzoic acid high-carbon alcohol ester |
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| US5360926A (en) * | 1992-10-22 | 1994-11-01 | Sumitomo Chemical Company, Limited | Process for producing methyl methacrylate |
| US5426199A (en) * | 1991-12-13 | 1995-06-20 | Rohm And Haas Company | Catalyzed esterification process |
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| JP3345985B2 (en) * | 1992-10-22 | 2002-11-18 | 住友化学工業株式会社 | Method for producing methyl methacrylate |
| JPH1180082A (en) * | 1997-09-10 | 1999-03-23 | Kao Corp | Production of (meth)acrylic higher alkyl ester |
| JPH11152248A (en) * | 1997-11-19 | 1999-06-08 | Mitsubishi Chemical Corp | Production of unsaturated carboxylic acid ester |
| JPH11319574A (en) * | 1998-05-14 | 1999-11-24 | Asahi Chem Ind Co Ltd | Catalyst for esterification |
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|---|---|---|---|---|
| US5426199A (en) * | 1991-12-13 | 1995-06-20 | Rohm And Haas Company | Catalyzed esterification process |
| US5360926A (en) * | 1992-10-22 | 1994-11-01 | Sumitomo Chemical Company, Limited | Process for producing methyl methacrylate |
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| Title |
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| JP特开平11-152248A 1999.06.08 |
| JP特开平11-80082A 1999.03.23 |
| 张立等.含磺酸基的介孔分子筛SBA-15- SO3H 催化合成乙酸乙酯.抚顺石油学院学报23 2.2003,23(2),20-23页. |
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