CN101437786A - Method for producing (meth)acrylate and (meth)acrylate composition - Google Patents

Abstract

Disclosed is a simple method for producing a (meth)acrylate which enables to obtain a (meth)acrylate improved in storage stability and thermal stability. Also disclosed is a (meth)acrylate composition. The production method comprises an esterification step wherein a (meth)acrylic acid and an alcohol having an oxyalkylene group are dehydrated with an organic sulfonic acid catalyst in an organic solvent, thereby obtaining a (meth)acrylate; and an adjustment step wherein a compound A represented by the formula (1) below is controlled to be 0-100 ppm in the thus-obtained (meth)acrylate. The production method also comprises an addition step wherein a specific processing agent is added into an organic reaction liquid which contains not less than 1 ppm of the compound A relative to the (meth)acrylate obtained through the esterification step and a step for performing neutralization and water rinsing. (1) [In the formula (1), R<1> represents an alkyl group or an aryl group; R<2> represents an alkylene group; and R<3> represents a hydrogen atom or a methyl group.

Description

The manufacture method of (methyl) acrylate and (methyl) acrylate composition

Technical field

The present invention relates to manufacture method and (methyl) acrylate composition of a kind of (methyl) acrylate.

Background technology

(methyl) acrylate is owing to solidify under uviolizing or under the electron rays irradiation, so as the gradation composition of Photocurable composition, be used for optical lens or various industrial uses such as printing ink liquid, Liniment and caking agent.

But, if the storage stability or the thermostability of (methyl) acrylate are bad, bad situation then appears sometimes.

For example, if the storage stability of (methyl) acrylate is bad, thereby then sometimes in keeping polymerization reaction take place generate component of polymer, perhaps (methyl) acrylate decomposes sour compositions such as producing (methyl) vinylformic acid.

Include component of polymer (methyl) acrylate composition since take place to solidify uneven or muddy, so can not in the optical lens purposes of paying attention to homogeneity or photopermeability etc., use well.

In addition, (methyl) acrylate that produces sour composition is except the problem of foul smell or corrosion of equipment, and water tolerance worsens, so when being used for Liniment or caking agent purposes, cured article absorbs moisture sometimes, causes peeling off or bonding strength low of applicator surface.

And then, (methyl) acrylate is heated stirring sometimes for homogenization when cooperating, perhaps after photocuring, be exposed in the oven test, and how bad (methyl) acrylate of thermostability can not be used for being necessary for transparent optical lens purposes etc. owing to take place painted except aforesaid component of polymer or sour composition take place.

In addition, in this manual, vinylformic acid and methacrylic acid general name are recited as " (methyl) vinylformic acid ".

Storage stability and thermostability as (methyl) acrylate become one of bad reason, can enumerate the influence of remaining impurities in goods.

(methyl) acrylate normally makes the manufacturing of (methyl) vinylformic acid and alcohols generation dehydration esterification form in the presence of acid catalyst, and by-product goes out various impurity when esterification.In order to remove such impurity, the reaction solution after the esterification of dewatering relatively usually implements to utilize the cleaning operation of water or alkali aqueous solution, but removing of impurity may not be abundant.

So, the method for the matting when having inquired into various manufacturings (methyl) acrylate.

For example, in patent documentation 1, after the resultant of reaction after neutralizing treatment dehydration esterification, and then with the method for amine processing.

But, if utilize this method, then after with amine processing reaction resultant,, have to follow the cleaning reaction resultant with acidic aqueous solution in order to remove this amine from resultant of reaction, sneak into acidic component to resultant of reaction sometimes.Thereby, in the method, after cleaning, cleaning with alkali aqueous solution once more with acidic aqueous solution, triplicate cleans with soft then, and operation is numerous and diverse and needs are long-time, so productivity is significantly low.In addition, if this processing of industrial enforcement, then have to use the rinse bath of the material of the special and high price that the both sides of relative alkali aqueous solution and acidic aqueous solution are not corroded, perhaps in different rinse baths, implement the processing utilize the processing of alkali aqueous solution and to utilize acidic aqueous solution, be adapted at industrial enforcement hardly.

In addition, in patent documentation 2, disclose and the reaction solution after making (methyl) acrylate is being neutralized or during clean, adding positively charged ion is the method for tensio-active agent, if disclose this method of utilizing, then can prevent near interface generation emulsification, thereby shorten the disengaging time of organic layer and water layer at organic layer and water layer, as a result, can remove impurity effectively.

But although the method for patent documentation 2 records is outstanding aspect the cripeturaization of the disengaging time of organic layer and water layer, the storage stability and the thermostability of (methyl) acrylate that obtains are insufficient.

Patent documentation 1: 6-No. 219991 communiques of Japanese kokai publication hei

Patent documentation 2: 2001-No. 048831 communique of TOHKEMY

Summary of the invention

The object of the present invention is to provide a kind of manufacture method that can utilize (methyl) acrylate of storage stability that easy method improves (methyl) acrylate that obtains and thermostability.And then, the present invention also aims to provide a kind of (methyl) acrylate composition that improves storage stability and thermostability.

Below the described problem utilization of the present invention＜1,＜3 and＜9〉the middle means solution of putting down in writing.With as preferred embodiment＜2,＜4～＜8,＜10 and＜11 be recorded in following.

＜1〉manufacture method of a kind of (methyl) acrylate is characterized in that,

Comprise:

In organic solvent, utilize the organic sulfonic acid catalyzer to (methyl) thereby vinylformic acid and alcohol with oxyalkylene group dewater the esterification step of formation (methyl) acrylate, and

Compd A shown in the formula (1) in (methyl) acrylate that utilizes described esterification step to obtain is controlled to the management operation that 0ppm is above and 100ppm is following,

[in formula (1), R ¹The expression alkyl or aryl, R ²The expression alkylidene group, R ³Expression hydrogen atom or methyl.]。

＜2〉manufacture method of basis＜1〉described (methyl) acrylate, wherein,

The management operation comprise following 1)～4) at least 1 step.

1) in esterification step, Chun hydroxyl is 1 mole relatively, uses more than 0.8 mole and (methyl) below 2.0 moles vinylformic acid.

2) to carry out esterification more than 70 ℃ and below 140 ℃.

3) finish in the moment that esterification is roughly finished.

4) in the presence of moisture, to getting reaction solution compd A heating in the resulting thick resultant after neutralizing treatment and washing processing by esterification step, being hydrolyzed.

＜3〉manufacture method of a kind of (methyl) acrylate is characterized in that,

Comprise:

In organic solvent, utilize the organic sulfonic acid catalyzer to (methyl) thereby vinylformic acid and alcohol with oxyalkylene group dewater the esterification step (1) of formation (methyl) acrylate,

The reaction solution that utilizes operation (1) to obtain is carried out neutralizing treatment and washes the operation of handling (2),

(methyl) acrylate that obtains in relative operation (2) contains in the reaction solution of compd A shown in the formula (1) more than the 1ppm, add the interpolation operation that is selected from least 1 particular procedure agent in quaternary ammonium salt, quaternary alkylphosphonium salt, amidine, compound, Urea,amino-and the pyridine with primary amino and/or secondary amino group

In the formula (1), R ¹The expression alkyl or aryl, R ²The expression alkylidene group, R ³Expression hydrogen atom or methyl.

＜4〉according to the manufacture method of＜3〉described (methyl) acrylate, it is characterized in that,

After the interpolation operation of adding described particular procedure agent, comprise the precipitation matchmaker operation of heating up in a steamer organic solvent.

＜5〉manufacture method of basis＜3〉described (methyl) acrylate, wherein,

In described operation (2) afterwards, comprising:

Heat up in a steamer the precipitation matchmaker operation of organic solvent,

Add the interpolation operation of described particular procedure agent in the reaction solution after precipitation matchmaker operation, and

The heating process that heats.

＜6〉manufacture method of basis＜5〉described (methyl) acrylate, wherein,

Described Heating temperature is 30～100 ℃.

＜7〉according to＜1 〉～＜6 in the manufacture method of any described (methyl) acrylate, wherein,

Alcohol with oxyalkylene group is the alkylene oxide affixture of polyvalent alcohol.

＜8〉according to＜1 〉～＜7 in the manufacture method of any described (methyl) acrylate, wherein,

Oxyalkylene group with alcohol of oxyalkylene group is oxyethylene group or oxypropylene group, the R in the formula (1) ²Alkylidene group be ethylidene or propylidene.

＜9〉a kind of (methyl) acrylate composition, it contains (methyl) acrylate with oxyalkylene group, described have (methyl) acrylate of oxyalkylene group by in the presence of the organic sulfonic acid catalyzer, make (methyl) vinylformic acid and alcohol that the dehydration esterification take place and obtain with oxyalkylene group, wherein

Contain the compd A that formula (1) is represented with the amount more than the 0ppm and below the 100ppm,

[in formula (1), R ¹The expression alkyl or aryl, R ²The expression alkylidene group, R ³Expression hydrogen atom or methyl.]。

＜10〉according to＜9〉described (methyl) acrylate compositions, wherein,

Alcohol with oxyalkylene group is the alkylene oxide affixture of polyvalent alcohol.

＜11〉according to＜9〉or＜10〉described (methyl) acrylate compositions, wherein,

Oxyalkylene group with alcohol of oxyalkylene group is oxyethylene group or oxypropylene group, the R in the formula (1) ²Alkylidene group be ethylidene or propylidene.

If utilize the present invention, a kind of storage stability and the thermostability that can utilize easy method to improve (methyl) acrylate that obtains then can be provided, more specifically, can suppress the manufacture method of (methyl) acrylate of acid number rising.And then, if utilize the present invention, then can provide a kind of and can improve storage stability and thermostability, more specifically, can suppress (methyl) acrylate composition that acid number rises.

Embodiment

The inventor etc. have carried out various discussions to package stability and the bad origin material of thermostability that causes (methyl) acrylate in the manufacture method of (methyl) acrylate.

Found that if there is the specific compound of specified quantitative in (methyl) acrylate, then sour composition rises through time ground, can improve the storage stability or the thermostability of (methyl) acrylate by making this value below specified quantitative, down to finishing the present invention.

And then also find, surpass under the situation of specified quantitative at described specific compound, by handling the storage stability or the thermostability that can improve (methyl) acrylate, so that finish the present invention with specific treatment agent as the origin material.

Below describe the present invention in detail.

The manufacture method of the 1st (methyl) of the present invention acrylate is characterised in that, comprise: in organic solvent, utilize the organic sulfonic acid catalyzer to (methyl) thus vinylformic acid and alcohol with oxyalkylene group dewater and become the esterification step of (methyl) acrylate, and compd A control the becoming 0ppm of the expression of the aftermentioned formula (1) in (methyl) acrylate that will obtain is above and 100ppm is following, and (in the present invention, " 0ppm is above and 100ppm is following " also is recited as " 0～100ppm " or " 0ppm～100ppm ".Below same) the management operation.

In addition, the manufacture method of the 2nd (methyl) of the present invention acrylate is characterised in that, comprising: in organic solvent, utilize the organic sulfonic acid catalyzer to (methyl) thus vinylformic acid and alcohol with oxyalkylene group dewater and become the esterification step of (methyl) acrylate (1); The reaction solution that is obtained by operation (1) is carried out the operation (2) of neutralizing treatment and washing processing; (methyl) acrylate that in relative operation (2), obtains, contain in the organic reaction liquid of compd A of above aftermentioned formula (1) expression of 1ppm the interpolation operation of adding at least 1 the particular procedure agent that is selected from quaternary ammonium salt, quaternary alkylphosphonium salt, amidine, compound, Urea,amino-and pyridine with primary amino and/or secondary amino group.

(compd A)

Below the compd A of formula (1) expression is described.

In formula (1), R ¹The expression alkyl or aryl, R ²The expression alkylidene group, R ³Expression hydrogen atom or methyl.

R ¹The expression alkyl or aryl, this alkyl or aryl can not replace for having, and can have the substituting group more than 1 yet.Alkyl is preferably carbonatoms 1～10, and aryl is preferably carbonatoms 6～12.In addition, alkyl can be straight chain shape, branch-like, also can have ring texture.

The substituting group that allows as alkyl can the illustration aryl, alkoxyl group, halogen atom, is preferably aryl and halogen atom, and more preferably aryl is preferably phenyl especially.

In addition, the substituting group that allows as aryl can the illustration alkyl, halogen atom, alkoxyl group, is preferably alkyl, more preferably the alkyl of carbonatoms 1～3.

Particularly, as R ¹, preferably illustration methyl, phenyl, toluyl, ethylphenyl and benzyl.

In compd A, R ¹Derive from the organic sulfonic acid catalyzer that in esterification, uses.

At R ¹Under the situation for methyl; be to use the situation of methylsulfonic acid as acid catalyst, below same, under the situation that is phenyl; be to use the situation of Phenylsulfonic acid; under the situation that is toluyl, be to use the situation of tosic acid, under the situation that is ethylphenyl; be to use the situation of ethyl phenenyl azochlorosulfonate acid; in addition, under the situation that is benzyl, be to use the situation of benzyl sulfonic acid.

As R ²Alkylidene group, the preferred alkylidene group of carbonatoms below 4, more preferably ethylidene and propylidene.R ²Alkylene oxide base corresponding to the alcohol that in esterification, uses.

R ³Expression hydrogen atom or methyl.R ³Corresponding to (methyl) vinylformic acid that in esterification, uses.

Compd A is inferred as the alcohol that uses and the reactant of organic sulfonic acid catalyzer in esterification.If in (methyl) acrylate, have compd A, then decompose and produce acid through time ground, infer that storage stability or thermostability that this makes (methyl) acrylate become bad.

As the proportional analytical procedure that contains of the compd A in (methyl) acrylate, can enumerate liquid phase chromatography and vapor-phase chromatography etc., because compd A do not decompose and can stably observe, so the preferred liquid chromatography.

And then, as liquid chromatography, because quantitatively the property detection sensitivity is outstanding, so preferred liquid chromatography/mass spectrometry (hereinafter referred to as LC/MS).

As the quantitative conditions of the compd A that utilizes LC/MS, can enumerate following.

Zero LC condition

Device: high performance liquid chromatography (HPLC), the kind of post: the ODS post, the temperature of post: 40 ℃, elutriant: water/alkaline methanol

Zero MS condition

Detector: ESI (+)

(manufacture method of (methyl) acrylate)

In the present invention, at first, carry out in organic solvent, utilizing the organic sulfonic acid catalyzer to make (methyl) thus vinylformic acid and dehydration of alcohols with oxyalkylene group become the esterification step of (methyl) acrylate.Below esterification step is described.

1. esterification step

In the present invention, at first, esterification becomes (methyl) acrylate thereby generation is dewatered with the alcohol (following be expressed as simply sometimes " alcohol ") with oxyalkylene group to make (methyl) vinylformic acid in organic solvent in the presence of the organic sulfonic acid catalyzer.The dehydration esterification is preferably carried out under heated and stirred.

As the oxyalkylene group in the alcohol, preferred carbonatoms is the oxyalkylene group below 4, more preferably oxyethylene group or oxypropylene group.

As the oxyalkylene group in the alcohol, also can be for having the polyoxyalkylenes of 2 above repeating units.

As alcohol, can use all cpds, particularly, can enumerate the alkylene oxide affixture of alcohol shown below etc.

[1] monobasic alkyl alcohol and their alkylene oxide affixtures such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, hexalin, n-Heptyl alcohol, n-Octanol, 2-ethylhexanol, isooctyl alcohol, nonanol-, isononyl alcohol.

[2] phenol, chlorophenol, bromophenol, fluorophenol, naphthols, phenylphenol, cumyl phenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, thiobisphenol and 4,4 '-alkylsulfonyl biphenol etc. has the compound of phenol hydroxyl and their alkylene oxide affixture.

[3] glycols and their alkylene oxide affixtures such as ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, triglycol, polyoxyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol.

[4] glycerine and their alkylene oxide affixtures such as glycerine, two glycerine, triglycerin, Polyglycerine.

[5] polyvalent alcohol and their alkylene oxide affixtures such as butyleneglycol, pentanediol, hexylene glycol, TriMethylolPropane(TMP), ditrimethylolpropane, tetramethylolmethane, Dipentaerythritol.

[6] three-2-hydroxyethyl isocyanuric acid esters.

In addition, as described alkylene oxide, more preferably carbonatoms is the alkylene oxide below 4, and then preferred ethylene oxide and propylene oxide.

Average addition mole number as the alkylene oxide of per 1 mole compound is preferably 1～10 mole.

In described alcohol, the present invention can more preferably be useful in the alkylene oxide affixture or the big alcohol of alkylene oxide adduct number of the polyvalent alcohol that is easy to generate a lot of impurity in (methyl) acrylate that obtains.

Preferred concrete example as the alkylene oxide affixture of polyvalent alcohol, can enumerate the alkylene oxide affixture of TriMethylolPropane(TMP), the alkylene oxide affixture of dihydroxyphenyl propane and the alkylene oxide affixture of two glycerine etc., as the concrete example of alkylene oxide affixture, can enumerate ethylene oxide adduct and propylene oxide adduct.

The alcohol that the alkylene oxide adduct number is big is meant to have the alcohol that average addition mole number is the alkylene oxide base more than 3 moles in per 1 mole compound, particularly, can enumerate 4 moles of affixtures of alkylene oxide of nonylphenol etc., as the concrete example of alkylene oxide affixture, can enumerate ethylene oxide adduct and propylene oxide adduct.

(methyl) vinylformic acid in the dehydration esterification and the hydroxyl of relative 1 mol of alcohol of usage ratio of alcohol, (methyl) vinylformic acid is preferably 0.8～2.0 mole, more preferably 1.0～1.5 moles.If acrylic acid usage ratio is more than 0.8 mole; the time of the esterification of then dewatering is short; alcoholic hydroxyl is few to the side reaction that (methyl) acryl of (methyl) acrylate carries out Michael addition etc., can obtain good goods purity, so preferred.In addition; if acrylic acid usage ratio is below 2.0 moles, then (methyl) vinylformic acid is few to the addition reaction that (methyl) acryl of (methyl) acrylate carries out Michael addition etc., goods purity that can be good; and it is there is no need to remove unreacted vinylformic acid, so preferred.

As the organic sulfonic acid catalyzer that in the dehydration esterification, uses, can enumerate the organic sulfonic acid catalyzer of formula (2) expression.

In formula (2), R ¹With the R in the formula (1) ¹Identical, in addition, preferable range is also identical.

As the organic sulfonic acid catalyzer, particularly, can enumerate tosic acid, methylsulfonic acid, Phenylsulfonic acid, ethyl phenenyl azochlorosulfonate acid and benzyl sulfonic acid etc., can be used alone or at random be used in combination two or more.

The usage ratio of organic sulfonic acid catalyzer is provided to the mole number of the alcoholic hydroxyl of dehydration esterification relatively, is preferably 0.05mol%～10mol%, more preferably 0.5mol%～5mol%.If the usage ratio of organic sulfonic acid catalyzer is more than the 0.5mol%, then can obtain the speed of response in the practicality, so preferred.In addition, if be below the 10mol%, then side reaction is few, and the purity height of goods is painted few in addition, the catalyzer in purification procedures remove or the decolouring of goods to operate needed labour few, so preferred.

In the present invention, as the organic solvent that in esterification step, uses, the low organic solvent of solubleness of the preferred water that uses and in the dehydration esterification, generate.In addition, thus esterification step preferably carries out when the water azeotropic is heated up in a steamer.

As the organic solvent that can in esterification step, preferably use, for example can enumerate aliphatic hydrocarbons such as aromatic hydrocarbonss such as toluene, benzene and dimethylbenzene, hexane, hexanaphthene and heptane, and ketone such as methyl ethyl ketone and pimelinketone.

Organic solvent can consider that also the solvability of matrix etc. uses a kind or arbitrary combination to use two or more separately.

As the ratio of organic solvent, preferably in reaction solution 30～70 weight %.

As esterification reaction temperature, preferred 70～140 ℃.If temperature of reaction is more than 70 ℃, then react apace, so preferred.In addition, if be below 140 ℃, then the by-product of the impurity in the esterification step is few, and then, gelation can not take place, so preferred.

In the esterification,, preferably use polymerization retarder, and then also can in reaction solution, import oxygen-containing gas in order to prevent the polymerization of (methyl) acryl.

As polymerization retarder, for example can enumerate quinhydrones, tertiary butylated hydroquinone, quinhydrones monomethyl ether, 2,6-di-t-butyl-4-methylphenol, 2, organic system polymerization retarder, cupric chloride and copper sulfate etc. such as 4,6-tri-butyl-phenol, benzoquinones, thiodiphenylamine are inorganic to be that polymerization retarder and dibutyl disulfide are for organic salt series polymerization retarders such as carboxylamine copper etc.Polymerization retarder can use a kind separately, also can arbitrary combination use two or more.As the ratio of polymerization retarder, preferably in reaction solution 5～20000wtppm, more preferably 25～3000wtppm.

As oxygen-containing gas, for example can enumerate the mixed gas etc. of mixed gas, oxygen and the helium of air, oxygen and nitrogen.

2. the compd A in (methyl) acrylate is controlled to the above and 100ppm of 0ppm with Under the management operation

In the manufacture method of the 1st (methyl) of the present invention acrylate, comprise that the compd A of formula (1) expression in (methyl) acrylate that will obtain is controlled to the management operation that 0ppm is above and 100ppm is following.

The ratio of the compd A in (methyl) acrylate surpasses under the situation of 100ppm, and the storage stability of composition or thermostability become bad.

As the ratio of compd A, it is above and below the 80ppm to be preferably 0ppm, 0～50ppm more preferably, and then be preferably 0～30ppm, special preferred detection is less than (1ppm is following).

Especially at R ¹Contain under the situation of aromatic series base, compd A is preferably 0～80ppm, 0～50ppm more preferably, and then be preferably 0～30ppm.In addition, at R ¹Do not contain under the situation of aromatic series base, for example under the situation for the alkyl that do not have to replace, compd A is preferably 0～30ppm, 0～10ppm more preferably, and then be preferably 0～5ppm.

Ratio as the compd A in (methyl) acrylate that finally obtains is the following method of 100ppm, can illustration

(a) method of enforcement esterification under the condition of gentleness,

(b) in the manufacture method of (methyl) acrylate, be implemented in the method for the purification procedures of implementing after the esterification etc.

Under the condition of gentleness, implement the method for esterification as (a), particularly, can following (a-1)～(a-3) of illustration.

(a-1) be alcohol relatively, does not excessively use (methyl) acrylic acid

Chun 1 mole of hydroxyl preferably uses 0.8～2.0 mole of (methyl) vinylformic acid relatively, more preferably uses 1.0～1.5 moles, and then preferably uses 1.0～1.2 moles.

(a-2) excessively do not carry out the method for esterification under hot conditions

Preferably under 70～140 ℃, carry out esterification, more preferably under 80～130 ℃, carry out, and then preferably under 90～120 ℃, carry out.

The method that (a-3) finished in the moment that esterification is roughly finished

Esterification is roughly finished and can be passed through the acid number of assaying reaction liquid termly, and unreacted (methyl) acrylic acid that includes from (methyl) vinylformic acid conversion response liquid that adds perhaps detects the amount of distilled water in esterification and confirms.

In esterification, after esterification, heat (post-heating) a few hours usually in order to react slaking, but may produce compd A because of heating afterwards.Therefore, preferably after finishing, esterification do not carry out the method for long-time heating.As heat-up time in this case, be preferably in 3 hours, in more preferably 1 hour.

In addition, in the present invention, also preferably suitably make up (a-1)～(a-3).

In addition, in the manufacture method of (methyl) acrylate, be implemented in the method for the purification procedures of implementing after the esterification,, can enumerate neutralizing treatment and washing processing etc. as purification procedures at (b).

And then, even carrying out described method, the ratio of the compd A in (methyl) acrylate also surpasses under the situation of 100ppm, perhaps, heat the method for hydrolysis through the compd A in the thick resultant that obtains after neutralizing treatment and the washing processing thereby also can be illustrated in the reaction solution that will utilize esterification step to obtain under the existence of moisture for the further ratio that reduces compd A.

As the Heating temperature time in this case, the ratio of the compd A in suitably corresponding (methyl) acrylate is set and is got final product, as Heating temperature, and preferred 60～140 ℃, more preferably 60～120 ℃, and then preferred 60～100 ℃.In addition, as heat-up time, preferred 0.5 hour～300 hours, more preferably 5～200 hours, and then preferred 20～150 hours.

Adopt more than any one of method of described (a)～(b), monitor the ratio of the compd A in (methyl) acrylate that obtains termly, the compd A in (methyl) acrylate that finally obtains is managed into below the 100ppm.

In described method, the selection of adopt which kind of means, implementing under which kind of condition is suitably selected to get final product according to the ratio of the compd A in the kind of (methyl) vinylformic acid, alcohol and the sulfonic acid catalyst that use and amount, (methyl) acrylate of obtaining and the purposes of end article etc.

In described method, preferably implementing the method for esterification under the condition of gentleness and in the presence of moisture, heating (methyl) acrylate that has carried out neutralizing after washing, make the compd A hydrolysis, the method that neutralizes once more afterwards and wash, from point easy and that can implement with technical scale, more preferably under the condition of gentleness, implement the method for esterification.

3. neutralizing treatment and washing are handled

To the neutralizing treatment of the purification procedures that in the 1st manufacture method of the present invention, adopts and washing handle wait and in the 2nd manufacture method of the present invention relatively neutralizing treatment and the washing processing carried out of the reaction solution after the esterification step illustrate successively.

3-1. neutralizing treatment

Neutralizing treatment is to remove unreacted (methyl) vinylformic acid in the reaction solution and organic Acidic components such as sulfonic acid catalyst are that purpose is carried out, and reaction solution is contacted with alkali aqueous solution Carry out.

Neutralizing treatment gets final product according to ordinary method, for example can enumerate method of the alkali aqueous solution that interpolation in reaction solution, stirring, mixed dissolution have the alkali composition etc.

As described alkali composition, can enumerate an alkali metal salts such as lithium hydroxide, sodium hydroxide and potassium hydroxide and ammonia etc.As the alkali composition, can be used alone, also can at random be used in combination two or more.Wherein, because effect is outstanding, cheap and obtain and preferred sodium hydroxide easily.

In this case, the sour composition of the amount relative response liquid of alkali composition is preferably mol ratio more than 1 times, more preferably 1.1～2.0 times.If the sour composition of the addition relative response liquid of alkali composition is more than 1 times with molar ratio computing, then can carry out the neutralization of sour composition fully, so preferred.

In addition, the concentration of alkali aqueous solution is preferably 1～25 weight %, more preferably 10～25 weight %.If the concentration of alkali aqueous solution is more than the 1 weight %, then can reduce neutralizing treatment water displacement afterwards, so preferred.In addition, if the concentration of alkali aqueous solution is below the 25 weight %, then (methyl) acrylate does not carry out polymerization, so preferred.

Stirring when alkali aqueous solution adds, the mixing time suitably amount of amount, the sour composition that wherein includes of corresponding reaction solution and purpose etc. are set and are got final product, but be preferably 5 minutes～and about 120 minutes.

3-2. washings are handled

In the present invention, described esterification liquid (reaction solution after the esterification step) or neutralizing treatment liquid (further having carried out the reaction solution of neutralizing treatment after esterification step) are washed processing.Which washes constantly the suitably composition and the purpose selections of corresponding use such as processing at.

Washing is handled and is got final product according to ordinary method.Particularly, can enumerate the relative esterification liquid that in described esterification, obtains or the method for the interpolation of described neutralizing treatment liquid, stirring, mixing water or inorganic aqueous solution etc.

In washing step, make water usually.On the other hand, improving and the separating or require under the situation of highly purified goods of organic layer, the preferred aqueous solution that includes inorganic salt that uses, particularly, can enumerate sour waters such as sodium-salt aqueous solutions such as ammonium salt aqueous solution such as ammonium sulfate solution and aqueous ammonium chloride solution, sodium-chlor and aqueous hydrochloric acid.

3-3. other

In described neutralizing treatment and/or washing processing, can heat as required.

As Heating temperature, can enumerate 30～80 ℃, as heat-up time, can enumerate 5 minutes～5 hours.

Water as using in described neutralizing treatment and/or washing processing preferably uses distilled water.

Under the situation of heating, in order to prevent the polymerization of (methyl) acryl, preferably use polymerization retarder, and then also can in reaction solution, import oxygen-containing gas.

As polymerization retarder, can enumerate and described identical polymerization retarder, its ratio also can be enumerated ratio same as described above.

As oxygen-containing gas, can enumerate oxygen-containing gas same as described above.

In the manufacture method of the 1st (methyl) of the present invention acrylate, the treatment solution of washing in neutralization contains under the situation of organic solvent, carries out the desolventizing operation.

The desolventizing operation is described: neutralizing treatment liquid or washing treatment solution are moved to the desolventizing groove, remove the organic solvent in the organic layer of water layer after separating in neutralizing treatment or washing are handled.

Desolventizing is handled and to be got final product according to ordinary method, under reduced pressure heats the method etc. that the desolventizing groove is removed organic solvent thereby for example can enumerate.

As the decompression degree of desolventizing groove, suitably corresponding raw material that uses and purpose are set and get final product, are preferably 0.5～50kPa, preferably the method for increase decompression degree according to the degree of removing of organic solvent and lentamente.

Heating temperature is suitably set according to (methyl) acrylate that obtains, decompression degree and purpose and is got final product, and is preferably 40～100 ℃, more preferably 60～80 ℃.In order to suppress the thermopolymerization of (methyl) acrylate, preferably with temperature maintenance below 80 ℃.

In the desolventizing operation,, preferably supply with oxygen or add polymerization retarder in order to suppress the thermopolymerization of (methyl) acrylate.As polymerization retarder, can enumerate polymerization retarder same as described above, its ratio also can be enumerated ratio same as described above.

Under the situation that further requires Products Quality, can after the desolventizing operation, further filter.

This filtration operation gets final product according to ordinary method.

4. treatment agent adds operation

The manufacture method of the 2nd (methyl) of the present invention acrylate has having carried out described esterification step, neutralizing treatment, washing relatively handles (methyl) acrylate that obtains, contain in the organic reaction liquid of compd A of the above formula of 1ppm (1) expression, add at least 1 particular procedure agent (the following treatment agent that also abbreviates as sometimes that is selected from quaternary ammonium salt, season sulfonium salt, amidine, compound, Urea,amino-and the pyridine with primary amino and/or secondary amino group.) interpolation operation (treatment agent interpolation operation).

These treatment agents can add a kind, also can and use and use more than 2 kinds.

Below each treatment agent is described respectively.

4-1. quaternary ammonium salts

As quaternary ammonium salt, can use all cpds, can preferably enumerate the compound (hereinafter referred to as compound 3) of following formula (3) expression.

[in addition, in formula (3), R ¹～R ³The expression alkyl, R ⁴Expression alkyl or benzyl, X ^-The expression inorganic anion.]

R in described formula (3) ¹～R ⁴In, as alkyl, can be the straight chain shape, also can be branch-like, but preferred straight chain shape.In addition, the preferred alkyl of carbonatoms below 8.

X as described formula (3) ^-In inorganic anion, can enumerate halide ions, hydroxide ion and hydrogen sulfate ion etc.Wherein, preferred halide ions and hydroxide ion, as halide ions, more preferably chlorion and bromide anion.

As the concrete example of compound 3, can enumerate the example of following (1) and (2).

(1) R ¹～R ⁴Example with compound of alkyl

Tetramethyl ammonium chloride, 4 bromide, Tetramethylammonium hydroxide, tetrabutylammonium chloride, tetra-n-butyl ammonium bromide, 4-n-butyl ammonium hydroxide and 4-butyl ammonium hydrogen sulfate etc.

(2) R ¹～R ³Be alkyl and R ⁴Example with compound of benzyl

Benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride and benzyl three normal-butyl chlorination ammoniums etc.

4-2. quaternary alkylphosphonium salts

As quaternary alkylphosphonium salt, can use all cpds, can preferably enumerate the compound (hereinafter referred to as compound 4) of following formula (4) expression.

[in addition, in formula (4), R ¹～R ³The expression alkyl, R ⁴Expression alkyl or benzyl, X ^-The expression inorganic anion.]

R in described formula (4) ¹～R ⁴In, as alkyl, can be the straight chain shape, also can be branch-like, but preferred straight chain shape.In addition, the preferred alkyl of carbonatoms below 8.

X as described formula (4) ^-In inorganic anion, can enumerate halide ions, hydroxide ion and hydrogen sulfate ion etc.Wherein, preferred halide ions and hydroxide ion, as halide ions, more preferably chlorion and bromide anion.

As the concrete example of compound 4, can enumerate benzyl three normal-butyl chlorination Phosphonium and four normal-butyl bromination Phosphonium etc.

4-3. amidines

As amidine, get final product so long as have the compound of amidine skeleton, can use all cpds.Particularly, can enumerate 1,8-diazabicyclo (5.4.0) hendecene-7 (diazabicyclo[5.4.0] undec-7-ene; DBU) and 1,5-diazabicyclo (4.3.0) nonene-5 (diazabicyclo[4.3.0] non-5-ene; DBN) etc.

4-4. have the compound of primary amino and/or secondary amino group

As the compound with primary amino and/or secondary amino group (hereinafter referred to as amine compound), can enumerate compound (hereinafter referred to as primary amine), compound (hereinafter referred to as secondary amine) and have primary amino and the compound of secondary amino group (hereinafter referred to as primary-secondary amine) etc. with secondary amino group with primary amino.

As amine compound, can use all cpds, for example can enumerate following example.

As primary amine, can enumerate alkylamines such as methylamine, ethamine, propylamine, butylamine, 2-ethylhexylamine and cetylamine; Alkyl diamines such as 1,6-hexanediamine; 3-methoxy propanamine, 3-ethoxy propylamine and 3-alkoxyalkyl amine such as (2-ethylhexyl oxygen) propylamine; Dialkyl aminoalkyl amine such as 3-dimethylaminopropylamine, 3-diethylaminopropylamine and 3-dibutylaminopropylamine; Hydroxyalkyl such as oxyethylamine and isopropanolamine amine; N-methyl-3, the two N-alkyl-imino-s such as (propylamine) of 3 '-imino-two (alkylamine); And allylamine etc.

Wherein, in having the compound of alkyl, also can be the alkyl of branch-like.

In addition, in described compound, (dialkyl amido) alkylamine and N-alkyl-imino-two (alkylamine) has uncle's amino, but owing to have primary amino, so given play to effect of the present invention.

As secondary amino group, can use all cpds, can enumerate dimethylamine, diethylamine, dipropyl amine, dibutylamine and two-2-dialkylamines such as ethylhexylamine; Two-2-ethoxy propylamine and two-3-dialkoxy alkylamines such as (2-ethylhexyl) propylamine etc.; And diallylamine etc.

Wherein, in having the compound of alkyl, also can be the alkyl of branch-like.

As primary-secondary amine, can enumerate 3, two (propyl group) amine and 6 of 3 '-imino-, two (alkyl) amine and 3 of imino-s such as two (hexyl) amine of 6 '-imino--(alkylamino) alkylamines such as (methylamino) propylamine etc.

As amine compound of the present invention, also can use with the form of inorganic salt as required.Particularly, can enumerate the hydrochloride of described compound and vitriol etc.

Wherein, as amine compound, owing to be not that the effect of the present invention of compound of form of inorganic salt is outstanding, so preferred.

As amine compound, wherein, in the desolventizing operation, because treatment agent is difficult to evaporation, preferred boiling point is the above compounds of 200 temperature, and more preferably the boiling point under the 0.5kPa is more than 60 ℃ and the compound below 300 ℃.

Particularly, can enumerate 6, two (hexyl) amine of 6 '-imino-, 1,6-hexanediamine, cetylamine etc.

4-5. Urea,amino-

Urea,amino-is for having the compound of 1 Semicarbazido at least.

The Urea,amino-that can use in the present invention is preferably the compound of following formula (5) expression.

In the formula (5), R ¹And R ²The organic radical of representing 1 valency, identical or different respectively.In addition, R ¹And R ²Be preferably the alkyl or phenyl that replaces or do not have replacement.Particularly, can the illustration methyl, ethyl, propyl group, sec.-propyl, stearyl-, benzyl and hydroxyethyl etc.Wherein, the low alkyl group of carbonatoms 1～4 more preferably.

In the formula (5), R ³And R ⁴Represent the organic radical of hydrogen atom or 1 valency independently of one another, be preferably hydrogen atom.

In the formula (5), A represents the organic radical of hydrogen atom or n valency.A is preferably the organic radical of n valency, more preferably the organic radical of divalent or 3 valencys.

In the formula (5), n is the integer more than 1, is preferably 1～3 integer, more preferably 2 or 3.

Organic radical as described n valency is not particularly limited, and is preferably the base that is made of hydrogen atom, carbon atom, nitrogen-atoms and/or Sauerstoffatom, more preferably fatty group or alicyclic group.

Urea,amino-can add a kind, and also two or more kinds may be used.

As Urea,amino-, can use all cpds, can enumerate and utilize isocyanate compound and N, N-two replaces the compound that the reaction between the hydrazine obtains.

As isocyanate compound, be preferably diisocyanate cpd, for example can illustration 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4 (or 2,4,4)-trimethylammonium-1,6-hexamethylene diisocyanate, lysinediisocyanate, isophorone diisocyanate, 1,3-two (isocyanic ester ylmethyl)-hexanaphthenes, 4,4 '-dicyclohexyl methane diisocyanate, aliphatics or alicyclic diisocyanates such as xylyl vulcabond and tetramethyl xylene group diisocyanate; 4, aromatic diisocyanates such as 4 '-'-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate and naphthalene diisocyanate.In addition, can also enumerate the polymeric polyisocyanate that utilizes these vulcabond to derive and form; And monoisocyanates such as n-butyl isocyanate, n-hexyl isocyanic ester, n-octyl isocyanic ester and phenyl isocyanate etc.

In these isocyanate compounds, preferred aliphat or alicyclic diisocyanate and the polymeric polyisocyanate that utilizes it to derive and form.Also two or more kinds may be used for these isocyanate compounds.

As N; N-two replaces hydrazine; for example can enumerate N; N-dimethylhydrazine, N; N-diethyl hydrazine, N, N-dipropyl hydrazine, N, N-di-isopropyl hydrazine, N; N-distearyl acyl group hydrazine, N-methyl-N-ethyl hydrazine, N-methyl-N-sec.-propyl hydrazine, N-methyl-N-benzyl hydrazine and N, N-two (β-hydroxyethyl)-hydrazine etc.

Isocyanate compound and N, the reaction that N-two replaces between the hydrazine can be carried out with having or not irrespectively of solvent.Use under the situation of solvent, must use relative isocyanic ester to be the inert solvent.

Reaction is preferably carried out more preferably 0～100 ℃ under-20～150 ℃.

Preferably make isocyanic ester and N, N-two replaces hydrazine roughly to wait quantitative response.

Wherein, from acid number rising inhibit feature aspect outstanding, that obtain easily, be preferably the R in the described formula (5) ¹And R ²Low alkyl group, R for carbonatoms 1～4 ³And R ⁴Urea,amino-for hydrogen atom with Semicarbazido.And then, except these advantages, in desolventizing operation described later, because treatment agent is difficult to evaporation, the R in the more preferably described formula (5) ¹And R ²Low alkyl group, R for carbonatoms 1～4 ³And R ⁴For hydrogen atom have Semicarbazido, molecular weight is the compound more than 200.

As this compound, preferred 1,4-tetramethylene is two-N, N-dimethylamino urea, 1,6-hexa-methylene is two-N, and N-dimethylamino urea, 1,1,1 ', 1 '-tetramethyl--4,4 '-(two pairs of phenylenes of methylene radical) diaminourea and following compound etc.

4-6. pyridine compounds

As pyridine compounds, get final product so long as have the compound of pyridine ring, can use all cpds.Particularly, be preferably basic cpd, can enumerate pyridine, picoline, ethylpyridine, propyl group pyridine, butyl-pyridinium, 4-(1-butyl amyl group) pyridine, two picolins, trimethylpyridine, triethyl pyridine, phenylpyridine, aminopyridine, 2-Dimethylamino pyridine and 4-Dimethylamino pyridine etc.

Wherein, pyridine compounds is preferably aminopyridine compounds, more preferably 2-dimethyl aminopyridine or 4-dimethyl aminopyridine.

4-7. preferred particular procedure agent

In the manufacture method of the 2nd (methyl) of the present invention acrylate, use at least a particular procedure agent that is selected from quaternary ammonium salt, quaternary alkylphosphonium salt, amidine, compound, Urea,amino-and the pyridine with primary amino and/or secondary amino group.Wherein, preferred quaternary ammonium salt, quaternary alkylphosphonium salt, amidine and Urea,amino-, more preferably Urea,amino-.By using Urea,amino-, (methyl) acrylate that obtains suppresses effect except acid number rises, and can also give the painted effect that prevents, so preferred.

The addition means of 4-8. treatment agents

As the period of the interpolation of described particular procedure agent, so long as the reaction solution that obtains after through neutralizing treatment and washing processing gets final product, can be for arbitrarily, particularly, can enumerate the desolventizing operation front and back, carry out filtering under the filtering situation front and back and then the finished product of operation.

Wherein, preferably before the desolventizing operation, add the method for particular procedure agent.If utilize this method, then can merge the interpolation operation of desolventizing operation and particular procedure agent, carry out with 1 operation, can omit the interpolation operation of particular procedure agent, so preferred.

As the addition means of described treatment agent, can enumerate the method that in (methyl) acrylate, mixes and add simultaneously etc.

As the adding proportion of described particular procedure agent, relatively (methyl) acrylate is preferably 2～10000wtppm, 5～3000wtppm more preferably, and then be preferably 50～1000wtppm.If this is worth for more than the 2wtppm, then can bring into play the effect of particular procedure agent effectively, on the other hand, if be below the 10000wtppm, then the solvability to (methyl) acrylate that obtains is outstanding, is being used as under the situation of composition, also go out with the mutual solubility of other compositions, so preferred.

The interpolation of this treatment agent also can be carried out at normal temperatures, also can heat as required.

Especially using under the situation of polyvalent alcohol as alcohol preferred heating.This is because under the situation of use polyvalent alcohol as alcohol, (methyl) acrylate that obtains becomes the high viscosity thing, can utilize heating to cooperate treatment agent at short notice equably.

(methyl) acrylate that Heating temperature and heat-up time, basis obtained and purpose are suitably set and are got final product, and as Heating temperature, are preferably 30～100 ℃, more preferably 30～80 ℃, as heat-up time, be preferably 5 minutes～5 hours, more preferably 30 minutes～3 hours.

Under the situation of heating, in order to prevent the polymerization of (methyl) acryl, preferably use polymerization retarder, and then also can in reaction solution, import oxygen-containing gas.

As polymerization retarder, can enumerate polymerization retarder same as described above, its ratio also can be enumerated ratio same as described above.

As oxygen-containing gas, can enumerate oxygen-containing gas same as described above.

5. precipitation matchmaker operation

Treatment solution in the neutralization washing contains under the situation of organic solvent, carries out precipitation matchmaker operation.At this moment, organic solvent can be the organic solvent that uses in esterification step, also can for after neutralizing treatment and/or the organic solvent that handle to add of washing.

If precipitation matchmaker operation is described, then neutralizing treatment liquid or washing treatment solution are moved to the desolventizing groove, remove the organic solvent in the organic layer of water layer after separating in neutralizing treatment or washing are handled.

The precipitation matchmaker handles and to get final product according to ordinary method, under reduced pressure heats the method etc. that precipitation matchmaker groove is removed organic solvent thereby for example can enumerate.

As the decompression degree of precipitation matchmaker groove, suitably corresponding raw material that uses and purpose are set and get final product, are preferably 0.5～50kPa, preferably the method for increase decompression degree according to the degree of removing of organic solvent and lentamente.

Suitably corresponding (methyl) acrylate that obtains of Heating temperature, decompression degree and purpose are set and are got final product, and are preferably 40～100 ℃, more preferably 60～80 ℃.In order to suppress the thermopolymerization of (methyl) acrylate, preferably with temperature maintenance below 80 ℃.

In the desolventizing operation,, preferably supply with oxygen or add polymerization retarder in order to suppress the thermopolymerization of (methyl) acrylate.As polymerization retarder, can enumerate polymerization retarder same as described above, its ratio also can be enumerated ratio same as described above.

Under the situation that further requires Products Quality, can after the desolventizing operation, further filter.

This filtration operation gets final product according to ordinary method, preferred pressure filtration.

As the method for pressure filtration, for example can enumerate and in the filter that filter paper is set, drop into desolventizing reaction solution afterwards, in filter, exert pressure and carry out filtering method simultaneously.In this case, from improving the aspect of filtration efficiency, preferably add the method for flocculating aids in the reaction solution behind desolventizing, to the method for filter paper surface pre-coated filter aid agent and and with their method.As the gas that utilizes pressurization to use, can enumerate nitrogen, oxygen-containing gas (oxygen 5 capacity %, nitrogen 95 capacity %) and air etc.

6. composition

(methyl) acrylate that utilizes manufacture method of the present invention to obtain can improve the storage stability and the thermostability of (methyl) acrylate that obtains.So (methyl) acrylate that obtains can be used as the gradation composition of active energy ray-curable composition, be preferred for various industrial uses such as optical lens, printing ink liquid, Liniment and caking agent.

The 3rd invention of the present invention relates to a kind of (methyl) acrylate composition, it contains (methyl) acrylate with oxyalkylene group, this has oxyalkylene group (methyl) acrylate is in the presence of acid catalyst, (methyl) vinylformic acid and the alcohol generation dehydration esterification with oxyalkylene group are obtained, wherein, contain compd A with the amount more than the 0ppm and below the 100ppm.

The ratio of the compd A in composition surpasses under the situation of 100ppm, and the storage stability of composition and thermostability become bad.

As the ratio of compd A, it is above and below the 80ppm to be preferably 0ppm, 0～50ppm more preferably, and then be preferably 0～30ppm, most preferably do not detect.

As (methyl) acrylate composition, can preferably use active energy ray-curable composition.

As under the situation of active energy ray-curable composition, can cooperate Photoepolymerizationinitiater initiater, described (methyl) acrylate (methyl) acrylate [other (methyl) acrylate] in addition.Below, the concrete example of each composition is described.

As other (methyl) acrylate, the compound [hereinafter referred to as poly-(methyl) acrylate] that can enumerate compound [hereinafter referred to as one (methyl) acrylate] and have (methyl) acryl more than 2 etc. with 1 (methyl) acryl.

As one (methyl) acrylate, for example can enumerate (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate and (methyl) butyl acrylate; (methyl) vinylformic acid hydroxyalkyl acrylates such as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate and 1,4-butyleneglycol one (methyl) acrylate; Isobornyl acrylate etc. alicyclic one (methyl) acrylate etc.In addition, can also enumerate (methyl) vinylformic acid tetrahydro furfuryl ester, Trivalin SF (methyl) acrylate, (methyl) acryloyl morpholine, maleinamide (methyl) acrylate and (methyl) glycidyl acrylate etc.

As poly-(methyl) acrylate, for example can enumerate tetramethylolmethane two (methyl) acrylate monostearate etc. and have (methyl) acrylate of 2 (methyl) acryls and tetramethylolmethane three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate etc. and have (methyl) acrylate of 3 (methyl) acryls etc.In addition, can also use Dipentaerythritol six (methyl) acrylate, two (TriMethylolPropane(TMP)) four (methyl) acrylate etc. to have (methyl) acrylate of (methyl) acryl more than 4.

In addition, can also use oligopolymer such as carbamate (methyl) acrylate, polyester (methyl) acrylate and epoxy group(ing) (methyl) acrylate.

Under the situation that is visible rays or ultraviolet-curable composition, in composition, cooperate Photoepolymerizationinitiater initiater.In addition, under the situation that is electron(beam)curing type composition, not necessarily need to cooperate Photoepolymerizationinitiater initiater.

As the concrete example of Photoepolymerizationinitiater initiater, can enumerate bitter almond oil camphors such as bitter almond oil camphor, benzoin methylether and bitter almond oil camphor propyl ether; Methyl phenyl ketone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 2,2-diethoxy-2-phenyl methyl phenyl ketone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methyl sulfo-) phenyl]-2-morpholino-propane-1-ketone and N, N-methyl phenyl ketones such as dimethylamino methyl phenyl ketone; Anthraquinones such as 2-tectoquinone, 1-chloroanthraquinone and 2-amyl anthraquinone; Thioxanthone such as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-clopenthixal ketone and 2,4-di-isopropyl thioxanthone; Ketone acetals such as methyl phenyl ketone dimethyl ketone acetal and benzyl dimethyl ketone acetal; Benzophenone, methyldiphenyl ketone, 4,4 '-dichloro benzophenone, 4,4 '-two diethylin benzophenone, Michler ' s ketone and 4-benzoyl-4 '-benzophenone such as dimethyl diphenyl sulfide; And 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.

Also can be as required in Photoepolymerizationinitiater initiater and use photosensitizers.As photosensitizers, can enumerate N, N-dimethyl ethyl aminobenzoate, N, N-dimethylaminobenzoic acid isopentyl ester, triethylamine and trolamine etc.

Except described composition, also can cooperate foam killer, flow agent, inorganic filler, organic filler, oxidation inhibitor and UV light absorber etc. as required.In addition, as required, also can add oxidation inhibitor, photostabilizer, UV light absorber and polymerization retarder etc. on a small quantity.

Embodiment

Below record embodiment and comparative example further specify the present invention.

[various analytical procedure]

Zero acid number

According to JIS K-0070-1992, the acrylate that obtains is dissolved in ethanol, phenolphthalein as indicator, is carried out titration with potassium hydroxide solution.Calculate the acid number of sample from following formula.

Acid number [mg-KOH/g]=N * T * f * 56.11/W

N: the concentration of pure formula potassium hydroxide solution [mol/L]

T: the titer of pure formula potassium hydroxide solution [ml]

F: the titre of pure formula potassium hydroxide solution

W: example weight [g]

Zero forces deterioration test

In the 30ml Glass Containers, add the acrylate that 5g obtains, leave standstill a few days, thus the moisture concentration that contains in the acrylate is adjusted to 1000～3000wtppm at the atmosphere dark cold place.

Afterwards, the Glass Containers of acrylate has been put in sealing, heats 72 hours in remaining on 80 ℃ well heater (Heating Block).Put cold after, measure acid number with described method.

Zero comparative example 1-1

In being provided with the 1L band side pipe four-hole boiling flask of return line, drop into 4 moles of affixture 350g of ethylene oxide, vinylformic acid 180g, toluene 348g, tosic acid monohydrate 20.9g, quinhydrones 0.52g and the cupric chloride 0.52g of dihydroxyphenyl propane.Spray into oxygen-containing gas (oxygen 5 capacity %, nitrogen 95 capacity %, below identical), simultaneously with 100～119 ℃ of heated and stirred of reacting liquid temperature, lateral dominance removes the water that generates with the Dean-Stark pipe and goes to the dehydration esterification that carried out 9 hours the system outside.

Then, reaction solution is cooled to below 40 ℃, adds toluene and water, carry out extracting and clean, add the 20wt% aqueous sodium hydroxide solution afterwards, carry out neutralizing treatment, and then, add water, carry out extracting and clean.

Add 0.2g quinhydrones monomethyl ether (hereinafter referred to as MQ) in the organic layer that obtains, the limit sprays into oxygen-containing gas limit [665Pa under reduced pressure; 5mmHg] heat to 60～80 ℃, heat up in a steamer toluene.

Add depress filtration after, obtain acrylate as goods.

To the acrylate that obtains, use LC/MS, with following condition analysis compd A, results verification: the R in formula (1) that contains 382ppm ¹Be toluyl, R ²Be ethylidene, R ³Compound (hereinafter referred to as compd A 1) for hydrogen atom.

In addition, the hold-time of the reference material of the identification and utilization compd A 1 of compd A 1 and cataclasm pattern (Fragment Pattern) are confirmed.In addition, compd A 1 quantitatively in, the reference material of compd A 1 is made typical curve, carry out quantitatively based on this result.

(UPLC)

Device: Japanese WATERS (strain) system Acquity UPLC system

Post: ODS post; Acquity BEH 1.7 μ m C18 (posts: internal diameter; 2.1mm length; 50mm)

Column temperature: 40 ℃

Elutriant: water/methyl alcohol=70/30 (Initial) → 65/35 (10min) → 50/50 (20min) → 0/100 (21-23min)

Flow velocity: 0.4mL/min

Detector: photodiode array (Photo Diode Array) (PDA) (200-400nm)

Sample concentration: 1% methanol solution

Injection rate: 5 μ L

(MS)

Device: Quattro premier API four utmost points of connecting

Detect: the ESI positively ionized detects

Capillary voltage: 3.5kV

MS:MRM (monitoring ion (monitor ion): m/z 271〉99), extractor (extractor): 4.0V, RF Lens:3.0V, precipitation gas body: 800L/hr, taper hole voltage: 30V

Taper hole gas flow: 50L/hr

Source (source) temperature: 120 ℃, precipitation matchmaker temperature: 400 ℃, collision energy (CollisionEnergy): 30V

The acrylate that obtains is measured acid number.And then, in order to estimate storage stability and to add thermostability, force deterioration test, measure acid number afterwards.These results are as shown in table 1.

Zero embodiment 1-1

In comparative example 1-1, respectively acrylic acid add-on is altered to 150g from 180g, the temperature of reaction of dehydration esterification is altered to 100～117 ℃ from 100～119 ℃, to the reaction times be altered to 5 hours 30 minutes from 9 hours, in addition, according to the method identical with comparative example 1-1, make acrylate, carry out purifying with identical method.

To the acrylate that obtains, utilize the method identical with comparative example 1-1, quantification compound A1 measures acid number and forces deterioration test acid number afterwards.These results are as shown in table 1.

Zero embodiment 1-2

In embodiment 1-1, the thick resultant that obtains after the desolventizing operation is added in the 500ml flask, utilize 80 ℃ of heated and stirred, add water then, moisture concentration is adjusted to 4000～5000ppm.Then, sealed flask continued heated and stirred 72 hours.

Then, thick resultant is cooled to below 40 ℃, adds toluene and 20wt% aqueous sodium hydroxide solution, carry out neutralizing treatment, and then add water, carry out extracting and clean.

Add 0.2gMQ in the organic layer that obtains, the limit sprays into the oxygen-containing gas limit and under reduced pressure heats to 60～80 ℃, heats up in a steamer toluene.

Add depress filtration after, obtain acrylate as goods.

To the acrylate that obtains, utilize the method identical with comparative example 1-1, quantification compound A1 measures acid number and forces deterioration test acid number afterwards.These results are as shown in table 1.

Zero comparative example 1-2

In the flask identical, drop into 1 mole of affixture 350g of ethylene oxide, vinylformic acid 142g, toluene 321g, tosic acid monohydrate 16.5g, quinhydrones 0.48g and cupric chloride 0.48g to cumyl phenol with comparative example 1-1.Spray into oxygen-containing gas, simultaneously with 100～119 ℃ of heated and stirred of reacting liquid temperature, lateral dominance removes the water that generates with the Dean-Stark pipe and goes to the dehydration esterification that carried out 9 hours the system outside.

Then, reaction solution is cooled to below 40 ℃, adds toluene and water, carry out extracting and clean, add the 20wt% aqueous sodium hydroxide solution afterwards, carry out neutralizing treatment, and then, add water, carry out extracting and clean.

Add 0.2gMQ in the organic layer that obtains, the limit sprays into the oxygen-containing gas limit and under reduced pressure heats to 60～80 ℃, heats up in a steamer toluene.

Add depress filtration after, obtain acrylate as goods.

To the acrylate that obtains, utilize the method identical with comparative example 1-1, quantification compound A1 measures acid number and forces deterioration test acid number afterwards.These results are as shown in table 1.

Zero embodiment 1-3

In comparative example 1-2, the thick resultant that obtains after the desolventizing operation is added in the 500ml flask, utilize 80 ℃ of heated and stirred, add water then, moisture concentration is adjusted to 4000～5000ppm.Then, sealed flask continued heated and stirred 72 hours.

Then, thick resultant is cooled to below 40 ℃, adds toluene and 20wt% aqueous sodium hydroxide solution, carry out neutralizing treatment, and then add water, carry out extracting and clean.

Add 0.2gMQ in the organic layer that obtains, the limit sprays into the oxygen-containing gas limit and under reduced pressure heats to 60～80 ℃, heats up in a steamer toluene.

Add depress filtration after, obtain acrylate as goods.To the acrylate that obtains, utilize the method identical with comparative example 1-1, quantification compound A1 measures acid number and forces deterioration test acid number afterwards.These results are as shown in table 1.

Zero comparative example 1-3

In the flask identical, drop into 2.5 moles of affixture 350g of propylene oxide, vinylformic acid 106g, toluene 295g, tosic acid monohydrate 12.3g, quinhydrones 0.44g and the cupric chloride 0.44g of nonylphenol with comparative example 1-1.Spray into oxygen-containing gas, simultaneously with 100～119 ℃ of heated and stirred of reacting liquid temperature, lateral dominance removes the water that generates with the Dean-Stark pipe and goes to the dehydration esterification that carried out 9 hours the system outside.

Then, reaction solution is cooled to below 40 ℃, adds toluene and water, carry out extracting and clean, add the 20wt% aqueous sodium hydroxide solution afterwards, carry out neutralizing treatment, and then, add water, carry out extracting and clean.

Add 0.2gMQ in the organic layer that obtains, the limit sprays into the oxygen-containing gas limit and under reduced pressure heats to 60～80 ℃, heats up in a steamer toluene.

Add depress filtration after, obtain acrylate as goods.

To the acrylate that obtains, use LC/MS, with following condition analysis compd A.Results verification: the middle R of formula (1) that contains 288ppm ¹Be toluyl, R ²Be propylidene, R ³Compound (hereinafter referred to as compd A 2) for hydrogen atom.

In addition, the hold-time of the reference material of the identification and utilization compd A 2 of compd A 2 and cataclasm pattern are confirmed.In addition, compd A 2 quantitatively in, the reference material of compd A 2 is made typical curve, carry out quantitatively based on this result.

(UPLC)

Identical with comparative example 1-1.

(MS)

Except following, identical with comparative example 1-1.

MS:MRM (monitoring ion: m/z 285〉113), extractor: 3.0V, RF Lens:2.0V, precipitation gas body: 800L/hr, taper hole voltage: 30V, taper hole gas flow: 50L/hr, source temperature: 120 ℃, precipitation matchmaker temperature: 400 ℃, collision energy: 10V)

Zero embodiment 1-4

In comparative example 1-3, the thick resultant that obtains after the desolventizing operation is added in the 500ml flask, utilize 80 ℃ of heated and stirred, add water then, moisture concentration is adjusted to 4000～5000ppm.Then, sealed flask continued heated and stirred 72 hours.

Then, thick resultant is cooled to below 40 ℃, adds toluene and 20wt% aqueous sodium hydroxide solution, carry out neutralizing treatment, and then add water, carry out extracting and clean.

Add 0.3gMQ in the organic layer that obtains, the limit sprays into the oxygen-containing gas limit and under reduced pressure heats to 60～80 ℃, heats up in a steamer toluene.

Add depress filtration after, obtain acrylate as goods.To the acrylate that obtains, utilize the method identical with comparative example 1-3, quantification compound A2 measures acid number and forces deterioration test acid number afterwards.These results are as shown in table 1.

Zero embodiment 1-5

In the flask identical, drop into 4 moles of affixture 350g of ethylene oxide, vinylformic acid 180g, toluene 341g, methanesulfonic 10.6g, quinhydrones 0.51g and the cupric chloride 0.51g of dihydroxyphenyl propane with comparative example 1-1.Spray into oxygen-containing gas, simultaneously with 100～119 ℃ of heated and stirred of reacting liquid temperature, lateral dominance removes the water that generates with the Dean-Stark pipe and goes to the dehydration esterification that carried out 9 hours the system outside.

Then, reaction solution is cooled to below 40 ℃, adds toluene and water, carry out extracting and clean, add the 20wt% aqueous sodium hydroxide solution afterwards, carry out neutralizing treatment, and then, add water, carry out extracting and clean.

Add 0.2gMQ in the organic layer that obtains, the limit sprays into the oxygen-containing gas limit and under reduced pressure heats to 60～80 ℃, heats up in a steamer toluene.

The thick resultant that obtains is added in the 500ml flask, utilize 80 ℃ of heated and stirred, add water then, moisture concentration is adjusted to 4000～5000ppm.Then, sealed flask continued heated and stirred 72 hours.

Then, thick resultant is cooled to below 40 ℃, adds toluene and 20wt% aqueous sodium hydroxide solution, carry out neutralizing treatment, and then add water, carry out extracting and clean.

Add 0.2gMQ in the organic layer that obtains, the limit sprays into the oxygen-containing gas limit and under reduced pressure heats to 60～80 ℃, heats up in a steamer toluene.

Add depress filtration after, obtain acrylate as goods.

To the acrylate that obtains, use LC/MS, with following condition analysis compd A.Results verification: the middle R of formula (1) that contains 23ppm ¹Be toluyl, R ²Be ethylidene, R ³Compound (hereinafter referred to as compound A-13) for hydrogen atom.

In addition, the hold-time of the reference material of the identification and utilization compound A-13 of compd A 1-3 and cataclasm pattern are confirmed.In addition, compound A-13 quantitatively in, the reference material of compound A-13 is made typical curve, carry out quantitatively based on this result.

(UPLC)

Except following, identical with comparative example 1-1.

Elutriant: (Initial-5min) → 0/100 (10-11min) in water/methyl alcohol=10/90

Sample concentration: 2% methanol solution

(MS)

Except following, identical with comparative example 1-1.

MS:MRM (monitoring ion: m/z 195〉99), extractor: 2.0V, RF Lens:3.0V, precipitation gas body: 800L/hr, taper hole voltage: 20V, taper hole gas flow: 50L/hr, source temperature: 120 ℃, precipitation matchmaker temperature: 400 ℃, collision energy: 10V)

Zero embodiment 1-6

In the flask identical, drop into 6 moles of affixture 350g of propylene oxide, vinylformic acid 227g, toluene 372g, methanesulfonic 13.3g, quinhydrones 0.56g and the cupric chloride 0.56g of TriMethylolPropane(TMP) with comparative example 1-1.Spray into oxygen-containing gas, simultaneously with 100～120 ℃ of heated and stirred of reacting liquid temperature, lateral dominance removes the water that generates with the Dean-Stark pipe and goes to the dehydration esterification that carried out 9 hours the system outside.

Then, reaction solution is cooled to below 40 ℃, adds toluene and water, carry out extracting and clean, add the 20wt% aqueous sodium hydroxide solution afterwards, carry out neutralizing treatment, and then, add water, carry out extracting and clean.

Add 0.2gMQ in the organic layer that obtains, the limit sprays into the oxygen-containing gas limit and under reduced pressure heats to 60～80 ℃, heats up in a steamer toluene.

The thick resultant that obtains is added in the 500ml flask, utilize 80 ℃ of heated and stirred, add water then, moisture concentration is adjusted to 4000～5000ppm.Then, sealed flask continued heated and stirred 72 hours.

Then, thick resultant is cooled to below 40 ℃, adds toluene and 20wt% aqueous sodium hydroxide solution, carry out neutralizing treatment, and then add water, carry out extracting and clean.

Add 0.2gMQ in the organic layer that obtains, the limit sprays into the oxygen-containing gas limit and under reduced pressure heats to 60～80 ℃, heats up in a steamer toluene.

Add depress filtration after, obtain acrylate as goods.

To the acrylate that obtains, use LC/MS, with following condition analysis compd A, results verification: the middle R of formula (1) that contains 7ppm ¹Be toluyl, R ²Be propylidene, R ³Compound (hereinafter referred to as compd A 4) for hydrogen atom.

In addition, the hold-time of the reference material of the identification and utilization compd A 4 of compd A 4 and cataclasm graphic affirmation.In addition, compd A 4 quantitatively in, the reference material of compd A 4 is made typical curve, carry out quantitatively based on this result.

(UPLC)

Except following, identical with comparative example 1-1.

Elutriant: (Initial-5min) → 0/100 (10-11min) in water/methyl alcohol=10/90

Sample concentration: 2% methanol solution

(MS)

Except following, identical with comparative example 1-1.

Capillary voltage: 4.5kV

MS:MRM (monitoring ion: m/z 209〉113), extractor: 2.0V, RF Lens:3.0V, precipitation gas body: 800L/hr, taper hole voltage: 20V, taper hole gas flow: 50L/hr, source temperature: 120 ℃, precipitation matchmaker temperature: 400 ℃, collision energy: 10V)

[table 1]

Zero comparative example 2-1

In being provided with the 1L band side pipe four-hole boiling flask of return line, drop into 4 moles of affixture 350g of ethylene oxide, vinylformic acid 150g, toluene 348g, tosic acid monohydrate (hereinafter referred to as PTS) 20.9g, quinhydrones (hereinafter referred to as HQ) 0.52g and the cupric chloride 0.52g of dihydroxyphenyl propane.Spray into oxygen-containing gas (oxygen 5 capacity %, nitrogen 95 capacity %, below identical), simultaneously with 100～118 ℃ of heated and stirred of reacting liquid temperature, lateral dominance removes the water that generates with the Dean-Stark pipe and goes to the dehydration esterification that carried out 7 hours the system outside.

Then, reaction solution is cooled to below 40 ℃, adds toluene and water, carry out extracting and clean, add the 20wt% aqueous sodium hydroxide solution afterwards, carry out neutralizing treatment, and then, add water, carry out extracting and clean.

Add 0.2g quinhydrones monomethyl ether (hereinafter referred to as MQ) in the organic layer that obtains, the limit sprays into the oxygen-containing gas limit and under reduced pressure heats to 60～80 ℃, heats up in a steamer toluene.

Add depress filtration after, obtain acrylate as goods.

To the acrylate that obtains, utilize the method identical with comparative example 1-1, quantification compound A1 measures acid number and forces deterioration test acid number afterwards.These results are as shown in table 2.

[table 2]

Zero embodiment 2-1

Utilize method and the condition identical, carry out esterification, neutralizing treatment and extracting cleaning with comparative example 2-1.

Add the Tetrabutyl amonium bromide that 0.2gMQ and relative acrylate add the 348ppm treatment agent in the organic layer that obtains, stir, the limit sprays into the oxygen-containing gas limit and under reduced pressure heats to 60～80 ℃, heats up in a steamer toluene.

Filter adding the reaction solution of depressing behind the desolventizing, obtain acrylate.

The acrylate that obtains is measured acid number after just making the back and forcing deterioration test.These results are as shown in table 3.

Zero embodiment 2-2～with 2-8

In embodiment 2-1, in the desolventizing operation, adding the following table 3 of specified amount the treatment agent of record, utilize the method manufacturing acrylate identical with embodiment 2-1.

Filter adding the reaction solution of depressing behind the desolventizing, obtain acrylate.

The acrylate that obtains is measured acid number after just making the back and forcing deterioration test.These results are as shown in table 3.

[table 3]

The brevity code of table 3 is represented following meaning.

TBAB: Tetrabutyl amonium bromide

TBAOH: TBAH

TMAOH: Tetramethylammonium hydroxide

TBPB: four butyl phosphonium bromides

IBHA:6, two (hexyl) amine of 6 '-imino-

DMAP:4-diformazan case yl pyridines

HMSC:1,6-hexa-methylene is two-N, N-dimethylamino urea

Zero embodiment 2-9～embodiment 2-11

In described embodiment 2-1, do not add treatment agent, carry out desolventizing and handle.

Add the treatment agent of following table 4 record of specified amount in the raw product that after heating up in a steamer toluene, obtains,, it is mixed equably with 70 ℃ of stirrings 1 hour.Then, filter adding to depress, obtain acrylate then.

The acrylate that obtains is measured acid number after just making the back and forcing deterioration test.These results are as shown in table 4.

[table 4]

The brevity code of table 4 is represented following meaning.

DBA: dibutylamine

BA: butylamine

DEAHCl: diethylamine hydrochloride

Zero embodiment 2-12

In described embodiment 2-1～2-8, do not add treatment agent, carried out the desolventizing processing.

Add treatment agent with the ratio identical in the raw product that after heating up in a steamer toluene, obtains, stirred 1 hour with 70 ℃, it is mixed equably with embodiment 2-1～2-8.Then, filter adding to depress, obtain acrylate then.

Same with described embodiment 2-1～2-8, the acid number after the pressure deterioration test of the acrylate that obtains is low.

Zero comparative example 2-2

In the flask identical with comparative example 2-1, drop into 6 moles of affixture 372g of propylene oxide, vinylformic acid 200g, toluene 294g, PTS19.0g, HQ0.89g and the cupric chloride 0.89g of TriMethylolPropane(TMP), spraying into oxygen-containing gas, is the scope internal heating stirring of pressure 400～650mmHg simultaneously in 80～110 ℃ of reacting liquid temperatures, reaction.Lateral dominance removes the water that generates with the Dean-Stark pipe and goes to the dehydration esterification that carried out 7 hours the system outside.

After reaction finishes, utilize the method identical that reaction solution is carried out neutralizing treatment, and then add water, carry out extracting and clean, carry out the desolventizing processing with comparative example 2-1.

Utilize the method identical with comparative example 1-3, to the acrylate that obtains, quantification compound A2 measures the acid number after acid number and the pressure deterioration test.These results are as shown in table 5.

[table 5]

Zero embodiment 2-13

Utilize method and the condition identical, carry out esterification, neutralizing treatment and extracting cleaning with comparative example 2-2.

Add the TBAH that 0.2gMQ and relative acrylate add the 570ppm treatment agent in the organic layer that obtains, stir, the limit sprays into the oxygen-containing gas limit and under reduced pressure heats to 60～80 ℃, heats up in a steamer toluene.

Filter adding the reaction solution of depressing behind the desolventizing, obtain acrylate.

The acrylate that obtains is measured acid number, forcing to measure acid number after the deterioration test.These results are as shown in table 6.

Zero embodiment 2-14～embodiment 2-18

In described embodiment 2-13, in the desolventizing operation, add the treatment agent of following table 6 record of specified amount, in addition, utilize the method manufacturing acrylate identical with embodiment 2-13.

Filter adding the reaction solution of depressing behind the desolventizing, obtain acrylate.

The acrylate that obtains is measured acid number after just making the back and forcing deterioration test.These results are as shown in table 6.

[table 6]

Zero embodiment 2-19

In described embodiment 2-13, do not add treatment agent, carry out desolventizing and handle.

Add the treatment agent of following table 7 record of specified amount in the raw product that after heating up in a steamer toluene, obtains,, it is mixed equably with 70 ℃ of stirrings 1 hour.Then, filter adding to depress, obtain acrylate then.

The acrylate that obtains is measured acid number after just making the back and forcing deterioration test.These results are as shown in table 7.

[table 7]

Zero embodiment 2-20

In described embodiment 2-13～2-18, do not add treatment agent, carry out desolventizing and handle.

Add treatment agent with the ratio identical in the raw product that after heating up in a steamer toluene, obtains, stirred 1 hour with 70 ℃, it is mixed equably with embodiment 2-13～2-18.Then, filter adding to depress, obtain acrylate then.

Same with described embodiment 2-13～2-18, the acid number after the pressure deterioration test of the acrylate that obtains is low.

Utilizability on the industry

Manufacture method of the present invention can be utilized in the manufacture method of (methyl) acrylate.

And then (methyl) acrylate that obtains can joining preferably as Photocurable composition Use synthetic the branch in the various industrial uses such as optical lens, printer's ink liquid, coating agent and bonding agent.

Claims (11)

1. the manufacture method of (methyl) acrylate is characterized in that, comprising:

In organic solvent, utilize the organic sulfonic acid catalyzer to (methyl) thereby vinylformic acid and alcohol with oxyalkylene group dewater the esterification step of formation (methyl) acrylate, and

Compd A shown in the formula (1) in (methyl) acrylate that utilizes described esterification step to obtain is controlled to the management operation that 0ppm is above and 100ppm is following,

In the formula (1), R ¹The expression alkyl or aryl, R ²The expression alkylidene group, R ³Expression hydrogen atom or methyl.

2. the manufacture method of (methyl) according to claim 1 acrylate, wherein,

The management operation comprise following 1)～4) at least 1 step,

1) in esterification step, Chun hydroxyl is 1 mole relatively, uses more than 0.8 mole and (methyl) below 2.0 moles vinylformic acid,

2) carrying out esterification more than 70 ℃ and below 140 ℃,

3) finish in the moment that esterification is roughly finished,

4) in the presence of moisture, to getting reaction solution compd A heating in the resulting thick resultant after neutralizing treatment and washing processing by esterification step, being hydrolyzed.

3. the manufacture method of (methyl) acrylate is characterized in that, comprising:

In organic solvent, utilize the organic sulfonic acid catalyzer to (methyl) thereby vinylformic acid and alcohol with oxyalkylene group dewater the esterification step (1) of formation (methyl) acrylate,

The reaction solution that utilizes operation (1) to obtain is carried out neutralizing treatment and washes the operation of handling (2),

(methyl) acrylate that obtains in relative operation (2) contains in the reaction solution of compd A shown in the formula (1) more than the 1ppm, add the interpolation operation that is selected from least 1 particular procedure agent in quaternary ammonium salt, quaternary alkylphosphonium salt, amidine, compound, Urea,amino-and the pyridine with primary amino and/or secondary amino group

In the formula (1), R ¹The expression alkyl or aryl, R ²The expression alkylidene group, R ³Expression hydrogen atom or methyl.

4. the manufacture method of (methyl) according to claim 3 acrylate is characterized in that,

After the interpolation operation of adding described particular procedure agent, comprise the precipitation matchmaker operation of heating up in a steamer organic solvent.

5. the manufacture method of (methyl) according to claim 3 acrylate, wherein,

In described operation (2) afterwards, comprising:

Heat up in a steamer the precipitation matchmaker operation of organic solvent,

Add the interpolation operation of described particular procedure agent in the reaction solution after precipitation matchmaker operation, and

The heating process that heats.

6. the manufacture method of (methyl) according to claim 5 acrylate, wherein,

Described Heating temperature is 30～100 ℃.

7. according to the manufacture method of each described (methyl) acrylate in the claim 1～6, wherein,

Alcohol with oxyalkylene group is the alkylene oxide affixture of polyvalent alcohol.

8. according to the manufacture method of each described (methyl) acrylate in the claim 1～7, wherein,

Oxyalkylene group with alcohol of oxyalkylene group is oxyethylene group or oxypropylene group, the R in the formula (1) ²Alkylidene group be ethylidene or propylidene.

9. (methyl) acrylate composition, it contains (methyl) acrylate with oxyalkylene group, described have (methyl) acrylate of oxyalkylene group by in the presence of the organic sulfonic acid catalyzer, make (methyl) vinylformic acid and alcohol that the dehydration esterification take place and obtain with oxyalkylene group, wherein

Contain the compd A that formula (1) is represented with the amount more than the 0ppm and below the 100ppm,

In the formula (1), R ¹The expression alkyl or aryl, R ²The expression alkylidene group, R ³Expression hydrogen atom or methyl.

10. (methyl) according to claim 9 acrylate composition, wherein,

Alcohol with oxyalkylene group is the alkylene oxide affixture of polyvalent alcohol.

11. according to claim 9 or 10 described (methyl) acrylate composition, wherein,

Oxyalkylene group with alcohol of oxyalkylene group is oxyethylene group or oxypropylene group, the R in the formula (1) ²Alkylidene group be ethylidene or propylidene.