CN100432040C - Process for the production of adamantyl esters of polymerizable unsaturated carboxylic acids - Google Patents
Process for the production of adamantyl esters of polymerizable unsaturated carboxylic acids Download PDFInfo
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- CN100432040C CN100432040C CNB2004800375098A CN200480037509A CN100432040C CN 100432040 C CN100432040 C CN 100432040C CN B2004800375098 A CNB2004800375098 A CN B2004800375098A CN 200480037509 A CN200480037509 A CN 200480037509A CN 100432040 C CN100432040 C CN 100432040C
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Abstract
A process for the production of adamantyl esters of polymerizable unsaturated carboxylic acids which is characterized by comprising the esterification step of reacting a mixture of a polymerizable unsaturated carboxylic acid and a polymerizable unsaturated carboxylic acid anhydride with an adamantanol in the presence of an acid catalyst and a polymerization inhibitor. According to the process, the formation of oligomeric impurities as by-products is remarkably inhibited.
Description
Technical field
The manufacture method of the adamantyl esters of polymerizable unsaturated carboxylic acids that the starting monomer when the present invention relates to as manufacturing function material, electronic material is useful.
Background technology
Adamantane derivative is owing to have the excellent thermotolerance and the transparency, and the starting material when therefore the contour functional material of thermotolerance polymer, semi-conductor are made in the expectation conduct with electronic materials such as resists use.In adamantane derivative, adamantyl esters of polymerizable unsaturated carboxylic acids is very useful compound.This adamantyl esters of polymerizable unsaturated carboxylic acids is individually or with other monomers, uses as the starting monomer of macromolecular material, anticorrosive additive material.
For example, carry out single-esterification, can obtain as the useful hydroxyadamantane base ester class of monomer by making diamantane glycols and polymerizable unsaturated carboxylic acids.This monomer has the high hydroxyl of polarity, therefore carries out copolymerization by cooperation ratio and other monomers that changes it, can obtain having various polar anticorrosive additive materials.The polar size that this anticorrosive additive material had results from the various rerum naturas of polar of anticorrosive additive material for solvability in solvent etc. and exerts an influence.Therefore, by this monomeric cooperation ratio of control, can obtain being subjected to being controlled to be the anticorrosive additive material of feature with rerum natura.
Up to now, as the manufacture method of this class adamantyl esters of polymerizable unsaturated carboxylic acids (following also abbreviate as " polymerizability adamantyl esters "), known have: make the method (spy opens the 2000-119220 communique) of the unsaturated acid halide of diamantane alcohols and polymerizability reaction and the method (spy opens clear 63-33350 communique) that makes diamantane alcohols and polymerizable unsaturated carboxylic acids condensation in the presence of acid catalyst such as sulfuric acid and stopper.
Yet person's method is only made the occasion of the hydroxyadamantane base ester class that a hydroxy esterification of diamantane glycols forms before use, except generating the monoesters class as target, has also generated the diester class of a great deal of as by product.Its result, the problem that exists the yield of monoesters class relatively to reduce.Different therewith, the latter's method has the feature that can make various polymerizability adamantyl esters with high yield.Therefore, making above-mentioned hydroxyadamantane base ester time-like, the growing amount of diester class (by product) is few, can obtain monoesters class (target compound) with high yield.
Therefore, using the latter's of acid catalyst method is to make the method for the excellence of polymerizability adamantyl esters.Yet, in the method, can not avoid generating molecular weight and be about 300～5000 impurity component (hereinafter also this impurity component being called " oligopolymer impurity ").
The polymerizability adamantyl esters that contains this oligopolymer impurity might produce ill effect to the rerum natura (solvability in solvent, thermotolerance etc.) of polymkeric substance that its polymerization is obtained.Therefore, particularly, strictly limit sneaking into of above-mentioned oligopolymer impurity in the occasion that the polymerizability adamantyl esters is used for the electronic material purposes.
This oligopolymer impurity is difficult to usually confirm by vapor-phase chromatography (GC) analysis, at first is to confirm by gel permeation chromatography (GPC) therefore.And it is very difficult from the polymerizability adamantyl esters that contains big weight oligomers impurity this impurity being removed.For example, even want to come purifying polymerizability adamantyl esters by partial crystallization, but the polymerizability adamantyl esters that contains big weight oligomers impurity is difficult to crystallization.Therefore, purifying needs long-time, and the segregation yield reduces significantly, and this is the problem that exists.
For the generation (by-product) that suppresses this oligopolymer impurity, known method is to use the few diamantane glycols of the halide content of basic metal or alkaline-earth metal to make the method (for example the spy opens the 2001-106650 communique) of polymerizability adamantyl esters as raw material.Yet according to this method, must keep temperature of reaction is high temperature.Therefore can not avoid the generation of the oligopolymer impurity that thermopolymerization causes, its result may not satisfy and suppresses the effect that oligopolymer impurity generates.
Summary of the invention
The object of the present invention is to provide a kind ofly can obtain target compound, using acid catalyst the esterification of diamantane alcohols to be made the considerably less method of generation that makes oligopolymer impurity in the method for adamantyl esters of polymerizable unsaturated carboxylic acids with high yield.
Present inventors have carried out deep research in order to solve above-mentioned problem.Found that, if use the reaction raw materials of mixture conduct with the reaction of diamantane alcohols of polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride, even for example the occasion of reacting under 10～60 ℃ of low like this temperature also can make reaction carry out with speed no problem in the practicality.And, by under low reaction temperatures, reacting, can avoid opening the generation (by-product) that the method for putting down in writing in the 2001-106650 communique is carried out the oligopolymer impurity that thermopolymerization caused under the high temperature according to above-mentioned spy, so far just finished the present invention.
Promptly, the present invention is the manufacture method of adamantyl esters of polymerizable unsaturated carboxylic acids, it is characterized in that comprising: in the presence of acid catalyst and stopper, make polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride mixture, with the esterification step of diamantane alcohols reaction.
According to the present invention, can make the polymerizability adamantyl esters with high yield and high selectivity with the state of the generation that highly suppresses oligopolymer impurity.The solvability excellence of poor polymerizability adamantyl esters in solvent of oligopolymer impurity, and use the excellent heat resistance of the polymkeric substance that this polymerizability adamantyl esters makes.Therefore, the manufacture method of the starting monomer that uses when making electronic materials such as functional material, resist such as thermotolerance polymer etc. of the present invention is very useful.
Embodiment
Explain the reaction raw materials that in manufacture method of the present invention, uses, catalyzer, reaction conditions, reactions steps, resultant etc. below.
(diamantane alcohols)
As the diamantane alcohols of the reaction raw materials that uses in the present invention, can unrestrictedly use on the carbon atom that constitutes diamantane skeleton bonding that the known adamantane compound of at least one hydroxyl is arranged.Calm facile viewpoint is considered, the compound of preferably following (1) expression.
(in the formula, R
1, R
2, R
3And R
4Represent hydrogen atom, hydroxyl or low alkyl group independently of one another, R
1To R
4In at least one is a hydroxyl).
Wherein, at the R of formula (1)
1, R
2, R
3And R
4In, any group beyond the hydroxyl is the occasion of low alkyl group, as this low alkyl group, can enumerate the alkyl of carbonatomss 1～5 such as methyl, ethyl, propyl group, butyl, amyl group.Wherein, the viewpoint wide from the industrial utilization field considered, special preferable methyl.
In the diamantane alcohols shown in the above-mentioned formula (1), if the preferred compound of illustration particularly, then can enumerate: the 1-adamantanol, the 2-adamantanol, 1,3-diamantane glycol, 1,4-diamantane glycol, the 2-methyl isophthalic acid, 3-diamantane glycol, 2-ethyl-1,3-diamantane glycol, 3-methyl isophthalic acid-adamantanol, 3-ethyl-1-adamantanol, the 5-methyl isophthalic acid, 3-diamantane glycol, 5-ethyl-1,3-diamantane glycol, 5-propyl group-1,3-diamantane glycol, 5,7-dimethyl-1,3-diamantane glycol, 5,7-diethyl-1,3-diamantane glycol, 5-ethyl-7-methyl isophthalic acid, 3-diamantane glycol, 1,3,5-diamantane triol etc.
In the compound shown in the formula (1), preferred R
1To R
3In at least one is the compound of hydroxyl, more preferably at least two is the compound of hydroxyl.
Particularly from the considerations such as viewpoint of the availability of the polymerizability adamantyl esters that obtains, as the diamantane alcohols, the diamantane glycols of preferred following formula (2) expression, preferred especially 1,3-diamantane two is pure and mild 5,7-dimethyl-1,3-diamantane glycol.
(in the formula, R
5And R
6Represent hydrogen atom or low alkyl group independently of one another).
(polymerizable unsaturated carboxylic acids)
Polymerizable unsaturated carboxylic acids as the reaction raw materials that uses in the present invention can unrestrictedly use the carboxylic acid with polymerizability unsaturated group.From the considerations such as viewpoint of the availability of the polymerizability adamantyl esters that obtains, preferably use the compound of following formula (3) expression.
(in the formula, R
7For having substituent polymerizability unsaturated alkyl).
As substituting group, can enumerate: cyano group; Halogen atoms such as fluorine, chlorine, bromine, iodine; The alkoxyl group that carbonatoms such as methoxyl group, oxyethyl group is 1～5 etc.
As by R
7That represents can have substituent polymerizability unsaturated alkyl, can be any of straight chain shape, chain, cyclic polymerizability unsaturated alkyl, if example illustrates wherein preferred group particularly, then can enumerate: the alkenyl of carbonatomss 2～5 such as vinyl, pseudoallyl, allyl group, 1-propenyl, 3-butenyl, 3-methyl-3-butenyl, 4-pentenyl, 1,3-butadiene base.
If example illustrates the preferred polymerizable unsaturated carboxylic acids that uses among the present invention particularly, then can enumerate: vinylformic acid, methacrylic acid, vinylacetic acid, Ba Dousuan, 4-pentenoic acid, 4-methyl-4-pentenoic acid, 5-hexenoic acid and 2, the polymerizable unsaturated carboxylic acids that carbonatomss such as 4-pentadienoic acid are 2～6.In these compounds, consider preferred especially acrylic or methacrylic acid from the viewpoint of the availability of resultant.
Should illustrate, pressing known method in the past, by the occasion of using acid catalyst to carry out the esterification of diamantane alcohols, if will use vinylformic acid to compare with the situation of using other polymerizable unsaturated carboxylic acids as the situation of polymerizable unsaturated carboxylic acids, then the previous case has the stronger tendency that generates big weight oligomers impurity in resultant.In contrast to this, according to method of the present invention, can suppress the generation of oligopolymer impurity efficiently.Therefore, even use vinylformic acid, also be difficult to take place above-mentioned problem as polymerizable unsaturated carboxylic acids.Therefore, using vinylformic acid to carry out the occasion of esterification, the advantage of the inventive method is brought into play more significantly.
(polymerizable unsaturated carboxylic acids acid anhydride)
As the polymerizable unsaturated carboxylic acids acid anhydride, can unrestrictedly use carboxylic acid anhydride with polymerizability unsaturated group.Yet,, preferably use the compound of following formula (4) expression from the considerations such as viewpoint of the practicality of the polymerizability adamantyl esters of gained.
(in the formula, R
8For having substituent polymerizability unsaturated alkyl).
As R
8Substituting group, can enumerate: cyano group; Halogen atoms such as fluorine, chlorine, bromine, iodine; Carbonatoms such as methoxyl group, oxyethyl group is 1～5 a alkoxyl group etc.
As by R
8That represents can have substituent polymerizability unsaturated alkyl, can be any of straight chain shape, chain, cyclic polymerizability unsaturated alkyl, if the routine particularly preferred group that illustrates in the above-mentioned group, then can enumerate: the alkenyl of carbonatomss 2～5 such as vinyl, pseudoallyl, allyl group, 1-propenyl, 3-butenyl, 3-methyl-3-butenyl, 4-pentenyl, 1,3-butadiene base.
If example illustrates the preferred polymerizable unsaturated carboxylic acids acid anhydride that uses among the present invention particularly, then can enumerate: acrylic anhydride, methacrylic anhydride, vinylacetic acid acid anhydride, crotonic anhydride, 4-pentenoic acid anhydride, 4-methyl-4-pentenoic acid anhydride, 5-hexene acid anhydrides and 2, the polymerizable unsaturated carboxylic acids acid anhydride of carbonatomss 6～12 such as 4-pentadiene acid anhydrides.In addition, can use mixed acid anhydride as required.In these compounds, consider preferred especially acrylic anhydride or methacrylic anhydride from the viewpoint of the practicality of resultant.
In the present invention, the mixture of polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride is used for reaction with adamantanol.Combination to polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride is not particularly limited, but, use to have the polymerizable unsaturated carboxylic acids of same polymeric unsaturated group and the mixture of polymerizable unsaturated carboxylic acids acid anhydride in the occasion of wanting to obtain single adamantyl esters of polymerizable unsaturated carboxylic acids.For example, in the occasion of using vinylformic acid as polymerizable unsaturated carboxylic acids, use acrylic anhydride as the polymerizable unsaturated carboxylic acids acid anhydride.Similarly, in the occasion of using methacrylic acid as polymerizable unsaturated carboxylic acids, use methacrylic anhydride as the polymerizable unsaturated carboxylic acids acid anhydride.
In the method for the invention, the usage quantity of the mixture of above-mentioned polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride does not have particular determination, the number of the hydroxyl that can be had according to the diamantane alcohols as raw material, determines aptly as the degree of the esterification of target.In order to reduce raw materials used waste and to obtain target product, be preferably as follows and carry out with high yield and high selectivity.
That is, when the diamantane alcohols has the occasion of n hydroxyl in its 1 molecule, in order to make the whole esterifications of this n hydroxyl, the diamantane alcohols with respect to 1 mole in principle is as long as the usage quantity of polymerizable unsaturated carboxylic acids has the n mole.Yet in the method for the invention, this polymerizable unsaturated carboxylic acids has the effect of reaction solvent simultaneously concurrently, does not therefore preferably use the scheme of other solvents.Thereby the usage quantity of polymerizable unsaturated carboxylic acids is preferably more than the n mole.On the other hand, if the usage quantity of polymerizable unsaturated carboxylic acids is too much, then can causes diamantane alcohols and the polymerizability acid anhydrides concentration in reaction system to reduce, thereby cause reaction efficiency to reduce sometimes.Therefore, the diamantane alcohols with respect to 1 mole, the usage quantity of polymerizable unsaturated carboxylic acids is preferably smaller or equal to 35 moles, more preferably smaller or equal to 25 moles, is preferably especially smaller or equal to 20 moles.
Similarly, with respect to per 1 mole diamantane alcohols, as long as the usage quantity of polymerizable unsaturated carboxylic acids acid anhydride has the n mole.Yet,, perhaps, can use the polymerizable unsaturated carboxylic acids acid anhydride more excessive a little than n mole in the occasion that temperature of reaction is reduced in order to suppress oligopolymer impurity to generate as byproduct in order to shorten the reaction times.In the case, the usage quantity of polymerizable unsaturated carboxylic acids acid anhydride is preferably the mole smaller or equal to 4 * n, more preferably smaller or equal to 2 * n mole, is preferably the mole smaller or equal to 1.5 * n especially.
More particularly, for example, the occasion that has the diamantane alcohols manufacturing monoesters class of 1 hydroxyl in use, this diamantane alcohols with respect to 1 mole, can use the mixture that is formed in following ratio by polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride, wherein, polymerizable unsaturated carboxylic acids is 1～35 mole, be preferably 1～25 mole, be preferably 1～20 mole especially; The polymerizable unsaturated carboxylic acids acid anhydride is 1～4 mole, more preferably 1～2 mole, be preferably 1～1.5 mole especially, and most preferably be 1 mole.
Similarly, the occasion that has the diamantane alcohols manufacturing diester class of 2 hydroxyls in use, this diamantane alcohols with respect to 1 mole, can use the mixture that forms in following ratio by polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride, wherein, polymerizable unsaturated carboxylic acids is 2～35 moles, is preferably 2～25 moles, is preferably 2～20 moles especially; The polymerizable unsaturated carboxylic acids acid anhydride is 2～8 moles, more preferably 2～4 moles, be preferably 2～3 moles especially, and most preferably be 2 moles.
The diamantane alcohols that has 3 hydroxyls in use is made the occasion of three ester classes, this diamantane alcohols with respect to 1 mole, can use the mixture that forms in following ratio by polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride, wherein, polymerizable unsaturated carboxylic acids is 3～35 moles, be preferably 3～25 moles, be preferably 3～20 moles especially; The polymerizable unsaturated carboxylic acids acid anhydride is 3～12 moles, more preferably 3～6 moles, be preferably 3～4.5 moles especially, and most preferably be 3 moles.
The diamantane alcohols that has 4 hydroxyls in use is made the occasion of four ester classes, this diamantane alcohols with respect to 1 mole, can use the mixture that forms in following ratio by polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride, wherein, polymerizable unsaturated carboxylic acids is 4～35 moles, be preferably 4～25 moles, be preferably 4～20 moles especially; The polymerizable unsaturated carboxylic acids acid anhydride is 4～16 moles, more preferably 4～8 moles, be preferably 4～6 moles especially, and most preferably be 4 moles.
In making 1 molecule, has the occasion that the adamantanol of a plurality of hydroxyls carries out esterification, in reaction, compare with high order esterifications such as two esterifications reaction, three esterifications, at first be that single-esterification preferentially carries out, when single-esterification finishes basically, two esterifications reaction is carried out, and then carries out three esterifications.Therefore, in esterification, even make polymerizable unsaturated carboxylic acids or polymerizable unsaturated carboxylic acids acid anhydride excessive a little, also can be by shortening the reaction times, perhaps reduce temperature of reaction and regulate the degree of esterification, its result can obtain the target compound of any gamma value.
For example, by using the polyvalent alcohol that in its molecule, has a plurality of (n (n represents 2～4 integer)) hydroxyl as the diamantane alcohols, make m (m represents 1～(n-1) the integer) esterification in the intramolecular n hydroxyl, also can optionally be manufactured on intramolecularly and have the adamantyl esters of polymerizable unsaturated carboxylic acids of (n-m) individual hydroxyl.
In this occasion, make intramolecularly have the diamantane alcohols and the mixture reaction that forms by polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride of n hydroxyl, in this mixture, with respect to 1 mole of above-mentioned diamantane alcohols with n hydroxyl, the polymerizable unsaturated carboxylic acids acid anhydride is the mole of m mole～(m+0.8), be preferably the mole of m mole～(m+0.5), more preferably the mole of m mole～(m+0.2) is preferably the m mole especially.
In addition, according to above-mentioned same reason, with respect to 1 mole of diamantane alcohols, the usage quantity of polymerizable unsaturated carboxylic acids is preferably m～35 mole, more preferably uses m～25 mole, especially preferably uses m～20 mole.
More particularly, for example, the occasion that has the diamantane alcohols manufacturing monoesters class of 2,3 or 4 hydroxyls in use, the mixture that use is formed in following ratio by polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride: with respect to 1 mole of this diamantane alcohols, polymerizable unsaturated carboxylic acids is 1～35 mole, be preferably 1～25 mole, be preferably 1～20 mole especially; The polymerizable unsaturated carboxylic acids acid anhydride is 1～1.8 mole, is preferably 1～1.5 mole, more preferably 1～1.2 mole, is preferably 1 mole especially.
Similarly, the occasion that has the diamantane alcohols manufacturing diester class of 3 or 4 hydroxyls in use, can use the mixture that forms in following ratio by polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride: with respect to 1 mole of this diamantane alcohols, polymerizable unsaturated carboxylic acids is 2～35 moles, be preferably 2～25 moles, be preferably 2～20 moles especially; The polymerizable unsaturated carboxylic acids acid anhydride is 2～2.8 moles, is preferably 2～2.5 moles, more preferably 2～2.2 moles, is preferably 2 moles especially.
The diamantane alcohols that has 4 hydroxyls in use is made the occasion of three ester classes, can use the mixture that forms in following ratio by polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride: with respect to 1 mole of this diamantane alcohols, polymerizable unsaturated carboxylic acids is 3～35 moles, be preferably 3～25 moles, be preferably 3～20 moles especially; The polymerizable unsaturated carboxylic acids acid anhydride is 3～3.8 moles, is preferably 3～3.5 moles, more preferably 3～3.2 moles, is preferably 3 moles especially.
As the mixture of polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride,, can easily reach by product reduction and operation this two aspect easily by using the mixture of above-mentioned scope.
Should illustrate that polymerizable unsaturated carboxylic acids acid anhydride ratio is easier to decompose with the water reaction, generates 2 normal polymerizable unsaturated carboxylic acids.Therefore, when the occasion of having sneaked in raw materials such as diamantane alcohols, polymerizable unsaturated carboxylic acids as the water of impurity, the usage quantity of above-mentioned polymerizable unsaturated carboxylic acids acid anhydride is preferably calculated according to the amount of having removed by water decomposition.
In the occasion of using manufacture method in the past, except generating adamantyl esters of polymerizable unsaturated carboxylic acids, go back the big weight oligomers impurity of by-product as target.Perhaps generate the different plural polymerizable unsaturated carboxylic acid adamantyl esters of gamma value simultaneously, therefore can not only produce adamantyl esters of polymerizable unsaturated carboxylic acids with good selectivity with specific gamma value.Therefore, be difficult to reach in the past and both suppress oligopolymer impurity and generate, be manufactured on the adamantyl esters of polymerizable unsaturated carboxylic acids that intramolecularly has at least one hydroxyl with high yield again as by product.Just can solve the above problems according to manufacture method of the present invention.
(acid catalyst)
In manufacture method of the present invention, above-mentioned " diamantane alcohols " implemented down with the existence that is reflected at acid catalyst of " mixture of polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride ".
As acid catalyst, can there be any known known acid of restrictedly using with acid catalyst function.Specifically, sulfonic acid classes such as preferably sulfuric acid, methylsulfonic acid, Phenylsulfonic acid, tosic acid; Acetate classes such as trifluoroacetic acid, trichoroacetic acid(TCA), tribromoacetic acid etc.In these strong acid, sulfonic acid, sulfuric acid or their mixtures such as preferred especially methylsulfonic acid, Phenylsulfonic acid, tosic acid.These acid catalysts have the effect that high inhibition by product generates, and price is also cheap, and are therefore preferred.
The usage quantity of acid catalyst is not particularly limited, if but very few, then speed of response extremely slows down.If the usage quantity of acid catalyst is too much, then can causes side reaction, thereby the yield of target compound is reduced.Therefore, be benchmark with the quality of the diamantane alcohols that uses in the esterification, the usage quantity of acid catalyst is preferably 0.01～10 quality %, more preferably 0.1～3 quality %.
(stopper)
In general, when in the presence of acid catalyst, using polymerizable unsaturated carboxylic acids to carry out esterification,, polymerizable unsaturated carboxylic acids generation polymerization increases owing to making the growing amount of oligopolymer impurity.
For fear of the generation of this oligopolymer, in manufacture method of the present invention, preferably temperature of reaction is remained on smaller or equal to 70 ℃, in the presence of stopper, react simultaneously.As stopper, can from known stopper, select to use effective stopper aptly.
If illustration is applicable to the stopper among the present invention, can enumerate: phenol system compounds such as quinhydrones, hydroquinone monomethyl ether, 2,6 di tert butyl 4 methyl phenol; Quinone such as benzoquinones, naphthoquinones based compound; Amine compound such as thiodiphenylamine, aniline; 2,2,6,6-tetramethyl piperidine-N--oxyl nitroxyl based compounds such as (oxyl); Copper compounds such as dithiocarbamic acid copper; Sulphur compound; Phosphorus compound; Oxygen; Sumitomo Chemical (strain) system trade(brand)name " ス ミ ラ イ ザ one GM " [compound name: the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-aminomethyl phenyl acrylate], Sumitomo Chemical (strain) system trade(brand)name " ス ミ ラ イ ザ one TP-D " [compound name: tetramethylolmethane four (3-lauryl thiopropionate)], Sumitomo Chemical (strain) system trade(brand)name " ス ミ ラ イ ザ one WX-R " [compound name: 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol)] etc.
These stoppers can be used in combination two or more.
From suppressing the polymeric effect and prevent that the viewpoint of excessive use from considering, be benchmark with the quality of polymerizable unsaturated carboxylic acids, the usage quantity of stopper is preferably 0.01～10 quality %, more preferably 0.01～2 quality %.
(organic solvent)
The reaction of the mixture of polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride and diamantane alcohols can be carried out under any condition in the presence of organic solvent or not.Yet, in the diamantane alcohols, have the material low to the solvability of organic solvent.In this occasion, if with an organic solvent react, speed of response diminishes sometimes.In addition, even in the occasion of using the high organic solvent of the solubleness of diamantane alcohols,, therefore also there is the tendency of speed of response reduction because the concentration of reaction raw materials reduces.And, also can cause undesirable side reaction sometimes.Therefore, above-mentioned reaction among the present invention preferably organic solvent in reaction solution for smaller or equal to 10 quality %, preferably smaller or equal to 5 quality %, be more preferably less than and carry out under the state that equals 1 quality %, particularly preferably in carrying out under the condition that does not have organic solvent.
Should illustrate that as mentioned above, polymerizable unsaturated carboxylic acids has the function as solvent sometimes simultaneously.In this occasion, this polymerizable unsaturated carboxylic acids is not included in the said herein organic solvent.In addition, the reaction raw materials of other that use in the reaction (polymerizable unsaturated carboxylic acids acid anhydride, acid catalyst and stopper) is not included in the said herein organic solvent yet.
(reaction method)
The mixture of polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride and the method for diamantane alcohols reaction are not particularly limited.Each starting compound that for example can enumerate at room temperature specified amount imports in the reaction vessel, and stirring method is carried out on control reaction temperature limit in limit then.The importing of each starting compound is not particularly limited in proper order, but in order to reduce the growing amount of oligopolymer impurity, the preferred last acid catalyst that adds.In addition, reaction can add depress, reduce pressure under, carry out under any condition under the normal pressure, but consider from simplicity, preferably under normal pressure, carry out.
Temperature of reaction more preferably 10～60 ℃, is preferably 20～50 ℃ especially preferably smaller or equal to 70 ℃.By temperature of reaction being remained in the said temperature scope, can suppress the generation of oligopolymer impurity efficiently, in addition, can make the water that generates in the esterification and polymerizable unsaturated carboxylic acids anhydride reactant and remove.
In manufacture method of the present invention, by polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride are also used, their mixture and diamantane alcohols are reacted, even under smaller or equal to 70 ℃ low temperature, also can react with enough big speed of response.Its result, the generation (by-product) of the oligopolymer impurity that is caused by thermopolymerization can suppress to heavens.
Reaction times can be according to other reaction conditions, and the limit confirms that the degree limit that reaction is carried out determines aptly.Usually, the reaction times be preferably 0.5 hour～24 hours.By reacting, can obtain target compound with sufficient transformation efficiency with this reaction times.
(segregation of target compound)
Segregation does not have particular determination as the method for the unsaturated adamantyl esters of polymerizability of target compound from adopt the reaction solution that above-mentioned reaction method obtains.Preferable methods is by the emanate method of target compound of the treatment process that comprises treatment process such as extraction process, partial crystallization operation, adsorption treatment operation.
Specifically, preference method described as follows.
That is, after reaction finishes, in the reaction solution of gained, add organic solvent, the extraction target compound.Then, will remain in polymerizable unsaturated carboxylic acids neutralization in the reaction solution, and make remaining polymerizable unsaturated carboxylic acids acid anhydride resolve into unsaturated carboxylic acid simultaneously and its neutralization by adding alkali aqueous solution.Then, wash above-mentioned organic solvent phase with water, organic solvent and water are emanated.Washing is carried out repeatedly till water becomes neutrality.Then, use sorbent material to carry out adsorption treatment as required after, distillation removes desolvates, and then carries out drying, obtains thick product (containing the polymerizability adamantane esters as target compound more than or equal to 80 quality % usually).
In the isolation operation of above-mentioned target compound, further refining by adopting known method such as partial crystallization (recrystallization), underpressure distillation, steam distillation, sublimation purifying to do, can obtain highly purified target compound.Should illustrate that above-mentioned target compound is liquid sometimes, be solid sometimes, and above-mentioned method for refining can be selected aptly according to these proterties.Under the situation of majority, the monoesters that hydroxyl does not also have is a liquid, is solid in other cases.
(extraction process)
In the method for the unsaturated adamantyl esters of the above-mentioned polymerizability of segregation, the organic solvent that uses as extraction solvent is not particularly limited.From concentrating easily and the easy viewpoint consideration of extracting operation, the preferably solvent of putting down in writing below.
That is, can illustration: halogenated aliphatic hydrocarbon classes such as methylene dichloride, chloroform, tetracol phenixin; Fat hydrocarbons such as hexane, heptane, octane; Halogenated aromatic hydro carbons such as chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene; Ethers such as diethyl ether, diisopropyl ether, di-n-butyl ether, two uncle's butyl ether; Ketone such as butanone, methyl iso-butyl ketone (MIBK); Ester classes such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butylacetate, isobutyl acetate etc.
Wherein, as extraction solvent, preferred especially ester class.In the ester class, from the solubleness of the unsaturated adamantyl esters of polymerizability big and also and the viewpoint that also is difficult in the operation decompose consider preferred especially isobutyl acetate.
The usage quantity of the above-mentioned organic solvent that uses in extraction is not particularly limited.The solubleness of considering the unsaturated adamantyl esters of polymerizability is big and easily concentrated, and with respect to the diamantane alcohols of raw material, the usage quantity of organic solvent is preferably 0.1～100 quality doubly, and especially preferably 0.5～50 quality doubly.
(in and operation)
When the segregation target compound, preferably undertaken: will remain in the polymerizable unsaturated carboxylic acids neutralization in the reaction solution by following step, make remaining polymerizable unsaturated carboxylic acids acid anhydride be decomposed into polymerizable unsaturated carboxylic acids simultaneously, and then will decompose the polymerizable unsaturated carboxylic acids neutralization that generates, carried out the target compound of emanating under the neutral state at this.Preferably after above-mentioned extraction process, carry out with operation in being somebody's turn to do.
Specifically, undertaken by in the solution that contains the unsaturated adamantyl esters of polymerizability (hereinafter being also referred to as extraction liquid), adding alkali aqueous solution with operation in this.Wherein, the alkali aqueous solution as using can use known alkali aqueous solution.For example can enumerate: aqueous sodium hydroxide solution, potassium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical etc.The concentration of alkali aqueous solution does not have particular restriction, can use 5～50% the aqueous solution usually.In addition, neutralization preferably make the pH of water layer and organic layer be 5～9, preferred 6～8, be preferably 7 especially and carry out.Then, wash organic phase with water, with organic phase and aqueous phase separation.In addition, when the occasion of the separation difficulty of organic layer and water layer, can use salt solution etc. to make to separate and become easy.
(absorption process)
Target compound of the present invention was colourless originally.But, from through above-mentioned extraction process and and to remove the compound that obtains that desolvates in the solution that obtains of operation be colored as a rule.And, even thisly paintedly also be difficult to it is removed fully by the partial crystallization operation.Therefore, this painted in order to remove, preferably use the sorbent material processing of decolouring.
In absorption process, can use known sorbent material.Can enumerate particularly: activated carbon treatment, silica dioxide gel processing, activated alumina processing etc.The usage quantity of sorbent material is not particularly limited, with respect to the diamantane alcohols of raw material be 0.001～2 quality doubly, be preferably 0.005～1 quality doubly, be preferably 0.01～0.5 quality especially doubly.In addition, the adsorption treatment time is not particularly limited, but can handle fully in 0.5～48 hour usually.In addition, the temperature during adsorption treatment also is not particularly limited, and can handle fully under 0～50 ℃ usually.
Should illustrate, in absorption process, can carry out adsorption treatment by extraction solvent being exchanged into other solvents.Carry out the occasion of adsorption treatment by the exchange solvent, utilize extraction solvent to carry out adsorption treatment can not carry out sufficient purified occasion even be.Usually because of the method for using extraction solvent to carry out adsorption treatment can shorten manufacturing process, therefore preferred.In return the solvent of usefulness can unrestrictedly use known solvent, for example by the lower solvent of fat hydrocarbon polarity such as heptane until methyl alcohol, acetonitrile, the higher solvent of water isopolarity.
(partial crystallization operation)
The most occasions of target compound are solid at normal temperatures.Therefore,,, preferably utilize organic solvent that it is dissolved for by removing the thick product that desolvates and obtain in such occasion, by the partial crystallization operation of recrystallization that thick product is further refining then.The partial crystallization operation is preferably carried out after the adsorption treatment operation of utilizing sorbent material to handle.
The organic solvent that uses when partial crystallization is not particularly limited so long as dissolve the solvent of thick product and get final product.Reason is considered to access the unsaturated adamantyl esters of highly purified polymerizability and obtain easily after partial crystallization etc., preferably the solvent of putting down in writing below.
Halogenated aliphatic hydrocarbon classes such as methylene dichloride, chloroform, tetracol phenixin; Fat hydrocarbons such as hexane, heptane, octane; Halogenated aromatic hydro carbons such as chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene; Ethers such as diethyl ether, diisopropyl ether, di-n-butyl ether, two uncle's butyl ether; Ketones such as acetone, butanone, methyl iso-butyl ketone (MIBK); Ester classes such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butylacetate, isobutyl acetate etc.
Can two or more be used in combination with these organic solvents.In these solvents, consider from the aspect that the required quantity of solvent of partial crystallization can be lacked, more preferably ethers, especially preferably diisopropyl ether.Usage quantity to the organic solvent in the partial crystallization operation is not particularly limited.If consider the solubleness of the unsaturated adamantyl esters of polymerizability and the balance of the purity and the rate of recovery, then with respect to the diamantane alcohols of raw material, preferably use 0.1～10 quality doubly, especially preferably use 0.5～5 quality organic solvent doubly.Perhaps,,, preferably use 0.1～15 quality doubly, especially preferably use 0.5～10 quality organic solvent doubly with respect to this thick product when being the occasion of benchmark with the thick product of adamantyl esters of polymerizable unsaturated carboxylic acids that obtains.
(adamantyl esters of polymerizable unsaturated carboxylic acids)
The adamantyl esters of polymerizable unsaturated carboxylic acids that can make as stated above (target compound) is the resultant of reaction of diamantane alcohols and polymerizable unsaturated carboxylic acids and/or polymerizable unsaturated carboxylic acids acid anhydride.Therefore, the adamantyl esters of polymerizable unsaturated carboxylic acids that obtains as stated above has and the corresponding chemical structure of using of starting compound.
When the occasion of the diamantane alcohols that uses as polyalcohols such as di-alcohols, ternary alcohols, use the adamantyl esters of polymerizable unsaturated carboxylic acids of these starting compound manufacturings to be not only the monoesters class, also comprise the product of high order esterifications such as diester class, three ester classes.
In the adamantyl esters of polymerizable unsaturated carboxylic acids of making as stated above, from the considerations such as viewpoint of industrial applicibility, preferably by the compound shown in the following formula (5).
(in the formula, R
9, R
10, R
11And R
12Be the group of hydrogen atom, hydroxyl, low alkyl group (alkyl of preferred carbonatoms 1～5) or following formula (6) expression independently of one another, at R
9, R
10, R
11And R
12In at least one is the group of above-mentioned formula (6) expression).
(in the formula, R
13Be to have substituent polymerizability unsaturated alkyl).
R
13With above-mentioned R
7And/or R
8Identical.
As such polymerizability adamantyl esters, can enumerate: vinylformic acid 1-adamantane esters, methacrylic acid 1-adamantane esters, vinylformic acid 2-adamantane esters, methacrylic acid 2-adamantane esters, vinylformic acid 3-hydroxyl-1-adamantane esters, methacrylic acid 3-hydroxyl-1-adamantane esters, vinylformic acid 4-hydroxyl-1-adamantane esters, methacrylic acid 4-hydroxyl-1-adamantane esters, vinylformic acid 3-methyl isophthalic acid-adamantane esters, methacrylic acid 3-methyl isophthalic acid-adamantane esters, vinylformic acid 3-ethyl-1-adamantane esters, methacrylic acid 3-ethyl-1-adamantane esters, vinylformic acid 3-hydroxy-2-methyl-1-adamantane esters, methacrylic acid 3-hydroxy-2-methyl-1-adamantane esters, vinylformic acid 3-hydroxyl-2-ethyl-1-adamantane esters, methacrylic acid 3-hydroxyl-2-ethyl-1-adamantane esters, vinylformic acid 3-hydroxy-5-methyl base-1-adamantane esters, methacrylic acid 3-hydroxy-5-methyl base-1-adamantane esters, vinylformic acid 3-hydroxyl-5-ethyl-1-adamantane esters, methacrylic acid 3-hydroxyl-5-ethyl-1-adamantane esters, vinylformic acid 3-hydroxyl-5-propyl group-1-adamantane esters, methacrylic acid 3-hydroxyl-5-propyl group-1-adamantane esters, 2-ethylacrylic acid 3-hydroxyl-1-adamantane esters, 2-propyl group vinylformic acid 3-hydroxyl-1-adamantane esters, vinylformic acid 3-hydroxyl-5,7-dimethyl-1-adamantane esters, methacrylic acid 3-hydroxyl-5,7-dimethyl-1-adamantane esters, vinylformic acid 3-hydroxyl-5,7-diethyl-1-adamantane esters, methacrylic acid 3-hydroxyl-5,7-diethyl-1-adamantane esters, vinylformic acid 3-hydroxyl-5-ethyl-7-methyl isophthalic acid-adamantane esters, methacrylic acid 3-hydroxyl-5-ethyl-adamantyl monoesters classes such as 7-methyl isophthalic acid-adamantane esters; 1, the two acryloxy diamantane, 1 of 3-, two (methacryloxy) diamantane of 3-, 5-hydroxyl-1, the two acryloxy diamantane of 3-, 5-hydroxyl-1, two (methacryloxy) diamantane, 5 of 3-, 7-dimethyl-1, the two acryloxy diamantane, 5 of 3-, 7-dimethyl-1, diamantane diester classes such as two (methacryloxy) diamantane of 3-; 1,3,5-three acryloxy diamantane, 1,3, diamantane three ester classes such as 5-three (methacryloxy) diamantane etc.
In these compounds, the 3-hydroxyadamantane base monoesters class of preferred especially following formula (7) expression.
(in the formula, R
14, R
15Be hydrogen atom or low alkyl group independently of one another, R
16For having substituent polymerizability unsaturated alkyl).
R
16With above-mentioned R
7And/or R
8Identical.
In above-claimed cpd, preferred especially vinylformic acid 3-hydroxyl-1-adamantane esters, methacrylic acid 3-hydroxyl-1-adamantane esters, vinylformic acid 3-hydroxyl-5,7-dimethyl-1-adamantane esters, methacrylic acid 3-hydroxyl-5,7-dimethyl-1-adamantane esters.
Embodiment
Be described more specifically the present invention below by embodiment, but the present invention is not subjected to any restriction of these embodiment.
Embodiment 1
In the four-hole boiling flask of 1000ml, add 1, (2.778 moles, 1 of 3-diamantane glycol 50.0g (0.298 mole), vinylformic acid 200g, 9.3 times of molar weights of 3-diamantane glycol), acrylic anhydride 37.6g is (0.298 mole, 1,1 times of molar weight of 3-diamantane glycol), thiodiphenylamine 1.0g (for acrylic acid 0.5 quality %), vitriol oil 0.5g (are 1,1 quality % of 3-diamantane glycol), 50 ℃ of following heated and stirred 4 hours.Initial owing to existence 1, the insoluble part of 3-diamantane glycol, reaction solution is suspended state, and along with the carrying out of reaction, reaction solution becomes transparent homogeneous solution at leisure.It is filbert that reaction solution is.
Reaction is cooled to room temperature with reaction solution after finishing.Add the isobutyl acetate 200g as extraction solvent in reaction solution, the extraction target product separates the organic phase of gained.The aqueous sodium hydroxide solution 620g that in organic phase, splashes into 20 quality % with the organic phase washing after, with 10 quality % salt solution 200ml organic phase is washed again, wash with pure water 200ml then.Distillation removes and desolvates, and has obtained the thick product of vinylformic acid 3-hydroxyl-1-adamantane esters.This thick product is dissolved under 50 ℃ in the normal heptane of 250g, with temperature be reduced at leisure 3 ℃ so that crystallization separate out.Collection is filtered in crystallization, obtained the faint yellow solid of 39g (yield 59%).This solid is used GC that has hydrogen flame ionization detector and the gpc analysis that has differential formula RI-detector.The GC analytical results shows that the amount of vinylformic acid 3-hydroxyl-1-adamantane esters (GC purity) is 99%; Gpc analysis is the result show, the amount of oligopolymer impurity is 0.2 quality % (being converted into polystyrene).
Embodiment 2～4
Except acid catalyst being changed to the acid catalyst shown in the table 1, operation similarly to Example 1.It the results are shown in the table 1.
Table 1
Embodiment 5
In embodiment 1, use the methacrylic acid substitution vinylformic acid of identical weight (200g), use methacrylic anhydride 45.9g (0.298 mole, 1,1 times of molar weight of 3-diamantane glycol) to replace acrylic anhydride, similarly to Example 1 operation.Behind the partial crystallization, obtain the faint yellow solid of 42g (yield 60%).This solid is used GC and gpc analysis.The GC analytical results shows that the amount of methacrylic acid 3-hydroxyl-1-adamantane esters is 99%; Gpc analysis is the result show, the amount of oligopolymer impurity is 0.1 quality % (being converted into polystyrene).
Embodiment 6～8
Except acid catalyst being changed to the acid catalyst shown in the table 2, operation similarly to Example 5.It the results are shown in the table 2.
Table 2
Embodiment 9
Except using acrylic anhydride 75.1g (0.596 mole, 1,2 times of molar weights of 3-diamantane glycol), use methyl alcohol to replace normal heptane, operation similarly to Example 1 as beyond the partial crystallization solvent.Behind the partial crystallization, obtain the faint yellow solid of 54g (yield 66%).This solid is used GC and gpc analysis.The GC analytical results shows, 1, and the amount of the two acryloxy diamantane of 3-is 99%, and gpc analysis is the result show, and the amount of oligopolymer impurity is 0.2 quality % (being converted into polystyrene).
Embodiment 10～12
Except acid catalyst being changed to the acid catalyst shown in the table 3, operation similarly to Example 9.It the results are shown in the table 3.
Table 3
Embodiment 13
Except using methacrylic anhydride 91.8g (0.596 mole, 1,2 times of molar weights of 3-diamantane glycol), use methyl alcohol to replace normal heptane, operation similarly to Example 5 as beyond the partial crystallization solvent.Behind the partial crystallization, obtain the faint yellow solid of 62g (yield 68%).This solid is used GC and gpc analysis.The GC analytical results shows, 1, and the amount of two (methacryloxy) diamantane of 3-is 99%, and gpc analysis is the result show, and the amount of oligopolymer impurity is 0.1 quality % (being converted into polystyrene).
Embodiment 14～16
Except acid catalyst being changed to the acid catalyst shown in the table 4, operation similarly to Example 13.It the results are shown in the table 4.
Table 4
Embodiment 17
In the four-hole boiling flask of 1000ml, add 1-adamantanol 50.0g (0.329 mole), vinylformic acid 100g 4.2 times of molar weights of 1-adamantanol (1.389 moles), acrylic anhydride 41.5g 1 times of molar weight of 1-adamantanol (0.329 mole), thiodiphenylamine 0.5g (being acrylic acid 0.5 quality %), vitriol oil 0.5g (for 1 quality % of 1-adamantanol).50 ℃ of following heated and stirred 4 hours.The reaction solution that obtains is filbert.
After the reaction, reaction solution is cooled to room temperature, adds isobutyl acetate 100g.To the aqueous sodium hydroxide solution 345g of the 20 quality % that wherein drip, the washing organic phase.And then, with the salt solution 100ml washing organic phase of 10 quality %, then with pure water 100ml washing.With the organic phase underpressure distillation, obtain the colourless transparent liquid of 47g (yield 69%).With this liquid GC and gpc analysis.The GC analytical results shows that the amount of vinylformic acid 1-adamantane esters is 99%; Gpc analysis is the result show, the amount of oligopolymer impurity is 0.2 quality % (being converted into polystyrene).
Embodiment 18～20
Except acid catalyst being changed to the acid catalyst shown in the table 5, operation similarly to Example 17.It the results are shown in the table 5.
Table 5
Embodiment 21
In embodiment 17,, use methacrylic anhydride 50.7g 1 times of molar weight of 1-adamantanol (0.329 mole) to replace outside the acrylic anhydride operation similarly to Example 17 except using 100g methacrylic acid substitution vinylformic acid.After the underpressure distillation, obtain the colourless transparent liquid of 52g (yield 72%).With this liquid GC and gpc analysis.The GC analytical results shows that the amount of methacrylic acid 1-adamantane esters is 99%; Gpc analysis is the result show, the amount of oligopolymer impurity is 0.1 quality % (being converted into polystyrene).
Embodiment 22～24
Except acid catalyst being changed to the acid catalyst shown in the table 6, operation similarly to Example 21.It the results are shown in the table 6.
Table 6
Embodiment 25
Operation obtains reaction solution similarly to Example 1.Use isobutyl acetate to carry out extracting operation similarly to Example 1, obtain the isobutyl acetate solution of vinylformic acid 3-hydroxyl-1-adamantane esters.In this solution, add gac 5g (be 1 of raw material, 0.1 quality of 3-diamantane glycol doubly), at room temperature carry out stirring in 3 hours.Then, remove by filter gac, obtain the isobutyl acetate solution of transparent vinylformic acid 3-hydroxyl-1-adamantane esters.Add hydroquinone monomethyl ether 0.25g (being 1 of raw material, 0.5 quality % of 3-diamantane glycol) in isobutyl acetate solution, concentrating under reduced pressure then obtains the thick product of vinylformic acid 3-hydroxyl-1-adamantane esters.In the thick product of vinylformic acid 3-hydroxyl-1-adamantane esters, add diisopropyl ether 100g (be 1 of raw material, 2 quality of 3-diamantane glycol doubly), 40 ℃ of dissolvings down.With the temperature of this solution be reduced at leisure 3 ℃ so that crystallization separate out.The slaking after-filtration obtains the colorless solid of 39g (yield 59%).With this solid GC and gpc analysis.The GC analytical results shows that the amount of vinylformic acid 3-hydroxyl-1-adamantane esters is 99%; Gpc analysis is the result show, the amount of oligopolymer impurity is 0.2 quality % (being converted into polystyrene).
Embodiment 26～28
Except stopper being changed to the stopper shown in the table 7, operation similarly to Example 25.What obtain the results are shown in the table 7.
Table 7
*Trade(brand)name, Sumitomo Chemical (strain) system
Embodiment 29～32
Except acid catalyst being changed to the acid catalyst shown in the table 8, operation similarly to Example 25.What obtain the results are shown in the table 8.
Table 8
Embodiment 33
Operation obtains reaction solution similarly to Example 5.Carry out extracting operation similarly to Example 5, obtain the isobutyl acetate solution of methacrylic acid 3-hydroxyl-1-adamantane esters.In this solution, add gac 5g (be 1 of raw material, 0.1 quality of 3-diamantane glycol doubly), at room temperature carry out stirring in 3 hours.
Remove by filter gac, obtain the isobutyl acetate solution of transparent methacrylic acid 3-hydroxyl-1-adamantane esters.Add hydroquinone monomethyl ether 0.25g (being 1 of raw material, 0.5 quality % of 3-diamantane glycol) in isobutyl acetate solution, concentrating under reduced pressure obtains the thick product of methacrylic acid 3-hydroxyl-1-adamantane esters.In thick product, add diisopropyl ether 100g (be 1 of raw material, 2 quality of 3-diamantane glycol doubly), be heated to 40 ℃ of dissolvings.With temperature be reduced at leisure 3 ℃ so that crystallization separate out.The crystallization of slaking after-filtration obtains the colorless solid of 41g (yield 58%).With this solid GC and gpc analysis.The GC analytical results shows that the amount of methacrylic acid 3-hydroxyl-1-adamantane esters is 99%; Gpc analysis is the result show, the amount of oligopolymer impurity is 0.1 quality % (being converted into polystyrene).
Embodiment 34～36
Except stopper being changed to the stopper shown in the table 9, similarly operate with embodiment 33.What obtain the results are shown in the table 9.
Table 9
*Trade(brand)name, Sumitomo Chemical (strain) system
Embodiment 37～39
Except temperature of reaction and reaction times are changed to the data shown in the table 10, operation similarly to Example 25.What obtain the results are shown in the table 10.
Table 10
Embodiment 40～42
Except temperature of reaction and reaction times are changed to the data shown in the table 11, similarly operate with embodiment 33.What obtain the results are shown in the table 11.
Table 11
Embodiment 43
In the four-hole boiling flask of 1000ml, add 1,3, (4.08 moles, 1 of 5-diamantane triol 36.8g (0.20 mole), vinylformic acid 294g, 3,20.4 times of molar weights of 5-diamantane triol), acrylic anhydride 25.2g is (0.20 mole, 1,3,1 times of molar weight of 5-diamantane triol), thiodiphenylamine 1.47g (for acrylic acid 0.5 quality %), vitriol oil 0.37g (are 1,3,1 quality % of 5-diamantane triol), 50 ℃ of following heated and stirred 10 hours.Initial owing to existence 1,3, the insoluble part of 5-diamantane triol, reaction solution is suspended state.But along with the carrying out of reaction, reaction solution becomes transparent homogeneous solution at leisure.It is filbert that reaction solution is.
Reaction is cooled to room temperature with reaction solution after finishing.In reaction solution, add isobutyl acetate 400g as extraction solvent.To the 20 quality % aqueous sodium hydroxide solution 860g that wherein drip, the washing organic phase.With 10 quality % salt solution 200ml and then with pure water 200ml washing organic phase.Obtain vinylformic acid 3, the isobutyl acetate solution of 5-dihydroxyl-1-adamantane esters.
In this solution, add gac 3.7g (be 1,3 of raw material, 0.1 quality of 5-diamantane triol doubly), at room temperature carry out stirring in 3 hours.Remove by filter gac then, obtain transparent vinylformic acid 3, the isobutyl acetate solution of 5-dihydroxyl-1-adamantane esters.Then, add hydroquinone monomethyl ether 0.18g (being 1,3 of raw material, 0.5 quality % of 5-diamantane triol) in isobutyl acetate solution, concentrating under reduced pressure obtains vinylformic acid 3, the thick product of 5-dihydroxyl-1-adamantane esters.In this thick product, add diisopropyl ether 110.4g (be 1,3 of raw material, 3 quality of 5-diamantane triol doubly), be heated to 40 ℃ of dissolvings.With temperature be reduced at leisure 3 ℃ so that crystallization separate out.The slaking after-filtration is collected crystalline product, obtains the colorless solid of 19g (yield 40%).With this solid GC and gpc analysis.The GC analytical results shows, vinylformic acid 3, and the amount of 5-dihydroxyl-1-adamantane esters is 99%; Gpc analysis is the result show, the amount of oligopolymer impurity is 0.2 quality % (being converted into polystyrene).
Embodiment 44～46
Except acid catalyst being changed to the acid catalyst shown in the table 12, similarly operate with embodiment 43.What obtain the results are shown in the table 12.
Table 12
Embodiment 47
In embodiment 43, except the methacrylic acid substitution vinylformic acid of use, use (0.20 mole, 1,3 of methacrylic anhydride 30.8g with vinylformic acid equal in quality 294g, 1 times of molar weight of 5-diamantane triol) replaces similarly operating with embodiment 43 outside the acrylic anhydride.Behind the partial crystallization, obtain the colorless solid of 20g (yield 40%).With this solid GC and gpc analysis.The GC analytical results shows, methacrylic acid 3, and the containing ratio of 5-dihydroxyl-1-adamantane esters is 99%; The amount of oligopolymer impurity is 0.1 quality % (being converted into polystyrene).
Embodiment 48～50
Except acid catalyst being changed to the acid catalyst shown in the table 13, similarly operate with embodiment 47.What obtain the results are shown in the table 13.
Table 13
Embodiment 51
In the four-hole boiling flask of 1000ml, add 5,7-dimethyl-1, (2.18 moles, 5 of 3-diamantane glycol 39.2g (0.20 mole), vinylformic acid 156.8g, 7-dimethyl-1,10.9 times of molar weights of 3-diamantane glycol), acrylic anhydride 25.2g is (0.20 mole, 5,7-dimethyl-1,1 times of molar weight of 3-diamantane glycol), thiodiphenylamine 0.78g (for acrylic acid 0.5 quality %), vitriol oil 0.39g (are 5,7-dimethyl-1,1 quality % of 3-diamantane glycol), 50 ℃ of following heated and stirred 5 hours, obtain hazel reaction solution.
After the reaction, reaction solution is cooled to room temperature, adds isobutyl acetate 160g as extraction solvent.In reaction solution, the drip aqueous sodium hydroxide solution 860g of 20 quality %, the washing organic phase.With 10 quality % salt solution 200ml, and then, obtain vinylformic acid 5, the isobutyl acetate solution of 7-dimethyl-3-hydroxyl-1-adamantane esters with pure water 200ml washing organic phase.
Adding gac 3.9g in this solution (be 5 of raw material, 7-dimethyl-1,0.1 quality of 3-diamantane glycol is doubly), at room temperature carry out stirring in 3 hours.Then, remove by filter gac, obtain transparent vinylformic acid 5, the isobutyl acetate solution of 7-dimethyl-3-hydroxyl-1-adamantane esters.
Add hydroquinone monomethyl ether 0.20g (being 5 of raw material, 7-dimethyl-1,0.5 quality % of 3-diamantane glycol) in this solution, concentrating under reduced pressure obtains vinylformic acid 5, the thick product of 7-dimethyl-3-hydroxyl-1-adamantane esters.Adding diisopropyl ether 78.4g in thick product (be 5 of raw material, 7-dimethyl-1,2 quality of 3-diamantane glycol are doubly), be heated to 40 ℃ of dissolvings.With temperature be reduced at leisure 3 ℃ so that crystallization separate out.The slaking after-filtration obtains the colorless solid of 30g (yield 60%).With this solid GC and gpc analysis.The GC analytical results shows, vinylformic acid 5, and the amount of 7-dimethyl-3-hydroxyl-1-adamantane esters is 99%; The amount of oligopolymer impurity is 0.2 quality % (being converted into polystyrene).
Embodiment 52
In embodiment 51, (0.20 mole is 5,7-dimethyl-1 except using methacrylic acid 156.8g to replace vinylformic acid and use methacrylic anhydride 30.8g, 1 times of molar weight of 3-diamantane glycol) replaces similarly operating with embodiment 51 outside the acrylic anhydride.Behind the partial crystallization, obtain the colorless solid of 34g (yield 64%).With this solid GC and gpc analysis.The GC analytical results shows, methacrylic acid 5, and the containing ratio of 7-dimethyl-3-hydroxyl-1-adamantane esters is 99%; Gpc analysis is the result show, the amount of oligopolymer impurity is 0.1 quality % (being converted into polystyrene).
Embodiment 53
In embodiment 25, except using 45.0g acrylic anhydride (0.357 mole is 1,1.2 times of molar weights of 3-diamantane glycol) in addition, operation similarly to Example 25.Behind the partial crystallization, obtain the colorless solid of 38g (yield 57%).With this solid GC and gpc analysis.The GC analytical results shows that the containing ratio of vinylformic acid-3-hydroxyl-1-adamantane esters is 99%; The amount of oligopolymer impurity is 0.2 quality % (being converted into polystyrene).
Embodiment 54
In embodiment 25, the acrylic anhydride 39.5g (0.298 mole is 1,1 times of molar weight of 3-diamantane glycol) that contains 5 quality % methylene dichloride except use in addition, operation similarly to Example 25.Behind the partial crystallization, obtain the colorless solid of 39g (yield 59%).With this solid GC and gpc analysis.The GC analytical results shows that the containing ratio of vinylformic acid-3-hydroxyl-1-adamantane esters is 99%; The amount of oligopolymer impurity is 0.2 quality % (being converted into polystyrene).
Comparative example 1
With the four-hole boiling flask of the 1000ml of Dean-Rodney Stark pipe coupling in add 1, (0.894 mole of 3-diamantane glycol 50g (0.298 mole), toluene 250ml, vinylformic acid 64.4g, be 1,3 times of molar weights of 3-diamantane glycol), thiodiphenylamine 1.0g (is 1,2 quality % of 3-diamantane glycol), vitriol oil 1.0g (is 1,2 quality % of 3-diamantane glycol), the limit feeds the nitrogen limit 90 ℃ of stirrings down.During this period, the steam of generation is liquefied by condenser, utilize Dean-Rodney Stark pipe, be back in the flask except that after anhydrating.After 15 hours, 1,3 diamantane glycol is a suspended state.Add new vitriol oil 2.0g, reacted again 30 hours.After 30 hours, 1, the suspended state of 3-diamantane glycol is eliminated.But can observe, have a large amount of insolubless to adhere in flask interior.Carry out aftertreatment similarly to Example 1, but resultant of reaction there is not crystallization.This solution decompression is concentrated, obtain the dope of 500g.With gained dope GC and gpc analysis.The GC analytical results shows that the amount of vinylformic acid 3-hydroxyl-1-adamantane esters is 74%; Gpc analysis is the result show, the amount of oligopolymer impurity is 6.0 quality % (being converted into polystyrene).
Comparative example 2
In the four-hole boiling flask of 1000ml, add 1, (0.298 mole of 3-diamantane glycol 50.0g (0.298 mole), vinylformic acid 21.5g, be 1,1 times of molar weight of 3-diamantane glycol), thiodiphenylamine 1.0g (for acrylic acid 0.5 quality %), vitriol oil 0.5g (are 1,1 quality % of 3-diamantane glycol), stirred 50 hours down at 50 ℃.
Last from first arrival, 1 in the reaction solution, the insoluble part of 3-diamantane glycol is the state that suspends all the time.Can not obtain vinylformic acid 3-hydroxyl-1-adamantane esters as target.
Comparative example 3
For fear of the suspended state of the reaction solution that in comparative example 2, takes place, add toluene 200g (1,4 quality of 3-diamantane glycol doubly) and, in addition similarly operate with comparative example 2 as solvent.But, last from first arrival, 1 in the reaction solution, the insoluble part of 3-diamantane glycol is suspended state all the time, can not obtain the vinylformic acid 3-hydroxyl-1-adamantane esters as target.
Comparative example 4
In the four-hole boiling flask of 1000ml, add 1, (0.298 mole of 3-diamantane glycol 50.0g (0.298 mole), acrylic anhydride 37.6g, be 1,1 times of molar weight of 3-diamantane glycol), thiodiphenylamine 1.0g (for acrylic acid 0.5 quality %), vitriol oil 0.5g (are 1,1 quality % of 3-diamantane glycol), stirred 50 hours down at 50 ℃.
Last from first arrival, 1 in the reaction solution, the insoluble part of 3-diamantane glycol is the state that suspends all the time.Can not obtain vinylformic acid 3-hydroxyl-1-adamantane esters as target.
Comparative example 5
For fear of the suspended state of the reaction solution that in comparative example 4, takes place, add toluene 200g (be 1,4 quality of 3-diamantane glycol doubly) and, in addition similarly operate with comparative example 4 as solvent.But, last from first arrival, 1 in the reaction solution, the insoluble part of 3-diamantane glycol is suspended state all the time, can not obtain the vinylformic acid 3-hydroxyl-1-adamantane esters as target.
Claims (6)
1. the manufacture method of adamantyl esters of polymerizable unsaturated carboxylic acids, it is characterized in that comprising: in the presence of acid catalyst and stopper, make the diamantane alcohols that has n hydroxyl in the molecule, with under smaller or equal to 70 ℃ temperature, react for the polymerizable unsaturated carboxylic acids of m～35 mole with respect to 1 mole of the diamantane alcohols of the above-mentioned n of a having hydroxyl mixture with respect to 1 mole of the diamantane alcohols of the above-mentioned n of a having hydroxyl for m～(m+0.8) mole polymerizable unsaturated carboxylic acids acid anhydride, make m hydroxy esterification in n the hydroxyl that above-mentioned diamantane alcohols has, thereby make the esterification step that intramolecularly has the adamantyl esters of polymerizable unsaturated carboxylic acids of (n-m) individual hydroxyl, wherein n is 2～4 integer, m represents 1～(n-1) integer
Wherein above-mentioned diamantane alcohols is the compound of following formula (1) expression,
In the formula, R
1, R
2, R
3And R
4The alkyl of representing hydrogen atom, hydroxyl or carbonatoms 1～5 independently of one another, R
1To R
4In at least two be hydroxyl,
Above-mentioned polymerizable unsaturated carboxylic acids is the compound of following formula (3) expression,
In the formula, R
7For having or do not have the polymerizability unsaturated alkyl of substituent carbonatoms 2～5, above-mentioned substituting group is the alkoxyl group of 1～5 in cyano group, halogen atom, carbonatoms,
Above-mentioned polymerizable unsaturated carboxylic acids acid anhydride is the compound of following formula (4) expression,
In the formula, R
8For having or do not have the polymerizability unsaturated alkyl of substituent carbonatoms 2～5, above-mentioned substituting group is the alkoxyl group of 1～5 in cyano group, halogen atom, carbonatoms.
2. the manufacture method of adamantyl esters of polymerizable unsaturated carboxylic acids as claimed in claim 1, wherein the diamantane alcohols is the diamantane glycols of following formula (2) expression,
In the formula, R
5And R
6Be the alkyl of hydrogen atom or carbonatoms 1～5 independently of one another.
3. the manufacture method of adamantyl esters of polymerizable unsaturated carboxylic acids as claimed in claim 1, wherein the mixture of polymerizable unsaturated carboxylic acids and polymerizable unsaturated carboxylic acids acid anhydride is the mixture of vinylformic acid and acrylic anhydride or the mixture of methacrylic acid and methacrylic anhydride.
4. the manufacture method of adamantyl esters of polymerizable unsaturated carboxylic acids as claimed in claim 1, wherein being reflected under the condition that does not have organic solvent of esterification step carried out.
5. the manufacture method of adamantyl esters of polymerizable unsaturated carboxylic acids as claimed in claim 1, wherein also comprise: the extraction process of thick product of extraction adamantyl esters of polymerizable unsaturated carboxylic acids from the reaction solution that obtains by esterification step, and make the thick product of the adamantyl esters of polymerizable unsaturated carboxylic acids by this extraction process extraction carry out the partial crystallization operation of partial crystallization.
6. the manufacture method of adamantyl esters of polymerizable unsaturated carboxylic acids as claimed in claim 1, wherein also comprise: the extraction process of the thick product of extraction adamantyl esters of polymerizable unsaturated carboxylic acids from the reaction solution that obtains by esterification step, the adsorption treatment operation of using sorbent material that the thick product of the adamantyl esters of polymerizable unsaturated carboxylic acids by this extraction process extraction is handled, and make the partial crystallization operation of carrying out partial crystallization through the thick product of this adsorption treatment operation.
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| WO2001030739A1 (en) * | 1999-10-27 | 2001-05-03 | Daicel Chemical Industries, Ltd. | Process for the production of adamantyl (meth)acrylates |
| JP2001192356A (en) * | 1999-10-27 | 2001-07-17 | Daicel Chem Ind Ltd | Method for producing (meth)acrylic acid ester having cyclic skeleton |
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| WO2001030739A1 (en) * | 1999-10-27 | 2001-05-03 | Daicel Chemical Industries, Ltd. | Process for the production of adamantyl (meth)acrylates |
| JP2001192356A (en) * | 1999-10-27 | 2001-07-17 | Daicel Chem Ind Ltd | Method for producing (meth)acrylic acid ester having cyclic skeleton |
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