JP6614996B2 - Method for producing polymerizable monomer - Google Patents

Description

  The present invention relates to a novel method for producing a polymerizable monomer.

  (Meth) acrylate-based polymerizable monomers include dental hardened compositions such as dental materials such as dental adhesives, optical materials, printing plate making, photoresist materials, paints, adhesives, inks, and optical modeling resins. (Patent documents 1 to 4). In particular, as a (meth) acrylate polymerizable monomer from which a cured product having excellent mechanical strength can be obtained, bisphenol A diglycidyl di (meth) acrylate (hereinafter sometimes abbreviated as Bis-GMA) (for example, a patent) Documents 2 and 3) and bisphenol A polyethoxydi (meth) acrylate (hereinafter sometimes abbreviated as Bis-MPEPP) (for example, see Patent Document 2) are known. In addition, a polymerizable monomer having a biphenyl skeleton is known (see, for example, Patent Document 4).

  In general, such a (meth) acrylate polymerizable monomer is often used as a mixed composition mixed with other components depending on the intended use. At that time, from the viewpoint of easy handling, it is advantageous that the mixed composition of polymerizable monomers has a low viscosity in a room temperature environment.

  However, in Bis-GMA, in addition to the rigid structure derived from the bisphenol A skeleton, the presence of a hydroxyl group in the molecule causes intermolecular hydrogen bonding, and the mixed composition has a relatively high viscosity at room temperature. .

On the other hand, Bis-MPEPP is a polymerizable monomer having a relatively low viscosity because it does not have a hydroxyl group in the molecule and therefore does not form a hydrogen bond between molecules. However, Bis-MPEPP also has room for improvement depending on the application. Specifically, the polymerizable monomer is often used in a mixture with a polymerization initiator, an inorganic filler, and the like.
When using for a dental hardening composition, a polymerizable monomer, a polymerization initiator, and an inorganic filler may be mixed and used. In general, since inorganic fillers are relatively hydrophilic, they hardly interact with hydrophobic polymerizable monomers such as Bis-MPEPP. Therefore, the dental curable composition in which Bis-MPEPP and an inorganic filler are mixed may increase in viscosity, and there is room for improvement.

  In order to solve the above problems, a compound represented by the following general formula (6) has been developed as a relatively hydrophilic polymerizable monomer having no hydroxyl group and the like while maintaining mechanical strength. (For example, refer to Patent Document 4).

  The polymerizable monomer represented by the general formula (6) has a biphenyl skeleton, and has high mechanical strength like Bis-GMA and Bis-MPEPP. Moreover, since it does not have a hydroxyl group in a molecule | numerator, there is no formation of the hydrogen bond between molecules and the high viscosity of the mixed composition of a polymerizable monomer is suppressed. On the other hand, it is more hydrophilic than Bis-MPEPP due to the effect of having a benzoate skeleton (ester group), and the viscosity increase when mixed with an inorganic filler to form a dental hardened composition is also suppressed. have.

  As a synthesis example of a benzoate type polymerizable monomer represented by the general formula (6), the following synthesis method (1) is shown.

In the synthesis method (1), a dicarboxylic acid and a chlorinating reagent such as thionyl chloride (SOCl ₂ ) are reacted to synthesize a carboxylic acid chloride, and then the carboxylic acid chloride and the hydroxyalkyl methacrylate are converted into triethylamine (Et ₃ N). The method of making it react on basic conditions like this is used.

Special table 2008-534256 JP 2007-126417 A JP-A-9-157124 JP 5-170705 A

  However, according to the study by the present inventors, when a cured body of a dental curing composition using the polymerizable monomer of the general formula (6) synthesized by the synthesis method (1) is stored in water. It has been found that the strength of the cured product may decrease. The cause of this is not clear, but is estimated as follows. That is, in the synthesis method (1), it is predicted that one of the causes is that a compound represented by the following general formula (7) is by-produced.

  In general formula (7), r is 1 or more.

  The compound represented by the general formula (7) is a compound in which r diphenyl skeletons in the polymerizable monomer of the general formula (6) are bonded by an acid anhydride bond. The compound represented by the general formula (7) is produced by synthesizing an acid chloride from a corresponding dicarboxylic acid compound. The compound represented by the general formula (7) is considered to be produced by the reaction mechanism shown below. That is, when the dicarboxylic acid compound is converted to an acid chloride with sulfonyl chloride, the resulting acid chloride reacts with an unreacted carboxylic acid to give a polysubstituted acid chloride having an acid anhydride structure. It is considered that the compound represented by the general formula (7) is obtained by reacting this polysubstituted acid chloride with hydroxyalkyl methacrylate.

  Since the compound represented by the general formula (7) has a structure similar to the compound represented by the general formula (6), it is difficult to remove easily and coexists with a benzoate type polymerizable monomer. It is thought to do. And in the compound shown by the said General formula (7), it is thought that the part which becomes an acid anhydride structure is because it is easily hydrolyzed by the following mechanism (n1, n2 in the following mechanism is arbitrary) integer).

  With the mechanism as described above, it is considered that the cured product of the polymerizable monomer containing the compound represented by the general formula (7) tends to decrease in strength after storage in water.

  Therefore, the present invention provides a method for producing a benzoate-type polymerizable monomer having a low viscosity and an excellent balance between hydrophilicity and hydrophobicity when a high yield and high purity are used as a cured product. Another object of the present invention is to provide a method for producing a polymerizable monomer that can reduce by-products that lead to a decrease in mechanical strength.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. And the method of manufacturing without using a carboxylic acid chloride body using thionyl chloride etc. was examined. As a result, the purity of the resulting polymerizable monomer can be improved, and in particular, as a method for producing a polymerizable monomer capable of suppressing the reduction in mechanical properties of the cured product, a dehydration condensation reaction between a dicarboxylic acid compound and a diol compound. As a result, the present inventors have found that it is only necessary to complete the present invention.

That is, the present invention
The following general formula (1)

(Where
X is a divalent group represented by —O— ,
m is 1 ,
n is 1 ,
o it is 1,

Ar ¹ and Ar ² are each a divalent unsubstituted aromatic group;
L ¹ is a divalent hydrocarbon group having 2 to 50 carbon atoms,
R ¹ and R ² are each a hydrogen atom or a methyl group. And a method for producing a polymerizable monomer represented by:
The following general formula (2)

(Wherein, X, m, n, Ar ¹ and Ar ² have the same meanings as those in the general formula (1)),
The following general formula (3)

(In the formula, L ¹ has the same meaning as in the general formula (1)). After dehydration condensation reaction with the diol compound represented by the formula (1), (meth) acryl groups are formed at both ends of the obtained compound. It is a manufacturing method characterized by introducing.

  In the process of the present invention, when a specific polymerizable monomer (polymerizable monomer represented by the general formula (1)) is produced, first, a starting dicarboxylic acid compound and a diol compound are subjected to a dehydration condensation reaction. Synthesize benzoate alcohols. Subsequently, the obtained benzoate alcohol is (meth) acrylated. The polymerizable monomer represented by the general formula (1) obtained by this method is obtained in a high yield and high purity, and is a technique that can reduce compounds that cause a decrease in the cured product. Thus, the polymerizable monomer represented by the general formula (1) obtained by the present invention (hereinafter sometimes simply referred to as “benzoate-type polymerizable monomer”) is obtained by the synthesis method (1). Compared with the obtained benzoate type polymerizable monomer, it is often obtained in a high yield, and the strength of the cured product is hardly lowered.

The production method of the present invention is a method for producing a polymerizable monomer represented by the general formula (1), which is represented by the same general formula (1), and is represented by X, m, n, o, Ar ¹ , It is also useful as a method for producing other polymerizable monomers having different Ar ² and L ¹ . Then, the manufacturing method of the polymerizable monomer containing these other polymerizable monomers which are the target objects of the manufacturing method of this invention is demonstrated below. That is, the polymerizable monomer produced by this production method is represented by the following general formula (1)

(Where
X is a divalent group,
m is 0 or 1,
n is a number selected from the range of 0 to 3,
o is a number selected from the range of 1-10,
Ar ¹ and Ar ² are each a divalent aromatic group, and the aromatic group may have a substituent,
L ¹ is a divalent hydrocarbon group having 2 to 50 carbon atoms, or a divalent group in which some of the carbon atoms of the hydrocarbon group are replaced with heteroatoms;
R ¹ and R ² are each a hydrogen atom or a methyl group. ). When producing the polymerizable monomer represented by the general formula (1) of the present invention, a particularly excellent effect is exhibited.

  Hereinafter, the present invention will be described in order. First, the polymerizable monomer represented by the general formula (1) will be described.

(Polymerizable monomer represented by the general formula (1))
In the polymerizable monomer represented by the general formula (1),
X is a divalent group. However, when m is 0, Ar ¹ and Ar ² are directly joined, and X is not present. Only when m is 1 will the group X be present. A suitable group X is a divalent group having 1 to 3 atoms constituting the main chain that bridges Ar ¹ and Ar ^2, and preferably 1 atom constituting the main chain. May have a substituent. Specifically, the group X includes —O—, —S—, —SO ₂ —, —CH ₂ —, a divalent group in which a hydrogen atom of a methylene group is substituted with an alkyl group, and two methylene groups. Examples thereof include a divalent group in which a hydrogen atom is substituted to form a hydrocarbon ring, and a divalent group that becomes an amide bond. More specific examples of the preferred group X include the following structural formulas X-1 to X-10.

In the polymerizable monomer represented by the general formula (1),
Ar ¹ and Ar ² are each a divalent aromatic group, and the aromatic group is a group which may have a substituent. Specific examples of the divalent aromatic group having no substituent include the following structural formulas Ar-a1 to Ar-a4.

In the above structural formula, two bonds can be provided on any carbon of the benzene ring constituting the aromatic groups Ar ¹ and Ar ² . For example, in the case of the structural formula Ar1-a1, two bonds can be provided at any of the ortho, meta, and para positions.

Ar ¹ and Ar ² may have a substituent. In this case, the hydrogen atom of the benzene ring constituting the aromatic groups Ar ¹ and Ar ² is replaced with another substituent. The substituents of the aromatic groups Ar ¹ and Ar ² are not particularly limited, and those having the number of atoms constituting the substituent in the range of 1 to 60 can be appropriately selected. Specific examples include a hydrocarbon group having 1 to 20 carbon atoms, —COOR ³ , —OR ³ , a halogen group, an amino group, a nitro group, and a carboxyl group. R ³ may be a linear or branched alkyl group having 1 to 5 carbon atoms, an alicyclic hydrocarbon group such as a cyclohexyl group, a heterocyclic group such as a phenyl group or a monovalent furan. . The substituents of the aromatic groups Ar ¹ and Ar ² are not particularly limited as described above, but are preferably reactive groups, for example, those that are not (meth) acrylic groups.

n is a number selected from the range of 0-3. Here, when n = 0, the two bonds of Ar ¹ are bonded to the carbon of the ester bond. When n = 1 and m = 0, Ar ¹ and Ar ² are directly bonded to form a structure Ar ¹ -Ar ² , and the remaining bonds are bonded to ester bond carbon. When n is 2 to 3, the unit of [— (X) m—Ar ₂ —] is repeatedly present (however, when m = 0, the group X does not exist).

In the general formula (1), L ¹ is a divalent hydrocarbon group having 2 to 50 carbon atoms, or a divalent group in which a part of carbon atoms of the hydrocarbon group is replaced with a hetero atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. Specific examples thereof include the following structural formulas Lb1 to Lb9.

  In L-b1 to L-b9, a bond marked with * means a bond bonded to an oxygen atom of an ester bond constituting the benzoate structure at the center of the molecule. A, b, c and d each represent a repeating unit, a = 1 to 49, b = 1 to 16, c = 1 to 11, d = 1 to 10, and e. = 1-9. Among these, L-b1 is preferable, a = 1 to 10 is preferable, and a = 1 to 4 is more preferable.

In the said General formula (1), o is a number selected from the range of 1-10. o is
This represents a repetition of-(CO-Ar ¹ -((X) _m -Ar ² ) _n -CO-OL ¹ )-. In one molecule, o is an integer, but the polymerizable monomer represented by the general formula (1) is usually obtained as a mixture of molecules having different values of o. Therefore, in the case of a mixture, o may be expressed as an average value. In addition, in order for the hardened | cured body obtained to exhibit the outstanding effect, it is preferable to satisfy | fill the range of 1-10 for both o of 1 molecule and o of the average value of a mixture.

R ¹ and R ² are each a hydrogen atom or a methyl group.

  The present invention is a method for producing a polymerizable monomer represented by the general formula (1). Next, the raw material compound will be described.

(Dicarboxylic acid compound)
In the present invention,
The following general formula (2)

(Wherein X, m, n, Ar ¹ and Ar ² have the same meanings as those in the general formula (1)) and a diol compound described in detail below are reacted. Let In the general formula (2), X, m, n, Ar ¹ , and Ar ² are the same as those described in the general formula (1). This is the same as that described in the general formula (1). Among these dicarboxylic acid compounds, those to which the method of the present invention can be suitably applied include those represented by the following general formula (4).

(Wherein, X and m are the same as those in the general formula (2)). By using this dicarboxylic acid compound, not only the performance of the resulting cured product is improved, but the effects of the present invention are easily exhibited.

(Diol compound)
In the present invention, the diol compound to be reacted with the dicarboxylic acid compound represented by the general formula (2) is represented by the following general formula (3).

(Wherein, L ¹ is the same meanings as those in formula (1).) A diol compound represented by. In the general formula (3), L ¹ is the same as that described in the general formula (1). Naturally, preferred groups and numbers are also those described in the general formula (1). The same.

  Specific examples of the diol compound include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -Linear diols such as octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propane Diols, diols having a branched structure such as 1,3-butanediol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, pentaethylene glycol, octaethylene glycol, nonaethylene glycol, deca Ethylene glycol Diols having an ether bond or thioether bond in the molecule, 1,4-dihydroxymethylcyclohexane, tricyclodecane dimethanol, such as alcohol, undecaethylene glycol, dodecaethylene diol, butanedecaethylene glycol, pentanedecaethylene glycol, thioglycol A diol having a cyclic structure such as

Among these diol compounds, the method of the present invention can be suitably applied as follows:
The following general formula (5)

A diol compound represented by the formula (wherein p is an integer selected from the range of 1 to 10) is particularly preferred. Specifically, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, Examples include 1.9-nonanediol and 1,10-decanediol. Furthermore, it is preferable that p is 1-4, and specific examples include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and ethylene glycol. 1,3-propanediol is preferred.

  Next, the dehydration condensation reaction of the dicarboxylic acid compound represented by the general formula (2) and the diol compound represented by the general formula (3) will be described.

(Step 1; reaction of dicarboxylic acid compound and diol compound (production of intermediate))
In the present invention, first, the dicarboxylic acid compound represented by the general formula (2) and the diol compound represented by the general formula (3) are subjected to a dehydration condensation reaction. This reaction is generally performed according to the following reaction formula.

In the reaction formula (synthesis method step 1), X, m, n, o, Ar ¹ , Ar ² , and L ¹ have the same meanings as in the general formula (1). Of course, the preferred groups and numbers are the same as those described for the polymerizable monomer represented by the general formula (1). o is determined by the molar ratio (reaction conditions) of the dicarboxylic acid compound to be reacted and the diol compound.

(Molar ratio of raw material compounds)
In the present invention, the diol compound represented by the general formula (3) used in the reaction (hereinafter sometimes simply referred to as a diol compound) is a dicarboxylic acid compound represented by the general formula (2) (hereinafter simply referred to as dicarboxylic acid). 2 to 50 equivalents (2 to 50 mol of a diol compound is used per 1 mol of a dicarboxylic acid compound). The value of o in the general formula (1) can be adjusted by the number of equivalents of the diol compound used here. The value of o decreases as the number of equivalents of the diol compound used increases. Therefore, the equivalent number of the diol compound to be used is preferably 5 equivalents to 50 equivalents, more preferably 10 equivalents to 50 equivalents, relative to the dicarboxylic acid.

(Dehydration condensation reaction)
The synthesis method Step 1 is a dehydration condensation reaction between a dicarboxylic acid compound and a diol compound, and a known method can be adopted for this reaction. Specifically, an esterification reaction using a dehydration condensation agent as a catalyst or a dehydration condensation reaction using an acid catalyst can be employed.

(Reaction catalyst; dehydration condensation agent)
In the present invention, known dehydrating condensing agents can be used. Specifically, dicyclohexylcarbondiimide (hereinafter sometimes referred to as “DCC”), diphenylphosphoric acid azide (hereinafter sometimes referred to as “DPPA”), hexafluorophosphoric acid (benzotriazol-1-yloxy) Tripyrrolidinophosphonium (hereinafter sometimes referred to as “Py-BOP”), benzotriazol-1-yloxy-trisdimethylaminophosphonium salt (hereinafter also referred to as “BOP”), bromotripyrrolidinophosphonium hexa Fluorophosphate (hereinafter sometimes referred to as “PyBroP”), diphenyl phosphate diazide (hereinafter sometimes referred to as “DPPA”), 4- (4,6-dimethoxy-1,3,5-triazine-2 -Yl) -4-methylmorpholinium chloride (hereinafter referred to as “DMT-MM”) 1-ethyl- (3-dimethylaminopropyl) -carbodiimide (hereinafter sometimes referred to as “EDC”), diisopropylcarbodiimide (hereinafter sometimes referred to as “DIC”), hexafluorophosphoric acid —O— (7-azabenzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium (hereinafter sometimes referred to as “HATU”) {{{(1-cyano-2 -Ethoxy-2-oxoethylidene) amino} oxy} -4-morpholinomethylene} dimethylammonium hexafluorophosphate (hereinafter sometimes referred to as “COMU”), 2-methyl-6-nitrobenzoic anhydride ( Hereinafter, it may be referred to as “MNBA”).

(Reaction catalyst; acid catalyst)
In the present invention, the acid catalyst includes p-toluenesulfonic acid, 4-ethylbenzenesulfonic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, 2-mesitylbenzenesulfonic acid. 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 5-dimethylamino-naphthalenesulfonic acid, 8-anilino-1-naphthalenesulfonic acid, 1,5-naphthalenedisulfonic acid, 6-dimethyl-amino-4hydroxy-2- Naphthalene-sulfonic acid, flavianic acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, 2-cyclohexylaminoethanesulfonic acid, 3-cyclohexylaminopropanesulfonic acid, 3-morpholinopropanesulfonic acid, 10-camphorsulfo Acid, can be used sulfuric acid, and the like. Among them, preferred is p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, 10-camphorsulfonic acid, and more preferred is p-toluenesulfonic acid.

  In the present invention, either the reaction using the dehydration condensing agent or the reaction using the acid catalyst can be adopted. However, when using the dehydrating condensing agent, a stoichiometric amount of the dehydrating condensing agent is required. In addition, the dehydrating condensing agent generally gives a large amount of by-products after completion of the reaction. On the other hand, dehydration condensation with an acid catalyst requires only a catalytic amount of acid and can be easily removed by washing with water after the reaction. Therefore, the reaction using an acid catalyst is more preferable.

(Amount of reaction catalyst used)
Hereinafter, since it is preferable that the other reaction conditions using a dehydration condensing agent and an acid catalyst are the same conditions, both may be collectively used as a reaction catalyst. In the synthesis method of the present invention, in Step 1, the number of equivalents of the reaction catalyst is preferably in the range of 0.01 to 5.0 equivalents with respect to the diol compound, and 0.05 to 5 in order to further promote the reaction. A range of 0.0 equivalents is preferable, and a range of 0.1 to 5.0 equivalents is more preferable.

(Reaction solvent; organic solvent)
Synthesis Method In Step 1, when the reaction can be performed without using an organic solvent, the reaction is preferably performed without using an organic solvent. However, when the diol compound used for the reaction is a solid, an organic solvent can be used as necessary. In the case of using an organic solvent, it is not particularly limited as long as it does not affect the raw material compound and the like. Specifically, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, o -Halogenated hydrocarbons such as dichlorobenzene and tetrahydrofuran; Alcohols such as methanol, ethanol, isopropyl alcohol, t-butyl alcohol, and t-amyl alcohol; Dimethyl ether, ethyl methyl ether, diethyl ether, diisopropyl ether, diglyme, tert- Ethers such as butyl methyl ether, dimethoxyethane, ethylene glycol diethyl ether, tetrahydrofuran, 1,4-dioxane; N, N-dimethylformamide, N, N-dimethylaceamide Amides such as N- methyl pyrrolidone; sulfoxides such as dimethyl sulfoxide; acetonitrile, propionitrile, nitriles such as benzonitrile; acetone, methyl ethyl ketone, may be selected from such ketones such as methyl isobutyl ketone. Also preferred are toluene, benzene, xylene, mesitylene, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, cyclopentyl methyl ether, ethyl methyl ketone, methyl isobutyl ketone, and more preferred are toluene, 1,4-dioxane. 1,2-dimethoxyethane, cyclopentyl methyl ether, ethyl methyl ketone, methyl isobutyl ketone.

(Mixing method)
In the present invention, in the synthesis method Step 1, the method of mixing the raw material dicarboxylic acid compound, diol compound, and reaction catalyst blended as necessary is not particularly limited, but after mixing the diol compound and the dicarboxylic acid compound It is preferable to add a reaction catalyst. Also, when using an organic solvent, the mixing method is not particularly limited, but it is preferable to add the reaction catalyst after diluting the diol compound and the raw dicarboxylic acid with the organic solvent, and the concentration of the raw dicarboxylic acid with respect to the organic solvent. Is preferably 0.0001 mol / L or more, more preferably 0.001 mol / L or more, and still more preferably 0.01 mol / L.

(Reaction temperature, reaction time)
The reaction temperature is not particularly limited, but is preferably in the range of 60 ° C to 200 ° C, and more preferably in the range of 100 ° C to 150 ° C. As the reaction time, the consumption state of the raw material compound is confirmed, and a time during which the raw material compound is sufficiently used may be appropriately adopted.

(Dehydration conditions)
In the present invention, since the reaction in Step 1 of the synthesis method is a dehydration condensation reaction with the raw carboxylic acid compound and diol compound, it is preferable to accelerate the reaction by removing water by-produced by the reaction. As a method for removing water, fractional distillation under reduced pressure conditions can be used. In that case, the degree of reduced pressure in the system is preferably in the range of 0.1 mmHg to 50 mmHg.

  The by-product water may be removed by azeotropy with the reaction solvent, and in that case, it is necessary to use a solvent azeotroped with water.

(Operation after reaction)
As the operation after the reaction in Step 1, as the operation for removing the remaining diol, washing with water may be performed, or it may be removed by distillation. When removing by water washing, the reaction mixture containing the obtained intermediate may be dissolved in the poorly water-soluble organic solvent in the organic solvent exemplified as the reaction solvent, followed by water washing. The number of water washing needs to be at least once, more preferably 2 or more, and even more preferably 3 or more.

  In addition, when removing the diol compound by distillation, it is preferable to distill by adding an equimolar amount of an organic base such as triethylamine or diisopropylethylamine to the added reaction catalyst. The temperature during distillation is preferably 30 ° C to 250 ° C, more preferably 50 ° C to 200 ° C, and further preferably 80 ° C to 200 ° C. Moreover, you may reduce pressure as needed, and the pressure reduction degree has the preferable range of 0.1 mmHg-500 mmHg. The upper limit of the degree of vacuum is more preferably 100 mmHg, further preferably 10 mmHg or less, and still more preferably 5 mmHg or less.

  Next, in the present invention, a (meth) acryl group is introduced into the hydroxyl groups at both ends of the intermediate obtained in Step 1 (this reaction may be referred to as “Step 2”). Next, step 2 will be described.

(Step 2: Method of introducing (meth) acrylic group into intermediate)
In the present invention, the following general formula

After obtaining the intermediate shown in (1), (meth) acryl groups are introduced into both ends of the obtained intermediate.

In the intermediate, X, m, n, o, Ar ¹ , Ar ² and L ¹ have the same meanings as those in the general formula (1). Of course, the preferred groups and numbers are the same as those described for the polymerizable monomer represented by the general formula (1).

  In the present invention, Step 2 is a method of introducing a (meth) acryl group into the hydroxyl groups at both ends of the intermediate, and the following three methods are exemplified. First, dehydration condensation reaction between (meth) acrylic acid and intermediate (step 2-1), reaction with (meth) acrylic anhydride (step 2-2), reaction with (meth) acrylic acid chloride (step) Any of 2-3) can be used.

(Step 2-1; dehydration condensation reaction with (meth) acrylic acid)
First, step 2-1 will be described. In step 2-1, the following reaction is performed.

  The dehydration condensation reaction with methacrylic acid in Step 2-1 produces the polymerizable monomer represented by the general formula (3) by the dehydration condensation reaction between the intermediate synthesized in Step 1 and (meth) acrylic acid. Is the method.

(Amount of (meth) acrylic acid used)
The number of equivalents of (meth) acrylic acid used here is 2 equivalents or more and 40 equivalents or less (2 to 40 moles of dicarboxylic acid compound is used for 1 mole of the intermediate) with respect to the obtained intermediate. be able to. More preferably, they are 4 equivalents or more and 50 equivalents or less, More preferably, they are 8 equivalents or more and 40 equivalents or less. In addition, when an intermediate body is a mixture from which the value of o differs, the molecular weight of an intermediate body is calculated | required using the average value of o, and what is necessary is just to calculate an equivalent.

(Dehydration condensation reaction conditions)
Step 2-1 is a dehydration condensation reaction between the intermediate and (meth) acrylic acid, and a known method can be adopted for this reaction. Specifically, an esterification reaction using a dehydration condensation agent as a catalyst or a dehydration condensation reaction using an acid catalyst can be employed.

(Reaction catalyst; dehydration condensation agent, acid catalyst)
Examples of the dehydrating condensation agent and acid catalyst that can be used in Step 2 include the reaction catalyst exemplified in Step 1 above. Preferred reaction catalysts are also the same as those exemplified in Step 1. Also in this step 2-1, it is preferable to use an acid catalyst in consideration of ease of processing in the subsequent process.

(Reaction solvent; organic solvent)
In Step 2-1, when the reaction can be performed without using an organic solvent, the reaction is preferably performed without using an organic solvent. However, when the intermediate used for the reaction is a solid, an organic solvent can be used as necessary. Examples of the organic solvent that can be used include the organic solvents described in Step 1 above.

(Mixing method)
In the present invention, in the synthesis method Step 2-1, the method of mixing the intermediate, (meth) acrylic acid, and the reaction catalyst is not particularly limited, but after mixing the intermediate and (meth) acrylic acid, the reaction catalyst Is preferably added. Also, when using an organic solvent, the mixing method is not particularly limited, but it is preferable to add a reaction catalyst after diluting the intermediate and (meth) acrylic acid with the organic solvent. The concentration is preferably 0.0001 mol / L or more, more preferably 0.001 mol / L or more, and further preferably 0.01 mol / L.

(Reaction temperature, reaction time)
The reaction temperature is preferably in the range of 40 ° C to 110 ° C, more preferably 60 ° C to 100 ° C, and further preferably 80 ° C to 100 ° C. As the reaction time, the consumption state of the raw material compound is confirmed, and a time during which the raw material compound is sufficiently used may be appropriately adopted.

(Dehydration conditions)
Since the reaction in Step 2-1 is a dehydration condensation reaction, the reaction may be promoted by removing water by-produced by the reaction. As a method for removing water, fractional distillation under reduced pressure conditions can be used. In that case, the degree of reduced pressure in the system is preferably in the range of 0.1 mmHg to 50 mmHg. The by-product water may be removed by azeotropy with the reaction solvent, and in that case, it is necessary to use a solvent azeotroped with water.

(Operation after reaction)
In the post-treatment of the reaction, it is preferable to remove the remaining (meth) acrylic acid by base washing. As the basic aqueous solution that can be used in this case, a solution obtained by dissolving a carbonate such as potassium carbonate, sodium carbonate, or sodium bicarbonate, or a hydroxide such as potassium hydroxide or sodium hydroxide in water can be used. The concentration of the base is preferably in the range of 0.1 wt% to 30 wt%, more preferably in the range of 0.5 wt% to 10 wt%. Moreover, it is preferable to perform the frequency | count of water washing with a base 1 time or more, More preferably, it is 2 times or more. Thereafter, in order to obtain a polymerizable monomer represented by the general formula (1) with higher purity, it can be purified by a known method, for example, column treatment with silica gel or the like, or recrystallization if solid. That's fine.
By the above operation, the polymerizable monomer represented by the general formula (1) can be produced.

(Step 2-2; reaction with (meth) acrylic anhydride)
Step 2-2 will be described. In step 2-2, the following reaction is performed.

(Amount of (meth) acrylic acid used)
(Meth) acrylation by reaction with (meth) acrylic anhydride in Step 2-2 is a reaction between the intermediate obtained in Step 1 and an acid anhydride. The amount of (meth) acrylic anhydride used is 2 to 20 equivalents of the intermediate (2 to 20 moles of (meth) acrylic acid with respect to 1 mole of the intermediate (o uses an average value). An anhydride is used). Preferably, it is 2 to 10 equivalents, more preferably 2 to 5 equivalents.

(Reaction conditions)
In Step 2-2, the intermediate and the (meth) acrylic anhydride may be mixed, but an anhydride reaction catalyst such as an amine catalyst or Lewis acid can be used in consideration of the progress of the reaction.

(Anhydride reaction catalyst; amine catalyst)
In step 2-2, an amine can be used. Specifically, aromatic amines such as 4,4-dimethylaminopyridine, pyridine, imidazole, trimethylamine, dimethylethylamine, diethylmethylamine, tripropylamine, dimethylisopropylamine, diisopropylethylamine, triethylamine, dimethylbutylamine, methyldibutylamine , Tributylamine, trihexylamine, dimethyloctylamine, methyldioctylamine, trioctylamine, triisooctylamine, triisodecylamine, dimethylundecylamine, dimethyldodecylamine, tridodecylamine, tetramethyldiaminomethane, ethyldiisopropyl Alkyl tertiary amine such as amine, tetramethylethylenediamine, tetraethylethylenediamine, tetraethylpropa Tertiary diamines such as diamine, tetramethylpropanediamine, tetramethyl-1,3-butanediamine, tetramethylpropanediamine, tetramethylhexanediamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine, dimethylcyclohexane And cycloalkyl tertiary amines such as methylamine. Preferably 4,4-dimethylaminopyridine, pyridine, imidazole, trimethylamine, dimethylethylamine, diethylmethylamine, tripropylamine, dimethylisopropylamine, triethylamine, diisopropylethylamine, dimethylbutylamine, methyldibutylamine, tributylamine, and further Preferred are 4,4-dimethylaminopyridine, triethylamine, and diisopropylethylamine.

  When the amine catalyst is used, the amount of the amine catalyst used is 0.001 to 10 equivalents relative to the intermediate (0.001 to 10 moles relative to 1 mole of the intermediate (o uses an average value)). The amine catalyst is preferably used. In consideration of the post-process and the progress of the reaction, the amount of the amine catalyst used is more preferably from 0.1 equivalents to 5 equivalents, and even more preferably from 0.3 equivalents to 3 equivalents.

(Anhydride reaction catalyst; Lewis acid catalyst)
In Step 2-2, a Lewis acid catalyst can be used instead of the amine catalyst. Specific examples include scandium (III) triflate, bismuth (III) triflate, dichlorodioxide molybdenum (VI), tetrachlorotitanium (IV), tin (IV) chloride, and the like.

  The amount of the Lewis acid catalyst used is 0.001 to 10 equivalents relative to the intermediate (0.001 to 10 mol of Lewis acid catalyst is used per 1 mol of the intermediate (o uses an average value)). It is preferable that In consideration of the post-process and the progress of the reaction, the use amount of the Lewis acid catalyst is more preferably from 0.1 equivalents to 5 equivalents, and further preferably from 0.3 equivalents to 3 equivalents.

(Reaction solvent (step 2-2); organic solvent)
In Step 2-2, when the reaction can be performed without using an organic solvent, the reaction is preferably performed without using an organic solvent. However, when the intermediate used for the reaction is a solid, an organic solvent can be used as necessary. Examples of the organic solvent that can be used include the organic solvents described in Step 1, and ester compounds such as methyl acetate, ethyl acetate, and isopropyl acetate can also be used.

  Among them, preferred reaction solvents include toluene, benzene, xylene, mesitylene, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, cyclopentyl methyl ether, ethyl methyl ketone, methyl isobutyl ketone, acetonitrile, propionitrile, Hexane and heptane are preferable, and toluene, 1,4-dioxane, 1,2-dimethoxyethane, cyclopentyl methyl ether, ethyl methyl ketone, methyl isobutyl ketone, hexane and heptane are more preferable.

(Mixing method)
Synthesis method In step 2-2, the method of mixing the intermediate, the (meth) acrylic anhydride, and the catalyst is not particularly limited, but after the intermediate and the catalyst are mixed, the (meth) acrylic anhydride is added. Is preferred. Also, in the case of using an organic solvent, the mixing method is not particularly limited, but it is preferable to add (meth) acrylic anhydride after diluting the intermediate and the catalyst with the organic solvent, and the concentration of the intermediate with respect to the organic solvent Is preferably 0.0001 mol / L or more, more preferably 0.001 mol / L or more, and still more preferably 0.01 mol / L.

(Reaction temperature, reaction time)
The reaction temperature is not particularly limited, but considering reaction time, purity, etc., 50 ° C. or higher and 100 ° C. or lower is preferable, 60 ° C. or higher and 90 ° C. or lower is more preferable, and 70 ° C. or higher and 80 ° C. or lower is more preferable. . Also, the reaction time is not particularly limited, and is preferably 10 minutes to 48 hours within the above reaction temperature range, more preferably 1 hour to 48 hours from the viewpoint of reaction yield, More preferably, it is 3 hours or more and 48 hours or less.

(Operation after reaction)
In the post-treatment of the reaction, it is preferable to remove the remaining (meth) acrylic acid by base washing. As the basic aqueous solution that can be used in this case, a solution obtained by dissolving a carbonate such as potassium carbonate, sodium carbonate, or sodium bicarbonate, or a hydroxide such as potassium hydroxide or sodium hydroxide in water can be used. The concentration of the base is preferably in the range of 0.1 wt% to 30 wt%, more preferably in the range of 0.5 wt% to 10 wt%. Moreover, it is preferable to perform the frequency | count of water washing with a base 1 time or more, More preferably, it is 2 times or more. Thereafter, in order to obtain a polymerizable monomer represented by the general formula (1) with higher purity, it can be purified by a known method, for example, column treatment with silica gel or the like, or recrystallization if solid. That's fine.
By the above operation, the polymerizable monomer represented by the general formula (1) can be produced.

(Step 2-3; reaction with (meth) acrylic acid chloride)
Step 2-3 will be described. In step 2-3, the following reaction is performed.

(Amount of (meth) acrylic acid chloride used)
(Meth) acrylation by reaction with (meth) acrylic acid chloride in Step 2-3 is a reaction between the intermediate obtained in Step 1 and acid chloride. The amount of (meth) acrylic acid chloride used is 1.5 equivalents or more and 20 equivalents or less with respect to the intermediate product obtained in Step 1 (1.5 mol of intermediate product (o uses an average value)). ~ 20 mol (meth) acrylic acid chloride is used). Preferably, it is 2.0 equivalents or more and 10 equivalents or less, more preferably 2.0 equivalents or more and 5 equivalents or less. More preferably, it is 2.0 equivalents or more and 3.0 equivalents or less.

(Neutralizing agent; amine)
In addition, when the (meth) acrylic acid chloride and the intermediate are reacted, the reaction can be promoted by neutralizing the by-produced hydrogen chloride. It is more preferable to use The amine that can be used can be the same as the amine reaction catalyst described in Step 2-2; However, preferred amines used for neutralization in Step 2-3 are trimethylamine, dimethylethylamine, diethylmethylamine, tripropylamine, dimethylisopropylamine, triethylamine, diisopropylethylamine, dimethylbutylamine, methyldibutylamine, tributylamine, tetramethylethylenediamine. It is.

  It is preferable that the usage-amount of an amine is 0.1 equivalent or more and 10 equivalent or less (0.1-10 mol amine is used with respect to 1 mol of intermediate bodies (o uses an average value)). More preferably, it is 1.0 equivalent or more and 5.0 equivalent or less, More preferably, it is 1.5 equivalent or more and 5.0 equivalent or less, More preferably, it is 2.0 equivalent or more and 3.0 equivalent or less.

(Reaction solvent; organic solvent)
In Step 2-3, when the reaction can be performed without using an organic solvent, it is preferable to perform the reaction without using an organic solvent. However, when the intermediate used for the reaction is a solid, an organic solvent can be used as necessary. Examples of the organic solvent that can be used include the organic solvents described in Step 2-2.

  Among them, preferred reaction solvents are toluene, benzene, xylene, mesitylene, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, cyclopentyl methyl ether, ethyl methyl ketone, methyl isobutyl ketone, acetonitrile, propionitrile. , Methylene chloride and chloroform, more preferably toluene, 1,4-dioxane, 1,2-dimethoxyethane, cyclopentyl methyl ether, ethyl methyl ketone, methyl isobutyl ketone, methylene chloride and chloroform.

(Mixing method)
In the present invention, in the synthesis method Step 2-3, the method of mixing the intermediate with (meth) acrylic acid chloride and amine is not particularly limited, but after mixing the intermediate and amine, (meth) acrylic acid chloride is mixed. Is preferably added. Also, when using an organic solvent, the mixing method is not particularly limited, but it is preferable to add (meth) acrylic acid chloride after diluting the intermediate and the amine with the organic solvent, and the concentration of the intermediate with respect to the organic solvent is 0.0001 mol / L or more is preferable, 0.001 mol / L or more is more preferable, and 0.01 mol / L is further more preferable.

(Reaction temperature, reaction time)
The reaction temperature is not particularly limited, but is preferably −40 ° C. or higher and 50 ° C. or lower, more preferably −30 ° C. or higher and 30 ° C. or lower, more preferably −30 ° C. More preferably, it is 20 ° C. or lower. The reaction time is not particularly limited, and is preferably 1 minute to 24 hours, more preferably 10 minutes to 12 hours, and further preferably 30 minutes to 6 hours in the above reaction temperature range.

(Operation after reaction)
In the post-treatment of the reaction, it is preferable to remove residual hydrogen chloride by base washing. As the basic aqueous solution that can be used in this case, a solution in which a carbonate such as potassium carbonate, sodium carbonate, or sodium bicarbonate, a hydroxide such as potassium hydroxide or sodium hydroxide, or the like is dissolved in water can be used. The concentration is preferably in the range of 0.1 wt% to 30 wt%, more preferably in the range of 0.5 wt% to 10 wt%. Moreover, it is preferable to perform the frequency | count of water washing with a base 1 time or more, More preferably, it is 2 times or more. Thereafter, in order to obtain a polymerizable monomer represented by the general formula (1) with higher purity, it can be purified by a known method, for example, column treatment with silica gel or the like, or recrystallization if solid. That's fine.
By the above operation, the polymerizable monomer represented by the general formula (1) can be produced.

  Moreover, when an amine is used at the time of reaction, it is preferable to remove the remaining amine with an acid. As the acidic aqueous solution that can be used at this time, a solution in which hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoroacetic acid, phosphoric acid, citric acid or the like is dissolved in water can be used, and the concentration is 0.1 wt% to 30 wt%. A range is preferable, and a range of 0.5 wt% to 10 wt% is more preferable. Moreover, it is preferable to perform the frequency | count of the water washing by an acid 1 time or more, More preferably, it is 2 times or more. Thereafter, the obtained polymerizable monomer represented by the general formula (1) can be purified by recrystallization, column treatment or the like.

(Preferred step 2)
In the present invention, the method for introducing the (meth) acrylic group into the intermediate may be selected from the above 2-1, 2-2, and 2-3. However, since the (meth) acrylic acid chloride used in Step 2-3 is unstable because it is easily decomposed by water in the air, the method of Step 2-1 and Step 2-2 can be adopted. preferable.

  In addition, (meth) acrylic acid used in Step 2-1 is an inexpensive raw material, and can be easily removed by a water washing step after completion of the reaction. Therefore, since an excess amount of (meth) acrylic acid can be used with respect to the intermediate, the reaction efficiency is good and the synthesis can be performed in a shorter reaction time. Therefore, the method of step 2-1 is more preferable.

  In addition, in step 2-2 and 2-3, the value of o in the general formula (1) cannot be adjusted. However, in step 2-1, the value of o can be adjusted by adjusting the reaction conditions. Can also be prepared. Therefore, step 2-1 is advantageous in that the range of manufacturing conditions can be widened.

(About the characteristic of the polymerizable monomer shown by the said General formula (1), and its preparation method)
The polymerizable monomer represented by the general formula (1) synthesized by the present invention is obtained in the range of o = 1 to 10. This value can be prepared depending on the synthesis conditions, and the physical properties of the resulting polymerizable monomer can be controlled according to the use according to the value. As the value of o increases, the refractive index of the polymerizable monomer of the resulting benzoate monomer tends to increase, and as the molecular weight increases, the shrinkage rate during polymerization tends to decrease. On the other hand, as the value of o is smaller, a polymerizable monomer having a relatively low refractive index can be synthesized.

  As a method for adjusting the value of o by the synthesis method, it can be prepared by adjusting the equivalent of the diol compound to the dicarboxylic acid compound in the synthesis method step 1. Further, in step 2-2 and step 2-3, while the value of o does not change (the reaction proceeds with the value obtained in step 1), as described above, step 2-1 further includes The value of o can be increased.

  Hereinafter, the present invention will be described in detail by way of examples and comparative examples, but the present invention is not limited to these examples. Various evaluation methods will be described.

(Measurement of viscosity of polymerizable monomer)
The viscosity of the polymerizable monomers produced in Examples, Reference Examples and Comparative Examples was measured using a CS rheometer. As a measuring device, a viscoelasticity measuring device CS rheometer “CVO120HR” (manufactured by Borin) equipped with a cone / plate geometry 4 cm / 2 ° and a temperature control system was used. Then, the measurement was performed three times under the measurement conditions of the measurement temperature (plate temperature) 25 ° C. and the shear rate of 1 rps, and the average value of the three measurements was taken as the viscosity. This viscosity was measured as it was with the purity shown in Table 1.

Example 1: 4-DPEHP synthesis
(Step 1)
4,4-dicarboxybiphenyl ether (52.1 g, 0.2 mol), 1,3-propanediol (290 ml, 4 mol) and p-toluenesulfonic acid monohydrate (3.44 g, 0.02 mol) The mixture was mixed in an eggplant-shaped flask and stirred at 120 ° C. for 2 hours using an oil bath. Under the present circumstances, it stirred, distilling off the water to produce | generate using a vacuum pump. After leaving the reaction solution to room temperature, triethylamine (2.8 ml, 0.02 mol) was added, and unreacted 1,3-propanediol was distilled off by distillation using a vacuum pump. A white solid of the product (4,4-bis (3-hydroxypropoxycarbonyl) biphenyl ether oligomer mixture (A)) was quantitatively obtained with HPLC purity of 97.3% (o = 1.25, average molecular weight: 453).

(Step 2-1)
The resulting 4,4-bis (3-hydroxypropoxycarbonyl) biphenyl ether oligomer mixture (A) (72.5 g) and p-toluenesulfonic acid monohydrate (3.44 g, 0.02 mol), methacryl Acid (330 ml, 2.0 mol) and BHT (700 ppm) were added as a polymerization inhibitor, and the mixture was stirred at 85 ° C. for 8 hours. After the reaction solution was allowed to cool to room temperature, 200 ml of toluene was added, washed three times with an aqueous potassium carbonate solution, washed three times with a saturated aqueous sodium chloride solution, dried over magnesium sulfate, and then filtered off. The obtained filtrate was concentrated by a rotary evaporator and then vacuum-dried to obtain a liquid of a polymerizable monomer (abbreviation: 4-DPEHP) with a yield of 85% and HPLC purity of 92.5% (o = 1.39, average molecular weight: 621). The H ¹ -NMR spectrum data of the obtained 4-DPEHP was as follows.
H ¹ -NMR δ 1.94 (s, 6H), 2.17 (quin, 4.8H), 4.31-4.45 (m, 9.6H), 5.57 (quin, 2H), 6. 12 (quin, 2H), 7.06 (d, 5.6H) 8.05 (d, 5.6H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 1 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 2: 4-DPEHPI synthesis
(Step 2-2)
Intermediate (4,4-bis (3-hydroxypropioxycarbonyl) biphenyl ether (A) (72.5 g)) synthesized in Step 1 of Example 1 and methacrylic anhydride (154 g, 0.44 mol), 4 4-dimethylaminopyridine (2.5 g, 0.02 mol) and BHT (700 ppm) as a polymerization inhibitor were added, and the mixture was stirred at 80 ° C. for 8 hours. After allowing the reaction solution to cool to room temperature by allowing to cool, 200 ml of toluene was added, washed with 1N aqueous hydrochloric acid solution three times, washed with 5% potassium carbonate aqueous solution three times, and washed with saturated brine aqueous solution three times, magnesium sulfate And dried by filtration. The obtained filtrate was concentrated by a rotary evaporator and then vacuum-dried to obtain a liquid of a polymerizable monomer (abbreviation: 4-DPEHPI) at a yield of 85% and an HPLC purity of 90.5% (o = 1.25, average molecular weight: 518). The H ¹ -NMR spectrum data of the obtained 4-DPEHPI was as follows.
H ¹ -NMR δ 1.94 (s, 6H), 2.17 (quin, 4.5H), 4.31-4.45 (m, 9H), 5.57 (quin, 2H), 6.12 ( quin, 2H), 7.06 (d, 5H) 8.05 (d, 5H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 2 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1. This compound is the same as the compound of Example 1 except for the value of o.

Example 3: 4-DPEHPII synthesis
(Step 2-3)
A methylene chloride solution of the intermediate (4,4-bis (3-hydroxypropoxycarbonyl) biphenyl ether (A) (72.5 g)) obtained in Example 1 was ice-cooled, and then methacrylic acid chloride (46 g, 0 .44 mol), triethylamine (44 g, 0.44 mol) and BHT (700 ppm) as a polymerization inhibitor were added and stirred for 3 hours. Washed 3 times with 1N aqueous hydrochloric acid solution, washed 3 times with 5% aqueous potassium carbonate solution, washed 3 times with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and filtered. The obtained filtrate was concentrated by a rotary evaporator and further vacuum-dried to obtain a liquid of a polymerizable monomer (4-DPEHPII) at a yield of 85% and an HPLC purity of 91.2% (o = 1). .25, average molecular weight: 518). The H ¹ -NMR spectrum data of the obtained 4-DPEHPII was as follows.
H ¹ -NMR δ 1.94 (s, 6H), 2.17 (quin, 4.5H), 4.31-4.45 (m, 9H), 5.57 (quin, 2H), 6.12 ( quin, 2H), 7.06 (d, 5H) 8.05 (d, 5H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 3 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1. This compound is the same as the compound of Example 1 except for the value of o.

Example 4: 4-DPEHE synthesis (Step 1)
In Step 1 of Example 1, an intermediate was produced in the same manner as in Example 1 except that 1,2-ethanediol (220 ml, 4.0 mol) was used instead of 1,3-propanediol. did.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was performed, and a yellow liquid of polymerizable monomer (4-DPEHE) was obtained with a yield of 83%, HPLC. Obtained with a purity of 91.7% (o = 1.53 average molecular weight: 625). The H ¹ -NMR spectrum data of the obtained 4-DPEHE was as follows.
H ¹ -NMR δ 1.95 (s, 6H), 4.50-4.60 (m, 10.1H), 5.57 (s, 2H), 6.12 (s, 2H), 7.07 ( d, 6.1H) 8.05 (d, 6.1H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 4 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 5: 4-DPEHH synthesis (Step 1)
In Step 1 of Example 1, an intermediate was produced in the same manner as in Example 1 except that 1,6-hexanediol (490 ml, 4.0 mol) was used instead of 1,3-propanediol. did.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was performed, and a yellow liquid of polymerizable monomer (4-DPEHH) was obtained in a yield of 87%, HPLC. Obtained with a purity of 92.9% (o = 1.37 average molecular weight: 721). The H ¹ -NMR spectrum data of the obtained 4-DPEHH was as follows.
H ¹ -NMR δ 1.93 (s, 6H), 1.51-1.80 (m, 19H), 4.00-4.40 (m, 9.5H), 5.57 (s, 2H), 6.12 (s, 2H), 7.61 (d, 5.5H) 8.20 (d, 5.5H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 5 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 6: 4-DPEHD synthesis (Step 1)
In Step 1 of Example 1, an intermediate was produced in the same manner as in Example 1 except that 1,10-decanediol (697 g, 4.0 mol) was used instead of 1,3-propanediol. did.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was performed, and a yellow liquid of polymerizable monomer (4-DPEHD) was obtained in a yield of 85%, HPLC. Obtained with a purity of 92.2% (o = 1.35 average molecular weight: 865). The H ¹ -NMR spectrum data of the obtained DPEHD was as follows.
H ¹ -NMR δ 1.94 (s, 6H), 1.51-1.79 (m, 14.1H), 4.09-4.40 (m, 9.4H), 5.57 (s, 2H) ), 6.12 (s, 2H), 7.61 (d, 5.4H) 8.20 (d, 5.4H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 6 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 7: 4-DPEHCy synthesis (Step 1)
In Step 1 of Example 1, the same operation as in Example 1 was performed except that 1,4- (dihydroxymethyl) cyclohexane (570 g, 4.0 mol) was used instead of 1,3-propanediol. The body was manufactured.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was performed, and a yellow liquid of a polymerizable monomer (4-DPEHCy) was obtained in a yield of 82%, HPLC. Obtained with a purity of 93.1% (o = 1.38 average molecular weight: 786). The H ¹ -NMR spectrum data of the obtained 4-DPEHCy was as follows.
H ¹ -NMR δ 1.20-2.05 (m, 34.5H), 4.11-4.44 (m, 9.5H), 5.57 (s, 2H), 6.12 (s, 2H) ), 7.61 (d, 5.5H) 8.20 (d, 5.5H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 7 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 8: 4-DPEHTD synthesis (Step 1)
In Step 1 of Example 1, an intermediate was produced in the same manner as in Example 1 except that tricyclodecane dimethanol (785 g, 4.0 mol) was used instead of 1,3-propanediol. .

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was performed, and a yellow liquid of a polymerizable monomer (4-DPEHTD) was obtained in 86% yield, HPLC. Obtained with a purity of 93.1% (o = 1.40 average molecular weight: 995). The H ¹ -NMR spectrum data of the obtained 4-DPEHTD was as follows.
H ¹ -NMR δ0.83-2.60 (m, 42H), 3.82-4.15 (m, 9.6H), 5.57 (s, 2H), 6.12 (s, 2H), 7.61 (d, 5.6H) 8.20 (d, 5.6H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 8 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 9: 4-DPEHTG synthesis (Step 1)
In Step 1 of Example 1, an intermediate was produced in the same manner as in Example 1 except that triethylene glycol (600 g, 4.0 mol) was used instead of 1,3-propanediol.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was performed, and a yellow liquid of a polymerizable monomer (4-DPEHTD) was obtained in 88% yield, HPLC. Obtained with a purity of 91.7% (o = 1.46 average molecular weight: 830). In addition, the H ¹ -NMR spectrum data of the obtained 4-DPEHTG was as follows.
H ¹ -NMR δ 1.94 (s, 6H), 3.58-3.64 (m, 19.7H), 4.40-4.55 (m, 9.8H), 5.57 (s, 2H) ), 6.12 (s, 2H), 7.61 (d, 5.8H), 8.20 (d, 5.8H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 9 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 10: 4-DPEHES synthesis (Step 1)
In Step 1 of Example 1, an intermediate was produced in the same manner as in Example 1 except that 2,2-thiodiethanol (600 g, 4.0 mol) was used instead of 1,3-propanediol. did.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was performed, and a yellow liquid of a polymerizable monomer (4-DPEHES) was obtained with a yield of 83%, HPLC. Obtained with a purity of 91.7% (o = 1.32 average molecular weight: 713). Incidentally, ^H 1 -NMR spectral data of the obtained DPEHES were as follows.
H ¹ -NMR δ 1.94 (s, 6H), 2.56 (t, 9.3H), 4.38-4.59 (m, 9.3H), 5.57 (s, 2H), 6. 12 (s, 2H), 7.61 (d, 5.3H), 8.20 (d, 5.3H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 10 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 11: 2-BPHE synthesis (Step 1)
The same operation as in Example 1 except that 48.4 g (0.2 mol) of 4,4-biphenyldicarboxylic acid was used in Step 1 of Example 1 instead of 52.1 g of 4,4-dicarboxybiphenyl ether. To produce an intermediate.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was performed, and a yellow liquid of polymerizable monomer (4-BPHE) was obtained in 86% yield, HPLC. Obtained with a purity of 93.0% (o = 1.41 average molecular weight: 610). The H ¹ -NMR spectrum data of the obtained 2-BPHE was as follows.
H ¹ -NMR δ 1.94 (s, 6H), 2.17 (quin, 4.8H), 4.31-4.45 (m, 9.6H), 5.57 (quin, 2H), 6. 12 (quin, 2H), 7.61 (d, 5.6H) 8.20 (d, 5.6H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 11 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 12: 2-BPHEI synthesis (Step 1)
The same operation as in Example 1 except that 48.4 g (0.2 mol) of 4,4-biphenyldicarboxylic acid was used in Step 1 of Example 1 instead of 52.1 g of 4,4-dicarboxybiphenyl ether. To produce an intermediate.

(Step 2-2)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-2 of Example 2 was performed, and a yellow liquid of a polymerizable monomer (2-BPHEI) was obtained in a yield of 84%, HPLC. Obtained with a purity of 92.0% (o = 1.26 average molecular weight: 568). In addition, the H ¹ -NMR spectrum data of the obtained 2-BPHEI was as follows.
H ¹ -NMR δ 1.94 (s, 6H), 2.17 (quin, 4.5H), 4.31-4.45 (m, 9H), 5.57 (quin, 2H), 6.12 ( quin, 2H), 7.61 (d, 5H) 8.20 (d, 5H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 12 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 13: 2-BPHP synthesis (Step 1)
The same operation as in Example 1 except that 48.4 g (0.2 mol) of 2,2-biphenyldicarboxylic acid was used in Step 1 of Example 1 instead of 52.1 g of 4,4-dicarboxybiphenyl ether. To produce an intermediate.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was performed to obtain a yellow liquid of polymerizable monomer (2-BPHP) at a yield of 90%, HPLC. Obtained with a purity of 94.2% (o = 1.45 average molecular weight: 632). In addition, the H ¹ -NMR spectrum data of the obtained 2-BPHP was as follows.
H ¹ -NMR δ 1.94 (s, 6H), 2.17 (quin, 4.9H), 4.31-4.45 (m, 9.8H), 5.57 (quin, 2H), 6. 12 (quin, 2H), 7.11 (d, 5.8H) 8.15 (d, 5.8H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 13 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 14: 2-BPHPI Synthesis (Step 1)
The same operation as in Example 1 except that 48.4 g (0.2 mol) of 2,2-biphenyldicarboxylic acid was used in Step 1 of Example 1 instead of 52.1 g of 4,4-dicarboxybiphenyl ether. To produce an intermediate.

(Step 2-2)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-2 of Example 2 was performed, and a yellow liquid of polymerizable monomer (2-BPPHPI) was obtained with a yield of 93%, HPLC. Obtained with a purity of 93.2% (o = 1.28 average molecular weight: 545). In addition, the H ¹ -NMR spectrum data of the obtained 2-BPHPI was as follows.
H ¹ -NMR δ 1.94 (s, 6H), 2.17 (quin, 4.6H), 4.31-4.45 (m, 9.1H), 5.57 (quin, 2H), 6. 12 (quin, 2H), 7.11 (d, 5.1H) 8.15 (d, 5.1H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 14 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 15: DPSHP synthesis (Production of dicarboxylic acid compound)
In 4 ml of t-butanol and 100 ml of water, 96.8 g (0.4 mol) of 4,4-diformyldiphenyl sulfide synthesized by the synthesis method described in JP-A-2005-15379 was dissolved, and then phosphorus A reaction solution was prepared by adding 50 mL of an aqueous sodium hydrogen oxyhydrate solution and 280 g (4.0 mol) of 2-methyl-2-butene, and further adding 72 g (0.8 mol) of sodium chlorite. Next, after stirring this reaction solution for 5 hours, the reaction solution was acidified with 1N hydrochloric acid aqueous solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and then the precipitated solid was washed with water. The solid (compound) obtained after washing was vacuum-dried to obtain 91.0 g (yield 83%) of 4,4-dicarboxydiphenyl sulfide.

(Step 1)
Subsequently, in Step 1 of Example 1, except that 54.9 g (0.2 mol) of 4,4-dicarboxydiphenyl sulfide was used instead of 52.1 g of 4,4-dicarboxybiphenyl ether, The same operation as in Example 1 was performed to produce an intermediate.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was performed, and a yellow liquid of a polymerizable monomer (DPSHP) was obtained with a yield of 81% and HPLC purity of 89. 0.7% (o = 1.52 average molecular weight: 690). The H ¹ -NMR spectrum data of the obtained DPSHP was as follows.
H ¹ -NMR δ 1.94 (s, 6H), 2.17 (quin, 5.0H), 4.31-4.45 (m, 10.1H), 5.57 (quin, 2H), 6. 12 (quin, 2H), 7.34 (d, 6.1H) 7.89 (d, 6.1H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 15 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 16: DPSOHP Synthesis (Step 1)
In Step 1 of Example 1, 61.3 g (0.2 mol) of 4,4-dicarboxydiphenyl sulfone was used instead of 52.1 g of 4,4-dicarboxybiphenyl ether. The operation was performed to produce an intermediate.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was carried out to obtain a yellow liquid of polymerizable monomer (DPSOHP) in a yield of 78%, HPLC purity of 90 Obtained at 0% (o = 1.22 average molecular weight: 635). Incidentally, ^H 1 -NMR spectral data of the obtained DPSOHP were as follows.
H ¹ -NMR δ 1.94 (s, 6H), 2.17 (quin, 4.4H), 4.31-4.45 (m, 8.9H), 5.57 (quin, 2H), 6. 12 (quin, 2H), 8.05 (d, 4.9H) 8.20 (d, 4.9H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 16 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 17: DPFHP synthesis (Production of dicarboxylic acid compound)
After dissolving 89.6 g (0.4 mol) of 4,4-diformyldiphenylmethane synthesized by the synthesis method described in JP-A-2005-15379 in 400 mL of t-butanol and 100 mL of water, phosphoric acid was dissolved. A reaction solution was prepared by adding 50 mL of an aqueous sodium hydrogen solution and 280 g (4.0 mol) of 2-methyl-2-butene, and further adding 72 g (0.8 mol) of sodium chlorite. Next, after stirring this reaction solution for 5 hours, the reaction solution was acidified with 1N hydrochloric acid aqueous solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and then the precipitated solid was washed with water. The solid (compound) obtained after the washing was vacuum-dried to obtain 79.6 g (yield 78%) of 4,4-dicarboxydiphenylmethane.

(Step 1)
Example 1 except that 51.3 g (0.2 mol) of 4,4-dicarboxydiphenylmethane prepared by the above method was used in place of 52.1 g of 4,4-dicarboxybiphenyl ether in Step 1 of Example 1. The same operation as 1 was performed to produce an intermediate.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was carried out to obtain a polymerizable monomer (yield 86% of a yellow liquid of DPFHP, HPLC purity 94. (O = 1.36 average molecular weight: 615) The H ¹ -NMR spectrum data of the obtained DPFHP was as follows.
H ¹ -NMR δ 1.94 (s, 6H), 2.17 (quin, 4.7H), 4.31-4.45 (m, 9.4H), 5.57 (quin, 2H), 6. 12 (quin, 2H), 7.20 (d, 5.4H) 7.87 (d, 5.4H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 17 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 18: DPAHP synthesis (Step 1)
In Step 1 of Example 1, instead of 52.1 g of 4,4-dicarboxybiphenyl ether, 2,2-bis (4-carboxyphenylphenyl) propane 56. synthesized by the synthesis method described in British Patent GB753384 An intermediate was produced in the same manner as in Example 1 except that 8 g (0.2 mol) was used.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was performed to obtain a yellow liquid of polymerizable monomer (DPAHP) in a yield of 88% and HPLC purity of 94. 0.0% (o = 1.48 average molecular weight: 692). The H ¹ -NMR spectrum data of the obtained DPAHP was as follows.
H ¹ -NMR δ 1.65 (s, 8.9H) 1.94 (s, 6H), 2.17 (quin, 5.0H), 4.31-4.45 (m, 9.9H), 5 57 (quin, 2H), 6.12 (quin, 2H), 7.23 (d, 5.9H) 7.87 (d, 5.9H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 18 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 19: DPALHP synthesis (Production of dicarboxylic acid compound)
After 16.8 g (0.4 mol) of 1,1-bis (4-formylphenyl) cyclohexane synthesized by the synthesis method described in Japanese Patent No. 20766603 was dissolved in 400 mL of t-butanol and 100 mL of water, phosphoric acid was then dissolved. A reaction solution was prepared by adding 50 mL of an aqueous sodium hydrogen solution and 280 g (4.0 mol) of 2-methyl-2-butene, and further adding 72 g (0.8 mol) of sodium chlorite. Next, after stirring this reaction solution for 5 hours, the reaction solution was acidified with 1N hydrochloric acid aqueous solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and then the precipitated solid was washed with water. The solid (compound) obtained after washing was vacuum-dried to obtain 108.8 g (yield 84%) of 1,1-bis (4-carboxyphenyl) cyclohexane.

(Step 1)
Example 1 except that in the step 1 of Example 1, 64.9 g (0.2 mol) of 1,1-bis (4-carboxyphenyl) cyclohexane was used instead of 52.1 g of 4,4-dicarboxybiphenyl ether. The same operation as 1 was performed to produce an intermediate.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was performed to obtain a yellow liquid of polymerizable monomer (DPFHP) in a yield of 86% and HPLC purity of 93. 0.7% (o = 1.37 average molecular weight: 712). Incidentally, ^H 1 -NMR spectral data of the obtained DPALHP were as follows.
H ¹ -NMR δ1.42 (t, 8.2H), 1.94 (s, 6H), 2.10 (t, 5.5H), 2.17 (quin, 4.7H), 4.31- 4.45 (m, 9.5H), 5.57 (quin, 2H), 6.12 (quin, 2H), 7.24 (d, 5.9H) 7.90 (d, 5.9H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 19 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 20: BHP synthesis (Step 1)
In Step 1 of Example 1, the same operation as in Example 1 was carried out except that 33.2 g (0.2 mol) of terephthalic acid was used instead of 52.1 g of 4,4-dicarboxybiphenyl ether. Manufactured.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was performed, and a yellow liquid of a polymerizable monomer (DPAHP) was obtained with a yield of 81% and an HPLC purity of 92. Obtained at 2% (o = 1.42 average molecular weight: 505). Incidentally, ^H 1 -NMR spectral data of the obtained BHP were as follows.
H ¹ -NMR δ 1.94 (s, 6H), 2.17 (quin, 4.8H), 4.31-4.45 (m, 9.7H), 5.57 (quin, 2H), 6. 12 (quin, 2H), 8.04 (d, 5.7H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 20 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 21: NHP synthesis (Step 1)
The same operation as in Example 1 except that 43.2 g (0.2 mol) of 2,6-naphthalenedicarboxylic acid was used in Step 1 of Example 1 instead of 52.1 g of 4,4-dicarboxybiphenyl ether. To produce an intermediate.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was performed, and a yellow liquid of polymerizable monomer (DPNHP) was obtained with a yield of 85% and HPLC purity of 93. Obtained at 1% (o = 1.47 average molecular weight: 663). Incidentally, ^H 1 -NMR spectral data of the obtained NHP were as follows.
H ¹ -NMR δ 1.94 (s, 6H), 2.17 (quin, 4.9H), 4.31-4.45 (m, 9.9H), 5.57 (quin, 2H), 6. 12 (quin, 2H), 7.90 (d, 2.9H), 8.09 (d, 2.9H), 8.57 (d, 2.9)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 21 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Example 22: AHP synthesis (Step 1)
The same operation as in Example 1 except that 53.2 g (0.2 mol) of 2,6-naphthalenedicarboxylic acid was used instead of 52.1 g of 4,4-dicarboxybiphenyl ether in Step 1 of Example 1. To produce an intermediate.

(Step 2-1)
Except that the intermediate produced in Step 1 was used, the same operation as in Step 2-1 of Example 1 was performed, and a yellow liquid of polymerizable monomer (AHP) was obtained with a yield of 85% and HPLC purity of 92. Obtained at 4% (o = 1.47 average molecular weight: 589). The H ¹ -NMR spectrum data of the obtained AHP was as follows.
H ¹ -NMR δ 1.94 (s, 6H), 2.17 (quin, 4.9H), 4.31-4.45 (m, 9.9H), 5.57 (quin, 2H), 6. 12 (quin, 2H), 7.55 (d, 5.8H), 8.62 (d, 5.8H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Example 22 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Reference example 1
A commercially available bisphenol A diglycidyl di (meth) acrylate (Bis-GMA) represented by the following formula was prepared, and HPLC purity and viscosity were measured by the above methods. The results of the purity and the viscosity measured by the above method are shown in Table 1.

Comparative Example 1; 4-DPEHEI
To a solution of 25 g of 4,4-dicarboxybiphenyl ether, 0.85 g (0.012 mol) of dimethylformamide and 80 ml of toluene, a solution of 58.4 g (0.46 mol) of thionyl chloride and toluene was added dropwise at room temperature. After completion of the dropwise addition, the resulting solution was stirred at 95 ° C. for 3 hours. After allowing the reaction solution to cool, 27.4 g of a white solid of 4,4-di (benzoyl chloride) ether was obtained by removing toluene and thionyl hydrogen chloride using a rotary evaporator.

Subsequently, 16.9 g (0.13 mol) of hydroxyethyl methacrylate, 14.7 g of pyridine and 50 ml of tetrahydrofuran were added to a solution of the obtained white solid of 4,4-di (benzoyl chloride) ether in 100 ml of tetrahydrofuran at room temperature. After dropwise addition, the mixture was heated to reflux for 3 hours. After the reaction solution was allowed to cool, tetrahydrofuran was removed using a rotary evaporator, and then 100 ml of toluene was added. The obtained toluene solution was washed with 1% hydrochloric acid three times, then with distilled water three times, and then dried over magnesium sulfate. After the magnesium sulfate was filtered off, the removal of the solvent yielded a yield of 73% and a HPLC purity of 76.2%, giving 35 g of a yellow liquid of DPEHEI (all the yields described here were obtained as 4-DPEHEI). Yield of the product).
The H ¹ -NMR spectrum data of the obtained 4-DPEHEI was as follows.
H ¹ -NMR δ 1.93 (s, 6H), 4.40 (s, 8H), 5.57 (s, 2H), 6.12 (s, 2H), 7.61-8.20 (m, 8H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Comparative Example 1 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1. This compound is the same as the compound of Example 1 except for the value of o.

Comparative Example 2; 4-DPEHHI
It was the same as the synthesis method of 4-DPEHEI except that 24.2 g (0.13 mol) of hydroxyhexyl methacrylate was used in place of hydroxy methacrylate, and the yellow color of DPEHHI was obtained with a yield of 75% and an HPLC purity of 75.1%. Of 45 g of a liquid (all yields given here are the yields when obtained as 4-DPEHHI).
The H ¹ -NMR spectrum data of the obtained 4-DPEHHI was as follows.
H ¹ -NMR δ 1.93 (s, 6H), 1.51-1.80 (m, 16H), 4.00-4.40 (m, 8H), 5.57 (s, 2H), 6. 12 (s, 2H), 7.61-8.20 (m, 8H)
From the above measurement results, it was confirmed that the polymerizable monomer synthesized in Comparative Example 2 had a structure represented by the following formula. The results of the purity and the viscosity measured by the above method are shown in Table 1. This compound is the same as the compound of Example 5 except for the value of o.

Example 23
60 parts by mass of 4-DPEHP produced in Example 1 (using the same purity as shown in Table 1), 40 parts by mass of triethylene glycol dimethacrylate, photopolymerization initiator (0.5 parts by mass of camphorquinone, p- N, N-dimethylaminoethyl benzoate 0.8 parts by mass) and a polymerization inhibitor (2,6-di-t-butyl-p-cresol 0.1 parts by mass) were stirred in the dark until uniform. . Thereby, a matrix monomer sample was obtained. 101.4 parts by mass of a matrix monomer sample and 205.9 parts by mass of the following inorganic filler F1 were weighed and mixed in an agate mortar to obtain a mixture. Subsequently, the mixture was defoamed under vacuum to remove bubbles to obtain a paste-like curable composition. About the curable composition obtained by the said method, the measurement evaluation of the following flow property and the evaluation of underwater stability were performed.

  Inorganic filler F1; spherical silica-zirconia (average particle size 0.4 μm) hydrophobized with γ-methacryloyloxypropyltrimethoxysilane, and spherical silica-zirconia (average particle size 0.07 μm) γ-methacryloyloxy A mixture obtained by mixing the material hydrophobized with propyltrimethoxysilane at a mass ratio of 70:30.

(Measurement evaluation of flow properties)
The obtained paste-like curable composition sample was placed on a slide glass in such a manner that 0.1 mg each had a diameter of 5 mm or less. Subsequently, the slide glass was placed in an incubator at 37 ° C., taken out after 2 minutes, and irradiated on one side for 10 seconds with a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation). Two points were measured so that the diameter of the bottom surface of the obtained cured body was 90 degrees. The test was performed twice for each paste, and the average value was calculated. The results are shown in Table 2.

(Evaluation of underwater stability)
According to JIS T6514: 2013, according to the bending strength measurement method for a class 2 group 1 dental filling composite resin, visible light irradiation is performed for 20 seconds by a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation), respectively. Then, the curable composition was cured to prepare a cured body sample, the bending strength was measured, and this was used as the initial value of the bending strength. A universal testing machine (Autograph, manufactured by Shimadzu Corporation) was used for the measurement. Further, the cured body samples were further immersed in water for 4 weeks and 12 weeks, the bending strength was measured, and the bending strengths were measured after immersion in water for 4 weeks and 12 weeks, respectively.

Examples 24-44, Reference Example 2, Comparative Examples 3, 4
In Example 23, 4-DPEHP was replaced with the polymerizable monomer produced in Examples 2 to 22, Bis-GMA in Reference Example 1, and the polymerizable monomer produced in Comparative Examples 2 and 3. The same operation as in Example 23 was performed to prepare a paste-like curable composition. The blending ratio of each component is naturally the same as in Example 23. The polymerizable monomers used are summarized in Table 2.

  Moreover, about the curable composition obtained by each Example, the reference example, and the comparative example, the measurement evaluation of flow property and the evaluation of underwater stability were performed similarly to Example 23, and the result is put together in Table 2. It was.

Claims (4)

(Where
X is a divalent group represented by —O— ,
m is 1 ,
n is 1 ,
o it is 1,
Ar ¹ and Ar ² are each a divalent unsubstituted aromatic group;
L ¹ is a divalent hydrocarbon group having 2 to 50 carbon atoms,
R ¹ and R ² are each a hydrogen atom or a methyl group. And a method for producing a polymerizable monomer represented by:
The following general formula (2)

(Wherein, X, m, n, Ar ¹ and Ar ² have the same meanings as those in the general formula (1)),
The following general formula (3)

(In the formula, L ¹ has the same meaning as in the general formula (1)). After dehydration condensation reaction with the diol compound represented by the formula (1), (meth) acryl groups are formed at both ends of the obtained compound. The manufacturing method characterized by introducing.   The method of introducing a (meth) acryl group is a method in which a hydroxyl group at both ends and (meth) acrylic acid are subjected to a condensation reaction, or a hydroxyl group at both ends and (meth) acrylic anhydride are reacted. The manufacturing method according to claim 1. The dicarboxylic acid compound represented by the general formula (2) is represented by the following general formula (4).

(Wherein, X and m are the same as those in formula (2)). 3. The production method according to claim 1, wherein the compound is a dicarboxylic acid compound. The diol compound represented by the general formula (3) is represented by the following general formula (5).

(Wherein p is an integer selected from the range of 1 to 10), and the production method according to any one of claims 1 to 3.