JPS61293951A - Acrylate compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R1 is alkyl; R2 is H, alkyl or formula II (R4 is H or alkyl; R5 is alkylene); X and Y are H, alkali metal, alkyl or aryl]. USE:Effective as a metallic material, organic high polymer material, ceramic material and adhesive material component for hard tissues of human bodies, etc. and capable of improving the adhesive strength, fire resistance and durability in heat cycles. PREPARATION:A vinyl compound expressed by formula III (Z is OH or halogen) is reacted with an alcoholic compound expressed by formula IV R3' is H, alkyl or a group expressed by the formula -R5-OH; X' and Y' are H, alkyl or alkyl), and, as necessary, an alkali metal (compound) is reacted with the resultant compound to afford the aimed compound expressed by formula I.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to novel acrylate compounds.

More specifically, the present invention relates to acrylate compounds that are effective as adhesive components for metal materials, organic polymer materials, ceramic materials, human hard tissues, and the like.

[Prior art and problems to be solved by the invention] In recent years, adhesives have been widely used in metals, organic polymers, ceramics, and the medical sector, etc., and have been used to reduce the weight of equipment, save energy,
It plays an important role in achieving high functionality. Conventional reactive adhesives include epoxy resins, urethane resins, unsaturated polyesters, cyanoacrylates, and the like.

Among these materials, those that have excellent adhesive strength have a slow curing speed and require high temperature or long curing, while those that harden in a short time, such as cyanoacrylate, have problems such as poor water resistance.

On the other hand, acrylate monomer-based adhesives can be cured using various curing agents such as heating, room temperature, and light, depending on the application, and have the characteristic that the curing time can be adjusted within a wide range. However, the adhesive strength of this adhesive is mainly due to the so-called fitting force obtained by performing various surface treatments to create irregularities on the adhered surface.

Therefore, there is a need for an adhesive that has adhesive strength without surface treatment.

In response to the above demands, the use of various acrylate compounds having carmexyl groups has been reported as a method of increasing adhesive strength. For example, Dental Science and Engineering Journal No. 8
Vol. 14, pages 36-43 states that acrylate compounds such as the following are effective for adhesion to ivory.

Although adhesive strength has been improved by the above-mentioned acrylate compounds having a carmexyl group, the adhesion in wet conditions, long-term water resistance, and durability against thermal cycling in water are still not sufficient. Improvements in properties are desired.

[Means and Effects for Solving the Problems] In order to solve the above problems, the present inventors conducted intensive research on compounds with high adhesive strength and durability. They discovered that a compound with a specific structure in which two alkali gold salts and two carboxyesters are bonded to the same carbon atom has extremely excellent adhesive strength and durability, leading to the completion of the present invention. Ta.

That is, the present invention is based on the following general formula (1) [However, R1 represents a hydrogen atom or an alkyl group, R2 represents a hydrogen atom or an alkyl group, and R5 represents an alkylene group. ), and X and Y represent the same or different hydrogen atoms, alkali metals, alkyl groups, or aryl groups. ] This is an acrylate compound represented by:

R4 and R4 in the above general formula (I) can be used without any restriction as long as they are hydrogen atoms or alkyl groups, but for reasons such as ease of obtaining raw materials, isolation and purification, hydrogen atoms or 4 More preferably, 1 to 2 alkyl groups are suitable. In addition, R2 and R5 in the above general formula (I) can be used without any restriction as long as they are alkylene groups, but
20, and more preferably in the range of 4 to 12 to obtain high adhesive strength, and can be used without any restriction if preferred; however, in the case of an alkyl group, carbon numbers in the range of 1 to 20. More preferably 1-
A range of 10 is most preferred. X in the above general formula (1)
and Y represent the same or different hydrogen atoms, alkali metals, alkyl groups or aryl groups. As an alkaline earth genus, L
i, Na, K, Rb, C8 are used, the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and the aryl group has 6 to 14 carbon atoms. is suitable.

Examples of generally preferred alkylene groups, alkyl groups or aryl groups are as follows. For example R4 and R4
Examples of the alkyl group include -CH, -C2H5, etc., and alkylene groups for R2 and R5.

+CH2+ 91 + CH2"+. 2 minutes CH2+11
Examples of the alkyl group for R5 include -C9H19.''Cl0H21, and examples of the alkyl group or aryl group for X and Y include the following.

When the acrylate compound of general formula (1) above is used as an adhesive component, the adhesive strength is high when X and Y are hydrogen atoms or alkali metals, and particularly excellent adhesive strength is obtained when they are hydrogen atoms. is obtained. Also, a compound in which R6 is a hydrogen atom, or a compound in which R2 or R5 has 4 to 4 carbon atoms.
The compound having No. 12 exhibits high adhesive strength as an adhesive component.

The acrylate compound of the present invention represented by the above general formula (1) is a colorless or pale yellow transparent liquid when X and Y are hydrogen atoms, alkyl groups, or aryl groups, and when X and Y are alkali metals. is solid.

The acrylate compound of the present invention can be confirmed as such by the following measurements.

(~ infrared absorption), /I/(IR) measurement When the IR of the compound represented by general formula (I) is measured, it is 3000.
Absorption based on aliphatic carbon-hydrogen bonds around ~2800cfn, strong absorption based on carbonyl groups around 1800~1600crn-', 1650~1620crn
Absorption based on the C=0 double bond is seen near -'.

(B) H-nuclear magnetic resonance spectrum ('H-NMR
) measurement (tetramethylsilane standard; measurement at 699 m) ■ 0.8 to 2. A peak based on protons of methylene or methyl groups appears near Oppm.

■ When R1 is CH in general formula (I), 1.9
A peak based on the proton of the methyl group appears near ppm.

■ When number 5 is a hydrogen atom in general formula (1), 3.
A peak based on the proton of the vinyl group based on the proton of the methyl group appears around 0 to 3.6 ppm.

(2) A peak based on double bond protons appears around 5.2 to 6.6 ppm.

(2) When X and Y are aryl groups in general formula (I), a peak based on the protons of the aryl group appears around 6.5 to 8 ppm.

(2) A peak based on calgenic acid protons appears around 9 to 12 ppm. This peak disappears by substitution with heavy water.

C) Mass spectrometry As a means of mass spectrometry, field desorption ionization method (MS-F
(abbreviated as D) can be used to confirm the molecular weight.

If the molecular weight of the acrylate compound of the present invention is M, then M
A molecular ion is observed at the +1 or Mo position.

(2) Elemental Analysis The acrylate compound of the present invention can be confirmed by comparing the carbon and hydrogen analysis results with the theoretical values calculated from the general formula (I).

(6) Atomic absorption analysis When X and Y are alkali metals, the alkali metals can be quantified by calcining the compound represented by formula (I) at 700°C and then performing atomic absorption analysis as an aqueous solution.

The acrylate compound of the present invention represented by the general formula CI) can be confirmed by the various measuring methods described above.

The method for producing the acrylate compound of the present invention represented by the general formula (1) is not particularly limited, and any method may be employed. A concrete example of an industrially suitable method is as follows.

In other words, the following formula 〇) CH2-C(IF) O2 (However, R1 represents a hydrogen atom or an alkyl group.

2 represents a hydrogen group or a halodane atom. ) and the following formula (g) [wherein R2 represents an alkylene group, and R/ is a hydrogen atom, an alkyl group, or a group represented by HO-R5- (provided that R5 is an alkylene group). and ! and Y' represent the same or different hydrogen atoms, alkyl groups, or aryl groups] or by further reacting with an alkali metal or an alkali metal compound, the above-mentioned An acrylate compound of general formula (1) is obtained.

As the vinyl compound represented by the general formula (10), any known vinyl compound can be used without restriction. For example, when 2 is a hydroxyl group, examples include acrylic acid, methacrylic acid, ethyl acrylic acid, etc., and when 2 is a rhodan atom Preferred examples include acrylic chloride, methacrylic chloride, ethyl acrylic chloride, acrylic bromide, methacrylic bromide, and ethyl acrylic bromide.

As the alcohol compound represented by the general formula a), any compound synthesized by any method can be used.

A specific example of the manufacturing method is as follows.

That is, a malonic acid ester represented by the following formula (g) (where Rtt represents a hydrogen atom or an alkyl group, and R and R7 represent the same or different alkyl group or aryl group) and a malonic acid ester represented by the following formula (■ HO-R2 -Z' (
V: (However, R2 is an alkylene group, and 2' represents a rodan atom.) React with a halodanated alcohol compound represented by
By carrying out hydrolysis if necessary, an alcohol compound represented by the above general formula can be obtained.

As the malonic acid ester shown in the above-mentioned general second shield, publicly known malonic esters can be used without any restriction. For example, dimethyl malonate, diethyl malonate, zopropyl malonate, diisopropyl malonate, diptyl malonate, di-t malonate.
er-butyl, zophenyl malonate, bismethylphenyl malonate, naphthyl malonate, trimethyl methyl malonate, diethyl methyl malonate, dimethyl ethyl malonate, diethyl ethyl malonate, noethyl furopyl malonate, diethyl isoglobil malonate, butyl Dimethyl malonate, butyl dimethyl malonate, pentyl diethyl malonate, hexyl diethyl malonate, octyl soethyl malonate, nonyl soethyl malonate, decyl diethyl malonate, and the like.

Further, as the general formula (denoted by Vl)/logonated alcohol, known ones can be used without any restriction.

In particular, in the general formula (to), 2' is preferably a bromine atom or an iodine atom. Examples of those preferably used in the present invention include 4-bromo-1-ethanol, 5-bromo-1-pentanol, 5-bromo-2-methanol, 6-f-bromo-1-hexanol, 5
-Bromo-2-hexanol, 7-bromo-1-hesitanol, 8-bromo-1-octatool, 9-! Romu-1-nonanol, 10-bromo-1-decanol, 11
-bromo-1-undecanol, 12-bromo-1-dodecanol, 6-iodo-1-hexanol.

Examples include 10-iodo-1-decanol.

In the above reaction, the malonic acid ester of the above general formula (g) and the halodanated alcohol of the general formula (Vl) can be reacted at a molar ratio in the range of 0.1 to 10,
For 1 mole of malonic acid ester, when obtaining an alcohol compound in which R/ in the general formula (g) is a hydrogen atom or an alkyl group, equal moles are used, and R' is -R5-OH (however, R5
represents an alkylene group. ), it is preferable to react with twice the molar amount of halogenated alcohol. The above reaction includes metallic sodium, metallic potassium, sodium hydride,
It is preferable to use an alkali metal such as sodium ethylate, an alkali metal hydride, or an alkali metal alcoholade, and it is appropriate to react an equimolar to twice the molar amount with respect to the malonic acid ester. Solvents for this reaction include methanol, ethanol, isoglobil alcohol, 2-methyl-2-f/'P-nol, benzene, and chloroform.
A suitable range is 0 or more, preferably 100 to 1000.

The reaction conditions are not particularly limited, but the appropriate reaction temperature is 50°C or higher, preferably 60 to 100°C, and the reaction time is 30 minutes or more, preferably 1 to 5 hours. . After completion of the reaction, the mixture is filtered and the solvent is distilled off under reduced pressure to obtain an alcohol compound in which K and Y' in the general formula (2) are the same or different alkyl groups or aryl groups.

The alcohol compound in which and Y' in the general formula (to) are hydrogen atoms can be obtained by further hydrolyzing the alcohol compound obtained in the above reaction with an alkali. As the alkali, 5 to 50% by weight of alkali hydroxide such as sodium hydroxide or potassium hydroxide;
The appropriate amount is preferably 10 to 300 to 30% by weight, preferably 2.5 to 4 mol or more based on the malonic acid ester.
A double range is appropriate. The suitable hydrolysis temperature is 50°C or higher, preferably 80 to 120°C. After completion of hydrolysis, by-product alcohol produced by hydrolysis is distilled off under reduced pressure, and then an acid such as hydrochloric acid or sulfuric acid is added dropwise to i+3.
The following shall apply. The reaction product varies depending on R2 or Hl in the general formula (g), but is usually solid or liquid.

If it is a solid, it can be isolated and obtained by washing with water and drying under reduced pressure, and if it is a liquid, it can be extracted with a solvent that can be separated from water, such as ethyl acetate, diethyl ether, or methyl isobutyl ketone.

The method for reacting the vinyl compound represented by the general formula (ID) with the alcohol compound represented by the general formula (g),
Although not particularly limited, specifically, the following method is preferably employed.

When 2 in the vinyl compound represented by the above general formula (It) is a halodane atom, the above general formula (It) can be obtained by the following reaction.
The acrylate compound I) is obtained. That is, the vinyl compound represented by the general formula (n) is reacted in an equimolar or slightly excess amount with respect to the OH group of the alcohol compound on the general formula side. Solvents include tetrahydrofuran, acetone, diethyl ether, sochloromethane, chloroform,
Solvents such as benzene can be used. As for the amount of solvent, the alcohol compound concentration of the above general formula (to) is 0.1 to 50 w
t%, preferably in the range of 1 to 10 wt%.

The reaction temperature is 30°C or less when adding the vinyl compound dropwise.
It is preferably carried out under water cooling, and after the dropwise addition is completed, the temperature is suitably 70°C or lower, preferably in the range of 10 to 40°C. This reaction is preferably carried out in the presence of an aliphatic amine such as trimethylamine or triethylamine or a base such as pyridine.

It is appropriate to add the base in equimolar or slightly excess amount to the vinyl compound. It is also preferable to add a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, butylhydroxytoluene, etc. After the reaction is complete,
After the by-product salt is removed by filtration, the solvent is distilled off under reduced pressure to isolate and obtain the acrylate compound of the present invention. More preferably, the above product is dissolved in a solvent such as dichloromethane, chloroform, benzene, toluene, n-hexane, cyclohexane, etc., washed with a dilute aqueous hydrochloric acid solution, further washed with water 2 to 5 times, and then the solvent is distilled off under reduced pressure. f
It is preferable to make it by illumination.

In the reaction between the vinyl compound represented by the general formula (II) and the alcohol compound represented by the general formula (II), when 2 of the vinyl compound is a hydroxyl group, the acrylate compound of the present invention can be obtained by the following reaction. can. That is, the acrylate compound of the present invention can be obtained by carrying out a dehydration reaction between the alcohol compound of the general formula (to) and the vinyl compound of the general formula (IO). It is preferable when x/ and y/ are the same or different alkyl groups or aryl groups, and when X' and Y' are hydrogen atoms, by-products tend to increase.

In the above reaction, it is preferable to use an acidic catalyst,
As the acidic catalyst, P-)luenesulfonic acid, benzenesulfonic acid, sulfuric acid, etc. can be suitably used.

The catalyst amount is O, 1 to 20 Wt relative to the vinyl compound.
, preferably 1 to 10 wt. As the dehydration method, a method using reduced pressure, reflux dehydration using benzene or toluene, etc. are used. Although the reaction conditions are not particularly limited, a suitable reaction temperature range is from 50°C to 120°C. Further, it is preferable to add a small amount of a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether.

After the reaction is complete, transfer to a separating funnel and add benzene, toluene,
Add a solvent such as chloroform or dichloromethane, add sodium carbonate or hydrogen carbonate, neutralize with an aqueous solution such as iJium, and then wash with dilute hydrochloric acid and water. The acrylate compound shown can be isolated and obtained.

In addition, X of the acrylate compound of the above general formula (I).

When Y is an alkali metal, it can be obtained by the following reaction.

That is, X obtained by X in the above reaction.

It is obtained by reacting an acrylate compound in which Y is a hydrogen atom with an alkali metal or an alkali metal compound. Lithium, sodium, and potassium are suitable as alkali metals. As the alkali metal compound, the above-mentioned alkali metal oxides, hydroxides, carbonates, etc. are preferable.

The acrylate compound of the present invention can be suitably used as a monomer component of an adhesive, as is clear from the application examples described below. The 7-acrylate compound of the present invention is
It can also be used in combination with monomer components of conventionally known adhesives, such as acrylate or methacrylate. A radical initiator is preferably used as the polymerization initiator for the monomer component containing the acrylate compound of the present invention. For example, organic peroxides such as benzoyl peroxide, lauroyl peroxide, cumenehydrono-oxide, di-t-butyl peroxide; azo compounds such as azobisisobutyronitrile and azobiscyclohexanenitrile; camphoraquinone, benzoin methyl ether , acetoinbenzophenone, p-chlorobenzophenone, and other photosensitizers.

An adhesive prepared by mixing a monomer component containing the acrylate compound of the present invention with the above polymerization initiator is used for adhering adherends by initiating polymerization by means such as heating or light irradiation.

The adhesive containing the acrylate compound of the present invention can be used to bond metals, ceramic materials, human hard tissues such as teeth and bones, organic polymer materials, and the like.

When the acrylate compound of the present invention is used as a monomer component of an adhesive, it is possible to improve not only adhesive strength but also water resistance and thermal cycle durability compared to conventionally known monomer components. Therefore, the acrylate compound of the present invention is an extremely important and useful compound as a new monomer component in adhesives in all fields.

EXAMPLES Examples are given below to explain the present invention more specifically, but the present invention is not limited to these Examples.

Example-1 33.8 g of soethyl malonate and 150 g of ethanol were placed in a 300-meal flask equipped with a dropping funnel and a cooling tube, and while cooling on ice, 4.85.9 g of metallic sodium was added.
Stirring was performed until a homogeneous solution was obtained. Subsequently, 50.0 I of 10-bromo-1 decanol was added dropwise using a dropping funnel, and then heated at 80° C. for 3 hours.

The above solution was transferred to a 5 oy eggplant flask, and ethanol was distilled under reduced pressure. Next, add 20wt% NaOH solution to 120%
After heating at 100℃ for 2 hours, add 6N hydrochloric acid to
30 mA' was added dropwise to bring the solution to about 2. The obtained solid was rinsed with water through a glass filter, then dissolved in acetone and dehydrated with anhydrous sodium sulfate and anhydrous magnesium sulfate. Subsequently, acetone was distilled off under reduced pressure at room temperature.

Next, 10% of the above solid was placed in a 300-inch three-necked flask equipped with a dropping funnel. l triethylamine 4.27I, hydroquinone 20m9 and tetrahydrofuran 200m/
Add 4.42 methacrylic acid chloride while cooling on ice.
ml was added dropwise using a dropping funnel. Subsequently, the mixture was allowed to stand overnight with stirring at room temperature, and then passed through a 0.51!1N filter to remove the l-IJ ethylamine hydrochloride. This solution was distilled under reduced pressure at room temperature to remove tetrahydrofuran, and then mixed with 200 ml of dichloromethane and 100 ml of 0.1N hydrochloric acid.
rLl! Extraction and purification were carried out, and the dichloromethane layer was concentrated to obtain a viscous pale yellow liquid of 8.5y. The isolated product was confirmed to be an acrylate compound represented by the following formula according to various measurement results described below.

(b) The IR chart was shown in Figure 1 of the attached drawings.

Absorption based on aliphatic carbon-hydrogen bonds at 3000 to 2800 crn-1, absorption based on carbonyl groups at 1800 to 1640 cIn, and c=c at 1640 to 1620 crn-1
Absorption based on double bonds was observed.

(b) 1H-NMR (tetramethylsilane standard,
δppm, 60 MHz) See Figure 2 of the attached drawings.
A H-NMR chart is shown.

Two carboxylic acid protons appear in a single line at 9.5 ppm (disappeared due to heavy water substitution), and at 5.6 ppm and 6.2
Two double bond protons appear as a double line in ppm,
Two triplet protons of the methylene group next to the ester bond appear at 4.3 to 3.9 ppm, and 3.55 to 3.9 ppm.
At 15 ppm, one methane group proton appears as a triple line, at 1.9 ppm, three methyl group protons appear as a single line, and at 1.3 ppm, a methylene group proton has a wide range. 188 single lines appeared.

(c) Mass spectrometry (MS-FD) As a result of mass spectrum measurement, ry'e 329 has M■+
1 peak appeared.

B) Elemental analysis values The elemental analysis values were C62.05% and H8.61, which agreed well with the theoretical values of C62.17 and H8.59%.

Example 2 The following acrylate compound was obtained by carrying out the same operation as in Example 1, except that acrylic acid chloride was used as a raw material instead of methacrylic acid chloride.

O (a) lR Absorption based on aliphatic carbon-hydrogen bond at 3000-2800 cm-', absorption based on carbonyl group at -1 at 1800-1640, c at 1640-1620 cm-'
=c Absorption based on type 2 packing was observed.

(e+)'H-NMR (tetramethylsilane standard, δppm, 60 MI(z)) A chart of 'H-NMH is shown in Figure 3 of the attached drawings.

At 9.2 ppm, two nolotons of force/V bonic acid appear in a single line (disappeared by heavy water substitution), and at 6.5 to 5,5 p.
Three protons of the 2X bond appear as a multiplet between pm, two protons of the methylene group next to the ester bond appear as a triplet at 4.3-3.9 ppm, and 3.55 to 3.9 ppm.
One methine group proton appeared as a triple line at 3.15 ppm, and 188 methylene group norotons appeared as a wide single line at 1.30 ppm' (ll-center).

e→Mass spectrometry As a result of mass spectrometry, a peak of M''+1 appeared at m/'e315.

B) Elemental analysis value The elemental analysis value was C61.05, H8,40, which was in excellent agreement with the theoretical value of C61.13%, H8,34.

Example 3 44.2 g of diethyl malonate and 100 g of ethanol were placed in a 300 m/3-neck flask equipped with a dropping funnel and a cooling tube, and 6.49 g of sodium metal was added while cooling on ice, followed by stirring until a homogeneous solution was obtained. .

Subsequently, 6-promu-1-decanol so, o, Ft[i
After dropping through the lower funnel, the mixture was heated at 70°C for 5 hours.

Transfer the above solution to a 500 Gonas flask and add 30wt%
100 ml of NaOH aqueous solution was added and heated at 110° C. for 1 hour. After cooling, add 12N hydrochloric acid dropwise to make - 2 or less,
Most of the ethanol was removed by vacuum distillation. 50% of the above solution
The mixture was transferred to a separatory funnel with a diameter of 0.2 mm, and 200 n/ml of ethyl acetate was added thereto. After washing with water three times, the ethyl acetate layer was dehydrated with anhydrous sodium sulfate and anhydrous magnesium sulfate. Next, the solvent was distilled off under reduced pressure to obtain malonic acid compound 33.8F.

Thereafter, methacrylic acid chloride was reacted in the same manner as in Example 1 to obtain the following acrylate compound.

(b) Absorption based on aliphatic carbon-hydrogen bond at lR 3000-2800α-1, absorption based on carzanyl group at 1800-1640crn, KC== at 1640-1620cm
Absorption based on C2 type packing was observed.

←) 'H-NMR (tetramethylsilane standard; δ
ppm, 60 MHz) The spectra were the same as in FIG. 1 shown in Example 1, except that the proton of the methylene group centered at 1.30 ppm appeared as a broad single line corresponding to ION.

(c) Mass spectrometry (MS-FD) As a result of the mass spectrum, a Me+1 peak appeared at TV/s 273.

B) Elemental analysis values The elemental analysis values were C57.20 and H7.45%, which agreed well with the theoretical values of 57.34 and H7.40.

Example 4 The following acrylate compound was obtained by carrying out the same operation as in Example-1 except that the following compound was used as a raw material.

Acrylate compound (a) lR Absorption based on aliphatic carbon-hydrogen bond at 3000-2800 cm, absorption based on cargonyl group at 1800-1640 rho1, 1640-1620 c! C=C2 in n
Absorption based on heavy bonds was observed.

(b) ” H-NMR (tetramethylsilane standard,
δppm, 60■h) 'H-NM in Figure 4 of the attached drawings.
A chart of R is shown.

Two carboxylic acid protons appear in a single line at 9.8 ppm (disappeared due to heavy water substitution), and at 5.6 ppm and 6.2
ppm and 2! Two protons of the i bond appear as a double line, and two protons of the methylene group next to the ester bond appear as a triple line at 4.3 to 3.9 ppm, and 1.9 ppm.
Three protons of the methyl group on the double bond appear in a single line, and the protons of the methylene group at 1.3 ppm and the fr:1 ton of the methyl group on the quaternary carbon appear in a wide single line. 21 pieces appeared.

(c) Mass spectrometry (MS-FD) As a result of the mass spectrum, a peak of M''+1 appeared at m/@343.

B) Elemental analysis values The elemental analysis values were C63.19% and H8.91%, which agreed well with the theoretical values of C63.13% and H8.83%.

Example 5 Diethyl malonate 33.8.9. 150 d of ethanol was added, and while cooling on ice, 4,851 d of metallic sodium was added and stirred until a homogeneous solution was obtained. Next] 0-Brom-
1-decanol 50F was added dropwise through the entire dropping funnel and then heated at 80°C for 3 hours. After cooling this solution, 4.85# of metal sodium was further added and dissolved, and then 10-bromine-
After dropping 1-decanol 501, it was heated at 80°C for 5 hours. Thereafter, the same operation as in Example 1 was performed to obtain the following acrylate compound.

(b) Absorption based on aliphatic carbon-hydrogen bond at lR 3000-2800 rho 1, absorption based on carbonyl group at 1800-1640ffi, C=C at 1640-1620 rho 1
Absorption based on double bonds was observed.

(o) 'H-NMR (tetramethylsilane standard e
'p prri #60 MHz) A chart of I(-NMR) is shown in FIG. 5 of the attached drawings.

Two carboxylic acid protons appear in a single line at 9.3 ppm (disappeared due to deuterium substitution), and at 5.6 ppm and 6.
At 2 ppm, four double bond protons appear as a double line, and at 4.3 to 3.9 ppm, four triple line protons of the methylene group next to the ester bond appear, and at 1.9 ppm.
Six protons of the methyl group appear in a single line, and 1.3
36 methylene group protons appeared as a wide single line centered on ppm.

(c) Mass spectrometry (MS-FD) Mass spectrometer measurement result M +1 for rn7/e554
peak appeared.

B) Elemental analysis value The elemental analysis value was C67.45%, H9.51chi, and was in good agreement with the theoretical value of 067.36%, H9,48chi.

Example 6 Acrylate compound 5I obtained in Example 1 was 1001
A total of 20 g of methanol was poured into a 100 liter beaker to make a homogeneous solution. Add 30 liters of NaOH solution to this.
The mixture was stirred for 1 hour.

Next, methanol was distilled off under reduced pressure to produce a white precipitate.

This was passed through a filter and washed with water to obtain 4.2 g of the following acrylate compound as a white solid.

(a) Absorption based on carbon-hydrogen bond of K aliphatic at 1R 3000-2800ffi, and absorption based on carbonyl group at 1800-1640crTt were observed.

←) Atomic absorption analysis value The result of atomic absorption analysis was 12.2% Na, which was in good agreement with the theoretical value of 12.34% Na.

(c) Elemental analysis value The elemental analysis value was C54.68%, H7.03, which was in good agreement with the theoretical value of C54.83%, H7,04.

Example 7 Noethyl malonate was placed in a 300ml three-neck flask equipped with a dropping funnel and a cooling tube. x ta/ -/l/
Add 150m/ml of metallic sodium 4.8I while cooling on ice.
was added and stirred until a homogeneous solution was obtained.

followed by lO-bromo-1-decanol/l150. o,s
After dropping i with a dropping funnel, the mixture was heated at 703°C for 5 hours.

The above solution was passed through a 0.5μ filter to remove NaBr, a reaction by-product. While heating the oral fluid to 100° C., vacuum distillation was performed using a vacuum pump to remove the solvent and unreacted raw materials, thereby obtaining a liquid malonic acid ester compound (46.51).

Thereafter, methacrylic acid chloride was reacted in the same manner as in Example 1 to obtain the following methacrylic ester compound.

(a) Absorption based on aliphatic carbon-hydrogen bonds was observed at lR 3000-2800 cm, absorption based on cargenyl group at 1800-1640 crn-1, and absorption based on C=C double bond at 1640-1620 crn.

←) 'H-NMR (tetramethylsilane standard, δ
ppm, 60 MHz) A H-NMR chart is shown in FIG. 6 of the attached drawings.

Two double bond protons appear as double lines at 5.6 ppm and 6.2 ppm, and protons of the methylene group next to the methacrylic ester and the methylene group of the ethyl ester appear at 4.3 to 3.9 ppm. Six multiple lines appear, 3.
At 55 to 3.15, one proton of the methane group appears as a triple line, three protons of the methyl group appear as a single line at 1.9 ppm, and the proton of the methylene group appears at 1.3 pprn. Protons and 24 protons of the methyl group of the ethyl ester appeared as a broad peak.

(c) Mass spectrometry (MS-FD) As a result of the mass spectrum, a Me peak appeared at m/e 385.

B) Elemental analysis values The elemental analysis values were C65.50% and H9.32%, which agreed well with the theoretical values of C65.60 and H9.44.

Example 8 In Example 3, a methacrylic ester compound was synthesized using methacrylic acid as a substitute for methacrylic acid chloride. That is, 10 g of the liquid malonic acid ester compound obtained in Example 3, 2.8 J of methacrylic acid, p-
) 0.1 g of 0.5F hydroquinone monomethyl ether of luenesulfonic acid was placed in a 100 d three-way flannel and heated to 80° C. under reduced pressure (approximately 50 μHg), and the reaction was continued until no water came out. After the reaction was completed, the reaction solution was cooled, transferred to a separating funnel, added with 200 ml of n-hexane, and washed with an aqueous solution of IJ carbonate, followed by washing with 0.1N hydrochloric acid and water three times. After dehydrating the hexane layer with anhydrous sodium sulfate and anhydrous magnesium sulfate, 1101 n of butylated hydroxytoluene was added and the hexane was distilled off under reduced pressure to obtain 9.5 g of the same product as obtained in Example 3.

Example 9 Malonic acid 1 was added to an aoomz three-necked flask equipped with a cooling tube.
5.6. ? , 7! No #28.2.9, sulfuric acid 11n! ,
Toluene isomg was added and dehydration was performed under reflux for 48 hours. After the reaction is complete, transfer to a separatory funnel and wash with water 5 times.
The toluene layer was dehydrated with anhydrous sodium sulfate and then distilled under reduced pressure to obtain 319 liquid phenyl malonates.

The following ester compound was obtained in the same manner as in Example 7 except that the solvent ethanol was replaced with tetrahydrofuran.

(b) Absorption based on aromatic carbon-hydrogen bonds at lR 3100-3000on-'', absorption based on aliphatic carbon-hydrogen bonds at 3000-2800ffi-1, 1800-1640c!n
Absorption based on cargenyl group, 1640-1620c
Absorption based on C=C double bond was observed at 1n-'.

(o) "H-NMR (tetramethylsilane standard, δppm, 60■h)" in the attached drawings and Figure 7'!
(-NMR chart is shown.

10 phenyl group zolotones appear in the multiplet at 7.6 to 6.6 ppm, and 2 zolotones appear at 5.6 ppm and 6.2 ppm.
Two protons of the double bond appear as a double line, and 4.3-3
．． At 9 ppm, two protons of the methylene group next to the ester bond appear as a triple line, and at 3.8 to 3.5 ppm, one proton of the methylene group appears as a triple line, and 1.9
At 1.3 ppm, 3 protons of the methyl group appeared in a single line, and 188 protons of the methylene group appeared in a wide single line at the center of 1.3 ppm.

(c) Mass spectrometry (MS-FD) As a result of mass spectrum measurement, m/e 481 K MΦ
peak appeared.

B) Elemental analysis values The elemental analysis values were C72.32chi and R7.46excellent, which agreed well with the theoretical values of C72.47chi and R7.55chi.

Example 10 Various acrylate compounds were synthesized by conducting reactions in the same manner as in Examples 1, 6.7, and 9. The results are shown in Table 1. Among the Omote Nakaya, 1 to 74 were processed in the same manner as in Example 1, 75 to 109 in the same manner as in Example 6, and 110 to 133 in the same manner as in Example 7.
134-142 were synthesized by the same method as in Example 9. R7, R2, R, , X and Y in the table correspond to the symbols of the general formula written at the top of the table.

Example 11 A mild acrylate compound was synthesized by carrying out the reaction in the same manner as described in Examples 5, 6 and 7. The results are shown in Table 2. Among the black circles in the table, 1 to 16 were processed in the same manner as in Example 5, 17 to 24 were processed in the same manner as in 6, and 25 to 3.
Compound 2 was synthesized in the same manner as in Example 7. R in the table,
, R2, R4, R5°X and Y correspond to the symbols in the general formula shown at the top of the table.

Application Examples 1 to 74 and Comparative Examples 1 to 7 Adhesive strength was measured using the acrylate compound synthesized according to the present invention as an adhesive component. The measurement method is as follows. After polishing a Ni-Cr alloy of 101 mm long x 10 wm wide x 3 mm thick with 1000 abrasive paper, a 0.3 μm At
203 was used for polishing. A 5-mesh φ hole was drilled on that surface. An adhesive tape with a thickness of 50 mμ was pasted and an adhesive was applied to the hole. 8w polished with 320 on top of the adhesive
Press a stainless steel rod of aφ x 20 pieces and heat to 100℃15
Heated for minutes.

When the adhesive was immediately cooled (A), immersed in 23°C water for 6 months (B), and subjected to 5000 thermal cycles of 1 minute each in 4°C and 60°C water (each adhesive strength of Q The composition of the adhesive was as follows.

Adhesive composition OD-2,6'E 40 parts by weight 0 Neopentyl dimethacrylate 30 parts by weight 0 Hydroxyethyl methacrylate 20 parts by weight 0 Acrylate compound of the present invention 10 parts by weight Q Silanized quartz fine powder 100 parts by weight Q Penzoyl note oxide 2 Parts by weight [However, D-2,
6E indicates a compound with an average value of m + n of 2.6.

] As a comparative example, the adhesive strength was similarly measured using the following compound in place of the acrylate compound of the present invention in the adhesive component.

Comparative example 1 Additive-free comparative example 2 H2C-C-C0-NH-CH-COOH
CH2-C0OH Comparative Example 4 H2C-c-CO-■-CH-COONa
CH2-000Na CH2-C00C2H5 [In addition, in the above comparative example, 4 and 5 had poor solubility and a slightly cloudy appearance occurred. ] In the above usage example, X of the acrylate compound of general formula (1),
The cases where Y is a hydrogen atom are shown in Table 3, the cases where Y is an alkali metal are shown in Table 4, and the cases where Y is an alkyl group are shown in Table 5 together with comparative examples.

Table 3 Table 5

[Brief explanation of drawings]

Figure 1 shows the infrared absorption spectrum of the acrylate compound obtained in Example 1, Figure 2 shows Example 1, Figure 3 shows Example 2, Figure 4 shows Example 4, and Figure 5 shows the infrared absorption spectrum of the acrylate compound obtained in Example 1. 6 shows the 1H-nuclear magnetic resonance absorption spectrum of the acrylate compound obtained in Example 5, FIG. 6 shows Example 7, and FIG. 7 shows the 1H-nuclear magnetic resonance absorption spectrum of the acrylate compound obtained in Example 9.

Claims (2)

[Claims] (1) The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R_1 represents a hydrogen atom or an alkyl group, and R_
2 represents an alkylene group, and R_3 is a hydrogen atom, an alkyl group, or a group represented by ▼ where there are mathematical formulas, chemical formulas, tables, etc. (However, R_4 is a hydrogen atom or an alkyl group, and R_5 is an alkylene group.) , and X and Y represent the same or different hydrogen atoms, alkali metals, alkyl groups, or aryl groups. ] An acrylate compound represented by (2) Vinyl compound represented by the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_1 represents a hydrogen atom or an alkyl group, and Z represents a hydroxyl group or a halogen atom.) and the following formula ▲ Numerical formula, chemical formula , tables, etc. ▼ [However, R_2 represents an alkylene group, R'_3 represents a hydrogen atom, an alkyl group, or a group represented by HO-R_5- (however, R_5 is an alkylene group), and X' and Y' represent the same or different hydrogen atoms, alkyl groups, or aryl groups. ] The following formula is characterized by reacting with an alcohol compound represented by, or further reacting with an alkali metal or an alkali metal compound ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R_1 is a hydrogen atom or an alkyl group and R_2
represents an alkylene group, and R_3 is a hydrogen atom, an alkyl group, or a group represented by ▲, which has a mathematical formula, chemical formula, table, etc.
However, R_4 is a hydrogen atom or an alkyl group, and R_5
is an alkylene group. ), and X and Y represent the same or different hydrogen atoms, alkali metals, alkyl groups, or aryl groups. ] A method for producing an acrylate compound shown in the following.