WO2005097769A1

WO2005097769A1 - Oxetanes having naphthalene rings

Info

Publication number: WO2005097769A1
Application number: PCT/JP2005/004915
Authority: WO
Inventors: Atsuhiko Katayama; Niranjan Kumar Shrestha; Kiyotaka Onishi; Mahito Soeda; Osamu Fujimura; Yumiki Noda
Original assignee: Nippon Steel Chemical Co., Ltd.; Ube Industries, Ltd.
Priority date: 2004-03-30
Filing date: 2005-03-18
Publication date: 2005-10-20
Also published as: JP4654179B2; JPWO2005097769A1

Abstract

Novel compounds having naphthalene rings which are expected to be useful as the raw material for resins excellent in thermal resistance, water resistance (resistance to water absorption), and mechanical strengths; and a process for the production of the same. The compounds are oxetanes represented by the general formula (1), and these oxetanes can be produced by reacting 3-alkyl-3-hydroxymethyloxetane or 3-hydroxymethyloxetane with an alkali metal hydride or an alkali metal hydroxide to obtain an alkali metal alcoholate of the oxetane and then reacting the alcoholate with 1,4- or 1,5-bis(chloromethyl)naphthalene: wherein R is hydrogen or alkyl having 1 to 6 carbon atoms and the groups containing oxetane rings are bonded to the naphthalene ring at the 1,4- or 1,5-positions.

Description

Specification

Oxetane compounds having a naphthalene ring

Technical field

The present invention relates to an oxetane conjugate having a naphthalene ring capable of cationic polymerization and a method for producing the same.

Background art

[0002] Prior art documents related to the present invention include the following documents.

Patent Document 1: DE 1,021,858

Patent Document 2: JP-A-6-16804

Patent Document 3: JP-A-11-106380

Patent Document 4: JP-A-8-245783

Patent Document 5: JP-A-7-17958

Non-Patent Document 1: J. Macromol. Sci., Part A- Pure Appl. Chem., A29 (10), pp. 915 (1992) Non-Patent Document 2: J. Macromol. Sci., Part A- Pure Appl. Chem., A30 (2 & 3), ρρ.189 (1993)

[0003] The oxetane conjugate is a compound that has recently attracted attention as a monomer capable of photoinitiated cationic polymerization or curing, and many monofunctional and polyfunctional oxetane compounds have been reported. For example, J. Macromol. Sci., Part A- Pure Appl. Chem., A29 (10), pp. 915, J. Macromol. Sci., Part A- Pure Appl. Chem., A30 (2 & 3), pp. l89 describes the synthesis of various oxetane derivatives.

[0004] DE 1,021,858 discloses an oxetaney conjugate represented by the general formula (3).

(In the formula, R is an aromatic residue having a valence of 2 or more, and n is 1 or 2.) Japanese Patent Application Laid-Open No. 6-16804 discloses an oxetane disulfide represented by the general formula (4). There is description of thing

(Wherein, R1 is a hydrogen atom, an alkyl group having 16 carbon atoms, a fluoroalkyl group, an aryl group, an aryl group, a furyl group or a chel group, or a fluorine atom. R2 is a chain or branched poly group. (Alkyleneoxy) group, xylylene group, siloxane bond, and ester bond force group is a polyvalent group selected, Z is an oxygen atom or a sulfur atom, and m is 2, 3, or 4. o)

[0006] Japanese Patent Application Laid-Open No. H11-106380 discloses an oxetane conjugate having a biphenyl skeleton represented by the general formula (5).

(Wherein, R represents a hydrogen atom or an alkyl group having 116 carbon atoms)

[0007] JP-A-7-17958 describes a method for synthesizing an oxetane compound by reacting aryl chloride with hydroxymethyloxetane.

However, these documents do not describe any oxetane conjugates containing a naphthalene ring.

[0008] Japanese Patent Application Laid-Open No. 8-245783 describes a large number of oxetane conjugates including a bifunctional oxetane having a 2,2'-vitrilenylene skeleton. Some examples of oxetane compounds containing a naphthalene ring include only 1,8-bis [(3-alkyl-3-oxetal) methoxymethyl] naphthalene. Specific examples of synthesis examples and physical properties are shown below. It has not been. This 1,8-bis [(3-alkyl-3-oxetal) methoxymethyl] naphthalene has a very low substitutional position at the 1,8-position, and therefore, when used as a resin raw material, Since it has a bent structure, physical properties such as heat resistance are inferior, and it is difficult to utilize the heat-resistant properties of the naphthalene skeleton, its use is also limited. In addition, an oxetal group is introduced at the 1,8-position To do so, a multi-stage reaction must be performed, which is economically disadvantageous.

Disclosure of the invention

Problems to be solved by the invention

[0009] The present invention provides a novel oxetane conjugate having a naphthalene ring and a process for producing this oxetane conjugate using bis (clomethylmethyl) naphthalene as a raw material.

Means for solving the problem

[0010] The present invention is an oxetane conjugate having an oxetane ring-containing group represented by the general formula (1).

In the formula, R represents a hydrogen atom or an alkyl group having 116 carbon atoms, and the substitution position of the oxetane ring-containing group on the naphthalene ring is 1,4-position or 1,5-position.

Further, the present invention relates to a method for producing an alkali metal alcoholate by reacting a 3-alkyl-3-hydroxymethyloxetane or a 3-hydroxymethyloxetane with an alkali metal hydride or an alkali metal hydroxide to form the alkali metal alcoholate. Is reacted with bis (chloromethyl) naphthalene in the above-mentioned method for producing an oxetane compound. Further, the present invention is a method for producing a composition containing the above-mentioned oxetane compound by the above-mentioned method for producing an oxetane compound.

Hereinafter, the present invention will be described in detail.

The oxetane conjugate of the present invention is represented by the general formula (1) and has two oxetane ring-containing groups, which are located at the 1,4-position or the 1,5-position of the naphthalene ring. More specifically, it is represented by the following formula (a) or (b). R is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, preferably an ethyl group. Hereinafter, an oxetane having an oxetane ring-containing group at the 1,4-position of the naphthalene ring The tanixi compound is also referred to as an oxetane conjugate (a), and the oxetane compound having the 1,5-position is also referred to as an oxetane compound (b).

In the formula, R represents a hydrogen atom or an alkyl group having 116 carbon atoms.

[0012] The oxetane conjugate of the present invention is not limited to the force that can be advantageously produced by the production method of the present invention. The oxetane conjugate obtained by the production method of the present invention includes not only the oxetane compound of the present invention but also a mixture thereof, and a composition containing these as a main component.

[0013] In the production method of the present invention, first, 3-alkyl-3-hydroxymethyloxetane or 3-hydroxymethyloxetane is mixed with an alkali metal hydride or an alkali metal hydroxide in a solvent, The reaction is carried out at 20-120 ° C, preferably 50-90 ° C, to synthesize an alkali metal alcoholate of 3-alkyl-3-hydroxymethyloxetane or an alkali metal alcoholate of 3-hydroxymethyloxetane.

[0014] The alkali metal hydride used at this time is preferably sodium hydroxide sodium hydroxide or potassium hydroxide sodium powder as the alkali metal hydroxide. As the solvent, an aromatic hydrocarbon solvent is preferably exemplified, and as the aromatic hydrocarbon solvent, benzene, toluene, xylene and the like are suitably used.

Next, the alkali metal alcoholate synthesized above is reacted with bis (chloromethyl) naphthalene. The temperature at this time is preferably from 80 to 150 ° C, more preferably from 100 to 120 ° C. The reaction time depends on the reaction temperature, but 2 to 10 hours is sufficient. As the reaction solvent, it is desirable to use the aromatic hydrocarbon solvent used in the synthesis of the alkali metal alcoholate.

[0016] Bis (chloromethyl) naphthalene used as a raw material is usually easily obtained by a method of converting naphthalene into chloromethyl with hydrochloric acid and formaldehyde, or by subjecting naphthalene to chloromethyl ether with chloromethyl ether. At this time, the chloromethylanilide reaction proceeds selectively to the α-position of naphthalene, so the main product as bis (chloromethyl) naphthalene is

It becomes 1.4-bis (chloromethyl) naphthalene and 1,5-bis (chloromethyl) naphthalene.

[0017] As a raw material used in the production method of the present invention, these 1,4-bis (chloromethyl) naphthalene, 1,5-bis (chloromethyl) naphthalene, or a mixture thereof can be used. When using 1,4-bis (chloromethyl) naphthalene as a raw material, an oxetanei conjugate (a) is obtained,

When using 1.5-bis (chloromethyl) naphthalene as a raw material, an oxetane conjugate (b) is obtained.When using a mixture of both, the oxetane conjugate (a) and the oxetane conjugate (b) are obtained. ) Is obtained.

After completion of the reaction, the reaction mixture is cooled to room temperature, the by-produced salts are separated, washed with water and dried to obtain the desired oxetane compound having a naphthalene ring represented by the general formula (1). This is a novel compound that can be confirmed by FD-MS, GC-MS, and -NMR (CDCl).

Three

The mixture of the oxetane ligature of the present invention includes both the oxetane ligature (a) and the oxetane ligature (b). The content ratio of the oxetane compound (a) and the oxetane conjugate (b) is preferably in the range of 8/2 to 2/8.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

Example 1

4.4 g (0.11 mol) of 60% pure oily sodium hydride and 25 ml of toluene were placed in a 300 ml three-necked round bottom flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, and heated at 80 ° C. Stirred. 12.8 g (0.11 mol) of 3-ethyl-3-hydroxymethyloxetane with 98.5% purity Was dissolved in 20 ml of toluene, and the solution was added dropwise over a dropping funnel force of 30 minutes. In the meantime, a vigorous foaming phenomenon was observed, but the stirring was continued after the end of the dropping until the foaming phenomenon was no longer observed. Subsequently, a solution in which 11.5 g (0.05 mol) of 1,5-bis (chloromethyl) naphthalene having a purity of 98.2% was dissolved in 175 ml of toluene was added dropwise over 30 minutes with a dropping funnel force. After the completion of the dropwise addition, the reaction was further continued at 80 ° C for 8 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitate was separated. The mouth liquid and the precipitate were washed twice with 20 ml of toluene, and the obtained washings were combined and washed three times with 100 ml of water. The oil phase was separated, sodium sulfate was dried and dried, and toluene was distilled off under reduced pressure to obtain 16.5 g of pale yellow crystals. As a result of GC analysis, the purity of the obtained compound was 97.5%, and the yield was 83.4%. 5 g of the obtained crystals were dissolved by heating with 10 g of toluene, cooled to room temperature, and purified by recrystallization. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain 2.4 g of white crystals. As a result of GC analysis, the purity of the obtained compound was 99.0%. The molecular weight of the compound obtained by FD-MS measurement was confirmed to be 384. Melting point was 113-114 ° C. Furthermore, NMR (CDC1)

From the measurement results of 3, the obtained compound was identified as 1,5-bis [(3-ethyl-3-oxetanyl) methoxymethyl] naphthalene represented by the formula (6).

^ -NMRCCDCl) δ (ppm); 0.77-0.81 (t, 6H, CH-CH), 1.70-1.76 (q, 4H, CH-CH)

3 3 2 3 2

, 3.62 (s, 4H, -OCH-), 4.35-4.36 (d, 4H,-OCH-(oxetane ring)), 4.42-

twenty two

4.44 (d, 4H, -OCH- (oxetane ring)), 5.00 (s, 4H, Ph-CH0-), 7.46-7.52 (m, 4H, aromatic

twenty two

Ring), 8.12-8.15 (d, 2H, aromatic ring)

[0021]

Example 2

In the same reaction vessel as in Example 1, 3-ethyl-3-hydroxymethyloxeta having a purity of 98.5% was added. 12.8 g (0.1 lmol), 4.5 g (0.1 lmol) of 97% pure NaOH powder and 25 ml of toluene were stirred and heated and stirred at 90 ° C. for 30 minutes. A solution in which 11.5 g (0.05 mol) of 1,5-bis (chloromethyl) naphthalene having a purity of 98.2% was dissolved in 175 ml of toluene was added dropwise over 30 minutes with a dropping funnel force. The reaction was further continued at 90 ° C for 10 hours. After completion of the reaction, the mixture was treated in the same manner as in Example 1 to obtain 17.6 g of pale yellow crystals. As a result of GC analysis, the purity of the obtained compound was 84.6%, and the yield was 77.4%. FD-MS and ¹ H-NMR (CDC1) of this compound

From the measurement results of 3, it was confirmed that the compound was the same as the compound obtained in Example 1. The main impurity was monooxetane in which only one (3-ethyl-3-oxetal) methoxymethyl group was substituted on the naphthalene ring according to the result of GC-MS, and the content was 13.5% by GC analysis.

Example 3

In a reaction vessel similar to that of Example 1, 12.8 g (0.1 lmol) of 3-ethyl-3-hydroxymethyloxetane having a purity of 98.5%, 4.5 g (0.1 lmol) of NaOH powder having a purity of 97%, and 25 ml of toluene were placed. The mixture was heated and stirred at 90 ° C for 30 minutes. Bis (chloromethyl) naphthalene containing 53.4% of 1,5-bis (chloromethyl) naphthalene and 45.5% of 1,4-bis (chloromethyl) naphthalene

A solution prepared by dissolving 11.5 g (0.05 mol) in 175 ml of toluene was added dropwise over a dropping funnel force of 30 minutes. The reaction was further continued at 90 ° C for 10 hours. After completion of the reaction, the mixture was treated in the same manner as in Example 1 to obtain 15.3 g of pale yellow crystals. As a result of GC analysis, the purity of the obtained compound as a bisoxetane compound was 86.2% (1,4-form: 1,5-form = 28:72), and the yield was 68.6%. . The main impurity was monooxetane, and its content was 11.2% by GC analysis. Melting point was 89-97 ° C. FD-MS, GC-MS and ¹ ! "I-NMR (CDC1

Three

) Was identified as a mixture of the compound obtained in Example 1 and 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] naphthalene represented by the formula (7). .

1, 4-bis [(3-Echiru - - 3 Okiseta Le) methoxymethyl] naphthalene ¹ H- NMR of (CDC1)

3 The measurement results are as follows.

^ -NMRCCDCl) δ (ppm); 0.78-0.81 (t, 6H, CH-CH), 1.71-1.76 (q, 4H, CH-CH)

3 3 2 3 2

, 3.62 (s, 4H, -OCH-), 4.35-4.37 (d, 4H, -OCH-(oxetane ring)), 4.43-

twenty two

4.45 (d, 4H, -OCH- (oxetane ring)), 5.00 (s, 4H, Ph-CH0-), 7.45 (s, 2H, aromatic ring), 7.53

Example 4

A heat-curing catalyst (manufactured by Sanshin Chemical Co .; San-Aid SI-110L) (5 mol%) was added to the oxetanei ligated product produced in Example 3, and the mixture was heated at 180 ° C. for 3 hours to be cured. The cured product was pale yellow and transparent. The physical properties of the obtained cured product are shown below. Tensile strength 5.8 kgf / mm ² , tensile elongation at break 11.8%, tensile modulus 92.2 kgf / mm ² , Tg 108 ° C, water absorption (room temperature for one week) 0.1%, cure shrinkage 3.2%

Comparative Example 1

In a 50 ml three-necked round bottom flask equipped with a thermometer, a condenser and a stirrer, 1.0 g (5.3 mmol) of 1,8-bishydroxymethylnaphthalene (manufactured by ACROS) having a purity of 99% and 100 ml of concentrated hydrochloric acid were placed. The mixture was stirred at 90 ° C for 0.5 hr. After cooling to room temperature, 100 ml of toluene was used to extract the syrup product. After liquid separation, the toluene layer was washed twice with 100 ml of pure water. The toluene was distilled off under reduced pressure to obtain a pale yellow crystal l.lg. GC analysis and GCMS analysis confirmed that the product was 98% pure 1,8-bishydroxymethylmethylnaphthalene. Melting point was 81 ° C.

In a 50 ml three-necked round bottom flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel, 0.92 g (7.82 mmol) of 3-ethyl-3-hydroxymethyloxetane of 98.5% purity and 97% of purity were added. 0.32 g (7.82 mmol) of NaOH powder and 10 ml of toluene were mixed and heated and stirred at 90 ° C. for 30 minutes. To this, a solution of 0.80 g (3.48 mmol) of the above 1,8-bis (chloromethyl) naphthalene dissolved in 10 ml of toluene was added dropwise from a dropping funnel over 5 minutes. The reaction was further continued at 90 ° C for 10 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature and washed three times with 10 ml of water. The oil phase was separated, and toluene was distilled off under reduced pressure to obtain 1.25 g of a single yellow transparent oily liquid. GC As a result of analysis, GCMS analysis and 1 H-NMR, the obtained compound was 1,8-bis [(3-ethyl-3-oxetanyl) methoxymethyl] naphthalene having a purity of 90%.

To this oxetane compound was added 5% by weight of a thermosetting catalyst (Sun-Aid SI-110L), and the mixture was heated at 180 ° C for 3 hours to be cured. The cured product was pale yellow and transparent. The Tg of the obtained cured product was 69 ° C.

Comparative Example 2

5 mol% of 4,4'-bis [(3-ethyl-3-oxeta-l) methoxymethyl] biphenyl (manufactured by Ube Industries, Ltd .; ETERNACOLL OXBP) is added with 5 mol% of a thermosetting catalyst (San-Aid SI-110L). Then, it was heated at 180 ° C. for 3 hours to be cured. The cured product was pale yellow and transparent. The physical properties of the obtained cured product are shown below. Tensile strength 4.2 kgf / mm ² , Tensile elongation at break 12.5%, Tensile modulus 72.0 kgf / mm ² , Tg 98 ° C, Water absorption (room temperature for 1 week) 0.2%, Cure shrinkage 3.8%

Industrial applicability

[0028] A photocurable or thermosetting resin derived from an oxetane compound having a naphthalene ring has excellent heat resistance, mechanical properties, and adhesion, and is used for paints and adhesives. Further, the oxetane compound of the present invention gives a cured product having excellent water resistance (low water absorption), heat resistance and mechanical strength.

Claims

The scope of the claims

Oxetane diversion having a naphthalene ring and an oxetane ring-containing group represented by the general formula (1)

[2] The oxetane conjugate according to claim 1, wherein in the general formula (1), R is an ethyl group.

[3] The oxetane conjugate according to claim 1, wherein the oxetane ring-containing group is substituted at the 1,4-position at the naphthalene ring, and the oxetane conjugate according to claim 1, which is at the 1,5-position. A mixture of oxetane compounds containing both.

[4] 3-Alkyl-3-hydroxymethyloxetane or 3-hydroxymethyloxetane is reacted with an alkali metal hydride or an alkali metal hydroxide to form the alkali metal alcoholate, and then the alkali metal alcoholate is converted to an alkali metal alcoholate. 2. The process for producing an oxetane conjugate according to claim 1, wherein the reaction is carried out with 1,4-bis (chloromethyl) naphthalene or 1,5-bis (chloromethyl) naphthalene.

[5] 3-Alkyl-3-hydroxymethyloxetane or 3-hydroxymethyloxetane is reacted with an alkali metal hydride or an alkali metal hydroxide to form the alkali metal alcoholate, and then the alkali metal alcoholate is converted to an alkali metal alcoholate. Reacting 1,4-bis (chloromethyl) naphthalene, 1,5-bis (clomethylmethyl) naphthalene or both with the 1,4-position of the naphthalene ring represented by the general formula (1) or A process for producing an oxetane conjugate having a oxetane ring-containing group at the 1,5-position or a mixture thereof.

In the formula, R represents a hydrogen atom or an alkyl group having 116 carbon atoms,