JP2001226365A - Oxetane compound, method of preparing the same and polymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oxetane compound for cationic polymerization having high polymerizing property and improved heat resistance, a method of preparing the compound and further a cationically polymerizable composition containing the compound. SOLUTION: An oxetane compound expressed by the general formula 1. The compound is obtained by carrying out the transesterification of a carbonic acid diester with an alicyclic diol followed by decarboxylation. The cationically polymerizable composition is obtained by compounding the compound with a cationic-polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an oxetane compound for cationic polymerization, a method for producing the oxetane compound, and a cationically polymerizable composition containing the oxetane compound. In addition, a photocurable or thermosetting resin using the oxetane compound has excellent heat resistance, mechanical properties, and adhesion, and is suitable for a paint, an adhesive, and the like.

[0002]

2. Description of the Related Art Up to now, epoxide compounds have been mainly used as compounds for cationic polymerization. Epoxide compounds are widely used because of their characteristic that a film having good chemical resistance and adhesion can be obtained. However,
Conventional photocurable epoxide compounds have the drawback that, since chain transfer of terminal cations easily occurs, it is difficult to increase the molecular weight, and the resulting film is hard and brittle.

On the other hand, oxetane compounds have high cationic polymerization reactivity, and although the initial polymerization rate is inferior to epoxide compounds, high molecular weight is possible and a good film excellent in mechanical properties and adhesion is obtained. can get. From these characteristics, the oxetane compound is expected to be used as a homopolymer or as a copolymer with an epoxide compound.

Representative oxetane compounds used in these compounds are represented by the general formula 3 (DE 1,02
1,858).

(General formula 3)

[0006]

Embedded image (Wherein R is an aromatic residue having a valence of 2 or more;
(n is 1 or 2) Further, JP-A-6-16804 describes an oxetane compound represented by the general formula 4.

(General formula 4)

[0008]

Embedded image (Wherein, R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
A fluoroalkyl group, an allyl group, an aryl group, a furyl group, a thienyl group, and a fluoro group. R ² is a polyvalent group selected from the group consisting of a chain or branched poly (alkyleneoxy) group, a xylene group, a siloxane bond and an ester bond, and Z is an oxygen atom or a sulfur atom. m is 2, 3 or 4. Further, since the polymerizability depends on the magnitude of the strain energy of the ring, an oxetane compound having a spiro ring structure having a large ring strain energy has been studied in order to further improve the polymerizability. These compounds have the chemical formula 1
(US3388105) (Chemical formula 1)

[0009]

Embedded image The polymerizability is improved as compared with the oxetane compounds represented by the general formulas 2 and 3. However, practically, since the required physical properties are not satisfied in terms of heat resistance, development of an oxetane compound having improved heat resistance is desired. Furthermore, chemical formula 2 (US3110068)
8), (Chemical formula 2)

[0010]

Embedded image Chemical formula 3 (Chem. Lett., 11, 1785-8)
(1985)) are also known, but since these compounds have a double bond, they are cured (Chemical Formula 3).

[0011]

Embedded image There is a concern that peroxide may be generated therein, which is not preferable from the viewpoint of processability, and has a disadvantage that storage stability is poor. Therefore, development of a new oxetane compound has been desired.

[0012]

SUMMARY OF THE INVENTION The present invention relates to an oxetane compound having improved cationic polymerizability and improved heat resistance capable of increasing the molecular weight, a method for producing the compound, and a cationic polymerizable composition containing the compound. The task is to provide.

[0013]

Means for Solving the Problems The present inventors have studied the cationic polymerizability of various oxetane compounds and found that the oxetane compound having the structure represented by the general formula 1 has high polymerizability and heat resistance. And completed the present invention. That is, the invention consists of the following inventions. (1) An oxetane compound represented by the general formula 1.

(General formula 1)

[0015]

Embedded image (Wherein, R ¹ is fluorine, chlorine, bromine, or C 1-2
0 alkyl groups, aryl groups, fluoroalkyl groups,
A chloroalkyl group and a bromoalkyl group. ) (2) an oxetane compound according to R ¹ in the general formula 1 is characterized in that it is a methyl group (1). (3) The method for producing an oxetane compound according to (1), wherein the starting material is an alicyclic diol represented by the general formula 2 (general formula 2)

[0016]

Embedded image (Wherein, R ¹ is fluorine, chlorine, bromine, or C 1-2
0 alkyl groups, aryl groups, fluoroalkyl groups,
A chloroalkyl group and a bromoalkyl group. ) Manufacturing method. (4) The alicyclic diol is 2-methyl-cyclohexane-
The method for producing an oxetane compound according to (3), wherein the oxetane compound is 1,1-dimethanol and R1 in the general formula 1 is a methyl group. (5) The method for producing an oxetane compound according to (3), wherein an oxetane-forming reaction is performed after reacting the alicyclic diol with the carbonic acid diester. (6) The method for producing oxetane according to (5), wherein the carbonate diester is dimethyl carbonate. (7) A cationically polymerizable composition containing the oxetane compound and the epoxide compound according to (1). (8) A cationically polymerizable composition comprising the oxetane compound, the epoxide compound and the cationic photopolymerization initiator according to (1). (9) A cationically polymerizable composition comprising the oxetane compound, the epoxide compound and the thermal cationic polymerization initiator according to (1). (10) The cationically polymerizable composition according to (7), wherein the epoxide compound is a bisphenol A type oligomer. (11) The cationically polymerizable composition according to (7), wherein the epoxide compound has a molecular weight of less than 1,000. (12) The cationically polymerizable composition according to (8) or (10), wherein the photocationic polymerization initiator is triarylsulfonium hexafluorophosphate. (13) The cationically polymerizable composition according to (9) or (10), wherein the thermal cationic polymerization initiator is 2-butenyltetramethylenesulfonium hexafluoroantimonate.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The oxetane compound of the present invention has high polymerizability and is unsubstituted spirooxetane compound or 7-position compound due to the effect of the 5-position alkyl group adjacent to the oxetane group.
Higher heat resistance than position-substituted spirooxetane. further,
Since it does not have a double bond as in Chemical Formulas 1 and 3, it has excellent long-term storage stability and processability.

The oxetane compound of the present invention may be synthesized by any method, but a method using the corresponding diol as a starting material is preferably used. General formula 2
(General formula 2)

[0019]

Embedded image Using an alicyclic diol as a starting material, reaction with a carbonic acid diester as shown in Reaction Formula 1 (Reaction Formula 1)

[0020]

Embedded image There is a method of synthesizing by a two-stage reaction of a steal exchange reaction and a decarboxylation reaction.

The transesterification is carried out in the presence of a catalyst in a heated state by distilling off the generated alcohol out of the system. As the catalyst, at least one metal selected from the group consisting of alkali metals such as Li, Na, K, and Cs or alkaline earth metals such as Mg and Ca, or a metal salt thereof is suitably used. The reaction temperature is 50 to 200 ° C, preferably 70 to 150 ° C. The reaction pressure is optimally normal pressure, but there is no problem even if pressure is increased or reduced. The reaction solvent may be any solvent that does not adversely affect the reaction, such as hydrocarbons such as toluene, xylene, ethylbenzene, hexane, heptane, octane, and cyclohexane; 1,4-dioxane; ethers such as tetrahydrofuran; chlorobenzene dichloromethane; Chlorinated compounds such as chloromethane and carbon tetrachloride are preferably used. The use of an excess of carbonic acid diester as a solvent is particularly advantageous in this reaction, and is preferably used.

The decarboxylation reaction is carried out in the presence of a catalyst in a heated state. The catalyst is the same as in the transesterification reaction. Therefore, the catalyst for the transesterification reaction can be used as it is. Of course, it is also possible to add a new catalyst, and it is possible to add a new catalyst after removing the catalyst used in the transesterification, but it is more advantageous to use the catalyst continuously and continuously. .

The reaction temperature is from 150 to 350 ° C., preferably from 180 to 300 ° C. The generated carbon dioxide is discharged out of the system.

As the diester carbonate of the present invention, dimethyl carbonate, diethyl carbonate, diphenyl carbonate and the like are preferably used, but not limited thereto, and dimethyl carbonate is most preferably used.

As the alicyclic diol used in the present invention, a compound represented by the general formula 2 is used (general formula 2)

[0026]

Embedded image Can be Here, R1 is fluorine, chlorine, bromine, or an alkyl group having 1 to 20 carbon atoms, an aryl group, a fluoroalkyl group, a chloroalkyl group, or a bromoalkyl group, but is not limited thereto. Compounds in which R1 is a methyl group are most preferably used.

The ratio of the carbonic acid diester to the alicyclic diol (carbonic acid diester (mol) / alicyclic diol (mol)) used in the present invention is preferably 0.5 to 5; Particularly preferred. If the ratio between the carbonic acid diester and the alicyclic diol is too large, polycarbonate and the like are produced as by-products, leading to a decrease in the yield of the cyclic carbonate and a decrease in the yield of the oxetane compound as the target product.

The alicyclic diol used as a raw material of the oxetane compound of the present invention can be easily synthesized by a known Diels-Alder reaction and Cannisterro reaction.

The polymerizable composition of the present invention comprises at least the oxetane compound of the present invention and an epoxide compound, and further comprises the oxetane compound of the present invention, an epoxide compound and a cationic polymerization initiator.

As the epoxide compound, any monomers and oligomers containing an epoxy group can be used, and specific examples thereof include conventionally known aromatic epoxides, alicyclic epoxides and aliphatic epoxides. As the oligomer in the present invention, a compound having a low molecular weight is preferable, and an oligomer having a molecular weight of less than 1,000 is more preferable. Preferred as the aromatic epoxide are polyhydric phenols having at least one aromatic ring or di- or polyglycidyl ethers produced by reacting an alkylene oxide adduct thereof with epichlorohydrin, for example, bisphenol A or its alkylene oxide addition. Di- or polyglycidyl ethers, di- or polyglycidyl ethers of hydrogenated bisphenol A or its alkylene oxide adducts, and novolak epoxy resins. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

As the alicyclic epoxide, cyclohexene oxide or cyclopentene oxide obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene with a suitable oxidizing agent such as hydrogen peroxide or peracid. Contained compounds are preferred.

Preferred examples of the aliphatic epoxides include di- or polyglycidyl ethers of aliphatic polyhydric alcohols and alkylene oxide adducts thereof. Representative examples are diglycidyl ether of ethylene glycol and diglycidyl ether of propylene glycol. Or polyglycidyl ether of polyhydric alcohol such as diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, di- or triglycidyl ether of glycerin or an alkylene oxide adduct thereof, polyethylene glycol or alkylene oxide thereof. Diglycidyl ether, polypropylene glycol or its alkylene oxide adduct diglycidyl ether, etc. . Here, examples of the alkylene oxide include ethylene oxide and propylene oxide. In addition to these, monoglycidyl ethers of aliphatic higher alcohols and the like can also be used.

As the compound for initiating cationic polymerization by ultraviolet light or heat, various conventionally known cationic polymerization initiators can be used. Among these initiators, preferred are diaryliodonium salts,
Triarylsulfonium salts and tetramethylenesulfonium salts are exemplified. As the photocationic polymerization initiator, triarylsulfonium hexafluorophosphate is most preferably used, and as the thermal cationic polymerization initiator,
Butenyl tetramethylene sulfonium hexafluoroantimonate is most preferably used.

The amount of the initiator to be used for curing the polymerizable composition of the present invention is determined by the amount of the epoxide compound charged, the amount of water in the composition, and the type of the solvent when a diluting solvent is used.
The amount used of the catalyst in the curing method of the present invention is from 0.1 to 30 phr, preferably from 0.5 to 30 phr in the composition.
~ 20 phr.

The polymerizable composition of the present invention can be used in the presence of a solvent or a dispersion medium, if necessary. Solvents or dispersion media that can be used here, for example, toluene,
Hydrocarbon solvents such as xylene, ethylbenzene, hexane, heptane, octane, and cyclohexane; halogenated hydrocarbon solvents such as dichloromethane, chloroform, carbon tetrachloride, and chlorobenzene; methanol, ethanol, propampanol, isopropanol, and butano-
Alcohol solvents such as toluene, pentanol and hexanol; ether solvents such as diethyl ether, dipropyl ether and cellosolve; ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; acetate esters such as ethyl acetate, propyl acetate and butyl acetate. A solvent or the like can be used, but is not limited thereto.

[0036]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. (Example 1) [Synthesis of oxetane compound of the present invention] In a 1 L three-necked flask, 2-methyl-cyclohexane-
474 g (3.0 mol) of 1,1-dimethanol, 405 g (4.5 mol) of dimethyl carbonate, 1.
4 g (0.3% by mass based on the substrate) was added, and the mixture was heated and stirred in an oil bath at a temperature of 100 ° C., and the reaction was carried out for 14 hours while distilling off generated methanol outside the system at normal pressure. Finally, the pressure in the reaction vessel was reduced to 10 mmHg, and the corresponding cyclic carbonate was obtained in a yield of 95%.

The obtained cyclic carbonate was used as it was in 25
The mixture was heated and spread at 0 ° C., and the reaction was carried out for 10 hours while discharging the generated carbon dioxide gas from the upper part of the cooling device to the outside of the system. This reaction solution was purified by distillation to obtain 230 g of a colorless and transparent liquid. ¹ H-NMR (CDCl 3) and ¹³ C-N of the obtained liquid
The measurement results of MR (CDCl3) are shown below. 1 and 2 show measurement charts. ¹ H-NMR: δ (ppm); 0.9 to 1.1 (m, 3
H, —CH ₃ ), 1.2 to 1.8 (m, 8H, cyclohexane ring —CH ₂ —), 1.9 to 2.0 (m, 1H, −).
CH-), 4.1 to 4.5 (m, 4H, oxetane ring-
CH ₂ —O—) ¹³ C-NMR: δ (ppm); 15 (—CH ₃ ), 22
To 35 (cyclohexane ring -CH _2- ), 36 (cyclohexane ring -CH-), 43 to 44 (spiro C), 65
80 (oxetane ring -CH ₂ -) Thus, it is apparent that the present liquid is an object of 2- oxaspiro [3,5] -5- nonanoic (hereinafter referred to as "Compound 1".). Further, the purity of the obtained compound was 97.8% as a result of gas chromatography, and the total yield was 55%.
%Met. The column of the gas chromatograph is OV-17.
1.1m glass column packed with
I went in. (Comparative Example 1) [Synthesis of existing oxetane] Known method (JOC, 26, 4654 (196)
4-methylcyclohexane-1, synthesized according to 1)),
474 g (3.0 mol) of 1-dimethanol was placed in a 1 L three-necked flask, and then 405 g of dimethyl carbonate (4.
5 mol), 1.4 g of potassium carbonate (0.
3% by mass), and the mixture was heated and stirred at a temperature of 100 ° C. in an oil bath to carry out a reaction while distilling off generated methanol to the outside of the system. Finally, the pressure in the reaction vessel was reduced, and the corresponding cyclic carbonate was obtained in a yield of 20% in the same manner as in Example 1.

The obtained cyclic carbonate was heated at a temperature of 250 ° C., and the reaction was performed while discharging the generated carbon dioxide gas out of the system. The resulting reaction solution is purified by distillation to obtain the desired 2-
20.9 g of oxaspiro [3,5] -7-methylnonane (hereinafter referred to as “Comparative 1”) was obtained. The purity of the obtained comparative product 1 was 97.1% by GC analysis, and the total yield was 5%. Comparative Example 2 Synthesis of Existing Oxetane 510 g of 2-carbethoxycyclohexanone (3.0 g)
mol), a known method (Chem. Lett.,
1785 (1985)) through an 8-step reaction.
174.2 g of methyl-2-oxaspirononan-5-ol (hereinafter referred to as “Comparative 2”) was obtained. As a result of GC analysis, the purity of the obtained compound was 97.4%, and the total yield was 44%. (Example 2) [Cationic photopolymerizable composition containing oxetane of the present invention and polymerization] Compound 1 (10 phr) in a 200 ml beaker, bisphenol A type epoxy resin (Epicoat 828: manufactured by Yuka Shell Epoxy Co., Ltd .; hereinafter referred to as “EPOXY Resin”) ) After charging 90 phr and mixing, the viscous liquid was heated to 50 ° C. in a gear oven, uniformly stirred with a Teflon spatula, and then UVI-69 was used as a polymerization initiator.
90 (manufactured by Union Carbide Co., Ltd.) was added, and the mixture was coated on a polyethylene film with a bar coder so as to have a thickness of about 6.0 μm to prepare a sample for photopolymerization. Was. HAM for UV irradiation
AMATSU PHOTONICS K. K. PHO
A TOCURE 200 UV lamp was used. The irradiation intensity of the ultraviolet light was 45 mJ / (s · cm ² ).

The photopolymerization rate was determined during the photopolymerization under the above conditions.
RKIN ELMER Spectrometer G
Using an X-infrared spectrometer, 980 cm ^{−1 of} a cyclic ether characteristic of an oxetane compound was analyzed using EPOXY Resin.
For, the absorption derived from 1100 cm ^-1 was measured over time to determine the conversion. (Comparative Example 3) [Photocationic polymerizable composition containing no oxetane and polymerization] A sample for photopolymerization was prepared in the same manner as in Example 2 except that Compound 1 was not used (0 phr), and the same as in Example 2. Was measured. (Comparative Example 4) [Cation cationically polymerizable composition containing existing oxetane and polymerization] Example 2 except that Compound 1 was used instead of Compound 1.
A sample for photopolymerization was prepared in the same manner as described above, and the measurement was performed in the same manner as in Example 2. (Comparative Example 5) [Photocationic polymerizable composition containing existing oxetane and polymerization] Example 3 except that compound 2 was used instead of compound 1.
A sample for photopolymerization was prepared in the same manner as described above, and the measurement was performed in the same manner as in Example 2.

FIG. 3 shows the measurement results of Example 2 and Comparative Examples 3 to 5. In the case of Comparative Example 3 containing no oxetane compound, the rise at the beginning of irradiation was good, but the conversion was 32% even after 5 seconds, indicating that the curing rate was low. On the other hand, in the system containing the oxetane compound, the initial conversion rate is low, but the conversion rate is improved from around 2 seconds after irradiation, and after 5 seconds, it is 64% in Comparative Example 4 and 60% in Comparative Example 5. In Example 2 containing oxetane of the present invention, the curing speed was particularly high after 3 seconds and reached 83% after 5 seconds. (Measurement of Pencil Hardness) The pencil hardness of each coating film after irradiation for 5 seconds was measured according to JIS K5400. Table 1 shows the results. Cure with EPOXY Resin only

[0041]

[Table 1] In the case of Comparative Example 3 performed, the pencil hardness is H. Comparative Example 4
Is H, which is equivalent to Comparative Example 3, but Comparative Example 5 is soft and B. On the other hand, in Example 2 containing oxetane of the present invention, the pencil hardness was 2H, and it can be seen that a coating film having sufficient hardness can be obtained in a short time. (Example 3) [Thermal cationically polymerizable composition containing oxetane of the present invention and polymerization] Compound 1 was added in a 200 ml beaker at 10 phr and EPOX.
90 phr of Y Resin and 2.5 mol% of a thermal polymerization initiator (Opton CP-66: manufactured by Asahi Denka Kogyo KK)
The mixture was heated to 50 ° C. After uniformly dissolving, the resin solution was poured into a mold (glass plate) having a thickness of 3 mm and a size of 200 mm × 100 mm after vacuum degassing and replacement with nitrogen. 60 ° C
And heated and polymerized for 1 hour to obtain a cured product. (Comparative Example 6) [Thermal cationic polymerizable composition containing no xetane and polymerization] A sample for thermal polymerization was prepared in the same manner as in Example 3 except that Compound 1 was not used (0 phr), and further the same method was used. Heat polymerization was performed to obtain a cured product. (Comparative Example 7) [Thermal cationically polymerizable composition containing existing oxetane and polymerization] Example 3 except that Compound 1 was used instead of Compound 1.
A thermopolymerized sample was prepared in the same manner as described above, and further heat-polymerized in the same manner to obtain a cured product. (Comparative Example 8) [Thermal cationic polymerizable composition containing existing oxetane and polymerization] Example 3 except that compound 2 was used instead of compound 1.
A heat-polymerized sample was prepared in the same manner as described above, and further heat-polymerized in the same manner to obtain a cured product (measurement of thermal deformation temperature). According to 7207, the heat distortion temperature (HDT temperature) was measured. Table 2 shows the results. Comparative Example 6 (EPOX

[0042]

[Table 2] Y Resin alone has a heat distortion temperature of 150 ° C., whereas Comparative Example 7 has a heat deformation temperature of 147 ° C. and Comparative Example 8 has a heat deformation temperature of 142 ° C. I have. On the other hand, in Example 3 in which oxetane of the present invention was added, the heat deformation temperature was 151 ° C.
It maintains the same thermal deformation temperature as XY Resin.

[0043]

According to the present invention, there is provided an oxetane compound having improved polymerizability, a high molecular weight and improved heat resistance, a method for producing the compound, and a cationically polymerizable composition containing the compound. You.

[Brief description of the drawings]

FIG. 1. Compound 1 (2-oxaspiro [3,5] -5
2 shows the measurement results of ¹ H-NMR of methyl nonane).

FIG. 2. Compound 1 (2-oxaspiro [3,5] -5-
Nonanoic) is a ¹³ C-NMR measurement results of the.

FIG. 3 is a time course of photopolymerization.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Uchida 2nd Nakanoshu, Oaza Oita City, Oita Prefecture Showa Denko Corporation Technology Development Department, Oita Factory (72) Inventor Shoichiro Wakabayashi 2nd Onaka Nakanoshu, Oita City, Oita Prefecture Showa Denko Co., Ltd. Oita Factory Technology Development Department F term (reference) 4C048 TT08 UU05 XX01 XX02 XX04 4J005 AA07 AA11 BB01

Claims (13)

[Claims] An oxetane compound represented by the general formula 1.
(General formula 1) (Wherein, R ¹ is fluorine, chlorine, bromine, or C 1-2
0 alkyl groups, aryl groups, fluoroalkyl groups,
A chloroalkyl group and a bromoalkyl group. ) Wherein the oxetane compound of claim 1 wherein R ¹ in the general formula 1 is characterized in that it is a methyl group. 3. The method for producing an oxetane compound according to claim 1, wherein the starting material is an alicyclic diol represented by the general formula 2 (general formula 2). (Wherein, R ¹ is fluorine, chlorine, bromine, or C 1-2
0 alkyl groups, aryl groups, fluoroalkyl groups,
A chloroalkyl group and a bromoalkyl group. ) Manufacturing method. 4. The process for producing an oxetane compound according to claim 3, wherein the alicyclic diol is 2-methyl-cyclohexane-1,1-dimethanol, and the oxetane compound is a compound represented by the general formula 1 wherein R1 is a methyl group. 5. The process for producing an oxetane compound according to claim 3, wherein an oxetane-forming reaction is carried out after reacting the alicyclic diol with the carbonic acid diester. 6. The method for producing oxetane according to claim 5, wherein the diester carbonate is dimethyl carbonate. 7. A cationically polymerizable composition comprising the oxetane compound according to claim 1 and an epoxide compound. 8. A cationically polymerizable composition comprising the oxetane compound according to claim 1, an epoxide compound and a cationic photopolymerization initiator. 9. A cationically polymerizable composition comprising the oxetane compound according to claim 1, an epoxide compound and a thermal cationic polymerization initiator. 10. The cationically polymerizable composition according to claim 7, wherein the epoxide compound is a bisphenol A type oligomer. 11. The cationically polymerizable composition according to claim 7, wherein the epoxide compound has a molecular weight of less than 1,000. 12. The cationically polymerizable composition according to claim 8, wherein the cationic photopolymerization initiator is triarylsulfonium hexafluorophosphate. 13. The cationically polymerizable composition according to claim 9, wherein the thermal cationic polymerization initiator is 2-butenyltetramethylenesulfonium hexafluoroantimonate.