JP3082373B2 - New pyridinium salt compound and polymerization initiator - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel pyridinium salt compound and a cationic polymerization initiator containing the same. The cationically polymerizable composition containing the polymerization initiator and the cationically polymerizable compound can be cured in a short time at a low temperature by heat, and the resulting cured product has excellent physical properties. It is suitably used as a material for mold resins, paints, adhesives, inks and the like.

[0002]

2. Description of the Related Art Conventionally, epoxy resins include, as curing agents, active amine-containing compounds and carboxylic anhydrides widely used in two-part systems. However, in a two-pack system using these curing agents, it is necessary to completely mix the components, and it takes several hours to cure. On the other hand, one that cures an epoxy resin as a one-part system includes boron fluoride-monoethylamine, which takes 1 to 8 hours to completely cure at 160 ° C. or higher. I have. Also, T.I. Endo et al, Chemistry
In Letters, 1861-1964 (1989), various p-cyanopyridinium salt compounds have been observed in studies of heat-latent cationic polymerization catalysts, but these compounds have not been able to achieve satisfactory activity.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and is a novel cationic polymerization initiator capable of curing a cationically polymerizable compound by heat at a low temperature in a short time. Further, it is an object of the present invention to obtain a one-package cationically polymerizable composition containing the initiator and having storage stability and to provide a cured product having excellent physical properties.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, by using a cationic polymerization initiator composed of a specific pyridinium salt compound, the present invention has been achieved in a short time at a low temperature. The present invention has been completed by finding a novel cationic polymerization initiator which can be cured and gives excellent performance to the cured product.

The present invention relates to the following general formula [1]

[0006]

Embedded image [Wherein, R ₁ represents a hydrogen atom, an alkyl group or a cyano group, R ₂ represents an alkyl group or an optionally substituted phenyl group, and R ₃ and R ₄ represent a hydrogen atom, an alkyl group, and a halogen atom, respectively. , An alkoxy group, a cyano group, -CH ₂
CN, hydroxyl group, vinyl group, nitro group, -CON
R ¹ R ² , -NR ¹ R ² , -COR ¹ , -COOR ¹ ,
—OCOR ¹ (R ¹ represents a hydrogen atom, an alkyl group, an optionally substituted phenyl group, or an optionally substituted benzyl group, and R ² represents a hydrogen atom, an alkyl group, an acyl group, An optionally substituted phenyl group, an optionally substituted benzoyl group or an optionally substituted benzyl group), an optionally substituted phenyl group, an optionally substituted benzoyl group or an optionally substituted A good benzyl group, X is SbF ₆ , AsF ₆ , PF ₆
Or a cationic polymerization initiator, characterized by containing at least one pyridinium salt compound and the compound represented by the BF ₄ illustrates a].

Hereinafter, the present invention will be described in detail. The pyridinium salt compound of the present invention has the general formula [1]

[0008]

Embedded image In this formula, R ₁ is a hydrogen atom, an alkyl group or a cyano group, and the alkyl group is preferably a lower alkyl group such as methyl, ethyl, propyl, isopropyl and butyl. R ₂ is an alkyl group or a phenyl group which may be substituted; examples of the substituent of the substituted phenyl group include halogen atoms such as F, Cl and Br), alkyl groups such as methyl, ethyl and propyl, and methoxy and ethoxy; , Propoxy, isopropoxy and the like. R ₃ and R ₄ are each a hydrogen atom, an alkyl group such as methyl, ethyl, propyl, isopropyl, or butyl group; a halogen atom such as F, Cl, or Br; or an alkoxy group such as methoxy, ethoxy, propoxy, isopropoxy, or butoxy group. , Cyano group, -CH ₂ CN, hydroxyl group, vinyl group, nitro group, -CONR ¹ R ² , -NR ¹
R ^2, over COR ^1, a -COOR ¹ or chromatography COR ^1, -CONR ¹ R ² above, over NR ¹ R ^2, -COO
R ¹ , —COR ¹ , and R ¹ and R ² of the —OCOR ¹ group are
Each represents a hydrogen atom, an alkyl group of C ₁ -C ₄ (methyl,
Ethyl, propyl, isopropyl, butyl, etc.), C ₁
A C ₄ to acyl group (acetyl, propionyl group or the like), a phenyl group, a benzoyl group or a benzyl group; the phenyl group, the benzoyl group and the benzyl group may be substituted with a halogen atom, an alkyl group or the like; X is SbF ₆ , A
sF ₆ , PF ₆ or BF ₄ , of which SbF ₆ is preferably used.

The pyridinium salt compound can be obtained, for example, by the following method. 3-substituted-1-halogenated-2-butene such as cinnamyl bromide, crotyl bromide, 1-bromo-3-methyl-2-butene and pyridine or a pyridine derivative are equimolarly, if necessary, methyl alcohol. , Acetone, acetonitrile, and the like, and reacted at room temperature to 80 ° C for several hours to 30 days. Sodium antimonate is added and stirred vigorously to separate the precipitated liquid or solid product, followed by drying.

As typical pyridinium salt compounds of the present invention, those represented by the following chemical formulas [2] to [13] are exemplified. In the formula, X is SbF ₆ , AsF ₆ , PF ₆
Or show the BF _4.

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[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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The pyridinium salt compound of the present invention is useful as a cationic polymerization initiator and is used in combination with a cationically polymerizable compound. Examples of the cationic polymerizable compound used here include the following compounds. (A) As a compound having an epoxy group, 1,1,3-
Tetradecadiene dioxide, limonenedioxide, 4-vinylcyclohexene dioxide, (3,4
-Epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate, di (3,4-epoxycyclohexyl) adipate, phenylglycidyl ether, bisphenol A type epoxy resin, halogenated bisphenol A type epoxy resin, o-, m-, There are epoxy compounds such as p-cresol novolak type epoxy resin, phenol novolak type epoxy resin and polyglycidyl ether of polyhydric alcohol.

(B) Styrene, α as the vinyl compound
Styrenes such as -methylstyrene and p-chloromethylstyrene; alkyl vinyl ethers such as n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether and hydroxybutyl vinyl ether;
Alkenyl vinyl ethers such as allyl vinyl ether and 1-octahydronaphthyl vinyl ether; alkynyl vinyl ethers such as ethynyl vinyl ether and 1-methyl-2-propenyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether and p-methoxyphenyl vinyl ether; butanediol divinyl ether Divinyl ethers such as triethylene glycol vinyl ether and cyclohexanediol divinyl ether; aralkyl divinyl ethers such as 1,4-benzene dimethanol divinyl ether, Nm-chlorophenyldiethanolamine divinyl ether and m-phenylenebis (ethylene glycol) divinyl ether Vinyl ethers: hydroquinone divinyl ether, resorcinol divinyl ether Aryl divinyl ethers such as ether; N- vinylcarbazole, there is a cationic polymerizable nitrogen-containing compounds such as N- vinylpyrrolidone.

(C) As a bicycloorthoester compound, 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2,2,2] octane, 1-ethyl-4-
Hydroxymethyl-2,6,7-trioxabicyclo [2,2,2] octane and the like (d) Spiro orthocarbonate compounds include
5,7,11-tetraoxaspiro [5,5] undecane, 3,9-dibenzyl-1,5,7,11-tetraoxaspiro [5,5] undecane, and 1,4,6-trioxaspiro [4,4] nonane, 2-methyl-1,4,4
6-trioxaspiro [4,4] nonane, 1,4,6-
Spiroorthoester compounds such as trioxaspiro [4,5] decane and the like. These may be used alone or in combination of two or more. Among (a) to (d), the compound having an epoxy group of (a) is particularly preferably used.

In the present invention, the mixing ratio of the cationic polymerizable compound and the cationic polymerization initiator is 0.01 to 20 parts by weight, preferably 100 parts by weight of the cationic polymerizable compound. , 0.1-10
It can be blended in parts by weight and can be easily cured by heat. The heat curing is performed at a temperature of 20 to 200 ° C, preferably 50 to
It is in the range of 180 ° C. In addition, it is also possible to cure using both heat and radiation.

The cationic polymerization initiator of the present invention is generally used alone, but may be used in combination with another cationic polymerization initiator.

When the compound having an epoxy group of the above (a) is used, a curing agent such as a phenol-based curing agent or an acid anhydride curing agent which is usually used as a curing agent for epoxy resin is used. You may use together, as long as it is not damaged. When the initiator of the present invention is blended and used in the cationic polymerizable compound, a reactive diluent, a curing accelerator, a solvent, a pigment, a dye, a coupling agent, if necessary,
It is used by adding an inorganic filler, carbon fiber, glass fiber, surfactant and the like.

[0028]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples.

Example 1 <Synthesis of cinnamyl-2-cyanopyridinium hexafluoroantimonate> Cinnamyl bromide 9.85 and 2
5.21 g of cyanopyridine was mixed and reacted at 50 ° C. for 13 days. The solid obtained is washed with ether and
It dried under reduced pressure at ℃, and obtained cinnamyl-2-cyanopyridinium bromide of a precursor. Yield: 86% Then, 3.01 g of cinnamyl-2-cyanopyridinium bromide was dissolved in 15 g of distilled water, 3.10 g of sodium hexafluoroantimonate was added, and the mixture was stirred well and cooled. The precipitated solid was washed with distilled water, filtered,
And dried under reduced pressure. Yield: 85% The obtained cinnamyl-2-cyanopyridinium hexafluoroantimonate of the present invention is represented by the following structural formula [14].

[0030]

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The spectrum data of this product was as follows. IR (KBr, cm ^-1 ): 1657, 1612, 1496, 1140, 97
8, 659 ¹ H-NMR (acetonitrile-d ³ ): δ 5.56 (d,
2H), 6.46 (m, 1H), 7.01 (d, 1H), 7.34-
7.44 (m, 3H), 7.49 to 7.54 (m, 2H), 8.33
(T, 1H), 8.55 (d, 1H), 8.71 (t, 1H),
9.10 (d, 1H) ¹³ C-NMR (acetonitrile-d ³ ): δ 64.8,
111.4, 119.6, 127.8, 128.1, 129.9, 130.3, 13
3.2, 135.9, 136.0, 140.9, 148.1, 149.2

Example 2 <Synthesis of cinnamyl-4-cyanopyridinium hexafluoroantimonate> 9.85 g of cinnamyl bromide and 5.21 g of 4-cyanopyridine were dissolved in 10 g of acetonitrile and reacted at 50 ° C. for 5 days. The obtained solid was washed with ether and dried at 40 ° C. under reduced pressure to obtain a precursor cinnamyl-4-cyanopyridinium bromide.
Yield: 65% Next, 3.01 g of cinnamyl-4-cyanopyridinium bromide was dissolved in 15 g of distilled water, 3.30 g of potassium hexafluoroantimonate was added, and the mixture was stirred well and cooled. Decant the supernatant, add ether,
Cool. The precipitated solid was filtered and dried under reduced pressure at 40 ° C. Yield: 98% The obtained cinnamyl-4-cyanopyridinium hexafluoroantimonate of the present invention is represented by the following structural formula [15].

[0033]

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The spectrum data of this product was as follows. IR (KBr, cm ^-1 ): 1641, 1459, 1145, 977,
764, 658, ¹ H-NMR (DMSO-d ⁶ ): δ 5.51 (d, 2
H), 6.59 (m, 1H), 6.93 (d, 1H), 7.92-7.
43 (m, 3H), 7.49 (d, 2H), 8.73 (d, 2H)
, 9.41 (d, 2H), ¹³ C-NMR (DMSO-d ⁶ ): δ 63.1, 114.7
, 121.6, 126.8, 127.2, 128.7, 131.0, 135.0
, 137.1, 146.1

Example 3 <Synthesis of cinnamyl-2-chloropyridinium hexafluoroantimonate> 9.85 g of cinnamyl bromide and 5.68 g of 2-chloropyridine were mixed and reacted at 50 ° C. for 20 days. The obtained solid was washed with ether and dried at 40 ° C. under reduced pressure to obtain a precursor cinnamyl-2- chloropyridinium bromide. Yield: 93% Then, 3.11 g of cinnamyl-2-chloropyridinium bromide was dissolved in a mixed solvent of 15 g of distilled water and 3 g of methyl ketone, and sodium hexafluoroantimonate was dissolved.
10 g was added, well stirred, and cooled. After removing the supernatant liquid separated into two layers, ether was added and the mixture was stirred well while cooling. The precipitated solid was filtered and dried under reduced pressure at 40 ° C. Yield: 85% The obtained cinnamyl-2-chloropyridinium hexafluoroantimonate of the present invention is represented by the following structural formula [16].

[0036]

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The spectrum data of this product was as follows. IR (KBr, cm ^-1 ): 1655, 1618, 1492, 1288, 11
^{43,971, 777, 659 1 H-} NMR ( acetonitrile ^{-d 3): δ 5.42 (d} ,
2H), 6.42 (m, 1H), 6.90 (d, 1H), 7.31-
7.44 (m, 3H), 7.49 (d, 2H), 7.99 (t, 1
H), 8.14 (d, 1H), 8.48 (t, 1H), 8.84
(D, 1H) ¹³ C-NMR (acetonitrile-d ³ ): δ 63.0,
120.0, 127.9, 128.0, 129.9, 130.1, 131.7, 13
6.3, 139.4, 147.9, 148.7

Example 4 <Synthesis of cinnamyl-2-benzoylpyridinium hexafluoroantimonate> Ginnamyl bromide 9.85
g and 2-benzoylpyridine 9.16 g, and mixed at 50 ° C.
For 4 days. The obtained solid was washed with ether and dried at 40 ° C. under reduced pressure to obtain a precursor cinnamyl-2-benzoylpyridinium bromide. Yield: 97% Then, 3.80 g of cinnamyl-2-benzoylpyridinium bromide was dissolved in 15 g of distilled water, 3.10 g of sodium hexafluoroantimonate was added, the mixture was stirred well, and cooled. The precipitated solid is washed with distilled water, filtered, and filtered.
It dried under reduced pressure at 0 degreeC. Yield: 89% The obtained cinnamyl-2-benzoylpyridinium hexafluoroantimonate of the present invention is represented by the following structural formula [17].

[0039]

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The spectrum data of this product was as follows. IR (KBr, cm ^-1 ): 1669, 1617, 1451, 128
^{5,1153,976, 935, 757,662 1 H-} NMR ( acetonitrile ^{-d 3): δ 5.40 (d} ,
2H), 6.31 (m, 1H), 6.64 (d, 1H), 7.17-
7.29 (m, 5H), 7.51 (t, 2H), 7.70 (t, 1
H), 7.88 (d, 2H), 8.09 (d, 1H), 8.23
(T, 1H), 8.67 (t, 1H), 9.17 (d, 2H) ¹³ C-NMR (acetonitrile-d ³ ): δ 62.7,
121.3,127.8,129.6130.0,130.3,130.6,131.8
, 135.0, 136.0, 137.0, 140.2, 148.0, 148.8,
150.6, 188.9,

Example 5 <Synthesis of (2-butenyl) -2-cyanopyridinium hexafluoroantimonate> 1-bromo-2-butene
6.75 g and 5.21 g of 2-cyanopyridine are mixed, and 50
The reaction was performed at a temperature of 3 ° C for 3 days. The obtained solid was washed with ether and dried under reduced pressure at 40 ° C. to obtain a precursor (2-butenyl).
-2-Cyanopyridinium bromide was obtained. Yield: 9
4% Then, 2.39 g of (2-butenyl) -2-cyanopyridinium bromide was dissolved in 15 g of distilled water, 3.10 g of sodium hexafluoroantimonate was added, and the mixture was stirred well and cooled. The precipitated solid is washed with distilled water, filtered, and filtered.
It dried under reduced pressure at 0 degreeC. Yield: 76% The obtained (2-butenyl) -2-cyanopyridinium hexafluoroantimonate of the present invention has the following structural formula [18]
Indicated by

[0042]

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The spectrum data of this product was as follows. IR (KBr, cm ^-1 ): 1674, 1614, 1511, 1232,
1152, 976, 790, 658 ¹ H-NMR (acetonitrile-d ³ ): δ 1.82 (d,
6H), 5.31 (d, 2H), 5.63-5.82 (m, 1H),
6.13 to 6.26 (m, 1H), 8.31 (t, 1H), 8.52
(T, 1H), 8.69 (t, 1H), 8.96 (t, 1H) ¹³ C-NMR (acetonitrile-d ³ ): δ 13.9,
18.2, 59.7, 64.6, 111.3, 120.3, 121.6, 127.7,
133.2, 135.8, 135.9, 137.3, 139.9, 148.8, 14
8.8

Examples 6 to 10 <DSC measurement> The compounds (polymerization initiators) synthesized in Examples 1 to 5 were dissolved in propylene carbonate.
These are added to each epoxy compound of ERL-4221 (alicyclic epoxy manufactured by UCC) and UVR-6410 (glycidyl epoxy manufactured by UCC) so as to be 2.5 parts as a pure component, and the composition is added. AE were prepared. DSC measurement was performed on this blended composition to determine the exothermic onset temperature and the peak top temperature. The DSC measurement conditions are as follows. DSC measuring instrument: DSC220C (manufactured by Seiko Instruments Inc.) Atmosphere: 30 ml / min in a nitrogen gas stream Heating rate: 10 ° C./min Sample amount: 0.3 to 0.8 mg

Comparative Examples 1-4 In place of the polymerization initiator of the present invention of Examples 6-10, benzyl-2-cyanopyridinium hexafluoroantimonate (R-1) and benzyl-2-cyanopyridinium hexafluoroantimonate were used for comparison.
4-cyanopyridinium hexafluoroantimonate (R-2), benzyl-2-chloropyridinium hexafluoroantimonate (R-3), and benzyl-2-
Using benzoylpyridinium hexafluoroantimonate (R-4) as an initiator, DSC measurements were performed in the same manner as in Examples 6 to 10. As described above, Examples 6-1
Table 1 shows the results of the DSC measurement of Comparative Examples 1 to 4.

[0046]

[Table 1]

[0047]

As described in detail above, the novel pyridinium salt compound of the present invention is effective as a polymerization initiator for cationically polymerizable compounds, and a composition containing these compounds can be rapidly and at low temperature by heat treatment. It can be polymerized and cured. The one-part composition is stable even after mixing, and has excellent storage stability at room temperature.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07D 213/81 C07D 213/81 213/84 213/84 C08F 4/00 C08F 4/00 C08G 59/68 C08G 59/68 (58) Field (Int.Cl. ⁷ , DB name) C07D 213/00-213/84 C08F 4/00 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound of the general formula [1] [Wherein, R ₁ represents a hydrogen atom, an alkyl group or a cyano group, R ₂ represents a phenyl group which may be substituted,
R _3, R ₄ are each a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, a cyano group, -CH ₂ CN, hydroxyl group, a vinyl group, a nitro group, over CONR ¹ R ^2, over NR
¹ R ^2, over ^{COR 1, -COOR 1, -OCOR 1} (R 1 represents a hydrogen atom, an alkyl group, a phenyl group which may be substituted, or an optionally substituted benzyl group, R ²
Represents a hydrogen atom, an alkyl group, an acyl group, an optionally substituted phenyl group, an optionally substituted benzoyl group or an optionally substituted benzyl group), an optionally substituted phenyl group, a which may be a benzoyl group, or an optionally substituted benzyl radical, R
_{When 1} is a cyano group, R ₂ is an alkyl group, and X is Sb
F _6, AsF _6, PF ₆ or pyridinium salt compounds represented by BF ₄ showing a. 2. A cationic polymerization initiator comprising at least one pyridinium salt compound according to claim 1.