KR970011640B1 - Cationic polymerable composition and polymerization catalyst - Google Patents

Abstract

Cation polymer composite is produced by including one or more of cation polymer initiator indicated in general formula(1). In formula, R1 is methyl group, benzyl group, para-methoxy benzyl group, or para-nitro benzyl group and R2 is hydrogen atom and R3 is methyl group, phenyl group, or para-nitro phenyl group.

Description

Cationic polymerizable composition, polymerization catalyst and polymerization method

The present invention relates to a novel cationically polymerizable composition, a polymerization initiator and a polymerization method. More specifically, the present invention relates to a polymerization initiator for polymerizing a cationically polymerizable material in a short time by heat to obtain a cured product having good physical properties or an oligomer of a practical cationically polymerizable compound, and a polymerization initiator and a polymerization method for polymerizing the polymerization composition.

Cationic polymerization has the characteristic that the polymerization reaction rate is extremely fast. Conventionally, halogens such as Lewis acidic initiators such as BF ₃ , ZnCl ₂ , and AlCl ₃ , AlR ₂ Cl, and AlRCl ₂ (where R is a general organic functional group including an alkyl group, an aryl group, etc.) as an initiator of the reactor. Although containing organoaluminum compounds and the like have been used, these initiators have a problem that the cationic polymerization reaction is too vigorous at a temperature of 0 ° C. or higher, so that the polymerization reaction cannot be removed and the degree of polymerization does not increase. Therefore, in order to use these as polymerization initiators, the cationic polymerizable monomer dissolved in a suitable solvent is usually cooled to a predetermined cryogenic temperature (-130 to 140 ° C.), and then polymerization is carried out by adding an initiator solution. It's not an industrially satisfying way. In addition, there are known boron trifluoride-amine complexes which are cationic polymerization initiators exhibiting polymerization activity by thermal decomposition or the like, and onium salts having a specific structure (Japanese Patent Publication No. 56-152838). Salts have low utility such as activity at 150 ° C or higher. Benzylsulfone salts and benzyl ammonium salts (European patent EP 0 343 690 A2) developed to solve this problem have characteristics of the selectivity of the reaction temperature. That is, it is possible to cure the cationically polymerizable composition (for example, epoxy resin) in a short time in the range of 80 ~ 150 ℃ lower than 150 ℃, non-absorbent, excellent storage stability, easy to use because it can be mixed and stored for a long time with the resin Its use has been proposed as an initiator for polymerization of cationically polymerizable compositions such as sealing agents, composite resins and matrix resins. These cationic polymerization initiators are designed with sulfone salts and ammonium salts having benzyl groups as their starting species.

The present invention is to provide a novel thermal latent cationic polymerization initiator and a cationically polymerizable composition containing the same as the prior art of the prior art is designed as a proton instead of a benzyl group, the curable cationically polymerizable compound in a short time by heat. Has a purpose.

In order to achieve the above object, the present invention provides a cationic polymerization initiator represented by the following general formula (I).

(Herein, R ₁ is a methyl group, benzyl group, para-methoxybenzyl group, or para-nitro benzyl group, R ₂ is a hydrogen atom, R ₃ is a methyl group, phenyl group, or para-nitro phenyl group.)

The polymerization initiator of the present invention having the above formula (I) releases protons by heat to advance the polymerization of the cationic polymerizable compound, and at the same time, the amineamide, a nitrogen-containing compound produced by thermal decomposition, stops the polymerization reaction. Has That is, according to the present invention, the cationic polymerization initiator having the structural formula (I) changes the basicity of the amine amide produced by thermal decomposition of the polymerization initiator when the kind of the side chain functional groups R ₁ and R ₃ is changed to improve the activity of the polymerization reaction. It has a very characteristic catalytic function that allows control.

According to the present invention, the cationic polymerization initiator (hydrazinium salt) represented by the above structural formula (I) is preferably 1,1,1-trimethyl-2-benzoylhydrazinium hexafluoro antimonate, 1,1 -Dimethyl-1-benzyl-2-benzoylhydrazinium hexafluoro antimonate, 1,1-dimethyl-1-benzyl-2-P-nitrobenzoyl hydrazinium hexafluoro antimonate, 1,1-dimethyl- 1-P-methoxybenzyl-2-P-nitro benzoyl hydrazinium hexafluoro antimonate, etc. are mentioned.

The cationic polymerization initiator represented by the above formula (I) according to the present invention synthesizes the halide ions of the halide salts formed by the reaction of the alkyl hydride with the corresponding hydrazide compound and the menthtokine at high yield by anion exchange with SbF ₆ ^θ . It is done.

Moreover, since these salts do not start a cationic polymerization reaction at room temperature, it is also possible to preserve | save a monomer and an initiator previously using a solvent free or a suitable solvent as needed.

The present invention also provides a polymerization composition comprising one or two or more of the cationic polymerizable material and a hydrazinium salt represented by the following general formula (I).

(Wherein R ₁ is a methyl group, benzyl group, para-methoxybenzyl group, or para-nitrobenzyl group, R ₂ is a hydrogen atom, R ₃ is a methyl group, a phenyl group, or a para-nitrophenyl group.)

Examples of the cationically polymerizable material in the present invention are not particularly limited in kind, but epoxide monomers, epoxy resins, phenol / formaldehyde resins, melamine / formaldehyde resins, urea / formaldehyde resins, spirorthoesters and the like. The same cyclic ethers and cyclic thioethers (substances other than epoxides and episulfides) and polymers thereof, lactones, styrene, vinyl ethers and vinyl thioethers, and resins having functional groups which can be crosslinked or cured in the case of acid treatment, alone or both Mixtures of more than one kind are also included.

The hydrazinium salt, which is a polymerization initiator used in the cationic synthesis composition of the present invention, has heat selectivity.

That is, the hydrazinium salt excited by heat above a certain temperature releases protons, initiates the polymerization of the above cationic polymerizable materials, and at the same time produces a corresponding amineamide by pyrolysis, which is the degree of polymerization reaction by the stop reaction. Adjust it.

In the present invention, in the case where the cationic polymerizable material is a vinyl compound, the solution polymerization method is usually performed in a polymerization reaction using a solvent which is inert to an initiator monomer or the like, but in some cases, a bulk polymerization method is also performed. As the solvent, for example, aromatic hydrocarbons such as toluene, benzene and xylene, aliphatic hydrocarbons such as n-hexane and n-butane, hydrocarbon mixtures such as petroleum ether and ligroin, and halogenated hydrocarbons such as chlorobenzene and dichloroethane are used. The polymerization is possible in a homogeneous or uniform system. Moreover, the polymerization reaction of these vinyl compounds is performed under normal pressure or pressurization reaction, and reaction temperature is 20 degreeC or more, Preferably it is 60-150 degreeC which is industrially easy to heat.

In the present invention, the amount of the cationic polymerization initiator to be used is usually 0.1 to 10% and preferably 0.5 to 5% with respect to the cationically polymerizable organic compound. When the addition amount exceeds 10%, the cured product may be colored by the heat of reaction generated during curing, resulting in poor physical properties and poor cost. In the polymerization, a solvent can be used.

The composition of the present invention may optionally be used by mixing a weighting agent, a flame retardant, an antistatic agent, a surfactant, a representative acid anhydride, a pigment, a dye, an inorganic filler, a processing aid, and the like.

The composition of the present invention is suitable for applications such as encapsulation, insulation and adhesion of electrical and electronic components. Other applications include the processing of metals, rubber, plastics, fibers, paper, glass, ceramics, cement and wood. Specifically, the present invention can be applied to printing inks, sealants, adhesives, paints, laminates for printed boards, coatings, dental materials, and molding materials.

The cured composition according to the present invention can be stored for a long time, and has a function of initiating polymerization at a temperature of 150 ° C. or less within a short time, thereby producing a cured product having excellent high temperature curing resistance, no hygroscopicity, and excellent water resistance and chemical resistance.

Moreover, in the cationically polymerizable vinyl compound polymerization, not only the monolithic storage of the monomer and the initiator, which have been conventionally difficult, but also cationic polymerization can be achieved at 20 ° C or higher, and there is an advantage that a practical polymer can be obtained by simple heating.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the present invention is not limited to the following examples. Table 1 lists the synthesis results of the cationic polymerization initiator represented by formula (I).

Synthesis Example 1

[Synthesis of Cationic Polymerization Initiator]

Synthesis of 1,1,1-trimethyl-2-benzoylhydrazinium hexafluoro antimonate (Ia)

end. Synthesis of 1,1-dimethyl-2-benzoylhydrazine

To a solution of benzoyl chloride (10.5 g) in benzene (20 ml) was slowly added dropwise over about 10 minutes to maintain 1,1-dimethylhydrazine (4.5 g) below the boiling point of 1,1-dimethylhydrazine (60 ° C). The reaction was reacted at a reflux temperature of benzene for about 2 hours, and the resulting solid was filtered, washed with benzene (20 ml × 3), and dried. This white solid was dissolved in water (50 ml), and dehydrochlorination (titration) with 0.1 N NaOH aqueous solution using 1% phenolphthalein-ethyl alcohol solution as an indicator, and most of the water was evaporated under reduced pressure and chloroform (20 ml × 3) was used. After extraction, the solvent was synthesized by evaporation (dry) under reduced pressure.

Yield: 83%

Melting Point: 106.1-109.8 ℃

¹ H NMR (CDCl ₃ ): δ = 2.67 [s, 6H, (CH ₃ ) _2- ], 7.03-7.86 (m, 5H, Ph), (br, 1H, -NH-)

I. Synthesis of 1,1,1-trimethyl-2-benzoylhydrazinium iodide

Methyl iodide (3.7 g) was added dropwise over about 10 minutes to a solution of 1,1-dimethylbenzoylhydrazine (4.3 g) dissolved in acetone (15 ml). After reacting the reaction for about 15 hours, the resulting solid was filtered, washed with acetone (20 ml × 3), and dried.

Yield: 78%

Melting Point: 169.8-173.7 ℃

¹ H NMR (CDCl ₃ ): δ = 3.84 [s, 9H, (CH ₃ ) ₃ −], 4.83 (s, 1H, NH—), 7.43-7.97 (m, 5H, Ph)

All. Synthesis of 1,1,1-trimethyl-2-benzoylhydrazonium hexafluoroantimonate

Iodide 1,1,1-trimethyl-2-benzoylhydrazonium (3.5 g) was dissolved in 20 ml of methanol, potassium hexafluoroantimonate (2.7 g) was added thereto, and water was added to obtain a white solid. This was purified by recrystallization from methanol.

Yield: 54.8%

Melting Point: 194.9-197.5 ℃

¹ H NMR (acetone-d ₆ , DMSO): δ = 3.87 [s, 9H, (CH ₃ ) _3- ], 7.53-8.17 (m, 5H, Ph)

Synthesis Example 2

Synthesis of 1-benzyl-1,1-dimethyl-2-benzoylhydrazinium hexafluoro antimonate (Ib)

end. Synthesis of 1,1-dimethyl-1-benzyl-2-benzoylhydrazinium bromide

Benzyl bromide (3.42 g) was added dropwise over about 10 minutes to a solution of 1,1-dimethylbenzoylhydrazine (3.67 g) dissolved in benzene (20 ml). After reacting the reaction for about 3 days, the resulting solid was filtered, washed with benzene (20ml × 3), and dried.

Yield: 88.8%

Melting Point: 154.6-155.7 ℃

¹ H NMR (CDCl ₃ ): δ = 7.97-7.23 (m, 10H, Ph), 5.58 (s, 2H, -CH _2- ), 3.90 [s, 6H, (CH ₃ ) _2- ]

I. Synthesis of 1,1, -dimethyl-1-benzyl-2-benzoylhydrazinium hexafluoro antimonate

Brominated 1,1-dimethyl-1-benzyl-2-benzoylhydrazinium (2.4g) was dissolved in 20ml of water, and sodium hexafluoroantimonate (1.8g) was added thereto, and water was added to obtain a white solid. This was purified by recrystallization from methanol.

Yield: 91%

Melting Point: 127.2-129.3 ℃

¹ H NMR (Acetone-d ₆ ): δ = 7.50-7.92 (m, 10H, Ph), 5.35 (s, 2H, -CH _2- ), 3.80 [s, 6H,-(CH ₃ ) _2- ]

Synthesis Example 3

Synthesis of 1,1-dimethyl-1-benzyl-2-P-nitrobenzoylhydrazinium hexafluoro antimonate (Ic)

end. Synthesis of 1,1-dimethyl-2-P-nitrobenzoylhydrazine

To a solution of P-nitrobenzoyl chloride (7.4 g) dissolved in 15 ml of ether, 1,1-dimethylhydrazine (2.4 g) was slowly added dropwise over about 10 minutes to keep the boiling point of 1,1-dimethylhydrazine. After reacting the reaction at room temperature for one day, the resulting solid was filtered, washed with ether (15 ml × 3), and dried. This yellow solid was dissolved in methanol (50 ml), dehydrochlorination (titration) with 0.1 N NaOH aqueous solution using 1% phenolphthalein-ethyl alcohol solution as an indicator, and water and methanol were evaporated to dryness under reduced pressure, and chloroform (20 ml) was used. After extraction with x3), the solvent was evaporated under reduced pressure (dry) for synthesis.

Yield: 80%

Melting Point: 143-145.5 ℃

¹ H NMR (acetone-d ₆ ): δ = 8.48 (m, 4H, Ph), 2.63 (s, 6H, (CH ₃ ) ₂ )

I. Synthesis of 1,1-dimethyl-1-benzyl-P-nitrobenzoylhydrazinium bromide

After benzyl bromide (2.8 g) was dissolved in acetone (25 ml), 1,1-dimethyl-2-P-nitrobenzoylhydrazine (3.4 g) was slowly added dropwise and reacted at room temperature for one day. The resulting solid was filtered and washed well with acetone (20ml × 3) and dried.

Yield: 35.5%

Melting Point: 134.8-137.4 ℃

¹ H NMR (CDCl ₃ ): δ = 8.02 (s, 4H, Arom), 7.33 (s, 5H, Ph), 5.37 [s, 2H, -CH _2- ), 3.87 [s, 6H, -CH ₃ ) ₂ ]

All. Synthesis of 1,1-dimethyl-1-benzyl-2-P-nitrobenzoylhydrazinium hexafluoro antimonate

After dissolving brominated 1,1-dimethyl-2-P-nitrobenzoylhydrazinium (2.2g) in 50 ml of methanol, animal potassium hexafluoroantimonate was added and reacted for 2 hours, methanol was evaporated under reduced pressure, and then ethyl Extract with acetate. The resulting solid is recrystallized from methanol.

Yield: 92%

Melting Point: 203.9-206.1 ℃

¹ H NMR (acetone-d ₆ , DMSO): δ = 8.46-7.87 (q, 4H, Arom), 7.47 (s, 5H, Ph), 5.20 (s, 2H, -CH _2- ), 3.73 [s, 6H, -CH ₃ ) _2- ]

Synthesis Example 4

Synthesis of 1,1-dimethyl-1-P-methoxybenzyl-2-P-nitrobenzoylhydrazinium hexafluoro antimonate (Id)

end. Synthesis of 1,1-dimethyl-1-P-methoxybenzyl-2-nitrobenzoylhydrazinium bromide

After dissolving 1,1-dimethyl-2-P-nitrobenzoylhydrazine (3.8 g) in acetone, bromine P-methoxybenzyl (3.7 g) was slowly added dropwise and reacted at room temperature for 4 days. The resulting solid was filtered and washed with acetone (20ml × 3) and dried.

Yield: 62.8%

Melting Point: 48.6-149.9 ℃

¹ H NMR (acetone-d ₆ ): δ = 8.33-7.88 (q, 4H, Arom), 7.68-7.00 (q, 4H, Arom), 5.40 (s, 2H, -CH _2- ), 3.95-3.67 [ d, 9H,-(CH ₃ ) _3- ]

I. Synthesis of 1,1-dimethyl-1-P-methoxybenzyl-2-P-nitrobenzoylhydrazinium hexafluoro antimonate

Brominated 1,1-dimethyl-1-P-methoxybenzyl-2-P-nitrobenzoylhydrazinium (2.4 g) was dissolved in 50 ml of methanol, and then added to the animal's carium hexafluorofluoromonate, and reacted for 2 hours. After extraction with ethyl acetate, the resulting solid is recrystallized with methanol.

Yield: 92.0%

Melting Point: 98.5-102.1 ℃

¹ H NMR (acetone-d ₆ ): δ = 8.37-7.87 (q, 4H, Arom), 7.57-6.82 (q, 4H, Arom), 5.33 (d, 2H, -CH _2- ), 3.93 [s, 6H,-(CH ₃ ) _2- ] 3.77 [s, 3H, -CH ₃ O-]

TABLE 1

Synthesis Example of Cationic Polymerization Initiator According to the Present Invention

Formula (I) is It is a compound represented by structural formula.

EXAMPLES 1-8

Glycidylphenyl ether, a model compound of epoxy resin, was polymerized using a cationic polymerization initiator of hydrazinium salts represented by Ia, Ib, Ic, and Id in Table 1 above. The polymerization was carried out by mixing 0.3 g of glycidyl phenyl ether and 3 mol% of cationic polymerization initiator with respect to this monomer in a pyrex glass tube, followed by a block polymerization according to the reaction temperature and time shown in [Table 2]. The reaction mixture was pale yellow or reddish brown high viscosity solution or solid. After completion of the reaction, the reaction mixture was dissolved in methylene chloride and the solution was added dropwise to methanol to obtain a pale yellow or reddish brown high viscosity polymer. It was confirmed by NMR and IR that the structure of this polymer was a polyether structure. The molecular weight and molecular weight distribution were calculated by GPC using polystyrene as a reference material, and are shown in [Table 2].

The effect of the present invention can be confirmed by comparing the selectivity to the synthesis of the cationic polymerization initiator represented by the general formula (II) and its synthesis and its polymerization reactivity and oligomer, which is widely used as a cationic polymerization initiator.

In the following Comparative Synthesis Examples, the synthesis results of the cationic polymerization initiator represented by the general formula (II) are shown.

Comparative Example 1

Synthesis of benzyl p-cyanopyridinium hexafluoroantimonate (IIa)

A mixture of benzyl chloride (6.1 g) and p-cyanopyridine (5.0 g) was reacted for 3 days at 45 ° C. in methanol (80 mL). After the reaction, methanol was evaporated under reduced pressure, extracted with a mole / ether (30 mL / 100 mL) mixed solution, sodium hexafluoroantimonate (13.0) was added to the aqueous layer, and the resulting white solid was filtered and washed, and then recrystallized from methanol. White crystals (5.2 g) were obtained.

Yield: 25.0%

mp: 156-157 ℃

¹ H NMR (acetone-d ₆ ): δ = 9.10-8.83 (d, 2H, py), 8.55-80.15 (br, 2H, py), 7.50 (s, 5H, Ph), 5.76 [s, 2H,- CH _2- ]

Comparative Example 2

Synthesis of p-methoxybenzyl-p-cyanopyridinium hexafluoroantimonate (IIa)

A mixture of p-methoxybenzyl chloride (3.2 g) and p-cyanopyridine (2.0 g) was reacted for 96 hours at room temperature in acetonitrile (30 mL). After the reaction, acetonitrile was evaporated under reduced pressure, extracted with a mixture of water / ether (30 mL / 100 mL), sodium hesafluoroantimonate (5.2 g) was added to the aqueous layer, and the resulting white solid was filtered and washed, and then recrystallized from methanol. To give white crystals.

Yield: 19.4%

mp: 157.5-158.5 ℃

¹ H NMR (acetone-d ₆ ): δ = 9.00-8.75 (q, 2H, py), 8.45-8.15 (br, 2H, py), 7.63-6.85 (q, 4H, Arom), 5.81 (s, 2H , -CH _2- ), 3.81 (s, 3H, CH ₃ O)

[Comparative Examples 1-4]

Except for using the cationic polymerization initiators (IIa, IIb) prepared in Comparative Synthesis Examples 1 to 2 in Examples 1 to 8 were substantially the same as in Example.

TABLE 2

Cationic Polymerization Conditions and Polymer Properties

From the results of the above [Table 2], the polymerization composition and polymerization initiator using the hydrazinium salt according to the present invention as a cationic polymerization initiator are in the range of 80 to 180 ° C compared with the case of using the conventional onium salt as the polymerization initiator. That is, it showed temperature selectivity in a wide range and was able to obtain a low molecular weight polyglycidyl phenyl ether which is an oligomer. From these results, the cationic polymerization initiator according to the present invention does not possess a conventional epoxy resin curing agent such as Lewis acid, amine or acid anhydride, or a polymerization initiator, but has a heat latent characteristic, which is characterized by a cationic polymerization initiator which is an onium salt. Because of its stability against moisture, air and protonic solvents (alcohols), and its ability to control non-hygroscopicity and initiation activity, mixing and storage with monomers are possible, and it is easy to use. Is wide. Furthermore, it is better to control the initiation reaction than the conventional onium salt, which means that it can be used in a wider temperature range and that the selectivity for the synthesis of oligomers is excellent.

As a property of the cationic polymerization initiator according to the present invention, the polymerization composition using the cationic polymerization initiator of the present invention may have a larger use in applications such as encapsulation, insulation, and adhesion of electrical and electronic components.

Claims (8)

Cationic polymerization initiator represented by the following general formula (I). (Herein, R ₁ is a methyl group, benzyl group, para-methoxybenzyl group, or para-nitro benzyl group, R ₂ is a hydrogen atom, R ₃ is a methyl group, phenyl group, or para-nitro phenyl group.) 2. The compound of claim 1 wherein 1,1,1-trimethyl-2-benzoylhydrazinium hexafluoro antimonate, 1,1-dimethyl-1-benzyl-2-benzoylhydrazinium hexafluoro antimonate, 1, 1-dimethyl-1-benzyl-2-P-nitrobenzoyl hydrazinium hexafluoro antimonate, 1,1-dimethyl-1-P-methoxybenzyl-2-P-nitrobenzoylhydrazinium hexafluoro antimo Cation polymerization initiator, characterized in that selected from the group consisting of nate. A polymerization composition comprising one or two or more of the cationic polymerizable material and a hydrazinium salt represented by the following general formula (I). (Herein, R ₁ is a methyl group, benzyl group, para-methoxybenzyl group, or para-nitro benzyl group, R ₂ is a hydrogen atom, R ₃ is a methyl group, phenyl group, or para-nitro phenyl group.) The cyclic ether and cyclic thioether according to claim 3, wherein the cationic polymerizable material is epoxide monomers, epoxy resins, phenol / formaldehyde resins, melamine / formaldehyde resins, urea / formaldehyde resins, cyclic ethers such as spirorthoesters. (Substances other than epoxides and episulfides) and polymers thereof, lactones, styrenes, vinyl ethers and vinylthioethers, and resins having functional groups capable of crosslinking or curing in the case of acid treatment, and the like, or a group consisting of two or more kinds thereof. Polymeric composition, characterized in that selected from. The polymerization composition according to claim 3 or 4, wherein the cationically polymerizable material is an epoxy resin. The polymerization composition according to claim 3 or 4, wherein the cationically polymerizable material is a vinyl compound. The polymerization composition according to claim 3, wherein the cationic polymerization initiator is added in an amount of 0.1 to 10% by weight based on the cationically polymerizable material. The method according to claim 3 or 7, wherein the cationic polymerization initiator is 1,1,1-trimethyl-2-benzoylhydrazinium hexafluoro antimonate, 1,1-dimethyl-1-benzyl-2-benzoylhydra Zhenium hexafluoro antimonate, 1,1-dimethyl-1-benzyl-2-P-nitrobenzoyl hydrazinium hexafluoro antimonate, 1,1-dimethyl-1-P-methoxybenzyl-2-P -A nitrobenzoyl hydrazinium hexafluoro antimonate selected from the group consisting of.