JPH1143495A - New curable phosphazene, polymerizable composition and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new curable phosphazene having a curable group such as an epoxy group or oxetane group and capable of providing a cured product, excellent in mechanical characteristics and manifesting higher flame retardance and heat resistance and useful as a coating agent, an adhesive, etc. SOLUTION: This new curable phosphazene has a recurring structure represented by formula I [(n) is an integer of 3-100,000; X denotes one or more of a curing group having an alicyclic epoxy group represented by formula II, etc., a curing group having exetane group represented by formula III, a curing group other than the alicyclic epoxy group and oxetane group; however, at least one of 2n ×groups X is the curing group having the alicylic epoxy group or oxetane group] and is useful as an overcoating agent, a water repellent coating agent, a surface modifier, an adhesive, a functional filler, a coating material, an encapsulant, an electrolytic diaphragm, etc. The compound is obtained by reacting hexachlorocyclotriphosphazene, etc., with 3,4- epoxycyclohexylmethanol, etc., in the presence of NaH, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel curable phosphazene, a polymerizable composition containing the curable phosphazene, and a cured product thereof.

[0002]

2. Description of the Related Art At present, epoxy resins are widely used in sealing materials, electric and electronic materials, paints, adhesives, civil engineering and building materials, composite materials for aerospace, and the like. Under these circumstances,
Particularly in electric and electronic materials, composite materials for aerospace and space, etc., higher flame retardancy and heat resistance are required, so use halogen compounds or add antimony trioxide or aluminum hydroxide, Has high flame retardancy.

However, when a halogen compound is used,
There is a problem that toxic gas is generated during combustion. Also, the addition of antimony trioxide lowers the arc resistance and deteriorates the insulation, and the addition of aluminum hydroxide causes
There is a problem that the mechanical strength is reduced.

[0004]

Therefore, development of a cured product having excellent mechanical properties and exhibiting higher flame retardancy and heat resistance and a compound providing the same have been desired. An object of the present invention is to provide a compound which gives such a cured product, that is, a cured product having excellent mechanical properties and high flame retardancy and high heat resistance.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, a compound having a repeating structure represented by the following formula (A) provides a cured product capable of realizing the object. The present invention has been found to be extremely useful in various fields, and has completed the present invention. That is, the present invention
(1) a curable phosphazene having a repeating structure represented by the formula (A),

[0006]

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(In the formula (A), n represents an integer of 3 to 100,000, and X represents a curable group having an alicyclic epoxy group, a curable group having an oxetane group, an alicyclic epoxy group, and an oxetane group. Represents at least one selected from a curable group and a non-curable group other than the above, but at least one of the 2n Xs is a curable group having an alicyclic epoxy group or an oxetane group. The present invention relates to a polymerizable composition containing the curable phosphazene described in (1) above, and (3) a cured product obtained by curing the polymerizable composition described in (2) above.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The curable phosphazene of the present invention comprises:
Among the substituents represented by X in the formula (A), the following formula (1)

[0009]

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A curable group having an alicyclic epoxy group represented by the following formula (2):

[0011]

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Has at least one curable group having an oxetane group represented by Regarding the curable group having a group represented by the formula (1) and the curable group having a group represented by the formula (2), the structure represented by the formula (1) and the formula (2) is added to the skeleton. As long as it has a functional group, it may have the same structure or different structures, and is not particularly limited. For example, a curable group having a group represented by the formula (1) is represented by the general formula (3)

[0013]

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Wherein a is an integer of 0 to 3, b is an integer of 1 to 3, c is an integer of 0 to 4, R ₁ is an alkylene group having 1 to 4 carbon atoms, and R ₂ is One or more selected from alkylene groups and halogenated alkylene groups of Formulas 2 to 12,
R ₃ represents one or more selected from an alkyl group having 1 to 4 carbon atoms and a halogenated alkyl group. One or more types selected from the structures represented by the formula (2) are preferable, and the curable group having a group represented by the formula (2) is represented by the general formula (4)

[0015]

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Wherein d is an integer of 0 to 3, e is an integer of 0 to 4, R ₄ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₅ is an alkylene having 1 to 4 carbon atoms. R ₆ is one or more selected from an alkylene group having 2 to 12 carbon atoms and a halogenated alkylene group, and R ₇ is one or more selected from an alkyl group having 1 to 4 carbon atoms and a halogenated alkyl group. 1) selected from the structures represented by
More than species are preferred. For the curable group represented by X in the formula (A) and other than the groups represented by the formulas (1) and (2) (hereinafter, referred to as other curable groups), a heating operation or an ultraviolet ray or an electron beam As long as it is a group having an unsaturated bond or a ring-opening polymerizable group that is cured by irradiation such as irradiation, it may have the same structure or different structures, and is not particularly limited.

[0017]

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(Wherein f is an integer of 1 to 3, g is an integer of 0 to 3, R ₈ is a hydrogen atom or a methyl group, and R ₉ is an alkylene group having 2 to 12 carbon atoms and a halogenated alkylene group. R ₁₀ represents an alkylene group having 1 to 4 carbon atoms or a halogenated alkylene group, and R ₁₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group. One or more types selected from the structures represented by the formula (1) are preferable. For the non-curable group represented by X in the formula (A), for example, the general formula (6)

[0019]

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Wherein h is an integer of 0 to 5, R ₁₂ is an alkyl group having 1 to 18 carbon atoms or a halogenated alkyl group,
R ₁₃ is at least one selected from an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group, a formyl group, an acetyl group, a nitro group, and a halogen atom, and Y is an oxygen atom, a sulfur atom, or an imino group, respectively. Represent. One or more types selected from the structures represented by the formula (1) are preferable. Specific examples of the group represented by the formula (6) include alkoxy groups such as methoxy group, ethoxy group and propoxy group, alkylthio groups such as methylthio group, ethylthio group and propylthio group, methylimino group, ethylimino group and propyl group. Alkyl imino groups such as imino group, phenoxy group, thiophenyl group,
Examples include a formylphenoxy group, an acetophenoxy group, a nitrophenoxy group, and halogenated substituents thereof.

N in the formula (A) is 3 to 100,000
The repeating structure may be any of a cyclic structure and a chain structure. In the case of a cyclic structure, 3 to 20 is preferable, 3 or 4 and a mixture thereof are particularly preferable. In the case of a chain structure, it is preferably from 20 to 100,000, particularly preferably from 1,000 to 10,000.

The synthesis of the curable phosphazene represented by the formula (A) itself can be performed according to a known method such as a reaction between an alcohol and a halogen compound, and the group represented by the formula (1) or (2) can be synthesized. The introduction of a curable group having a chlorophosphazene such as hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, and polydichlorophosphazene obtained by ring-opening polymerization thereof;
It can be obtained by reacting a compound having a group represented by the formula (1) or (2) and having a hydrogen atom bonded to a terminal thereof in the presence of a basic compound.

Specific examples of the compound having a group represented by the formula (1) and having a hydrogen atom bonded to its terminal include 3,4-
Epoxycyclohexylmethanol, 2-hydroxyethyl-3 ′, 4′-epoxycyclohexanecarboxylate and the like having the formula (2), and specific examples of the compound having a hydrogen atom bonded to its terminal include: -Methyl-3-hydroxymethyloxetane, 3-ethyl-3
-Hydroxymethyloxetane and the like.

The above reaction is carried out in an inert solvent such as N, N
Aprotic polar solvents such as dimethylacetamide, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, N, N-dimethylimidazolidone;
It may be carried out in a nonpolar solvent such as toluene, hexane, heptane, etc., tetrahydrofuran, diglyme, 1,4-dioxane or the like, or a mixed solvent thereof. The amount of these solvents used is usually 0 to 20 g of chlorophosphazene.
５００500 ml, preferably 50-300 ml. In addition, the reaction can be allowed to proceed while removing low-boiling substances out of the reaction system.

Specific examples of the basic compound that can be used include:
Alkali metal compounds such as sodium hydride, sodium hydroxide and potassium hydroxide; alkali metals such as sodium metal and potassium potassium; alkali metal alcoholates such as sodium methylate; and tertiary amines such as triethylamine, tripropylamine and pyridine And the like. The amount of the compound 1 has a group represented by the formula (1) or the formula (2), and a hydrogen atom is bonded to a terminal of the compound 1.
Usually 1.0 mol or more, preferably 1.2 mol, per 0 mol.
10 to 10 mol.

In the above reaction, it is preferable that all chlorine is substituted, but a part of chlorine may remain.
This residual chlorine is reacted with a compound or the like having a group represented by, for example, the formula (5) or the formula (6), and having a hydrogen atom bonded to the terminal thereof in the same manner as described above. Non-curable groups can be introduced.

Specific examples of the compound having a group represented by the formula (5) and having a hydrogen atom bonded to a terminal thereof include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, and 2-hydroxyethyl vinylyl. Specific examples of compounds having ether, 4-hydroxybutylvinylyl ether, glycidol and the like having a group represented by the formula (6) and a hydrogen atom bonded to the terminal thereof include methanol, ethanol and propanol. Alcohols and their halogen-substituted products, alkylthiols such as methanethiol, ethanethiol and propanethiol, and their halogen-substituted products, alkylamines such as methylamine, ethylamine and propylamine, and their halogen-substituted products , Phenol, halogenated Nord group, thiophenol, halogenated thiophenol, formyl phenol, acetoacetic phenol, nitro phenol.

Next, the polymerizable composition of the present invention will be described. The curable phosphazene of the present invention and a curing agent and a curing accelerator, and various other polymerizable compounds, a polymerization initiator, a dye, a pigment, a plasticizer, an inorganic filler, a solvent, etc. A polymerizable composition can be obtained. The curing agent / curing accelerator is not particularly limited as long as the above-mentioned curable group can cause polymerization.

As a specific example of the curing agent / curing accelerator, when a curing method using ultraviolet light or visible light is used, a cationic photopolymerization initiator may be used as a photo-cationic polymerization initiator.
No. 31, Japanese Patent Publication No. 52-14277, Japanese Patent Publication No. 52-14
No. 278, Japanese Patent Publication No. 52-14279, Japanese Patent Publication No. 52-2
No. 5686, JP-B-61-34752, JP-A-54-54.
53181, JP-A-54-95686, JP-B-61
-36530, JP-B-59-19581, JP-B-6
3-65688, JP-A-55-164204, JP-B-60-30690, JP-B-63-36332, JP-B1-39423, JP-B2-10171, JP-B5-15721, JP-B-5-15721 No. 4-62310, Japanese Patent Publication No. 62-57653, Japanese Patent Publication No. 3-12081, Japanese Patent Publication No. 3-12082, Japanese Patent Publication No. 3-16361, Japanese Patent Publication No. 6
3-12092, JP-B-63-12093, JP-B-63-12095, JP-B-63-12094, JP-B-2-37924, JP-B-2-35764, JP-B-4-13374, JP-B-4 -75908, Tokuhei 4
-73428, JP-B-53-32831, and JP-A-Hei 2
-150848, JP-A-2-296514, U.S. Pat. No. 4,069,055, U.S. Pat.
No. 56, U.S. Pat. No. 3,703,296, and the like, sulfonium salts, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, arsonium salts, iron / arene complexes, and the like.
Polyhydric alcohols may be used.

When a heat curing method or a room temperature curing method is used, acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and maleic anhydride, phenol novolaks, etc. Polyhydric alcohols,
Lewis acids such as boron trifluoride, zinc dichloride, and aluminum trichloride may be used.

These curing agents and curing accelerators are usually used in an amount of 0.01 to 200% by weight, preferably 1 to 100% by weight, based on the curable phosphazene of the present invention. It may be mixed with the curable phosphazene of the present invention, or may be mixed with the polymerizable composition of the present invention.

The cured product of the present invention can be obtained by irradiating the curable phosphazene of the present invention as it is, preferably as the polymerizable composition of the present invention, with an ultraviolet ray, an electron beam, or a radiation, or by heating.

[0033]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 20 g of 60 wt% sodium hydride was charged into a 500 ml reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device, and a stirring device.
Washed three times with 00 ml of dehydrated tetrahydrofuran. Thereafter, 200 ml of dehydrated tetrahydrofuran was added, 50 g of 3,4-epoxycyclohexylmethanol was added dropwise over 1 hour while stirring at room temperature, and the mixture was further stirred at 60 ° C. for 2 hours to obtain 3,4-epoxycyclohexylmethanol sodium salt. A dispersion was obtained.

Next, 22.5 g of hexachlorocyclotriphosphazene was dissolved in 100 ml of dehydrated tetrahydrofuran. This solution was added dropwise to the 3,4-epoxycyclohexylmethanol sodium salt dispersion over a period of 2 hours while maintaining the inside of the reactor at 60 ° C and stirring. Thereafter, the reaction was further performed at 60 ° C. for 5 hours to complete the reaction.

After completion of the reaction, the reaction mixture was cooled to room temperature, and tetrahydrofuran was removed with an evaporator.
Add 200 ml of water, and add 3
Extracted times. Next, the extracted diethyl ether solution was concentrated to 200 ml, washed with 100 ml of water three times, and anhydrous sodium sulfate and activated carbon were added thereto, followed by drying and decoloring overnight.
Thereafter, the mixture was filtered and the diethyl ether was removed under reduced pressure to obtain the curable phosphazene of the present invention (yield: 25 g).

The above compound is represented by the IR spectrum
The hydroxyl group (around 3400 cm ^-1 ) disappears from 3,4-epoxycyclohexylmethanol, and the P = N bond (1
240 cm ^-1 ) was confirmed. Also, FA
According to the B mass spectrum, all chlorine and 5 chlorines in hexachlorocyclotriphosphazene were 3,4-
It was confirmed that the mixture was substituted with epoxycyclohexylmethanol.

[0038]

The curable phosphazene of the present invention gives a flame-retardant and heat-resistant cured product, and is used as an overcoat agent, a water-repellent coat agent, a surface modifier, an adhesive, a functional filler, a paint, and a sealant. It is suitable for applications such as materials and electrolyte diaphragms, and is extremely useful in various fields such as electric / electronic materials, civil engineering / building materials, and aviation / space composite materials.

Claims (3)

[Claims] 1. A curable phosphazene having a repeating structure represented by the formula (A). Embedded image (In the formula (A), n represents an integer of 3 to 100,000;
Represents one or more selected from a curable group having an alicyclic epoxy group, a curable group having an oxetane group, a curable group other than an alicyclic epoxy group and an oxetane group, and a non-curable group; At least one of certain X is a curable group having an alicyclic epoxy group or an oxetane group. ) 2. A polymerizable composition containing the curable phosphazene according to claim 1. 3. A cured product obtained by curing the polymerizable composition according to claim 2.