JPH06145183A - New cyclophosphazene derivative containing substituted nadiimidophenoxy group, its production and production of its polymer - Google Patents

Abstract

(57) [Summary] [Structure] An alkyl- or alkenyl-substituted nadiimidophenoxy group-containing cyclophosphazene derivative represented by the general formula (1), a process for producing the same, and a process for producing a polymer thereof. [Chemical 1] [Effect] The compound (1) is useful as a coating material, an adhesive agent, etc. because it can be formed by a general curing molding method because it produces few voids during curing and is soluble in various solvents.
In addition, the method for producing the compound (1) is one step, and since the yield and the selectivity are high, it is economical.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a cyclophosphazene derivative containing an alkyl- or alkenyl-substituted nadiimidephenoxy group useful as a heat-resistant and flame-retardant adhesive and a coating material, a method for producing the same, a structural member, electric and electronic parts materials, etc. And a process for producing a polymer of the cyclophosphazene derivative, which is useful as

[0002]

2. Description of the Related Art With the progress of science and technology, materials used are required to have higher performance and higher functions, and various materials have been developed to meet the demand. For example, various high-performance polymers called so-called super engineering plastics (engineering plastics) such as polyetherketone, polyphenylene sulfide, and polyimide are on the market in a considerable amount. These organic polymers have excellent properties in strength, elongation, toughness, etc., but are inferior to inorganic polymers in heat resistance. On the other hand, the inorganic polymer has excellent heat resistance, but it is hard and brittle.

Therefore, research on polymers having both inorganic and organic properties, particularly on cyclic and chain phosphazene polymers, has been made for a long time. Among them, for example, a method of introducing a formylphenoxy group into cyclophosphazene and crosslinking it with an aromatic diamine to obtain a polymer having excellent heat resistance and flame retardancy and having a high weight residual rate upon thermal decomposition (Japanese Patent Laid-Open Publication No. HEI-HEI-KOKAI) No. 2-24325), maleimidophenoxy group [D. Kumar et al., Macromolecule
les, 16 , 1250 (1983)] or nadiimidophenoxy group (JP-A-63-77889) to obtain a polymer having similar properties by thermal polymerization. It has attracted attention as a matrix resin for composite materials, a heat resistant adhesive, and the like.

Of these, the cyclophosphazene derivative containing a maleimidophenoxy group or a nadiimidophenoxy group has the advantage that the polymerization proceeds through an addition reaction, but
It has the following drawback that the synthetic method of the derivative is complicated. The maleimidephenoxy group- or nadiimidophenoxy group-containing cyclophosphazene derivative is synthesized in the same manner as the formylphenoxy group-containing cyclophosphazene derivative, that is, (1) cyclophosphazene chloride and an alkali metal salt (phenolate) of formyl group-substituted phenol. Neither the method via the phenolate for reacting the compound with (2) the direct method in which the phosphazene chloride and the formyl group-substituted phenol are directly reacted with the hydrochloric acid scavenger in the presence of the catalyst and the inert solvent are not applicable. That is, when an imide group-containing phenol is allowed to act on an alkali metal in an attempt to obtain a phenolate, the alkali metal causes a cleavage reaction of the imide ring in addition to the hydroxyl group, and does not form the desired salt. Further, in the direct method, the maleimide phenols, nadiimide phenols as the raw material, or the phosphazene substituted derivative as the target product is insoluble in an inert solvent such as hydrocarbon, halogenated hydrocarbon, ether, pyridine, or Immediately after adding the catalyst even if it is dissolved, the reaction system becomes heterogeneous and the reaction does not proceed further, and if a solvent with strong polarity is used to make the system uniform, then these polar solvents and phosphazene chloride can be used. However, it was impossible to smoothly carry out the substitution reaction without side reactions.

Therefore, conventionally, all of the maleimidephenoxy group- or nadiimidophenoxy group-containing cyclophosphazene derivatives have been synthesized through the following steps (a) to (c). (A) Synthesis of nitrophenoxy group-substituted phosphazene by reacting phosphazene chloride with nitrophenol in the presence of a hydrochloric acid scavenger. (B) Synthesis of an aminophenoxy group-substituted phosphazene by reducing the nitrophenoxy group-substituted phosphazene with hydrogen in the presence of a platinum oxide catalyst. (C) A maleimidephenoxy group or a nadiimidophenoxy group obtained by a condensation reaction of the aminophenoxy group-substituted phosphazene with maleic anhydride or nadic acid anhydride at a temperature at which a product does not undergo a polymerization reaction in the presence of a catalyst and a dehydrating agent. Synthesis of substituted phosphazenes. As described above, all of the maleimidephenoxy group- or nadiimidophenoxy group-containing cyclophosphazene derivatives have the drawback that they must be synthesized through a plurality of steps as described above.

Further, these derivatives themselves also have the following drawbacks. That is, the maleimidophenoxy group-containing phosphazene derivative has higher solubility than other bismaleimide compounds, but is soluble only in a limited solvent such as DMF, DMSO, N-methylpyrrolidone, MEK, tetrahydrofuran, dioxane, Since the melting point of the derivative and the curing temperature are very close to each other, the workability of molding is extremely poor, and therefore, general molding methods such as cast molding, injection molding and compression molding cannot be practically adopted. Further, the cured product has extremely poor mechanical properties like the bismaleimide cured product. On the other hand, the nadiimidophenoxy group-containing cyclophosphazene derivative seems to have good workability in molding at the point that the melting point and the curing temperature are different, but like the maleimidophenoxy group-containing phosphazene derivative, There is a problem that it dissolves only in a limited solvent, and further, during curing, a reverse Diels-Alder reaction occurs partially and liberates cyclopentadiene, which causes voids in the molded body and improves mechanical performance. It has the essential drawback of lowering it.

[0007]

SUMMARY OF THE INVENTION The present invention is intended to overcome such drawbacks of the prior art, and its first purpose is to be soluble in a wide range of general-purpose solvents and to be cast, injection molded, Ordinary curing molding method such as compression molding can be adopted, and the cured molded article exhibits excellent adhesiveness and heat resistance, flame retardancy, and in order to obtain a polymer having a high weight residual rate upon thermal decomposition, It is an object of the present invention to provide a novel substituted nadiimidophenoxy group-containing cyclophosphazene derivative in place of the conventional nadiimidophenoxy group-containing cyclophosphazene derivative. A second object is a method of directly reacting phosphazene chloride with a substituted nadiimidophenol to produce the substituted nadiimidophenoxy group-containing cyclophosphazene derivative in one step, which is economical in both yield and selectivity. To provide a new method.

[0008]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to achieve the above object. As a result, when an alkyl group or an alkenyl group is introduced into nadiimidephenol, it becomes soluble in a general-purpose solvent and phosphazene chloride is obtained. The reaction proceeds directly with, and a novel alkyl- or alkenyl-substituted nadiimidophenoxy group-containing phosphazene derivative can be easily obtained in a high yield and a high selectivity without requiring a complicated step in the reaction step. The alkyl- or alkenyl-substituted nadiimidophenoxy group-containing phosphazene derivative is a conventional nadiimidophenoxy group-containing phosphazene derivative, in which voids are generated in the molded article as described above, and the mechanical performance is reduced. Seen to give an excellent polymer that does not impair characteristics such as adhesion, heat resistance, and flame retardancy. And, to complete the present invention.

That is, the present invention provides the following general formula (1):

[0010]

[Chemical 4]

[Wherein n is 3 or 4 and at least one of R ¹ and R ² is represented by the following formula (2):

[0012]

[Chemical 5]

[Wherein R ³ represents a hydrogen atom or a non-reactive group, R ⁴ represents an alkyl or alkenyl group having 1 to 6 carbon atoms], and a residual nadiimidophenoxy group, the rest of which is And an alkyl- or alkenyl-substituted nadiimidophenoxy group-containing cyclophosphazene derivative, which is represented by a phenoxy group which may have a reactive substituent.

The present invention also provides cyclophosphazene chloride having the following general formula (3) in the presence of 4- (N-mono- or dialkylamino) pyridine and a hydrochloric acid scavenger.

[0015]

[Chemical 6]

[Wherein R ³ and R ⁴ have the same meanings as described above] or a substituted nadiimidophenol or a substituted nadiimidophenol and a phenol which may have a non-reactive substituent (hereinafter , And abbreviated as phenols). The present invention relates to a process for producing an alkyl- or alkenyl-substituted nadiimidophenoxy group-containing cyclophosphazene derivative represented by the general formula (1).

Further, the present invention is characterized in that the alkyl- or alkenyl-substituted nadiimidophenoxy group-containing cyclophosphazene derivative represented by the general formula (1) is heated in the presence or absence of a cation catalyst. The present invention relates to a method for producing a polymer of a cyclophosphazene derivative containing a substituted nadiimidephenoxy group.

In the general formulas (1) and (2) representing the cyclophosphazene derivative containing an alkyl- or alkenyl-substituted nadiimidophenoxy group (1) of the present invention (hereinafter referred to as the compound (1) of the present invention), R ³ and R The position of the substituent represented by ⁴ and the position of the non-reactive substituent in the phenoxy group are not particularly limited. Also, R ³
The non-reactive group represented by and the non-reactive group in the phenoxy group do not participate in the reaction during the substitution reaction of the phenoxy group with chlorine on cyclophosphazene or during the thermal polymerization or cationic polymerization reaction of the compound (1) of the present invention. The substituent is not particularly limited as long as it is a substituent, and examples thereof include an alkyl group, a halogen atom, a cyano group and a nitro group.
Further, as the alkyl or alkenyl group having 1 to 6 carbon atoms represented by R ⁴ , a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, allyl group, isopropenyl group, 3
Examples include -butenyl group and 2-pentenyl group.

A typical group represented by the formula (2) is 4- (N'-methylbicyclo [2.2.1] hept-5'-ene-2 ', 3'-dicarboximide. ) Phenoxy group, 3- (N'-methylbicyclo [2.2.
1] Hept-5'-ene-2 ', 3'-dicarboximido) phenoxy group, 2- (N'-methylbicyclo [2.2.1] hept-5'-ene-2', 3'- Dicarboximido) phenoxy group, 4- (N'-ethylbicyclo [2.2.1] hept-5'-ene-2 ', 3'
-Dicarboximido) phenoxy group, 3- (N'-ethylbicyclo [2.2.1] hept-5'-ene-
2 ', 3'-dicarboximido) phenoxy group, 2-
(N'-ethylbicyclo [2.2.1] hept-5'-
Ene-2 ', 3'-dicarboximido) phenoxy group, 4- (N'-propylbicyclo [2.2.1] hept-5'-ene-2', 3'-dicarboximido) phenoxy group, 3- (N'-propylbicyclo [2.2.
1] Hept-5'-ene-2 ', 3'-dicarboximido) phenoxy group, 2- (N'-propylbicyclo [2.2.1] hept-5'-ene-2', 3'- Dicarboximido) phenoxy group, 3-methyl-4-
(N'-methylbicyclo [2.2.1] hept-5'-
Ene-2 ', 3'-dicarboximido) phenoxy group, 4-methyl-3- (N'-methylbicyclo [2.
2.1] Hept-5'-ene-2 ', 3'-dicarboximido) phenoxy group, 3-methyl-4- (N'-ethylbicyclo [2.2.1] hept-5'-ene-
2 ', 3'-dicarboximido) phenoxy group, 4-
Methyl-3- (N'-ethylbicyclo [2.2.1] hept-5'-ene-2 ', 3'-dicarboximide)
Phenoxy group, 3-chloro-4- (N'-methylbicyclo [2.2.1] hept-5'-ene-2 ', 3'-dicarboximide) phenoxy group, 3-chloro-4-
(N'-ethylbicyclo [2.2.1] hept-5'-
Ene-2 ', 3'-dicarboximido) phenoxy group, 3-cyano-4- (N'-methylbicyclo [2.
2.1] hept-5'-ene-2 ', 3'-dicarboximido) phenoxy group, 4-cyano-3- (N'-ethylbicyclo [2.2.1] hept-5'-ene-
2 ', 3'-dicarboximido) phenoxy group, 3-
Cyano-4- (N'-ethylbicyclo [2.2.1] hept-5'-ene-2 ', 3'-dicarboximide)
Phenoxy group, 4-cyano-3- (N'-propylbicyclo [2.2.1] hept-5'-ene-2 ', 3'-
Dicarboximide) phenoxy group, 4-cyano-3-
(N'-propylbicyclo [2.2.1] hept-5 '
-Ene-2 ', 3'-dicarboximidophenoxy group, 3-cyano-4- (N'-ethylbicyclo [2.
2.1] hept-5'-ene-2 ', 3'-dicarboximido) phenoxy group, 3-nitro-4- (N'-methylbicyclo [2.2.1] hept-5'-ene-
2 ', 3'-dicarboximido) phenoxy group, 3-
Nitro-4- (N'-ethylbicyclo [2.2.1] hept-5'-ene-2 ', 3'-dicarboximide)
Phenoxy group, 4- (N'-allylbicyclo [2.2.
1] Hept-5'-ene-2 ', 3'-dicarboximido) phenoxy group, 3- (N'-allylbicyclo [2.2.1] hept-5'-ene-2', 3'- Dicarboximido) phenoxy group, 2- (N'-allylbicyclo [2.2.1] hept-5'-ene-2 ', 3'
-Dicarboximido) phenoxy group, 4- (N'-methallylbicyclo [2.2.1] hept-5'-ene-
2 ', 3'-dicarboximido) phenoxy group, 3-
(N'-methallylbicyclo [2.2.1] hept-5 '
-Ene-2 ', 3'-dicarboximido) phenoxy group, 3-methyl-4- (N'-allylbicyclo [2.
2.1] Hept-5'-ene-2 ', 3'-dicarboximido) phenoxy group, 4-methyl-3- (N'-allylbicyclo [2.2.1] hept-5'-ene-
2 ', 3'-dicarboximido) phenoxy group, 3-
Chloro-4- (N'-allylbicyclo [2.2.1] hept-5'-ene-2 ', 3'-dicarboximide)
Phenoxy group, 3-cyano-4- (N'-allylbicyclo [2.2.1] hept-5'-ene-2 ', 3'-dicarboximide) phenoxy group, 3-nitro-4-
(N'-allylbicyclo [2.2.1] hept-5'-
Ene-2 ', 3'-dicarboximido) phenoxy group and the like. Among these, more preferable group of formula (2) is 4- (N'-methylbicyclo [2.2.1]].
Hept-5'-ene-2 ', 3'-dicarboximido) phenoxy group, 3- (N'-methylbicyclo [2.
2.1] Hept-5'-ene-2 ', 3'-dicarboximido) phenoxy group, 2- (N'-methylbicyclo [2.2.1] hept-5'-ene-2', 3 ′ -Dicarboximido) phenoxy group, 4- (N′-allylbicyclo [2.2.1] hept-5′-ene-2 ′, 3 ′
-Dicarboximido) phenoxy group, 3- (N'-allylbicyclo [2.2.1] hept-5'-ene-
2 ', 3'-dicarboximido) phenoxy group, 2-
(N'-allylbicyclo [2.2.1] hept-5'-
Ene-2 ', 3'-dicarboximido) phenoxy group and the like, more preferably 4- (N'-methylbicyclo [2.2.1] hept-5'-ene-2', 3'-.
Dicarboximido) phenoxy group, 4- (N'-allylbicyclo [2.2.1] hept-5'-ene-2 ',
3'-dicarboximido) phenoxy group.

On the other hand, typical examples of the phenoxy group which may have a non-reactive substituent include a phenoxy group and o
-, M- or p-methylphenoxy group, o-, m-
Alternatively, a p-chlorophenoxy group, an o-, m- or p-cyanophenoxy group, an o-, m- or p-nitrophenoxy group or an o-, m- or p-methoxyphenoxy group may be mentioned. Groups are particularly preferred.

In the compound (1) of the present invention, at least one of R ¹ and R ² is a group of the formula (2), and the rest is the above-mentioned phenoxy group. The ratio of the group of the formula (2) in the cyclophosphazene and the phenoxy group can be appropriately selected depending on the physical properties required for curing and molding.
Generally, as the proportion of the group of the formula (2) increases, the glass transition temperature, heat distortion temperature and the like of the cured product increase.

The compound (1) of the present invention is, for example, 4- (N
Produced by reacting cyclophosphazene chloride with a substituted nadiimidophenol (3) or the substituted nadiimidophenol and phenols in the presence of a mono- or dialkylamino) pyridine and a hydrochloric acid scavenger. As-(N-mono- or dialkylamino) pyridine, one in which an alkyl group having 1 to 6 carbon atoms is substituted with 1 or 2 amino groups is preferable. Typical examples of the 4- (N-mono- or dialkylamino) pyridine include 4-methylaminopyridine, 4-ethylaminopyridine, 4-propylaminopyridine and 4- (N-methyl-N-ethylamino). Pyridine, 4- (N-methyl-N-butylamino) pyridine,
4- (N-ethyl-N-butylamino) pyridine, 4-
(N-butyl-N-hexylamino) pyridine, 4-dimethylaminopyridine, 4-diethylaminopyridine,
4-dibutylamino pyridine, 4-dipentylamino pyridine, 4-dihexyl amino pyridine, etc. are mentioned.

The hydrochloric acid scavenger used in this method is preferably an aliphatic tertiary amine, and typical examples thereof include trimethylamine, triethylamine, tributylamine, tripentylamine, trihexylamine, dimethylethylamine, Examples include, but are not limited to, dimethylbutylamine, diethylbutylamine, dibenzylethylamine, diethylhexylamine, dicyclohexylethylamine, and the like.

Examples of the starting material cyclophosphazene chloride include hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, and a mixture thereof. For example, hexachlorocyclotriphosphazene or octachlorocyclotetraphosphazene made from phosphorus pentachloride and ammonium chloride as raw materials, which does not remove a small amount of other cyclic phosphazene and linear phosphazene chloride produced as a by-product during production, is used. Phosphazene and the like can also be used.

In this reaction, the starting materials, cyclophosphazene chloride, the substituted nadiimide phenol (3) and the phenols may be sequentially reacted, or they may be mixed in advance and then the reaction may be started. 4- (N
The amount of mono- or dialkylamino) pyridine used is preferably 0.01 to 1.0 mol, particularly preferably 0.05 to 0.5 mol, based on the basic unit (PNCl ₂ ) of the phosphazene chloride compound. Use of a hydrochloric acid scavenger The amount is 1.0 to 4. per basic unit (PNCl ₂ ) of the phosphazene chloride compound.
0 mol, especially 1.5 to 3.0 mol is preferred. The amount of substituted nadiimidophenol (3) and phenols used is the basic unit (PNCl ₂ ) of the phosphazene chloride compound.
Therefore, the total amount of these is preferably 2.0 to 10 mol, and particularly preferably 2.0 to 5.0 mol. The ratio of the substituted nadiimidophenol (3) and phenols can be arbitrarily selected according to the purpose.

The substituted nadiimidophenol (3) and phenols as raw materials are both soluble in the hydrochloric acid scavenger, and the hydrochloric acid scavenger can be used as the solvent, but generally a general-purpose solvent is used. Any general-purpose solvent may be used as long as it does not react with cyclophosphazene chloride and can dissolve the substituted nadiimidophenol (3), the phenol and the compound (1) of the present invention, such as benzene and toluene. Aromatic hydrocarbons; halogenated hydrocarbons such as methylene chloride and chloroform; ethers such as diethyl ether, dioxane and tetrahydrofuran; ketones such as MEK and MIBK.
The amount of the solvent used is not particularly limited, but 50 to 2000 parts by weight is suitable with respect to 100 parts by weight of the starting material cyclophosphazene chloride. The reaction is preferably -10 to 200
℃, more preferably at a temperature of 0 to 150 ℃, preferably 1
Minutes to 40 hours, more preferably 10 minutes to 25 hours.

The compound (1) of the present invention thus obtained is usually semi-solid or solid.
Or, when heated in the presence of a cationic catalyst, it polymerizes and hardens, and exhibits excellent adhesiveness with inorganic substances such as metals and ceramics, and the cured product has excellent flame retardancy and heat resistance. It is useful as an electronic member, an adhesive, a filler, a covering material, a binder, and the like.

When no catalyst is used in the polymerization and curing reaction,
Preferably 130-300 ° C, more preferably 150-
It is carried out by heating at a temperature of 280 ° C., preferably for 10 minutes to 30 hours, more preferably for 30 minutes to 20 hours. Further, in the presence of a cation catalyst, preferably 10
The heating is carried out at a temperature of 0 to 280 ° C, more preferably 120 to 250 ° C, preferably 5 minutes to 30 hours, more preferably 10 minutes to 20 hours. Further, if necessary, 200 to 35
You may post-cure at 0 degreeC for 1 to 20 hours. Examples of the cation catalyst used include p-toluenesulfonic acid,
Organic sulfonic acids such as naphthalene sulfonic acid; Organic sulfonic acid esters such as methyl p-toluene sulfonate and ethyl naphthalene sulfonate; Phosphoric acid or phosphorous acid esters such as diphenyl phosphate and dibutyl phosphite;
Mineral acids such as hydrochloric acid and sulfuric acid; mineral acid esters such as methyl sulfate and ethyl sulfate; Lewis acids such as aluminum chloride and boron trifluoride; or ammonium compounds such as benzyltriethylammonium and tetrabutylammonium bromide; methyltriphenyl Phosphonium bromide,
Phosphonium compounds such as benzyltriphenylphosphonium chloride; Stibonium compounds such as benzyltriphenylstibonium chloride; Sulfonium compounds such as triphenylsulfonium tetrafluoroborate, triphenylphosphonium hexafluoroarsinate;
Examples include selenonium compounds such as triphenylselenonium tetrafluoroborate; those commonly called onium compounds such as iodonium compounds such as diphenyliodonium hexafluorophosphate and diphenyliodonium perchlorate. The amount of the catalyst used is not particularly limited, but is generally 0.0 with respect to the substituted nadiimidophenoxy group-containing cyclophosphazene derivative (1).
It is preferably used in the range of 1 to 5% by weight.

The substituted nadiimidophenoxy group-containing cyclophosphazene derivative polymer of the present invention may optionally contain
Various fillers, pigments, coupling agents, release agents and the like can be added. For example, as the filler, glass fiber, carbon fiber, metal fiber, ceramic fiber, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, antimony oxide, molybdenum oxide, gypsum, silica, alumina, clay, talc, quartz. Powder, iron powder, carbon black, graphite and the like can be mentioned, but not limited to these. The amount used is selected according to the application, but is generally 10 to 1000 parts by weight with respect to 100 parts by weight of the phosphazene derivative (1).

[0030]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 115.18 g (0.39) was added to a 500 ml flask.
mol) 4- (N'-allylbicyclo [2.2.1] hept-5'-ene-2 ', 3'-dicarboximide)
Phenol (hereinafter abbreviated as 4-allylnadiimidophenol) was added, and 90 ml of 1,4-dioxane was added and dissolved. An additional 39.46 g (0.39 g) was added to the flask.
mol) triethylamine and 2.2 g (0.018 m)
ol) 4-dimethylaminopyridine was added to homogenize. Next, immerse the flask in a water bath and, while stirring, 90 ml
1,4-dioxane and 20.86 g (0.06 mo
l) cyclotriphosphazene chloride solution
It took a minute and was dripped. Then, stirring was continued for another 20 hours while maintaining the temperature at 50 ° C. to cause a reaction. After concentrating the filtrate obtained by filtering off the salt formed, it is poured into 2 l of water,
The target substance was precipitated. The precipitate was filtered and washed with water and methanol. Next, it was dissolved in a small amount of acetone (insoluble matter was filtered off), the solution was poured into a large amount of water, precipitation, filtration and washing operations were performed, and finally it was dried under reduced pressure to give 109.20 g ( The target product, hexaallylnadiimidophenoxy-substituted cyclophosphazene (structural formula (4), hereinafter abbreviated as 3PNC / ANI-1), was obtained with a yield of 95.7% based on cyclophosphazene chloride.

[0032]

[Chemical 7]

The IR spectrum and NMR spectrum of 3PNC / ANI-1 are shown in FIGS. 1 and 2, respectively. As a result of elemental analysis, C: 67.7 wt% and H: 4.
9wt%, N: 6.7wt%, P: 4.9wt% (Theoretical value is
68.24 wt%, 5.09 wt%, 6.63 wt
%, 4.89 wt%). The 3PNC / AN
I-1 has the following properties. 1) Melting point by trace melting point measuring device: about 140 ° C. 2) Tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, ethyl acetate, acetonitrile, chloroform, benzene, toluene, N-methyl-
It is easily soluble in 2-pyrrolidone, dimethyl sulfoxide, N, N'-dimethylformamide and the like, and partially soluble in xylene. 3) In DSC analysis (temperature rise at 10 ° C / min), 220-
An exothermic reaction associated with thermal polymerization was observed at 340 ° C. 4) In TG analysis (heating at 10 ° C / min), almost no weight loss was observed up to 413 ° C, and a clear weight loss inflection point due to thermal decomposition was observed at this temperature. In a nitrogen stream,
The weight residual rate at 800 ° C. was 58%.

Example 2 In Example 1, 105.0 g (0.39 mol) of 4- (N ') was used instead of 4-allylnadiimidophenol.
-Methylbicyclo [2.2.1] hept-5'-ene-
Except for using 2 ', 3'-dicarboximido) phenol, the same experimental procedure as in Example 1 was carried out to find that 73.1 g of the desired product (yield 70.3% based on cyclophosphazene chloride) was obtained. Hexamethylnadiimidephenoxy-substituted cyclophosphazene (structural formula (5), hereinafter abbreviated as 3PNC / MNI) was obtained.

[0035]

[Chemical 8]

The IR and NMR spectra of 3PNC / MNI are shown in FIGS. 3 and 4, respectively. The results of elemental analysis are C: 65.7 wt%, H: 5.3
wt%, N: 7.2 wt%, P: 5.3 wt% (Theoretical values are 65.86 wt%, 5.18 wt%, 7.20 wt%,
It was 5.31 wt%). In addition, the 3PNC / MNI
Has the following properties. 1) Melting point by trace melting point measuring device: about 202 ° C. 2) Tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, acetonitrile, chloroform, benzene, N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N′-dimethylformamide Etc., and is partially soluble in ethyl acetate and toluene.

Example 3 21.26 g of 4-allylnadiimidophenol (0.0
72 mol) and 33.88 g of phenol (0.36 mo)
l) containing 90 ml of 1,4 in a 500 ml flask
-Dioxane was added and it was dissolved. The flask was further homogenized by adding 39.46 g (0.39 mol) of triethylamine and 2.2 g (0.018 mol) of 4-dimethylaminopyridine. The flask was then immersed in a water bath and a solution of 90 ml of 1,4-dioxane and 20.86 g (0.06 mol) of cyclotriphosphazene chloride was added dropwise over 30 minutes with stirring. Then, stirring was continued for another 20 hours while maintaining the temperature at 50 ° C. to cause a reaction. After the formed salt was filtered off, the obtained filtrate was concentrated and then poured into 2 l of water to precipitate the desired product. The precipitate was filtered and washed with water and methanol.
Next, it was dissolved in a small amount of acetone (insoluble matter was filtered off), and it was poured into a large amount of water for precipitation, filtration, and washing. Finally, it was dried under reduced pressure, and 35.7 g of {chlorochloride Yield 93.5% based on phosphazene (4-allylnadiimidophenoxy group / phenoxy group = 1 mol / 5 m
(calculated on the assumption that it was introduced at the ratio of ol)}, the target product is hexa (allylnadiimidophenoxy / phenoxy)
Substituted cyclophosphazene (Structural formula (6), hereinafter 3PNC
/ ANI-2) was obtained.

[0038]

[Chemical 9]

The structure of 3PNC / ANI-2 was determined as an average composition by analysis of IR spectrum and NMR spectrum. IR spectrum and NMR spectrum are shown in FIG. 5 and FIG. 6, respectively. The results of elemental analysis are C: 64.7 wt%, H: 4.5 wt%, N: 6.3 wt%
%, P: 9.6 wt% (theoretical value is 64.97 wt.
%, 4.69 wt%, 6.31 wt%, 9.61 wt%), which also supports the above structural formula. The 3PNC /
ANI-2 has the following properties. 1) Melting point by trace melting point measuring device: about 58 ° C. 2) Tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, acetonitrile, chloroform, benzene, N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N′-dimethylformamide Easily soluble in ethyl acetate, benzene, toluene, etc.

Example 4 4-allynadiimidophenol 42.52 g (0.1
44 mol) and 27.10 g of phenol (0.288 m)
ol) in a 500 ml flask containing 90 ml of 1,4
-Dioxane was added and it was dissolved. The flask was further homogenized by adding 39.46 g (0.39 mol) of triethylamine and 2.2 g (0.018 mol) of 4-dimethylaminopyridine. Next, the flask was immersed in a water bath, and a solution of 90 ml of 1,4-dioxane and 20.86 g (0.06 mol) of cyclotriphosphazene chloride was added dropwise over 30 minutes while stirring. Then, stirring was continued for another 20 hours while maintaining the temperature at 50 ° C. to cause a reaction. After the formed salt was filtered off, the obtained filtrate was concentrated and then poured into 2 l of water to precipitate the desired product. The precipitate was filtered and washed with water and methanol. Then dissolve it in a small amount of acetone (filter insoluble material),
It was poured into a large amount of water, subjected to operations of precipitation, filtration, and washing, and finally dried under reduced pressure to obtain 62.5 g (yield 95.0% based on cyclophosphazene chloride chloride (4-allylnadiimidophenoxy group / Phenoxy group = calculated on the assumption that it was introduced at a ratio of 2 mol / 4 mol)}, a hexa (allylnadiimidophenoxyphenoxy) -substituted cyclophosphazene (structure formula (7), hereinafter 3PNC / AN)
I-3) was obtained.

[0041]

[Chemical 10]

The structure of 3PNC / ANI-3 was determined as an average composition by analysis of IR spectrum and NMR spectrum. The IR spectrum and the NMR spectrum are shown in FIGS. 7 and 8, respectively. The results of elemental analysis are C: 65.7 wt%, H: 4.6 wt%, N: 6.5 wt%
%, P: 8.1 wt% (Theoretical value is 65.97 wt.
%, 4.81 wt%, 6.41 wt%, 8.16 wt%), which also supports the above structural formula. The 3PNC /
ANI-3 has the following properties. 1) Melting point by a trace melting point measuring device: about 96 ° C. 2) Tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, acetonitrile, chloroform, benzene, N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N′-dimethylformamide Easily soluble in ethyl acetate, benzene, toluene, etc.

Example 5 27.81 g (0.08 mol) of cyclotriphosphazene chloride was charged into a flask having an inner volume of 500 ml, and 10
It was dissolved in 0 ml of 1,4-dioxane, to which 22.59 g of phenol (0.24 mol), triethylamine 2
After adding a solution of 4.29 g (0.24 mol) and 1.466 g (0.012 mol) of 4-dimethylaminopyridine in 60 ml of 1,4-dioxane, the temperature was 50 ° C.
And reacted for 20 hours. Next, 82.70 g (0.28 mol) of 4-allylnadiimidophenol, 28.33 g (0.28 mol) of triethylamine and 1.71 g (0.014 mol) of 4-dimethylaminopyridine were added to 1,4
-Add the solution dissolved in 60 ml of dioxane and add 50 more
Reaction was carried out at 0 ° C for 20 hours. After the formed salt was filtered off, the obtained filtrate was concentrated and then poured into 2 l of water to precipitate the desired product. The precipitate was filtered and washed with water and methanol. Next, it was dissolved in a small amount of acetone (insoluble matter was filtered off), and it was poured into a large amount of water to carry out operations of precipitation, filtration and washing, and finally vacuum drying.
0.02 g (yield based on cyclophosphazene chloride 86.
7% (calculated on the assumption that it was introduced at a ratio of 4-allylnadiimidophenoxy group / phenoxy group = 3 mol / 3 mol)} hexa (allylnadiimidophenoxy phenoxy) -substituted cyclophosphazene (structural formula ( 8), hereinafter abbreviated as 3PNC / ANI-4) was obtained.

[0044]

[Chemical 11]

The structure of 3PNC / ANI-4 was determined as an average composition by analysis of IR spectrum and NMR spectrum. The IR spectrum and the NMR spectrum are shown in FIGS. 9 and 10, respectively. The results of elemental analysis are as follows: C: 66.1 wt%, H: 4.9 wt%, N: 6.5
wt%, P: 7.1 wt% (theoretical value is 66.66 respectively)
wt%, 4.90 wt%, 6.48 wt%, 7.16 wt%), which also supports the above structural formula. The 3PNC
/ ANI-4 has the following properties. 1) Melting point by a trace melting point measuring device: about 125 ° C. 2) Tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, acetonitrile, chloroform, benzene, N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N′-dimethylformamide Easily soluble in ethyl acetate, benzene, toluene, etc. 3) In DSC analysis (temperature rise at 10 ° C / min), 220-
An exothermic reaction associated with thermal polymerization was observed at 340 ° C. 4) In TG analysis (heating at 10 ° C./min), almost no weight loss was observed up to 398 ° C., and a clear weight loss inflection point due to thermal decomposition was observed at this temperature. In a nitrogen stream,
The weight residual rate at 800 ° C. was 54%.

Example 6 In Example 4, the amounts of 4-allylnadimide phenol and phenol used were 85.05 g (0.
288 mol) and 13.55 g (0.144 mol) except that the same experimental procedure as in Example 4 was carried out to obtain 84.5 g (yield 9 based on cyclophosphazene chloride).
4.0% of hexa (allylnadiimidophenoxy-phenoxy) -substituted cyclophosphazene (structural formula (9), hereinafter abbreviated as 3PNC / ANI-5) was obtained.

[0047]

[Chemical 12]

The structure of 3PNC / ANI-5 was determined as an average composition by analysis of IR spectrum and NMR spectrum. The IR spectrum and the NMR spectrum are shown in FIGS. 11 and 12, respectively. As a result of elemental analysis, C: 67.5 wt%, H: 4.9 wt%, N: 6.
6 wt%, P: 5.6 wt% (theoretical value is 67.7, respectively)
1 wt%, 5.02 wt%, 6.58 wt%, 5.65 wt%)
Which also supports the above structural formula. The 3PN
C / ANI-5 has the following properties. 1) Melting point by a trace melting point measuring device: about 174 ° C. 2) Tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, acetonitrile, chloroform, benzene, N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N′-dimethylformamide Easily soluble in ethyl acetate, benzene, toluene, etc.

Example 7 In a glass test tube having a volume of 30 ml, the amount of 3 obtained in Example 1 was used.
After taking 5 g of PNC / ANI-1 and degassing at 200 ° C. for 5 minutes under reduced pressure, at atmospheric pressure, 200 ° C. for 1 hour, and then 2
When heated at 50 ° C. for 24 hours, a cured product having no bubbles, dark brown, glossy and very hard was obtained. The IR spectrum is shown in FIG.

Examples 8 to 11 3PNC / ANI-2 and 3PN obtained in Examples 3 to 6
C / ANI-3, 3PNC / ANI-4 and 3PNC
/ ANI-5 2g each in a small Petri dish 2
After degassing under reduced pressure at 00 ° C. for 5 minutes, it was heated at 200 ° C. under atmospheric pressure for 1 hour and then at 250 ° C. for 24 hours to obtain a brown to dark brown sheet-like cured product as shown in Table 1. . IR spectra are shown in FIGS. 14 to 17, respectively.

[0051]

[Table 1]

Example 12 A glass test tube having a volume of 30 ml was charged with 3 obtained in Example 2.
After degassing 5 g of PNC / MNI under reduced pressure at 200 ° C. for 5 minutes, at atmospheric pressure at 200 ° C. for 1 hour, followed by 280
When heated at 24 ° C. for 24 hours, a cured product with almost no bubbles, dark brown color, gloss, and very hardness was obtained. The IR spectrum is shown in FIG.

Example 13 3PNC / ANI-4 and diphenyliodonium perchlorate obtained in Example 5 were placed in 3 g and 0.03 g small Petri dishes, respectively, and melt-mixed at 150 ° C.
After degassing under reduced pressure at 150 ° C for 5 minutes, at atmospheric pressure, 200 ° C
When heated at 25 ° C. for 25 hours, the same I as in Example 10 was obtained.
A cured product having an R spectrum and properties was obtained.

Example 14 The 3PNC / ANI-1 obtained in Example 1 was subjected to the following adhesion test. 3PNC / ANI-1 was dissolved in MEK to form a 50 wt% solution, which was used as a mild steel plate test piece (2.0 mm × 25 mm × 100 mm mild steel plate, # 240
After polishing with abrasive paper of No. 1, washed with trichlene, apply on one corner (25 mm x about 15 mm), and at 80 ° C for 10 minutes,
Furthermore, the solvent was dried and removed by heating at 140 ° C. for 20 minutes. The two plates prepared in this way have an adhesive area of 25 mm.
Put the coated surfaces on top of each other to be 12.5 mm,
It was fixed with an eyeball clip, cured at 220 ° C. for 1 hour under atmospheric pressure, then removed from the clip, and further held at 280 ° C. for 10 hours to perform post-curing. The test piece was pulled at room temperature at a speed of 1.0 mm / min to determine the tensile shear strength.
It was 100.2 kg / cm ² .

Example 15 The 3PNC / ANI-1 obtained in Example 1 was subjected to the following adhesion test. 3PNC / ANI-1 was dissolved in MEK to form a 50 wt% solution, which was used as an aluminum plate test piece (2.0 mm x 25 mm x 100 mm mild steel plate,
After polishing with # 240 abrasive paper, washed with trichlene), apply it to one corner (25 mm x about 15 mm), and apply at 80 ° C for 1
Dry the solvent by heating for 0 minutes and then at 160 ° C for 20 minutes,
Removed. The two plates prepared in this way were laminated with their coated surfaces so that the adhesive area would be 25 mm x 12.5 mm, and fixed with eyeball clips, and at 1 ° C under atmospheric pressure at 230 ° C.
After curing for an hour, remove the clip and further 10 at 295 ° C.
It was held for a time to perform post-curing. Test pieces at room temperature and 2
Tensile shear strength was obtained by pulling at 40 ° C and a speed of 1.0 mm / min, and the values were 87.3 kg each.
/ Cm ² and 70.4 kg / cm ² .

Example 16 The 3PNC / ANI-1 obtained in Example 1 was subjected to the following adhesion test. 3PNC / ANI-1 was dissolved in MEK to form a 30 wt% solution, which was used as a mild steel plate test piece (2.0 mm x 25 mm x 100 mm mild steel plate, # 240
(25 mm × about 15 mm) was applied to one corner of a piece of trichlene-washed paper after polishing with the polishing paper (1), and the solvent was dried and removed by heating at 120 ° C. for 10 minutes and then at 160 ° C. for 10 minutes. Two plates prepared in this way were
mm × 12.5mm, the coated surfaces are overlaid and fixed with eyeball clips. At atmospheric pressure, 260 ° C for 10
Hold for time to cure. Test piece under atmospheric pressure at 280 ℃
After heat-treating in an oven for 0 to 30 days, the test piece was taken out, and the change with time of the shear adhesive strength (at room temperature, pulling speed of 1.0 mm / min) was determined. The results shown in FIG. 19 were obtained. .

Reference Example 1 According to the method described in JP-A-63-77889.
Synthesized Hexanadiimidophenoxy Substituted Cyclotri
For phosphazene in exactly the same manner as in Example 14.
A test piece was prepared and subjected to an adhesion test.
And tensile shear strength at 240 ° C (1.0 mm / min
Tension speed) is 60.6 kg / cm ²And 36.
2 kg / cm²Met.

[0058]

INDUSTRIAL APPLICABILITY The alkyl- or alkenyl-substituted nadiimidophenoxy group-containing cyclophosphazene derivative (1) produces less voids during curing than conventional unsubstituted nadiimidophenoxy group-containing cyclophosphazene derivatives. Therefore, ordinary curing molding methods such as cast molding, injection molding, and compression molding can be adopted, and since it is soluble in a wide range of organic solvents, it is heat-resistant, flame-retardant, and a paint that forms a film with high hardness, It is useful as an adhesive, etc.
Since the adhesive strength to a metal is significantly higher than that of a conventional unsubstituted nadiimidephenoxy group-containing cyclophosphazene derivative, it is also useful as a binder for binding an inorganic substance. Furthermore, while the conventional method for producing an unsubstituted nadiimidophenoxy group-containing cyclophosphazene derivative requires multiple steps, the method for producing a substituted nadiimidophenoxy group-containing cyclophosphazene derivative of the present invention requires only one step. ,
Moreover, both the yield and the selectivity are high, which is economical.

[Brief description of drawings]

FIG. 1 I of 3PNC / ANI-1 obtained in Example 1
It is an R spectrum.

FIG. 2 N of 3PNC / ANI-1 obtained in Example 1
It is an MR spectrum.

3 is an IR spectrum of 3PNC / MNI obtained in Example 2. FIG.

FIG. 4 NMR of 3PNC / MNI obtained in Example 2
It is a spectrum.

FIG. 5: I of 3PNC / ANI-2 obtained in Example 3
It is an R spectrum.

6 is N of 3PNC / ANI-2 obtained in Example 3. FIG.
It is an MR spectrum.

FIG. 7: I of 3PNC / ANI-3 obtained in Example 4
It is an R spectrum.

FIG. 8: N of 3PNC / ANI-3 obtained in Example 4
It is an MR spectrum.

FIG. 9: I of 3PNC / ANI-4 obtained in Example 5
It is an R spectrum.

10 is an NMR spectrum of 3PNC / ANI-4 obtained in Example 5. FIG.

11 is an IR spectrum of 3PNC / ANI-5 obtained in Example 6. FIG.

12 is an NMR spectrum of 3PNC / ANI-5 obtained in Example 6. FIG.

FIG. 13 is an IR spectrum of the polymer of 3PNC / ANI-1 obtained in Example 7.

14 is an IR spectrum of the polymer of 3PNC / ANI-2 obtained in Example 8. FIG.

FIG. 15 is an IR spectrum of the polymer of 3PNC / ANI-3 obtained in Example 9.

FIG. 16: 3PNC / ANI-4 obtained in Example 10
3 is an IR spectrum of the polymer of.

FIG. 17: 3PNC / ANI-5 obtained in Example 11
3 is an IR spectrum of the polymer of.

18 is an IR spectrum of the 3PNC / MNI polymer obtained in Example 12. FIG.

FIG. 19: 3PNC / ANI-1 obtained in Example 16
3 is a graph showing the change over time in the shear adhesive strength of the polymer.

Claims (3)

[Claims] 1. The following general formula (1): [Wherein n is 3 or 4 and at least one of R ¹ and R ² is represented by the following formula (2): [Wherein R ³ represents a hydrogen atom or a non-reactive group, and R ⁴
Represents an alkyl or alkenyl group having 1 to 6 carbon atoms]
A substituted nadiimidophenoxy group and the rest represent a phenoxy group which may have a non-reactive substituent.] An alkyl- or alkenyl-substituted nadiimidophenoxy group-containing cyclophosphazene derivative. 2. Cyclophosphazene chloride in the presence of 4- (N-mono- or dialkylamino) pyridine and a hydrochloric acid scavenger having the following general formula (3): [In the formula, R ³ represents a hydrogen atom or a non-reactive group, and R ⁴
Represents an alkyl or alkenyl group having 1 to 6 carbon atoms]
A substituted nadiimidophenol represented by or a substituted nadiimidophenol and a phenol which may have a non-reactive substituent are reacted with each other, wherein the alkyl- or alkenyl-substituted nadiimidophenoxy group is contained. Process for producing cyclophosphazene derivative. 3. An alkyl- or alkenyl-substituted nadiimidophenoxy group-containing cyclohexylate comprising heating the alkyl- or alkenyl-substituted nadiimidophenoxy group-containing cyclophosphazene derivative according to claim 1 in the presence or absence of a cation catalyst. Process for producing polymer of phosphazene derivative.