JPH0413683A - Cyclophosphazene derivative containing p-vinyl-phenoxy group, its production, its polymer and curable composition thereof - Google Patents

Abstract

NEW MATERIAL:The cyclophosphazene derivative of formula I (n is 3 or 4; p+q is 2; p>0; q>=0; pn is positive integer; R1 is alkyl positioned at ortho, meta or para position of benzene ring or H) having p-vinylphenoxy group or p-vinylphenoxy group and a phenoxy group which may or may not have an alkyl-substituent. USE:A monomer for the production of a polymer (composition) useful as a raw material for laminate, casting material, etc., PREPARATION:The objective compound can be produced by reacting cyclophosphazene chloride with p-vinylphenol or a mixture of p-vinylphenol and a phenol which may have alkyl-substituent in the presence of a 4-(N- alkylamino)pyridine compound of formula II (R2 is H or 1-6C alkyl; R3 is 1-6C alkyl) and a hydrochloric acid acceptor.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a p-vinylphenoxy group-containing cyclophosphazene derivative, a method for producing the same, a polymer thereof, and a heat-resistant and The polymer and thermosetting resin composition of the present invention are used as raw materials for laminated materials, casting materials, molding materials, etc., and are used as structural materials. , useful as electrical and electronic component materials.

(Prior art) Phosphazene derivatives are generally flame retardant and their combustion gases have low toxicity, so similar properties are expected for their polymers, so they are one of the raw materials for matrix resins for advanced composite materials. Many attempts have been made to synthesize flame-retardant and heat-resistant polymers using cyclophosphazene chloride as a starting material.

For example, a method for obtaining a crosslinked resin with excellent heat resistance by the reaction of hexachlorocyclotriphosphazene and hydroquinone (U.S. Pat. Nos. 2,866,773 and 3,121)
, No. 704). However, according to this method, hydrochloric acid gas is generated during resin formation, which causes problems such as corrosion of the metal and generation of voids, which limits its use. In addition, Zhivukhin et al. attempted to create a crosslinked resin through transesterification of a butoxy-substituted hexachlorocyclotriphosphazene with resorcinol, hydroquinone, or dihydric phenols; however,
Similar to the above, volatile alcohol may be generated or
A product with a high molecular weight cannot be obtained, and the physical properties of the cured product are not clear (Vysokomoj, 5oed, 8.72
7 (1966)).

In order to improve these drawbacks, polymerizable allyl group-containing phenoxy groups (e.g. derived from allyl oxybenzoate, metaallyl oxybenzoate, allylphenol)
, a method has been proposed in which a cyclophosphazene substituted product containing a phenoxy group, an alkylphene/dl-group, etc. is cured to form a resin with a crosslinked structure (for example, Japanese Patent Publication No. 47-11
No. 226, No. 48-8620, No. 4g-11099, No. 48-20793).

These methods are convenient for molding work because they do not generate volatile components as described above, but the reactivity of the Ryoryl group is not necessarily good, so it is necessary to activate the resin to complete the curing reaction. It is necessary to use a catalyst with a high temperature or heat treatment at high temperature for a long time.

Therefore, in order to further improve this drawback, a method was proposed to introduce a vinyl group that is more reactive than an allyl group (
Special Publication No. 48-27316). However, with this method,
In the first step, an equivalent amount or less of phenols and/or alcohols is reacted with hexachlorocyclotriphosphazene in the presence of an amine or as an alkali metal salt to partially substitute cyclophosphazene chloride with a phenoxy group and/or an alkoxy group. In the second step, an equivalent amount of sodium salt of a polyhydric phenol such as resorcinol or catechol is reacted with the compound to form a partially substituted chlorinated cyclophosphazene oligomer, and in the third and final step, residual chlorine is removed to zero. - The prepolymer is completely substituted with the sodium salt of vinylphenol, which has the disadvantage that the synthesis process of the resin raw material is extremely complicated.

Further, although the cured product obtained by further crosslinking the prepolymer obtained by K in this way has excellent heat resistance, it also has the disadvantage that its mechanical strength is insufficient and its uses are limited.

In addition, the present inventors previously provided a linear phosphazene polymer in which a vinylphenoxy group or an isopropenylphenoxy group was introduced as a JI+1 or curing site (%
This polymer had a drawback in that the cured product after crosslinking was an elastomer, and the use of this polymer was limited in that a cured product with high hardness could not be obtained.

As mentioned above, the conventional proposal of combining phosphazene with vinylphenols involves introducing a vinylphenoxy group into a cyclophosphazene oligomer or a linear polymer obtained by ring-opening polymerization of cyclophosphazene. Cyclotriphosphazene or cyclotetraphosphazene into which a phenoxy group has been introduced has not yet been proposed.

(Problems to be Solved by the Invention) Therefore, the present inventors provided cyclotriphosphazene or cyclotetraphosphazene into which a p-vinylphenoxy group was introduced, and also provided a cyclotriphosphazene or cyclotetraphosphazene into which a p-vinylphenoxy group was introduced. As a result of intensive research to improve the above-mentioned drawbacks of oligomers of cyclophosphazene or linear polymers formed by ring-opening polymerization of cyclophosphazene, we found that
A method in which an alkali metal salt of p-vinylphenol is applied to cyclophosphazene chloride, which has been conventionally adopted as a method for introducing a vinylphenoxy group into a cyclophosphazene oligomer or a linear polymer obtained by ring-opening polymerization of cyclophosphazene, is used. However, since the alkali metal salts of p-vinylphenol have high polymerization reactivity, the nuclear phenolate can exist in the form of a monomer under the substitution reaction conditions. Even if a method of reacting in the presence of p-vinylphenol is applied, the substitution reaction between the chlorine and p-vinylphenoxy groups of cyclophosphazene chloride will only proceed under conditions severe enough to cause the polymerization reaction of p-vinylphenol, and in the end, the desired reaction cannot be achieved. It was discovered that it was not possible to suitably obtain a cyclophosphazene derivative with a p-vinylphenoxy group introduced therein, and further research revealed that cyclophosphazene and p-vinylphenol could be obtained in the presence of a certain pyridine compound and a hydrochloric acid scavenger. When reacting with p-vinylphenol, the polymerization reaction of p-vinylphenol is suppressed, and the chlorine of cyclophosphazene chloride and p-
The present invention was completed based on the discovery that only the substitution reaction of the -vinylphenoxy group proceeds to yield the desired cyclophosphazene derivative having a p-vinylphenoxy group.

Therefore, an object of the present invention is to provide a novel cyclophosphazene derivative having a p-vinylphenoxy group and a simple and high-yield method for producing the same, as well as to provide excellent heat resistance, flame retardance, mechanical properties, etc. An object of the present invention is to provide a polymer of the cyclophosphazene derivative, and a thermosetting resin composition containing the cyclophosphazene derivative and a vinyl monomer as essential components.

(Means for Solving the Problems) The gist of the present invention is, firstly, a p-vinylphenoxy group represented by the following general formula (1), or a p-vinylphenoxy group with or without an alkyl substituent. Cyclophosphazene derivative containing a phenoxy group (hereinafter referred to as compound (1)); [1] (However, n = 3 or 4, p + q = 2, p > O1
q≧0, pn is a positive integer, qn is O or a positive integer, R1 is an alkyl group or hydrogen located in the ortho, meta, or para position of the benzene ring), and the second is 4-( represented by the following general formula [II]
N-alkylamino)pyridine compound (hereinafter referred to as compound [I
I]; (n) (wherein R2 is hydrogen or an alkyl group of 01 to C6,
R3 represents a C1 to C6 alkyl group, respectively) and a method for producing compound CI) in the presence of a hydrochloric acid scavenger,
The third problem lies in the vinyl polymer of compound (1), and the fourth problem lies in the thermosetting resin composition containing the compound [I] and a vinyl monomer as essential components.

To elaborate on the present invention, one of the raw materials for compound CI) is cyclophosphazene chloride, and in the present invention, hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, or a mixture thereof is used.

The other raw material is p-vinylphenol or the p-
It is a mixture of vinylphenol and phenols having or not having an alkyl substituent (hereinafter referred to as a phenol mixture).As the alkylphenol, those having an alkyl group of 1 to 5 carbon atoms are suitable, and preferably p-
Ethylphenol or p-methylphenol is used.

It is particularly preferable to use the dehydrogenation reaction product containing p-vinylphenol and p-ethylphenol as well as other impurities obtained by dehydrogenation of p-ethylphenol, which is carried out industrially, as a raw material as it is. be.

In addition, compound [11] acts as a phase transfer catalyst, and representative examples include 4-methylaminopyridine, 4-ethylaminopyridine, 4-propylaminopyridine, 4-((N-methyl, -ethyl)amine)pyridine, 4-1(N-methyl,N-butyl)amine)pyridine, 4-((N-ethyl,N-butyl)amino)pyridine, 4-((N-butyl,N-hexyl) ) amine) pyridine, 4-dimethylaminopyridine, 4-diethylaminopyridine, 4-dibutylaminopyridine, 4-dibentylaminopyridine, 4-diethylaminopyridine and the like, but are not limited to these. Preference is given to using 4-dimethylaminopyridine.

Aliphatic tertiary amines are suitable as hydrochloric acid scavengers, and representative examples include trimethylamine, triethylamine, tributylamine, tripentylamine,
Examples include, but are not limited to, trihexylamine, dimethylethylamine, dimethylbutylamine, diethylbutylamine, dibenzylethylamine, dibutylhexylamine, dicyclohexylethylamine, and the like.

In the presence of such a phase transfer catalyst and hydrochloric acid scavenger, a cyclophosphazene chloride compound and p-vinylphenol or a phenol mixture are reacted, but the reaction can also be carried out without a solvent, or with hydrocarbons, halogenated hydrocarbons, The reaction can also be carried out in the presence of suitable solvents that have low reactivity with cyclophosphazene chloride and can dissolve them, such as esters, ethers, esters, and ketones.

The amount of the 4-(N-alkylamino)pyridine compound used is 0.01 to 1.0 mol, preferably 0.05 to 1.0 mol, based on the basic unit of cyclophosphazene chloride (PNCI2).
It is 0.5 mole. The amount of hydrochloric acid scavenger used is 2.0 to 4 per basic unit of cyclophosphazene chloride (PNC12).
．． 0 mol, preferably 2.0 to 3.0 mol.

The amount of p-vinylphenol or phenol mixture to be used is such that at least one p-vinylphenoxy group is substituted per molecule of cyclophosphazene chloride;
0.17 to 6.0 mol based on vinylphenol, preferably 0.4 to 5.0 mol, 1.0 based on phenol mixture
~7.0 mol Preferably 1.0 to 5.0 mol, and in the case of tetrachlorocyclophosphazene, 0.13 to 4.0 mol based on p-vinylphenol per chlorine atom, preferably 0.3 3.0 mol, preferably 1.0 to 7.0 mol, preferably 1.0 to 5.0 mol, based on the phenol mixture. In addition, in the substitution reaction, p-vinylphenol generally has a higher reactivity than phenol or alkylphenol, so even if the amount of p-vinylphenol or phenol mixture used is increased with respect to the raw material cyclophosphazene chloride, p - Substituted products containing a high concentration of vinylphenoxy groups can be obtained.

Although the amount of the solvent to be used is not particularly limited, it is suitably 0 to 1.000 parts per 100 parts of cyclophosphazene chloride as the raw material.

The substitution reaction is -10~200r, preferably θ~150C
It is carried out at a temperature of 1 minute to 30 hours, preferably 10 minutes to 25 hours.

In this way, when cyclophosphazene chloride and a phenol mixture are reacted in the presence of a phase transfer catalyst with a specific structure, although p-vinylphenol has extremely high polymerization reactivity, during the reaction, A cyclophosphazene derivative or compound in which the substitution reaction proceeds preferentially without causing a polymerization reaction, and is substituted with a p-vinylphenoxy group or a p-vinylphenoxy group and a phenoxy group with or without an alkyl substituent [ I] is generated. In the thus obtained compound (1), the introduction rate of p-vinylphenoxy group is 1 for tetraphosphazene.
The molar ratio is 2.5 or more, and for triphosphazene it is 16.7 or more. The compound [I] is usually a highly viscous liquid or solid and has an extremely high boiling point, making it impossible to distill and almost impossible to crystallize. Although this product is a monomer in that it has a cyclophosphazene ring as its basic skeleton, it can also be considered an oligomer in which three or four basic units are connected in a ring. Isomers with slightly different introduction ratios or different introduction positions of vinylphenoxy groups and alkyl-substituted or unsubstituted phenoxy groups can hardly be separated by separation methods such as rectification, fractional crystallization, fractional extraction, and chromatography. It is possible, and in industrial applications, these separations are essentially unnecessary.

The compound [I] polymerizes and cures when heated alone or in the presence of a suitable 1-intermediate initiator, and the cured product has flame retardant properties.
It is useful as laminates, structural materials, and electrical and electronic components with excellent heat resistance.

Polymerization and curing reactions are carried out at 80C or higher when no initiator is used.
The process is completed by heating at a temperature of 280t11', preferably 100C to 280C, for 30 minutes to 10 hours, preferably 1 hour to 10 hours. In addition, in the presence of a polymerization initiator,
The reaction is completed by heating at a temperature of 20C to 280r, preferably 60C to 250C, for 10 minutes to 20 hours, preferably 20 minutes to 15 hours. That is, by using a polymerization initiator, polymerization can be carried out at a low temperature.

As the polymerization initiator, cationic initiators such as various ammonium compounds, sulfonium compounds, iodonium compounds, and stannonium compounds, and various radical initiators are effective.

Examples of ammonium compounds include tetraethylammonium salt (((C2H5)4Nl+X), tetrabutylammonium salt (((C4H0)4N)+X
-), the sulfonium salt is, for example, dimethyl-benzoylmethylsulfonium! (IC61(5COC
H2S(CH3) 2)"r'), diethyl-p-methoxybenzylsulfonium salt ((p-CH3QC,H
4C)i2S(C2H,)2)"
((C6H,) 2I)”
C6H5).

Sn)"X"-). However, the above chemical formula % formula % PF6 etc. are represented.

Further, as the radical initiator, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, azobisin butyronitrile, etc. can be used, but the invention is not limited thereto.

Although the amount of the polymerization initiator to be used is not specified by tK, it is generally preferable to use it in a range of 0.1 to 5% by weight based on compound (1). The polymer thus obtained is insoluble in solvents and cannot be analyzed by 1HNMH. However, according to their IR analysis, the absorption 1650 cIn-1 based on the C=C (vinyl bond) stretching vibration observed in the raw material compound (1) disappeared, while the absorption based on the P=N (cyclophosphazene) stretching vibration disappeared. The absorption of 1220 m-' was observed essentially unchanged, and the elemental analysis value was also substantially the same as that of the raw material compound CI). It is clear that it is a polymerized product. T of the polymer of the present invention
Glass transition temperature determined by BA method is 120-160C
is within the range of

In addition, when the compound [I] is reacted with a vinyl monomer exhibiting cationic or radical polymerizability under the same conditions as the above polymer, a cured product can be obtained, and the cured product has flame retardancy, heat resistance, etc. It is useful as an excellent laminate, structural material, and electrical and electronic components. In this case, the amount of the polymerization initiator to be used is not particularly limited, but it is generally preferred to use it in an amount of 0.1 to 5% by weight based on the mixture of compound [I] and vinyl monomer.

The above-mentioned cationically or radically polymerizable vinyl monomers include styrene, styrene derivatives such as a-methylstyrene, p-methylstyrene, chlorostyrene, acrylic acid, acrylic esters such as methyl acrylate, ethyl acrylate, etc. , methacrylic acid, methacrylic esters, such as methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, etc., carboxylic acid vinyl esters, such as vinyl acetate, vinyl propionate, vinyl benzoate, etc., unsaturated nitriles Examples include, but are not limited to, acrylonitrile, vinylidene cyanide, maleimide conductors such as phenylmaleimide, 1.1'(methylene di4.1-)unicine) bismaleimide, and the like.

The amount of these vinyl monomers used is not particularly specified, but
Generally, 0.1 mol to 20 mol is suitable for 1 mol of p-vinylphenoxy group in the cyclophosphazene derivative.

The cyclophosphazene derivative polymer of the present invention and the thermosetting resin composition comprising the phosphazene derivative and a vinyl monomer may contain various fillers, pigments, coupling agents, mold release agents, etc., as necessary. be able to. For example, fillers include glass fiber, carbon fiber, metal fiber, calcium phosphate, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, antimony oxide, gypsum, silica, alumina, clay talc, quartz powder, iron powder, and carbon. Examples include, but are not limited to, black. The amount used is determined depending on the application, but is generally 10 to 500 parts by weight per 100 parts by weight of the phosphazene derivative or the thermosetting resin composition.

(Effects of the Invention) The present invention provides novel p-
A vinylphenoxy group-containing cyclophosphazene conductor can be obtained easily and in high yield. Further, the phosphazene derivative is a high viscosity liquid or a low melting point solid,
Because it is soluble in general-purpose solvents, it is easy to handle, and the curing reaction is completed under relatively mild conditions.Also, thermosetting resin compositions composed of the phosphazene derivative and various vinyl monomers are also highly reactive, and their Since the cured product has excellent heat resistance, flame retardancy, and mechanical strength, it can be used as a raw material resin for laminated materials, casting materials, molding materials, etc.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited by this K.

Example 1 Synthesis of cyclophosphazene derivative containing p-vinylphenoxy group and alkylphenoxy group - Part 1 - Crude p-vinylphenol (p-vinylphenol 35 mol, p-ethylphenol 58 mol and p-cresol 7 mol) ) 17.7 grams, 4-
To a mixture consisting of 0.53 g of dimethylaminopyridine, 19.11 g of triethylamine, and 49 ml of dioxane, 5.0 g of hexachlorocyclotriphosphazene (hereinafter abbreviated as 3PNC) and 40
A solution consisting of m/m dioxane was added dropwise over a period of 10 minutes. Thereafter, stirring was continued for 8 hours while maintaining the temperature at 40 to 50C. The formed salts were filtered off, and the filtrate was treated under reduced pressure to remove the solvent. The residue was treated with an aqueous sodium hydroxide solution to extract and remove unreacted phenols, and the separated liquid was thoroughly washed with water and dried under vacuum.
1.3 grams of highly viscous liquid remained.

As a result of NMR and IR analysis, this product has an average composition of 2 $61 moles of p-vinylphenoxy, 34 moles of p-ethylphenoxy groups, and 5 moles of p-methylphenoxy groups.
It was found to be a cyclotriphosphazene conductor containing substituents consisting of molar ratios, ie, mostly tetra(p-vinylphenoxy)-di(p-ethylphenoxy)cyclotriphosphazene.

NMR result D Attribution Peak area 1.2 ppm D 5
22.3ppmA
72.6ppmE
355.2-5.6ppm H63 6.6ppm (6.7-7.2ppm The peak observed at 2.34ppmK in B, C, F, G, J, is the methyl group of the residual toluene used during raw material purification. This seems to be due to

Molar fraction CH+O-7/3=2.3 0.05 CHCM+o-35/2=17.5 0.34CH=
cti+o-63/2=31.5 0.61 total 51
．． 3 1.00 IR result 1220cm-' P=N (cyclophosphazene) stretching vibration one! 1200.950 on P -0-C stretching vibration 1610, l510cTn aromatic ring
〃16506n' C=C (vinyl bond)
%) were as follows.

CHN P 67.38 5.46 4.94 10.93 Almost no active chlorine was detected in the target product, and the GPC analysis showed a single peak. Vapor pressure osmometry (VP
O method) Measuring the molecular weight of VC 1. The value was 8.
50 (IJ theoretical value 850).

The IR and NMR spectra of the target product are shown in Figures 1 and 2, respectively.

Example 2 Synthesis of cyclophosphazene derivative containing p-vinylphenoxy group and alkylphenoxy group - Part 2- 11 p-vinylphenol < p-vinylphenol l
7-v-#%, a mixture consisting of 72 moles of p-x thylphenol and 11 moles of p-cresol)
200 grams, 9.2 grams of 4-dibutylaminopyridine, and 3201 tributylamine;
Under water cooling, a solution consisting of 82 grams of octachlorocyclotetraphosphazene (4PNC) and 400 d of chlorobenzene was added dropwise over 20 minutes. After that, 30r
The mixture was heated and stirred at 60 tl' for 16 hours, and then heated and stirred at 60 tl' for 15 hours. The formed salts were filtered off and the filtrate was treated under reduced pressure to remove the solvent.

The residue was treated with an aqueous IJ solution to extract and remove unreacted phenols, and the separated liquid was thoroughly washed with water and vacuum dried, leaving 205 grams of a highly viscous liquid.

NMR and IR analyzes were performed in the same manner as in Example 1, and the average composition was 22 moles of p-vinylphenoxy groups, 68 moles of p-ethylphenoxy groups, and 10 moles of p-methylphenoxy groups. It was found to be a cyclotetraphosphazene derivative containing a substituent, ie essentially di(p-vinylphenoxy)-penta(p-ethylphenoxy)-mono(p-methylphenoxy)cyclotetraphosphazene.

Elemental analysis value (wt%) CHN P 66.92 5.94 4.94 10.92Also, almost no active chlorine was observed in the target product, and GPC analysis showed a single peak, and ■Molecular weight by PO method is 113
8 (theoretical value 1137).

The IR and NMR spectra of the target product are shown in Figures 3 and 4, respectively.

Example 3 Synthesis of cyclophosphazene derivative containing p-vinylphenoxy group and alkylphenoxy group - Part 3 - 14.5 g of crude p-vinylphenol used in Example 2, 0.4 g of 4-dimethylaminopyridine, triethylamine 14.To the mixture consisting of 8-, under water cooling, 4.
A solution consisting of 1 gram of 3PNC and 12.3-chlorobenzene was added dropwise over a period of 5 minutes. Thereafter, stirring was continued for 24 hours at room temperature. The formed salts were filtered off and the filtrate was treated under reduced pressure to remove the solvent. The residue was treated with an aqueous sodium hydroxide solution to extract and remove unreacted phenols, and the separated liquid was thoroughly washed with water and dried in vacuum, yielding a highly viscous target product weighing 9.0 grams. .

As a result of NMR and IR analysis conducted in the same manner as in Example 1,
This product has an average composition of 33 p-vinylphenoxy groups.
Cyclotriphosphazene derivatives containing substituents consisting of 60 molar groups of p-ethyl phenoxy groups and 7 molar groups of p-methylphenoxy groups, i.e. mainly di(p-vinylphenoxy)-tetra(p-ethylphenoxy)cyclotriphosphazenes It turned out to be.

Elemental analysis value (wt%) CHN P 67.07 5.82 4.93 10.9] Active chlorine was not detected in the target product, and GPC analysis showed a single peak, and its molecular weight by vPO method is 85
It was 0 (31 logical value 852).

Its IR and NMR spectra are shown in FIGS. 5 and 6, respectively.

Example 4 Synthesis of cyclophosphazene derivative containing p-vinylphenoxy group and alkylphenoxy group - Part 4 - Crude p-vinylphenol (p-vinylphenol 45 mols, p-ethylphenol 49 mols and p-cresol 6 mols) 23.0 grams of 4-
To a mixture consisting of 0.20 g of ethylaminopyridine and 40 g of trihexylamine, 5.0 g of
A solution consisting of 3 grams of PNC and 40 iu of dioxane was added dropwise over 5 minutes. Thereafter, stirring was continued for 20 hours at a temperature of 40 to 50 r. The formed salts were filtered off and the filtrate was treated under reduced pressure to remove the solvent. The residue was treated with an aqueous sodium hydroxide solution to extract and remove unreacted phenols, and the separated liquid was thoroughly washed with water and vacuum dried to obtain 1010 grams of a highly viscous liquid.

As a result of NMR and IR analysis conducted in the same manner as in Example I,
This product has an average composition of 75 p-vinylphenoxy groups.
molar ratio, p-ethylphenoxy group 22 molar ratio and p-
Cyclotriphosphazene derivatives containing substituents consisting of 3 molar groups of methylphenoxy groups, i.e., substantially penta(
It was found to be an equimolar mixture of p-vinylphenoxy)-mono(p-ethylphenoxy)cyclotriphosphazene and tetra(p-vinylphenoxy)-di(p-ethylphenoxy)cyclotriphosphazene.

Elemental analysis 1 [(wt%) CHN P 67.55 5.29 4.94 10.93 Active chlorine was not detected in the target product, its GPC spectrum had a single peak, and its molecular weight by VPO method was 850 (theoretical value 850).

The In and NMR spectra of the target product are shown in FIGS. 7 and 8, respectively.

Example 5 Synthesis of cyclophosphazene derivative containing p-vinylphenoxy group and alkylphenoxy group - Part 51 18.5 g of crude p-vinylphenol used in Example 2, 0.5 g of 4-dimethylaminopyridine, 2011 triethylamine / to a mixture consisting of 4. at room temperature.
A solution consisting of 1 gram of 4PNC and 2 Q ml of dioxane was added dropwise over 5 minutes, followed by continued stirring at room temperature for 24 hours. The formed salts were filtered off, and the filtrate was treated under reduced pressure to remove the solvent. The residue was treated with an aqueous IJ solution to extract and remove unreacted phenols, and the separated liquid was thoroughly washed with water and dried under vacuum.9.1
A product with a high viscosity of 1.5 grams was obtained.

As a result of NMR and IR analysis conducted in the same manner as in Example 1,
This product has an average composition of 38 p-vinylphenoxy groups.
molar ratio, p-ethylphenoxy7 groups 54 molar ratio and p-
A cyclotetraphosphazene conductor containing a substituent consisting of 8 mol% of methylphenoxy groups, i.e., mainly tri(
It was found to be p-vinylphenoxy)-penta(p-ethylphenoxy)cyclotriphosphazene.

Elemental analysis value (Ashif section) CHN P 67.10 5.75 4.94 10.93 Active chlorine was not detected in the target product, and GPC analysis showed a single peak12, and its molecular weight by VPO method is 11
35 (theoretical value 1134). The IR and NMR spectra of the target product are shown in FIGS. 9 and 10, respectively.

Example 6 Cyclotriphosphazene derivative 10 obtained in Example 1
When the sample was placed in a glass polymerization tube and heated at 200℃ for 5 hours, the contents were completely solidified.

The glass tube was broken and the contents were taken out, crushed 1 to 12, washed with methanol, and vacuum dried to obtain 9.9 grams of polymer. This polymer showed no melting point and was insoluble in various solvents. According to IR analysis, this polymer contains C=C(
The IR absorption is based on the stretching vibration of the vinyl bond (with the exception of no absorption at 1650 cm-1)
Based on the stretching vibration of (cyclophosphazene) <1220c
The absorption including rn-1 was essentially consistent with that of the product of Example 1, and the results of elemental analysis were also essentially consistent with the values shown in Example 1. From these results, it was found that this product was obtained by vinyl polymerization of the p-vinylphenoxy group in the cyclotriphosphazene derivative. Further, the glass transition temperature was measured by TBA method and was found to be 140C.

The IR spectrum is shown in FIG.

Example 7 Cyclotetraphosphazene derivative 1 obtained in Example 2
0 grams was charged into a glass polymerization tube together with 0.1 grams of benzoyl peroxide and heated at 200 C for 2 hours, and the contents were completely solidified.

The contents were taken out, crushed, washed with methanol, and dried under vacuum to obtain 9.9 grams of polymer. This polymer showed no melting point and was insoluble in various solvents.

As a result of the analysis, it was found that the p-vinylphenoxy group in the cyclotetraphosphazene derivative obtained in Example 2 was vinyl-polymerized for the same reason as described in Example 6. Further, the glass transition temperature was measured by the TBA method and was found to be 125C. The IR spectrum is shown in FIG.

Example 8 Cyclotriphosphazene derivative 10 obtained in Example 3
gram was charged into a glass polymerization tube together with 0.1 gram of azobisisobutyronitrile and heated at 180 C for 5 hours, and the contents were completely solidified. When the contents were taken out, crushed, washed with methanol, and dried under vacuum, the result was 9.
．． Nine grams of polymer was obtained. This polymer showed no melting point and was insoluble in various solvents. As a result of the analysis, for the same reason as stated in Example 6, this product was classified as Example 3.
It was recognized that the p-vinylphenoxy group in the cyclotriphosphazene derivative obtained in the above was vinyl polymerized. According to the TBA method, the glass transition temperature was 130C. The IR spectrum is shown in FIG.

Example 9 Cyclotriphosphazene derivative 10 obtained in Example 4
When the sample was placed in a glass polymerization tube and heated at 260C for 5 hours, the contents were completely solidified.

The contents were taken out and crushed, washed with methanol and vacuum dried to obtain 9.9 grams of polymer.

This polymer showed no melting point and was insoluble in various solvents.

The glass transition temperature determined by the TBA method was 145C. As a result of the analysis, for the same reason as stated in Example 6, it was found that this product was obtained by vinyl polymerization of the p-vinylphenoxy group in the cyclotriphosphazene derivative obtained in Example 4.

The IR spectrum is shown in FIG.

Example 10 Cyclotetraphosphazene derivative 1 obtained in Example 5
0 grams to 0.2 grams of diphenyl iodonium hexafluoroarsine)(((C6H5)2)AsF
When the mixture was charged into a glass polymerization tube together with 6) and heated at 220C for 2 hours, the contents were completely solidified.

The contents were taken out, crushed, washed with methanol, and dried under vacuum to obtain 9.9 grams of polymer. This polymer showed no melting point and was insoluble in various solvents.

As a result of the analysis, it was found that the p-vinylphenoxy group in the cyclotetraphosphazene derivative obtained in Example 5 was vinyl-polymerized for the same reason as described in Example 6.

The glass transition temperature determined by the TBA method was 133C. I
The R spectrum is shown in FIG.

Example 11 A cyclotriphosphazene derivative containing substituents consisting of 33 moles of p-vinylphenoxy groups, 60 moles of p-ethylphenoxy groups, and 7 moles of p-methylphenoxy groups as the average network structure obtained in Example 3. 60 parts of tricalcium phosphate and 40 parts of tricalcium phosphate were uniformly mixed together with 1% by weight of benzoyl peroxide based on the derivative, and the mixture was charged into a mold. Next, it was pressed at 200C for 3 hours under a pressure of 50 kp/F2. Remove the sample from the mold and
Post-cure was performed at 0C for 3 hours. The hardness of the cured product is 11
5 (Rockwell hardness, R scale), and the bending strength and bending modulus are respectively 6.5 kl/1III
2 and 475k) 7w2.

Example 12 A cyclotetraphosphazene derivative containing substituents consisting of 38 mol % of p-vinylphenoxy groups, 54 mol % of p-ethylphenoxy groups, and 8 mol % of p-methylphenoxy groups as the average composition obtained in Example 5. 60 parts of silica and 40 parts of silica were uniformly mixed together with 2 parts by weight of tetrabutylammonium bromide (((C4H8)4N)Br), and the mixture was charged into a mold. Next, it was pressed at 200C for 3 hours under a pressure of 50ky/cm2.

The sample was taken out and air-boosted at 250C for 3 hours.The bending strength and bending modulus of the cured product were 5, respectively.
．． It was 4ky/w2 and 500 kg/la2.

Example 13 A cyclotriphosphazene derivative containing a substituent consisting of 33 moles of p-vinylphenoxy group, 60 moles of p-ethylphenoxy group, and 7 moles of p-methylphenoxy group as the average composition obtained in Example 3. 20 grams and 20 grams of methacrylic acid methyl ester (MMA), 0
．． When the mixture was charged into a glass polymerization tube together with 1 gram of benzoyl peroxide and heated at 100 C for 1.0 hours, the contents were completely solidified. The yield is 39.8? Met.

When the contents were taken out and extracted with benzene, the insoluble portion was 9.
5%, and the soluble portion was 5%. As a result of analysis, it was found that the insoluble portion was a copolymer consisting of 9 moles of cyclotriphosphazene conductor and 91 moles of MMA, and the soluble portion was a mixture of a homopolymer of MMA and an oligomer of the derivative.

When thermogravimetric analysis was performed on the copolymer, it was found that 300C
The weight reduction rate was 7 times. By the way, Bo IJMMA
Under the same conditions, the value was 38.

Example 14 50 grams of the cyclotriphosphazene derivative used in Example 13 and MMAIO Dalam were charged into a glass polymerization tube along with 0.15 grams of benzoyl peroxide, and 1
When heated at 00C for 10 hours, the contents were completely solidified. The yield was 59.854.

When the extracted contents were subjected to the same extraction operation as in Example 13, the benzene insoluble portion (copolymer consisting of 40 moles of cyclotriphosphazene derivative and 60 moles of MMA) was 90%.

When thermogravimetric analysis was performed on the copolymer, it was found that 300C
The weight reduction rate was 3%.

Example 15 A cyclotetraphosphazene derivative containing substituents consisting of 22 moles of p-vinylphenoxy groups, 68 moles of p-ethylphenoxy groups, and 10 moles of p-methylphenoxy groups as the average composition obtained in Example 2. 20 grams of MMA and 20 grams of MMA were placed in a glass polymerization tube along with 0.15 grams of azobisisobutyronitrile, and heated at 100C.
When heated for 8 hours, the contents were completely solidified. The yield was 39.77.

When the contents taken out were subjected to the same treatment as in Example 13, 92% was found to be benzene-insoluble.

Example 16 Cyclotetraphosphazene derivative 5 synthesized in Example 5
0 grams and 10 grams of styrene were charged into a glass polymerization tube along with 0.3 grams of benzoyl peroxide, and heated at 120C.
When heated for 3 hours, the contents were completely solidified. The yield was 59.9F.

When the extracted contents were subjected to the same treatment as in Example 13, the benzene insoluble portion (a copolymer consisting of 38 moles of cyclotetraphosphazene derivative and 62 moles of stereophthalate) was 88%.

Thermogravimetric analysis of the copolymer revealed that it was 400C.
and the weight loss rate at 450C is 12 and 3, respectively.
It was 7%. Incidentally, these values for polystyrene conducted under the same conditions were 32% and 95%, respectively.

Example 17 Cyclotriphosphazene derivative 2 used in Example 13
0 grams and 20 grams of vinyl acetate were charged into a glass polymerization tube together with 0.2 grams of azobisin butyronitrile and heated at 100 C for 12 hours, and the system was completely solidified. The yield was 39.954.

When the contents taken out were subjected to the same treatment as in Example 13, the benzene insoluble portion (a copolymer consisting of 66 moles of cyclotriphosphazene derivative and 34 moles of vinyl acetate) was 80 moles.

It was also found that the benzene soluble portion was a mixture of vinyl acetate homopolymer and the derivative oligomer.

When thermogravimetric analysis was performed on the copolymer, it was found that 350C
The weight reduction rate was 8 times. Incidentally, the value for polyvinyl acetate tested under the same conditions was 58.

Example 18 A cyclotriphosphazene derivative containing a substituent consisting of 75 moles of p-vinylphenoxy group, 22 moles of p-ethylphenoxy group, and 3 moles of p-methylphenoxy group as the average composition obtained in Example 4. 30 grams and MM
After uniformly mixing 100 grams of A, it was heated to 100C.
for 2 hours, followed by cast molding at 200C for 3 hours.

The flexural strength and flexural modulus of the obtained test piece are
11 kl/ws2 and 400kf/va2 respectively
Met.

Example 19 A cyclotriphosphazene derivative containing a substituent consisting of 61 moles of p-vinylphenoxy groups, 34 moles of p-ethylphenoxy groups, and 5 moles of p-methylphenoxy groups as the average composition obtained in Example 1. 30 grams and 1.
Mix 10 grams of 1'-(methylene di-4.1-phenylene) bismaleimide uniformly at 120C, and
1 hour at 0C, 2 hours at 200C, and 5 hours at 230C.
Time cast molded. The heat distortion temperature (HDT) of this sample
) was 245C.

[Brief explanation of drawings]

Figure 1 is the IR spectrum of the product of Example 1, Figure 2 is its ``HNMR spectrum, Figure 3 is the IR spectrum of the product of Example 2, Figure 4 is its ``HNMR spectrum, Figure 5 is its ``HNMR spectrum''. IR spectrum of the product of Example 3, FIG. 6 is its HNMR spectrum, FIG. 7 is its IR spectrum of the product of Example 4, FIG. 8 is its HNMR spectrum, and FIG. 9 is its HNMR spectrum. IR spectrum of, 1st
Figure 0 is its HNMR spectrum, and Figures 11 to 15 are IR spectra of the polymers of Examples 6 to 100, respectively. Patent applicant: Maruzen Petrochemical Co., Ltd.

Claims (6)

[Claims] (1) A cyclophosphazene derivative containing a p-vinylphenoxy group represented by the following general formula [I], or a p-vinylphenoxy group and a phenoxy group with or without an alkyl substituent; ▲mathematical formula, chemical formula, There are tables, etc.▼ [I] (However, n=3 or 4, p+q=2, p>0, q≧
0 and pn are positive integers, qn is 0 or a positive integer, and R_1 is an alkyl group or hydrogen located in the ortho, meta, or para position of the benzene ring). (2) 4-(N-alkylamino)pyridine compound represented by the general formula [II] below; ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [II] (However, R_2 is hydrogen or alkyl of C_1 to C_6 group, R_3 is an alkyl group of C_1 to C_6) and a hydrochloric acid scavenger, cyclophosphazene chloride and p
2. The method for producing a cyclophosphazene derivative according to claim 1, which comprises reacting -vinylphenol or p-vinylphenol with a phenol mixture having or not having an alkyl substituent. (3) The method for producing a cyclophosphazene derivative according to claim 2, wherein the 4-(N-alkylamino)pyridine compound is 4-dimethylaminopyridine. (4) A cyclophosphazene derivative containing a p-vinylphenoxy group represented by the following general formula [I], or a p-vinylphenoxy group and a phenoxy group with or without an alkyl substituent; ▲mathematical formula, chemical formula, There are tables, etc.▼ [I] (However, n=3 or 4, p>0, q≧0, pn is a positive integer, qn is 0 or a positive integer, and R_1
is an alkyl group or hydrogen located in the ortho, meta, or para position of the benzene ring) and has a glass transition temperature (TBA method) of 120 to 160°C.
A polymer that is (5) A cyclophosphazene derivative containing a p-vinylphenoxy group represented by the following general formula [I], or a p-vinylphenoxy group and a phenoxy group with or without an alkyl substituent; ▲Mathematical formula, chemical formula, table etc.▼ [I] (However, n=3 or 4, p+q=2, p>0, q≧0
, pn is a positive integer, qn is 0 or a positive integer, and the alkyl group is an alkyl group or hydrogen located in the ortho, meta, or para position of the benzene ring) and cationically or radically polymerizable vinyl A thermosetting resin composition containing a monomer as an essential component. (6) the vinyl monomer is styrene, a styrene derivative,
6. The thermosetting resin composition according to claim 5, wherein the thermosetting resin composition is acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, carboxylic acid vinyl ester, unsaturated nitrile, or maleimide derivative.