JPS6341537A - Production of phosphazene polymer - Google Patents

Abstract

PURPOSE:To produce a polymer containing a controlled molecular weight distribution of soluble components in high conversion, producing little gel, by thermally polymerizing a cyclic phosphazene compound in the presence of a compound containing an atomic group SO4, thereby facilitating polymerization reaction. CONSTITUTION:A cyclic phosphazene compound represented by formula (NPCl2)y (y is 3 and/or 4) is thermally polymerized in the presence of a compound containing an atomic group SO4. The compound containing the atomic group SO4 includes sulfuric acid or a complex of sulfuric acid with a nitrogen- containing compound (e.g. hydroxylamine, hydrazine or an oxime compound), an anhydrous sulfate salt of Cu, Mg, or the like, an anhydroud hydrogen sulfate salt containing a cation such as NH4<+> or NO<+> and an anhydrous sulfate salt containing cations of N2H5<+> or NH3OH<+>. The cyclic phosphazene compound includes hexachlorocyclotriphosphazene.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a phosphazene polymer. More specifically, the present invention relates to a novel catalytic polymerization method in which a compound containing an atomic group SO4 is used as a catalyst when polymerizing hexachlorocyclotriphosphazene and/or octachlorocyclotetraphosphazene.

(Conventional Technique #) Research on polyphosphazenes is old; IL
N-5tokes obtained a phosphazene polymer by igniting hexachlorocyclotriphosphazene (hereinafter abbreviated as 3PNC), but CAtner and Chem.
-J, 19.782 (1897)], it is a rubbery substance that is insoluble in organic solvents and has the property of being extremely easily hydrolyzed, so it has been overlooked until recently.

In the 1960s) 1. It was discovered by R-AI Icock et al. that a phosphazene polymer soluble in organic solvents could be obtained by carefully heating 3PNC without a catalyst in a vacuum sealed tube (U.S. Pat. No. 3,370,020).
), and further substituents (for example, fluoroalkoxy groups, perfluoroalkoxy groups, allyloxy groups, aryloxy groups, alkoxy groups, and amino It has become possible to obtain polymers that are extremely stable against water, acids, bases, etc.

These phosphazene polymers have excellent properties such as heat resistance, flame resistance, and oil resistance, and are low in toxicity from combustion gas and pyrolysis gas, so they are used as flame retardants for foam rubber materials and glass materials used in housing. It is said to be excellent. It can also be used as a rubber that maintains flexibility even at low temperatures of -80 to -90°C, and has excellent properties such as oil resistance and needle hydraulic oil resistance, so it can be used for O-rings, gaskets, etc.
Research is being conducted on its use in the industrial field as fuel hoses, etc.

Recently, this phosphazene polymer has been used in the biological and medical fields as sutures, blood vessel substitutes, artificial organs, pharmaceutical carriers, etc. because its interaction with living tissue is extremely small and its substitute is harmless. Research on the use of is also actively being conducted.

Despite the increasing utility of these phosphazene polymers, problems remain in how to successfully prepare the starting 3PNC polymers.

In addition, increasing the polymerization rate is often accompanied by the formation of gels that are insoluble in solvents, which has made it difficult to produce useful polymer products such as those described above.

Furthermore, it was extremely difficult to control the molecular weight of the polymer using these early thermal polymerization methods.

Much work has been done on catalytic polymerization to overcome or minimize the shortcomings of these earlier methods. For example, a method using aluminum or boron Lewis acid catalysts such as boron trifluoride, alkyl aluminum and alkyl aluminum halides (% open 52-44900)
, inorganic salts especially CrCA! 2. A method using a metal halide such as N1 (J2, MgCJ2, etc.) as a catalyst (%
29300), a method using a metal alkoxide of the formula M (OR) Method of using combined catalyst threads (% 1976-16076),
Triphenylantimony (JP-A-55-120629
) or a method using thread combining triphenylantimony and halogen (Japanese Unexamined Patent Publication No. 55-123623) as a catalyst,
A method using sulfur or a thiocarbamate compound as a catalyst (JP-A-54-152693, JP-A No. 58-1646, 9)
, a method using a thread made of a combination of a Lewis acid and a neutral salt as a catalyst (
% Kaisho 55-123624).

In polymerization reactions using these catalysts, the catalyst is first 3PN
It is believed that polymerization is initiated by abstracting the chlorine atom bonded to the phosphorus atom of C in the form of a chlorine anion. Taking aluminum chloride (AJ) catalyst as an example, the polymerization initiation reaction occurs as shown in the following formula.

PNC l That is, these catalysts act as so-called Lewis acids.

According to this mechanism, when a protonic acid such as HCJ or HNo3 is used as a catalyst instead of a Lewis acid such as AlCl3 in the above equation, as a result of the initiation reaction, the same protonic acid HCA! is generated, which shifts the equilibrium in the above equation significantly to the left, and as a result, it is explained that the initiation reaction is difficult to proceed (
% Kaisho 53-71000).

In fact, it has been reported that polymerization is significantly inhibited in the presence of fluorotonic acids such as HCI and HBr, and only oligomers with very low molecular caps are produced.
1600, Macronolecules8,
36-42 (1975), Polymer l
I, 31-43 (1970)). On the other hand, contrary to this idea, there are also examples of using protonic acids with specific structures as catalysts to obtain high-molecular blue polymers in high yields. For example, a method using as a catalyst a strong acid such as methanesulfonic acid and polyphosphoric acid, a metal salt or an organic metal salt of these strong acids, and a reaction product of these salts and a halo massive phosphazene (
%Kaisei 5l-1600), a method using an organic sulfonic acid as a catalyst (%Kaisei 58-45230), etc. In these cases, the anion moiety constituting the protonic acid plays an important role in polymerization activity. be understood.

As described above, the results reported on the polymerization reaction of phosphazene are complex and cannot be interpreted in a unified manner1, and the polymerization mechanism has not yet been fully elucidated.

Moreover, although the polymerization method using the above-mentioned catalyst has many advantages over the initial thermal polymerization method, it cannot be said that the above-mentioned drawbacks have been fully overcome.

In other words, by using these catalysts, polymers can be obtained at relatively low temperatures and in a short reaction time, but if the polymerization rate is increased beyond a certain value, gels will still form, and even if the polymerization rate is increased, gels will still form. The reality is that in cases where no t7 is produced, the molecular weight of the polymer produced is extremely low, and in some cases, polymerization is accelerated and at the same time gel formation is also promoted. .

(Problems to be Solved) As a result of intensive studies to overcome or minimize these drawbacks, the present inventors discovered that a compound containing an atomic group represented by the chemical formula SO4 is used as a catalyst when polymerizing phosphazene. We have discovered a new polymerization method.

An object of the present invention is to provide a method for producing a phosphazene polymer that can easily produce a high molecular weight phosphazene polymer at a high conversion rate and that does not substantially involve the formation of gel. The object of the present invention is to provide a method for producing a phosphazene polymer whose distribution can be easily adjusted as desired.

(Means for Solving the Problems) The novel catalyst of the present invention, a compound containing an atomic group SO4, that is, a compound containing an atomic group represented by the chemical formula SO4, is:
Compounds containing sulfate anions (SO4) or tahasulfonyldioxy M (-〇-80□-〇-), specifically compounds containing sulfate anions include sulfuric acid, complexes of sulfuric acid and nitrogen-containing compounds, sulfuric acid Salts, hydrogen sulfates, sulfates or complexes of hydrogen sulfates and sulfuric acid, and compounds containing sulfonyldioxy groups include, but are not limited to, sulfuric acid. Note that the term sulfate is used herein to include oxysulfate as well.

It has been found that the novel catalyst of the present invention, a compound containing an atomic group represented by the chemical formula SO4, is essentially different from the above-mentioned protonic acids such as HCI J+)HI3 r and Lewis acids such as AlCl3. In other words, by using these catalysts, polymerization occurs easily and there is almost no gel formation, so it is possible to obtain phosphazene polymers at a high conversion rate. It is clear that this method also has the advantage that the molecular weight and molecular weight distribution of the resulting polymer can be easily controlled by changing conditions such as the type of catalyst, its polymerization time, and polymerization temperature. Became.

The nitrogen-containing compounds constituting the complex of sulfuric acid and nitrogen-containing compound, which is an example of the novel catalyst of the present invention, include amines, amides,
imide, hydroxylamine, oxime, hydrazine,
hydrazide, hydrazone, nitrosamine, nitroamine, amidine, amidoxime, guanidine, urea, semicarbazide, aminocarboxylic acid, amic acid, sulfamic acid, nitrogen-containing thiocarboxylic acid, nitrogen-containing thiourea, aralkylamine, benzoquinoneimine, anil, anilide,
Ammonia derivatives such as imidic acid and hydroxamic acid, nitrogen-containing aliphatic and aromatic compounds, and nitrogen-containing 5-membered ring compounds such as virol, viroline, pyrrolidine, indole, indoline, isoindole, carbazole, indigo, and porphyrin. , pyridine, hydropyridine, piperidine, quinoline, hydroquinoline, isoquinoline, acridine, benzoquinoline, naphthoquinoline, phenanthroline, etc. Nitrogen 1
5-membered ring compounds containing 2 nitrogen atoms, such as i-containing 6-membered ring compounds, pyrazole, imidazole, imidacilline, imidazolidine, benzimidazole, etc., 6-membered ring compounds containing 2 nitrogen atoms, such as diazine, hydropyrimidine, piperazine, benzodiazine, dibenzodiazine, etc. , 5-membered ring compounds containing 3 nitrogen atoms such as triazole, benzotriazole and triazine; heterocyclic compounds containing nitrogen and acid atoms such as oxazole, isoxazole and oxazine; 1 nitrogen atom such as thiazole, benzothiazole, inthiazole and thiazine and nitrogen-containing cyclic compounds such as sulfur l atom-containing heterocyclic compounds, oxadiazole, oxadiazine, etc., two nitrogen atoms and oxygen one atom containing heterocyclic compounds, thiandiazole, thiandiazine, etc. Examples include compounds.

The cations constituting the sulfate, which is another example of the novel catalyst of the present invention, include Cu%Mg, Zn, Al, TI! , T
M, Zr, Th, Sb, Bi, VSTa%C
r.

Mn, Fe%Co, Ni, T, a, Ce, U
Eliminate Ia (alkali metals) in the periodic table of equal elements (Ib~■
Examples include metal cations such as group elements, lanthanide group elements, actinide group elements, and furthermore, N2I]5, N2H6,
Cations such as Nll and Ofl can also be mentioned.

In addition to the metal ions mentioned above, the cations constituting the sulfate and hydrogen sulfate, which are components of catalyst systems such as hydrogen sulfate, sulfate, or complexes of hydrogen sulfate and sulfuric acid, include group Ia elements, NH4, NR4 , N01N2II5, N2H6, N
Cations such as ■I30■11C6115N30N and Pl-14 are also included. Here, R represents a substituted or unsubstituted aromatic group, or a linear or branched alkyl or alkenyl group, and the number of carbon atoms thereof is preferably 1 to 8.

Other examples of the novel catalyst of the present invention, such as Nisdel sulfate, are:
These are a series of compounds represented by the general formula R, -0-8O2-0-1't2. where R1 is an alkali metal, hydrogen, a substituted or unsubstituted aromatic group, or has 1 to 10 carbon atoms;
represents a straight-chain or branched alkyl, alkenyl group, or alicyclic group, and R2 is a substituted or unsubstituted aromatic group, or a straight-chain or branched alkyl, alkenyl group, or alicyclic group having 1 to 10 carbon atoms. group or an amino group (Nl12').

In the method of the present invention, the amount of the compound containing the atomic group represented by the chemical formula SO4 is not particularly limited and may be appropriately selected within a wide range. .01 to 20 mol%, preferably 0
．． 05 to 10% by weight is preferable.

If the amount of polymerization catalyst used is small, it is difficult to obtain a phosphazene polymer in high yield, and if the amount used is large, the polymer yield increases, but the molecular weight tends to decrease.

The polymerization reaction is usually carried out without a solvent or in the presence of a suitable solvent. The solvent is appropriately selected from those that do not react with the raw material monomer, the produced polymer, and the catalyst, such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, nitrobenzene, benzenesulfonyl chloride, Examples include aromatic solvents such as dihydronaphthalene, tetrahydronaphthalene, and biphenyl, and aliphatic solvents such as carbon tetrachloride, perchlorethylene, trichloroethylene, tetrachloroethane, dichloroethane, and [chlorinated paraffin]. In the present invention, the above polymerization reaction may be carried out using a closed thread or an open thread. The polymerization temperature is usually 1
50 to 300°C, preferably 150 to 260°C
, more preferably 180 to 250°C. If the polymerization temperature is too low, the polymerization reaction tends to be difficult to occur, and conversely, if the polymerization temperature is too high, the resulting phosphazene polymer tends to undergo depolymerization and gelation.

The polymerization time is generally about 0.5 to 1750 hours.

The phosphazene polymer thus produced can be easily isolated and purified by conventional isolation methods such as reprecipitation.

(Effects of the Invention) According to the method of the present invention, the polymerization reaction occurs easily and there is almost no gel formation, so it is possible to easily obtain a soluble phosphazene polymer with a high conversion rate. By appropriately selecting polymerization conditions such as the amount used, polymerization time, and polymerization temperature, the molecular weight and molecular weight distribution of the target phosphazene polymer can be easily changed as desired.

(Examples) Examples of the present invention are shown below, but the scope of the present invention is not limited by these Examples.

Example 1 Sulfuric acid and 1.2.4- ) +3 chlorobenzene 3 equivalent to 1.7 mol % based on 31) NC3,59,3PNC were added to a glass polymerization tube with an internal volume of about 20 ml that was purged with nitrogen.
．． After charging 5 mJ, the tube was sealed under reduced pressure while being pulled with a vacuum pump. Next, it was immersed in a Wood alloy bath at 220°C for 35 hours to polymerize.

After polymerization, the contents were poured into 1 Oml of toluene and separated into insoluble components (gel and catalyst residue) and soluble components (unreacted raw materials, soluble polymer, etc.).

The soluble content was further poured into 30 ml of hebutane to separate the polymer as a precipitate.

The obtained polymer was dissolved again in 10ml of toluene, and a diglyme solution of p-cresol Na salt (1 mol/ml) was added.
l) It was slowly added dropwise into 50 ml under stirring at 50 to 60°C.

After the reaction was continued under stirring for 40 hours under reflux, the contents were poured into a large amount of methanol to separate the p-cresol substituted polymer. The yield was 2.19.9, which corresponds to a yield of 28% in terms of raw material 3PNC.

As a result of GPC analysis of this substituted polymer, the number average molecular weight was 55,000, and the weight average molecular weight was 546,000. No gel formation was observed during the polymerization of 3PNC.

Implementation 1'! i2-5 In Example 1, polymerization was carried out under the same conditions as in Example 1 except that the sulfuric acid used as a catalyst was changed, and for some of the polymers, p-cresol substituted products were further synthesized. Table 1 The following results were obtained.

In any case, almost no gel formation was observed during the polymerization.

Table 1 *) Molecular needle polymerization conditions of p-cresol substituted polymer
3PNC3.4M, trichlorobenzene 3.5ml!
Polymerization at 220°C for 3.5 hours Example 6 In a glass polymerization tube with an internal volume of about 20 TrLl, which was purged with nitrogen, sulfuric acid and 1,2.4-) equivalent to 1.5 mol% were added to 3PNC3,5,9,3PNC. Lichlorbenzene 3.5
After charging ml, the tube was sealed under reduced pressure while being pulled with a vacuum pump. Next, it was immersed in a Wood alloy bath at 220°C and allowed to stand for 5 hours to polymerize, resulting in a polymer with a yield of 58.6%.

Incidentally, during the polymerization, almost no gel formation was observed.

Example 7 3P in a glass polymerization tube with an internal volume of about 20 m7 that was purged with nitrogen.
After charging hydroxylamine sulfate and 3.5 mJ of 1,2,4-trichlorobenzene equivalent to 0.7 mol % based on NC3,5&,3PNC, the tube was sealed under reduced pressure while being pulled with a vacuum pump. Next, it was immersed in a Wood alloy bath at 220°C and allowed to stand and polymerize for 3.5 hours. After 1 go, implementation N
A p-cresol substituted polymer was obtained by post-treatment in the same manner as in 1.

The yield was 1.781, which corresponds to a yield of 22.8% in terms of raw material 3PNC. In addition, GP of this substituted polymer
As a result of C analysis, the number average molecular weight was IO, 20,000, and the weight average molecular weight was 660,000.

There was almost no gel formation during polymerization.

Examples 8 to 11 Polymerization was carried out under the same conditions as in Example 7, except that 1 of the hydroxylamine sulfate used as the catalyst was changed and the polymerization time was changed to 3 hours instead of 3.5 hours. When p-cresol substituted products were further synthesized for some of the products, the results shown in Table 2 were obtained.

In any case, almost no gel formation was observed during polymerization.

Table 2) Molecular weight polymerization conditions of p-cresol substituted polymer 3
PNC3,5,9,) Lichlorbenze: / 3.5m
l.

Polymerization at 220°C for 3 hours Reference Example 1 The same conditions as Example 10 were used except that in Example 1O, 0.72 mol% hydroxylamine hydrochloride was used instead of 0.72 mol% hydroxylamine sulfate. Polymerization was attempted, but no polymer was produced.

Examples 12-21 3P in a glass polymer tube with an inner volume of 20 m1 of cotton that was purged with nitrogen
NC3,5,! i', a complex of various types of nitrogen compounds and sulfuric acid, and 1.2.4-) IJ dichlorunzene 3.5- were charged, and the mixture was sealed under reduced pressure while being pulled with a vacuum pump. Next, it was immersed in a Wood alloy bath at 220° C. and polymerized by standing for a predetermined period of time. Post-treatment of the contents after polymerization was carried out in accordance with Example 1. As a result, the results shown in Table 3 were obtained.

Table 3 Polymerization conditions 3PNC3.5g, trichlorobenzene 3
．． Polymerization at 5-1220°C 24-Example 22 3P in a glass tube with an internal volume of 20 mJ of nitrogen-substituted cotton
43% sulfuric acid solution of NC3,5,91 nitrosyl sulfuric acid 20
．． 1m,9 and 1,2.4-)lychlorobenzene3.
After charging 5 ml, the tube was sealed under reduced pressure while being pulled with a vacuum pump. Next, it was immersed in a Wood alloy bath at 220° C. and allowed to stand for 8 hours for polymerization. After that, it was subjected to the same post-treatment as in Example 1, and a soluble polymer was obtained in a yield of 47%.

Examples 23 to 28 Into a glass polymerization tube with an internal volume of 20 ml of cotton that was purged with nitrogen,
After adding 3.5 g of PNC, a predetermined amount of a complex of various nitrogen-containing compounds and sulfuric acid, and 3.5 m/l of tetralin, the tube was sealed under reduced pressure while being pulled with a vacuum pump.

Next, it was immersed in a Wood alloy bath at 220° C. and polymerized by standing for a predetermined period of time. Post-treatment of the contents after polymerization was carried out according to Example 1, and the results shown in Table 4 were obtained.

Table 4 Polymerization conditions 3PNC3,5,9, Tetralin 3.5
ml.

Polymerization at 220°C Example 29 3P in a 20m1 glass polymerization tube with nitrogen A replacement
NC3,5,9, anhydrous copper sulfate 80 ml and 1.2
．． 4-) After charging 3.5 mA' of lychlorobenzene,
The tube was sealed under reduced pressure while being pulled with a Tei 9 pump.

Next, it was immersed in a Wood's alloy bath and allowed to stand at 220°C for 2 hours of polymerization, followed by the same post-treatment as in Example 1. A soluble polymer was obtained in a yield of 27%, and its p-cresol substituted product The number average and weight average molecular weights were 210,000 and 1,590,000, respectively. Incidentally, almost no gel formation was observed during the polymerization.

Example 30 Polymerization and post-treatment were carried out in exactly the same manner as in Example 29, except that 171.4 ml of anhydrous aluminum sulfate was used instead of 80 m9 of anhydrous copper sulfate.
A soluble polymer was obtained with a yield of 19%, the number average and weight average molecular weight of the p-cresol substituted product being 2, respectively.
50,000 and 1.43 million. Incidentally, almost no gel formation was observed during the polymerization.

Examples 31 to 41 A 20 ml glass polymerization tube with nitrogen exchanged contents was charged with 3PNC3,59, a predetermined amount of anhydrous sulfate, and 3.5 m7I of 1,2,4-)lychlorobenzene. After that, the tube was sealed under reduced pressure while being pulled with a true pump.

Next, it was placed in a Wood alloy bath at 220° C. and allowed to stand for polymerization for a predetermined period of time, and then subjected to the same post-treatment as in Example 1, and the results shown in Table 5 were obtained.

U) Practical Example 42 3PN was added to the glass polymer tube of the nitrogen-substituted content ridge line 204.
After charging C3,5,9, 115.1 mJ of anhydrous copper sulfate, and 3.5 ml of tetralin, the tube was sealed under reduced pressure while being pulled with a vacuum pump.

Next, it was immersed in a Wood alloy bath at 220° C. to polymerize for 24 hours, and then the same post-treatment as in Example 1 was carried out, and a soluble polymer was obtained in a yield of 51%.

Note that no gel formation was observed during the polymerization.

Example 43 3PN in a glass polymerization tube with nitrogen-substituted content line 20-
03.5,9. Complex of nickel sulfate and sulfuric acid 35 ml
After charging 3.5 ml of 1,2,4-trichlorobenzene, the tube was sealed under reduced pressure while being pulled with a vacuum pump.

Next, it was immersed in a Wood alloy bath and polymerized at 220°C for 3 hours, followed by the same post-treatment as in Example 1. A soluble polymer was obtained in a yield of 31%, and the number of p-cresol substituted products was The average and weight average molecular weights were 150,000 and 880,000, respectively. Gel formation during polymerization was 3%.

The complex of nickel sulfate and sulfuric acid was synthesized as follows.

Finely ground nickel sulfate hexahydrate (Ni 804.6 H2O) 2I was placed in an Erlenmeyer flask with an internal volume of 100 mj, and 30 ml of concentrated sulfuric acid was slowly added to the flask while stirring. After continuing stirring at 80° C. for 3 hours, the mixture was left at room temperature for 16 hours.

Next, 60 mj of dry ether was slowly added while cooling and stirring. After continuing stirring for an additional 30 minutes, the device was
The supernatant liquid of the separated precipitate was removed. After repeating the above procedure of adding dry ether to the precipitate, stirring and separating to remove excess sulfuric acid, the precipitate was filtered through a glass filter and dried under vacuum at room temperature for 30 hours to obtain a pale yellow powder. It was done.

It is thought that the complex with nickel sulfate hexahydrate has a structure in which the water molecules in nickel sulfate hexahydrate are replaced with sulfuric acid molecules.

Examples 44 to 51 In Example 43, instead of the complex of nickel sulfate and sulfuric acid, prescribed complexes of various sulfates and sulfuric acid synthesized in the same manner as described in Example 43 were used, Example 43 except that instead of polymerizing at 220°C for 3 hours, polymerization was performed for a predetermined period of time.
When polymerization and post-treatment were carried out in exactly the same manner as in Table 6,
The results shown are obtained.

Example 53 3PNC3,! in a glass polymerization tube with an internal volume of 201rLl that was purged with nitrogen! Ml, ferric sulfate/sulfuric acid complex 35 ml
After charging 3.5 mJ of tetralin, the tube was sealed under reduced pressure while being pulled with a vacuum pump.

Next, it was immersed in a Wood alloy bath and polymerized at 220° C. for 24 hours, followed by the same post-treatment as in Example 1, and a soluble polymer was obtained in a yield of 43%. Note that no gel formation was observed during the polymerization.

Example 54 3PN was placed in a 20-volume glass polymerization tube purged with nitrogen.
C3.5g, copper sulfate/sulfuric acid complex 16m9 and 1,2.
After charging 7 m of 4-1-lichlorobenzene, the tube was sealed under reduced pressure while being pulled with a vacuum pump.

Next, it was immersed in a Wood alloy bath and polymerized at 220° C. for 24 hours, followed by the same post-treatment as in Example 1, and a soluble polymer was obtained in a yield of 30%.

Example 55 3PN was placed in a 20-volume glass polymerization tube purged with nitrogen.
03.5 g, ammonium hydrogen sulfate 11.5- and 1
, 2.4-) After charging 3.54 chlorbenzene,
The tube was sealed under reduced pressure while being pulled with a vacuum pump.

Next, it was immersed in a Wood alloy bath and polymerized at 220°C for 4 hours, followed by the same post-treatment as in Example 1. A soluble polymer was obtained in a yield of 24%, and the p-cresol substituted product was The number average and weight average molecular weights were 210,000 and 2.2 million, respectively.

Examples 56 to 58 Completely the same as Example 55, except that in Example 55, a prescribed amount of anhydrous various hydrogen sulfate compounds was used instead of ammonium hydrogen sulfate, and the polymerization time was polymerized for a prescribed time instead of 4 hours. When the operation was carried out, the results shown in Table 7 were obtained.

Table 7 Polymerization conditions 3PNC3,5,9,) Lichlorobenzene 3.5ml.

1 cup at 220°C Example 59 3PN was placed in a glass polymerization tube with an internal volume of 20 m purged with nitrogen.
Ca, sy, tetrabutylammonium hydrogen sulfate 34.
1mfI and 1,2.4-)lychlorobenzene 3.5
After charging ml, the tube was sealed under reduced pressure while being pulled with a vacuum pump.

Next, it was immersed in a Wood alloy bath and polymerized at 250° C. for 5.5 hours, and then subjected to the same post-treatment as in Example 1, resulting in a soluble polymer with a yield of 50%. The amount of gel produced during polymerization was 2%.

Example 60 Tetrabutylammonium hydrogen sulfate 3 in Example 59
4.1 m, 1 full 15.5- was used instead of 9, and 7 was used instead of 5.5 hours for polymerization time.
The same procedure as in Example 59 was carried out except that the polymerization was carried out over a period of time, and a soluble polymer was obtained in a yield of 18%. The amount of gel produced during polymerization was 2%.

Example 61 3P in a glass polymerization tube with an internal volume of 20 m1 purged with nitrogen
3. Diethyl sulfate and 1,2.4-)lychlorobenzene equivalent to 1.4 mol% based on NC3,5#, 3PNC.
After charging 5 ml, the tube was sealed under reduced pressure while being pulled with a vacuum pump.

Next, it was immersed in a Wood alloy bath and polymerized at 220°C for 6 hours, followed by the same post-treatment as in Example 1. A soluble polymer was obtained in a yield of 38%, and the number of p-cresol substituted polymers was 38%. The average and weight average molecular weights were 50,000-20,000 and 1,070,000, respectively. Note that gel formation during polymerization is as follows: 1.
It was 5%.

Example 62 In Example 61, instead of using diethyl sulfate equivalent to 1.4 mol% based on 3PNC, diethyl sulfate equivalent to 0.6 mol% was used, and the polymerization time was 5 hours instead of 6 hours. When the same operation as in Example 61 was carried out except for the time polymerization, a soluble polymer was obtained in a yield of 42%.

Examples 63 to 67 In Example 61, instead of using diethyl sulfate equivalent to 1.4 mol% based on 3PNC, an apparatus containing various compounds containing a sulfonyldioxy group was used, and 6 When the same operation as in Example 61 was carried out, except that the polymerization was carried out at a predetermined temperature for a predetermined time instead of a time polymerization, the results shown in Table 8 were obtained.

Example 68 Hydrogen sulfate hydrazinium sulfate complex (N 2 H
After charging IISO4.ll2SO4) and 3.5TrLl of 1,2.47) lychlorobenzene, the tube was sealed under reduced pressure while being pulled with a vacuum pump.

Next, it was placed in a wood alloy bath at 220°C for 1 hour at 20°C.
After the partial polymerization, the same post-treatment as in Example 1 was performed, and a soluble polymer was obtained in a yield of 29%.

Example 69 Octachlorocyclotetraphosphazene (4PNC) was added to a 20 yd glass polymerization tube purged with nitrogen.3.
5.9.4 Sulfuric acid and 1,2.4-)IJ dichlorunzene 3.5TrL equivalent to 1.8 mol% based on PNC
1 was charged, and the tube was sealed under reduced pressure while pulling the vacuum pump C.

Next, it was placed on a wood alloy liner at 220° C. and polymerized for 4 hours, and then subjected to the same post-treatment as in Example 1, and a soluble polymer was obtained in a yield of 13%.

Fushimi Example 2 Polymerization was attempted under the same conditions as in Example 55 except that 13.2ml of ammonium sulfate, 9 was used instead of 11.5ml of ammonium hydrogen sulfate, but no polymer formation was observed. There wasn't.

Reference Example 3 In Example 58, hydrogen sulfate (IJum) 12.1 m
Polymerization was attempted under the same conditions as in Example 58, except that 14.3 ml of sodium sulfate was used instead of 1, and the polymerization time was changed to 7 hours instead of 2 hours, but no polymer formation was observed.

% Applicant: Maruzen Petrochemical Co., Ltd. Nippon Sokako Co., Ltd. Procedures Amendment September 90, 1988 Patent Application No. 186164 2, Name of Invention Process for Producing Phosphazene Polymer 3, Amended Relationship with the Patent Applicant’s Case Patent Applicant Address Name Maruzen Petrochemical Co., Ltd. (1 other person) (Name) 4. Agent Showa Month, Day (Voluntary) (1) Line 4 from the bottom of page 16 of the specification Correct "r20 molar ratio" to "20% by weight".

Claims (14)

[Claims] (1) Add a cyclic phosphazene compound represented by (NPCl_2)_y (where y is 3 and/or 4) to the atomic group S
A method for producing a phosphazene polymer, which comprises polymerizing by heating in the presence of a compound containing O_4. (2) The production method according to claim 1, wherein the compound containing the atomic group SO_4 is sulfuric acid or a complex of sulfuric acid and a nitrogen-containing compound. (3) The production method according to claim 2, wherein the nitrogen-containing compound is hydroxylamine, hydrazine, or an oxime compound. (4) Compounds containing the atomic group SO_4 are I of the Periodic Table of Elements
The manufacturing method according to claim 1, which is a sulfate anhydride of metal elements of groups B to VIII and elements of the lanthanide group and actinide group. (5) Metal elements of groups Ib to VIII of the Periodic Table of Elements and elements of the lanthanide group and actinide group include Cu, Mg, and Zn.
, Al, Ti, Zr, Th, Bi, V, Mn, Fe, N
The manufacturing method according to claim 4, wherein i and Ce. (6) Compounds containing the atomic group SO_4 are I of the Periodic Table of Elements
The manufacturing method according to claim 1, which is an anhydrous hydrogen sulfate of metal elements of groups A to VIII and elements of the lanthanide group and actinide group. (7) Compounds containing the atomic group SO_4 are NH_4^+, N
R_4^+ (R represents a substituted or unsubstituted aromatic group, or a straight or branched chain alkyl or alkenyl group), NO^+, N_2H^5^+, N_2H_6^2^
+, NH_3OH^+, C_6H_5N≡N^+, and PH_4^+, which is a hydrogen sulfate anhydride consisting of a cation selected from the group of NH_3OH^+, C_6H_5N≡N^+, and PH_4^+ and a hydrogen sulfate anion. . (8) A compound containing the atomic group SO_4 is N_2H_5^+
, N_2H_6^2^+ and NH_3OH^+ cations and sulfate anhydrides, which are sulfate anhydrides, according to claim 1. (9) Compounds containing the atomic group SO_4 are I of the Periodic Table of Elements
The production method according to claim 1, which is a complex of sulfuric acid or hydrogen sulfate of a metal element of groups A to VIII, a lanthanide group, or an actinide group element, and sulfuric acid. (10) The compound containing the atomic group SO_4 is NH_4^+,
NR_4^+ (R represents a substituted or unsubstituted aromatic group, or a straight or branched chain alkyl or alkenyl group), NO^+, N_2H_5^+, N_2H_6^2
^+, NH_3OH^+, C_6H_5N≡N^+ and PH_4^+ A complex of sulfate anhydride or hydrogen sulfate anhydride of a cation selected from the group of PH_4^+ and sulfuric acid. Manufacturing method described. (11) The compound containing the atomic group SO_4 has the general formula R_1
--O-SO_2-O-R_2 (where R_1 represents an alkali metal, hydrogen, a linear, branched or cyclic aliphatic hydrocarbon group of C_1 to C_1_0, or an aromatic group,
2. The manufacturing method according to claim 1, wherein R_2 is a compound represented by C_1 to C_1_0 (representing a linear, branched or cyclic aliphatic hydrocarbon group, aromatic group, or amino group). (12) Metal elements of groups I a to VIII of the periodic table of elements and elements of the lanthanide group and actinide group are Na, Cu, M
g, Zn, Al, Ti, Zr, Th, Bi, V, Mn,
The manufacturing method according to claim 6 or 9, wherein Fe, Ni and Ce are used. (13) The production method according to any one of claims 1 to 12, wherein the cyclic phosphazene compound is hexachlorocyclotriphosphazene. (14) Hexachlorocyclotriphosphazene under an inert atmosphere at a temperature of 150°C to 300°C with a compound containing 0.01 to 20% by weight of the atomic group SO_4,
The manufacturing method according to any one of claims 1 to 12, which comprises reacting for 0.5 to 50 hours.