JPS6013815A - Preparation of condensed polyalkoxyphosphazene - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as an imparter for providing an organic high polymer compound with fire resistance, heat resistance, etc., by heat-treating in the presence of a metal compound phosphonitrilic chloride which is partially alkoxylated with an alcohol or metal alkoxide. CONSTITUTION:Phosphonitrilic chloride which is partially alkoxylated with an alcohol or a metal alkoxide (preferably 1-7C in both the compounds) is heat- treated in the presence of a metal compound (e.g., metal oxide such as zinc oxide, cuprous salt such as CuCl, nitrogen-containing metal complex such as copper ethylenediaminetetraacetate) (usually 1-1.5 equivalent metal compound is used based on remaining active chlorine) under preferably 5-350mm.Hg reduced pressure at 5-150 deg.C for 1/4-20hr, to give the desired compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing condensed polymeric alkoxyphosphazenes.

Polymeric alkoxyphosphazene (polyalkoxyphosphazene) is a compound in which an alkoxy group is introduced as an organic substituent into an inorganic cyclic or linear skeleton consisting of phosphorus and nitrogen, and it is used to improve compatibility with various organic polymer compounds. Substituents can be selected appropriately, and it can be used as an additive to impart flame resistance and flame retardancy to organic polymer compounds, or to utilize its chemical stability, low-temperature properties, lubricity, electrical properties, etc. The compound is also useful for other applications.

For example, a method for producing flame-retardant fibers using polyalkoxyphosphazene is already known in Japanese Patent Publication No. 46-40489, but since then it has been improved to have a P-0-P bond as an excellent flame retardant with a smaller amount of addition. Condensed polyalkoxyphosphazenes have been studied and various methods have been proposed.

A representative example of these methods is the special public tJa 55-1
No. 7772, Special Publication No. 31577, Special Publication No. 58-
There are methods described in No. 4000, etc., but in these methods, the physical properties of the product may not be controlled beforehand.
It has been difficult to easily obtain a target product with favorable physical properties industrially.

Specifically, in Japanese Patent Publication No. 55-17772, a complete alkoxy compound is once produced using a tertiary amine, and then this is again mixed with a halogenated phosphonitrile oligomer of 50 to 2 oo
℃, and Japanese Patent Publication No. 57-31577 describes a method in which a partial alkoxy compound is produced and then treated at a temperature of 20°C or higher in the presence of a tertiary amine. Although various improvements have been made to reaction conditions and production processes to suppress excessive polycondensation caused by tertiary amines, it is difficult to maintain a constant viscosity and molecular weight of the product.

The present inventor completed the present invention as a result of intensive research in view of the above points.

The present invention is a method for producing a condensed polyalkoxyphosphazene, which is characterized by heat-treating chlorinated phosphonitrile partially alkoxylated with an alcohol or metal alkoxide in the presence of a metal compound.

The condensed polyalkoxyphosphazenes produced by the method of the present invention are substantially water-insoluble and neutralized, and can be incorporated into fibers (e.g., regenerated cellulose fibers) or textile products in effective amounts. It can be made flame resistant, and at the same time it can improve the yield in the fiber manufacturing process and the rewashability of textile products. Further, the condensed polyalkoxyphosphazene of the present invention is stable and inactive against strongly basic viscose, and is also stable and inactive against acid baths in which the viscose is extruded. Furthermore, it is not extracted during the spinning and post-processing steps, and does not cause problems in the spinning process such as clogging of the yarn opening.

The phosphonitrile chloride used in the present invention is not particularly limited; for example, JP-A-5, I-145394;
．． -145395, cyclic phosphazene oligomers containing a large amount of 3-4M isomers described in JP-A No. 58-4+889, linear phosphazene oligomers described in JP-A-54-143796, and these cyclic and linear phosphazene oligomers. Examples include mixtures, crude products thereof containing impurities, purified products of cyclic phosphazene trimers, and cyclic phosphazene oligomers containing a large amount of trimers and tetramers are particularly preferred.

The alcohol used in the present invention is also particularly limited, and includes, for example, aliphatic saturated alcohols having 1 to 12 carbon atoms such as methanol, ethanol, propenol, butanol, hexanol, octatool, and dotecanol, allyl alcohol, and methylbenzene. Aliphatic unsaturated alcohols such as tenol,
6 carbon atoms such as phenol, cresol, substituted phenol, etc.
~12 aromatic alcohols, aralkyl alcohols such as benzyl alcohol, alicyclic alcohols such as cyclohexanol, halogenated alcohols such as trifluoroethanol and bromophenol, furfuri Jl/7 l:
l-/l/'4 heterocyclic alcohol fx Tono I
For example, alcohols with a valence of 92 and 92 may be used. Further, the above alcohol may be substituted with halogen.

Examples of metal alkoxides include alkali metal salts and alkaline earth metal salts of the above-mentioned alcohols. Among these alcohols and metal alkoxides, those having 1 to 7 carbon atoms are preferred.

The method of carrying out the method of the present invention includes the above-mentioned phosphonide chloride.
A partially alkoxylated or allyloxylated chlorinated phosphonitrile oligomer (hereinafter referred to as partially alkoxyphosphacene) obtained from lyl and an alcohol or a metal alkoxide is heat-treated in the presence of a metal compound to determine its molecular weight and viscosity. An increased condensed polyalkoxy or allyloxyphosponitrile oligomer (hereinafter referred to as condensed alkoxyphosphazene) is obtained.

The heating temperature is approximately 5-. Approximately 5-150 to 200″c1Mj-
"c" is preferable, and the heating time varies depending on the temperature, required physical properties, etc., but may generally be 1/4 to 20 hours or more.The reaction can be carried out at normal pressure or under reduced pressure, and in particular, about 5 It is preferable to carry out the reaction under a reduced pressure of ~350 mmHy. The partial alkoxyphosphazene obtained above may be a condensed or non-condensed partial ester, and the residual active chlorine concentration is preferably 1 to 16% by weight. %.

Examples of the metal compound used in the present invention include metal oxides, cuprous salts, nitrogen-containing metal complexes, and the like. Suitable metal oxides include zinc oxide, cuprous oxide,
Examples include calcium oxide, silver oxide, and sodium oxide. Preferred cuprous salts include cuprous halides such as cuprous chloride and cuprous bromide, cuprous sulfate, cuprous tartrate, and the like. More suitable nitrogen-containing metal complexes include, for example, 4R ammonium metal complexes such as tetraethylammoniumtetrachlornickel and tetraethylammoniumtetrachlorcopper, zinc dichlordipyridine, copper ethylenediaminetetraacetate, and the like.

The amount of these metal compounds to be used is not particularly limited, but is generally used in an amount of 0.1 equivalent or more, preferably 1 equivalent or more, based on the remaining active salt □, and a range of 1 to 15 equivalents is particularly preferred.

It has been confirmed that the metal oxide used in the present invention reacts with the residual active chlorine of the partial alkoxyphosphazene to form a metal chloride, and the oxygen atoms in the resulting p-6-1) bridge originate from the metal oxide. It is considered that In addition, nitrogen-containing metal complexes are used to coordinate nitrogen compounds such as bosphazene to metals, and control the electronic state of the nitrogen compounds to efficiently carry out the desired reaction.
Side effects of this complex formation include simplification of separation operations due to decreased solubility, lower cost of equipment materials due to the neutral pli of the reaction system, and reduction of odor and exposure due to the low vapor pressure of the complex. It is highly effective in industrial production.

The condensed alkoxyphosphazene obtained by the method of the present invention is dissolved in an organic solvent with low solubility in water, such as 1.1.2-trichlorotrifluoroethane (Freon 113), and insoluble materials are removed separately. Afterwards, if necessary, the product can be purified by adjusting the pH, washing with water, and removing the solvent from the separated organic solvent phase. The obtained object is GP
The degree of condensation is measured by C analysis, the amount of residual active chlorine is measured by titration, and other physical properties such as viscosity and average molecular weight are used.

Examples will be described below, and % simply indicates weight %. In addition, residual active chlorine was determined by silver nitrate titration method.
The number average molecular weight was measured by the VPO method, the acid value was measured by the alkaline titration method, and the viscosity was the value at 25°C.

Example 1 650 ml of xylene was charged into 21 four-way flasks equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel.
Addition of 437 g of sodium metal and 126 g of n-propertool at a temperature of 102-115°C. was added dropwise over 1 hour. After the dropwise addition, alcoholade was prepared by reacting at 108 to 109°C for 1 hour. Next, chlorinated phosphonitrile oligomer (trimer 495%
, tetramer 17.9%, 5 or more bodies 243%, linear objects 83
%) 40% monochlorobenzene solution 290? (1 unit mole of phosphonitrile) was added dropwise over about 1 hour at a temperature of 108 to 129°C. After that 120~+30
After reacting at 'C for 5 hours and removing excess alcohol at 60℃ or less under reduced pressure, 800ml of toluene was added and 400ml of toluene was added.
The mixture was washed with rnl of water and washed nine times with sodium sulfate solution to adjust the pH to 7 to 8, followed by dehydration and concentration to obtain a slightly yellow product 142.79. The residual active chlorine in the reaction product was 1.44.

7f of powdered zinc oxide was added to this reaction mixture, and the reaction was stirred at 0 120'C for #4 hours. After the reaction,
The mixture was dissolved and extracted with 300 ml of toluene, and insoluble matter was filtered out, followed by washing three times with 200 ml of water. The toluene layer was dehydrated with magnesium sulfate and concentrated to obtain a slightly yellow viscous liquid 1332.

The residual active chlorine in the reaction product was determined to be 0.45% by silver nitrate titration method.
The average molecular weight is 1260 and the viscosity is 3750 cp.
It was s. Also, the acid value is B, 3 mgK, OH/f
There was a time.

GPC1IR analysis confirmed the condensation status and the presence of po-op bonds.

Example 2 N-propanol 18 (1 (8 mol)) and potassium carbonate 1'52F (1
, 1 mol) and stirred uniformly at about 50°C.

Next, phosphonitrile chloride oligomer (
Trimer 733%, tetramer is, a%, pentamer or more 5.3
%, linear substance 31%) of 4096 monok 50 lebenzene solution 29Of (1 unit mole) was added dropwise over about 2/3 hour, and 9
After raising the temperature to 35°C, the reaction was carried out at 93.5 to 95°C for 5 hours. Residual active chlorine in reaction product is 14-5%
After confirming that the grains are within the specified range, the
Excess n-propanol, monochlorobenzene, and water produced by the reaction were distilled off at 0 to 90°C over about 2 hours. The increase in molecular weight of this product was confirmed by GPC analysis, and the presence of a P-0-P bond was confirmed from the absorption of 9 (35m-') by IR analysis, and it was confirmed that it was a condensed partial alkoxyphosphazene.

Add 97f cupric oxide powder to this, and
The reaction was stirred at C for 5 hours. After the reaction, 300 d of toluene was added to dissolve it, and insoluble cupric oxide was removed in a furnace, followed by washing with 200 ml of diluted ammonia water, followed by water washing. The liquid was separated to obtain 116f. The residual active chlorine of the reaction product was m%, the average molecular weight was 1340, the viscosity was 4'' TOO cps, and the acid value was 52 ■KOH/y.

Example 3 Partial alkoxyphosphazene 142.79 containing 14% residual active chlorine obtained in the same manner as in Example I was added with powdered oxidized first
7 tons of copper was added, and the reaction was stirred at 120°C for 10 hours. After the reaction, add 800 ml of toluene and dissolve.
After removing the excess cuprous oxide, add 200 g of dilute ammonia water.
ml, followed by water washing, dehydration, and concentration to obtain 1BOf of brown viscous liquid.

The residual active chlorine of the reaction product is 0.17%, the average molecular KO
It was H/f.

Example 4 Using black powder 10f of silver oxide, reaction and post-treatment were carried out in the same manner as in Example 3 to obtain a pale yellow viscous liquid 1282.

The residual active chlorine of the reaction product is 0.25%, the average molecular weight is 1180, the viscosity is 3205 cpSv, and the acid value is 77 KOH.
/f.

Example 5 A reaction was carried out in the same manner as in Example 3 using powdered calcium oxide 52. After one reaction, 300 ml of toluene was added to dissolve it, ice water was added to digest excess calcium oxide, and it was neutralized with dilute hydrochloric acid. After that, the mixture was washed with water, dehydrated, and concentrated to obtain 125f of a yellow viscous liquid. The residual active chlorine of the reaction product is OJI%, and the average molecular weight is 1170. The viscosity is 3
245CI) S% acid value was 79 ■KOH/f.

Example 6 Trimer 61.4% as chlorinated phosphonitrile oligomer
, tetramer 10.9%, pentamer or more 20.1%, m-shaped substance 7
．． Partial alkoxyphosphazene 1, which is a reaction intermediate, was prepared in the same manner as in Example 1, except that 4096 monochlorobenzene liquid 291 (1 unit mole) having a composition of 6% was used.
I got 352. This product was a slightly yellow liquid with a residual active chlorine content of 1.21% and a viscosity of 1340 cps.

This reaction intermediate 185f and cuprous chloride 675f were mixed at 120
The mixture was heated and stirred at ±5°C for 10 hours. After the reaction was completed, 200 ml of monochlorobenzene was added to dissolve the product.

This was washed repeatedly with 100 ml of diluted sodium sulfate solution. 5 of anhydrous sodium sulfate was added to the thoroughly washed organic layer, and the mixture was left to stand for 5 hours for dehydration. After filtering the organic layer, the furnace liquid was
Monochlorobenzene was distilled off under reduced pressure of s+5tHf. After concentration and degassing, the product obtained was a yellow liquid with a yield of 126 f. The residual active chlorine in the reaction product is 0.
．． 42%, and the viscosity was 3800 cps.

The average molecular weight of this product was 1240. Moreover, in addition to the characteristic absorption such as -P=N-1P-0-C, an absorption based on 1)-0-P was confirmed near 9 aocmh from the spectral analysis. Estimating from the above molecular weight and IR spectrum, the reaction product has an average of about 82
It is a condensate of polyalkoxyphosphonitrile having a P-0-P bond corresponding to the polymer.

Example 7 A reaction intermediate was obtained in the same manner as in Example 1. The monochlorobenzene used for extraction was concentrated to a concentration of about 3%. The residual active chlorine of the intermediate was 1.26%. Reaction intermediate (containing 3 monochlorobenzene) and cuprous bromide 8
．． 52 was heated and stirred at 120±5°C for 10 hours. After the reaction was completed, 200 ml of monochlorobenzene was added to dissolve the product. This 50f of anhydrous sodium sulfate was added and left to stand for 5 hours for dehydration. - After filtering the organic layer, monochlorobenzene was distilled off from the p solution under reduced pressure of 1 gastric wHf. After concentration and degassing, the product obtained was a yellow liquid with a yield of 1261. The residual active chlorine in the reaction product is 0.
．． 4196, and the viscosity was 8650 cps.

The average molecular weight was 1200. Moreover, from IR spectrum analysis, -P=N-, P-0. In addition to characteristic absorptions such as -C, absorption based on P-0-P was confirmed near 960α. As estimated from the molecular weight and IR spectrum below, the reaction product is a polyalkoxyphosphonitrile condensate having po-o-p bonds corresponding to an average of about 8.0 mer based on PN units.

Example 8 Trimer 61.4% as chlorinated phosphonitrile oligomer
, Tetramer 10.9%, Pentamer or more 20.1%, Linear 7
．． 40% monochlorobenzene solution 2 with a composition of 6%
Partial alkoxyphosphazene 1, which is a reaction intermediate, was prepared in the same manner as in Example 2 except that 9Of (1 unit mole) was used.
I got 29f. . This product was a slightly yellow liquid with a residual active chlorine content of 145%.

Add cuprous chloride 1051 to this reaction intermediate and hold at 120°C.
The mixture was heated and stirred for 10 hours. After the reaction was completed, 200 ml of monochlorobenzene was added to dissolve the product. Add this to 1 part of water
Washing was repeated once with 00 ml. Anhydrous sodium sulfate (502) was added to the thoroughly washed organic layer, and the mixture was left to stand for 5 hours for dehydration. After filtering the organic layer, add 1 ml of HfI
Monochlorobenzene was distilled off under reduced pressure. The product obtained after concentration and degassing was a yellow liquid with a yield of 847 ml. The residual active chlorine of the reaction product was 0.48%, and the viscosity &
r1.4800cps. The average molecular weight of this product was 117Of.

Estimating from the molecular weight and the spectra, the reaction product is P- corresponding to an average of about 7.8 mer based on PN unit
It is a condensate of polyalkoxyphosphonitrile having a 0-P bond.

Example 9 Condensed partial alkoxyphosphazene 125f? obtained in the same manner as in Example 8? 11.5 t"i of cuprous sulfate was added to the solution, the reaction was carried out at 120°C for 5 hours, and the same treatment was carried out.
Light yellowish brown viscous liquid 82? I got it. The residual active chlorine of the product is 0.61%, the average molecular weight is 1230, and the viscosity is 299.
It was 5 cps.

Example 10 31 phosphonitrile chloride oligomers 61.4%
, 4I form 10.9%, pentamer or more 201%, linear substance 7.
40% monochlorobenzene solution with a composition of 6% 29
Partial alkoxyphosphazene 14, which is a reaction intermediate, was prepared in the same manner as in Example 1 except that 0P (1 unit mole) was used.
I got 17. This product was a slightly yellow liquid with a residual active chlorine content of 126% and a viscosity of 1130 cps.

Separately, add nickel chloride 1o4r (o, os mol) to
-11/ 80 ml, add 26.4s'(0,16-E:#) of tetraethylammonium chloride to
- Jl/80 ml Nisoh was dissolved, and both solutions were mixed and boiled for 15 minutes.

After the reaction, the ethanol used as a solvent was distilled off using a rotary evaporator to perform concentration. The blue crystals precipitated in the solution were separated by filtration and dried overnight under reduced pressure. After drying, 28 blue crystals were obtained. As a result of chlorine analysis of this product, the chlorine content was 30
．． It was 5%. This is C(C2I-15)4 N
[2 CN i C14] (7) Chlorine content 30.8'
7 and was found to be a 2:1 complex of tetraethylammonium chloride and nickel chloride.

Next, a condensation reaction of the compound synthesized above was carried out. The reaction intermediate + 41y Yoshitetraethylammonium tetrachloronickel (IJ) complex salt 2311 was heated and stirred at 120±5°C for 5 hours. After the reaction, monochlorobenzene 2
00 ml was added to dissolve the product.

This was washed repeatedly with 100 ml of diluted sodium sulfate solution once. 50 ff of anhydrous sodium sulfate was added to the thoroughly washed organic layer and left for 51 hours to dehydrate. After passing through the organic layer, the furnace solution was heated to 1 mH'? Monochlorobenzene was distilled off under reduced pressure. After concentration and dehydration, the product obtained was a yellow liquid with a yield of 1312. The residual active chlorine of the reaction product was 0.38%, and the viscosity was 3050 cps. The molecular weight of this product was 1200. Also I
From the R spectrum analysis, in addition to characteristic absorptions such as -P=N-1p-o-c, absorption based on P-0-P was confirmed near 960-01 arr.

Estimated from the above molecular weight and IR spectrum, the reaction product is a polyalkoxyphosphonitrile condensate having a P-0-P bond corresponding to an average of about octamer based on the PN unit.

Example 1 In the same manner as in Example 10, 1451 reaction intermediates were obtained. The residual active chlorine of this product was 1.42%.

Separately, cupric chloride CuCl2 ・21-120 13.6
9 (0.08 mol) in 80 ml of ethanol, (C2■15)4NCβ・I(20294F(0.16
mol) in 80 ml of ethanol, boiled for a while and then cooled. The resulting precipitate was separated and dried under reduced pressure overnight. Thus, the yellow crystals of 3241 tetraethylammonium tetrachlor M (II) complex C(C2115,)4Nl:+2 CCuC14) wo(n k.

Next, a condensation reaction of the compound synthesized above was carried out. Reaction intermediate 14! M and 270 ml of tetraethylammonium tetrachlorocopper(1) complex salt were subjected to a heating reaction at 100±5°C for 3 hours, and then treated in the same manner as in Example 10. The obtained product was a yellow liquid and the yield was 1357. The residual active chlorine of the reaction product was 0.33% and the viscosity was 2900 cps.

Moreover, the average molecular weight was 1210. IR spectrum analysis reveals an absorption based on P-0-P near 960 cm +j, and inferring from the above results, the reaction product is P-0, which corresponds to an average of about 81-mer based on the PN unit.
It is a condensate of polyalkoxyphosphonitrile having a -P bond.

Example 12 1392 reaction intermediates were obtained in the same manner as in Example 1'0. The residual active chlorine of this product was 136%.

Separately, cupric chloride CuC4・2H2013,617' (
0.08 mol) was dissolved in 80 ml of ethanol, 28.4 f (0.2'8 mol) of triethylamine was added dropwise to the solution, and after boiling for a while to complete the reaction, the reaction solution was depressurized. The mixture was concentrated to dryness. The temperature at this time was 40
The reaction was carried out at a temperature below .degree. C. and brown crystals of 184 f were obtained.

Next, a condensation reaction of the compound synthesized above was carried out. Reaction intermediate 1391 and triethylamine copper chloride (ID complex salt 1
502 was subjected to a heating reaction at 100±5°C for 3 hours, and then treated in the same manner as in Example 10. The product obtained was a yellow liquid and the yield was 1292. The residual active chlorine of the reaction product is 0.29%, and the viscosity is 3250 c.
It was ps. Moreover, the average molecular weight was 1260. ■
From the spectral analysis, 960 (JJr)
Absorption based on 0-P was confirmed. Estimating from the above results, the reaction product is approximately 84% on average based on PN units.
1) Corresponding to a shoulder body, it is a condensate of polyalkoxyphosphonitrile having a -0-P bond.

Example 13 Trimer (31,4
Same as Example 2 except that 290 liters (1 unit mole) of a 40% monochlorobenzene solution with a composition of 10.9% tetramer, 20.1% pentamer or higher, and 76% linear material was used. and the reaction intermediate partially alkoxyphosphazene 129? I got it. This product was a slightly yellow liquid with a residual active chlorine content of 14.5%.

Tetraethylammoniumtetrachlornickel (If
) Complex salt 243f was added and heated and stirred at 120±5"C for 2 hours. After the reaction was completed, 200T of monochlorobenzene was added.
! 1 was added to dissolve the product, and the product was washed repeatedly with 100 ml/time of diluted sodium sulfate solution. Anhydrous sodium sulfate (507) was added to the thoroughly washed organic layer, and the mixture was left to stand for 5 hours for dehydration. After filtering the organic layer, monochlorobenzene was distilled off from the p solution under reduced pressure of 1 mmHf. After concentration and dehydration, the resulting product was a yellow liquid with a yield of 85 grams. The residual active chlorine of this product is 0.36%, and the viscosity is 4400 c.
It was ps. The average molecular weight of this product was 1,250. Estimated from the average molecular weight and I, R spectrum,
The reaction product is a condensate of polyalkoxyphosphonitrile having a P-0-P bond corresponding to an average of about 83 mers based on PN units.

Example 14 Trimer 61.4% as chlorinated phosphonitrile oligomer
, 109% tetramer, 20.1% 5M or more, linear 7.
4096 monochlorobenzene solution 2 with a composition of 6%
Partial alkoxyphosphazene 1, which is a reaction intermediate, was prepared in the same manner as in Example 2 except that 901 (1 unit mole) was used.
I got 321. This product was a slightly yellow liquid with a residual active chlorine content of 9.7%. This reaction product contains dichlordipyridine zinc 50F synthesized from pyridine and zinc chloride.
was added and the reaction was carried out at 100°C for 5 hours. After the reaction, the complex was dissolved in 300 ml of benzene, and the precipitated complex was filtered, washed with sodium sulfate three times, dehydrated, and concentrated to obtain a slightly yellow viscous liquid 992.

The residual active chlorine of the product is 0.40% and the viscosity is 4245
The Cp5% average molecular weight was 1270.

(Above) Patent applicant Otsuka Chemical Co., Ltd. Agent Patent attorney stamp material Iwao procedural amendment (spontaneous) August 22, 1981 Patent application No. 122100 2, title of invention Manufacture of condensed polyalkoxyphosphazene Law 3, Relationship with the case of the person making the amendment Patent applicant Otsuka Chemical Co., Ltd. 4, Agent section

Claims (1)

[Claims] (+) A method for producing a condensed polyalkoxyphosphazene, characterized in that phosphonitrile chloride partially alkoxylated with an alcohol or a metal alkoxide is heat-treated in the presence of a metal compound. (2) The method according to claim 1, wherein the partially alkoxylated phosphonitrile chloride is a condensed partially alkoxy phosphonitrile chloride. (3) The method according to claim 1 or 2, wherein the residual active chlorine concentration in the partially alkoxylated phosphonitrile chloride is 1-16% by weight. (4) The method according to any one of claims 1 to 3, wherein the alcohol or metal alkoxide has 1 to 7 carbon atoms. (5) The method according to any one of claims 1 to 4, wherein the heat treatment is performed under reduced pressure. (6) Claim 1 in which the metal compound or substance is a metal oxide
5. The method according to any one of items 5 to 5. (7) Claims 1 to 5, wherein the metal compound is a cuprous salt.
The method described in any of the paragraphs. (8) The method according to any one of claims 1 to 5, wherein the metal compound is a nitrogen-containing metal complex.