JPS6392653A - Production of polyphosphazene - Google Patents

Abstract

PURPOSE:To obtain easily a polyphosphazene having useful characteristics in the fields of medical treatments, electrical components, etc., according to the type of substituents, by reacting a specified polyphosphazene with an alkali metal salt of an alcohol having an oligoalkyleneoxy chain. CONSTITUTION:A polydichlorophosphazene (a), obtd. by polymerizing a cyclic or linear low-molecular chlorophosphazene in a system contg. no water by heating, is reacted with an alkali metal alkoxide (b) to obtain a stable polyphosphazene (A) mainly composed of repeating units of formula I [wherein R1 and R2 are each an aliph. group such as a (halogen-substd.) 1-10C linear satd. hydrocarbon group, etc.]. The component A is reacted with an alkali metal salt of an alcohol (B) having an oligoalkyleneoxy chain (e.g., a chain of formula V), represented by formula II [wherein R3 is a group of formula III (wherein one of R5 and R6 is H and the other is H) and/or a group of formula IV (wherein m is 2-4); n is 1-10; M is an alkali metal; and R4 is a 1-7C org. group] in the presence of a solvent (C) such as an aprotic polar solvent to substitute part or the whole of R1 and/or R2 groups of the component A by the chain of formula V.

Description

[Detailed description of the invention] (a) Industrial application fields The present invention relates to a method for producing polyphosphazenes.

More specifically, after obtaining a stable polyphosphazene by minimizing the reaction time and number of reactions that are difficult to handle during the reaction process, A riboalkyleneoxy chains are introduced into the side chains of the polyphosphazene. This invention relates to a method for producing polyphosphazenes that have desired properties.

(b) Prior Art Polyphosphazene has a main chain consisting only of inorganic elements and is well known as an elastomer with good heat resistance and chemical resistance. It is also well known that polyphosphazenes having excellent properties such as abrasion resistance, oxidation resistance, water repellency, and biocompatibility can be produced by selecting substituents on the side chains.

These polyphosfabins are obtained by reacting polydichlorophosphazene obtained by the reaction shown in the following formula (IV) with various nucleophilic reactants.

(C) Problems that R-ming seeks to solve However, polydichlorophosphazene is extremely difficult to handle during the reaction process, easily hydrolyzed in the presence of moisture, and has insufficient stability. However, there is a disadvantage that the reactor is corroded by the hydrogen chloride that becomes a by-product. Therefore, the conventional method of producing polyphosphazene having excellent properties by reacting unstable polydichlorophosphazene with a nucleophile is not necessarily an industrially preferable method.

(d) Means for Solving the Problem The present inventors aim to reduce as much as possible the time and number of uses of unstable polydichlorophosphazene that has such disadvantages, and to easily produce polyphosphazene that has excellent properties. The present invention was achieved as a result of intensive research to provide a manufacturing method.

That is, the present invention provides the polyphosphazene having the following formula (I>) as a main constituent by reacting it with a compound represented by the following formula (II) in a solvent. I>R
This is a method for producing polyphosphazene imparted with desired characteristics by substituting at least a portion of 1 and/or R2 with O (R30) n R4 at J3 in a compound represented by the following formula (I).

OR+ -P=N-...(I>R2 MO(R30).R busy...value ■) In the method of the present invention, as the raw material (to be treated) polymer, the above general formula (I) is used. A polyphosphazene mainly composed of the repeating units represented by the formula (I) is used, and in this general formula (I), those in which R+ and Rz are linear saturated hydrocarbons having 1 to 10 carbon atoms are preferably used. These hydrogen atoms may be @-substituted by halogen atoms.

Suitable polyphosphazenes used in the method of the present invention include, for example, the following.

0CtlzCF3 MoP=N.

0CH20F3 00 H2O5F? 00 H2C3F7 (QC)-12cF3) yo+P=N+' [However, χ y=2] (OCH
2C3F7 t-1) y OC2Hs OC2Hs These may be homopolymers or copolymers. Furthermore, the side chain may be replaced with another aliphatic group. Furthermore, some side chains are aryloxy groups,
It may be substituted with an amino group or the like.

These polybosphazenes can be easily produced from alkoxide compounds corresponding to polydichlorophosphazenes. For example, polydichlorophosphazene obtained by heating polymerization of cyclic chlorophosphazene or linear low molecular weight chlorophosphazene in a system sufficiently excluded from water, and alkali such as sodium, potassium, libram, etc. obtained from the corresponding alcohol. It is synthesized by reaction with one or more alkoxides.

On the other hand, as a compound used for reacting with the polyphosfavine in the method of the present invention, the compound having the general formula (II>
The general formula (If) is used.
In, R3 is, for example, an edylene group.

Propylene group, tetramethylene group, etc. are preferred, and]
(I is, for example, a methyl group, an ethyl group, a phenyl group.

Preferred examples include t-butyl group and benzyl group.

The type of alkali metal salt of an alcohol having an oligoalkyleneoxy chain represented by the general formula (II>) used in the method of the present invention can be selected as appropriate depending on the properties imparted to the desired product. For example, to obtain a soft polyphosphazene, a long alkyleneoxy group is used.

Further, in the compound represented by the above general formula (II), M is an alkali metal, preferably Na, K,
Li, preferably Na and K.

Such an alkali metal salt compound may be prepared separately in advance, or an alkali metal alone, an alkali metal oxide, an alkali metal hydroxide, or an alkali metal hydrogen may be added to the corresponding alcohol compound during the reaction of the present invention. It is also possible to add compounds such as iJ. for example,
It can be prepared by reacting an alcohol compound such as 2-methoxyethanol or diethyl glycol monomethyl ether with metal zitorium.

In this case, the value (molar ratio) of the alcohol compound/alkali metal of the alkali metal base to be added is suitably 1 or more and 10 or less, and the value of the alkali metal salt of the alcohol compound/alkoxy group to be substituted is 1 or more. A ratio of 30 or less is suitable.

In the method of the present invention, the general formulas (I> and (Ill
By changing the ratio of the polyphosphazene represented by ) and the alkali metal salt compound and causing the reaction, the conversion ratio of the side chain substituents attached to the polyphosphazene produced can be changed at will.

In the method of the present invention, the reaction is carried out by the above general formulas (I> and (I
The substance represented by I) is dissolved in a solvent having no proton-donating group. Such solvents include, for example, hexymethylphosphoramide, N-
Methylpyrrolidone, dimethyl sulfoxide, dimebylformamide, detrahydrofuran, diethyl ether,
Examples include aprotic polar solvents such as dioquinone and diethylene glycol dimethyl ether. However, an aprotic nonpolar solvent such as benzene, toluene, xylene, hex(one, heptane, etc.) may be mixed as long as the substances represented by the above general formulas (I) and (II) can be dissolved together.

As for the solvent composition, it is usually preferable to use one in which the volume ratio of aprotic nonpolar solvent/aprotic polar solvent is 0 or more and 10 or less. ) and (II) can be used if they can be dissolved together.

In addition, when the substance represented by general formula (II) is soluble in a solvent, it is effective to use a phase transfer catalyst such as tetra-n-butylammonium bromide.

In this way, polyphosfabins having oligoalkyleneoxy groups in their side chains are produced.

d3. In the method of the present invention, metal salts such as lithium perchlorate, silver trifluoromethanesulfonate, etc. are uniformly dissolved or dispersed in polyphosphazene having an oligoalkyleneoxy chain in the side chain (q). An ionic conductor can be obtained by this method.

(e) As described in the detailed description of the invention, in the method of the present invention, stable polyphosfavines can be processed by ffi treatment with an alkali metal salt of a specific alcohol compound by reducing the time and number of uses of unstable polydichlorophosphazene. By doing so, it is possible to produce a polyphosphazene in which at least a portion of the side chain is substituted with an oligoalkyleneoxy group and has various properties depending on the substituent.

Conventionally, when polydichlorophosphazene is always used as a raw material to introduce various side chains for the purpose of functionalizing polyphosphazene, there is not only a great possibility of crosslinking and hydrolysis, but also a problem with the reaction equipment. There are problems such as corrosion, and the reaction process is extremely difficult to handle. However, in the method of the present invention, such a difficult reaction is required only in the first step, so the above-mentioned problems are significantly alleviated. That is, after the polyphosphazene represented by the above general formula (I) used as a starting material in the method of the present invention is produced manually from polydichlorophosphapine and an aliphatic alkoxide, the necessary polyphosfavine is produced when necessary. By reacting with a compound represented by the above general formula (I[>), polyphosphazenes having various functions can be easily produced with relatively easy handling.

The polyphosphazene thus obtained can have various properties by selecting the substituents introduced, so it can be applied to a wide range of fields such as medical use, electrical parts, and the chemical industry.

(f) Examples Hereinafter, the present invention will be explained in more detail with reference to Examples 16.
The present invention is not limited to this.

Example 1 13.3 () of 2-methoxyethanol and 1.9 g of metal Jtrium were reacted in 50 d of tetravitrofuran, and a solution of 10 g of polybis(trifluoro[111-xy)phosphazene in tetrahydrofuran (20 d of tetrahydrofuran) was added to the reaction. ) was added dropwise at room temperature and reacted for 3 hours under reflux of tetrahydrofuran (1 franc). After returning the reaction system to room temperature, the contents were poured into a large amount of water and neutralized with dilute sulfuric acid, and the reaction started. At the time, 7.72 (l) of polyphosfavine in which all trifluoroethoxy groups of polyphosphazene were substituted was 7.72 (l).

The infrared absorption spectrum of this polyphosfabin is 290
A characteristic absorption was observed near Ocnrl. The substitution rate is calculated based on the triflu J r present in the aqueous solution after the completion of the substitution reaction.
] The concentration of ethanol was determined by measuring with gas chromatography.

Example 2 A solution of polybis(trifluoro]nidoxy>phosphazene 10 (J) in tetrahydrofuran was reacted with diethylene glycol 7-methyl needles 20 (l) and total sodium chloride (1.99 g) in 507 g of trihydrofuran.
After dropping 20 ml of tetrahydrofuran at room temperature,
The reaction was carried out for 3 hours under reflux of tetrahydrofuran. After returning the reaction system to room temperature, the contents were poured into a large amount of water and neutralized with dilute sulfuric acid, resulting in polybosphazene with 97% substitution of all trifluoroethoxy groups of polyphosphazene at the start of the reaction. ) obtained.

The infrared absorption spectrum of this polyphosfabin is 2',
) A characteristic absorption was observed near OOcm-1. Note that the substitution rate was determined in the same manner as in Example 1.

Hand r%c Ne City Ding E Rod" November 1985) tEI 't:s "A /'J'-L's Miomi 't'a'
Relationship between f1 and the person making the amendment Patent applicant 11, Minamihonmachi, Higashi-ku, Osaka (300) Teijin Ltd. Representative Okamoto Sashibe tJ0 agent Chiyo, Tokyo [1-ku Uchisaiwai-cho, 1st ward] 2C1] No. 1 No. 1, Sleeve 1F, subject specification i (Claims column and I Detailed Description of the Invention column 6, contents of N+njE (I) Specification [ Particularly, amend jjl of ``Claims'' as shown in the attached sheet.

(2) I of Specification Lagoon No. 4 Tei No. 18 fi (2 lines from the bottom ['')
' O(R30) n RJ is "(RaO) n
R4J and supplementary.

(3) rMo in the 5th line of the specification (10th to 14th line)
(R30) n R4-...(II) J
1'MO(t<30) n R4-・'' (I
I) Correct as J.

Above (Attachment) 111 True Claim 1) The following 'i((
By reacting with a compound represented by If ), the polyphosphazene is reacted with the following formula (■)
and/or at least a part of R2 is substituted with a compound represented by the above formula (II) with (rbO) n r<4.

01ku1 ■ -1) -N-・・・・・・(,T > MO(RaO) n R4-・・・・・・(I■〉2)
Special feature that uses aprotic polar and [4 solvents as solvents! ]
Claim 1) The packaging method described in claim 1).

Claims (1)

[Scope of Claims] 1) A polyphosphazene containing a repeating unit represented by the following formula (I) as a main component is prepared by preparing a polyphosphazene containing the following formula (I) in a solvent.
By reacting with the compound represented by I), at least a part of R_1 and/or R_2 of the following formula (I) in the polyphosphazene is replaced with O(R_3O)_nR_4 in the compound represented by the following formula (II). A method for producing polyphosphazene, characterized by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [However, R_1 and R_2 are the same or different aliphatic groups, and may have a substituent. ]MO(R
_3O)_nR_4-...(II) [However, R_3 is a group represented by -CR_5R_6CR_7R_8- (herein, R_5, R_6, R_7, R_8
is a group in which one is a methyl group and the others are hydrogen atoms), and/or a group represented by -(CH_2)-_m (where m is 2 to
n is an integer of 1 to 10, M is an alkali metal, and R_4 is an organic group having 1 to 7 carbon atoms. 2) The manufacturing method according to claim 1), in which an aprotic polar solvent is used as the solvent.