JPS5817124B2 - (NPCl↓2)↓Production method of x-linear polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in the production of cyclic trimer (NP Ct2 )3 or other low molecular weight dichlorophosphazene oligomers or substantially linear (NPCl2)X polymers.

For example, U.S. Patent No. 3,370,020 (1968
In the known practical process, as described in U.S. Pat. No. 515,688 (issued June 2, 1970),
And in March 1974, Si enti fic Am
Benzene-insoluble gels are formed which are unacceptable for the production of useful products such as those described in the literature published on Erican and also in the literature on polyphosphacenes.

The published prior art describes efforts made to prevent the formation of benzene-insoluble gels and increase the percent conversion of cyclic trimers to soluble linear polymers.

Control of the molecular weight of linear polymers is the subject of much research as well, as the properties of the final derivatives are often altered thereby.

The main objective of the present invention is (NPCl2) n (n = 3
to 9) cyclic oligomers, mainly trimers and tetramers to benzene-soluble substantially linear (NPCl, 2) x polymers (x
>20) in high yield and without the formation of benzene-insoluble gels, the linear polymer products obtained having molecular weights and viscosities in the desired range.

Another object of the present invention is for the polymerization of differential or normally non-polymerizable cyclic low molecular weight (NPCl2)n oligomers to produce substantially linear (NPCl2)x polymers of desired molecular weight in high yields. The purpose is to provide a catalyst.

These and other objects will become clearer from the description below.

The data shown in Table 1 below was calculated as follows (NP
It was obtained by polymerizing Ct2)3.

The indicated weight of Crcls or other salt was added to 25 g of purified hexachlorocyclotriphosphazene (NPCl2) purified by recrystallization from hexane, and the mixture was charged to a glass polymerization tube, which was then evaporated under reduced pressure. The charge was heated to melt, cooled, again subjected to vacuum, cooled and then sealed, after which the sealed tube was heated to 250°C and held at this temperature for the number of times shown in Table 1. .

After completion of this experiment, the tube was opened to remove unreacted cyclic oligomer and the dilute solution viscosity, % gel, and % conversion of the substantially linear (or polymeric) product was measured.

The results are shown in Table 1.

In Table 1, 1 to 3 and 9 to 13 are comparative examples.

Also, percentages are based on weight.

Although not wishing to be bound by a specific explanation as the difference between the effects of hydrated compounds and the effects of anhydrous compounds, hydrates act as a source of water and therefore February 10, 1976 It appears to catalytically activate the polymerization as described in U.S. Pat. No. 3,937,79Q, issued by Japan.

When this is correct, the hydrated metal salt provides a very easily controlled means of introducing small amounts of water into the polymerization reaction.

From the data in Table 1, % conversion is usually lower in the absence of modifier than when it is present, and similarly, aqueous salts are more effective than non-hydrated salts in increasing % conversion. It is.

As also shown, polymers made in the presence of such modifiers exhibit lower dilute solution viscosity (DSV) than polymers made in the absence of such modifiers.

This provides significant advantages in the processing and use of such polymers.

A small amount of glue (3% by weight) does not adversely affect the subsequent induction.

A large amount of gel, such as the 16.5% by weight obtained in the control experiment, is not good for subsequent induction.

Other metal halide salts that can be used in place of chromium chloride include the following metals: Nj, Co, Cu, Mn,
Fe.

and Mg halide salts, with particularly preferred salts being metal chloride hydrates.

The amount of such inorganic metal halide salt used as a modifier in the polymerization process will vary somewhat.

Thus, approximately 0.00 based on the weight of the cyclic oligomer.
2 to about 0.50% by weight of such modifiers are commonly used, with a preferred range of 0.005 to 0.20% by weight.
It is.

The purity of the cyclic starting material (NPCt2)3 influences the effectiveness of the metal halide.

In the past, very pure trimmer (NPCt2)
In an attempt to thermally polymerize 3, it was found that some batches did not polymerize appreciably even after prolonged heating to 250°C.

Thus, the terms "slow" or "generally non-polymerizable" as used herein refer to cyclic oligomers that have a substantially higher degree of purity than those commonly used in polymerization processes.

Table 2 shows that such substances contain a small amount of Cr C-1s 6H2
The catalytic effect obtained by adding 0 is shown.

In Table 1, 1 to 4 are comparative examples.

Also, percentages are based on weight.

Tables 111(a) and 111(b1) show the effect of various other metal halide salts on the polymerization of cyclic trimers.

The desired influence on viscosity or molecular weight is clear.

However, the data in these tables shows that in some instances the polymerization rate (measured in % conversion) for polymers made with a modifier is similar to that of a polymer made without a modifier. It can be seen that the comparison has decreased.

This is due to the fact that the starting trimer used in these evaluations is less pure and thus polymerizes faster than the trimer used in the above examples;

Table ■1 and 11I (by, additives "none" and "
The one with Cu Cl 2 J is a comparative example.

Also, percentages are based on weight.

NH4Ct and pcz as described in Canadian Patent No. 614,267 (issued February 7, 1961).

The use of anhydrous metal salts to catalyze reactions between and thereby where (NPCt 2 )3 and other low molecular weight poly(dichlorophosphazenes) are products is not to be confused with the present invention.

That is, the product of such a step is the starting material of the process of the invention, and the product is to be polymerized (NP Ct 2 ).
n substantially linear C where the desired X is achieved by monitoring the amount of metal salt added to the cyclic oligomer
Ct2) x product.

Claims (1)

[Claims] 1 Formula (JJP(M2) n (where n is 3 to 9
a cyclic oligomer having an aqueous inorganic metal halide salt selected from the group consisting of nickel, cobalt, chromium, magnesium, copper, iron and manganese.
．． of the formula (NPCA2) x (where X
is 20 to 50,000). 2 The cyclic oligomer is (NPCl2)3 or (NPC
The method of item 1 above, in which there are t2 people. 3. The method of item 1 above, wherein the metal halide salt is a hydrated metal chloride. 4. The method of item 1 above, wherein the halogen of the metal halide salt is selected from the group consisting of chlorine, bromine, iodine and fluorine. 5. The method of item 1 above, wherein the metal halide imide salt is chromium chloride. 6. The method of item 1 above, wherein the metal halide salt is Cr C1s.6H20. 7 The inorganic metal halide salt is 0.005 to 0.2
The method of paragraph 1 above, wherein the method is present in an amount of 0% by weight.