JPS586733B2 - Yuuki Ganrin Polymero Seizouhouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention involves reacting propylene phosphorochloridite with a ketone to form a compound of the general formula: be.

), the purpose of which is to produce organic phosphorus-containing polymers that have excellent heat, acid, and alkali resistance, and are useful as flame retardants, plasticizers, and lubricants for various polymeric substances, mineral oils, etc. The object of the present invention is to industrially advantageously produce an organic phosphorus-containing polymer which is added to a phosphorus polymer, particularly a viscose spinning dope, and which has an extremely high yield in fibers and has good durability.

Recently, various organic phosphorus-containing polymers have been proposed as durable flame retardants for various polymeric substances.

However, although most of these have the effect of temporarily imparting flame retardance, they lack durability in use, and at present they are not put into practical use very often.

The reason for this is that the polymerization reaction of these organic phosphorus-containing polymers is complicated, so it is difficult to control the reaction and it is difficult to obtain the desired molecular weight, and the molecular weight distribution (Mw/Mn) (Mw : Weight average molecular weight, Mn: Number average molecular weight) It is thought that components in a wide range of low molecular weight ranges and extremely high molecular weight ranges are produced, which lowers durability.

Therefore, the emergence of a method for producing an organic phosphorus-containing polymer having an arbitrary molecular weight and a narrow molecular weight distribution is eagerly awaited.

Conventional methods for producing organic phosphorus-containing polymers having the general formula include, for example, a method for producing a two-component phosphonate using an enolizable ketone and a cyclic chloroosphite.
-19337) has been proposed.

However, with this method, the degree of polymerization increases with the passage of time, making it difficult to obtain a polymer with a desired molecular weight, and the resulting polymer contains many low polymers and has free terminal hydroxyl groups, resulting in poor thermal stability. However, it has poor alkali resistance, and particularly when added to a viscose spinning dope, the yield of viscose fibers obtained is poor and durability is poor.

The present inventors have arrived at the present invention as a result of various studies on methods to eliminate the deficiencies of these conventional methods.

That is, in the present invention, β-chloroalcohol is added as a polymerization regulator to crude propylene phosphorochloridite synthesized by controlling the molar ratio of phosphorus trichloride to 1,2-glopylene glycol to 1.02 to 1.03. and react the propylene phosphoroglolidite with a ketone in the substantial absence of water.
w) and the number average molecular weight (Mπ) (Mw/Mn) is 3.
This is a method for producing an organic phosphorus-containing polymer having a phosphorus content of 0 or less.

The propylene phosphorochloridite used in the method of the present invention is generally called a cyclic chlorophosphite, and is synthesized by the reaction of l,2-glopylene glycol and phosphorus trichloride, but in the present invention, it is synthesized by distillation, In order to avoid industrially disadvantageous operations such as refining and to fully utilize the adjustment ability of the polymerization modifier described below, the molar ratio of phosphorus trichloride to 1.2-gropylene glycol was adjusted to 1.
．． It is important to regulate it within the range of 0.02 to 1.03.

By doing so, it is possible to maximize the production rate of propylene phosphorochloridite, reduce by-products during synthesis of propylene phosphorochloridite, and reduce by-products during polymerization reaction.

That is, if the molar ratio of phosphorus trichloride to 1,2-glopylene glycol is less than 1.02, side reactions will proceed due to unreacted propylene glycol and the purity of the crude propylene phosphorochloridite will decrease.

When the same amount of the polymerization regulator of the present invention is added to such propylene phosphorochloridite and reacted, Mw/M
The adjustment range of Mw itself becomes smaller, although it is narrower than the speed.

In addition, when the molar ratio is greater than 1.03, the acid value of the organic phosphorus-containing polymer becomes relatively high compared to when the molar ratio is 1.03 or less due to excess phosphorus trichloride, resulting in low polymerization. As the number of materials increases and Mw/Mn increases, durability and alkali resistance deteriorate significantly.

Moreover, if the amount of polymerization regulator added is reduced within the same molar ratio, this tendency will be reversed.

The polymerization regulator in the present invention adjusts the molecular weight of the organic phosphorus-containing polymer to an arbitrary size during the polymerization reaction, and the molecular weight distribution (
β-chloroalcohol is preferably used as such a polymerization regulator.

Examples of the β-chloroalcohol include alcohols having 2 to 3 carbon atoms and having one or more CIs at the β-position, and specific examples thereof include dichlorohydrin, propylene chlorohydrin, and ethylene chlorohydrin.

Although it is not clear why the β-chloroalcohol used in the present invention is particularly excellent as a polymerization regulator, it is presumed to be due to the following reasons.

That is, since β-chloroalcohol is an electrocathode of the CI atom in the β position, the proton of the hydroxyl group is released more easily than alcohols such as methanol and ethanol, and it is more likely to react with propylene phosphorochloridite. Since polymerization initiation terminals are preferentially formed and not only the polymerization initiation reaction but all elementary reactions can be controlled, an organic phosphorus-containing polymer with a narrower molecular weight distribution can be obtained.

On the other hand, when polymerization proceeds with water, ring-opening polymerization occurs due to the reaction between water and propylene phosphorochloridite, producing by-products with a structure that creates more crosslinks than necessary. While an organic phosphorus-containing polymer, which is considered to be an extremely high molecular weight product, is produced, the formation of polymerization terminals stops midway and a small molecular weight organic phosphorus-containing polymer with free OH is also produced. It is thought that the substance has a wide molecular weight distribution.

Therefore, in the present invention, it is desirable to carry out the reaction substantially in the absence of water.

Ketones used in the present invention include acetone, methyl ethyl ketone, diether ketone, etc. The molar ratio of the ketone to propylene phosphorochloridite is 1.
．． It is in the range of 0.05 to 1.00, and is added at the same time as the polymerization regulator, or is added dropwise within a short time after the polymerization regulator is added.

Although the reaction of the present invention can be carried out in the absence of a solvent, it is advantageous to use a solvent in order to suppress heat generation and facilitate stirring when obtaining a product with a high molecular weight.

The solvent used in the reaction may be any solvent as long as it is inert to the reaction and dissolves the produced polymer.

Solvents that satisfy these requirements include ethylene dichloride,
■・2-propylene dichloride, methyl chloroform,
Examples include chlorinated aliphatic hydrocarbons such as tricrene, 1.1.2-}J chloroethane, and tetrachloroethane, and aromatic hydrocarbons such as benzene and toluene.

The amount of solvent is sufficient to make the reaction smooth, but if the product must be mixed with a solvent and used as a product, consider the dispersion of the organic phosphorus-containing polymer and reduce the amount of the polymer to 0. 5-2.

It is preferable to use 0 times the amount. In addition, when the product is not used in the form of a solution, by removing the solvent from the reaction product, products ranging from highly viscous to crystalline solid can be obtained.

Since the polymerization reaction in the present invention is presumed to be cationic polymerization, the reaction temperature is preferably carried out at as low a temperature as possible, generally from -10°C to 50°C.

The reaction time varies depending on the reaction temperature, but 20 to 72 hours is sufficient.

The reaction system of the present invention requires the absence of water in order to fully exhibit the effects of the polymerization regulator.

However, it is unavoidable that the ketones and solvents used in practical use contain a minimum amount of water in an industrially unavoidable state.

This condition is usually less than about 0.4% for ketones and less than about 0.02% for solvents.

In the present invention, such a state is referred to as substantially the absence of water.

Tables 1 and 2 shown later show the type and amount of polymerization regulator used when propylene phosphorochloridite is reacted with ketone, and the amount of PCl3/PG (molar ratio) (PG:7
ropylene glycol), Mw and Mw/Mn.

As is clear from the table.

When propylene phosphorochloridite is reacted with a ketone using β-1 chloroalcohol as a polymerization regulator, the smaller the amount of β-1 chloroalcohol added, the more
Mw becomes large and Mw/Mn becomes wide; conversely, when the amount added is large, MW becomes small and Mw/Mn becomes narrow.

In this case, Mw/Mn is set to 3.0 in a wide range of Mw.
To adjust the following, the molar ratio of phosphorus trichloride and 1,2-propylene glycol (PC13/PG) is 1.02 to 1.
．． It is preferable to use crude propylene phosphorochloridite synthesized under the control of No. 03.

This relationship tends to be similar in other comparative examples, but
It is clear that there are fundamental differences depending on the type of polymerization regulator used.

That is, when water or methanol is used as a polymerization modifier (actually, the action of a polymerization initiator or catalyst is large), a product with the same Mw as the method of the present invention can be produced by changing the amount of the polymerization modifier added. However, only an organic phosphorus-containing polymer can be obtained in which the Mw/Mn is considerably wider than when β-chloroalcohol is used (particularly in the case of water, the distribution is extremely wide).

Therefore, β-chloroalcohol is optimal as a polymerization modifier, and the amount used varies depending on the object to be used, but if the amount of polymerization modifier is too small, Mw/Mn will widen and become 3.0 or more. Durability and alkali resistance deteriorate,
Furthermore, if the amount is too large, the Mw will decrease, resulting in poor yield and the flame retardant effect will be inhibited, so 0.5 mol % to 5.0 mol % is optimal.

(5.0 when plotted from the mol% of modifier in the table)
In the case of mol%, Mw is approximately 5000.

Flame retardancy cannot be expected with Mw below this.

) In this case, Mw is approximately 5000 to 60000, and Mw/M
n is 3.0 or less.

As is clear from the above detailed description, the present invention provides a method for synthesizing propylene phosphorochloridite in the molar ratio of phosphorus trichloride to 1,2-propylene glycol (PC
13/PG) to 1.02 to 1.03, the resulting crude propylene phosphorochloridite can be subjected to polymerization without industrially disadvantageous operations such as distillation and purification. By using β-chloroalcohol as a polymerization modifier during the reaction of crude propylene phosphorochloridite and ketone, an organic phosphorus-containing polymer with a narrow molecular weight distribution can be obtained, and the amount of the polymerization modifier added can be varied. This has the great advantage that, while the molecular weight distribution is narrow, the molecular weight can be adjusted over a wide range at will, taking into consideration the compatibility with the polymeric substance to be used and the durability of the flame retardant effect.

Next, examples of the present invention will be described along with comparative examples.
The present invention is not limited to this.

Example A predetermined amount of 1,2-gropylene was added to a mixed solution consisting of 70 parts of ethylene dichloride (parts by weight...the same applies hereinafter) and 140.1 parts of phosphorus trichloride while keeping the temperature below 0°C and stirring. Glycol was added over a period of 2 hours, and the reaction was allowed to proceed while the generated hydrogen chloride was rapidly discharged from the system. After the reaction was completed, the dissolved hydrogen chloride was removed, and the ethylene dichloride of crude propylene phosphorochloridite was obtained. A solution was obtained.

Next, 35 parts of ethylene dichloride was added, and predetermined amounts of various polymerization modifiers and 58.7 parts of acetone were quickly added thereto, and the mixture was stirred and polymerized while the mixture was sealed.

The polymerization was carried out under cooling during the initial stage when a large amount of heat was generated, and after the heat generation subsided, it was carried out at room temperature, and the polymerization was carried out for 72 hours.

The analysis results of the obtained organic phosphorus-containing polymer are shown in Tables 1 and 2.

Among these organic phosphorus-containing polymers, 150 gr of 25% ethylene dichloride solution of ■ to ■ in Tables 1 and 2
and 100g of a 5% NaOH aqueous solution were added to a separatory funnel, shaken with a shaker and left overnight. 300L of an H2S04 aqueous solution (H2SO4 20gr1g) was added, shaken, and left to stand. The lower layer was taken out and dehydrated with Na2SO4.
P. In addition to measuring the molecular weight and comparing the alkali resistance using C, the organic phosphorus-containing polymers described above (■ to ■) were added to the viscose spinning dope, and recycled cellulose fibers were produced under normal conditions and methods, and the yield and flame retardancy were evaluated. A gender comparison test was conducted.

These results were as shown in Table 3. From the test results shown in the above table, it is clear that the effect of the product obtained by the present invention is excellent.

Claims (1)

[Claims] 1 A particularly appropriate amount of β-chloroalcohol is added as a polymerization regulator to crude propylene phosphorochloridite synthesized by controlling the molar ratio of phosphorus trichloride to 1,2-glopylene glycol to 1.02 to 1.03. and reacting the propylene phosphorochloridite with a ketone in the substantial absence of water.
W) and number average molecular weight (ME) (Mw/Mn) is 3.
A method for producing an organic phosphorus-containing polymer of 0 or less.