JPS5938973B2 - Manufacturing method of phosphorus-containing polyester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing flame-retardant polyester that can be added to various flammable materials, such as textile materials, to impart durable flame retardancy to the materials. It is.

BACKGROUND ART Conventionally, a widely used method for making various combustible materials flame retardant is to mix flame retardant phosphorus-containing polyester into the materials.

Conventionally, a method of dehydrohalogenating phosphoric acid dihalides and diols has been generally adopted as a method for producing such phosphorus-containing polyesters, but this method involves conducting the reaction at high temperature and reduced pressure, or Since a large amount of hydrogen halide is generated in the reactor, the reaction operation is complicated, and there are many problems such as corrosion of the reactor and discoloration of the produced polymer.

The present inventors conducted various studies in an attempt to produce a flame-retardant phosphorus-containing polyester more advantageously than conventional methods by a method free from such drawbacks, and as a result, they arrived at the present invention described below.

The present invention is based on the general formula: Alkyl group, X represents halogen.

Here, halogen refers to chlorine or bromine atoms. ) and a bisepoxy compound represented by the formula [] in the presence of a catalyst in an inert solvent, -
General formula [] characterized in that the reaction is carried out at a temperature of 50 to 200°C (wherein, Y and X are defined as before, and n is an integer of 1 to 50.

) is a method for producing a phosphorus-containing polyester having a repeating unit represented by: General formula in the present invention [? The reaction between the Rino\rad shown and the bisepoxy compound shown by the formula [] is an addition polymerization reaction in which the two are directly added together, and this reaction proceeds quickly even at room temperature and pressure, and during the reaction, No corrosive gases are generated.

Therefore, in the method of the present invention, the reaction operation is simple and there is no fear of corrosion of the reactor.

Further, the reaction product is not colored, and a high molecular weight phosphorus-containing polyester can be easily obtained.

Furthermore, in the present invention, the halogen in the raw material phosphorus halide is directly incorporated into the desired product without loss, so that a phosphorus-containing polyester with a high halogen content and excellent flame retardancy can be obtained. Furthermore, the fact that halogen is not lost during the reaction is economically advantageous compared to conventional methods.

Examples of the phosphorus halide represented by the general formula [1] used in the present invention include, but the present invention is not limited thereto.

In the present invention, the types of inert solvents used in the reaction of the above-mentioned phosphorus halide and the bisepoxy compound represented by the formula [] include, for example, ethane dichloride, tricrene, methylchloroform, chloroform, ethane tetrachloride,
Chlorinated solvents such as carbon tetrachloride and trichloroethane, ethereal solvents such as ethyl ether, isopropyl ether, tetrahydrofuran and dioxane, ketonic solvents such as methyl isobutyl ketone, acetophenone, benzophenone and cyclohexanone, benzene, toluene, xylene , monochlorobenzene, O-
Aromatic solvents such as dichlorobenzene and nitrobenzene, formamide, dimethylformamide, dimethylacetamide, hexamethylphosphoramide and N
-Amide solvents such as methylpyrrolidone can be mentioned.

Further, as the catalyst used in the present invention, for example, AlC
Examples include Lewis acids such as 13, TiCl4, SnCl4, FeCl3, BF3. The invention is preferably implemented as follows.

While passing a nitrogen stream into a suitable reactor, the raw material phosphorus halide and an appropriate amount of catalyst and inert solvent are charged and mixed,
This mixture usually contains -5'C to 200°C, preferably 0°C.
At a temperature of 150 DEG C. to 150 DEG C., an equimolar amount of the raw material bisepoxy compound to the raw material phosphorus halide is added little by little to carry out an addition polymerization reaction. In this way, by reacting the phosphorus halide represented by the general formula [1] with the bisepoxy compound represented by the general formula [], a phosphorus-containing polyester having a Z repeating unit represented by the general formula [] can be easily obtained. It will be done.

The molecular weight of the phosphorus-containing polyester can be changed by appropriately changing reaction conditions such as reaction temperature and reaction time.

The degree of polymerization n of the diphosphorus-containing polyester is usually 1 to 50, preferably 3 to 30, from the viewpoint of use as a twist-resistant agent. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to Example 6.

In addition, in the following examples, all parts simply refer to weight.

Example A flask with contents 11 equipped with a stirrer, a thermometer, a reflux condenser, a dropping load, and a nitrogen flow device was prepared, and 600 parts of 1,1,2,2-tetrachloroethane as a reaction solvent was placed in the flask. and raw material phenylphosphonic acid cyclolade 78
．． 0 parts and AlCl3O. as catalyst. Charge 5 parts and heat to a temperature of 55-60°C.

Pass nitrogen into the flask and add the bisepoxy compound 2-tetrachloroethane 2 in a nitrogen atmosphere while stirring the contents.
00 parts of the solution was added dropwise.

The dropping was completed in about 3 hours, but after the dropping was completed, the temperature was further increased to 90°C.
Stirring was continued at a temperature of 5 hours to complete the reaction.

A colorless and transparent viscous solution was obtained from this phase.

Then, the solvent was distilled off from this solution under reduced pressure and dried to obtain 141.4 parts of an almost colorless phosphorus-containing polyester solid. The softening point of this solid is 16°C to 170°C,
The average molecular weight was measured by the vapor pressure equilibrium method and was 6
200, and the yield was 98.5%.

Reference Example A phosphorus-containing polyester having a repeating unit represented by the formula obtained in Example was synthesized from dimethyl terephthalate and ethylene glycol using a conventional method. Polyethylene terephthalate having an intrinsic viscosity [η] = 0.70 ([η] is phenol) 50 copies and 1, 1, 2
, 2-tetrachloroethane in an amount of 5% by weight (measured at 25° C. (dl/g)), melt-spun in a conventional manner, and then stretched.

There were no operational problems in this spinning and drawing process, and the obtained fibers were almost colorless, [η] was 0.63, and the strength was 4.5 g/
d. The elongation was 23%, and the physical properties were very good.

This fiber was needle-punched to create a felt-like material, and the LO1 was measured to be 31.0, indicating excellent flame retardancy.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, Y represents R_1O or R_1, R_1
represents an aryl group, a halogenated aryl group, an alkyl group having 1 to 7 carbon atoms, or a halogenated alkyl group, and X represents a halogen. Here, halogen represents a chlorine atom or a bromine atom. ) A general formula characterized by reacting a bisepoxy compound represented by the phosphorus halide formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ in an inert solvent in the presence of a catalyst at a temperature of -50 to 200°C ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, the definitions of Y and X are the same as before, and n is 1 to 50.
represents an integer. ) A method for producing a phosphorus-containing polyester having a repeating unit represented by