JPS6039277B2 - Phosphoric acid amide compound and its production method, and flame retardant made from the phosphoric acid amide compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel phosphoric acid amide compound, a method for producing the same, and a flame retardant for regenerated cellulose, cellulose acetate, or polyester comprising the compound.

Polyesters represented by regenerated cellulose, cellulose diacetate, cellulose triacetate, and polyethylene terephthalate have excellent chemical and mechanical properties, and are widely used in large quantities as fibers, films, and various other molded products.

However, since these are all flammable substances, they have the serious drawback that once they are ignited, they will burn. In recent years, with the overcrowding of cities and the rise of high-rise buildings, large-scale damage from the combustion of these synthetic materials in building fires has been occurring more frequently, and there has been an increasing demand for the use of synthetic materials in interior products, clothing, and bedding products. Various flame retardant techniques have been proposed in the past.

For example, the use of various phosphorus compounds and halogen compounds has been proposed as a method for imparting flame retardancy to the length of regenerated cellulose woven fabric.In particular, methods of adding polyphosphonate to viscose and adding polyphosphonitrile have been proposed. The method to do this is well known.

However, among these methods, the method using polyphosphonates requires a large amount of flame retardant because these compounds themselves fundamentally lack flame retardant performance, which has the disadvantage of deteriorating the properties of the fiber itself. Also, the method using polyphosphonitrile shows excellent flame retardant properties due to the mutual effect of phosphorus and nitrogen contained in the core compound, but it is difficult to manufacture and is very expensive, so it is difficult to manufacture from an industrial standpoint. It is difficult in practice to use this compound as a flame retardant.

As a method of imparting flame retardancy to cellulose acetate fibers, a method of adding a flame retardant to the weaving yarn stock solution is being studied, and the flame retardant used here includes, for example, TBP.
Low-molecular compounds such as P (tris-1,2,3-dipromopropyl phosphate) are well known, but fibers obtained using such compounds do not contain the flame retardant added as a raw solution. In addition, since it is generally oily, it easily falls out of the fiber during processes such as scouring, bleaching, and dyeing after spinning, or during washing, and as a result, the flame retardancy of the fiber is low or it is economically degraded, which poses a practical problem.

As a method of imparting flame retardancy to polyester, in the case of fibers, the so-called kneading method, in which a halide and polyphosphoric acid (phosphonic acid) ester are added to the polyester before spinning, has been attracting attention and being studied. However, these flame retardants have disadvantages such as significantly reducing the whiteness of polyester, requiring a large amount of flame retardant to achieve sufficient flame retardant performance, and reducing the desirable physical properties inherent in polyester. ing. In view of the current situation, the present inventors searched for a new compound that can improve the above-mentioned drawbacks, and as a result, discovered a new compound having an excellent flame retardant effect and arrived at the present invention.

The gist of the present invention is the general formula [1] [wherein n is 0 or 1].

] A method for producing a phosphoric acid amide compound represented by the above general formula [1], which comprises reacting the phosphoric acid amide compound represented by the above general formula [1] with diethylenetriamine. There is also a flame retardant comprising a phosphoric acid amide compound represented by the general formula [1]. The features of the present invention are as follows.

'11 Since the compound of the present invention contains both phosphorus and nitrogen atoms, it exhibits extremely excellent flame retardant properties due to the mutual effect of phosphorus and nitrogen.

'2} Since the compound of the present invention has excellent heat resistance, it does not induce viscosity reduction or coloring of polyester, especially when exposed to high temperatures during spinning of polyester fabric.
3) The compound of the present invention is easily compatible with ketones such as acetone, chlorinated solvents such as methylene chloride, 1,2-dichloroethane, and chloroform, amide solvents such as dimethylformamide and dimethylacetamide, and carbon disulfide or mixed solvents thereof. Compared to other compounds, it can be used as a flame retardant for cellulose acetate fibers and regenerated cellulose fibers that are formed into fibers using these solvents, and the solvent can be easily recovered. , it has characteristics such as no problem with waste liquid treatment {
4) Since the compound of the present invention is solid at room temperature and does not twill in water, it does not fall off from the fiber during post-treatments such as dyeing or washing after twill yarn, and does not have flame retardant properties due to shedding. The compounds of the present invention have good film resistance, and no deterioration in weather resistance or properties due to the flame retardant of flame retardant fibers containing these compounds is observed.

In order to efficiently produce the compound of the present invention, it is preferable to carry out dehydrohalogenation condensation of diphenylphosphoryl chloride or diphenylphosinate chloride and jethylenetriamine in a cold solvent in the presence of an acid acceptor. Thereby, the desired phosphoric acid amide compound can be obtained in high yield.

Diphenylphosphoryl chloride or diphenylphosinate chloride used in the method of carrying out the present invention can be produced in a good yield by a known method, and jetylene triamine can be obtained by purifying a commercially available product by an appropriate method. Can be used in reactions.

To explain the above method in more detail, in a dry nitrogen atmosphere, diethylenetriamine and a tertiary amine (e.g., pyridine, N,N-dimethylaniline, N,N-diethylaniline, triethylamine, etc.) as an acid acceptor are mixed in an inert solvent. 100 qo or more to 100 oo, preferably -
The temperature is maintained at 500° to 7000°C, and diphenylphosphoric acid chloride or diphenyphosphinic acid chloride is added to carry out the condensation reaction.

Examples of insensitive solvents used here include methylene chloride, 1,2-dichloroethane, trichlene, methyl chloroform, chloroform, tetrachlorethane, carbon tetrachloride, trichlorethane, etc. as chlorinated solvents, and ethyl as ether solvent. Ether, Isoph.

Lopylether, tetrahydrofuran, dioxane, etc.
Ketone solvents such as methyl isobutyl ketone, acetophenone, benzophenone, dichlorohexane, aromatic solvents such as penzene, toluene, xylene, monochlorobenzene, dichlorobenzene, nitrobenzene, etc., amide solvents such as dimethylformamide, Dimethylacetamide, hexamethylphosphorylamide, N-
Methylpyrrolidone and the like can be used. Next, a method of applying the flame retardant made of the phosphoric acid amide compound of the present invention to regenerated cellulose, cellulose acetate, and polyester fiber will be explained.

i Application to regenerated cellulose The flame retardant for textiles made of the compound represented by the general formula [1] is generally solid at room temperature, but since it has good solubility in carbon disulfide, it can be used as a carbon disulfide solvent for the flame retardant. may be added to the piscose at an appropriate point before spinning and mixed uniformly.

Unlike when other flame retardants are used, there is no need to use a solvent other than the spinning solvent, so there are no problems such as contamination and corrosion of the solvent recovery system and wastewater system that occur when using a solvent other than the spinning solvent.

The amount added may be determined depending on the desired flame retardant level, but generally it may be added in an amount of 5 to 4% by weight based on the cellulose in piscose.

If it is less than this, the desired flame retardancy cannot be imparted, and if it is more than this, the quality of the fibers will deteriorate considerably, causing a practical problem. Next, there are no particular restrictions on the spinning conditions, and commonly used conditions can be applied as they are.

That is, the piscose has a cellulose concentration of 4 to 1% by weight, an alkali concentration of 3 to 8% by weight, a salt point of 5 to 20, a viscosity of 40 to 500 poise (at 20°C), and a paper yarn thickness composition of 10 to 120 g/night of sulfuric acid. , sodium sulfate 20-350
g/evening, zinc sulfate 0-150g/evening, temperature 10-70o
Conditions such as o are appropriate. ii) Cellulose acetate
Application to fibers Since the compound represented by the general formula [1] of the present invention is easily dissolved in acetone, methylene chloride, etc., which are threading solvents for cellulose acetate, the simplest method is to add and mix it into the spinning solution. It is.

The amount added can be changed freely depending on the desired flame retardant level, but generally it is 2 to 35% of cellulose acetate.
Weight percent is preferred. If it is less than this, the desired flame retardancy cannot be imparted, and if it is more than this, the performance of the obtained fiber will be significantly reduced, causing a practical problem.

Cellulose acetate as used in the present invention generally refers to diacetate and triacetate.

Further, as the yarn grading conditions for the fibers of the present invention, known yarn grading devices and spinning conditions can be applied as they are. iii Application to Polyester After the polycondensation reaction of polyester is completed, the phosphoric acid amide compound of the present invention is added directly into the polymerization kettle, or in the case of fibers, it is added to and mixed with polyester chips in a spinning machine to form a twill yarn.

Alternatively, it is also possible to preliminarily contain a large amount of the compound in polyester and add it in the form of a so-called master pellet to polyester to which no flame retardant has been added, thereby making various molded products.

In addition, in a composite fiber having a two-layer structure, it can be added and mixed with one of the constituent components to form a composite fiber.

The amount added can be freely changed depending on the desired level of flame retardancy, but is generally preferably 2 to 2% by weight. The term "polyester" used in the present invention refers to an aromatic polyester containing polyethylene terephthalate as a main component.

Furthermore, known equipment and conditions can be applied as they are to the molding conditions. As described above, the phosphoric acid amide compound of the present invention [
1] and its production method, and phosphoric acid amide compounds [
We have described examples of application to regenerated cellulose, cellulose acetate, and polyester using a flame retardant made of It can be produced at low cost, has various characteristics as an excellent flame retardant, and is a flame retardant fiber obtained using the flame retardant made of the phosphoric acid amide compound [1] of the present invention. Alternatively, the molded product has excellent flame retardant properties and durability, and combined with the ease of production, its industrial value is extremely high.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples.

In addition, in the examples, all parts or percentages represent weight unless otherwise specified.

Example 1 Loss filter, thermometer, reflux condenser (with two CaC drying tubes),
Prepare a flask equipped with a dropping funnel and a nitrogen flow device, charge 800 parts of 1,2-dichloroethane, 20.6 parts of jethylene triamine, and 60.6 parts of triethylamine as a reaction solvent in the flask, and add 5 to 10 qC.
It was cooled to

In a dry nitrogen atmosphere, 161.1 parts of diphenyl phosphoryl chloride was added dropwise from the dropping funnel under a light.

As the dropping progressed, the reaction also progressed, and triethylamine hydrochloride was precipitated.

The dropwise addition of diphenylphosphoric acid chloride was completed in about 2 hours, but after the dropwise addition was completed, the reaction was continued for another 4 hours at a temperature of 25 to 30 qo to complete the reaction.

After the reaction was completed, the solvent was distilled off from the reaction solution under reduced pressure and dried to absolute dryness, then poured into water, the hydrochloride was eluted, filtered in an oven, and dried to obtain a white powdery solid.

This **powder was purified by recrystallization from a mixed solution of 1,2-dichloroethane and ethyl ether to obtain colorless crystals. The infrared absorption spectrum of the crystal thus obtained is shown in the drawing. From this spectrum, it was estimated that the structure of the crystal was as follows.

Furthermore, the results of elemental analysis are shown in Table 1, and it was confirmed from these results that the obtained crystal had the above structure.

The yield of crystals was 150.2 parts, the yield was 94%, and the melting point was 108-110oo.

Table 1 Example 2 Using the same apparatus as in Example 1, 60 parts of monochlorobenzene, 20.6 parts of jethylenetriamine, and 60.6 parts of triethylamine were charged as a reaction solvent into a flask.
diphenylphosphinic acid chloride 141. at a temperature of 10-15 oo. The $ portion was dropped.

The dropping was completed in about 2 hours.

After the dropwise addition was completed, the same operation as in Example 1 was performed to obtain a very pale yellow solid. Colorless crystals were obtained by recrystallizing this solid from a mixed solution of 1,2-dichloroethane and ethyl ether. The yield of the obtained crystals is 1
29.4 parts, yield 92%, melting point 70-80 qo.

Table 2 shows the results of elemental analysis of this crystal.

As a result of elemental analysis in Table 2, the structure of this crystal is It was confirmed that

Example 3 Piscose having a cellulose concentration of 7.5% and an alkali concentration of 42%, which was produced by adding 48% carbon disulfide to cellulose, was aged to a viscosity of 200 poise and a salt point of 16.

Immediately before spinning, 5 parts of a 30% carbon disulfide solution of the flame retardant obtained in Example 2 was added to 10 anchor parts of this piscose,
After uniformly mixing with a static mixer, sulfuric acid 1 total/
and sodium sulfate 7 cough/evening, zinc sulfate 0. The fibers were spun in a 200C spinning chamber containing bamboo grass. The yarn leaving the spinning bath was 100% drawn in a second bath containing 80 qo of acid/sulfuric acid, and then continuously treated with a bath of 60 qo containing acid/sulfuric acid to complete regeneration.

Next, it was desulfurized, bleached, and treated with an acid using conventional methods, and then treated with an oil agent and dried. The fibers obtained in this way have no difference in fiber performance or other properties from ordinary fibers without the addition of flame retardants, and have a low oxygen index of L, 0,1 (lowest oxygen index).
It showed excellent flame retardancy of 28.0.

In addition, using this fiber, we made a prototype curtain with a fabric weight of 28, and measured the carbonized area using the 45 degree micro burner method according to JIS-L-1091 (A-1). It has become clear that he has sex. Example
4 Mixed solvent 73 consisting of 95.9% acetone and 4.1% water
．． A paper yarn solution obtained by dissolving 22.5 parts of diacetate in 5 parts and 4.5 parts of the flame retardant obtained in Example 2 was dry-spun using a known method to obtain 7/29 diacetate fibers. I got it.

Using this fiber, a plain woven fabric with a fabric weight of 20/20 was produced by a conventional method, dyed and washed under the following conditions. A flame retardant test was conducted. '1} Staining conditions: Diacellitio
n Brill BlueBO. 3%.

MDiaperTLO. 7g / evening 8000 x 45 minutes ■ Washing conditions: JISL-1042 compliant 60qo x 15 minutes, rinse 40 pm C x 5 minutes 5 times (3 times each time) '31 Flame retardant test: Fire and Disaster Management Agency Safety and Emergency Division Chief Notice Fire Safety No. 6
No. 5 (June 25, 1972), 45-degree tilt method and coil method.As a comparison material, a grade of 265% diacetate was prepared from a hydrated acetone solution (without flame retardant added) in the same manner as in Example 4. A threaded fiber was used.

The results are shown in Table 3.

Table 3 Example 5 Synthesized from dimethyl terephthalate and ethylene glycol according to a conventional method. = 0.70 = 5 parts of phenol, tetrac.

5% of the flame retardant obtained in Example 1 was added to polyethylene terephthalate (intrinsic viscosity value (dso/g) measured at 250°C in a mixed solvent from Lethane 5-g), and the usual method was used. After solvent spinning and then drawing, the 15th/3rd grade fiber had a 〔〔〕=0.63, a strength of 4.1 g/d,
The elongation was 22.2%, the physical properties were good, and the whiteness was also excellent. In addition, as a result of a light fastness test using Fademeter 15's unique irradiation, there was almost no coloration and no arming of the fibers was observed.

This fiber was made into a knitted fabric using a sock knitting machine, and when it was subjected to L,0,1 (oxygen index) measurement and a combustion test using the coil method of JS1, L-1091, method D, the result was L,0,1300. It showed excellent flame retardancy after being tested 5 times.

[Brief explanation of the drawing]

The drawing shows an infrared absorption spectrum of the phosphoric acid amide compound obtained in Example 1.

Claims (1)

[Claims] 1 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, n in the formula is 0 or 1. ] A phosphoric acid amide compound represented by 2 General formula characterized by reacting diphenylphosphoric acid chloride or diphenylphosphinic acid chloride with diethylenetriamine ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, n in the formula is 0 or 1. ] A method for producing a phosphoric acid amide compound. 3 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, n0 in the formula is or 1. A flame retardant for regenerated cellulose, cellulose acetate, or polyester consisting of a phosphoric acid amide compound represented by 4. A flame retardant made of a phosphoric acid amide compound according to claim 3, wherein the flame retardant is a undiluted solution type flame retardant.