JPS5847406B2 - Method for producing flame-retardant polyphosphoric acid amide or polyphosphonic acid amide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a flame-retardant copolycondensate, and in particular provides a method for producing a flame-retardant poly-IJ-IJ-acid amide or polyphosphonic acid amide. .

Its purpose is to impart a durable flame retardant effect when mixed with various combustible materials, especially textile materials.

The polyphosphoric acid amide or polyphosphonic acid amide according to the present invention has the following general formula (1) (wherein R1 is an alkyl group having 1 to 6 carbon atoms, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxy group, aryloxy group, halogenated alkoxy group, or halogenated aryloxy group, and R2 is an alkylene group or arylene group having 1 to 6 carbon atoms.

R3 and R4 represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an aryl group, and the case where R3 and R4 are bonded to each other to form a ring is also included.

The halogen shown here represents Cl or Br.

A is an integer of ClCH2CH2-0-1000).

Various phosphorus compounds and halogen compounds have been proposed as methods for making regenerated cellulose fibers flame retardant among fiber materials, and the most recent flame retardant methods are polyphosphonate-based compounds (Japanese Patent Publication No. 1983-31720) or phosphazene. This is a method of spinning by adding a type compound to viscose, and there have been many reports regarding this method.

However, polyphosphonate flame retardants fundamentally lack flame retardant performance, so a large amount of flame retardant is required, and P-
Due to its 0-C structure, it is susceptible to heat and alkali, and has defects that tend to cause problems such as gummy scum during spinning.

Among the phosphazene-based flame retardants, hexapropoxyphosphazene is a representative example, and there are many reports on related flame retardants, but these flame retardants are very expensive and have problems such as oozing from fibers due to the properties of low-molecular polymers, and The accompanying contamination of spinning and spinning equipment may also be a problem.

It also has somewhat poor heat resistance and insufficient washing resistance.

The present inventors have arrived at the present invention as described at the beginning as a result of intensive research into methods of improving the problems of conventional methods and making various fiber materials flame retardant in an extremely practical manner. be.

The features of the present invention are as follows.

(1) A polymer with a high degree of polymerization was obtained from the optimal relationship between the PKa value of the tertiary amine of the deoxidizer and the PKa value of the diamine compound.

(2) Since the main chain contains phosphorus and nitrogen, it is possible to obtain a synergistic effect of phosphorus and nitrogen on flame retardant performance.

(3) When halogen is introduced into the side chain group, a synergistic effect on flame retardant performance can be obtained.

(4) Good heat resistance due to the P-N structure in the main chain.

(5) Since the polymer ends are blocked, there is no problem with hydrolysis resistance.

In producing the above polyphosphoric acid amide or polyphosphonic acid amide, the phosphoric acid dihalide or phosphonic acid dihalide used is represented by the following general formula CI).

(However, R1 represents an alkyl group having 1 to 6 carbon atoms, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxy group, an aryloxy group, a halogenated alkoxy group, a halogenated aryloxy group, and the halogen shown here is Cl or Br.

X and Y represent Cl or Br, and X and Y may be different or equal.

) Incidentally, examples of general formula (II) include the following.

The diamine compound used in the present invention can be expressed by the following general formula (
III).

* (However, R2 represents a chain or cyclic alkylene group having 1 to 6 carbon atoms or an arylene group, R3 and R4 represent hydrogen or an alkyl group or aryl group having 1 to 6 carbon atoms, and R3 and R4
This also includes cases in which they are bonded to each other and form a ring.

) Examples of the general formula (III, l) include, but are not limited to, the following.

Further, A, which is the polymer terminal stabilizing group of the present invention, is formed by the reaction of the stabilizer shown in the next example with the active chlorine at the polymer terminal.

As a stabilizer that becomes the terminal stabilizing group A, etc., but are not limited to these.

Further, the polymer terminal stabilizing group B of the present invention is derived from the stabilizer shown in the following example and the imino group at the polymer terminal.

It is not limited to these.

In addition, as a method for stabilizing the polymer terminals, one type of base A or base B can be used by making the reaction molar ratio of phosphoric acid dihalide and diamine compound slightly excessive during the polymer synthesis reaction. Polymer ends can be stabilized with a stabilizer.

For example, when phosphoric acid dichloride is in excess, the active end of the polymer (also shown as a repeating part) is stabilized by combining it with base A as follows.

In addition, if the diamine compound is in excess, the active end of the polymer (
The repeating portion is also shown), which is stabilized as follows by combining base B.

However, if the balance of the reaction molar ratio of phosphoric acid dihalide and diamine compound is excessive, the degree of polymerization of the resulting polymer may be affected, so it is appropriate to keep the unbalance of the reaction molar ratio within 5%. It is.

The amount of A or B added as a terminal stabilizer is sufficiently effective within about 5% mole of the phosphoric acid dihalides.

In addition, a tertiary amine is usually used as a deoxidizing agent in the present invention, but in order to quickly carry out the polycondensation reaction and obtain the necessary degree of polymerization, an appropriate tertiary amine is selected from the acid of the diamine compound used in the reaction. It must be selected depending on the dissociation constant PKa value.

If the PKa value of the deoxidizing agent is considerably lower than that of the diamine compound, the degree of polymerization will decrease due to its low basicity, and if it is considerably high, its nucleophilicity will be large. It acts as an inhibitor of the polymerization reaction.

Therefore, it is desirable that the PKa value of the dehydrochlorination agent be around the PKa value of the diamine compound, with relatively little difference.

Most tertiary amines that meet the above conditions can be obtained by purifying commercially available products, but special products may require synthesis.

For example, pyridine PKa5.26, α-picoline PKa
= 6. 2 0, N. N-dimethylaniline PKa=
5,15,N,N-diethylaniline PKa = 6.
5 6,2,4-lutidine PKa = 6. 7 5
, N-ethylmorpholine PKa 7.70, N-allylpiperidine PKa = 9. 6 8, triethylamine PKa=1 0.7 4, N-methylpiperidine PKa
=1 1.5, etc., but is not limited to these.

In carrying out the present invention, the reaction between phosphoric acid dihalide and diamine compound is carried out in the presence of a deoxidizing agent in an inert solvent. Amides can be obtained.

The phosphoric acid dihalide or phosphonic acid dihalide used in the method of carrying out the present invention can be obtained in extremely good yield by reacting the corresponding alcohol or phenol with phosphorus oxychloride under appropriate conditions by a known method. I can do it.

In the case of phosphonic acid, it can be obtained in good yield by Friedel-Crafts reaction of alkyl halides or halogenated aromatics with phosphorus trichloride.

On the other hand, one of the diamine compounds can be used in the reaction by purifying a commercially available product by an appropriate method.

The method of the present invention involves mixing a diamine compound and a deoxidizing agent in an inert solvent in a nitrogen stream, and adding phosphoric acid dihalide or phosphonic acid dihalide at a temperature of -ioo'c to 100°C, preferably -50 to 50°C. Add to complete the polycondensation reaction, then add A agent, B agent, or A agent and B agent at room temperature to stabilize the terminal of the polycondensate, 0 to 100 ° C.
Preferably, the reaction is carried out by heating to 20 to 70°C.

This reaction is generally carried out in a chlorine-based, ether-based, ketone-based, or aromatic solvent, but amide-based solvents can also be used, and in this case, the degree of polymerization of the product is increased. .

Chlorinated solvents include methylene chloride, ethane dichloride, tricrene methyl chloroform, chloroform, carbon tetrachloride, ethane tetrachloride, trichloroethane, etc. Ether solvents include ethyl ether, isopropyl ether, tetrahydrofuran, dioxane, etc., and ketone solvents. Solvents include methyl isobutyl ketone, acetophenone, penzophenone, cyclohexanone, etc. Aromatic solvents include benzene, toluene, xylene, monochlorobenzene, 0
-Dichlorobenzene, nitrobenzene, etc.; amide solvents include formamide, dimethylformamide,
dimethylacetamide, hexamethylphosphoramide,
N-methylpyrrolidone and the like are used.

The polyamide, etc. synthesized by the above method has a high degree of polymerization, and because the terminals of the polymer are stabilized, it exhibits excellent heat resistance and alkali resistance, and can be expected to have a wide range of uses.

As an example, many polyphosphoric acid amides are soluble in most organic solvents and have excellent leakage properties, so they can be used in various textile materials, especially recycled cellulose fibers, to provide remarkable flame retardancy. It was confirmed that

EXAMPLES The present invention will be specifically described below with reference to Examples, but the content of the present invention is not limited to these Examples.

In the examples, parts mean parts by weight.

Example 1 A 1-liter flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen flow device was prepared, and 500 parts of methylene chloride, 60 parts of ethylenediamine, and 212.1 parts of triethylamine were charged as a reaction solvent into the flask. Cool to 5-10°C.

In a nitrogen atmosphere, 195 parts of phenylphosphonic acid dichloride was added dropwise from the dropping funnel with vigorous stirring, taking care not to raise the temperature inside the reaction above 15°C.

The reaction progresses as the addition progresses, but care must be taken not to reduce the stirring speed due to salt precipitation and increase in viscosity.

The dropwise addition time of phenylphosphonic acid dichloride was completed in about 2 hours, and after stirring for 2 hours at 5 to 10°C, 2.9 parts of propylene oxide and then 7.0 parts of diethyl phosphoric acid monochloride were added, and 40 to All reactions were completed by reacting at 500C for 5 hours.

After the reaction, the solvent was distilled off from the reaction solution under reduced pressure and dried completely.
Add hot water to leach the salt.

The obtained polymer is dried in a vacuum dryer and then ground to obtain a pale yellow solid.

The yield was 174.7 parts, and the average molecular weight of the obtained polymer (vapor pressure equilibrium method (measured by Haru, hereinafter the same) was 18.
It was 0 0 0.

Example 2 Using the same apparatus as in Example 1, 1,2-
500 parts of dichloroethane, 86 parts of piperazine, and 212.1 parts of triethylamine were charged and heated to 1.3 parts at a temperature of 0 to 5°C.
- 246 parts of dichloroprobyl phosphate dichloride is added dropwise to react.

Propylene oxide 2 as a stabilizer at the polymer end
．． 9 parts and 7.0 parts of penzoyl chloride were added, and 40 parts of
The reaction is completed at ~50°C for 5 hours.

The treatment after the reaction was carried out in the same manner as in Example 1, and 251.2 parts of a pale yellow solid was obtained, and the average molecular weight of this polymer was 21,000.

Example 3 Using the same apparatus as in Example 1, 500 parts of monochrome benzene and 1 part of 2,5--)methylpiperazine were used as reaction solvents.
14 parts of N-ethylmorpholine and 241.5 parts of N-ethylmorpholine were charged, and 300.5 parts of bromoprobyl phosphate monobromone monochloride was added dropwise under the same reaction conditions as in Example 2 to react.

Epichlorohydrin 4.6 as a stabilizer at the polymer end
Add 6.3 parts of topendyl chloride to 40-50 parts
The reaction was completed at 0C for 5 hours.

After the reaction, the precipitated salt is separated in a furnace under reduced pressure, monochlorobenzene is distilled off from the resulting furnace liquid under reduced pressure, and after drying in a vacuum dryer, the obtained polymer is crushed, washed with water, and dried to form a pale 274 parts of a yellow solid were obtained, and the average molecular weight of the polymer was 14,500.

Example 4 Using the same apparatus as in Example 1, 500 parts of dimethylacetamide and 116 parts of hexamethylene diamine were used as reaction solvents.
and 262.5 parts of N-allylpiperidine, and under the same reaction conditions as in Example 1, 335 parts of 2,3-dibromopyrphosphate dichloride was added dropwise to react.

Propylene oxide as a stabilizer at the end of the polymer2.
9 parts and 13.4 parts of diphenyl phosphate monochloride were added, and the reaction was carried out at 40-50°C for 5 hours to complete the reaction.

After the reaction, the precipitated salts are separated in a furnace under reduced pressure, dimethylacetamide is distilled off from the resulting furnace liquid under reduced pressure, and after drying in a vacuum dryer, the resulting polymer is crushed, washed with water, and dried to form a pale powder. 358 parts of a brown solid were obtained.

The average molecular weight of the polymer was 18,500.

Example 5 Using the same apparatus as in Example 1, **500 parts of tetrahydrofuran and 10 parts of p-phenylenediamine were used as reaction solvents.
8 parts of N,N-diethylaniline were charged, and 195 parts of phenylphosphonic acid dichloride was added dropwise under the same reaction conditions as in Example 1 to react.

2.9 parts of propylene oxide and 7.0 parts of penzoyl chloride are added as terminal stabilizers of the polymer, and the reaction is completed at the boiling point of tetrahydrofuran for 5 hours.

After the reaction, the precipitated polymer and salt are separated in a furnace under reduced pressure, and the mixture of polymer and salt is dried in a vacuum dryer.

The mixture was suspended in hot water and stirred to dissolve only the salt, and the polymer was separated in a furnace and dried to obtain 224.3 parts of a pale yellow solid.

The average molecular weight of the polymer was 20,000.

Example 6 Using the same apparatus as in Example 1, 500 parts of 0-dichlorobenzene, 86 parts of piperazine, and 217 parts of N-methylpiperidine were used as reaction solvents. 8 parts of phenylphosphonic acid dichloride 195 was prepared under the same reaction conditions as in Example 1.
dropwise to react.

Diphenylamine 8.4 as a stabilizer at the polymer end
1 part and 13.4 parts of diphenyl phosphoric acid monochloride were added and reacted at 50 to 60°C for 5 hours to complete the entire reaction.

After the reaction, the precipitated salt is separated in a furnace under reduced pressure, and 0 is extracted from the obtained furnace liquid.
- Dichlorobenzene is distilled off under reduced pressure and dried in a vacuum dryer, and the resulting polymer is pulverized, washed with water, and dried to form a pale yellow solid 197. 6 parts were obtained.

The average molecular weight of the polymer was 18,500.

Reference Example Viscose prepared by adding 48% carbon disulfide to cellulose and having a cellulose concentration of 7.5% and an alkali concentration of 4.2 or more was thoroughly tested to a viscosity of 200 poise and a salt point of 16.

To 100 parts of this viscose, 3.7 parts of a 1,2-dichloroethane solution (solid content concentration 50%) of the polymer shown by the following formula produced in Example 2 was added, mixed uniformly, and 18 g of sulfuric acid was added. /l, sodium sulfate 70 g/l, zinc sulfate 0
．． 4f! It was spun into a spinning bath containing /l.

The yarn that came out of the spinning bath was drawn 100 times in a second bath at 80°C containing 2 g/l of sulfuric acid, and then continuously stretched 100% in a second bath at 80°C containing 5 g/1 sulfuric acid. , continuously 5 g/
Regeneration was completed by treatment with a 60° C. bath containing 1 ml of sulfuric acid.

Next, it was desulfurized, bleached, and treated with an acid using conventional methods, and then treated with an oil solution and dried.

The spinning yield of the polymer used was very excellent at 97 yen, and there were no problems with the spinning operability or the various fiber properties of the obtained fibers.

In addition, plain woven fabric (fabric weight 24
09/m) has a limiting oxygen index (LOI) of 30.0 according to JIS-K-7201, and JIS-L-109
When we conducted a 45° flame retardancy test in accordance with 1 (A-I), the carbonized area was 24.5 cI1 even after 5 washes! L was very good.

Claims (1)

[Scope of Claims] 1. Condensation polymerization of phosphoric acid dihalides or phosphonic acid dihalides and a diamine compound in an organic solvent in the presence of an acid absorbing agent to produce a high polymer having repeating units represented by the following general formula, A method for producing poly-IJ phosphonic acid amide or polyphosphonic acid amide, which further comprises treating both ends of this high polymer with a compound containing groups shown in A and B below. (However, in the formula, R1 represents an alkyl group having 1 to 6 carbon atoms, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxy group, an aryloxy group, a halogenated alkoxy group, or a halogenated aryloxy group, and R2 is It is an alkylene group or arylene group having 1 to 6 carbon atoms. R3 and R4 represent hydrogen or an alkyl group or aryl group having 1 to 6 carbon atoms, and R3 and R4 are bonded to each other to form a ring. (Halogen shown here indicates CI or Br. n indicates an integer from 1 to 1000.)