JPS5836003B2 - Gun Halogen Yukirinji Yugoutaino Seizouhouhou - Google Patents

Description

Detailed Description of the Invention The present invention uses a halogenated aromatic dialkanol, a cyclic halophosphite, and a carbonyl compound as raw materials,
The present invention relates to a method for producing a novel halogen-containing organic phosphorus polymer.

More specifically, the present invention relates to a halogenated aromatic dialkanol having a structure represented by formula 1), a cyclic halophosphite represented by formula 2), and a carbonyl compound represented by formula (3), respectively described below. The reaction formula (
The present invention relates to a method for producing the halogen-containing organic phosphorus polymer shown in 4).

Here, R is an alkyl group or a haloalkyl group having 1 to 4 carbon atoms, R1 is hydrogen or a methyl group, R2 and R3 are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
It represents a phenyl group, an alkenyl group, or a cyclohexyl group, provided that the case where R2+ and R3 are both H is not included.

X represents a chlorine atom or a bromine atom.

(However, since k is an integer from 1 to 4, in that case, if k is 4, all four Xs are Ce or Br and there is no H, and S is O or an integer from 1 to 4. Therefore, in that case, when S is O, all four Xs are H and there is no C6 or Br. This makes the relationship of s clear as described later, and the in the chemical formula. The difference between and Xs is accepted.

) Z is a sulfone group or a divalent organic group -CH2-MoshiP,
, r is an integer of 1 or more, but when n = O, g = Q m is an integer of 1 or more, n is O or an integer of 1 to 10, k is an integer of 1 to 4, S is O or an integer of 1 to 4 Integers, respectively.

The purpose of the present invention is to provide a novel method for producing a halogen-containing organic phosphorus polymer, in which a metal polymer with excellent heat resistance and alkali resistance is used as a flame retardant for acrylic fibers, epoxy resins, cellulose fibers, etc. In particular, it is an object of the present invention to obtain an industrially advantageous flame retardant that can be added to a spinning dope for acetate fibers and viscose fibers to increase the retention in the fibers from an extremely high level and has good durability.

Conventionally, there has been a method of synthesizing phosphate from a halogenated aromatic diol and an organic phosphorus compound and using it as a flame retardant (Japanese Patent Publication No. 47-4290), and a method of synthesizing polyphosphonate from a cyclic chlorophosphite and a ketone ← Japanese Patent Publication No. 42-
No. 19337) and the like are already known.

However, the method disclosed in Japanese Patent Publication No. 47-4290 requires three steps for the flame retardant synthesis reaction, and since sulfur is used, the product leaves a bad odor, and the phosphorus content is insufficient to be used as a flame retardant for cellulose yarn. However, since it is not a polymer, it has the disadvantage that even if it is added to cellulose yarn, it does not show favorable flame retardant properties in dogs due to shedding.

Furthermore, in the method of Japanese Patent Publication No. 42-19337, it is difficult to control the molecular weight, and as the polymerization time passes, the viscosity of the polymer increases and gelation may occur, and the resulting polyphosphonate has a high acid value. There is a drawback.

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

That is, in the past, there has been no example of a halogenated aromatic dialkanol having excellent heat resistance and flame retardancy being used as a polymerization modifier and flame retardant acid component for polyphosnate, but in the present invention, by using it, heat resistance is improved. , provides a new method for producing stable polyphosphonates with excellent flame retardancy.

The polyphosphonate obtained by the present invention is useful as a flame retardant for various polymeric substances, but in particular, because halogen is introduced into the aromatic nucleus, it has better heat resistance than conventional phosphates and polyphosphonates. It has an excellent flame retardant effect.

Furthermore, the material obtained by the present invention has a very low acid value, so when used as a flame retardant, the fiber quality deteriorates (
Since it is insoluble in water and alkali, it has good washing resistance.

Another characteristic advantage is that there is almost no shedding during the wet spinning process.

By using the halogenated aromatic dialkanol (or halogenated aromatic diglycidyl ether) which is the raw material of the present invention during the polymerization reaction, the molecular weight of the polymer can be adjusted to an arbitrary size and the molecular weight distribution (Mw/Mn ) can be narrowed.

(Mn indicates the number average molecular weight, Mw indicates the weight average molecular weight, and Mw/Mn indicates the molecular weight distribution, and the smaller the value, the narrower the molecular weight distribution.

) The halogenated aromatic dialkanol is reacted with a cyclic halophosphite produced by adjusting the molar ratio of trihalogenated phosphorus to 1,2-alkylene glycol, and a carbonyl compound, and then the halogenated aromatic dialkanol is reacted with a carbonyl compound. By changing the amount of alkanol (or halogenated aromatic diglycidyl ether) used,
It is a noteworthy feature of the present invention that the degree of polymerization of the corresponding phosphonate moieties can be adjusted arbitrarily and extremely easily depending on the purpose of use.

Therefore, in the present invention, the content of halogen atoms and the content of phosphorus atoms bonded to the aromatic nucleus can be changed depending on the purpose of use.

Commonly used halogenated aromatic dialkanols represented by formula (1) used in the present invention include the following compounds.

(E) Instead of the above halogenated aromatic dialkanol,
The corresponding halogenated aromatic diglycidyl ether can be used as an equivalent in the presence of Hcl.

For example, there is something as shown by the following formula.

Commonly used cyclic halophosphites represented by the following formula (2) are as follows.

2-chloro-1,3,2-diophthaphosphorane 2-chloro-4-methyl-1,3,2,-diophthaphosphorane, 2-bromo-1,3,2-diophthaphosphorane 2- Bromo-4-methyl-1,3,2-diophthaphosphorane, the cyclic halophosphite used in the method of the invention is 1.2
- It is synthesized by the reaction of alkylene glycol and trihalogenated phosphorus, but in the present invention, industrially disadvantageous operations such as distillation purification are not performed, and the halogenated aromatic compound is a polymerization modifier and a flame retardant component, which will be described later. In order to fully demonstrate the polymerization control ability of group dialkanols, the molar ratio of phosphorus trihalide to 1.2-alkylene glycol was set to 1.0.
It is particularly desirable to regulate it to 2 to 1.03.

In this way, it is possible to maximize the production rate of cyclic halophosphite, suppress by-products during synthesis of cyclic halophosphite, and reduce by-products during polymerization reaction.

That is, when the molar ratio of phosphorus trihalide to 1.2-alkylene glycol is less than 1.02 (in this case, side reactions proceed with unreacted 1.2-alkylene glycol, and the purity of the crude cyclic halophosphite decreases). decreases.

When such a cyclic halophosphite is reacted with a halogenated aromatic dialkanol, the polymerization control ability decreases and the control range becomes narrower.

In addition, when the molar ratio is larger than 1.03, the acid value of the produced polymer is relatively high compared to when the molar ratio is 1.03 or less due to excess phosphorus trihalide, resulting in low polymerization. As the number of materials increases, durability and alkali resistance also deteriorate.

Therefore, the molar ratio is preferably 1.02 to 1.03.

Commonly used carbonyl compounds represented by formula (3) include ketones and aldehydes, and ketones include aliphatic or alicyclic ketones having 6 or less carbon atoms such as acetone, methyl ethyl ketone, and cyclohexanone. Examples of the aldehyde include aliphatic aldehydes having 6 or less carbon atoms such as acetaldehyde and propionaldehyde.

Although the reaction of the present invention can be carried out without a solvent, it is advantageous to use an inert volatile solvent to facilitate the reaction.

Typical solvents include halogen compounds such as ethane dichloride, carbon tetrachloride, and methylene chloride.

The halogen-containing organic phosphorus polymer obtained in the present invention is soluble in any of the above solvents, but when the solvent is distilled off under reduced pressure, it becomes a colorless, highly viscous liquid or a glassy crystalline solid.

The method of the present invention adds a carbonyl compound in the presence of a halogenated aromatic dialkanol and a cyclic halophosphite that have polymerization control ability and are stable as flame retardant components,
The reaction is carried out at a temperature of -10'C to 40C, but the preferred temperature range is -5C to 20C or less.

At the end of the reaction, residual hydrogen halide is removed by heating to 70°C to 80°C and introducing an inert gas.

The reaction in the present invention described above is itself a considerably exothermic reaction, and the temperature of the reaction system may rise more than necessary, but this can be controlled by an appropriate method as described below.

In general, the molar ratio of raw materials when carrying out the reaction is 1,00 moles of cyclic halophosphite to 1 mole of carbonyl compound.
．． 01 to 1.05 mol is preferred.

Regarding the halogenated aromatic dialkanol, use the amount necessary to obtain a substance with an average molecular weight depending on the purpose, and the halogenated aromatic dialkanol is a cyclic halophosphite.
．． It is preferably 0.5 mol or less relative to 0 mol.

In the present invention, the halogenated aromatic dialkanol is a highly heat-resistant flame retardant component, and is also useful for controlling the degree of polymerization of the polyphosphonate moiety.

The present inventors estimated the structure of the halogen-containing organic phosphorus polymer represented by formula (4) obtained in the present invention based on the following.

That is, as a result of conducting various analyzes of the obtained polymer, it was found that the number average molecular weight of the polymer had a correlation with the mol% of the halogenated aromatic dialkanol used.

Furthermore, the terminal group structure of the halogen-containing organic phosphorus polymer obtained by the method of the present invention is estimated to be an alcoholic 10H group by measuring the acenal value, and is composed of phenyl monoisocyanate, phosphoric acid ester monohalogenide, acetyl monoisocyanate, etc. It is thought that it can be easily blocked with chloride, benzoyl chloride, etc.

Although the method of the present invention has mainly been described above for kneading into polymers, it can of course be used for post-finishing.

Examples of the present invention will be described below, but it goes without saying that the present invention is not limited to these examples.

All parts mentioned in the examples indicate parts by weight.

Example 1 120 parts of 1,2-ethylene dichloride, phosphorus trichloride
A mixed solution consisting of 424 parts was cooled to -5°C and mixed with 1 while stirring.
．． 2-propylene glycol 228 parts (3.0 mol)
was added over a period of 8 hours, and the reaction was allowed to proceed while rapidly removing generated hydrogen chloride to obtain 420 parts of propylene phosphorochloridite.

177 parts of a solvent 1,2-dichloroethane was added to this to maintain cooling.

Next, 96 parts of 2.2-C isopropylidene bis(2,6-dipromo-P-phenoxy)]jetanol (5,
After adding 0 mol%), 176 parts of acetone was quickly added and cooling was continued while the mixture was sealed. The content reached 25°C 1.5 hours after the start of the reaction, but cooling was then stopped and the mixture was allowed to cool at room temperature. Stirred for 60 hours.

The analysis results of the obtained polymer were: 13.3% phosphorus, 6.9% bromine, 15.5% chlorine ※※
Acid value 1.2 (KOH/72@/f)V, P,
0. The number average molecular weight Mn was 4,570.

[V, P, 0. (Vapor pressure
e (abbreviation for Osmome-try) is called a vapor pressure osmosis method, and is a method for directly measuring the molecular weight of polymers with a molecular weight of 20,000 or less.

The measured molecular weight indicates the number average molecular weight.

)] Example 2 Using the same raw materials and reaction conditions as Example 1, simply changing the mol% of 2.2-[isopropylidenebis(2,6-dipromo-P-phenoxy)]jetanol and the molar ratio of phosphorus trichloride to propylene glycol. The results of measuring the number average molecular weight and acid value of the compounds synthesized by changing the additives as shown in the table are shown in Tables 1 and 2 below.

Example 3 281 parts of propylene phosphorochloridite obtained by the same method as Example 1 was dissolved in 400 parts of 1,2-ethylene dichloride, and after cooling to -10°C, 2.2-E
-isopropylidene bis(2,6-dipromo-P-phenoxy)] jetanol 177f (14,0 mol%
), then 89 parts of acetaldehyde were added over 1 hour and stirred, the temperature was raised to 20°C over 2 hours, and the mixture was reacted at the same temperature for 30 hours.

The analysis results of the obtained polymer were 11.2% phosphorus, 12.8% chlorine, and 16.1% bromine, and the acid value was 1.1 (KOHIII9/r), containing V, P,
The number average molecular weight Mn measured by OJC was 1980.

Example 4 1,2-ethylene dichloride 113 parts phosphorus trichloride
186 parts (3.0 mol) of ethylene glycol was added over 10 hours to a mixed solution consisting of 424 parts while stirring while cooling to -5°C, and the generated hydrogen chloride was quickly removed from the system. While the reaction proceeded, a solution containing ethylene phosphorochloridite 3781 was obtained.

In this ethylene phosphorochloridite solution, 1.
Add 500 parts of 2-ethylene dichloride, cool to -5°C and add bis[3,5-dibromo-4-(2-
Hydroxyethoxy[phenyl]sulfone 118? (
6.0 mol%) was added.

Next, 176 parts of acetone was quickly added, and cooling was continued while the mixture was sealed. The content reached 23°C one hour after the start of the reaction, but cooling was then stopped and stirring was continued at room temperature for 48 hours.

The analysis results of the obtained polymer were 13.7% phosphorus, 8.5% bromine, 15.9% chlorine, and acid value 1.
3 (KOHm9/L?), V, P, number average molecular weight Mn measured by OJC was 3840.

Example 5 ※※
Using the same raw materials and reaction conditions as in Example 4, simply bis[3,5-
Table 3 shows the results of measuring the number average molecular weight and acid value of products synthesized by changing only the mole percent of C.J. Romo 4-(2-hydroxyethoxy)phenyl]sulfone.

Example 6 1.2-ethylene dichloride 500 parts halogenated aromatic diglycidyl ether having the structure shown in the following formula 1
22.4 parts (5 mol %) are dissolved and cooled.

Add epoxy oxygen and an equivalent amount of H into this solution at 20°C or below.
el gas was introduced to form the corresponding dialkanol, then 281 parts (2.0 mol) of propylene phosphorochloridite obtained by the same method as in Example 1 were added, and 118 parts (1.02 mol) of acetone were added. After the addition, the mixture was sealed and after the initial heat generation had finished, the reaction was carried out at 40°C for 72 hours.

The analysis results of the obtained polymer were as follows: phosphorus 11.6% chlorine 13.2% bromine 6.0 acid value 1.5 (KOHIIIfI/f) v, p,
Mn measured at o. was 5180.

Example 7 Synthesis was carried out using the same raw materials and reaction conditions as in Example 6, but only by changing the mol% of halogenated aromatic diglycidyl ether, and the measurement results were as shown in Table 4.

Test Example: 10 parts of cellulose diacetate in 90 parts of acetone
1.2 parts of the nitrogen-containing organic phosphorus polymer shown in the above example was added to this solution to prepare a spinning solution.

※※ These spinning solutions were poured onto a flat stainless steel plate and dried to produce a film with a thickness of 0.3 mm.

This film was cut into pieces with a width of 1 Ocrr1 and a weight of 1 g, and the flame retardance was evaluated by the coil method, and the results were as shown in the following table.

From the above table, it is clear that the flame retardance of the composition according to the present invention is excellent.

Claims (1)

[Scope of Claims] 1. A halogenated aromatic dialkanol represented by formula (1), a cyclic halophosphite represented by formula (2), and a carbonyl compound represented by formula (3) are heated at -10°C to 50°C.
Equation (4) is characterized in that the reaction is carried out at a temperature in the range of
A method for producing a halogen-containing organic phosphorus polymer. Here, R is an alkyl group or haloalkyl group having 1 to 4 carbon atoms, R1 is hydrogen or a methyl group R2, R3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
It represents a phenyl group, an alkenyl group, or a cyclohexyl group, but does not include cases where R2 and R3 are both H. X represents a chlorine atom or a bromine atom. (However, since k is an integer from 1 to 4, in that case, if k is 4, all four Xs are C6 or Br and there is no H, and S is O or an integer from 1 to 4. Therefore, in that case, when S is O, all four Xs are H and there is no C/or Br. This makes the relationship of s clear as described later, and the chemical formula The error between Xk and Xs is accepted. ) Z is a sulfone group or a divalent organic group -CH2- if p
2g) r is an integer of 1 or more, provided that when n = 0, g20m is an integer of 1 or more n is O or an integer of 1 to 4 for an integer of 1 to 10 S is O or an integer of 1 to 4 are shown respectively.