JPS63135396A - Novel organic phosphorus compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R is bifunctional organic group; aromatic ring may have a substituent group). EXAMPLE:A compound expressed by formula II. USE:A raw material for polyesters having excellent flame retardance, additives, e.g. stabilizer, flame retardant. PREPARATION:For example, a phosphinic acid derivative, expressed by formula III and having an aromatic diol group is reacted with the corresponding glycidyl compound, e.g. polyethylene glycol diglycidyl ether, preferably at 1 equivalent ratio, if necessary, in a solvent, preferably in the presence of a catalyst, e.g. Li, Mg, Cu, Fe, while heating.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a novel organophosphorus compound.

More specifically, the present invention relates to a novel organic phosphorus compound that can be used as a raw material for polyester having excellent flame retardancy, or as an additive such as a stabilizer or a flame retardant.

(Prior Art) Conventionally, 9,10-dihydro-9-oxa-10-(2'
, 5'-dihydroxyphenyl)phosphaphenanthrene-10-oxide is known (Japanese Unexamined Patent Publication No. 1986-1
26293).

(Problems to be Solved by the Invention) However, when polyester is synthesized using the diol component represented by the above formula (ll), although it has excellent heat resistance and flame retardance, it is not only expensive but also .

It is difficult to increase the degree of polymerization in some cases, resulting in poor productivity.

Therefore, a main object of the present invention is to economically provide a novel organic phosphorus compound that can be used as a flame retardant for polyester or as a raw material for polyester having a high degree of flame retardancy.

(Means for Solving the Problems) As a result of intensive research into raw materials for such polyesters, the present inventors have found that organic phosphorus compounds having a specific structure are extremely suitable flame retardants for polyesters or raw materials thereof. Heading 9 This is what led to the present invention.

That is, the second invention is an organic phosphorus compound represented by the following structural formula (1).

(In the formula, R represents a divalent organic group. However, the aromatic "1" may have a substituent.) R in the structural formula (1) is an alkylene group.

Preferred are alkylidene groups, arylene groups, divalent acyl groups, and the like. Further, the aromatic ring in Structural Formula (1) may have a substituent such as an alkyl group, an aryl group, or an atom.

The compound of the present invention has the following formula (li
It can be produced by reacting the phosphinic acid derivative (hereinafter abbreviated as HCA) having an aromatic diol group represented by t) with the corresponding glycidyl compound directly or by heating in an appropriate solvent.

(2) The glycidyl compound used in the production of the organic phosphorus compound of the present invention may be l''J as long as it reacts with HCA to form a compound represented by the above formula (1).

Specific examples include sorbitol polyglycidyl ether,
Polyglycerol polyglycidyl ether.

Pentaerythritol polyglycidyl ether.

diglycerol polyglycidyl ether, triglycidyl ether, -tris-(2-hydroxyethyl) isocyanurate, glycerol polyglycidyl ether,
Trimethylolpronochloride polyglycidyl ether, resorcinol glycidyl ether, neopentyl glycol, 1,6-hexanethiol diglycidyl ether, bisphenol S diglycidyl ether, ethylene-polyethylene glycol diglycidyl ether, propylene Polypropylene diglycidyl ether, polytetramethylene glycol diglycidyl ether, allyl glycidyl ether.

2-ethylhexyl glycidyl ether, phenyl glycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, dibromophenyl glycidyl ether, dibromoneopentyl glycol diglycidyl ether, etc. From the viewpoint of preventing gelation of polyester when used as a raw material for polyester such as terephthalate or as a flame retardant, diglycidyl ether compounds and diglycidyl ester compounds, specifically ethylene glycol sifuricidyl ether, Polyethylene glycol diglycidyl ether, resorcin diglycidyl ether, phthalic acid diglycidyl ether, etc. are preferably used.

When producing the organic phosphorus compound of the present invention, the equivalent ratio of HCA and glycidyl compound at the time of charging is 08 to 1.2. Optimally, the equivalence ratio may be set to 1.

In order to obtain the organic phosphorus compound of the present invention in good yield, it is particularly preferable to use a catalyst, and examples of such solvents include lithium, sodium, potassium, magnesium, aluminum, calcium, iron, cobalt, ester, and copper. , +lead, kermanium, silver.

Gold such as tin, titanium, manganese, or lead
It is preferable to use one or more compounds selected from among the compounds.

In order to obtain the organic phosphorus compound of the present invention in a short time, HCA
Although it is preferable to directly react the glycidyl compound with the glycidyl compound, it is also effective to use a solvent.

Examples of such solvents include methanol, ethanol, impropatol, chloroform, dimethylformamide, dimethyl sulfoxide, dioxane, ethyl cellosol, methyl cellosol, tolune, ortho-xylene, meta-xylene, paraxylene, various mixed xylenes, ethylbenzene, cumene, pseudocumene. One or more compounds selected from alkyl aromatic hydrocarbons such as , cymene, methylnaphthalene, etc. may be used in an amount of usually 1 to 20 moles, preferably 3 to 6 moles, per mole of H CA used. In addition, 2 reaction temperature conditions and reaction time are below the boiling point of the glycidyl compound and solvent, preferably 80 to 250
The reaction is allowed to occur at a temperature of several minutes to several hours, preferably 30 minutes to 3 hours.

Further, as the solvent used for recrystallization to increase the purity of the product, an organic compound having a boiling point of 250° C. or lower and a melting point of 20° C. or lower is preferable. Two specific examples of these include ebuluene, ortho-xylene, meta-xylene, baraxylene,
Mixed xylenes of various compositions.

Examples include alkyl aromatic hydrocarbons such as ethylbenzene, cumene, punidocumene, cymene, methylnaphthalene, etc., ketones such as acetophenone, anisole, etc., and ether compounds, and alcohols such as methanol, ethanol, etc.

A novel polyester with good flame retardancy can be produced by using the organic phosphorus compound of the present invention as one component. Furthermore, it is also possible to use the compound of the present invention as it is or in the form of a polyester oligomer or polymer as an additive such as a stabilizer or flame retardant for other general-purpose polyesters such as polyethylene terephthalate and polybutylene terephthalate.

(Example) Next, the present invention will be explained in more detail with reference to Examples.

Note that the yield of the organic phosphorus compound referred to in the Examples was determined by dividing the yield by the theoretical yield. On the other hand, the two organic phosphorus compounds of the present invention were identified by nine elemental infrared absorption spectroscopy and molecular weight measurement using a hyperphleno-shear osmometer.

Example 1 Two moles of HCA and polyethylene glycol diglycidyl ether (molecular weight approx. 2, 000)4HC
An amount equivalent to A was prepared. The contents were heated to 110°C while slowly flowing nitrogen gas through the gas inlet. After stirring at that temperature for 2 hours, let it cool.
It was purified after returning to room temperature.

The yield of the obtained organic phosphorus compound was 98.1%.

When this was analyzed by infrared absorption spectrum and elemental analysis, the following results were obtained.

It was confirmed that it was an organic phosphorus compound having a structure represented by the following formula (GV).

HO-CH2CH-C1(20-(CH2C)(2-0
) In the m-CH2CH-CH20H infrared absorption spectrum, the chart shown in FIG. 1 was obtained, while the two-element analysis drop was -2. is': C-=45.7-. Coordination 2 (theoretical value 5
6.7 coefficient), H = 8.1 coefficient (theoretical value 8.2 coefficient).

A result of P = 2.44 (theoretical value 2.5%) was obtained. Also.

As a result of measuring the number of molecules, it was confirmed that m in formula (IV) was approximately 44.

Example 2 An organic phosphorus compound was obtained in the same manner as in Example 1 except that ethylene glycol diglycidyl ether was used instead of polyethylene glycol diglycidyl ether and the reaction time was extended from 2 hours to 3 hours.

The yield of the obtained organic phosphorus compound was 951 cm. When this was analyzed by infrared absorption spectrum and elemental analysis, the following results were obtained.

It was confirmed that it was an organic phosphorus compound having a structure represented by the following formula M.

In the infrared absorption spectrum, the chart shown in FIG.
．． Section 3).

A result of p=io, coefficient o (theoretical value coefficient 10.2) was obtained.

The results of Example 2 are listed in Table 1.

Examples 3 to 6 Organophosphorus compounds were obtained in the same manner as in Example 1, except that other glycidyl compounds shown in Table 1 were used instead of polyethylene glycol diglycidyl ether. .

The results of Examples 3 to 6 are listed in Table 1.

Examples 7 to 10 Organic phosphorus compounds were obtained in the same manner as in Example 1, except that the molar ratio of the charged materials was changed as shown in Table 1.

The results of Examples 7 to 10 are listed in Table 1.

Examples 11 to 17 Organic phosphorus compounds were obtained by reacting in the same manner as in Example 1, except that the solvents shown in Table 1 were used.

The results of Examples 11 to 17 are listed in Table 1.

Examples 18 to 22 Organic phosphorus compounds were obtained in the same manner as in Example 1, except that the reaction temperature or reaction time was changed as shown in Table 1.

The results of Examples 18 to 22 are listed in Table 1.

(Reference Example) The organic phosphorus compound obtained in Example 1 was prepared so that the concentration of phosphorus atoms in the polyester was 7,000 ppm.

It was added to bis(β-hydroxyethyl terephthalate) and its low polymer and polymerized to obtain polyethylene terephthalate.

The obtained polyester (infrared absorption spectrum is shown in Figure 3) had an intrinsic viscosity of 0.7. The remaining amount of IJ atoms was 6,670 ppm, and the number of times of flame contact was measured according to a conventional method, and it was found to be 4.8 times.

In addition, flame resistance is determined by spinning and drawing the yarn using a conventional method, making it into a tubular knitted fabric, and rolling the yarn into a length of 10α.
Insert it into the wire coil and hold it at a 45 degree angle 1'C.
Light it with a micro burner (diameter 0.64 mm) from the bottom end, and if the fire is extinguished by moving away from the fire source, repeat the ignition.
The number of ignitions required for all the samples to burn out was determined and expressed as the average value of the number of ignitions (number of flame contacts) for the five samples.

Table 1 In the table, the meanings of the abbreviations are as follows.

PEI: G: Polyethylene glycol DGE Nidiglycidyl ether PE: Pentaerythritol G); S Nigericidyl ester PTMG: Polytetramethylene glycol DMF Nidimethylformamide DMSO Nidimethyl sulfoxide (Effects of the invention) The organic phosphorus compound of the present invention is In addition to being used as a raw material for elegant polyester, it is a new compound that can also be used as a stabilizer for polymers and as a fuel agent.

[Brief explanation of the drawing]

FIG. 1 and FIG. M2 are diagrams showing infrared absorption spectra of the IN-IJ mixtures of the present invention obtained in Example 1 and Flame Example 2, respectively. FIG. 3 is a diagram showing the infrared and sand absorption spectra of the polyester obtained in Winding Example 1 and obtained by adding the organic phosphorus proboscis of the present invention.噸P ridge needle $

Claims (1)

[Claims] (1) An organic phosphorus compound represented by the following structural formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R represents a divalent organic group. However, the aromatic ring may have a substituent.)